Toluene (Methylbenzene) to Benzene by Asch

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165 reactions in Reaxys

2018-04-23 18h:47m:29s (UTC)

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Rx-ID: 3537687 View in Reaxys 1/165 Yield

Conditions & References With modified Y-type faujasites, T= 350 - 500 °C , Product distribution Azzouz, Abdelkrim; Fourar, Mokrane; Berrak, Abderrezak; Bulletin des Societes Chimiques Belges; vol. 95; nb. 12; (1986); p. 1059 - 1066 View in Reaxys With carbon monoxide, HM10 zeolite, T= 399.85 °C , atmospheric pressure, Product distribution, Further Variations: Reagents, Temperatures Agaeva; Dadashev; Tagiev; Abasov; Russian Journal of Applied Chemistry; vol. 78; nb. 11; (2005); p. 1854 - 1858 View in Reaxys 9 :Catalysts A, B, D and E were put through a toluene disproportionation test in the reaction system previously described hereinabove under the following conditions: constant temperature 425°C, pressure 30 bar, hydrogen /toluene molar relation of 8.5, and the spatial velocity was variable from 1 to 12 hr-1 such that it was possible to achieve different degrees of conversion for each catalyst. Figure 3 shows the molar yield of trimethyl benzene (y-axis) as compared for the toluene conversion (x-axis) for catalysts A, B, D and E, Catalyst A is that which makes it possible to obtain a smaller amount of the undesirable reaction product, by increasing the selectivity of the process toward the production of xylenes. Likewise, Figure 4 shows the molar yield of cracking products C1-C4 (y-axis) as compared to the toluene conversion (x-axis) for catalysts A, B, D and E. In this case, with catalyst A, the lowest yields of undesirable cracking products are obtained, by once again increasing the selectivity toward xylenes. With all of the catalysts tested, the same proportion was found to exist among the xylene ortho-, meta- and para-isomers, corresponding to that dictated by thermodynamic equilibrium. Therefore, catalyst A according to the invention shows a high catalytic activity and selectivity toward the production of benzene and xylenes. With hydrogen, ITQ-13 zeolite, T= 425 °C , p= 22502.3Torr , Product distribution / selectivity Patent; CONSEJO SUPERIOR DE INVESTIGACIONES CIENT FICAS; UNIVERSIDAD POLITECNICA DE VALENCIA; EP1775277; (2007); (A1) English View in Reaxys 9 :Catalysts A, B, D and E were put through a toluene disproportionation test in the reaction system previously described hereinabove under the following conditions: constant temperature 425°C, pressure 30 bar, hydrogen /toluene molar relation of 8.5, and the spatial velocity was variable from 1 to 12 hr-1 such that it was possible to achieve different degrees of conversion for each catalyst. Figure 3 shows the molar yield of trimethyl benzene (y-axis) as compared for the toluene conversion (x-axis) for catalysts A, B, D and E, Catalyst A is that which makes it possible to obtain a smaller amount of the undesirable reaction product, by increasing the selectivity of the process toward the production of xylenes. Likewise, Figure 4 shows the molar yield of cracking products C1-C4 (y-axis) as compared to the toluene conversion (x-axis) for catalysts A, B, D and E. In this case, with catalyst A, the lowest yields of undesirable cracking products are obtained, by once again increasing the selectivity toward xylenes. With all of the catalysts tested, the same proportion was found to exist among the xylene ortho-, meta- and para-isomers, corresponding to that dictated by thermodynamic equilibrium. Therefore, catalyst A according to the invention shows a high catalytic activity and selectivity toward the production of benzene and xylenes. With hydrogen, Beta zeolite, acid form, T= 425 °C , p= 22502.3Torr , Product distribution / selectivity Patent; CONSEJO SUPERIOR DE INVESTIGACIONES CIENT FICAS; UNIVERSIDAD POLITECNICA DE VALENCIA; EP1775277; (2007); (A1) English View in Reaxys 9 :Catalysts A, B, D and E were put through a toluene disproportionation test in the reaction system previously described hereinabove under the following conditions: constant temperature 425°C, pressure 30 bar, hydrogen /toluene molar relation of 8.5, and the spatial velocity was variable from 1 to 12 hr-1 such that it was possible to achieve different degrees of conversion for each catalyst. Figure 3 shows the molar yield of trimethyl benzene (y-axis) as compared for the toluene conversion (x-axis) for catalysts A, B, D and E, Catalyst A is that which makes it possible to obtain a smaller amount of the undesirable reaction product, by increasing the selectivity of the process toward the production of xylenes. Likewise, Figure 4 shows the molar yield of cracking products C1-C4 (y-axis) as compared to the toluene conversion (x-axis) for catalysts A, B, D and E. In this case, with catalyst A, the lowest yields of undesirable cracking products are obtained, by once again increasing the selectivity toward xylenes. With all of the catalysts tested, the same proportion was found to exist among the xylene ortho-, meta- and para-isomers,

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corresponding to that dictated by thermodynamic equilibrium. Therefore, catalyst A according to the invention shows a high catalytic activity and selectivity toward the production of benzene and xylenes. With hydrogen, Mordenite zeolite, acid form, T= 425 °C , p= 22502.3Torr , Product distribution / selectivity Patent; CONSEJO SUPERIOR DE INVESTIGACIONES CIENT FICAS; UNIVERSIDAD POLITECNICA DE VALENCIA; EP1775277; (2007); (A1) English View in Reaxys 9 :Catalysts A, B, D and E were put through a toluene disproportionation test in the reaction system previously described hereinabove under the following conditions: constant temperature 425°C, pressure 30 bar, hydrogen /toluene molar relation of 8.5, and the spatial velocity was variable from 1 to 12 hr-1 such that it was possible to achieve different degrees of conversion for each catalyst. Figure 3 shows the molar yield of trimethyl benzene (y-axis) as compared for the toluene conversion (x-axis) for catalysts A, B, D and E, Catalyst A is that which makes it possible to obtain a smaller amount of the undesirable reaction product, by increasing the selectivity of the process toward the production of xylenes. Likewise, Figure 4 shows the molar yield of cracking products C1-C4 (y-axis) as compared to the toluene conversion (x-axis) for catalysts A, B, D and E. In this case, with catalyst A, the lowest yields of undesirable cracking products are obtained, by once again increasing the selectivity toward xylenes. With all of the catalysts tested, the same proportion was found to exist among the xylene ortho-, meta- and para-isomers, corresponding to that dictated by thermodynamic equilibrium. Therefore, catalyst A according to the invention shows a high catalytic activity and selectivity toward the production of benzene and xylenes. With hydrogen, ZSM-5 zeolite, acid form, T= 425 °C , p= 22502.3Torr , Product distribution / selectivity Patent; CONSEJO SUPERIOR DE INVESTIGACIONES CIENT FICAS; UNIVERSIDAD POLITECNICA DE VALENCIA; EP1775277; (2007); (A1) English View in Reaxys With H-(Si,Fe)-MCM-22 zeolite, T= 399.84 °C , Inert atmosphere, Mechanism, Reagent/catalyst, Temperature Fechete, Ioana; Gautron, Eric; Dumitriu, Emil; Lutic, Doina; Caullet, Philippe; Kessler, Henri; Revue Roumaine de Chimie; vol. 53; nb. 1; (2008); p. 49 - 54 View in Reaxys With H-ZSM-5, Time= 0.0833333h, T= 300 - 350 °C Jo, Donghui; Park, Gi Tae; Shin, Jiho; Hong, Suk Bong; Angewandte Chemie - International Edition; vol. 57; nb. 8; (2018); p. 2199 - 2203; Angew. Chem.; vol. 130; (2018); p. 2221 - 2225,5 View in Reaxys

Rx-ID: 32171194 View in Reaxys 2/165 Yield

Conditions & References With TNU-9 zeolite, Time= 0.00555556h, T= 350 °C , Kinetics, Reagent/catalyst, Temperature, Time Al-Khattaf; Akhtar; Odedairo; Aitani; Tukur; Kubu; Musilova-Pavlackova; Cejka; Applied Catalysis A: General; vol. 394; nb. 1-2; (2011); p. 176 - 190 View in Reaxys With hydrated high silica zeolite, Time= 0.0833333h, T= 300 - 350 °C , Reagent/catalyst Jo, Donghui; Park, Gi Tae; Shin, Jiho; Hong, Suk Bong; Angewandte Chemie - International Edition; vol. 57; nb. 8; (2018); p. 2199 - 2203; Angew. Chem.; vol. 130; (2018); p. 2221 - 2225,5 View in Reaxys Rx-ID: 44763482 View in Reaxys 3/165

Yield

Conditions & References Catalyst Testing General procedure: The catalyst was tested in a reaction of the oxidationof the sulfur-containing molecules of thiophene, DBT, and 4,6-DMDBT dissolved in toluene (0.1 wt percent in terms of sulfur) with oxygen. The experiments were carried out in a flow reactor placed in a furnace with a fluidized bed of quartz sand for uniform temperature distribution; the catalyst sample

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weight was 2 g (partticle size of 0.5–1.0 mm). The molar ratio was O2/S =120, the gas hourly space velocity (GHSV) was 3000 h–1; the weight hourly space velocity (WHSV) of fuel was 6 h–1; and the temperature range was 245–430°C. The temperature in the catalyst bed was measured with a chromel–alumel thermocouple with an accuracy of 0.5percent. Model fuel was supplied to the reactor from bottom to top. A mixture of oxygen (20.8 vol percent) with helium and toluene were separately supplied to the catalyst bed for preventing the gas-phase combustion of toluene out of this bed. The liquid reaction products were collected in a sample receptacle by their cooling in a reflux condenser at 5°C. With oxygen, T= 430 °C , Gas phase, Flow reactor, Catalytic behavior, Temperature Yashnik; Salnikov; Kerzhentsev; Saraev; Kaichev; Khitsova; Ismagilov; Yamin; Koseoglu; Kinetics and Catalysis; vol. 58; nb. 1; (2017); p. 58 - 72; Kinet. Katal.; vol. 58; nb. 1; (2017); p. 62 - 77,16 View in Reaxys

Rx-ID: 44827234 View in Reaxys 4/165 Yield

Conditions & References Transalkylation Kinetic runs were carried out in a fixed-bed, continuous downflow reactor (SS 316) in vapour phase at 1 atm. Before conducting the experiments, catalyst was activated using nitrogen at a flow of 0.565 L/h (at 100 K higher than the reaction temperature) for 3 h. Reactant feed was introduced into the catalytic reaction system with the help of a pump. Nitrogen to feed flow ratio was kept constant during all experimental runs. The liquid product samples were collected by condensing the product vapors in a condenser. These samples were analyzed in a gas chromatograph equipped with FID detector. The deviations in the results are in the range of ±2percent. With Pr-modified beta zeolite in neat (no solvent), T= 249.84 °C , p= 760.051Torr , Inert atmosphere, Catalytic behavior, Kinetics, Activation energy, Reagent/catalyst, Temperature Thakur, Ruchika; Gupta, Raj K.; Barman, Sanghamitra; Chemical Papers; vol. 71; nb. 1; (2017); p. 137 - 148 View in Reaxys

(v3)

(v3) (v3)

1.5

(v3)

O (v3) O

(v3)

O (v6) (v6)O Mn (v4) O Mn ON (v3) N (v6) (v3) Mn O (v3) O (v4) O NO (v3) (v3) O O (v3) O(v6) (v4) Mn O (v3) (v3) O O (v3) O (v3)

(v3)

O (v4) H (v6) (v3) Mn+ O–O (v4) (v3) –HO (v6) +Mn O (v3) O (v6) (v4) – HO Mn+O (v3) (v3) O + – O Mn O (v3) (v6) H O O(v3) O (v4) O

(v3)

Rx-ID: 45944586 View in Reaxys 5/165 Yield

Conditions & References

77 %

Stage 1: in tetrahydrofuran, Sealed tube, Schlenk technique Stage 2: Kadassery, Karthika J.; Dey, Suman Kr; Friedman, Alan E.; Lacy, David C.; Inorganic Chemistry; vol. 56; nb. 15; (2017); p. 8748 - 8751 View in Reaxys

1.5

(v3)

O (v3) O

(v6) (v6)O Mn (v4) O Mn ON (v3) (v3) (v3) O (v4) NO (v3) (v3) O O O(v6) (v4) Mn (v3)

O (v3)

(v3) (v3) O

(v3)

(v3) (v3)

O O (v3)

O N Mn O

(v3)

(v6)

2H (v6) (v4) O (v3) (v3) O2 (v6) Mn MnO O O(v3) H (v4) O O O(v4) Mn (v3) 2OO(v6) H2 Mn(v4) H O (v6) (v3) O O

(v3)

O (v3)

(v3)

Rx-ID: 45944587 View in Reaxys 6/165 Yield

Conditions & References Stage 1: in tetrahydrofuran, Sealed tube, Schlenk technique Stage 2: Kadassery, Karthika J.; Dey, Suman Kr; Friedman, Alan E.; Lacy, David C.; Inorganic Chemistry; vol. 56; nb. 15; (2017); p. 8748 - 8751

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View in Reaxys

Rx-ID: 46273512 View in Reaxys 7/165 Yield

Conditions & References With water, Time= 0.5h, T= 299.84 °C , Heating Liu, Lina; Wang, Qiang; Song, Jianwei; Ahmad, Shakeel; Yang, Xiaoyi; Sun, Yifei; Catalysis Science and Technology; vol. 7; nb. 18; (2017); p. 4216 - 4231 View in Reaxys

Rx-ID: 46273513 View in Reaxys 8/165 Yield

Conditions & References With water, Time= 0.5h, T= 299.84 °C , Autoclave, Reagent/catalyst Liu, Lina; Wang, Qiang; Song, Jianwei; Ahmad, Shakeel; Yang, Xiaoyi; Sun, Yifei; Catalysis Science and Technology; vol. 7; nb. 18; (2017); p. 4216 - 4231 View in Reaxys

Rx-ID: 46451796 View in Reaxys 9/165 Yield

Conditions & References Stage 1: With ozone, T= 25 °C Stage 2:T= 525 - 870 °C , Inert atmosphere Aghbolaghy, Mostafa; Soltan, Jafar; Chen, Ning; Catalysis Letters; vol. 147; nb. 9; (2017); p. 2421 - 2433 View in Reaxys

Rx-ID: 750462 View in Reaxys 10/165 Yield 5 % Chromat.

Conditions & References With aluminum oxide, T= 550 °C , Product distribution Bragin, O. V.; Vasina, T. V.; Preobrazhenskii, A. V.; Lutovinova, V. N.; Liberman, A. L.; Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation); vol. 31; nb. 10; (1982); p. 2021 - 2027; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; nb. 10; (1982); p. 2296 - 2303 View in Reaxys

19 % Chromat.

With Rh/Al2O3, T= 500 °C , Product distribution Bragin, O. V.; Vasina, T. V.; Preobrazhenskii, A. V.; Lutovinova, V. N.; Liberman, A. L.; Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation); vol. 31; nb. 10; (1982); p. 2021 - 2027; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; nb. 10; (1982); p. 2296 - 2303 View in Reaxys

14.5 % Chromat.

With Pt/Al2O3, T= 550 °C , Product distribution

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Bragin, O. V.; Vasina, T. V.; Preobrazhenskii, A. V.; Lutovinova, V. N.; Liberman, A. L.; Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation); vol. 31; nb. 10; (1982); p. 2021 - 2027; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; nb. 10; (1982); p. 2296 - 2303 View in Reaxys With H-mordenite in H-form, Time= 4h, T= 150 - 200 °C , Mechanism Yatovt, I. L.; Kotov, E. I.; Bursian, N. R.; J. Appl. Chem. USSR (Engl. Transl.); vol. 55; nb. 10; (1982); p. 2276 - 2280,2087 2090 View in Reaxys With silica zeolite ZSM-5, T= 420 - 500 °C , disproportionation reaction, selectivity, Product distribution Penchev, V.; Mavrodinova, V.; Minchev, Khr.; Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation); vol. 31; nb. 5; (1982); p. 1042 - 1045; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; nb. 5; (1982); p. 1168 - 1171 View in Reaxys With NTsVM zeolite, T= 550 °C , other catalysts, var. temp., Product distribution Stepanova, E. A.; Rat'ko, A. I.; Komarov, V. S.; Russian Journal of Applied Chemistry; vol. 67; nb. 2.1; (1994); p. 225 - 228; Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation); vol. 67; nb. 2; (1994); p. 249 - 253 View in Reaxys With AsI2 (1+)*C6H6, Rate constant Sievers, Heinrich L.; Gruetzmacher, Hans-Fr.; Gruetzmacher, Hansjoerg; Pitter, Stefan; Journal of the American Chemical Society; vol. 117; nb. 8; (1995); p. 2313 - 2320 View in Reaxys T= 470 °C , p= 102971Torr , Leiten ueber MoS2 Putschkow; Nikolajewa; Zhurnal Obshchei Khimii; vol. 8; (1938); p. 1756,1760, 1761; Chem. Zentralbl.; vol. 110; nb. II; (1939); p. 4459 View in Reaxys Leiten ueber aktive Kohle Gurwitsch; Zeitschrift fuer Physikalische Chemie, Stoechiometrie und Verwandtschaftslehre; vol. 107; (1923); p. 246 View in Reaxys With hydrogen Hofmann; Lang; Brennstoff-Chemie; vol. 10; p. 204; Chem. Zentralbl.; vol. 100; nb. II; (1929); p. 164 View in Reaxys Durchleiten durch ein gluehendes Porzellanrohr Berthelot; Bulletin de la Societe Chimique de France; vol. <2> 7; (1867); p. 218; Justus Liebigs Annalen der Chemie; vol. 142; (1867); p. 254 View in Reaxys With lead(II) oxide, T= 335 °C Vincent; Bulletin de la Societe Chimique de France; vol. <3> 4; (1890); p. 7 View in Reaxys Rittman; Byron; Egloff; Chem. Zentralbl.; vol. 87; nb. I; (1916); p. 861 View in Reaxys With aluminium trichloride Anschuetz; Justus Liebigs Annalen der Chemie; vol. 235; (1886); p. 163 View in Reaxys Friedel; Crafts; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 100; (1885); p. 694; Bulletin de la Societe Chimique de France; vol. <2> 39; (1883); p. 195 View in Reaxys

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Lavaux; Annales de Chimie (Cachan, France); vol. <8> 20; (1910); p. 447,468 View in Reaxys With iron oxide, T= 450 °C Oda; Scientific Papers of the Institute of Physical and Chemical Research (Japan); vol. 17; (1931); p. 32,49, 50; ; vol. 34; (1931); p. 142,143 View in Reaxys I :An increased selectivity to A8s at the expense of light ends has been demonstrated in pilot plant tests and is shown in the following material balance comparison. The prior art, gas-phase transalkylation process, is compared against the present invention, which combines a liquid-phase transalkylation process with a gas-phase process. This comparison shows the benefits of the present invention as increased xylenes and ethylbenzene, and concomitantly decreased benzene and light-end gas (especially ethane). By reducing the production of ethane by de-ethylation in gas-phase reactions within an aromatics complex, the invention provides improved total retention of aromatics relative to prior art transalkylation units used in complexes that produce xylenes. With reference to the FIGURE, showing the flow scheme of the present invention, a simulated material balance is shown below. The liquid-phase transalkylation process unit is combined with the gas-phase transalkylation process unit, and results in the following changes over a prior art single gas-phase transalkylation unit. Hydrogen feed to the flow scheme decreases. Feed of toluene and A9+ remains constant. Production of A8s increases, while benzene production decreases. Heavies production remains constant. Most importantly, light-end gas production decreases. These changes are summarized in the following table: Single Gas-phase Two Transalkylation Units Feed (kMTA) Transalkylation Unit (as shown in FIGURE) A9+ 151.7 151.7 Hydrogen (H2) 2.8 2.0 Toluene 151.7 151.7 Total 306.1 305.4 Product (kMTA)A8 208.1 245.5 Benzene 53.1 25.8 Light-end Gas 33.4 22.6 Heavies 11.5 11.5 Total 306.1 305.4 Thus, the flow scheme of the present invention provides a benefit by producing more of the desirable A8 material, which is the valuable xylenes and ethyl benzene. With hydrogen, Product distribution / selectivity Patent; Bogdan, Paula L.; James, Robert B.; Maher, Gregory F.; US2005/215839; (2005); (A1) English View in Reaxys EXAMPLEIn one experiment a Zeolyst Mordenite Extrudate CPX51, from Zeolyst International of Valley Forge, Pa., USA, was used as the base material and was impregnated with 1.914 wt percent Niobium using a wetness incipient method according to the following procedure: 1. The catalyst was dried at 110° C. over night. Its void volume was then measured by filling with deionized water and was calculated as 0.45 ml/g. 2. 3.2703 grams of NbCl5 salt was dissolved in 33.8 ml to make an aqueous solution. 3. The Nb solution was impregnated to the dried catalyst by insipient wetness method. 4. The impregnated catalyst was dried at between 20° C. to 30° C., then dried further at 110° C. Later it was calcined at 550° C. for 2 hrs. The dried catalyst was measured to have 1.914 wt percent Niobium content. The reactor was flushed with flowing nitrogen for 15 minutes and pressure checked. It was switched to hydrogen flow at 1 L/min and the pressure increased to 600 psig. The temperature was ramped at 50° C./h to 200° C. (392° F.) and held overnight. The following morning it was ramped at a rate of 50° C./hr to 250° C. (485° F.) and held for two hours. The hydrogen flow was decreased from 1 L/min to a 1:1 hydrogen to hydrocarbon ratio. The temperature was ramped at 6° C./h to 350° C. (662° F.) after the feed was switched to toluene. Then the temperature was adjusted slowly during the following 2-3 days to achieve 47percent conversion of toluene (about 360° C. or 680° F.). After the nonaromatics content in the product fell below 1percent, the hydrogen ratio to hydrocarbon was increased to 3:1. The first sample showed very low liquid nonaromatics, at 0.5percent on day 1 and then below 0.4percent even without sulfiding during startup. Therefore the hydrogen rate was increased to 3:1 hydrogen to hydrocarbon ratio. With hydrogen, zeolyst mordenite extrudate CPX51 impregnated with 1.914 wtpercent niobium, T= 348.879 - 407.768 °C , p= 31789.8Torr , Product distribution / selectivity Patent; Fina Technology, Inc.; US2010/41934; (2010); (A1) English View in Reaxys 5 :Example 5; The catalysts of Examples 1-4 were tested in an aromatics transalkylation test. Prior to testing, the catalysts were sulfided in-situ as is well known in the art to convert the metals (Mo and Re) and/or their oxides at least partially, to the metal sulfide. An objective of catalyst sulfiding is to add a fixed amount of sulfur to the catalyst. This was accomplished by passing excess dimethyl disulfide (DMDS), equivalent to 150 ppm-wt as sulfur, in the feed over the catalyst at a temperature of 280° C., a pressure of 1,724 kPa(g), a weight hourly space velocity of 4 and a hydrogen to hydrocarbon ratio of 6 for 26 hours. Catalyst sulfiding was continued at a temperature of 360° C. for 12 hours, followed by 2 hours at 350° C. This procedure provides a sulfided catalyst with a relatively fixed sulfur content such that longer sulfiding with excess DMDS will not increase the sulfur content of the catalyst any further. After the sulfiding procedure was complete, feed without a sulfur source was continued to the catalyst for 10 hours as transalkylation conditions were lined out for testing. The following were common to all stages of the test. A pressure of 1,724 kPa(g), a weight hourly space velocity of 4 and a hydrogen to hydrocarbon ratio of 6. Product samples were obtained hourly throughout all stages of the test and were analyzed to determine the benzene purity calculated as benzene/

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(benzene+C6 and C7 non-aromatics) on a weight percent basis.Stage 1 was conducted at 350° C. to establish a base line "dry" performance during the first 10 hours of testing. To ensure the feed had essentially zero water, the feed for all stages of the test was dried first through 3A/13X molecular sieve driers followed by high surface area sodium driers. No water source was added in Stage 1. Tertiary-butyl alcohol (TBA) was then introduced to the dry feed to provide 150 ppm-wt of water based on the mass of the feed stream to begin Stage 2. After 15 hours at these conditions, the TBA was increased to provide 300 ppm-wt of water based on the mass of the feed stream to begin Stage 3. After 7 hours at Stage 3 conditions, the TBA was removed from the feed and water was purged from the system for about 15 hours when dry steady state conditions at 350° C. were attained in Stage 4. The reaction temperature was then increased to 365° C. and baseline dry data was obtained for 10 hours at the higher temperature in Stage 5. TBA was then introduced to the dry feed for 15 hours in Stage 6 to provide 150 ppm-wt of water based on the mass of the feed stream. Finally, the TBA was removed from the feed stream to re-establish dry conditions in Stage 7. The feed had nominally the composition in weight percent given in Table 1. The results for the steady state operation of each stage are reported below in Table 2. With Dimethyldisulphide, hydrogen, tert-butyl alcohol, sulfided molybdenium oxide/ZSM-5 (SiO2/Al2O3=23)/UZM-14 (SiO2/Al2O3=15.9)/Catapal B, Time= 22h, T= 350 °C Patent; UOP LLC; US2012/83635; (2012); (A1) English View in Reaxys 3 :Example 3; The catalysts of Examples 1 and 2 were tested in an aromatics transalkylation test following a standard transalkylation testing procedure. Prior to testing, the catalysts were sulfided in-situ as is well known in the art to convert the MoO3 of the calcined catalyst, at least partially, to molybdenum sulfide. An objective of catalyst sulfiding is to add a fixed amount of sulfur to the catalyst. This was accomplished by passing excess dimethyl disulfide (DMDS), equivalent to 150 ppm-wt as sulfur, in the feed over the catalyst at a temperature of 280° C., a pressure of 250 psig, a weight hourly space velocity of 4 and a hydrogen to hydrocarbon ratio of 6 for 26 hours. Catalyst sulfiding was continued at a temperature of 360° C. for 12 hours, followed by 2 hours at 350° C. This procedure provides a sulfided catalyst with a relatively fixed sulfur content such that longer sulfiding with excess DMDS will not increase the sulfur content of the catalyst any further. After the sulfiding procedure was complete, feed without a sulfur source was introduced to the catalyst for 10 hours. Then, standard transalkylation testing was conducted without sulfur at temperatures ranging from 350° C. to 405° C. for a total time of about 70 hours.Thereafter, the overall conversion, calculated as the net disappearance of toluene, C9 and C10 aromatics from the feed stream, i.e. (mass of toluene, C9 and C10 aromatics in the feed minus mass of toluene, C9 and C10 aromatics in the reaction product)/mass of toluene, C9 and C10 aromatics in the feed, on a weight percent basis; and the benzene purity, calculated as benzene/(benzene plus C6 and C7 non-aromatics) on a weight percent basis, were measured at 365° C., a pressure of 250 psig, a weight hourly space velocity of 4 and a hydrogen to hydrocarbon ratio of 6 during each of the four stages of the test. Product samples were obtained hourly throughout all four stages of the test for analysis. Stage 1 established a base line performance for the first 6 hours of testing with no sulfur addition at the above test conditions. Stage 2 then began when DMDS was added continuously to the feed to obtain 6 ppm-wt of sulfur based on the mass of the feed stream. After a transition period of about 5 hours, steady state performance was observed. For Stage 3, the rate of DMDS introduction was increased to obtain 45 ppm-wt of sulfur based on the mass of the feed stream. After a transition period of about 2 hours, steady state performance was observed. Finally, the sulfur addition as DMDS was discontinued to begin Stage 4. The feed had nominally the composition in weight percent given in Table 1. The results for the steady state operation of each stage are reported below in Table 2. No results are reported for Stage 4 because after sulfur addition was discontinued the benzene purity and overall conversion both trended back towards the sulfur free operating base line of Stage 1 showing the reversible nature of sulfur addition during the transalkylation process. The tests ended after about 20 hours after DMDS addition stopped and before steady state was attained. With Dimethyldisulphide, hydrogen, sulfided molybdenium oxide/ZSM-5 (SiO2/Al2O3=23)/UZM-14 (SiO2/Al2O3=17.7)/Catapal B, T= 365 °C , p= 13689.1Torr , Product distribution / selectivity Patent; UOP LLC; US2012/83636; (2012); (A1) English View in Reaxys 1 : Example 1 The impregnated catalysts were evaluated in a lab scale reactor for disproportionation of toluene to benzene and xylene. The testing conditions are summarized in Table 1:Each new catalyst was loaded into the reactor at the amount of 22 g, which corresponded to 30 cc volume. The reactor was flushed with flowing nitrogen for 15 minutes and pressure checked. The reactor was switched to hydrogen flow at 1 L/min and the pressure increased to 600 psig. The temperature was ramped at 20° C./hr to 360° C. (680° F.), and then the feed was switched to toluene. No sulfiding was done. The temperature was adjusted slowly attempting to maintain about a 40-45 wt percent conversion of toluene. [0045] Table 2 shows the activity and temperatures for the three Nb/ mordenite catalysts. For the Nb 2 wt percent Mordenite catalyst the toluene conversion was about 38percent at a temperature of about 420° C. For the Nb 3 wt percent Mordenite catalyst the toluene conversion was about 41percent at a temperature of about 420° C. FIG. 1 displays graphically the toluene conversion and reaction temperatures for the Nb 2 wt percent Mordenite catalyst and the Nb 3 wt percent Mordenite catalyst.

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With hydrogen, Time= 456h, T= 449 °C , p= 31789.8Torr , Reagent/catalyst, Temperature, Time Patent; FINA TECHNOLOGY, INC.; Butler, James; Khabashesku, Olga; Wachowicz, Darek; Bailey, Callum; US2013/331628; (2013); (A1) English View in Reaxys With tetramethyl-2,2,3,3 butane, cyclopentyl chloride, n-butane, T= 676.84 °C , Catalytic behavior, Reagent/catalyst, Temperature Manion, Jeffrey A.; Sheen, David A.; Awan, Iftikhar A.; Journal of Physical Chemistry A; vol. 119; nb. 28; (2015); p. 7637 7658 View in Reaxys With hierarchical mordenite nanosheets, T= 434.84 °C , Reagent/catalyst Liu, Min; Jia, Wenzhi; Li, Junhui; Wang, Yanan; Ma, Shuwen; Chen, Huanhui; Zhu, Zhirong; Catalysis Letters; vol. 146; nb. 1; (2016); p. 249 - 254 View in Reaxys

Rx-ID: 23138417 View in Reaxys 11/165 Yield

Conditions & References 8 : Example 8 [0034] The toluene selective disproportionation reaction was conducted in the presence of hydrogen using a fixed-bed reactor. The reactor was made from stainless steel tube with an inner diameter of φ25 mm, a length of 1000 mm. Glass beads of φ3 mm were filled both above and beneath the catalyst bed for distributing and supporting. The reactor was loaded with 20 g of a platinum-containing ZSM-5 molecular sieve catalyst. Toluene passed through the catalyst bed from top to bottom after mixing with hydrogen to conduct the toluene selective disproportionation reaction yielding benzene and C8A with a high concentration of pxylene. [0035] The toluene feedstock was from a petrochemical aromatics integrated device, and the H2 was electrolyzed hydrogen treated via dehydration for drying. The reaction temperature was 420° C., reaction pressure was 1.5 MPa, space velocity was 4.0 h-1, and hydrogen/hydrocarbon mole ratio was 3.0. The results are shown in Table 2. With hydrogen, platinum-containing ZSM-5 molecular sieve catalyst, T= 420 °C , p= 11251.1Torr Patent; China Petroleum and Chemical Corporation; US2004/186330; (2004); (A1) English View in Reaxys II :The catalyst was then pre-coked at conditions comprising a temperature of about 560° C., a pressure of 0.72 MPa and 4 weight hourly space velocity (WHSV) in the presence of a 0.5 hydrogen-to-hydrocarbon molar ratio for a period of time sufficient to effect approximately 90 mol-percent para-xylene in total xylenes. Disproportionation of pure toluene then was carried out at 2.45 MPa and 4 WHSV in the presence of pure hydrogen at varying temperatures as required achieving a range of toluene conversion levels.Test-runs were conducted at hydrogen-to-hydrocarbon ratios 3.0, 2.0, 1.0, 0.5 and 0.2 in order to illustrate the invention. FIG. 1 shows the yields of para-xylene at these hydrogen-to-hydrocarbon ratios as toluene conversion increases over the selectively pre-coked catalyst. FIG. 2 shows the yields of benzene at these hydrogen-to-hydrocarbon ratios. Surprisingly, a critical maximum yield of para-xylene was found near a conversion level of 30 wt-percent, and this maximum shifts to even higher conversion levels as the hydrogen-to-hydrocarbon ratio dropped below 3.0.Following FIG. 1, the hydrogen-to-hydrocarbon ratio of 1.0 appears to provide a maximum yield of para-xylene in the range of 12.5 wt-percent over a conversion level from about 30 to about 33 wt-percent. Moreover, when the hydrogen-to-hydrocarbon ratio dropped below 1.0, the maximum shifts to an even higher conversion level. This conversion shift permits even greater yields of para-xylene to be achieved, which are unavailable at higher ratios of hydrogen-to-hydrocarbon.Following FIG. 2, a benzene yield increase was observed as the conversion level of toluene increased in all cases. Yet, at every conversion level the yield of benzene decreases as the hydrogen-to-hydrocarbon ratio decreases. When the conversion level was less than about 33 wt-percent with the hydrogen-to-hydrocarbon ratio less than 1.0, the benzene yield was lower than 15 wt-percent in all cases. With hydrogen, alumina-phosphate-bound MFI catalyst, T= 560 °C , p= 18376.8Torr , Gas phase Patent; UOP LLC; US7230152; (2007); (B1) English View in Reaxys III :The addition of nitrogen during the selectivation phase was investigated by conducting a first test without nitrogen and a test with a nitrogen-to-hydrocarbon ratio of 2.5 while maintaining a ratio of 0.5 hydrogen-to-hydrocarbons for both tests. Tempera-

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tures were maintained at 560° C., pressures at 0.72 MPa, and WHSV at 3 hr-1. Disproportionation was subsequently carried out with pure toluene at 2.45 MPa, a WHSV of 4 hr-1 and at a hydrogen-to-hydrocarbon ratio of 3.0 to achieve a toluene conversion of 30 wt-percent.Data obtained in the disproportionation test showed that at a ratio of para-xylene to total xylenes of 90 wtpercent, the pure hydrogen selectivation procedure achieved a ration of benzene to total xylenes of about 1.6. However, the selectivation procedure using nitrogen achieved a ratio of benzene to total xylenes of about 1.3. Accordingly, the presence of an inert gas such as nitrogen during the selectivation procedure was confirmed to have a beneficial effect of reducing benzene production. With hydrogen, alumina-phosphate-bound MFI catalyst, T= 560 °C , p= 18376.8Torr , Gas phase Patent; UOP LLC; US7230152; (2007); (B1) English View in Reaxys II; III :The catalyst was then pre-coked at conditions comprising a temperature of 5600C, a pressure of 0.72 MPa and 4 weight hourly space velocity (WHSV) in the presence of a 0.5 hydrogen-to-hydrocarbon molar ratio for a period of time sufficient to effect approximately 90 mol-percent para- xylene in total xylenes. Disproportionation of pure toluene then was carried out at 2.45 MPa and 4 WHSV in the presence of pure hydrogen at varying temperatures as required achieving a range of toluene conversion levels.[0044] Test-runs were conducted at hydrogen-to-hydrocarbon ratios 3.0, 2.0, 1.0, 0.5 and 0.2 in order to illustrate the invention. FIG. 1 shows the yields of para-xylene at these hydrogen-to-hydrocarbon ratios as toluene conversion increases over the selectively pre-coked catalyst. FIG. 2 shows the yields of benzene at these hydrogen-to-hydrocarbon ratios.Surprisingly, a critical maximum yield of para-xylene was found near a conversion level of 30 wt-percent, and this maximum shifts to even higher conversion levels as the hydrogen-tohydrocarbon ratio dropped below 3.0. [0045] Following FIG. 1, the hydrogen-tohydrocarbon ratio of 1.0 appears to provide a maximum yield of para-xylene in the range of 12.5 wt-percent over a conversion level from 30 to 33 wt-percent. Moreover, when the hydrogen-to-hydrocarbon ratio dropped below 1.0, the maximum shifts to an even higher conversion level. This conversion shift permits even greater yields of para-xylene to be achieved, which are unavailable at higher ratios of hydrogen-tohydrocarbon. <n="14"/>[0046] Following FIG. 2, a benzene yield increase was observed as the conversion level of toluene increased in all cases. Yet, at every conversion level the yield of benzene decreases as the hydrogen-to-hydrocarbon ratio decreases. When the conversion level was less than 33 wt-percent with the hydrogen-to-hydrocarbon ratio less than 1.0, the benzene yield was lower than 15 wt-percent in all cases.EXAMPLE III[0047] The addition of nitrogen during the selectivation phase was investigated by conducting a first test without nitrogen and a test with a nitrogen-to-hydrocarbon ratio of 2.5 while maintaining a ratio of 0.5 hydrogen-to-hydrocarbons for both tests. Temperatures were maintained at 56O0C, pressures at 0.72 MPa, and WHSV at 3 hr"1. Disproportionation was subsequently carried out with pure toluene at 2.45 MPa, a WHSV of 4 hr"1 and at a hydrogen- to-hydrocarbon ratio of 3.0 to achieve a toluene conversion of 30 wt-percent. With hydrogen, alumina-phosphate-bound MFI catalyst, p= 18376.8Torr , Heating, Product distribution / selectivity Patent; UOP LLC; WO2008/136829; (2008); (A1) English View in Reaxys 1 :A toluene feedstock was obtained by separating a feedstock from a petrochemical aromatic hydrocarbon united plant. The toluene feedstock was subjected to toluene selective disproportionation reaction in a fixed bed reactor in the presence of hydrogen. The reactor had an inner diameter of 25 mm and a length of 1000 mm, and was made of stainless steel. The reactor was packed with 20 g of a ZSM-5 molecular sieve catalyst containing 0.05 wt percent platinum, which had been prepared according to the process as described in CN 1340486A (Process for the preparation of catalysts for toluene selective disproportionation). Glass beads of 3 mm were packed below and above the catalyst bed layer, to take the effect of distributing gas and supporting. The toluene feedstock was mixed with hydrogen and then passed through the catalyst bed layer downwards to perform toluene selective disproportionation reaction, thereby producing benzene and C8A consisting mainly of p-xylene. The hydrogen was electrolytic hydrogen, and was subjected to a dehydration drying treatment before use. The reaction temperature was 420° C., the reaction pressure was 1.5 MPa, the weight hourly space velocity was 4.0 hr-1, and the molar ratio of hydrogen/hydrocarbon was 3.0:1. The reaction results are listed in Table 2. With hydrogen, ZSM-5 zeolitic catalyst with 0.05 wtpercent platinum, T= 420 °C , p= 11251.1Torr , Product distribution / selectivity Patent; China Petroleum and Chemical Corporation; Shanghai Research Institute of Petrochemical Technology Sinopec; US2010/228066; (2010); (A1) English View in Reaxys With TUN/G zeolite, Time= 3h, T= 450 °C , Flow reactor Kub, Martin; Zilkova, Nadezda; Cejka, Jiri; Catalysis Today; vol. 168; nb. 1; (2011); p. 63 - 70 View in Reaxys

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With Al-UTL, T= 450 °C , Catalytic behavior, Reagent/catalyst Zilkova, Nadezda; Shamzhy, Mariya; Shvets, Oleksiy; Cejka, Jiri; Catalysis Today; vol. 204; (2013); p. 22 - 29 View in Reaxys Catalytic reactions General procedure: Toluene disproportionation and alkylation with isopropyl alcohol were investigated in the gas phase under atmospheric pressure using a glass fixed bed microreactor. Each catalyst was pressed into the pellets, crushed and sieved to obtain particles with a diam-eter in the range of 0.50–0.71 mm. Prior to the reaction, a given amount of the catalyst was in situ activated at 500°C for 120 min in a stream of nitrogen (40 ml min−1), and then the activated catalyst was cooled down to the preset reaction temperature. In the case of toluene disproportionation, the reaction temperature was at 450°C, WHSV 20 h−1, and the concentration of toluene in the feed stream using N2 as carrier gas was 18.5 molpercent. Toluene alkylation was studied at the reaction temperature of 250°C. The WHSV related to toluene was 10 h−1, the concentration of toluene was 18.5 molpercent in the feed stream and toluene to isopropyl alcohol molar ratio was 9.6. The reaction feeds and products were analyzed using an online gas chromatograph (HP 6890) equipped with an FID detector and a capillary column (DB-5, 50 m × 320 m × 1 m) in toluene alkylation, while HP-INNO Wax (30 m × 0.32 mm × 0.5 m) was used for toluene disproportionation studies. The first sample was taken after 15 min of time-on-stream (T-O-S) and the other samples were taken in the interval of 60 min. With zeolite TUN, T= 450 °C , p= 760.051Torr , Reagent/catalyst Kubů, Martin; Žilková, Naděžda; Zones, Stacey I.; Chen, Cong-Yan; Al-Khattaf, Sulaiman; Čejka, Jiří; Catalysis Today; vol. 259; (2016); p. 97 - 106 View in Reaxys

(v5) H (v5) (v5) H (v4) H (v5) –C (v4)

SiH SiH

(v5) (v5)H (v4)(v4) (v5) P C –H

Fe (v10) (v4) (v4)

H Si–

(v10)

2+ Fe (v5)

HH (v5) (v5) H Pt C – (v5) (v5) H (v4) (v5) (v4) P (v4)

(v4)

Pt2+ SP-4 – HH C H H P (v4) (v5) (v5) SiH– (v5)(v5)

(v4)

Rx-ID: 41964977 View in Reaxys 12/165 Yield 89 %

Conditions & References Time= 2h, T= 20 °C , Inert atmosphere Kalläne, Sabrina I.; Laubenstein, Reik; Braun, Thomas; Dietrich, Maren; European Journal of Inorganic Chemistry; vol. 2016; nb. 4; (2016); p. 530 - 537 View in Reaxys

(v5) H (v5) (v5) H (v4) (v5) –CH (v4)

(v10)

H2 Si

2+ Fe (v5)

HH (v5) H (v5) Pt C – (v5) (v5) H (v4) (v5) (v4) P (v4)

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(v4) (v5) (v4)(v5) (v5) (v5) H P– H C

H–

H H

2+ Fe (v4)

(v1)

(v10) Pt2+

SP-4 – H HC (v5) H P Si– (v4)(v5) (v5)(v5) H

(v4)

Rx-ID: 41964978 View in Reaxys 13/165 Yield

Conditions & References

94 %

Time= 0.75h, T= 20 °C , Inert atmosphere Kalläne, Sabrina I.; Laubenstein, Reik; Braun, Thomas; Dietrich, Maren; European Journal of Inorganic Chemistry; vol. 2016; nb. 4; (2016); p. 530 - 537 View in Reaxys

Rx-ID: 42278943 View in Reaxys 14/165 Yield

Conditions & References 2.3. Catalysts evaluation Catalytic oxidation runs for abatement of toluenewere performed in a continuous flow fixed bed Pyrexmicro-reactor at atmospheric pressure.About 0.2 g of catalystwas placed in the reactor for each run. To obtain accurate andstable gas flow rates, the mass flow controllers were used.The concentration of toluene was 800 ppm, which wascontrolled by the temperature of a homemade saturator andthe additional air stream. The flow rate of the gas mixturethrough the reactor was 100 mL min1, which gave a GasHourly Space Velocity (GHSV) of 15,000 h1. All the lineswere sufficiently heated at 120 C to prevent the adsorptionand condensation of toluene and water in the tubes.The micro-reactor is placed in an electrical furnacewhich provides the required temperature for catalyticreaction. Catalysts were evaluated in a temperature rangeof 300 Ceroom temperature, with a rate decrease of0.5 C min1. Before each run, the samples were pretreatedfor 4 h at 300 C under an air flow of 75 mL min1. With oxygen, T= 165 °C , p= 760.051Torr , Flow reactor, Catalytic behavior, Temperature, Reagent/catalyst Chlala, Dayan; Labaki, Madona; Giraudon, Jean-Marc; Gardoll, Olivier; Denicourt-Nowicki, Audrey; Roucoux, Alain; Lamonier, Jean-François; Comptes Rendus Chimie; vol. 19; nb. 4; (2016); p. 525 - 537 View in Reaxys

Ag+ O N

– 4 O

4 Ag+

1.08

O–

0.92

4 N

Rx-ID: 47422152 View in Reaxys 15/165 Yield 56 %

Conditions & References in methanol Wright, James S.; Vitórica-Yrezábal, Iñigo J.; Thompson, Stephen P.; Brammer, Lee; Chemistry - A European Journal; vol. 22; nb. 37; (2016); p. 13120 - 13126 View in Reaxys

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(v5)(v5)(v4) (v5) (v5) C –

(v8) (v4) (v4) H (v3) 32- NH 2N N (v5)(v5) (v8) (v5) C 4+Ni (v5) 4+ Ti Ti (v5) (v5) (v5) (v8) C– (v5)–C (v5) N 2(v4) (v4) (v5) H (v5) (v4)

(v8)

Ti4+

(v3) (v5) (v5) (v5) (v5)– (v4)

Ti4+ (v4) (v4) H 2N 2- NH (v5) (v8)(v5)4+ (v5) C Ni 4+ Ti Ti (v5) (v8) C– (v5) N 2(v4) (v5) H (v5)

3-N

(v4)

Rx-ID: 40204262 View in Reaxys 16/165 Yield

Conditions & References

0.06 g

Inert atmosphere Martínez-Espada, Noelia; Mena, Miguel; Pérez-Redondo, Adrián; Varela-Izquierdo, Víctor; Yélamos, Carlos; Dalton Transactions; vol. 44; nb. 21; (2015); p. 9782 - 9794 View in Reaxys

F 2 F

B– F 3

F N

2 F

B– F 3

Pd3( 2+)

Rx-ID: 40677147 View in Reaxys 17/165 Yield

Conditions & References in nitromethane, T= 80 °C , Inert atmosphere, Equilibrium constant Ishikawa, Yuki; Kimura, Seita; Takase, Kohei; Yamamoto, Koji; Kurashige, Yuki; Yanai, Takeshi; Murahashi, Tetsuro; Angewandte Chemie - International Edition; vol. 54; nb. 8; (2015); p. 2482 - 2486; Angew. Chem.; vol. 127; nb. 8; (2015); p. 2512 - 2516,5 View in Reaxys

Rx-ID: 41124693 View in Reaxys 18/165 Yield

Conditions & References Reaction Steps: 2 1: modified KX zeolites / 429.84 °C / 760.05 Torr / Inert atmosphere 2: carbon dioxide / 544.84 °C / 760.05 Torr With carbon dioxide Zhao, Guoqing; Chen, Huanhui; Li, Junhui; Wang, Qunlong; Wang, Yanan; Ma, Shuwen; Zhu, Zhirong; RSC Advances; vol. 5; nb. 92; (2015); p. 75787 - 75793 View in Reaxys Reaction Steps: 2 1: modified NaX zeolites / 429.84 °C / 760.05 Torr / Inert atmosphere 2: carbon dioxide / 544.84 °C / 760.05 Torr With carbon dioxide Zhao, Guoqing; Chen, Huanhui; Li, Junhui; Wang, Qunlong; Wang, Yanan; Ma, Shuwen; Zhu, Zhirong; RSC Advances; vol. 5; nb. 92; (2015); p. 75787 - 75793 View in Reaxys

Rx-ID: 41287993 View in Reaxys 19/165

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Yield

Conditions & References 2.4. catalytic test The total oxidation of toluene was studied in a conventional fixed-bed reactor loaded with 100 mg of catalyst. A toluene/air mixture was generated with a saturator in order to obtain 1000 ppm in a flow of 100 mL/min. Tests were made between 50 and 400 °C with a temperature ramp of 1.5 °C/min. Catalysts were pretreated at 200 °C (heating at 1 °C/min) during 2 h under an air flow (2 L/h). For the impregnated catalysts, they were reduced for 2 h at 200 °C (heating at 1 °C/min) under a dihydrogen (5.0) flow (2 L/h). The organic compounds were analysed by gas chromatography with a CP-4900 microGC (Agilent) coupled with a Pfeiffer-Vacuum OmnistarQuadrupole Mass Spectrometer (QMS-200). The mass spectrometer is configured with a measurement mode MID(Multiple Ion detection) that is adapted for the detection of compounds trace. CO and CO2 were quantified with an infrared analyser (ADEV 4410 IR). With air, palladium impregnated on φ-Al2O3 reduced form, T= 200 °C , Catalytic behavior, Reagent/catalyst, Temperature Brunet, Julien; Genty, Eric; Landkocz, Yann; Zallouha, Margueritta Al; Billet, Sylvain; Courcot, Dominique; Siffert, Stéphane; Thomas, Diane; De Weireld, Guy; Cousin, Renaud; Comptes Rendus Chimie; vol. 18; nb. 10; (2015); p. 1084 1093 View in Reaxys

O Br

(v3)

O Eu2+ (v3) N– O OC-6 N –(v3) (v6) (v3) O

(v3)

racemate

(v3) O N – (v3)O (v3) 2+

Eu (v6) (v2) N OC-6 Br–(v3) (v3)–Br N (v6) (v2) Eu2+ (v3) O OC-6 – (v3) O N (v3)

Rx-ID: 41955179 View in Reaxys 20/165 Yield

Conditions & References

54 %

1,2-Dibromostilbene (0.17 g, 0.5 mmol) was added to a solution of complex 4 (in situ prepared from diimine 1 (0.5 g, 1 mmol) in DME). The brown reaction mixture promptly turned bright cherry colored. Crystallization from benzene gave complex 6 (0.49 g, 54percent) as red crystals, m.p. 265 C. Found (percent): C, 61.12; H, 6.01. C92H112Br2Eu2N4O4 (1801.60 g mol–1). Calculated (percent): C, 61.34; H, 6.27. IR (Nujol), /cm–1: 1671 m, 1643 m, 1590 m, 1515 s, 1311 w, 1251 m, 1185 s, 1073 s, 1031 s, 924 m, 877 m, 836 w, 821 w, 795 w, 777 w, 755 s, 720 w, 667 w, 601 w, 538 w. Stage 1: in 1,2-dimethoxyethane, Schlenk technique Stage 2: Fedushkin; Skatova; Yambulatov; Cherkasov; Demeshko; Russian Chemical Bulletin; vol. 64; nb. 1; (2015); p. 38 - 43; Izv. Akad. Nauk, Ser. Khim.; nb. 1; (2015); p. 38 - 43,6 View in Reaxys

(v3)

O Eu2+ (v3) N– O OC-6 N –(v3) (v6) (v3)

(v3)

Cl racemate

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(v3) O N – (v3)O (v3) Eu2+ (v6) (v2) N OC-6 Cl –(v3) (v3)–Cl N (v6) (v2) 2+

Eu OC-6(v3) – (v3) O N

(v3)

Rx-ID: 41955182 View in Reaxys 21/165 Yield

Conditions & References

41 %

Triphenyltinchloride (0.39 g, 1.0 mmol) was added to a solution of complex 4 (in situ prepared from diimine 1 (0.5 g, 1 mmol) in DME). The brown reaction mixture promptly turned bright cherry colored. The solvent was replaced by benzene; the large colorless crystals of hexaphenyldistannane that formed were filtered off. The benzene solution was concentrated to give complex 5 (0.35 g, 41percent) as red orthorhombic crystals, m.p. 280 C. Found (percent): C, 64.12; H, 6.31. C92H112Cl2Eu2N4O4 (1712.67 g mol–1). Calculated (percent):C, 64.52; H, 6.59. IR (Nujol), /cm–1: 1670 m, 1643 m, 1592 m, 1520 s, 1311 w, 1251 m, 1183 w, 1073 s, 1113 m, 1073 m, 1038 m, 924 s, 861 w, 835 w, 816 w, 788 m, 751 s, 723 s, 664 w, 601 w, 536 w. Stage 1: in 1,2-dimethoxyethane, Schlenk technique Stage 2:, Schlenk technique Fedushkin; Skatova; Yambulatov; Cherkasov; Demeshko; Russian Chemical Bulletin; vol. 64; nb. 1; (2015); p. 38 - 43; Izv. Akad. Nauk, Ser. Khim.; nb. 1; (2015); p. 38 - 43,6 View in Reaxys

Rx-ID: 37387312 View in Reaxys 22/165 Yield

Conditions & References With HZSM-5, Time= 0.166667h, T= 420 °C , p= 760.051Torr Bi, Yi; Wang, Yingli; Wei, Yingxu; He, Yanli; Yu, Zhengxi; Liu, Zhongmin; Xu, Lei; ChemCatChem; vol. 6; nb. 3; (2014); p. 713 - 718 View in Reaxys

H O

Rx-ID: 37524124 View in Reaxys 23/165 Yield

Conditions & References The photocatalytic activities of the mesoporous SiO2doped TiO2fibers with different SiO2molar content were investigated by clean-ing gaseous toluene under UV irradiation. The gaseous toluene wasplaced in dark for 2 h without any light before photooxidation toachieve gas-solid adsorption equilibrium on the surface of fibrouscatalysts. Then, the toluene in bottle was irradiated by a 300 Whigh pressure mercury lamp ( = 365 nm, Yaming, Shanghai, China)while being stirred by a special magneton. The reacted gaseoussamples were withdrawn at regular time intervals from 5 to 30 minby a 50 L gastight pressure-locked precision analytical syringe(Gaoge, Shanghai, China) and measured with a gas chromatograph(Agilent 6890, USA) equipped with a flame ionization detectorand an HP-5MS capillary column (0.25 mm i.d. × 30 m). A blankexperiment without any catalyst under same conditions was alsoconducted as a comparison Stage 1: With SiO2 doped TiO2, Time= 2h, Darkness Stage 2:, UV-irradiation Zhan, Sihui; Yang, Yang; Gao, Xichao; Yu, Hongbing; Yang, Shanshan; Zhu, Dandan; Li, Yi; Catalysis Today; vol. 225; (2014); p. 10 - 17 View in Reaxys

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(v5) (v5) (v5) (v5) (v4)

C – (v3) C– (v4) (v12) – H (v2)(v3) – 2+ Y3+ –(v5) H Mo (v13) H (v12) (v5) – (v3) Y3+(v5) (v5)H (v5) (v3) –H (v12) – H (v3) Y3+ (v4) (v3) –C(v5)–H C– – (v4) (v4) C (v5) – H – 3+(v5) (v5) H (v2) Mo2+ – Y (v5) – (v5) H (v5) (v5) (v3) (v12)C (v13) (v5) (v5) (v5)(v5)

(v3)

(v4) (v5)

(v5)

(v5)(v2) (v5) – H(v5) (v4) (v5) (v5) – C –(v5) C (v5) (v11) Y3+ (v2) – (v5) (v4) 3+Y– (v5) – – H H H (v4)(v5) C (v10) (v3) (v5) (v3)H – (v2) H – Mo3+ (v2) (v11) (v5) – (v5) – (v3) 3+ H – (v2) (v9) (v2) H – Y C H (v10) (v4) (v5) –(v5) Y–3+ (v5) H (v5) H– Y–3+ (v2) – C (v3) (v5)(v4) (v5) C (v11) H (v4) (v2) (v5) (v5) (v5) (v5) (v5)

Rx-ID: 36119346 View in Reaxys 24/165 Yield

Conditions & References in benzene-d6, Time= 0.5h, T= 20 °C , p= 760.051Torr , Inert atmosphere, Glovebox, Schlenk technique Shima, Takanori; Hou, Zhaomin; Chemistry - A European Journal; vol. 19; nb. 10; (2013); p. 3458 - 3466 View in Reaxys

C–

O CH –

11 H –

W 4+

Y3+

5 H–

(v4) (v5) (v5) (v5) (v4)– (v2) (v5) (v5) – (v5) (v5) (v5) C(v4) (v5) W 4+H(v3) – (v5) (v2) (v2) – (v4) C–H(v10) H CH–– (v5) (v2) 3+ (v5) (v5) 3+ –H H– Y – Y (v11) (v10) 3+ H (v5) (v5) Y (v2) (v5) (v10) (v3)– C– (v2) H– – (v2) – H – HH H (v2) (v4) H (v2) 3+ 4+ (v10) (v2) Y–H W H– (v10) (v2) – C(v2) (v5) (v5) (v4) (v5)(v5) C –(v5) (v5) (v5)(v5) (v4)

C–

W 6+

Rx-ID: 36119354 View in Reaxys 25/165 Yield

Conditions & References

53 %

in toluene, Time= 6h, T= 50 °C , Inert atmosphere, Glovebox, Schlenk technique Shima, Takanori; Hou, Zhaomin; Chemistry - A European Journal; vol. 19; nb. 10; (2013); p. 3458 - 3466 View in Reaxys

Rx-ID: 36192798 View in Reaxys 26/165 Yield

Conditions & References In situ methylation The bifunctional catalyst (CrZ HZ) was pre-pelletized and sievedinto a 250–500 m fraction. Typically, 1.0 g of sieved catalyst(CrZ:HZSM-5 = 1:1 weight ratio) was loaded into the reactor. Theupper space of the catalyst bed was filled with glass beads(1–1.25 mm) for preheating and as a distribution zone of the feedstream. Then, the catalyst was subjected to pretreatment proce-dures involving drying and reduction with GHSVs of gases basedon the weight of methanol synthesis catalysts described above.After pretreatment, the reactor temperature was reduced to 120C,and the reaction feed mixture (H2/CO/N2/Toluene = 2/1/1/0.5,GHSV = 5835 cm3/h gcat, Toluene WHSV = 4 h−1) was introducedinto the reactor. The feed rate of toluene (Tol) was controlled byan HPLC pump while gas flow rates were controlled by mass flowcontrollers. The reactor pressure was raised to 460 psig, and thenthe reactor temperature was raised to the range of 350–500C toinvestigate the catalytic activities in the in situ methylation. Thereactor effluent was introduced on-line into a gas–liquid separa-tor with a liquid sampling port and a cooling jacket connected to a coolant circulator. The gas products from the separator overheadwere analyzed by an on-line GC equipped with a packed column(Porapack Q/MS 5A) connected to a TCD for H2/CO/N2and lighthydrocarbon products, and with a capillary column (HP-INNOWax,60 m × 0.32 mm × 0.5 m) connected to an FID for hydrocarbonproducts. Liquid product sampled from the bottom of the separatorwas analyzed by an off-line GC equipped with a capillary column(HP-INNOWax, 60 m × 0.32 mm × 0.5 m) connected to an FID. Toinvestigate the effect of catalytic functions on the in situ methyl-ation, bifunctional catalyst mixtures with three different weightratios of CrZ catalyst to HZSM-5 were tested (0.5:1, 1:1 and 1:0.5).For a control experiment, a stacked catalyst bed system (a methanolsynthesis catalyst on top of an HZSM-5 bed) was employed to inves-tigate the catalytic synergy in the in situ methylation in comparisonto the standard bed of well-mixed bifunctional catalyst. Productsamples were analyzed after the initial stabilization with time-on-stream (TOS) of 1.5–2 h.

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With hydrogen, T= 450 °C , p= 24549.5Torr , Flow reactor, Inert atmosphere, Temperature Lee, Seulah; Kim, Donguk; Lee, Jihye; Choi, Yeseul; Suh, Young-Woong; Lee, Changq; Kim, Tae Jin; Lee, Seong Jun; Lee, Jung Kyoo; Applied Catalysis A: General; vol. 466; (2013); p. 90 - 97 View in Reaxys

(v5) (v5) (v5) (v5) CH – (v4) (v7) Ru 2+

0.6

(v5)

(v4) (v5) H – C (v5) (v5)

C–

(v10)

(v5) (v5) N (v5)(v5) N

Ru–2+ CN (v5) (v4)

(v5) (v5)(v5)

Rx-ID: 37034440 View in Reaxys 27/165 Yield

Conditions & References in hexane, Schlenk technique, Glovebox, Inert atmosphere Annibale, Vincent T.; Batcup, Rhys; Bai, Tao; Hughes, Sarah J.; Song, Datong; Organometallics; vol. 32; nb. 21; (2013); p. 6511 - 6521 View in Reaxys

O (v2)

Ge 9K4

H 2N

NH 2

O O

C– H 2N 2 NH 2

O O (v3) (v3) N (v8) K+ N (v4) (v3) O (v3) O O (v3) O

(v4)

Zn 2+

(v3)

Ge 9( 4-)

Rx-ID: 37204726 View in Reaxys 28/165 Yield

Conditions & References Stage 1:Time= 0.0833333h, Inert atmosphere, Schlenk technique, Glovebox Stage 2:Time= 2h, T= 20 °C , Inert atmosphere, Schlenk technique, Glovebox Stage 3: Benda, Christian B.; Schaeper, Raphaela; Schulz, Stephan; Faessler, Thomas F.; European Journal of Inorganic Chemistry; nb. 35; (2013); p. 5964 - 5968 View in Reaxys

(v3)(v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3)(v3) (v3) (v3) (v3) (v3) (v3)(v3) (v3) (v3) (v3) (v3) (v3) (v3) Sm (v3) (v3) (v3) (v3) (v3) (v3) (v3)(v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3)(v3) (v3) (v3) (v3)

N (v4)

(v4)

Ni SP-4 (v4)

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N–

0.4

N (v3) 2+ (v4) (v4) Ni (v3) (v4) – N SP-4

1.6

(v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3)(v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3)(v3) (v3) (v3)(v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3)(v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3)(v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3)(v3) (v3) (v3) (v3)(v3) (v3) (v3) (v3)

Rx-ID: 33656104 View in Reaxys 29/165 Yield

Conditions & References in toluene, benzene Jin, Hongxiao; Yang, Hua; Yu, Meilan; Liu, Ziyang; Beavers, Christine M.; Olmstead, Marilyn M.; Balch, Alan L.; Journal of the American Chemical Society; vol. 134; nb. 26; (2012); p. 10933 - 10941 ; (from Gmelin) View in Reaxys

2+Al

Al2+

(v4)

N Al

(v4)

3.5

N–

(v4) (v4)

Al N

N–

Rx-ID: 34306809 View in Reaxys 30/165 Yield 57 %

Conditions & References Stage 1: in toluene, T= 20 °C , Schlenk technique Stage 2:T= 20 °C Fedushkin, Igor L.; Moskalev, Mikhail V.; Lukoyanov, Anton N.; Tishkina, Alexandra N.; Baranov, Evgenii V.; Abakumov, Gleb A.; Chemistry--A European Journal; vol. 18; nb. 36; (2012); p. 11264 - 11276,13 View in Reaxys

Rx-ID: 3536846 View in Reaxys 31/165 Yield

Conditions & References

41.4 % Chromat., 25.0 % Chromat., 21.3 % Chromat.

With oxygen, magnesium oxide, lead(II) oxide, Time= 3h, T= 699.9 °C , other temperatures, other reaction times, other catalysts, Product distribution

41.4 % Chromat., 25.0 % Chromat., 21.3 % Chromat.

With oxygen, magnesium oxide, lead(II) oxide, Time= 3h, T= 699.9 °C , other temperature, other reaction time, other catalysts

Osada, Yo; Okino, Nobutaka; Ogasawara, Sadao; Fukushima, Takakazu; Shikada, Tsumoto; Ikariya, Takao; Chemistry Letters; nb. 2; (1990); p. 281 - 282 View in Reaxys

With oxygen, magnesium oxide, lead(II) oxide, T= 700 °C , Yield given. Yields of byproduct given

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Osada, Yo; Enomoto, Koichi; Fukushima, Takakazu; Ogasawara, Sadao; Shikada, Tsutomu; Ikariya, Takao; Journal of the Chemical Society, Chemical Communications; nb. 16; (1989); p. 1156 - 1157 View in Reaxys 15.5 % Chromat., 53.3 % Chromat., 13.4 % Chromat.

With oxygen, magnesium oxide, lithium oxide, Time= 3h, T= 699.9 °C , other temperature, other reaction time, other catalysts Osada, Yo; Okino, Nobutaka; Ogasawara, Sadao; Fukushima, Takakazu; Shikada, Tsumoto; Ikariya, Takao; Chemistry Letters; nb. 2; (1990); p. 281 - 282 View in Reaxys

With oxygen, lithium superoxide, magnesium oxide, T= 700 °C , Yield given. Yields of byproduct given Osada, Yo; Enomoto, Koichi; Fukushima, Takakazu; Ogasawara, Sadao; Shikada, Tsutomu; Ikariya, Takao; Journal of the Chemical Society, Chemical Communications; nb. 16; (1989); p. 1156 - 1157 View in Reaxys D :An oxidative catalyst was prepared comprising an oxide substrate, MgO, that was promoted with Ca and La. The Ca/La/MgO catalyst was used in the oxidative coupling of methane to toluene. The catalyst included 5percent Ca by weight from Calcium oxide (2.10 g) and 5percent La by weight from lanthanum oxide (3.51 g) and was prepared from calcium oxide salt, La2O3 (Sigma Aldrich, 98.0percent) and MgO (24.38 g) (Fisher, 99percent) by incipient wetness impregnation methodology in aqueous solution. The mixture was dried at 120° C. for 3 hours and then calcined at 850° C. in air for 1 hour. The catalyst was ground and sieved to 20-40 mesh size and 0.661 g of catalyst was loaded in a quartz reactor using quartz wool plugs and quartz chips to hold the catalyst bed in place. As a form of catalyst pretreatment, the reactor was heated to 850° C. under 100 ml/min of air and held for 2 hours. The reactor was then cooled down to 600° C. under helium to prepare for the OMT experiments.Four OMT trials were conducted over the Ca/La/MgO catalyst at temperatures of from 550° C. to 700° C. Reactions conditions other than temperature were held constant. The oxygen source was air. The total flow of gasses was 498 cm3/min (244 cm3/min methane, 240 cm3/min air, 0.067 cm3/min liquid toluene). The methane to oxygen molar ratio was 5:1. The methane to toluene molar ratio was 15:1. The space velocity was 45,204 cm3g-1h-1. The products were analyzed after twenty minutes for product distribution. The table below shows results for the four OMT trials. TABLE 4 Results of OMT over Ca/La/MgO Temperature 550° C. 600° C. 650° C. 750° C. Toluene Conversion (percent) 3.0 5.8 7.5 12.6 Benzene Selectivity (mol percent) 60.6 40.4 39.5 28.1 Total Xylene Selectivity (mol percent) 5.0 4.6 4.1 3.5 Stilbene Selectivity (mol percent) 0.3 0.2 0.4 0.0 Benzaldehyde Selectivity (mol percent) 1.4 0.1 0.0 0.0 Ethylbenzene Selectivity (mol percent) 5.9 5.7 5.2 4.5 Styrene Selectivity (mol percent) 39.7 49.7 50.4 58.2 FIG. 4 is a graphical representation of the data shown in Table 4. Toluene conversion increased with increasing temperature, going from about 3percent conversion at 550° C. to nearly 13percent conversion at 700° C. Product distribution also varied with temperature. Styrene increased in selectivity from about 40percent at 550° C. to nearly 60percent at 700° C. All other products had low selectivity and generally decreased in selectivity as the temperature rose. With oxygen, Ca/La/MgO catalyst, Time= 0.333333h, T= 550 - 700 °C Patent; Fina Technology, Inc.; US2010/331593; (2010); (A1) English View in Reaxys 1 :EXAMPLESThe following examples are intended to give a better understanding of the present invention in its many embodiments, but are not intended to limit the scope of the invention in any way.Experimentations shows the utility of a ceramic lining by comparing the products of oxidative coupling reactions in stainless steel, quartz, and ceramic-lined stainless steel reactors. Each case utilized the same catalyst and same reaction conditions. The feedstocks used were methane, toluene, and oxygen. These feedstocks were used to produce styrene and/or ethylbenzene as a result of carbon-carbon bond formation.The details for the stainless steel reactor in carrying out the OMT reaction of the example is as follows. A stainless steel reactor with 0.5 inch outer diameter and 0.465 inch internal diameter was filled with silicon carbide (to a height of about 12.5 inches), then a bed of alumina (to a height of 2.125 inches; 2 mL) then followed by the catalyst (to a height of 2.0 inches; 1.5 mL) of size ranging from 250-425 μm, then a bed of alumina (to a height of 1.625 inches; 3 mL) and then more silicon carbide (of a height of about 7.75 inches) such that a 0.125 inch stainless steel thermowell was positioned in the middle of the bed.The details for the quartz reactor in carrying out OMT reaction of the example is as follows. A quartz reactor (0.75 inch outer diameter and 30.0 inch long) was fitted with a thermowell (0.25 inch outer diameter and 13.5 inch long) in the middle of the catalyst bed. The reactor was loaded according to the following sequence. First quart wool was placed in the bottom, then quartz chips (0.5 inches and 2 mL) and then catalyst (0.57 g; 1 mL), which was about 0.25 inches in height.The details for the stainless steel with ceramic liner insert reactor in carrying out OMT reaction of the example is as follows. A 0.75 inch outer diameter, 0.71 inch internal diameter and 33.0 inch long stainless steel reactor and a 0.125 inch wide and 17.0 inch long stainless steel thermowell were heated to 850° C. for 13 h. The walls were then sand blasted and rinsed with n-hexane. The cleaned reactor and thermowell were dried at room temperature and then were coated with pyropaint. A 0.68 inch outer diameter, 0.5 inch internal diameter and 33.0 inch long ceramic liner was inserted into the cleaned and coated reactor. The ceramic insert reactor was cured at room temperature for 2 h and then was gradually heated to 800° C. at 2° C./min and was held at 800° C. for 2 h and then was cooled to room temperature

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before it was used. The thermowell was coated with pyropaint and was cured as described above.The catalyst syntheses for carrying out OMT reactions is given below. The Ba/MgO catalyst was used in the oxidative coupling of methane and the oxidative methylation of toluene. The catalyst included 5percent Ba by weight and was prepared from barium nitrate (6.53 g) (Sigma Aldrich, 98.0percent) and MgO (23.46 g) (Fisher, 99percent) by incipient wetness impregnation methodology in aqueous solution. The mixture was dried at 120° C. for 3 h and then calcined at 850° C. in air for 1 h.The Mn, NaWO4/MgO catalyst was prepared by sol gel method from Mg(OH)2 (Aldrich 99.8percent), Mn(II) nitrate (Mn(II) nitrate 50.48percent solution), and sodium meta tungstate solution (Na2WO4)9WO3.H2O). A solution of magnesium hydroxide (15.2 g) in water (14.725 mL) was heated on a hot plate and then 2.0 g of Mn(II) nitrate (Mn(II) nitrate 50.48percent solution) was added slowly (5 minutes) and constantly stirring. To this hot mixture a solution of sodium meta tungstate solution (Na2WO4)9WO3.H2O) 0.87 g in 8 mL of water was prepared and added slowly. The mixture was now stirred constantly to boil off water until precipitation was formed. The precipitate was then transferred into a dish and dried at 110° C. for 12 h. The mixture is then ground with 2percent methyl cellulose and water (10 mL) to form a wet paste and binding agent (cement. 0.5 g) was added to form a fine paste. The paste was dried at 110° C. and calcined at 775° C. for 4 h.The results in Table 1 indicate that selectivity to the formation of carbon-carbon bonds is improved by using a more inert reactor surface such as quartz or ceramic lining. With oxygen, BaO/MgO, T= 650 °C , Gas phase, Quartz reactor, Product distribution / selectivity Patent; Fina Technology, Inc.; US2011/257453; (2011); (A1) English View in Reaxys 1 :EXAMPLESThe following examples are intended to give a better understanding of the present invention in its many embodiments, but are not intended to limit the scope of the invention in any way.Experimentations shows the utility of a ceramic lining by comparing the products of oxidative coupling reactions in stainless steel, quartz, and ceramic-lined stainless steel reactors. Each case utilized the same catalyst and same reaction conditions. The feedstocks used were methane, toluene, and oxygen. These feedstocks were used to produce styrene and/or ethylbenzene as a result of carbon-carbon bond formation.The details for the stainless steel reactor in carrying out the OMT reaction of the example is as follows. A stainless steel reactor with 0.5 inch outer diameter and 0.465 inch internal diameter was filled with silicon carbide (to a height of about 12.5 inches), then a bed of alumina (to a height of 2.125 inches; 2 mL) then followed by the catalyst (to a height of 2.0 inches; 1.5 mL) of size ranging from 250-425 μm, then a bed of alumina (to a height of 1.625 inches; 3 mL) and then more silicon carbide (of a height of about 7.75 inches) such that a 0.125 inch stainless steel thermowell was positioned in the middle of the bed.The details for the quartz reactor in carrying out OMT reaction of the example is as follows. A quartz reactor (0.75 inch outer diameter and 30.0 inch long) was fitted with a thermowell (0.25 inch outer diameter and 13.5 inch long) in the middle of the catalyst bed. The reactor was loaded according to the following sequence. First quart wool was placed in the bottom, then quartz chips (0.5 inches and 2 mL) and then catalyst (0.57 g; 1 mL), which was about 0.25 inches in height.The details for the stainless steel with ceramic liner insert reactor in carrying out OMT reaction of the example is as follows. A 0.75 inch outer diameter, 0.71 inch internal diameter and 33.0 inch long stainless steel reactor and a 0.125 inch wide and 17.0 inch long stainless steel thermowell were heated to 850° C. for 13 h. The walls were then sand blasted and rinsed with n-hexane. The cleaned reactor and thermowell were dried at room temperature and then were coated with pyropaint. A 0.68 inch outer diameter, 0.5 inch internal diameter and 33.0 inch long ceramic liner was inserted into the cleaned and coated reactor. The ceramic insert reactor was cured at room temperature for 2 h and then was gradually heated to 800° C. at 2° C./min and was held at 800° C. for 2 h and then was cooled to room temperature before it was used. The thermowell was coated with pyropaint and was cured as described above.The catalyst syntheses for carrying out OMT reactions is given below. The Ba/MgO catalyst was used in the oxidative coupling of methane and the oxidative methylation of toluene. The catalyst included 5percent Ba by weight and was prepared from barium nitrate (6.53 g) (Sigma Aldrich, 98.0percent) and MgO (23.46 g) (Fisher, 99percent) by incipient wetness impregnation methodology in aqueous solution. The mixture was dried at 120° C. for 3 h and then calcined at 850° C. in air for 1 h.The Mn, NaWO4/MgO catalyst was prepared by sol gel method from Mg(OH)2 (Aldrich 99.8percent), Mn(II) nitrate (Mn(II) nitrate 50.48percent solution), and sodium meta tungstate solution (Na2WO4)9WO3.H2O). A solution of magnesium hydroxide (15.2 g) in water (14.725 mL) was heated on a hot plate and then 2.0 g of Mn(II) nitrate (Mn(II) nitrate 50.48percent solution) was added slowly (5 minutes) and constantly stirring. To this hot mixture a solution of sodium meta tungstate solution (Na2WO4)9WO3.H2O) 0.87 g in 8 mL of water was prepared and added slowly. The mixture was now stirred constantly to boil off water until precipitation was formed. The precipitate was then transferred into a dish and dried at 110° C. for 12 h. The mixture is then ground with 2percent methyl cellulose and water (10 mL) to form a wet paste and binding agent (cement. 0.5 g) was added to form a fine paste. The paste was dried at 110° C. and calcined at 775° C. for 4 h.The results in Table 1 indicate that selectivity to the formation of carbon-carbon bonds is improved by using a more inert reactor surface such as quartz or ceramic lining. With oxygen, BaO/MgO, T= 650 °C , Gas phase, Ceramic lining reactor, Product distribution / selectivity Patent; Fina Technology, Inc.; US2011/257453; (2011); (A1) English View in Reaxys

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Rx-ID: 30004153 View in Reaxys 32/165 Yield

Conditions & References B :An oxidative catalyst was prepared comprising an oxide substrate, MgO, that was promoted with Li. The Li/MgO catalyst was used in the oxidative methylation of toluene. The catalyst included 2.5percent Li by weight and was prepared from Lithium carbonate (13.69 g) salt (Sigma Aldrich, 98.0percent) and MgO (16.304 g) (Fisher, 99percent) by incipient wetness impregnation methodology in aqueous solution. The mixture was dried at 120° C. for 3 hours and then calcined at 850° C. in air for 1 hour. The catalyst was ground and sieved to 20-40 mesh size and 0.542 g of catalyst was loaded in a quartz reactor using quartz wool plugs and quartz chips to hold the catalyst bed in place. As a form of catalyst pretreatment, the reactor was heated to 850° C. under 100 ml/min of air and held for 2 hours. The reactor was then cooled down to 600° C. under helium to prepare for the OMT experiments.For the oxidative methylation of toluene, the reaction temperature was 650° C., the oxygen source was air, the total flow of gasses was 335 cm3/min (150 cm3/min air, 150 cm3/min methane, 0.167 cm3/min liquid toluene), the methane to oxygen molar ratio was 5:1, and the methane to toluene molar ratio was 15:1. The reaction was performed twice, at two different space velocities. For the first trial, the space velocity was 37,085 cm3g-1h-1. For the second trial, the space velocity was adjusted to 70,295 cm3g-1h-1 by diluting the feed with nitrogen gas (150 cm3/min air, 150 cm3/min methane, 0.167 cm3/min liquid toluene, 300 cm3/min nitrogen). Space velocity is inversely related to residence time in the reactor, and modulation of space velocity influences the contact time between reactants and catalyst. At a higher space velocity, residence time and contact time are lower, and more reactants pass over the catalyst in a given period.The results of the two OMT trials are shown in Table 2 below. Gas and liquid samples were analyzed for product distribution at twenty minutes. TABLE 2 Results for OMT over Li/MgO catalyst Space Velocity (cm3g-1h-1) 37,085 70,295 Methane Conversion (mol percent) 1.3 - Acetylene Selectivity (percent) 0.000 0.000 CO2 Selectivity (percent) 18.0 13.0 Ethane Selectivity (percent) 0.0 0.3 Ethylene Selectivity (percent) 0.0 0.0 CO Selectivity (percent) 5.6 3.8 Toluene Conversion (mol percent) 4.3 3.7 Benzene Selectivity (percent) 58.6 58.3 Ethylbenzene Selectivity (percent) 2.6 2.3 Styrene Selectivity (percent) 9.9 10.4 C8 Selectivity (percent) 15.0 16.0 Stilbene Selectivity (percent) 2.6 8.1 At the higher space velocity, there was greater selectivity to styrene (10.4percent as compared to 9.9percent). For toluene, the conversion dropped from 4.3percent to 3.7percent. The selectivity to benzene and ethylbenzene formation did not change with increasing space velocity. However, stilbene selectivity increased dramatically from 2.6 to 8.1 mol percent. With oxygen, Li/MgO catalyst, Time= 0.333333h, T= 650 °C Patent; Fina Technology, Inc.; US2010/331593; (2010); (A1) English View in Reaxys C :[0055] Five OMT trials were conducted, at reaction temperatures between 55O0C and 75O0C. In all trials, the oxygen source was air, the total flow of gasses was 500 cm3/min (244 cm3/min methane, 240 cm3/min air, 0.076 cm3/min liquid toluene), the methane to oxygen molar ratio was 5:1, the methane to toluene molar ratio was 15:1, and the space velocity was 50,251 cm3g"1h"1. Product samples were taken after the first twenty minutes of run time and analyzed for product distribution. The results of the trials are shown in the table below.[0056] Table 5. Results for OMT over Na/Cs/Re/MgO[0057] Figures 2 and 3 are graphical representations of the data shown in Table 5. Figure 2 shows the data for toluene conversion, with temperature on the x-axis and percent conversion on the y-axis. The conversion of toluene increased from 1.7percent at 55O0C to 39.9percent at 75O0C. Figure 3 shows the data for selectivity. At temperatures from 55O0C to about 6850C, benzene is the predominant product, with selectivity above 50percent. At around 6850C, the selectivity for benzene and that of styrene intersect and above 6850C, styrene is the predominant product. This approximate temperature of 6850C also marks a transition in the rate of formation of styrene. The selectivity of styrene rises significantly from 55O0C to 6850C (from 11.6percent to 46.2percent) and rises relatively little (from 46.2percent to 49.4percent) above 6850C.[0058] The selectivity of the other products decreased or remained low over the temperatures explored. For instance, benzaldehyde selectivity decreased from 30.6percent at 55O0C to 2.0percent at 75O0C. [0059] Styrene is most commonly the desired product of OMT. However, depending on demand and process needs, other products can also be desired. Ethylbenzene, for instance, can be a desired product as the technology is well established for its conversion to styrene via dehydrogenation. It is thus a useful feature of this process that product distribution can be affected by modulation of reaction conditions such as temperature. Benzene was the product with the highest selectivity. However, its selectivity peaked at 6000C and steadily decreased thereafter. Styrene, on the other hand, steadily increased with temperature. Because conversion and the selectivity of key products can vary with temperature, it may be possible to adjust product selectivity based on temperature. Benzene and styrene, for instance, can both be valuable products. The demands for these products may vary, and it can thus be useful to be able to control which of the two is the predominant product of OMT by adjusting the temperature. With oxygen, T= 750 °C , Product distribution / selectivity Patent; FINA TECHNOLOGY, INC.; CHINTA, Sivadinarayana; THORMAN, Joseph; BUTLER, James, R.; WO2011/2664; (2011); (A1) English

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View in Reaxys 1 :EXAMPLESThe following examples are intended to give a better understanding of the present invention in its many embodiments, but are not intended to limit the scope of the invention in any way.Experimentations shows the utility of a ceramic lining by comparing the products of oxidative coupling reactions in stainless steel, quartz, and ceramic-lined stainless steel reactors. Each case utilized the same catalyst and same reaction conditions. The feedstocks used were methane, toluene, and oxygen. These feedstocks were used to produce styrene and/or ethylbenzene as a result of carbon-carbon bond formation.The details for the stainless steel reactor in carrying out the OMT reaction of the example is as follows. A stainless steel reactor with 0.5 inch outer diameter and 0.465 inch internal diameter was filled with silicon carbide (to a height of about 12.5 inches), then a bed of alumina (to a height of 2.125 inches; 2 mL) then followed by the catalyst (to a height of 2.0 inches; 1.5 mL) of size ranging from 250-425 μm, then a bed of alumina (to a height of 1.625 inches; 3 mL) and then more silicon carbide (of a height of about 7.75 inches) such that a 0.125 inch stainless steel thermowell was positioned in the middle of the bed.The details for the quartz reactor in carrying out OMT reaction of the example is as follows. A quartz reactor (0.75 inch outer diameter and 30.0 inch long) was fitted with a thermowell (0.25 inch outer diameter and 13.5 inch long) in the middle of the catalyst bed. The reactor was loaded according to the following sequence. First quart wool was placed in the bottom, then quartz chips (0.5 inches and 2 mL) and then catalyst (0.57 g; 1 mL), which was about 0.25 inches in height.The details for the stainless steel with ceramic liner insert reactor in carrying out OMT reaction of the example is as follows. A 0.75 inch outer diameter, 0.71 inch internal diameter and 33.0 inch long stainless steel reactor and a 0.125 inch wide and 17.0 inch long stainless steel thermowell were heated to 850° C. for 13 h. The walls were then sand blasted and rinsed with n-hexane. The cleaned reactor and thermowell were dried at room temperature and then were coated with pyropaint. A 0.68 inch outer diameter, 0.5 inch internal diameter and 33.0 inch long ceramic liner was inserted into the cleaned and coated reactor. The ceramic insert reactor was cured at room temperature for 2 h and then was gradually heated to 800° C. at 2° C./min and was held at 800° C. for 2 h and then was cooled to room temperature before it was used. The thermowell was coated with pyropaint and was cured as described above.The catalyst syntheses for carrying out OMT reactions is given below. The Ba/MgO catalyst was used in the oxidative coupling of methane and the oxidative methylation of toluene. The catalyst included 5percent Ba by weight and was prepared from barium nitrate (6.53 g) (Sigma Aldrich, 98.0percent) and MgO (23.46 g) (Fisher, 99percent) by incipient wetness impregnation methodology in aqueous solution. The mixture was dried at 120° C. for 3 h and then calcined at 850° C. in air for 1 h.The Mn, NaWO4/MgO catalyst was prepared by sol gel method from Mg(OH)2 (Aldrich 99.8percent), Mn(II) nitrate (Mn(II) nitrate 50.48percent solution), and sodium meta tungstate solution (Na2WO4)9WO3.H2O). A solution of magnesium hydroxide (15.2 g) in water (14.725 mL) was heated on a hot plate and then 2.0 g of Mn(II) nitrate (Mn(II) nitrate 50.48percent solution) was added slowly (5 minutes) and constantly stirring. To this hot mixture a solution of sodium meta tungstate solution (Na2WO4)9WO3.H2O) 0.87 g in 8 mL of water was prepared and added slowly. The mixture was now stirred constantly to boil off water until precipitation was formed. The precipitate was then transferred into a dish and dried at 110° C. for 12 h. The mixture is then ground with 2percent methyl cellulose and water (10 mL) to form a wet paste and binding agent (cement. 0.5 g) was added to form a fine paste. The paste was dried at 110° C. and calcined at 775° C. for 4 h.The results in Table 1 indicate that selectivity to the formation of carbon-carbon bonds is improved by using a more inert reactor surface such as quartz or ceramic lining. With oxygen, Mn, NaWO4/MgO, T= 760 °C , Gas phase, Stainless steel reactor Patent; Fina Technology, Inc.; US2011/257453; (2011); (A1) English View in Reaxys

N N

C– (v4) (v2)

(v4)

Au+

(v4)

Cl Au+ C–

V ClCl

(v2) (v4)

(v1)

Cl –

N (v2) (v4)

Au+ P (v4)

(v2)

Au+

(v4) (v1) (v5) 3+ Cl – C– V – (v4) Cl (v1) (v4)

Cl – (v1)

Rx-ID: 31659851 View in Reaxys 33/165

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Yield

Conditions & References

20 %

in benzene, (N2, Schlenk technique); addn. of benzene soln. of gold compd. to vanadium compd., stirring overnight; centrifugation, concg., recrystn. (benzene/hexane), elem. anal. Chuchuryukin, Alexey V.; Huang, Rubin; Van Faassen, Ernst E.; Van Klink, Gerard P. M.; Lutz, Martin; Chadwick, John C.; Spek, Anthony L.; Van Koten, Gerard; Dalton Transactions; vol. 40; nb. 35; (2011); p. 8887 - 8895 ; (from Gmelin) View in Reaxys

Rx-ID: 29164467 View in Reaxys 34/165 Yield

Conditions & References EXAMPLEA Ni/Mordenite disproportionation catalyst was modified with the addition of 420 ppm Rh (0.042 wt percent) and loaded into a catalytic reaction zone. At the conclusion of the initial transient conditions accompanying the initiation of toluene feed to the reaction zone, initial steady state conditions for disproportionation of toluene to benzene and xylene were established. The reactor was operated to maintain a generally consistent reactor severity and toluene conversion. The inlet reactor pressure was approximately 600 psig. The reactor temperature was found to hold steady, being 354° C. (670° F.) on day 2 as it was on day 23 when both conversions were 47percent, thereby not indicating catalyst deactivation as would normally be expected. The temperature of the Ni/Mordenite base catalyst without the Rh promoter under similar conditions would show an increase in temperature during the same time period, indicating catalyst deactivation. In one experiment a Ni/Mordenite catalyst with 1 wt percent nickel, Zeolyst CP-751 from Zeolyst International of Valley Forge, Pa., USA, was used as the base material. Rhodium was added using an incipient wetness method with an aqueous solution of RhCl3.H2O salt, dried at 110° C., and then calcined at 550° C. for 2 hr. The catalyst was measured to have 420 ppm Rh impregnation. Initially the startup used was 1:1 H2/oil molar ratio without sulfiding. The system pressure decreased due to very high hydrogen consumption. The hydrogen rate was increased to 3:1 H2/oil ratio at about 280° C. bed temperature during the temperature ramp from 250° C. to 350° C. at 6° C./hr. The effluent sample was analyzed at 10percent nonaromatics. The catalyst was then sulfided the next day using DMDS to have 50 mol percent sulfur relative to the catalyst nickel. With hydrogen, 420 ppm Rh-Ni/mordenite, T= 250 - 350 °C , p= 31789.8Torr , Product distribution / selectivity Patent; Fina Technology, Inc.; US2010/41933; (2010); (A1) English View in Reaxys

N HN HN

O O

0.5

Cl Y Cl

(v3)

0.5

(v1)

Cl – (v3)

N– N (v7)3+ N – Y (v4) O(v3) (v3) N (v3) (v4) O

Rx-ID: 29344104 View in Reaxys 35/165 Yield

Conditions & References With NaH in 1,2-dimethoxyethane, toluene, binaphthyl treated with excess of NaH in DME, treated with 1 equiv. of YCl3 in DME/toluene; recrystd. from benzene Zi, Guofu; Xiang, Li; Liu, Xue; Wang, Qiuwen; Song, Haibin; Inorganic Chemistry Communications; vol. 13; nb. 3; (2010); p. 445 - 448 ; (from Gmelin) View in Reaxys

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(v3) (v3)(v3) (v3) (v3) (v3) (v3)(v3) (v3) (v3)(v3)(v3) (v3)(v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3)(v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) Sc (v3) (v3) (v3) (v3) (v3)(v1) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3)(v3) (v3) (v3)(v3)(v3)(v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3)(v3) (v3)

(v4)

Ni SP-4

(v4)

O Sc (v1)

N–

0.6

N Ni 2+ (v4) (v4) N(v3) – N SP-4

(v3) (v4)

1.4

(v3) (v3)(v3) (v3) (v3) (v3) (v3) (v3)(v3) (v3)(v3) (v3)(v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3)(v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) Sc (v3) (v3) (v3) (v3) (v3)(v1) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3)(v3) (v3) (v3) (v3)(v3)(v3)(v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3) (v3)

O Sc (v1)

Rx-ID: 29972513 View in Reaxys 36/165 Yield

Conditions & References in benzene, layering benzene soln. of nickel compd. over benzene soln. of fullerene deriv., slow mixing and evapn.; isolation of crystals, X-ray anal. Mercado, Brandon Q.; Stuart, Melissa A.; MacKey, Mary A.; Pickens, Jane E.; Confait, Bridget S.; Stevenson, Steven; Easterling, Michael L.; Valencia, Ramon; Rodriguez-Fortea, Antonio; Poblet, Josep M.; Olmstead, Marilyn M.; Balch, Alan L.; Journal of the American Chemical Society; vol. 132; nb. 34; (2010); p. 12098 - 12105 ; (from Gmelin) View in Reaxys

Si O

H O

O Al

Si O

(v3)

O 4

(v4)

(v3)

Al O

(v3)

(v4)

O H

H 2N

NH 2

(v3)

O Si

2 H 2N

0.5

NH +3

0.5

(v2) (v2)– – O Si O Si O – Si (v2) – Si (v2) O 3+ 2- O3+ (v2) (v4) Al O Al (v4) O 2O (v2) O O2- (v2) (v4) (v2) (v4) 3+ 3+ 2Si –Al O Al – Si O O –O (v2) (v2) O–(v2) (v2)

Si O Si

Rx-ID: 29976986 View in Reaxys 37/165 Yield

Conditions & References in toluene, (N2) 1,3-diaminopropane in toluene was added slowly to aluminopolysiloxane in toluene (4:1) and stirred for 3 h; solvent was removed in vacuo, ppt. was crystd. from benzene-toluene (1:1); elem. anal. Veith, Michael; Caparrotti, Hinka; Huch, Volker; Organometallics; vol. 29; nb. 21; (2010); p. 5269 - 5273 ; (from Gmelin)

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View in Reaxys

H C

Rx-ID: 30004152 View in Reaxys 38/165 Yield

Conditions & References C :An oxidative catalyst was prepared comprising a MgO substrate that was promoted with Na, Cs, and Re. The Na/Cs/Re/MgO catalyst was used in the oxidative methylation of toluene. The catalyst included 5percent Na by weight (3.811 g) of sodium chloride, 5percent Cs by weight (2.199 g) of cesium nitrate, and 0.01percent Re by weight (0.5856 g) of rhenium chloride and MgO (23.4033 g) (Fisher, 99percent) by incipient wetness impregnation methodology in aqueous solution. The mixture was dried at 120° C. for 3 h and then calcined at 850° C. in air for 1 h. The catalyst was ground and sieved to 20-40 mesh size (420-841 μm) and 0.597 g of catalyst was loaded into a quartz reactor using quartz wool plugs and quartz chips to hold the catalyst bed in place. For catalyst pretreatment, the reactor was heated to 850° C. under 100 ml/min of air and held for 2 hours. The reactor was then cooled down to 600° C. under helium to prepare for the OMT experiments.Five OMT trials were conducted, at reaction temperatures between 550° C. and 750° C. In all trials, the oxygen source was air, the total flow of gasses was 500 cm3/min (244 cm3/min methane, 240 cm3/min air, 0.076 cm3/min liquid toluene), the methane to oxygen molar ratio was 5:1, the methane to toluene molar ratio was 15:1, and the space velocity was 50,251 cm3g-1h-1. Product samples were taken after the first twenty minutes of run time and analyzed for product distribution. The results of the trials are shown in the table below. TABLE 3 Results for OMT over Na/Cs/Re/MgO Temperature 550° C. 600° C. 650° C. 700° C. 750° C. Toluene Conversion (percent) 1.7 1.9 3.3 12.1 39.9 Benzene Selectivity (percent) 56.1 74.1 57.9 33.3 25.1 Total Xylene Selectivity 3.6 3.3 3.4 2.9 1.9 (percent) Stilbene Selectivity (percent) 3.3 0.9 0.5 0.2 0.2 Benzaldehyde Selectivity 30.6 12.6 6.3 2.0 2.0 (percent) Ethylbenzene Selectivity 3.7 5.0 8.4 8.6 4.5 (percent) Styrene Selectivity (percent) 11.6 16.7 29.0 46.2 49.4 FIGS. 2 and 3 are graphical representations of the data shown in Table 3. FIG. 2 shows the data for toluene conversion, with temperature on the x-axis and percent conversion on the y-axis. The conversion of toluene increased from 1.7percent at 550° C. to 39.9percent at 750° C. FIG. 3 shows the data for selectivity. At temperatures from 550° C. to about 685° C., benzene is the predominant product, with selectivity above 50percent. At around 685° C., the selectivity for benzene and that of styrene intersect and above 685° C., styrene is the predominant product. This approximate temperature of 685° C. also marks a transition in the rate of formation of styrene. The selectivity of styrene rises significantly from 550° C. to 685° C. (from 11.6percent to 46.2percent) and rises relatively little (from 46.2percent to 49.4percent) above 685° C.The selectivity of the other products decreased or remained low over the temperatures explored. For instance, benzaldehyde selectivity decreased from 30.6percent at 550° C. to 2.0percent at 750° C. With oxygen, Na/Cs/Re/MgO, Time= 0.333333h, T= 550 - 750 °C Patent; Fina Technology, Inc.; US2010/331593; (2010); (A1) English View in Reaxys H H

B O

H O B O

B O

H O BO

O B O

H H

racemate

Rx-ID: 30140041 View in Reaxys 39/165 Yield 91 %

Conditions & References in methanol, Time= 36h, T= 20 °C , In air Takahagi, Hiroki; Iwasawa, Nobuharu; Chemistry - A European Journal; vol. 16; nb. 46; (2010); p. 13680 - 13688 View in Reaxys

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H O

O H

racemate

H racemate

Rx-ID: 30140042 View in Reaxys 40/165 Yield 99 %

Conditions & References Time= 36h, T= 20 °C , In air Takahagi, Hiroki; Iwasawa, Nobuharu; Chemistry - A European Journal; vol. 16; nb. 46; (2010); p. 13680 - 13688 View in Reaxys

Rx-ID: 23310940 View in Reaxys 41/165 Yield

Conditions & References 1 : EXAMPLE 1 (Comparative example not according to the invention of an unmodified ZSM-5 zeolite at low contact time) A commercially manufactured sample of HZSM-5 with a silica/alumina ratio of 80 was pressed into discs, which were then crushed and sieved to produce particles in the size range 250 PM-850 GM. A packed bed of catalyst was prepared by mixing 0.3 g of the particles with 0.7 g of powdered cordierite (a catalytically inert filler), and loading the mixture midway along the length of a quartz tube reactor while it was held vertically. The bed was held in place by plugs of quartz wool. The reactor was mounted horizontally inside a tube furnace, so that the catalyst bed was both at the radial and axial centre of the furnace. A flow of 50 cm3 3MIN- OF nitrogen was passed through the catalyst bed for 30 minutes while the furnace temperature was ramped to 440 C. After the 30 minutes had elapsed, the flow was switched so that it bypassed the reactor, and left the catalyst bed isolated in an atmosphere of static nitrogen. Syringe pumps, supplying the liquid feeds (methanol, toluene and water), and a mass-flow controller, supplying hydrogen, were turned on. The liquid and gas flows were heated to 180 C to produce a homogeneous gasphase mixture (the reactant feed), which comprised methanol vapour (1.85 cm3 MIN~L), toluene vapour (14.8 CM3 MIFF 1), steam (16.65 CM3 MIN~1), and hydrogen (99.9 cm3 MIN~L). After 30 minutes, the reactant feed was fed to the reactor. As the volume of active catalyst was 0.6 cm3 and the reactant feed rate was 2.2 cm3 S-, the contact time was 0.27 s. The exit-stream from the reactor was analysed by gas chromatography. As shown in Table 1, the product stream, which had stabilised after 15 minutes, contained a near equilibrium concentration of para-xylene and sub-equilibrium concentrations of the ortho and meta isomers. The other products formed were benzene and CG aromatics. The latter were formed by disproportionation of some of the toluene, explaining why the toluene conversion was higher than expected for toluene methylation alone. With water, hydrogen, HZSM-5, Time= 7.5E-05h, T= 440 °C Patent; JOHNSON MATTHEY PUBLIC LIMITED COMPANY; WO2004/74219; (2004); (A2) English View in Reaxys 1 :EXAMPLES 1-19; The catalysts A-I, J-O and P-S described above and in Tables 1-3, were used in toluene methylation reactions. The reactions were each carried out in a fixed bed, continuous flow type reactor. In each case, a catalyst was dried by slowly raising the catalyst bed temperature (about 5° C./min) to 200° C. under hydrogen (H2) flow for at least one hour. A premixed methylation feed of toluene and methanol (molar ratio 2/1) was added to the reactor at 200° C. and the catalyst bed inlet temperature was increased to about 500° C. The liquid hourly space velocity (LHSV) (based on methylation feed) was maintained at about 31 hr-1 and a cofeed of H2 gas was fed and maintained to provide a H2/(toluene+methanol) molar ratio of about 0.1. Water was added to the methylation feed and was vaporized prior to introduction to reactor. The H2O/(toluene+methanol) molar ratio was about 0.65 and reactor pressure was about 20 psig. Liquid products were collected at about 3-4 hours of run time and were analyzed. The following results, as presented in Tables 5-7. FIG. 5 is a plot of para-xylene slectivity and selectivity for total xylenes for catalysts A-I. FIG. 6 is a plot of para-xylene selectivity and selectivity for total xylenes for catalysts J-O.

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With hydrogen, Catalyst A (prepared from NH4-ZSM-5 and H3PO4), T= 200 - 500 °C , p= 1034.32Torr , Product distribution / selectivity Patent; Ghosh, Ashim Kumar; Kulkarni, Neeta; Harvey, Pamela; US2005/240070; (2005); (A1) English View in Reaxys 2 :EXAMPLES 1-19; The catalysts A-I, J-O and P-S described above and in Tables 1-3, were used in toluene methylation reactions. The reactions were each carried out in a fixed bed, continuous flow type reactor. In each case, a catalyst was dried by slowly raising the catalyst bed temperature (about 5° C./min) to 200° C. under hydrogen (H2) flow for at least one hour. A premixed methylation feed of toluene and methanol (molar ratio 2/1) was added to the reactor at 200° C. and the catalyst bed inlet temperature was increased to about 500° C. The liquid hourly space velocity (LHSV) (based on methylation feed) was maintained at about 31 hr-1 and a cofeed of H2 gas was fed and maintained to provide a H2/(toluene+methanol) molar ratio of about 0.1. Water was added to the methylation feed and was vaporized prior to introduction to reactor. The H2O/(toluene+methanol) molar ratio was about 0.65 and reactor pressure was about 20 psig. Liquid products were collected at about 3-4 hours of run time and were analyzed. The following results, as presented in Tables 5-7. FIG. 5 is a plot of para-xylene slectivity and selectivity for total xylenes for catalysts A-I. FIG. 6 is a plot of para-xylene selectivity and selectivity for total xylenes for catalysts J-O. With hydrogen, Catalyst B (prepared from NH4-ZSM-5 and H3PO4), T= 200 - 500 °C , p= 1034.32Torr , Product distribution / selectivity Patent; Ghosh, Ashim Kumar; Kulkarni, Neeta; Harvey, Pamela; US2005/240070; (2005); (A1) English View in Reaxys 9 :EXAMPLES 1-19; The catalysts A-I, J-O and P-S described above and in Tables 1-3, were used in toluene methylation reactions. The reactions were each carried out in a fixed bed, continuous flow type reactor. In each case, a catalyst was dried by slowly raising the catalyst bed temperature (about 5° C./min) to 200° C. under hydrogen (H2) flow for at least one hour. A premixed methylation feed of toluene and methanol (molar ratio 2/1) was added to the reactor at 200° C. and the catalyst bed inlet temperature was increased to about 500° C. The liquid hourly space velocity (LHSV) (based on methylation feed) was maintained at about 31 hr-1 and a cofeed of H2 gas was fed and maintained to provide a H2/(toluene+methanol) molar ratio of about 0.1. Water was added to the methylation feed and was vaporized prior to introduction to reactor. The H2O/(toluene+methanol) molar ratio was about 0.65 and reactor pressure was about 20 psig. Liquid products were collected at about 3-4 hours of run time and were analyzed. The following results, as presented in Tables 5-7. FIG. 5 is a plot of para-xylene slectivity and selectivity for total xylenes for catalysts A-I. FIG. 6 is a plot of para-xylene selectivity and selectivity for total xylenes for catalysts J-O. With hydrogen, Catalyst I (prepared from NH4-ZSM-5 and H3PO4), T= 200 - 500 °C , p= 1034.32Torr , Product distribution / selectivity Patent; Ghosh, Ashim Kumar; Kulkarni, Neeta; Harvey, Pamela; US2005/240070; (2005); (A1) English View in Reaxys 15 :EXAMPLES 1-19; The catalysts A-I, J-O and P-S described above and in Tables 1-3, were used in toluene methylation reactions. The reactions were each carried out in a fixed bed, continuous flow type reactor. In each case, a catalyst was dried by slowly raising the catalyst bed temperature (about 5° C./min) to 200° C. under hydrogen (H2) flow for at least one hour. A premixed methylation feed of toluene and methanol (molar ratio 2/1) was added to the reactor at 200° C. and the catalyst bed inlet temperature was increased to about 500° C. The liquid hourly space velocity (LHSV) (based on methylation feed) was maintained at about 31 hr-1 and a cofeed of H2 gas was fed and maintained to provide a H2/(toluene+methanol) molar ratio of about 0.1. Water was added to the methylation feed and was vaporized prior to introduction to reactor. The H2O/(toluene+methanol) molar ratio was about 0.65 and reactor pressure was about 20 psig. Liquid products were collected at about 3-4 hours of run time and were analyzed. The following results, as presented in Tables 5-7. FIG. 5 is a plot of para-xylene slectivity and selectivity for total xylenes for catalysts A-I. FIG. 6 is a plot of para-xylene selectivity and selectivity for total xylenes for catalysts J-O. With hydrogen, Catalyst O (prepared from NH4-ZSM-5 and H3PO4), T= 200 - 500 °C , p= 1034.32Torr , Product distribution / selectivity Patent; Ghosh, Ashim Kumar; Kulkarni, Neeta; Harvey, Pamela; US2005/240070; (2005); (A1) English View in Reaxys 6 :Examples 1-7; The catalysts A-E, as referenced in Table 1 and prepared as described above, were used in toluene methylation reactions. The reactions were each carried out in a fixed bed, continuous flow type reactor. In each case, the catalyst used was dried by slowly raising the catalyst bed temperature (about 5° C./min) to 200° C. under hydrogen (H2) flow for at least one hour. A premixed toluene and methanol feed (molar ratio 2/1) was added to the reactor at 200° C. and the catalyst bed inlet temperature was increased to about 500° C. The liquid hourly space velocity (LHSV) based on toluene/methanol feed was maintained at

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about 31 hr-1 and cofeed of H2 gas was fed and maintained to provide a H2/(toluene+methanol) molar ratio of about 0.1. Water was added to the hydrocarbon (HC, where HC=toluene+methanol) feed and was vaporized prior to introduction into the reactor. The H2O/HC molar ratio was about 0.65 and the reactor pressure was about 20 psig. With hydrogen, non-modified HZSM-5 zeolite, T= 200 - 500 °C , Conversion of starting material Patent; Ghosh, Ashim Kumar; Harvey, Pamela; US2005/277795; (2005); (A1) English View in Reaxys 7 :Examples 1-7; The catalysts A-E, as referenced in Table 1 and prepared as described above, were used in toluene methylation reactions. The reactions were each carried out in a fixed bed, continuous flow type reactor. In each case, the catalyst used was dried by slowly raising the catalyst bed temperature (about 5° C./min) to 200° C. under hydrogen (H2) flow for at least one hour. A premixed toluene and methanol feed (molar ratio 2/1) was added to the reactor at 200° C. and the catalyst bed inlet temperature was increased to about 500° C. The liquid hourly space velocity (LHSV) based on toluene/methanol feed was maintained at about 31 hr-1 and cofeed of H2 gas was fed and maintained to provide a H2/(toluene+methanol) molar ratio of about 0.1. Water was added to the hydrocarbon (HC, where HC=toluene+methanol) feed and was vaporized prior to introduction into the reactor. The H2O/HC molar ratio was about 0.65 and the reactor pressure was about 20 psig. With hydrogen, H2SO4 treated NH4-ZSM-5 zeolite, T= 200 - 500 °C , Conversion of starting material Patent; Ghosh, Ashim Kumar; Harvey, Pamela; US2005/277795; (2005); (A1) English View in Reaxys 1; 2; 9; 15 :The catalysts A-I, J-O and P-S described above and in Tables 1-3, were used in toluene methylation reactions. The reactions were each carried out in a fixed bed, continuous flow type reactor. In each case, a catalyst was dried by slowly raising the catalyst bed temperature (about 5° C./min) to 200° C. under hydrogen (H2) flow for at least one hour. A premixed toluene and methanol feed (molar ratio 2/1) was added to the reactor at 200° C. and the catalyst bed inlet temperature was increased to about 500° C. The liquid hourly space velocity (LHSV) (based on toluene/methanol feed) was maintained at about 31 hr?1 and a cofeed of H2 gas was fed and maintained to provide a H2/HC molar ratio of about 0.1. Water was added to the hydrocarbon (HC) feed and was vaporized prior to introduction to reactor. The H2O/HC molar ratio was about 0.65 and reactor pressure was about 20 psig. Liquid products were collected at about 3-4 hours of run time and were analyzed. The following results, as presented in Tables 4-6. FIG. 4 is a plot of para-xylene selectivity and selectivity for total xylenes for catalysts A-I. FIG. 5 is a plot of para-xylene selectivity and selectivity for total xylenes for catalysts J-O. With hydrogen, NH4-ZSM-5 zeolite, Time= 3 - 4h, T= 200 - 500 °C , Product distribution / selectivity Patent; Ghosh, Ashim Kumar; Juttu, Gopalakrishnan; Harvey, Pamela; Kulkarni, Neeta; US2009/36723; (2009); (A1) English View in Reaxys

Rx-ID: 28272351 View in Reaxys 42/165 Yield

Conditions & References 1; 2 :Example 1In Accordance with the Prior ArtThe facility in the process of Example 1 corresponds to that indicated in FIG. 1, and comprises a SMB unit with a single raffinate and a dealkylation isomerization. However, the lines shown as dotted lines in said figure (line 7 and the first portion of line 11) are not included in this facility.The flow chart remains the same, between the start and end of the cycle, but with a flow rate of the first feed which reduces and a PX production leaving the SMB which substantially reduces at the end of the cycle to be able to maintain the required minimum purity (99.7percent) for para-xylene. The yield of SMB also falls, along with the benzene production.Table 1 shows a material balance (in tonnes per hour) for the various streams referred to in FIG. 1 at the start of the cycle (fresh absorbent) and Table 2 shows the same material balance, bat at the end of the cycle (used absorbent, just before its replacement). The following abbreviations are used: PX=para-xylene; OX=ortho-xylene; MX=meta-xylene; EB=ethylbenzene; T=toluene; BZ=benzene; LPG=C4/C3, and possibly small quantities of C2 and C1. TABLE 1 Start of Feed SMB Feed Outlet Inlet Outlet cycle 1 inlet R E Ea 2 DISP CRYST PX1 ML HPPX ISOM EB 17 22.4 22.4 - - - - - - - - 5.4 PX 19.6 90.8 2.7 88.1 - - 17 17 11.9 5.1 100 66.1 MX 40 177 177 - - - 2 2 - 2 - 135 OX 20.4 90.2 90.2 - - - 1 1 - 1 - 68.8 T - - - - - 42 -(*) - - - - - BZ - - - - - - 20 - - - - 12.4 LPG and - - - - - - 2 - - - - 4.6 losses Total 97 380.4 292.3 88.1 0 42 42 20 11.9 8.1 100 292.3 (*)After recycling unconverted toluene. The conversion per pass is typically 30percent. The purity of the distilled extract E is 99.85percent at the start of the cycle, with a high yield (at the SMB) of 97percent. TABLE 2 End of Feed SMB Feed Outlet Inlet Outlet cycle 1 inlet R E Ea 2 DISP CRYST PX1 ML HPPX ISOM EB 13.6 17.89 17.89 - - - - - - - 4.29 PX 15.68 78.37 6.27 72.1 - - 17 17 11.9 5.1 84 57.59 MX 32 151.53 151.53 - - - 2 2 - 2 - 117.53 OX 16.32 77.26

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77.26 - - - 1 1 - 1 - 59.94 T - - - - - 42 -(*) - - - - - BZ - - - - - - 20 - - - - 9.88 LPG and - - - - - - 2 - - - - 3.72 losses Total 77.6 325.05 252.95 72.1 0 42 42 20 11.9 8.1 84 292.3 It can be seen that at the end of the cycle, due to ageing of the absorbent, the rate of supply of the first feed (and thus the overhead cut from column D) has had to be reduced by about 20percent to maintain a minimum purity of the extract of 99.7percent. In parallel, the PX yield from the SMB has dropped, moving from 97percent to 92percent. This results in a drop in overall production (HPPX) of 16percent, which is a big drop. Further, the reduction in feed causes a drop in the overall production of benzene by about 8percent. , Product distribution / selectivity Patent; Hotier, Gerard; Seo Il, Kim; US2009/69612; (2009); (A1) English View in Reaxys

Rx-ID: 27810088 View in Reaxys 43/165 Yield

Conditions & References 2 :EXAMPLE 2; A second pilot plant test was conducted using a feed stream having by weight 30.5 g/hr methanol, 15.0 g/hr; water, 4.2 g/hr ethylene and 50.9 g/hr heavy hydrocarbons. The heavy hydrocarbons comprised by weight approximately 25percent C5, 12.5percent hexene, 25percent toluene, 12.5percent octenes and 25percent trimethyl benzenes. Hence the combined feed contained 19.4percent toluene and 19.4percent C9 aromatics by weight on a dry basis. The pilot plant reactor was operated at 440° C. at an inlet, under a pressure of 122 kPa (17.7 psig) at the inlet a GHSV of 6,100 hr-1. ZSM-5 catalyst was used as in Example 1. An effluent from the reactor was collected and analyzed to have by weight on a dry basis 12.2percent propylene, 5.12percent ethylene, 0.4percent benzene, 13.6percent toluene, 7.6percent xylene and 22.3percent C9 +. Example 2 shows an increased selectivity over Example 1 in terms of xylene and C9 aromatics while showing a disappearance of toluene. With ZSM-5 in water, T= 440 °C , p= 915.092Torr , Product distribution / selectivity Patent; Bozzano, Andrea G.; Voskoboynikov, Timur V.; Kalnes, Tom N.; Barger, Paul T.; Towler, Gavin P.; Glover, Bryan K.; US2008/161620; (2008); (A1) English View in Reaxys

N –(v4)

(v3)

(v3) (v5)

FeO2+ SP-5 –N N

(v4)

(v3)

(v5)

N N –(v4) (v3)

N (v4)

N (v5) 3+– (v1) N FeCl SP-5 –N

(v3)

(v5)

Rx-ID: 28068839 View in Reaxys 44/165 Yield

Conditions & References in dichloromethane, Fe complex treated with a few milliliters of CH2Cl2; solvent evapd. slowly from CHCl3-benzene-THF soln.; crystals collected by vac. filtration; washed with toluene; dried under vac.; elem. anal. Fitzgerald, Jeffrey P.; Lebenson, Joshua R.; Wang, Guangbin; Yee, Gordon T.; Noll, Bruce C.; Sommer, Roger D.; Inorganic Chemistry; vol. 47; nb. 11; (2008); p. 4520 - 4530 ; (from Gmelin)

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View in Reaxys

OH (v6) H (v6) H H HB B HB BH (v6) (v6) (v6) (v6) (v6)(v6)B BH B (v6) HB B H H BH (v6) H (v6)

HO OH

(v6) (v6) H (v6)

(v6)

B BH (v6) BH (v6) 7 HB HB BH HB B BH B (v6) (v6) H H

(v6) (v6)

(v6)(v6)

OH HO

OH 2 OH

Rx-ID: 28073137 View in Reaxys 45/165 Yield

Conditions & References in toluene, slow evapn. over 2-5 days Clark, Thomas E.; Makha, Mohamed; Sobolev, Alexandre N.; Raston, Colin L.; Dalton Transactions; nb. 36; (2008); p. 4855 - 4859 ; (from Gmelin) View in Reaxys

0.7

–C (v4) –Cl

P (v4) Pt2+ SP-4 (v4)(v4) P

0.5

–C (v4) –Cl

P (v4)

Pt2+ SP-4 (v4)(v4) P

(v1)

Rx-ID: 28083753 View in Reaxys 46/165 Yield

Conditions & References in pentane, benzene Bennett, Martin A.; Bhargava, Suresh K.; Priver, Steven H.; Willis, Anthony C.; European Journal of Inorganic Chemistry; nb. 22; (2008); p. 3467 - 3481 ; (from Gmelin) View in Reaxys

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OH (v6) (v6)

H BH

H B (v5) (v6) H (v6) B B B B H B (v7)B(v6) H H (v6) (v6) H B

(v6)H (v6)H

(v6)

HO OH

H (v6) BH (v6) H H B B (v6) H H (v5) (v6) B B 7 (v6) B B H (v6)H B (v7)B(v6) H H (v6) (v6) H B H

(v6)

OH 2

HO OH OH

Rx-ID: 28314721 View in Reaxys 47/165 Yield

Conditions & References Clark, Thomas E.; Makha, Mohamed; Sobolev, Alexandre N.; Raston, Colin L.; Dalton Transactions; nb. 36; (2008); p. 4855 - 4859 View in Reaxys

Rx-ID: 22834149 View in Reaxys 48/165 Yield

Conditions & References II With hydrogen, aluminum-phosphate-bound MFI catalyst, T= 406 - 455 °C , p= 18376.8Torr Patent; UOP LLC; US6359185; (2002); (B1) English View in Reaxys VI; VII With hydrogen, alumina-bound MFI catalyst, extruded, T= 420 - 455 °C , p= 18376.8Torr Patent; UOP LLC; US6359185; (2002); (B1) English View in Reaxys IV

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With hydrogen, alumina-bound MFI catalyst, T= 431 - 457 °C , p= 18376.8Torr Patent; UOP LLC; US6359185; (2002); (B1) English View in Reaxys [00016] The toluene disproportionation runs were carried out in a downflow reactor containing a nickel mordenite disproportionation catalyst formulated of about 70percent mordenite and about 30percent alumina support The catalyst was promoted with about 1percent nickel. As discussed in greater detail below, the toluene feedstocks were supplied to the reactor to provide liquid hourly space velocities (LHSV) of about 1.3-3.0 hrs.-1 The ratio of hydrogen to total hydrocarbon content of toluene or toluene plus the impurities varied from about 650-3,000 standard liters of hydrogen per liter of hydrocarbon feed. The temperature ranged from about 430° C.-450° C. and the reactor inlet pressure varied from 41-55 bars. The catalyst was employed in an amount of 30 ml, and was in the form of 14-20 mesh mordenite particles. [00017] In the experimental work, the initial feed of pure toluene (99+wt percent toluene) was introduced into the reactor for an initial 70-day period. Thereafter, the feed was switched to the dilute toluene feedstock and continued for an additional 90 days with interruption intervals at day 90 and day 100, during which intervals, the pure toluene feed was reinstituted. The operating conditions and selectivity values during the course of the 160 day run are illustrated in FIGS. 1 and 2. In FIG. 1, toluene conversion, TC, in wt percent () and temperature, T, in ° C. (.diamond.) are plotted on the ordinate versus the Days-On-Stream, D, on the abscissa. In FIG. 2, the xylenes yield (), benzene yield () and heavies yield (), Y, all in weight percent of the product, are plotted on the ordinate versus the time in stream, D, in days on the abscissa. In both FIGS. 1 and 2, the excursions from diluted toluene feed to pure toluene are circled at days 90, 110 and at the conclusion of the run. The product distribution from the diluted toluene stream at various temperatures, pressures, hydrogen/hydrocarbon ratios and space velocity are tabulated in Table 3. With hydrogen, Time= 1680 - 3840h, T= 430 - 450 °C , p= 30753.1 - 41254.1Torr , Product distribution / selectivity Patent; Fina Technology, Inc.; US6803493; (2004); (B1) English View in Reaxys 2 :Example 2 This example illustrates the performance capabilities of a mordenite catalyst (Catalyst "A" of Example 1) and an identical catalyst impregnated with molybdenum (Catalyst "B" of Example 1) to convert nitration-grade toluene to benzene and xylenes. In each run, the ground catalyst was packed into a 3/4-inch tubular, stainless steel, plug-flow reactor and treated with flowing hydrogen for two hours at 400° C. (752° F.) and 200 pounds per square inch gauge (psig) (about 1.4 megapascals (MPa)) prior to the introduction of the liquid feed. The feed stream was a mixture of hydrogen and toluene (4:1 hydrogen:toluene molar ratio), and the reaction conditions were 400° C. (752° F.) and 200 psig (about 1.4 MPa), and at a WHSV of 1.0 and 2.0 for catalyst "A", and 1.0, 2.0 and 5.0 for catalyst "B". Analyses of the liquid feeds (Feed Wt. percent) and products (Pdt. Wt. percent) obtained in each run are shown in Table 1. With hydrogen, mordenite zeolite, T= 400 °C , p= 10501.1Torr , Product distribution / selectivity Patent; Miller, Jeffrey T.; Huff, George A.; Henley, Brian J.; US2005/197518; (2005); (A1) English View in Reaxys 2 :Example 2 This example illustrates the performance capabilities of a mordenite catalyst (Catalyst "A" of Example 1) and an identical catalyst impregnated with molybdenum (Catalyst "B" of Example 1) to convert nitration-grade toluene to benzene and xylenes. In each run, the ground catalyst was packed into a 3/4-inch tubular, stainless steel, plug-flow reactor and treated with flowing hydrogen for two hours at 400° C. (752° F.) and 200 pounds per square inch gauge (psig) (about 1.4 megapascals (MPa)) prior to the introduction of the liquid feed. The feed stream was a mixture of hydrogen and toluene (4:1 hydrogen:toluene molar ratio), and the reaction conditions were 400° C. (752° F.) and 200 psig (about 1.4 MPa), and at a WHSV of 1.0 and 2.0 for catalyst "A", and 1.0, 2.0 and 5.0 for catalyst "B". Analyses of the liquid feeds (Feed Wt. percent) and products (Pdt. Wt. percent) obtained in each run are shown in Table 1. With hydrogen, ammonium heptamolybdate; mordenite zeolite; mixture of, calcined, T= 400 °C , p= 10501.1Torr , Product distribution / selectivity Patent; Miller, Jeffrey T.; Huff, George A.; Henley, Brian J.; US2005/197518; (2005); (A1) English View in Reaxys 1 :Example 1; This example illustrates the performance capabilities of a catalyst lacking macropore volume (catalyst "X") to convert nitration-grade toluene to a product comprising xylene isomers. Separate runs were conducted with identical feeds at a WHSV of 4.0 and at a WHSV of 6.0. The feed stream was a mixture of hydrogen and toluene (4:1 hydrogen:toluene molar ratio), and the reactor conditions were those as set out above. Analyses of the liquid feed (Feed. Wt. percent) and products (Pdt. Wt. percent) obtained in each run are shown in Table 2, below.; The conversion of toluene is determined by dividing the difference in the amount of toluene in the feed and product by the toluene present in the feed. For example, using the data obtained from the run with catalyst "X" and a WHSV of 4.0, the toluene conversion was about 39.0 (i.e., 39.0=100.x. (99.83-60.91).div.99.83). In contrast, using the data obtained from the run with catalyst "X" and a WHSV of 6.0, the toluene

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conversion was about 31.6 (i.e., 31.6=100.x.(99.83-68.29).div.99.83). The selectivity of any particular constituent in the product is determined by dividing the yield of the constitutent by the conversion of toluene. Thus, for example, using the data obtained from the run with catalyst "X" and a WHSV of 4.0, the benzene selectivity was about 40.3percent (i.e., 40.3=100.x. (15.73.div.39.0)), and the xylene isomers selectivity was about 46.2percent (i.e., 46.2=100.x.18.3.div.39.0)). In contrast, using the data obtained from the run with catalyst "X" and a WHSV of 6.0, the benzene selectivity was about 40.5percent (i.e., 40.5=100.x.(12.81.div.31.6)), and the xylene isomers selectivity was about 48.1percent (i.e., 48.1=100.x.15.2.div.31.6)). Additionally, the selectivity of C9+ aromatics at WSHV of 4.0 and 6.0 was 7.3percent and 6.6percent, respectively. At WSHV of 4.0, there is 15.7percent benzene and 18.0percent xylene isomers (0.87 weight ratio) as the major products. The ethylbenzene present in the product at WHSV of 4.0 comprises about 0.99 wt. percent of the C8 aromatics, based on the total weight of the C8 aromatics. At WSHV of 6.0, there is 12.8percent benzene and 15.2percent xylene isomers (0.84 weight ratio) as the major products. The ethylbenzene present in the product at WHSV of 6.0 comprises about 0.85 wt. percent of the C8 aromatics, based on the total weight of the C8 aromatics. With H-mordenite zeolite (Si/Al ratio of 41.6, Na level of 130 ppm) mixed with alumina and extruded to form 1/12-inch cylindrical pellets (80percent sieve/20percent binder), calcined, mixed with ammonium heptamolybdate/water; impregnated catalyst (2percent Mo) calcined at 500° C. (1-3 h); macropore volume (>50 nm) = 0.018 cc/g, T= 398.879 °C , p= 11103.3Torr , Product distribution / selectivity Patent; Schwartz, Hilary E.; Miller, Jeffrey T.; Henley, Brian J.; Huff, George A.; US2007/49780; (2007); (A1) English View in Reaxys 9 :Example 9; This example compares the performance capabilities of a catalyst lacking macropores (catalyst "H") versus a catalyst containing macropores (catalyst "I") to convert nitration-grade toluene to a product comprising xylene isomers. Separate runs with each catalyst were conducted with nearly-identical feeds at a WHSV of 6.0. The feed stream was a mixture of hydrogen and toluene (4:1 hydrogen:toluene molar ratio), and the reactor conditions were those as set out above. Analyses of the liquid feed (Feed. Wt. percent) and products (Pdt. Wt. percent) obtained with each catalyst on consecutive days, and analyses of the conversion are presented in Table 11 (catalyst "H") and Table 12 (catalyst "I"), below:; Based on the foregoing data, the catalyst containing no macropore volume, catalyst "H," had low toluene conversion (24percent on day 1 and 29percent on day 2) when compared to the toluene conversion achieved with catalyst "I" (consistently about 44percent on each day) which contains macropore volume. Additionally, it was observed that the catalyst "I" provided stable performance (i.e., no loss of activity), while catalyst "H" did not provide equally stable performance, losing 5percent toluene conversion in 1-2 days. Thus, the foregoing example demonstrates that a catalyst containing macropore volume is more stable than a catalyst lacking macropore volume. With H-mordenite zeolite (Si/Al ratio of 36.1, Na level of 260 ppm) mixed with alumina, pore forming reagent and extruded to form 1/16-inch trilobe pellets (80percent sieve/20percent binder), calcined, mixed with ammonium heptamolybdate/water; impregnated catalyst (2percent Mo); macropore volume (>50 nm) = 0.01 cc/g, T= 398.879 °C , p= 11103.3Torr , Product distribution / selectivity Patent; Schwartz, Hilary E.; Miller, Jeffrey T.; Henley, Brian J.; Huff, George A.; US2007/49780; (2007); (A1) English View in Reaxys 9 :Example 9; This example compares the performance capabilities of a catalyst lacking macropores (catalyst "H") versus a catalyst containing macropores (catalyst "I") to convert nitration-grade toluene to a product comprising xylene isomers. Separate runs with each catalyst were conducted with nearly-identical feeds at a WHSV of 6.0. The feed stream was a mixture of hydrogen and toluene (4:1 hydrogen:toluene molar ratio), and the reactor conditions were those as set out above. Analyses of the liquid feed (Feed. Wt. percent) and products (Pdt. Wt. percent) obtained with each catalyst on consecutive days, and analyses of the conversion are presented in Table 11 (catalyst "H") and Table 12 (catalyst "I"), below:; Based on the foregoing data, the catalyst containing no macropore volume, catalyst "H," had low toluene conversion (24percent on day 1 and 29percent on day 2) when compared to the toluene conversion achieved with catalyst "I" (consistently about 44percent on each day) which contains macropore volume. Additionally, it was observed that the catalyst "I" provided stable performance (i.e., no loss of activity), while catalyst "H" did not provide equally stable performance, losing 5percent toluene conversion in 1-2 days. Thus, the foregoing example demonstrates that a catalyst containing macropore volume is more stable than a catalyst lacking macropore volume. With H-mordenite zeolite (Si/Al ratio of 36.1, Na level of 260 ppm) mixed with alumina, pore forming reagent and extruded to form 1/16-inch trilobe pellets (80percent sieve/20percent binder), calcined, mixed with ammonium heptamolybdate/water; impregnated catalyst (2percent Mo); macropore volume (>50 nm) = 0.18 cc/g, T= 398.879 °C , p= 11103.3Torr , Product distribution / selectivity Patent; Schwartz, Hilary E.; Miller, Jeffrey T.; Henley, Brian J.; Huff, George A.; US2007/49780; (2007); (A1) English View in Reaxys 3 :Example 3; This example illustrates the performance capabilities of another catalyst containing macropores, catalyst "B," to convert nitration-grade toluene to a product comprising xylene isomers. Separate runs were conducted with nearly-identical

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feeds at a WHSV of 4.0 and at a WHSV of 6.0. The feed stream was a mixture of hydrogen and toluene (4:1 hydrogen:toluene molar ratio), and the reactor conditions were those as set out above. Analyses of the liquid feed (Feed. Wt. percent) and products (Pdt. Wt. percent) obtained in each run are shown in Table 4, below.; At WSHV of 4.0, there is 16.5percent benzene and 18.7percent xylene isomers (0.88 weight ratio) as the major products. At WSHV of 6.0, there is 19.6percent benzene and 21.4percent xylene isomers (0.92 weight ratio) as the major products. Based on the obtained data shown in Table 4, the toluene conversions at WSHV of 4.0 and 6.0 was 46.5percent, and 39.2percent respectively. In contrast, the toluene conversions of a similar feed at WSHV of 4.0 and 6.0 utilizing catalyst "X" was 39.0percent, and 31.6percent, respectively. At both space velocities, the conversion of toluene with catalyst "B" was higher than that obtained with catalyst "X," which lacks macropores. Based on first order, reversible equilibrium reaction kinetics, the relative activity of catalyst "B" is 1.43 times that of catalyst "X," which lacks macropores. At both space velocities, the conversion of toluene with catalyst "B" was higher than that obtained with catalyst "X," which lacks macropores. Based on first order, reversible equilibrium reaction kinetics, the relative activity of catalyst "B" is 1.43 times that of catalyst "X," which lacks macropores. The xylene isomers selectivity with catalyst "B" at WSHV of 4.0 and 6.0 was 46.0percent, and 47.7percent, respectively. As shown in Example 1, above, the xylene isomers selectivity with catalyst "X" at WSHV of 4.0 and 6.0 was 46.2percent, and 48.1percent, respectively. With H-mordenite zeolite (Si/Al ratio of 41.6, Na level of 130 ppm) mixed with alumina, pore forming reagent and extruded to form 1/12-inch cylindrical pellets (80percent sieve/20percent binder), calcined, mixed with ammonium heptamolybdate/water; impregnated catalyst (2percent Mo) calcined at 500° C. (1-3 h); macropore volume (>50 nm) = 0.255 cc/g, T= 398.879 °C , p= 11103.3Torr , Product distribution / selectivity Patent; Schwartz, Hilary E.; Miller, Jeffrey T.; Henley, Brian J.; Huff, George A.; US2007/49780; (2007); (A1) English View in Reaxys 2 :Example 2; This example illustrates the performance capabilities of a catalyst containing macropores, catalyst "A," to convert nitration-grade toluene to a product comprising xylene isomers. Separate runs were conducted with nearly-identical feeds at a WHSV of 4.0 and at a WHSV of 6.0. The feed stream was a mixture of hydrogen and toluene (4:1 hydrogen:toluene molar ratio), and the reactor conditions were those as set out above. Analyses of the liquid feed (Feed. Wt. percent) and products (Pdt. Wt. percent) obtained in each run are shown in Table 3, below.; At WSHV of 4.0, there is 18.3percent benzene and 21.4percent xylene isomers (0.86 weight ratio) as the major products. At WSHV of 6.0, there is 15.8percent benzene and 18.8percent xylene isomers (0.84 weight ratio) as the major products. Based on the obtained data shown in Table 3, the toluene conversions at WSHV of 4.0 and 6.0 was 44.0percent, and 38.0percent respectively. In contrast, the toluene conversions of a similar feed at WSHV of 4.0 and 6.0 utilizing catalyst "X" was 39.0percent, and 31.6percent, respectively. Similarly, the xylene isomers selectivity with catalyst "A" at WSHV of 4.0 and 6.0 was 48.5percent, and 49.6percent, respectively. In contrast, the xylene isomers selectivity with catalyst "X" at WSHV of 4.0 and 6.0 was 46.2percent, and 48.1percent, respectively. The benzene selectivity with catalyst "A" at WSHV of 4.0 and 6.0 was 41.6percent, and 41.5percent, respectively. In contrast, the benzene selectivity with catalyst "X" at WSHV of 4.0 and 6.0 was 40.3percent, and 40.5percent, respectively. At both space velocities, the conversion of toluene, the selectivity for xylene isomers, and the selectivity for benzene were higher than that of catalyst "X," which lacks macropores. Based on first order, reversible equilibrium reaction kinetics, the relative activity of catalyst "A" is 1.38 times that of catalyst "X," which lacks macropores. With H-mordenite zeolite (Si/Al ratio of 41.6, Na level of 130 ppm) mixed with alumina, pore forming reagent and extruded to form 1/16-inch trilobe pellets (80percent sieve/20percent binder), calcined, mixed with ammonium heptamolybdate/water; impregnated catalyst (2percent Mo) calcined at 500° C. (1-3 h); macropore volume (>50 nm) = 0.132 cc/g, T= 398.879 °C , p= 11103.3Torr , Product distribution / selectivity Patent; Schwartz, Hilary E.; Miller, Jeffrey T.; Henley, Brian J.; Huff, George A.; US2007/49780; (2007); (A1) English View in Reaxys

Rx-ID: 24272403 View in Reaxys 49/165 Yield

Conditions & References 3 :A third experiment was conducted to investigate the catalytic effects of palladium modification of a nickel-promoted catalyst and nickel modification of a palladium mordenite catalyst. The same nickel mordenite catalyst as described in Example 2 and containing about 1 wt. percent nickel, was used. A solution containing a palladium salt was added to a nickel-containing mordenite extrudate such that the final palladium concentration was about 116 ppm per weight in the catalyst. The extrudate was then dried and calcined similar to Example 1 palladium-modified nickel-promoted mordenite catalyst. The palladium modified

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nickel mordenite catalyst was then loaded into a reactor, and a stream of toluene was fed into the reactor over a period of from about day 1 to about day 17, and from about day 34 to about day 55. The toluene disproportionation process conditions, similar to that described above, were sufficient to provide about 46percent conversion of toluene. As illustrated in Table 2, the palladium modified nickel mordenite catalyst had toluene disproportionation activity with increased proportions of xylene production and decreased proportions of heavy aromatics, as compared to that typically observed for nickel mordenite. Average values for the product mixture from the palladium modified nickel mordenite catalyst comprised: about 40 wt. percent benzene; about 48 wt. percent xylenes; about 0.9 wt. percent ethylbenzenes; about 10.6 wt. percent heavy aromatics; and about 0.7 wt. percent nonaromatics.Yet another preparation of the palladium modified nickel mordenite catalyst was examined for 57 days of time-on-stream using a toluene feed and various process conditions. The palladium modified nickel promoted mordenite catalyst comprised about 76 ppm palladium and about 1 wt. percent nickel on a mordenite having a SiO2:Al2O3 molar ratio of about 90:1. Temperature and reactor inlet pressure were in the range of about 330 to about 500° C. and about 2 MPa to about 4.2 MPa, respectively. Hydrogen was supplied to the reaction zone in an amount sufficient to provide a hydrogen:toluene molar ratio (H2:HC) of about 0.9:1 to about 3:1. The LSHV was about 2.8 to about 3.5 hr-1. Specific process conditions for time-on-stream are presented in Table 3 and temperature and pressure adjustments are illustrated in FIG. 2 in which concentration in wt. percent and temperature in degrees Centigrade are plotted on the ordinate vs. time in days on the abscissa. As shown in Table 3, high proportions of nonaromatics were present in the product mixture immediately after startup. After 7 days, the reactor pressure was reduced from about 600 to about 300 psig. Within about 2 days of the reduction in pressure, nonaromatics and heavy aromatics decreased to below about 2percent and about 10percent, respectively. At day 15, with a reactor temperature of about 470° C. and pressure of 300 psig the conversion was about 31percent. Increasing the pressure to about 400 psig resulted in an increase in conversion to about 45percent. Similar to the above-described preparation of the palladium modified nickel mordenite catalyst containing about 116 ppm palladium, the palladium modified nickel mordenite catalyst containing about 76 ppm palladium also had toluene disproportionation activity with higher proportions of xylene and lower proportions of heavy aromatics production (FIG. 2), as compared with the previously studied nickel mordenite catalyst (see Examples 1 and 2). Up to about 25 days time-on-stream, the average values for the product mixture from this preparation of palladium modified nickel mordenite catalyst comprised: about 40 wt. percent benzene; about 48 wt. percent xylenes; about 1 wt. percent ethylbenzenes; about 9.5 wt. percent heavy aromatics; and about 1-2 wt. percent nonaromatics. The proportion of xylene in the product mixture remained above about 50percent from day 8 to about day 16. And, from day 20 to 29, the proportion of xylenes remained between about 48 and about 49percent. By 30 days time-on-stream, the improved selectivity towards xylene production as compared to nickel mordenite disappeared, and by 57 days time-on-stream, the proportion of xylene in the product mixture decreased to about 44-45 wt. percent and corresponding increase in the proportion of heavy aromatics. With hydrogen, palladium modification of a nickel-promoted catalyst, T= 330 - 500 °C , p= 15001.5 - 31503.2Torr , continuous proces, Product distribution / selectivity Patent; Xiao, Xin; Butler, James; Comeaux, Charles; Kelly, Kevin; US2006/211902; (2006); (A1) English View in Reaxys 4 :Example 4; This example illustrates the performance capabilities of still another catalyst containing macropores, catalyst "C," to convert nitration-grade toluene to a product comprising xylene isomers. Separate runs were conducted with nearly-identical feeds at a WHSV of 4.0 and at a WHSV of 6.0. The feed stream was a mixture of hydrogen and toluene (4:1 hydrogen:toluene molar ratio), and the reactor conditions were those as set out above. Analyses of the liquid feed (Feed. Wt. percent) and products (Pdt. Wt. percent) obtained in each run are shown in Table 5, below.; At WSHV of 4.0, there is 19.5percent benzene and 21.0percent xylene isomers (0.93 weight ratio) as the major products. At WSHV of 6.0, there is 16.8percent benzene and 18.5percent xylene isomers (0.91 weight ratio) as the major products. Based on the obtained data shown in Table 5, the toluene conversions at WSHV of 4.0 and 6.0 was 46.5percent, and 39.2percent respectively. In contrast, the toluene conversions of a similar feed at WSHV of 4.0 and 6.0 utilizing catalyst "X" was 39.0percent, and 31.6percent, respectively. At both space velocities, the conversion of toluene was higher than that obtained with catalyst "X," which lacks macropores. Based on first order, reversible equilibrium reaction kinetics, the relative activity of catalyst "C" is 1.42 times that of catalyst "X," which lacks macropores. The xylene isomers selectivity with catalyst "C" at WSHV of 4.0 and 6.0 was 45.7percent, and 47.2percent, respectively. As shown in Example 1, above, the xylene isomers selectivity with catalyst "X" at WSHV of 4.0 and 6.0 was 46.2percent, and 48.1percent, respectively. The benzene selectivity with catalyst "C" at WSHV of 4.0 and 6.0 was 42.6percent, and 42.7percent, respectively. In contrast, the benzene selectivity with catalyst "X" at WSHV of 4.0 and 6.0 was 40.3percent, and 40.5percent, respectively. This example demonstrates that a catalyst containing macropores has comparable selectivity, at higher conversions. Thus, the catalyst containing macropores provides significantly better activity without compromising selectivity for xylene isomers (and benzene). With H-mordenite zeolite (Si/Al ratio of 41.6, Na level of 130 ppm) mixed with alumina, pore forming reagent and extruded to form 1/12-inch cylindrical pellets (80percent sieve/20percent binder), calcined, mixed with ammonium heptamolybdate/water; impregnated catalyst (2percent Mo) calcined at 500° C. (1-3 h); macropore volume (>50 nm) = 0.288 cc/g, T= 398.879 °C , p= 11103.3Torr , Product distribution / selectivity Patent; Schwartz, Hilary E.; Miller, Jeffrey T.; Henley, Brian J.; Huff, George A.; US2007/49780; (2007); (A1) English

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View in Reaxys 6 :Example 6; This example illustrates the performance capabilities of yet another catalyst containing macropores, catalyst "E," to convert nitration-grade toluene to a product comprising xylene isomers. One run was conducted with the feed at a WHSV of 6.0. The feed stream was a mixture of hydrogen and toluene (4:1 hydrogen:toluene molar ratio), and the reactor conditions were those as set out above. Analyses of the liquid feed (Feed. Wt. percent) and product (Pdt. Wt. percent) obtained in the run are shown in Table 7, below.; The conversion of toluene was higher than that obtained with catalyst "X," which lacks macropores. Based on first order, reversible equilibrium reaction kinetics, the relative activity of catalyst "E" is 1.15 times that of catalyst "X," which lacks macropores. Catalyst "E" exhibits improved activity relative to catalyst "X" even though catalyst "E" contains only 70percent H-mordenite compared to catalyst "X," which has 80percent H-mordenite. At WSHV of 6.0, there is 13.7percent benzene and 15.7percent xylene isomers (0.87 weight ratio) as the major products. Based on the obtained data shown in Table 7, the toluene conversion at WSHV of 6.0 was 32.1percent. In contrast, the toluene conversions of a similar feed at WSHV of 6.0 utilizing catalyst "X" was 31.6percent. The xylene isomers selectivity with catalyst "E" at WSHV of 6.0 was 42.8percent. In contrast, the xylene isomers selectivity with catalyst "X" at WSHV of 6.0 was 48.1percent. The benzene selectivity with catalyst "E" at WSHV of 6.0 was 42.7percent. As shown in Example 1, above, the benzene selectivity with catalyst "X" at WSHV of 6.0 was 40.5percent. This example demonstrates that a catalyst containing macropores has comparable selectivity, at higher conversions. Thus, the catalyst containing macropores provides significantly better activity without compromising selectivity for xylene isomers (and benzene). With H-mordenite zeolite (Si/Al ratio of 41.6, Na level of 130 ppm) mixed with alumina, pore forming reagent and extruded to form 1/12-inch cylindrical pellets (70percent sieve/30percent binder), calcined, mixed with ammonium heptamolybdate/water; impregnated catalyst (2percent Mo) calcined at 500° C. (1-3 h); macropore volume (>50 nm) = 0.212 cc/g, T= 398.879 °C , p= 11103.3Torr , Product distribution / selectivity Patent; Schwartz, Hilary E.; Miller, Jeffrey T.; Henley, Brian J.; Huff, George A.; US2007/49780; (2007); (A1) English View in Reaxys 5 :Example 5; This example illustrates the performance capabilities of yet another catalyst containing macropores, catalyst "D," to convert nitration-grade toluene to a product comprising xylene isomers. One run was conducted with the feed at a WHSV of 6.0. The feed stream was a mixture of hydrogen and toluene (4:1 hydrogen:toluene molar ratio), and the reactor conditions were those as set out above. Analyses of the liquid feed (Feed. Wt. percent) and product (Pdt. Wt. percent) obtained in the run are shown in Table 6, below.; At WSHV of 6.0, there is 15.5percent benzene and 18.2percent xylene isomers (0.85 weight ratio) as the major products. Based on the obtained data shown in Table 6, the toluene conversion at WSHV of 6.0 was 37.5percent. In contrast, the toluene conversions of a similar feed at WSHV of 6.0 utilizing catalyst "X" was 31.6percent. The conversion of toluene was higher than that obtained with catalyst "X," which lacks macropores. Based on first order, reversible equilibrium reaction kinetics, the relative activity of catalyst "D" is 1.38 times that of catalyst "X," which lacks macropores. The xylene isomers selectivity with catalyst "D" at WSHV of 6.0 was 48.4percent. In contrast, the xylene isomers selectivity with catalyst "X" at WSHV of 6.0 was 48.1percent. The benzene selectivity with catalyst "D" at WSHV of 6.0 was 41.4percent. As shown in Example 1, above, the benzene selectivity with catalyst "X" at WSHV of 6.0 was 40.5percent. This example demonstrates that a catalyst containing macropores has comparable selectivity, at higher conversions. Thus, the catalyst containing macropores provides significantly better activity without compromising selectivity for xylene isomers (and benzene). With H-mordenite zeolite (Si/Al ratio of 41.6, Na level of 130 ppm) mixed with alumina, pore forming reagent and extruded to form 1/12-inch cylindrical pellets (80percent sieve/20percent binder), calcined, mixed with ammonium heptamolybdate/water; impregnated catalyst (2percent Mo) calcined at 500° C. (1-3 h); macropore volume (>50 nm) = 0.280 cc/g, T= 398.879 °C , p= 11103.3Torr , Product distribution / selectivity Patent; Schwartz, Hilary E.; Miller, Jeffrey T.; Henley, Brian J.; Huff, George A.; US2007/49780; (2007); (A1) English View in Reaxys 7 :Example 7; This example illustrates the performance capabilities of yet another catalyst containing macropores, catalyst "F," to convert nitration-grade toluene to a product comprising xylene isomers. One run was conducted with the feed at a WHSV of 6.0. The feed stream was a mixture of hydrogen and toluene (4:1 hydrogen:toluene molar ratio), and the reactor conditions were those as set out above. Analyses of the liquid feed (Feed. Wt. percent) and product (Pdt. Wt. percent) obtained in the run are shown in Table 8, below.; At WSHV of 6.0, there is 16.4percent benzene and 17.9percent xylene isomers (0.92 weight ratio) as the major products. Based on the obtained data shown in Table 8, the toluene conversion at WSHV of 6.0 was 38.1percent. In contrast, the toluene conversions of a similar feed at WSHV of 6.0 utilizing catalyst "X" was 31.6percent. The conversion of toluene was higher than that obtained with catalyst "X," which lacks macropores. Based on first order, reversible equilibrium reaction kinetics, the relative activity of catalyst "F" is 1.38 times that of catalyst "X," which lacks macropores. The xylene isomers selectivity with catalyst "F" at WSHV of 6.0 was 47.0percent. In contrast, the xylene isomers selectivity with catalyst "X" at WSHV of 6.0 was 48.1percent. The benzene selectivity with catalyst "F" at WSHV of 6.0 was 43.0percent. In contrast, the benzene selectivity with catalyst "X" at WSHV of 6.0 was 40.5percent.

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With H-mordenite zeolite (Si/Al ratio of 41.6, Na level of 130 ppm) mixed with alumina, pore forming reagent and extruded to form 1/12-inch cylindrical pellets (80percent sieve/20percent binder), calcined, mixed with ammonium heptamolybdate/water; impregnated catalyst (2percent Mo) calcined at 500° C. (1-3 h); macropore volume (>50 nm) = 0.281 cc/g, T= 398.879 °C , p= 11103.3Torr , Product distribution / selectivity Patent; Schwartz, Hilary E.; Miller, Jeffrey T.; Henley, Brian J.; Huff, George A.; US2007/49780; (2007); (A1) English View in Reaxys 8 :Example 8; This example illustrates the performance capabilities of another catalyst containing macropores, catalyst "G," to convert nitration-grade toluene to a product comprising xylene isomers. Separate runs were conducted with nearly-identical feeds at a WHSV of 4.0 and at a WHSV of 6.0. The feed stream was a mixture of hydrogen and toluene (4:1 hydrogen:toluene molar ratio), and the reactor conditions were those as set out above. Analyses of the liquid feed (Feed. Wt. percent) and products (Pdt. Wt. percent) obtained in each run are shown in Table 9, below.; At WSHV of 4.0, there is 20.0percent benzene and 21.4percent xylene isomers (0.93 weight ratio) as the major products. At WSHV of 6.0, there is 17.0percent benzene and 19.3percent xylene isomers (0.88 weight ratio) as the major products. Based on the obtained data shown in Table 9, the toluene conversions at WSHV of 4.0 and 6.0 was 47percent, and 40percent respectively. In contrast, the toluene conversions of a similar feed at WSHV of 4.0 and 6.0 utilizing catalyst "X" was 39.0percent, and 31.6percent, respectively. At both space velocities, the conversion of toluene was higher than that of catalyst "X," which lacks macropores. Based on first order, reversible equilibrium reaction kinetics, the relative activity of catalyst "G" is 1.48 times that of catalyst "X," which lacks macropores. The xylene isomers selectivity with catalyst "G" at WSHV of 4.0 and 6.0 was 45.5percent, and 48.3percent, respectively. As shown in Example 1, above, the xylene isomers selectivity with catalyst "X" at WSHV of 4.0 and 6.0 was 46.2percent, and 48.1percent, respectively. The benzene selectivity with catalyst "G" at WSHV of 4.0 and 6.0 was 42.5percent, and 42.4percent, respectively. As shown in Example 1, above, the benzene selectivity with catalyst "X" at WSHV of 4.0 and 6.0 was 40.3percent, and 40.5percent, respectively. This example demonstrates that a catalyst containing macropores has comparable selectivity, at higher conversions. Thus, the catalyst containing macropores provides significantly better activity without compromising selectivity for xylene isomers (and benzene). With H-mordenite zeolite (Si/Al ratio of 41.6, Na level of 130 ppm) mixed with alumina, pore forming reagent and extruded to form 1/16-inch trilobe pellets (80percent sieve/20percent binder), calcined, mixed with ammonium heptamolybdate/water; impregnated catalyst (2percent Mo) calcined at 500° C. (1-3 h); macropore volume (>50 nm) = 0.280 cc/g, T= 398.879 °C , p= 11103.3Torr , Product distribution / selectivity Patent; Schwartz, Hilary E.; Miller, Jeffrey T.; Henley, Brian J.; Huff, George A.; US2007/49780; (2007); (A1) English View in Reaxys

No structure RN: 12810329

No structure RN: 12810333

Rx-ID: 25613289 View in Reaxys 50/165 Yield

Conditions & References 1 Patent; Gwangju Institute of Science and Technology; US7173155; (2007); (B1) English View in Reaxys

Rx-ID: 25669433 View in Reaxys 51/165 Yield

Conditions & References 10 :Example 10; This example demonstrates the ability of catalyst "C" (a macroporous catalyst) to convert a feed containing toluene, benzene, and some light non-aromatics to xylene isomers. Three nearly identical feeds were converted by the catalyst. In the three runs, the reaction conditions were identical except that the temperature of the reactor and the WHSV were different. Analyses of the liquid feed (Feed. Wt. percent), obtained product (Pdt. Wt. percent), and the conversion are presented in Table 13, below.; Where the WHSV was 0.5, the net benzene obtained in the product of the conversion was 14.12, whereas the net xylene isomers obtained in the product of the conversion was 14.68. Accordingly, the ratio of net benzene to net xylene isomers (Benzene/Xylenes) obtained by converting this toluene feed is 0.96 (i.e., 0.96=(14.12.div.14.68)). This ratio is reported in the foregoing table as Benzene/Xylenes. The data in the foregoing table also show that, when the temperature and pressure remain constant (750° F. and 200 psig) and the WHSV is increased (from 0.5 to 3.0), toluene conversion, ethylbenzene selectivity in the C8 fraction, and selectivity to C9 aromatics decrease. The decrease in toluene conversion as WHSV is increased is an expected response because as more feed is passed over a catalyst over a given time, more demands are placed on the catalyst resulting in

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less conversion. Generally, toluene conversion will depend upon the temperature, pressure, and WHSV, the WHSV being a combination of the amount of catalyst and the feed rate. With H-mordenite zeolite (Si/Al ratio of 41.6, Na level of 130 ppm) mixed with alumina, pore forming reagent and extruded to form 1/12-inch cylindrical pellets (80percent sieve/20percent binder), calcined, mixed with ammonium heptamolybdate/water; impregnated catalyst (2percent Mo) calcined at 500° C. (1-3 h); macropore volume (>50 nm) = 0.288 cc/g, T= 382.212 398.879 °C , p= 11103.3Torr , Product distribution / selectivity Patent; Schwartz, Hilary E.; Miller, Jeffrey T.; Henley, Brian J.; Huff, George A.; US2007/49780; (2007); (A1) English View in Reaxys 11 :Example 11; This example demonstrates the ability of catalyst "G" (a macroporous catalyst) to convert a feed containing toluene, benzene, and some light non-aromatics to xylene isomers. Analyses of the liquid feed (Feed. Wt. percent), obtained product (Pdt. Wt. percent), and the conversion are presented in Table 14, below.; With H-mordenite zeolite (Si/Al ratio of 41.6, Na level of 130 ppm) mixed with alumina, pore forming reagent and extruded to form 1/16-inch trilobe pellets (80percent sieve/20percent binder), calcined, mixed with ammonium heptamolybdate/water; impregnated catalyst (2percent Mo) calcined at 500° C. (1-3 h); macropore volume (>50 nm) = 0.280 cc/g, T= 415.546 °C , p= 11103.3Torr , Product distribution / selectivity Patent; Schwartz, Hilary E.; Miller, Jeffrey T.; Henley, Brian J.; Huff, George A.; US2007/49780; (2007); (A1) English View in Reaxys

xylenes Rx-ID: 25669434 View in Reaxys 52/165 Yield 23.6 %, 24.3 %

Conditions & References 12 :Example 12. A catalyst I was prepared by wet impregnation of catalyst A with ammonium perrenate and then drying at 100°C for 8 hours, such that the final rhenium content was 0.3percent. This catalyst was conformed in particles of diameters between 0.2 and 0.5 mm, by means of tablet forming by compressing, grinding and sifting. This catalyst was put through a disproportionation experiment exactly the same as that described in Example 2, a 56percent toluene conversion being obtained after six-hour reaction time, with a molar yield of benzene, xylenes and cracking products respectively of 24.3percent, 23.6percent and 4.0percent. With hydrogen, ITQ-13 zeolite containing 0.3 percent Re, Time= 6h, T= 400 °C , p= 22502.3Torr , Product distribution / selectivity Patent; CONSEJO SUPERIOR DE INVESTIGACIONES CIENT FICAS; UNIVERSIDAD POLITECNICA DE VALENCIA; EP1775277; (2007); (A1) English View in Reaxys

21.1 - 22.2 %, 23.5 25.3 %

2; 3; 4; 5 :Example 2. Catalytic activity for toluene disproportionation of the zeolite described in Example 1. The ITQ-13 zeolite (Catalyst A) in Example 1 was conformed in particles of diameters within the 0.2 - 0.5 mm range, by means of forming tablets by compressing, grinding and sifting. 1 gram of this material is mixed with silicon carbon particles ranging from 0.6 to 0.9 mm in size up to the point at which the volume of the mixture of the two was 2.5 ml. The homogeneous mixture of these two materials was placed inside a steel tube reactor of a one-inch outer diameter. The catalytic toluene disproportionation experiment was conducted under the following reaction conditions: pressure 30 bar, spatial velocity , 1 hour-1 hydrogen / toluene molar relation of 8.5 and 400°C temperature. Under these conditions, following a six-hour reaction time, a 47.9percent conversion was achieved, with a molar yield of benzene and xylenes respectively of 23.5percent and 21.1percent. Example 3. Catalyst A was studied using the same experimental method and reaction conditions as in Example 2, the only modification being the reaction temperature, which was 420°C in this case. Under these conditions, a 50.3percent conversion was achieved, with a molar yield of benzene and xylenes respectively of 24.2percent and 21.8percent. Example 4. Catalyst A was studied using the same experimental method and reaction conditions as in Example 2, modifying the reaction temperature, which was 440°C in this case. Under these conditions, a 51.1percent conversion was achieved, with a molar yield of benzene and xylenes respectively of 24.5percent and 21.7percent. Example 5. Catalyst A was studied using the same experimental method and reaction conditions as in Example 2, modifying the reaction temperature, which was 460°C in this case. Under these conditions, a 53.1percent conversion was achieved, with a molar yield of benzene and xylenes respectively of 25.3percent and 22.2percent With hydrogen, ITQ-13 zeolite, Time= 6h, T= 400 - 460 °C , p= 22502.3Torr , Product distribution / selectivity

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Patent; CONSEJO SUPERIOR DE INVESTIGACIONES CIENT FICAS; UNIVERSIDAD POLITECNICA DE VALENCIA; EP1775277; (2007); (A1) English View in Reaxys 17.1 %, 19.8 %

8 :8. A catalyst (D) comprised of Mordenite zeolite in its acid form with Si/Al ratio of 10, supplied by PQ Corporation with code CBV-20A, a 39.1percent toluene conversion being obtained after a six-hour reaction time, with a molar yield of benzene and xylenes respectively of 19.8percent and 17.1percent. Catalysts B, C and D were studied using the same experimental method and reaction conditions as in Example 2, the only modification being the reaction temperature, such that three different temperatures, 420°C, 440°C and 460°C, were studied. With hydrogen, Mordenite zeolite, acid form, Time= 6h, T= 420 - 460 °C , p= 22502.3Torr , Product distribution / selectivity Patent; CONSEJO SUPERIOR DE INVESTIGACIONES CIENT FICAS; UNIVERSIDAD POLITECNICA DE VALENCIA; EP1775277; (2007); (A1) English View in Reaxys

3 - 10.6 %, 6; 7 :Example 6. A catalyst (B) comprised of ZSM-5 zeolite in its acid form with a Si/Al ratio of 17.5, supplied by PQ Corpora3.1 - 11.3 % tion with code CBV-3020, was used exactly as described in Example 2, a toluene conversion of 23.5percent being obtained after a six-hour reaction time, with a molar yield of benzene and xylenes respectively of 11.3percent and 10.6percent Example 7. A catalyst (C) comprised of ZSM-5 zeolite in its acid form with a Si/Al ratio of 32, supplied by PQ Corporation with code CBV-8020, was used exactly as described in Example 2, a 6.5percent toluene conversion being obtained after a six-hour reaction time with a molar yield of benzene and xylenes respectively of 3.1percent and 3percent; Catalysts B, C and D were studied using the same experimental method and reaction conditions as in Example 2, the only modification being the reaction temperature, such that three different temperatures, 420°C, 440°C and 460°C, were studied. With hydrogen, ZSM-5 zeolite, acid form, Time= 6h, T= 420 - 460 °C , p= 22502.3Torr , Product distribution / selectivity Patent; CONSEJO SUPERIOR DE INVESTIGACIONES CIENT FICAS; UNIVERSIDAD POLITECNICA DE VALENCIA; EP1775277; (2007); (A1) English View in Reaxys

Rx-ID: 25669436 View in Reaxys 53/165 Yield

Conditions & References 16 :Example 16; This example demonstrates the ability of catalyst "D" (a macroporous catalyst) to convert a feed containing C9 aromatics and toluene to xylene isomers. Analyses of the liquid feed (Feed. Wt. percent), obtained product (Pdt. Wt. percent), and the conversion are presented in Table 19, below.; This example also demonstrates the production of C9+ aromatics, which in accordance with the prior examples (e.g., Examples 12 and 13), can be recycled back to the feed for further conversion with the same type of catalyst. This example further demonstrates the flexibility of the method to accommodate multiple feed operations utilizing the same general process configuration, removing products of the specific conversion as desired. With H-mordenite zeolite (Si/Al ratio of 41.6, Na level of 130 ppm) mixed with alumina, pore forming reagent and extruded to form 1/12-inch cylindrical pellets (80percent sieve/20percent binder), calcined, mixed with ammonium heptamolybdate/water; impregnated catalyst (2percent Mo) calcined at 500° C. (1-3 h); macropore volume (>50 nm) = 0.280 cc/g, T= 359.99 °C , p= 11103.3Torr , Product distribution / selectivity Patent; Schwartz, Hilary E.; Miller, Jeffrey T.; Henley, Brian J.; Huff, George A.; US2007/49780; (2007); (A1) English View in Reaxys 17 :Example 17; This example demonstrates the ability of catalyst "G" to convert a feed containing C9+ aromatics, benzene, and toluene to xylene isomers. Five nearly identical feeds were converted by the catalyst. Such a feed is representative of a feed containing recycle and, as explained above, the benefits of the method with use of a macroporous catalyst impregnated with a hydrogenation component include its ability to convert such feeds without requiring complicated and expensive upstream and downstream purification operations. In the five runs, the reaction conditions were identical except that the temperature of the reactor was changed in each run. Analyses of the liquid feed (Feed. Wt. percent), obtained product (Pdt. Wt. percent), and the conversion are presented in Table 20, below.; Based on the foregoing data, at constant pressure and WHSV, the conversion of C9+ aromatics increases as the temperature increases. Similarly, at constant pressure and WHSV, ethylbenzene selectivity in the C8

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aromatics fraction decreases as the temperature increases. Toluene conversion, however, does not significantly change in response to temperature changes when the pressure and WHSV remain constant. With H-mordenite zeolite (Si/Al ratio of 41.6, Na level of 130 ppm) mixed with alumina, pore forming reagent and extruded to form 1/16-inch trilobe pellets (80percent sieve/20percent binder), calcined, mixed with ammonium heptamolybdate/water; impregnated catalyst (2percent Mo) calcined at 500° C. (1-3 h); macropore volume (>50 nm) = 0.280 cc/g, T= 371.101 - 426.657 °C , p= 11103.3Torr , Product distribution / selectivity Patent; Schwartz, Hilary E.; Miller, Jeffrey T.; Henley, Brian J.; Huff, George A.; US2007/49780; (2007); (A1) English View in Reaxys F F

(v5) (v4)– C– (v4) (v4) (v2) CH (v5) –H B2+ H (v4) – 4+H H ––(v2) (v5) (v5) Zr C (v5) 2+(v2) – (v14) (v5)

0.5

H B C –(v2) (v5) H (v5)H

F F

(v5)(v2) F

B–

(v14) Zr 4+

H F (v5) (v2)

(v5)(v5)

F F (v2) (v2) H

F F F (v5)

–HC (v5) (v4)

(v4)

B–

(v4)

(v5)

– C (v5) H (v4)

Rx-ID: 27428615 View in Reaxys 54/165 Yield

Conditions & References

52 %

in benzene, under N2 atm. to Zr complex and B(C6F5)3 benzene was added at -78°C, allowed to warm to room temp. and kept overnight; ppt. was washed with benzene and dried in vacuo Liu, Fu-Chen; Chen, Shou-Chon; Lee, Gene-Hsian; Peng, Shie-Ming; Journal of Organometallic Chemistry; vol. 692; nb. 12; (2007); p. 2375 - 2384 ; (from Gmelin) View in Reaxys

(v6) (v6)

B B B B B(v6)(v6) (v6) (v6) (v6)2.3 (v6) B BBr B (v6) (v6) BrB B Br Br B–Br (v6) Br

(v6)

C+

(v6)

B B B B B (v6)(v6) (v6) (v6) (v6) 2(v6) B (v6)(v6) Br B BrBB Br B Br – (v6) BBr Br (v6)

(v4) – H 2C (v3) –HO (v4) Ga 3+

OH –

4.5 2H 2H 2H

(v3)

3+ OH – (v3) Ga –HO (v4) Ga 3+ –(v4) (v3)(v4) 3+ CH 2 –HO Ga OH – (v3) (v3) CH –2 (v4)

–H C (v4) 2

(v4)

Rx-ID: 27579561 View in Reaxys 55/165 Yield

Conditions & References in benzene-d6, byproducts: (C6H5)3CH*C6H6; anaerobic, anhydrous condns., rotated at room temp. for 16 h; volatiles removed (vac.), oil dissolved (hexane), cooled to -20°Cfor 2 h, soln. pipetterd, allowed to evapt. slowly inside drybox, disso lved (C6D6), allowed to evapt. slowly inside glove box, separated mannually Young, Jackie D.; Khan, Masood A.; Powell, Douglas R.; Wehmschulte, Rudolf J.; European Journal of Inorganic Chemistry; nb. 12; (2007); p. 1671 - 1681 ; (from Gmelin) View in Reaxys

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NH (v4)

– N(v3) O(v3)

Yb3+ N

N NH

0.67

(v4) N–

(v6) Si N– (v3) (v3)

0.67

(v4) (v5) N N– (v3) (v5) (v3) (v5) N – – (v14) N 3+ N(v5) Yb (v4) Yb3+ OC-6-PI(v5)N – (v8) (v4) N – – (v3)(v5)(v4) N N (v5) (v3) (v5) N (v4)

(v4)

N N

(v4)

racemate

Rx-ID: 27579669 View in Reaxys 56/165 Yield

Conditions & References

65 %

in toluene, (N2); addn. of toluene soln. of binaphthyl deriv. to toluene soln. of ytterbium compd. at room temp., refluxing for 2 d; evapn., extn. (benzene), keeping soln. at room temp. for 2 wk, isolationof crystals, elem. anal. Xiang, Li; Wang, Qiuwen; Song, Haibin; Zi, Guofu; Organometallics; vol. 26; nb. 22; (2007); p. 5323 - 5329 ; (from Gmelin) View in Reaxys

(v4)N (v4) (v4) C– Ni 2+ –

N (v4) (v4) C– Ni 2+ SP-4(v4) P

–O (v2)

SP-4 O P (v2)

(v4)

4 –O (v2)

(v4)

N (v4) (v4) C– Ni 2+ SP-4(v4) P

(v4) (v4) C–

(v4)

Ni 2+ – SP-4 O (v4) (v2) P

(v4)

Rx-ID: 27579682 View in Reaxys 57/165 Yield

Conditions & References in hexane, benzene Chen, Qihui; Yu, Jing; Huang, Jiling; Organometallics; vol. 26; nb. 3; (2007); p. 617 - 625 ; (from Gmelin) View in Reaxys

H H O

H O

O H H

H O BO

H O

O H H

Rx-ID: 27579700 View in Reaxys 58/165 Yield 99 %

Conditions & References in benzene, compound was suspd. in C6H6 at room temp. for 1.5 days

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Iwasawa, Nobuharu; Takahagi, Hiroki; Journal of the American Chemical Society; vol. 129; nb. 25; (2007); p. 7754 - 7755 ; (from Gmelin) View in Reaxys H H

BO H

H H O

H H

H O B O

O BO

H O BO

OB O H H

O B O

O H

H H racemate

Rx-ID: 27579701 View in Reaxys 59/165 Yield 91 %

Conditions & References in methanol, benzene, compound was suspd. in mixt. MeOH-C6H6 (2:1) at room temp. for 36 h Iwasawa, Nobuharu; Takahagi, Hiroki; Journal of the American Chemical Society; vol. 129; nb. 25; (2007); p. 7754 - 7755 ; (from Gmelin) View in Reaxys

–HC

1.5

C–

F F F F F F

Zr 4+

B– F

F F

–HC

0.7

C–

F F F F F F

Zr 4+

B– F

F F

Rx-ID: 27595394 View in Reaxys 60/165 Yield

Conditions & References in neat (no solvent, solid phase), Zr complex was dried in vac. for 3 d; elem. anal. Sydora, Orson L.; Kilyanek, Stefan M.; Jordan, Richard F.; Organometallics; vol. 26; nb. 19; (2007); p. 4746 - 4755 ; (from Gmelin) View in Reaxys

Xylene; mixture of Rx-ID: 23828889 View in Reaxys 61/165

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Yield

Conditions & References In experimental work respecting the present invention, toluene disproportionation runs were carried out employing two nickel mordenite catalysts which were pre-sulfided with hydrogen sulfide or DMDS. Varying amounts of the sulfiding agents were used to provide sulfur to nickel mole ratios varying from 3percent to 100percent. The results were measured in terms of the nonaromatics content of the product of the toluene disproportionation procedure and the average catalysts bed temperature over the time of run. The catalysts employed in this experimental work are identified as Catalyst A and Catalyst B. Catalysts A and B are both nickel modified mordenites made out of different commercial batches. Both Catalyst A and B have a nickel content of 1.0 wt. percent and a silica/alumina mole ratio of 20. In a first set of experiments, Catalyst A was used without pre-sulfiding and with pre-sulfiding at 250° C. and 600 psig with a hydrogen flow rate of 2000 gas hourly space velocity (GHSV) in different doses of hydrogen sulfide or DMDS to provide a total sulfur treatment of the nickel ranging from 3-100 mole percent of the nickel. The experimental results are shown in FIG. 1 in which the nonaromatics content of the liquid product in wt. percent is plotted on the ordinate verses the time on stream T in days on the abscissa. In FIG. 1, the results obtained with the catalyst without pre-sulfiding (no sulfur) are indicated by data points . The data points for mole percent sulfur relative to nickel employing hydrogen sulfide are indicated by X and the corresponding data points for 10percent mole percent total sulfur provided by DMDS are indicated by . The corresponding data points for 25 mole percent of sulfur provided by hydrogen sulfide and 100 mole percent of sulfur provided by hydrogen sulfide are indicated by and a .diamond. respectively. As can be seen by the experimental work reported in FIG. 1, sulfur doses ranging from 10 to 100 mole percent (corresponding to a sulfur to nickel mole ratio of 1:10 to 1:1) produced about the same relatively low nonaromatics content during start-up whereas the catalyst without sulfiding and the catalyst sulfided with 3 mole percent sulfur resulting from hydrogen sulfide treatment showed substantially higher nonaromatic liquid content. The results of experimental work in terms of the weight average bed temperature (WABT) verses time on stream is shown in FIG. 2. In FIG. 2 the WABT B in ° C. is plotted on the ordinate verses the time T in days on the abscissa. In FIG. 2, the bed temperature for the catalyst without pre-sulfiding is shown by curve 10. The bed temperatures after pre-sulfiding with doses of 3 mole percent sulfur with H2S, 10 mole percent sulfur with DMDS, 25 mole percent sulfur with H2S and 100 mole percent sulfur with H2S are indicated by curves 12, 14, 16 and 17, respectively. Toluene conversion over the life of these runs was maintained constant at 47percent toluene conversion. As shown in the experimental work reported in FIG. 2, the average catalyst bed temperature was maintained within a relatively narrow range over the life of the runs. Further experimental work employing Catalyst B was carried out to demonstrate the impact of pre-sulfiding on nonaromatics production and average bed temperature on the start-up procedures employing a relatively low hydrogen to toluene low ratio followed by a higher hydrogen to toluene mole ratio as may used in normal toluene disproportionation procedures. In this experimental work the hydrogen to toluene mole ratio was maintained at a value of 1:1 during an initial start-up period of about six days followed by an increase of the hydrogen to toluene mole ratio to a value of 3:1 during the remainder of the run. The results of this experimental work are illustrated in FIGS. 3 and 4. In FIG. 3 the wt. percent of nonaromatics in the liquid products C is plotted on the ordinate verses the time on stream T in days on the abscissa. In FIG. 3, curve 20 indicates the amount of nonaromatics without pre-sulfiding. Curve 21 indicates the amount of nonaromatics after pre-sulfiding with 50percent DMDS mole ratio to nickel with the initial start-up procedure of the hydrogen to hydrocarbon mole ratio of 1:1 followed by an increase in the hydrogen to hydrocarbon mole ratio of 3:1 at day six. Curve 22 shows the corresponding data for pre-sulfiding with 50 mole percent sulfur relative to nickel provided by DMDS with the hydrogen to hydrocarbon mole ratio maintained at 3:1 throughout the life of the run. In FIG. 4 the weight average bed temperature B in ° C. is plotted on the ordinate verses time T in days on the abscissa for these same runs, with curve 24 indicating results without pre-sulfiding and curves 25 and 27 showing the results for pre-sulfiding with DMDS at a sulfur dose of 50 mole percent sulfur per mole of nickel. Curve 25 corresponds with the results shown in FIG. 3 by curve 21 as achieved by an increase in the hydrogen hydrocarbon mole ratio from 1:1 to 3:1 at about day six. Curve 27 shows the results employing the DMDS at a 50 mole percent sulfur dose with the hydrogen/hydrocarbon mole ratio maintained constant at 3:1 over the life of the run. As illustrated in FIG. 3 the absence of pre-sulfiding resulted in substantially higher nonaromatics content as indicated by curve 20 than for the pre-sulfiding runs depicted by curves 21 and 22. FIG. 4 shows the average bed temperature was maintained at a relatively narrow range with and without pre-sulfiding at a constant toluene conversion of 47percent. The data in FIG. 4, like the data in FIG. 2 demonstrates that the pre-sulfiding did not result in a significant loss in catalyst activity. With nickel (1.0 wt. percent)/mordenite (silica/alumina ratio 20) presulfided with various amounts of hydrogen sulfide or dimethyldisulfide (DMDS) (sulfur to nickel mole ratios 3 - 100 percent) Patent; Xiao, Xin; Fussell, Becky; Butler, James; Gomez, Brandi; US2006/149106; (2006); (A1) English View in Reaxys

Rx-ID: 23914714 View in Reaxys 62/165

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Yield

Conditions & References EXAMPLE; [0029] An increased selectivity to Ags at the expense of light ends has been demonstrated in pilot plant tests and is shown in the following material balance comparison. The prior art, gas-phase transalkylation process, is compared against the present invention, which combines a liquid-phase transalkylation process with a gas-phase process. This comparison shows the benefits of the present invention as increased xylenes and ethylbenzene, and concomitantly decreased benzene and light-end gas (especially ethane). By reducing the production of ethane by de-ethylation in gas-phase reactions within an aromatics complex, the invention provides improved total retention of aromatics relative to prior art transalkylation units used in complexes that produce xylenes.[0030] With reference to the FIGURE, showing the flow scheme of the present invention, a simulated material balance is shown below. The liquid-phase transalkylation process unit is combined with the gas-phase transalkylation process unit, and results in the following changes over a prior art single gas-phase transalkylation unit. Hydrogen feed to the flow scheme decreases. Feed of toluene and Ag+ remains constant. Production of Ags increases, while benzene production decreases. Heavies production remains constant. Most importantly, light-end gas production decreases. [0031] These changes are summarized in the following table: EPO <DP n="11"/>[0032] Thus, the flow scheme of the present invention provides a benefit by producing more of the desirable Ag material, which is the valuable xylenes and ethylbenzene. With hydrogen, gas-phase transalkylation catalyst, Gas phase, Product distribution / selectivity Patent; UOP LLC; WO2006/88439; (2006); (A1) English View in Reaxys

xylenes; mixture of Rx-ID: 24272402 View in Reaxys 63/165 Yield

Conditions & References 6 :A third experiment was conducted to investigate the catalytic effects of palladium modification of a nickel-promoted catalyst and nickel modification of a palladium mordenite catalyst. The same nickel mordenite catalyst as described in Example 2 and containing about 1 wt. percent nickel, was used. A solution containing a palladium salt was added to a nickel-containing mordenite extrudate such that the final palladium concentration was about 116 ppm per weight in the catalyst. The extrudate was then dried and calcined similar to Example 1 palladium-modified nickel-promoted mordenite catalyst. The palladium modified nickel mordenite catalyst was then loaded into a reactor, and a stream of toluene was fed into the reactor over a period of from about day 1 to about day 17, and from about day 34 to about day 55. The toluene disproportionation process conditions, similar to that described above, were sufficient to provide about 46percent conversion of toluene. As illustrated in Table 2, the palladium modified nickel mordenite catalyst had toluene disproportionation activity with increased proportions of xylene production and decreased proportions of heavy aromatics, as compared to that typically observed for nickel mordenite. Average values for the product mixture from the palladium modified nickel mordenite catalyst comprised: about 40 wt. percent benzene; about 48 wt. percent xylenes; about 0.9 wt. percent ethylbenzenes; about 10.6 wt. percent heavy aromatics; and about 0.7 wt. percent nonaromatics.Yet another preparation of the palladium modified nickel mordenite catalyst was examined for 57 days of time-on-stream using a toluene feed and various process conditions. The palladium modified nickel promoted mordenite catalyst comprised about 76 ppm palladium and about 1 wt. percent nickel on a mordenite having a SiO2:Al2O3 molar ratio of about 90:1. Temperature and reactor inlet pressure were in the range of about 330 to about 500° C. and about 2 MPa to about 4.2 MPa, respectively. Hydrogen was supplied to the reaction zone in an amount sufficient to provide a hydrogen:toluene molar ratio (H2:HC) of about 0.9:1 to about 3:1. The LSHV was about 2.8 to about 3.5 hr-1. Specific process conditions for time-on-stream are presented in Table 3 and temperature and pressure adjustments are illustrated in FIG. 2 in which concentration in wt. percent and temperature in degrees Centigrade are plotted on the ordinate vs. time in days on the abscissa. As shown in Table 3, high proportions of nonaromatics were present in the product mixture immediately after startup. After 7 days, the reactor pressure was reduced from about 600 to about 300 psig. Within about 2 days of the reduction in pressure, nonaromatics and heavy aromatics decreased to below about 2percent and about 10percent, respectively. At day 15, with a reactor temperature of about 470° C. and pressure of 300 psig the conversion was about 31percent. Increasing the pressure to about 400 psig resulted in an increase in conversion to about 45percent. Similar to the above-described preparation of the palladium modified nickel mordenite catalyst containing about 116 ppm palladium, the palladium modified nickel mordenite catalyst containing about 76 ppm palladium also had toluene disproportionation activity with higher proportions of xylene and lower proportions of heavy aromatics production (FIG. 2), as compared with the previously studied nickel mordenite catalyst (see Examples 1 and 2). Up to about 25 days time-on-stream, the average values for the product mixture from this preparation of palladium modified nickel mordenite catalyst comprised: about 40 wt. percent benzene; about 48 wt. percent xylenes; about 1 wt. percent ethylbenzenes; about 9.5 wt. percent heavy aromatics; and about 1-2 wt. percent nonaromatics. The proportion of xylene in the product mixture remained above about 50percent from day 8 to about day 16. And, from day 20 to 29, the proportion of xylenes remained between about 48 and about 49percent. By 30 days time-on-stream, the improved selectivity towards xylene production as compared to nickel mordenite disappeared, and by 57 days time-on-stream, the proportion of xylene in the product mixture decreased to about 44-45 wt. percent and corresponding increase in the proportion of heavy aromatics.

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With hydrogen, nickel modification of a palladium mordenite catalyst, T= 310 - 360 °C , p= 30753.1Torr , continuous proces, Product distribution / selectivity Patent; Xiao, Xin; Butler, James; Comeaux, Charles; Kelly, Kevin; US2006/211902; (2006); (A1) English View in Reaxys

xylenes; mixture of Rx-ID: 24272404 View in Reaxys 64/165 Yield

Conditions & References 2 :A second experiment was conducted to characterize the physical properties and catalytic selectivity of the nickel mordenite catalyst during toluene disproportionation. Nickel sites and acid sites for different lots of a commercial nickel mordenite catalyst were characterized by conventional TPR measurements. The nickel mordenite catalyst (containing about 1 wt. percent nickel) was introduced into the same reactor as used in Example 1. The reaction was allowed to proceed under process conditions similar to that described in Example 1, with the following exceptions. Temperature and reactor inlet pressure were in the range of about 300 to about 400° C. and at least about 4.1 MPa, respectively. Hydrogen was supplied to the reaction zone in an amount sufficient to provide a hydrogen:toluene molar ratio of about 2:1 and the LHSV was about 3 hr-1. The TPR curves for three representative lots, A, B and C, of nickel mordenite, respectively, were examined. The TPR cures had a large peak having a maximum between about 650 and about 670° C., is assigned to nickel tightly bound to the support (designated as "tightly bound nickel"). A relatively smaller peak having a maximum between about 290 and about 310° C., was assigned to nickel loosely bound to the support (designated as "loosely bound nickel"). For comparison, the curve for a non-nickel promoted support (labeled "none") had no peak at temperatures above about 150° C. Based on calibration of the peaks, it is estimated that loosely bound nickel comprised about 1 to about 3percent of the total nickel in the catalyst. The toluene disproportionation catalyzed reaction typically reached the target conversion of about 47percent toluene into the produced mixture at a reactor temperature of about 354° C. A typical product mixture comprised: about 47 wt. percent xylenes; about 40 wt. percent benzene; about 10 wt. percent heavy aromatics; and about 0.6 wt. percent ethylbenzene. During the course of these experiments, it was discovered that a relationship exists between the toluene disproportionation catalyzed reaction and the extent of loosely bound nickel present in the catalysis, as characterized by the TPR results. For example, it was discovered that the time production of on-specification product was faster for nickel mordenite catalysts having relatively lesser amounts of loosely bound nickel. For example, lots A and B, having relatively prominent TPR peaks at about 300° C., took about eight days to reach on-specification levels of benzene. In contrast, lot C having minimal TPR peaks at about 300° C. took only about 2-3 days to reach on-specification yields of benzene. Moreover, it was discovered that lots having relatively prominent TPR peaks at about 300° C., also had relatively large amounts of undesirable nonaromatics in the product mixture during the early stages after starting the reaction (i.e., during about the first 3 to 7 days). With hydrogen, nickel-promoted mordenite catalyst, continuous proces, Product distribution / selectivity Patent; Xiao, Xin; Butler, James; Comeaux, Charles; Kelly, Kevin; US2006/211902; (2006); (A1) English View in Reaxys

xylenes; mixture of Rx-ID: 24272405 View in Reaxys 65/165 Yield

Conditions & References 1 :The palladium mordenite and nickel mordenite catalysts were separately introduced into the reactor zone of a conventional fixed bed reactor for subsequent testing over several days time-on-stream. In the presence of hydrogen gas, a substantially pure toluene feedstock, i. e., greater than about 99percent toluene was supplied to a reaction zone containing each of the above metalpromoted mordenite catalysts under temperature and inlet pressure conditions within the range of about 250 to about 400° C. and about 1 MPa (400 psig) to about 4.1 MPa. The pressure was about 4.1 MPa at startup and subsequently reduced to about 2.7 MPa after five days continuous time-on-stream. Hydrogen was supplied to the reaction zone in an amount to provide a hydrogen:toluene molar ratio (H2:HC) of about 1:1. The feedstock liquid hourly space velocity (LHSV) was about 2 hr-1. For a reactor temperature and pressure maintained at between about 360 and 365° C., and about 2.7 MPa, respectively, the reaction over each catalyst resulted in about 47percent conversion of the toluene feed into a product mixture, as indicated by an observed approximately 53percent of toluene remaining in the reactor effluent. The product mixture was analyzed for xylenes, benzene, heavy aromatics, i.e., product having 9 carbon atoms or more, C1 to C5 gases (i.e., methane to pentane), and nonaromatics, using conventional methods. The palladium mordenite catalyst had greater selectivity towards the production of xylene as compared to the nickel mordenite catalyst. Using the palladium mordenite catalyst, the product mixture (normalized to 100 wt. percent), with the

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reactor maintained at steady state process conditions for at least about 5 days, comprised: about 48 wt. percent xylenes; about 37 wt. percent benzene; about 12 wt. percent heavy aromatics; about 1 wt. percent C1 to C5 gases; and about 2 wt. percent nonaromatics. In comparison, a reactor bed comprising nickel mordenite as the catalyst, under similar process conditions, produced a product mixture comprising: about 46 wt. percent xylenes, about 37 wt. percent benzene, about 11.5 wt. percent heavy aromatics, about 4 wt. percent C1 to C5 gases, and about 1.5 wt. percent nonaromatics. Thus, the palladium mordenite catalyst has about 2 wt. percent greater selectivity to xylenes and about 3 wt. percent less selectivity to C1 to C5 gases than the nickel mordenite catalyst. Further experiments were performed to characterize the selectivity of the palladium mordenite catalyst for producing increased proportions of xylene during toluene disproportionation. A palladium mordenite catalyst containing about 0.1 wt. percent of palladium was used. The reactor zone conditions were the same as described about with the following exceptions. Temperature and reactor inlet pressure were in the range of about 400 to about 500° C. and about 1 MPa, respectively. Hydrogen was supplied to the reaction zone in an amount sufficient to provide a hydrogen:toluene molar ratio of about 3:1 and the LHSV was about 7 hr-1. The reaction was allowed to proceed for a time-on-stream of about 9 days during which the temperature was increased by about 15° C. per day. The time course of changes in the reactor temperature, percent conversion of toluene and the proportions of compounds in the product mixture are presented in FIG. 1 in which concentration in wt. percent is plotted on the ordinate vs. time-on-stream in days on the abscissa. The conversion of toluene, ranging from about 16 to about 32percent, was lower than the 47percent conversion observed in the previously discussed experiment, due to the lower reactor pressure and higher LHSV. Similar to that discussed above, however, after about 2 days time-on-stream, the product mixture contained higher proportions of xylene (e.g., at least about 50percent), as compared to that previously observed for the nickel mordenite catalyst. The reaction mixture also contained lower proportions of nonaromatics (e.g., less than about 2 wt. percent) and C9+heavy aromatics (e.g., less than about 7 wt. percent), as compared to that expected for the nickel mordenite catalyst. Average percentages from about 1.3 to about 9.3 days on-stream were: 39.9 wt. percent benzene; 51.8 wt. percent xylenes; 5.9 wt. percent heavy aromatics; 0.2 wt. percent ethylbenzene; and 2.2 wt. percent nonaromatics. Another preparation of the palladium mordenite catalyst was examined using the reactor conditions summarized in Table 1. Temperature and reactor inlet pressure were in the range of about 400 to about 450° C. and about 1 MPa to about 2.1 MPa. Hydrogen was supplied to the reaction zone in an amount sufficient to provide a hydrogen:toluene molar ratio of about 2.3:1 to about 3.3:1 and the LHSV was about 6.5 to about 9 hr-1. As shown in Table 1, the conversion of toluene increased from about 14.6 to about 19percent when the reactor bed temperature was increased from about 397 to about 445° C. And, the conversion increased to about 26percent when the reactor pressure was increased to about 2.1 MPa (about 308 psig). With hydrogen, palladium-modified mordenite catalyst, T= 250 - 500 °C , p= 7500.75 - 30753.1Torr , continuous proces, Product distribution / selectivity Patent; Xiao, Xin; Butler, James; Comeaux, Charles; Kelly, Kevin; US2006/211902; (2006); (A1) English View in Reaxys 1 :The palladium mordenite and nickel mordenite catalysts were separately introduced into the reactor zone of a conventional fixed bed reactor for subsequent testing over several days time-on-stream. In the presence of hydrogen gas, a substantially pure toluene feedstock, i. e., greater than about 99percent toluene was supplied to a reaction zone containing each of the above metalpromoted mordenite catalysts under temperature and inlet pressure conditions within the range of about 250 to about 400° C. and about 1 MPa (400 psig) to about 4.1 MPa. The pressure was about 4.1 MPa at startup and subsequently reduced to about 2.7 MPa after five days continuous time-on-stream. Hydrogen was supplied to the reaction zone in an amount to provide a hydrogen:toluene molar ratio (H2:HC) of about 1:1. The feedstock liquid hourly space velocity (LHSV) was about 2 hr-1. For a reactor temperature and pressure maintained at between about 360 and 365° C., and about 2.7 MPa, respectively, the reaction over each catalyst resulted in about 47percent conversion of the toluene feed into a product mixture, as indicated by an observed approximately 53percent of toluene remaining in the reactor effluent. The product mixture was analyzed for xylenes, benzene, heavy aromatics, i.e., product having 9 carbon atoms or more, C1 to C5 gases (i.e., methane to pentane), and nonaromatics, using conventional methods. The palladium mordenite catalyst had greater selectivity towards the production of xylene as compared to the nickel mordenite catalyst. Using the palladium mordenite catalyst, the product mixture (normalized to 100 wt. percent), with the reactor maintained at steady state process conditions for at least about 5 days, comprised: about 48 wt. percent xylenes; about 37 wt. percent benzene; about 12 wt. percent heavy aromatics; about 1 wt. percent C1 to C5 gases; and about 2 wt. percent nonaromatics. In comparison, a reactor bed comprising nickel mordenite as the catalyst, under similar process conditions, produced a product mixture comprising: about 46 wt. percent xylenes, about 37 wt. percent benzene, about 11.5 wt. percent heavy aromatics, about 4 wt. percent C1 to C5 gases, and about 1.5 wt. percent nonaromatics. Thus, the palladium mordenite catalyst has about 2 wt. percent greater selectivity to xylenes and about 3 wt. percent less selectivity to C1 to C5 gases than the nickel mordenite catalyst. With hydrogen, nickel-promoted mordenite catalyst, T= 250 - 400 °C , p= 7500.75 - 30753.1Torr , continuous proces, Product distribution / selectivity Patent; Xiao, Xin; Butler, James; Comeaux, Charles; Kelly, Kevin; US2006/211902; (2006); (A1) English View in Reaxys

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-1 F

+ Ag(v6) Sb F F F

Ag+

0.5

H (v1) F–

(v1) –F F– –FSb5+F– (v1) (v6) (v1) – F (v1)

(v1)

Rx-ID: 27705994 View in Reaxys 66/165 Yield 57 %

Conditions & References in toluene, benzene, soln. of ligand (1 equiv.) in toluene was layered over soln. of Ag salt (2 equiv.) in C6H6; elem. anal. Dong, Yu-Bin; Geng, Yan; Ma, Jian-Ping; Huang, Ru-Qi; Organometallics; vol. 25; nb. 2; (2006); p. 447 - 462 ; (from Gmelin) View in Reaxys

H O

Rx-ID: 10435466 View in Reaxys 67/165 Yield

Conditions & References With oxygen, Time= 0.0025h, T= 619.85 °C , p= 760Torr , Product distribution, Further Variations: Temperatures, reaction time Bounaceur; Da Costa; Fournet; Billaud; Battin-Leclerc; International Journal of Chemical Kinetics; vol. 37; nb. 1; (2005); p. 25 - 49 View in Reaxys

Rx-ID: 23138427 View in Reaxys 68/165 Yield

Conditions & References 2 : Example 2 (Comparative) For Examples 2 through 10, catalyst performance data were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C. Pressure=100 kPa. H2 to reactants molar ratio=0.8. Pure methanol and toluene feeds at 1:3 molar ratio. WHSV=3.9 h-1 based on molecular sieve catalyst composition. Catalyst load=2.0 g of molecular sieve catalyst composition for all tests. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of methanol converted)/ (moles of xylene formed-moles of benzene formed). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene. For the multi-component molecular sieve catalyst compositions, a physical mixture of 2.0 g of the molecular sieve catalyst composition and 0.4 g of the mixed metal oxide was used. The toluene and methanol weight hourly space velocities were kept constant relative to the amount of molecular sieve catalyst composition in the bed. (Comparative). The reaction described above was run using a molecular sieve catalyst composition containing 65 weight percent ZSM-23 molecular sieve (further described in U.S. Pat. No. 4,076,842) with a Si/Al2 ratio about 100 which had been bound with an alumina-rich binder constituting 35 weight percent of the composition. The catalyst load was 2.0 g. The resulting toluene conversion, para-xylene selectivity, and methanol utilization at 2, 20, 40, 60, and 80 hours are shown in Table 2. With hydrogen, 65 weight percent of ZSM-23 molecular sieve (Si/Al2 ratio about 100) bound with 35 weight percent of alumina-rich binder, T= 500 °C , p= 750.075Torr , Continuous reaction, Conversion of starting material

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Patent; Dakka, Jihad Mohammed; Vartuli, James Clarke; Buchanan, John Scott; Santiesteban, Jose Guadalupe; Levin, Doron; US2004/97770; (2004); (A1) English View in Reaxys 7; 8 : Example 7 For Examples 2 through 10, catalyst performance data were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C. Pressure=100 kPa. H2 to reactants molar ratio=0.8. Pure methanol and toluene feeds at 1:3 molar ratio. WHSV=3.9 h-1 based on molecular sieve catalyst composition. Catalyst load=2.0 g of molecular sieve catalyst composition for all tests. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of methanol converted)/ (moles of xylene formed-moles of benzene formed). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene. For the multi-component molecular sieve catalyst compositions, a physical mixture of 2.0 g of the molecular sieve catalyst composition and 0.4 g of the mixed metal oxide was used. The toluene and methanol weight hourly space velocities were kept constant relative to the amount of molecular sieve catalyst composition in the bed. The same temperature, pressure, and flow rates were maintained as in Example 6, but 0.4 g of the LaxOy/ZrO2 material of Example 1 was added to 2.0 g of the comparison molecular sieve catalyst composition described in Example 6 as a physical mixture of particles. The catalytic performance of the molecular sieve catalyst composition comparative sample and of the multi-component molecular sieve catalyst composition are shown in Table 2. The data show that addition of LaxOy/ZrO2 to the aluminosilicate catalyst bed improved toluene conversion, methanol utilization, and catalyst life. The multi component molecular sieve catalyst composition containing LaxOy/ZrO2 maintained approximately constant toluene conversion for 170 hours, at which point the H2O cofeed was discontinued in an effort to cause the catalyst to require regeneration. Even so, the toluene conversion had not yet dropped to 50percent of the initial conversion rate at 300 hours. In contrast, the performance of the molecular sieve catalyst composition alone (Example 6) dropped to very low toluene conversion over a period of 30 hours, reaching 50percent of the initial toluene conversion at approximately 7.5 hours. Again, not extrapolating the half-life of the multi-component molecular sieve catalyst composition beyond the time tested, the HLEI is greater than 22.7. It should be noted that although the initial data points for these two examples were reported for different times, the HLEI would by inspection still have been 20 or more had those data points been taken at the same run time. Example 9The multi-component molecular sieve catalyst composition used in Example 7 was run for 380 hours, with the water pump shut down at 170 hours to speed de-activation, then regenerated in-situ at 530° C. with air flow of 100 cc/min for 10 hours. The regenerated multi-component molecular sieve catalyst composition's performance at the same reaction conditions as were used in Examples 6 and 7 shows that this multi-component molecular sieve catalyst composition is regenerable After 280 hours on-stream the toluene conversion was 20percent, methanol utilization was 50percent, and para-xylene selectivity was 91percent. With hydrogen, 25 weight percent of ZSM-5 (Si/Al2 ratio 450); 5 weight percent of phosphorus; clay; mixture of, steamed at 1090 ° C; LaxOy/ZrO2 (5 weight percent of La); mixture of, T= 500 °C , p= 750.075Torr , Continuous reaction, Conversion of starting material Patent; Dakka, Jihad Mohammed; Vartuli, James Clarke; Buchanan, John Scott; Santiesteban, Jose Guadalupe; Levin, Doron; US2004/97770; (2004); (A1) English View in Reaxys 6 : Example 6 (Comparative) For Examples 2 through 10, catalyst performance data were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C. Pressure=100 kPa. H2 to reactants molar ratio=0.8. Pure methanol and toluene feeds at 1:3 molar ratio. WHSV=3.9 h-1 based on molecular sieve catalyst composition. Catalyst load=2.0 g of molecular sieve catalyst composition for all tests. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of methanol converted)/ (moles of xylene formed-moles of benzene formed). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene. For the multi-component molecular sieve catalyst compositions, a physical mixture of 2.0 g of the molecular sieve catalyst composition and 0.4 g of the mixed metal oxide was used. The toluene and methanol weight hourly space velocities were kept constant relative to the amount of molecular sieve catalyst composition in the bed. A molecular sieve catalyst composition with 25 weight percent ZSM-5 molecular sieve crystals having a Si/Al2 ratio of 450 was spray dried with 5 weight percent phosphorus and clay and then steamed at 1090° C. to produce steamed ZSM-5. This molecular sieve catalyst composition was run in a fixed bed downflow reactor at a temperature of 585° C., a pressure of 280 kPa, an H2 to reactants molar ratio of 2:1, with pure methanol and toluene feeds at a 1:2 molar ratio, an H2O to reactants molar ratio of 2:1, and a WHSV of 8 h-1. The catalyst load was 2.0 g. Catalyst performance data for 2, 10, 20, and 30 hours are shown in Table 2. With hydrogen, 25 weight percent of ZSM-5 (Si/Al2 ratio 450); 5 weight percent of phosphorus; clay; mixture of, steamed at 1090 ° C, T= 500 °C , p= 750.075Torr , Continuous reaction, Conversion of starting material Patent; Dakka, Jihad Mohammed; Vartuli, James Clarke; Buchanan, John Scott; Santiesteban, Jose Guadalupe; Levin, Doron; US2004/97770; (2004); (A1) English

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View in Reaxys 3 : Example 3 For Examples 2 through 10, catalyst performance data were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C. Pressure=100 kPa. H2 to reactants molar ratio=0.8. Pure methanol and toluene feeds at 1:3 molar ratio. WHSV=3.9 h-1 based on molecular sieve catalyst composition. Catalyst load=2.0 g of molecular sieve catalyst composition for all tests. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of methanol converted)/ (moles of xylene formed-moles of benzene formed). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene. For the multi-component molecular sieve catalyst compositions, a physical mixture of 2.0 g of the molecular sieve catalyst composition and 0.4 g of the mixed metal oxide was used. The toluene and methanol weight hourly space velocities were kept constant relative to the amount of molecular sieve catalyst composition in the bed.This example used the same reaction conditions as Example 2, but 0.4 g of the LaxOy/ZrO2 product from Example 1 was added to 2.0 g of the ZSM-23 molecular sieve catalyst composition (as described in Example 2) as a physical mixture of particles to form a multicomponent molecular sieve catalyst composition. The catalytic performance of the multi-component molecular sieve catalyst composition (ZSM-23 with LaxOy/ZrO2) at 2, 20, 40, and 170 hours is also shown in Table 2. The data show that addition of LaxOy/ZrO2 to the aluminosilicate catalyst bed improved the catalyst activity, selectivity to para-xylene (which increased steadily with time to about 68percent at the end of the test), and the catalyst life. The multi-component molecular sieve catalyst composition containing LaxOy/ZrO2 maintained approximately constant toluene conversion activity for 170 hrs, while the molecular sieve catalyst composition activity in Example 2 dropped to approximately half the initial toluene conversion after 27 hours and approximately zero at 80 hours. The HLEI in this test was greater than 6.3, and has not been extrapolated to the time at which toluene conversion by the multi-component molecular sieve composition would have dropped to half of its initial value. With hydrogen, 65 weight percent of ZSM-23 molecular sieve (Si/Al2 ratio about 100) bound with 35 weight percent of alumina-rich binder; LaxOy/ZrO2 (5 weight percent of La); mixture of, T= 500 °C , p= 750.075Torr , Continuous reaction, Conversion of starting material Patent; Dakka, Jihad Mohammed; Vartuli, James Clarke; Buchanan, John Scott; Santiesteban, Jose Guadalupe; Levin, Doron; US2004/97770; (2004); (A1) English View in Reaxys 10 : Example 10 For Examples 2 through 10, catalyst performance data were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C. Pressure=100 kPa. H2 to reactants molar ratio=0.8. Pure methanol and toluene feeds at 1:3 molar ratio. WHSV=3.9 h-1 based on molecular sieve catalyst composition. Catalyst load=2.0 g of molecular sieve catalyst composition for all tests. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of methanol converted)/ (moles of xylene formed-moles of benzene formed). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene. For the multi-component molecular sieve catalyst compositions, a physical mixture of 2.0 g of the molecular sieve catalyst composition and 0.4 g of the mixed metal oxide was used. The toluene and methanol weight hourly space velocities were kept constant relative to the amount of molecular sieve catalyst composition in the bed.Two grams of the catalyst described in Example 9 were mixed with 0.4 grams of the LaxOy/ZrO2 of Example 1 and run at the same conditions as Example 3. The results for Examples 9 and 10 are shown in Table 2. The toluene conversion for the silicone-treated ZSM-48 dropped below 50percent of its initial rate at about 12 hours on stream, while for the mixed catalyst toluene conversion was approaching 50percent of its initial rate when the test ended at 60 hours, resulting in a HLEI greater than 5.0. With hydrogen, alumina bound ZMS-48 treated with silicone and calcinated; LaxOy/ZrO2 (5 weight percent of La); mixture of, T= 500 °C , p= 750.075Torr , Continuous reaction, Conversion of starting material Patent; Dakka, Jihad Mohammed; Vartuli, James Clarke; Buchanan, John Scott; Santiesteban, Jose Guadalupe; Levin, Doron; US2004/97770; (2004); (A1) English View in Reaxys 9 : Example 9 (Comparative) For Examples 2 through 10, catalyst performance data were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C. Pressure=100 kPa. H2 to reactants molar ratio=0.8. Pure methanol and toluene feeds at 1:3 molar ratio. WHSV=3.9 h-1 based on molecular sieve catalyst composition. Catalyst load=2.0 g of molecular sieve catalyst composition for all tests. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of methanol converted)/ (moles of xylene formed-moles of benzene formed). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene. For the multi-component molecular sieve catalyst compositions, a physical mixture of 2.0 g of the molecular sieve catalyst composition and 0.4 g of the mixed metal oxide was used. The toluene and methanol weight hourly space velocities were kept constant relative to the amount of molecular sieve catalyst composition in the bed. An alumi-

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na-bound ZSM-48 catalyst which had been treated with silicone three times, with calcination after each silicone treatment, and steamed for 24 hrs at 1000° F., was run at the same conditions as Example 2 to provide a comparison case for this catalyst composition. With hydrogen, alumina bound ZMS-48 treated with silicone and calcinated, T= 500 °C , p= 750.075Torr , Continuous reaction, Conversion of starting material Patent; Dakka, Jihad Mohammed; Vartuli, James Clarke; Buchanan, John Scott; Santiesteban, Jose Guadalupe; Levin, Doron; US2004/97770; (2004); (A1) English View in Reaxys 5 : Example 5 For Examples 2 through 10, catalyst performance data were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C. Pressure=100 kPa. H2 to reactants molar ratio=0.8. Pure methanol and toluene feeds at 1:3 molar ratio. WHSV=3.9 h-1 based on molecular sieve catalyst composition. Catalyst load=2.0 g of molecular sieve catalyst composition for all tests. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of methanol converted)/ (moles of xylene formed-moles of benzene formed). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene. For the multi-component molecular sieve catalyst compositions, a physical mixture of 2.0 g of the molecular sieve catalyst composition and 0.4 g of the mixed metal oxide was used. The toluene and methanol weight hourly space velocities were kept constant relative to the amount of molecular sieve catalyst composition in the bed.Two grams of the same catalyst composition as described in Example 4 was mixed with 0.4 grams of the LaxOy/ZrO2 of Example 1, and tested at the same conditions as Example 3. The results for Examples 4 and 5 at 2, 20, 60, and 106 hours are shown in Table 2. The toluene conversion for the molecular sieve catalyst composition in Example 4 (silicone-treated ZSM-5) dropped to approximately half of the initial conversion rate after about 63 hours, while the toluene conversion for the multi-component molecular sieve catalyst composition stayed roughly constant at about 15percent for over 106 hours, indicating that the HLEI in this comparison is greater than 1.7. Methanol utilization and para-xylene selectivity were also higher for the multi-component molecular sieve catalyst composition. With hydrogen, alumina bound ZMS-5 treated with silicone and calcinated; 65 weight percent of ZSM-23 molecular sieve (Si/Al2 ratio about 100) bound with 35 weight percent of alumina-rich binder; LaxOy/ZrO2 (5 weight percent of La); mixture of, T= 500 °C , p= 750.075Torr , Continuous reaction, Conversion of starting material Patent; Dakka, Jihad Mohammed; Vartuli, James Clarke; Buchanan, John Scott; Santiesteban, Jose Guadalupe; Levin, Doron; US2004/97770; (2004); (A1) English View in Reaxys 4 : Example 4 (Comparative) For Examples 2 through 10, catalyst performance data were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C. Pressure=100 kPa. H2 to reactants molar ratio=0.8. Pure methanol and toluene feeds at 1:3 molar ratio. WHSV=3.9 h-1 based on molecular sieve catalyst composition. Catalyst load=2.0 g of molecular sieve catalyst composition for all tests. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of methanol converted)/ (moles of xylene formed-moles of benzene formed). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene. For the multi-component molecular sieve catalyst compositions, a physical mixture of 2.0 g of the molecular sieve catalyst composition and 0.4 g of the mixed metal oxide was used. The toluene and methanol weight hourly space velocities were kept constant relative to the amount of molecular sieve catalyst composition in the bed. An alumina-bound ZSM-5 catalyst composition that had been treated with silicone three times, with calcination after each silicone treatment, and steamed for 24 hours at 10001° F. was tested at the same conditions as Example 2 to provide a comparison case for this molecular sieve catalyst composition. With hydrogen, alumina bound ZMS-5 treated with silicone and calcinated, T= 500 °C , p= 750.075Torr , Continuous reaction, Conversion of starting material Patent; Dakka, Jihad Mohammed; Vartuli, James Clarke; Buchanan, John Scott; Santiesteban, Jose Guadalupe; Levin, Doron; US2004/97770; (2004); (A1) English View in Reaxys 6A :The following catalytic data were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C., Pressure=15 psig, H2/hydrocarbon molar ratio=0.8, pure methanol and toluene feeds at 1:3 molar ratio, WHSV=3.9 h 1 based on sieve-containing base case catalyst. The catalyst load was 2 g for the base catalyst runs. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of xylene formed moles of benzene formed)/(moles of methanol con-

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verted). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene.Referring now to FIG. 1, Catalyst A is impregnated with a platinum hydrogenation component, however, the test data indicates poor stability at 10 hours. With hydrogen, 4x Silica-Selectivated, 0.1percentPt impregnated H-ZSM-5/SiO2, Time= 20h, T= 500 °C , p= 1535.79Torr , Product distribution / selectivity Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys 16 :Temperature=500° C., Pressure=15-150 psig, H2/hydrocarbon molar ratio=2, pure methanol and toluene feeds at 1:3 molar ratio, WHSV=8 hr 1 based on sieve-containing base case catalyst. The catalyst load was 2 g for the base catalyst runs. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of methanol converted)/(moles of xylene formed moles of benzene formed). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene.FIG. 14 shows the catalyst tested at different pressures, with and without co-feeding water. The catalyst is stable and selective. With hydrogen, 0.1 percent Rh, 0.76percent Mg, 1.5percent P impregnated zeolite bound zeolite ZSM-5 (Catalyst M), Time= 180h, T= 500 °C , p= 3345.86Torr , Product distribution / selectivity Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys 13 :Temperature=500° C., Pressure=15-150 psig, H2/hydrocarbon molar ratio=2, pure methanol and toluene feeds at 1:3 molar ratio, WHSV=8 hr 1 based on sieve-containing base case catalyst. The catalyst load was 2 g for the base catalyst runs. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of methanol converted)/(moles of xylene formed moles of benzene formed). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene. Referring to FIG. 10, Catalyst J was evaluated in a toluene methylation reaction at different hourly space velocities, with and without co-feeding water, and at different reaction temperatures. The data show that increasing the hourly space velocity from 4 to 8 resulted in higher para-xylene selectivity (78percent versus 63percent). In addition, the toluene conversion and methanol utilization were slightly improved. With hydrogen, 1.5percent P, 7percentMg impregnated zeolite bound zeolite ZSM-5 (Catalyst J), Time= 25h, T= 500 °C , p= 1535.79 - 8517.48Torr , Product distribution / selectivity Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys 14 :Temperature=500° C., Pressure=15-150 psig, H2/hydrocarbon molar ratio=2, pure methanol and toluene feeds at 1:3 molar ratio, WHSV=8 hr 1 based on sieve-containing base case catalyst. The catalyst load was 2 g for the base catalyst runs. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of methanol converted)/(moles of xylene formed moles of benzene formed). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene.Referring now to FIG. 11, increasing the phosphorus content over the 1.5 wt. percent provided in Example 13 improves the para-xylene selectivity from 75percent to 93percent at the same conditions. However the stability of the catalyst is affected, with the higher phosphorus content of this Example 14 deactivating the catalyst faster than the lower phosphorus content catalyst of Example 13. With hydrogen, 2.5percent P, 7percent Mg impregnatet zeolite bound zeolite ZSM-5 (catalyst K), Time= 60h, T= 500 °C , p= 3345.86Torr , Product distribution / selectivity Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys 20 :Referring now to FIG. 18, catalytic data shows that Catalyst Q maintains high para-selectivity and excellent catalyst stability.

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With hydrogen, 3x Silica-Selectivated, 0.1percent Rh ,1percentP impregnated H-ZSM-5/SiO2 (Catalyst Q), Time= 320h, T= 500 °C , p= 3345.86 - 8517.48Torr , Product distribution / selectivity Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys Re19N :Catalytic data herein were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C., Pressure=15 psig, H2/hydrocarbon molar ratio=0.8, pure methanol and toluene feeds at 1:3 molar ratio, WHSV=3.9 h-1 based on sieve-containing base case catalyst. The catalyst load was a mixture of 0.4-0.8 g of 0.1percent Pt/Al2O3 of Example 18 and 2 g for the respective steamed catalyst of Example 17.As shown in FIGS. 15-17, each of Catalyst N, O and P indicate good stability. With hydrogen, Catalyst N, Time= 110h, T= 500 °C , p= 1535.79Torr , Product distribution / selectivity Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys Re19O :Catalytic data herein were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C., Pressure=15 psig, H2/hydrocarbon molar ratio=0.8, pure methanol and toluene feeds at 1:3 molar ratio, WHSV=3.9 h-1 based on sieve-containing base case catalyst. The catalyst load was a mixture of 0.4-0.8 g of 0.1percent Pt/Al2O3 of Example 18 and 2 g for the respective steamed catalyst of Example 17.As shown in FIGS. 15-17, each of Catalyst N, O and P indicate good stability. Catalyst O appears to maintain the highest para-xylene selectivity of 85percent with toluene conversion at 7percent. With hydrogen, Catalyst O, Time= 90h, T= 500 °C , p= 1535.79Torr , Product distribution / selectivity Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys Re19P :Catalytic data herein were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C., Pressure=15 psig, H2/hydrocarbon molar ratio=0.8, pure methanol and toluene feeds at 1:3 molar ratio, WHSV=3.9 h-1 based on sieve-containing base case catalyst. The catalyst load was a mixture of 0.4-0.8 g of 0.1percent Pt/Al2O3 of Example 18 and 2 g for the respective steamed catalyst of Example 17.As shown in FIGS. 15-17, each of Catalyst N, O and P indicate good stability. Catalyst P exhibits the highest toluene conversion at 14percent with good para-xylene selectivity of 73percent. This Example indicates that the hydrogenation function does not have to be located directly on the molecular sieve to be effective in accordance with this invention, as long as the hydrogenation function is in proximity to the molecular sieve. As shown in this example, the hydrogenation metal can be impregnated onto an amorphous support that is comingled with the active molecular sieve catalyst. With hydrogen, Catalyst P, Time= 65h, T= 500 °C , p= 1535.79Torr , Product distribution / selectivity Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys 12b :Temperature=500° C., Pressure=15-150 psig, H2/hydrocarbon molar ratio=2, pure methanol and toluene feeds at 1:3 molar ratio, WHSV=8 hr 1 based on sieve-containing base case catalyst. The catalyst load was 2 g for the base catalyst runs. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of methanol converted)/(moles of xylene formed moles of benzene formed). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene.Referring now to FIG. 9, magnesium impregnation treatment boosts the para-xylene selectivity from about 30percent to about 60percent. However, a slight impact on the catalyst stability, toluene conversion and methanol utilization is shown. FIG. 9 also shows that higher reaction pressures (150 psig versus 50 psig) result in lower para-xylene selectivity (58percent versus 65percent). With hydrogen, Mg impregnated zeolite bound zeolite ZSM-5 (Catalyst I), Time= 25h, T= 500 °C , p= 1535.79 - 8517.48Torr , Product distribution / selectivity

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Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys 10G :The following catalytic data presented were obtained over Catalysts F and G using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted on the figure: Temperature=500-585° C., Pressure=40 psig, H2/hydrocarbon molar ratio=2, H2O/hydrocarbon molar ratio=2, pure methanol and toluene feeds at 1:2 molar ratio, WHSV=2-8 h-1 based on sieve-containing base case catalyst. The catalyst load was 2 g. For the 1:2 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 50percent. Methanol utilization is reported as (moles of xylene formed moles of benzene formed)/(moles of methanol converted). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene. The catalytic performance of Catalyst G is shown in FIG. 7. The data show that impregnation of Catalyst F with platinum dramatically enhances the catalyst life. The catalyst activity is maintained at 150 hours. With hydrogen, steamed, 0.1percent Pt impregnated silica/alumina/clay/phosphorus matrix calcinated H-ZSM-5 (Catalyst G), Time= 320h, T= 500 - 585 °C , p= 2828.7Torr , Product distribution / selectivity Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys 7C :The following catalytic data were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C., Pressure=15 psig, H2/hydrocarbon molar ratio=0.8, pure methanol and toluene feeds at 1:3 molar ratio, WHSV=3.9 h 1 based on sieve-containing base case catalyst. The catalyst load was 2 g for the base catalyst runs. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of xylene formed moles of benzene formed)/(moles of methanol converted). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene.Catalytic Evaluations of Catalysts C, D, and E FIGS. 3-5 compare the performance of Catalysts C, D, and E. The data show that platinum incorporation into the acidic molecular sieve catalysts enhances the catalyst stability, para-xylene selectivity, and methanol utilization of the toluene methylation reaction, when the alpha value is within the criteria of this invention. With hydrogen, steamed, 3x Silica-Selectivated, H-ZSM-5/SiO2, Time= 80h, T= 500 °C , p= 1535.79Torr , Product distribution / selectivity Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys 7D :The following catalytic data were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C., Pressure=15 psig, H2/hydrocarbon molar ratio=0.8, pure methanol and toluene feeds at 1:3 molar ratio, WHSV=3.9 h 1 based on sieve-containing base case catalyst. The catalyst load was 2 g for the base catalyst runs. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of xylene formed moles of benzene formed)/(moles of methanol converted). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene.Catalytic Evaluations of Catalysts C, D, and E FIGS. 3-5 compare the performance of Catalysts C, D, and E. The data show that platinum incorporation into the acidic molecular sieve catalysts enhances the catalyst stability, para-xylene selectivity, and methanol utilization of the toluene methylation reaction, when the alpha value is within the criteria of this invention. With hydrogen, steamed, 3x Silica-Selectivated, 0.1percentPt impregnated H-ZSM-5/SiO2, Time= 80h, T= 500 °C , p= 1535.79Torr , Product distribution / selectivity Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys 7E :The following catalytic data were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C., Pressure=15 psig, H2/hydrocarbon molar ratio=0.8, pure methanol and toluene feeds at 1:3 molar ratio, WHSV=3.9 h 1 based on sieve-containing base case catalyst. The catalyst load was 2 g for the base catalyst runs. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of xylene formed moles of benzene formed)/(moles of methanol con-

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verted). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene.Catalytic Evaluations of Catalysts C, D, and E FIGS. 3-5 compare the performance of Catalysts C, D, and E. The data show that platinum incorporation into the acidic molecular sieve catalysts enhances the catalyst stability, para-xylene selectivity, and methanol utilization of the toluene methylation reaction, when the alpha value is within the criteria of this invention. With hydrogen, steamed, 3x Silica-Selectivated, 0.1percentPt impregnated H-ZSM-5/SiO2, Time= 80h, T= 500 °C , p= 1535.79Torr , Product distribution / selectivity Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys 6B :The following catalytic data were obtained using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted: Temperature=500° C., Pressure=15 psig, H2/hydrocarbon molar ratio=0.8, pure methanol and toluene feeds at 1:3 molar ratio, WHSV=3.9 h 1 based on sieve-containing base case catalyst. The catalyst load was 2 g for the base catalyst runs. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of xylene formed moles of benzene formed)/(moles of methanol converted). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene.Referring to FIG. 2, the data indicates that impregnation of a hydrogenation component can enhance the catalyst stability for a toluene methylation process, while maintaining high para-xylene selectivity, when the catalyst has a low alpha value. With hydrogen, steamed, 4x Silica-Selectivated, 0.1percentPt impregnated H-ZSM-5/SiO2, Time= 120h, T= 500 °C , p= 1535.79Torr , Product distribution / selectivity Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys 10F :The following catalytic data presented were obtained over Catalysts F and G using a downflow fixed-bed reactor with the following operating conditions, unless otherwise noted on the figure: Temperature=500-585° C., Pressure=40 psig, H2/hydrocarbon molar ratio=2, H2O/hydrocarbon molar ratio=2, pure methanol and toluene feeds at 1:2 molar ratio, WHSV=2-8 h-1 based on sieve-containing base case catalyst. The catalyst load was 2 g. For the 1:2 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 50percent. Methanol utilization is reported as (moles of xylene formed moles of benzene formed)/(moles of methanol converted). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene. The catalytic performance for Catalyst F is shown in FIG. 6. The data show that the toluene conversion was decreased from 25percent to 12percent within 13 hours on stream. With hydrogen, steamed, silica/alumina/clay/phosphorus matrix calcinated H-ZSM-5 (Catalyst F), Time= 320h, T= 500 - 585 °C , p= 2828.7Torr , Conversion of starting material Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys 15 :Temperature=500° C., Pressure=15-150 psig, H2/hydrocarbon molar ratio=2, pure methanol and toluene feeds at 1:3 molar ratio, WHSV=8 hr 1 based on sieve-containing base case catalyst. The catalyst load was 2 g for the base catalyst runs. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of methanol converted)/(moles of xylene formed moles of benzene formed). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene.As shown in FIG. 12, significant catalyst stabilization was achieved by the addition of the hydrogenation component, rhodium, while maintaining high para-xylene selectivity. With hydrogen, zeolite boun0.1percent Rh, 2.5percent P, 7percent Mg impregnated zeolite ZSM-5 (Catalyst L), Time= 120h, T= 500 °C , p= 3345.86Torr , Product distribution / selectivity Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys

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11 :Temperature=500° C., Pressure=15-150 psig, H2/hydrocarbon molar ratio=2, pure methanol and toluene feeds at 1:3 molar ratio, WHSV=8 hr 1 based on sieve-containing base case catalyst. The catalyst load was 2 g for the base catalyst runs. For the 1:3 molar feed mixture, the maximum toluene conversion expected from reaction with methanol would be about 33percent. Methanol utilization is reported as (moles of methanol converted)/(moles of xylene formed moles of benzene formed). Benzene is subtracted to account for any xylene formed by the disproportionation of toluene to xylene plus benzene. Referring to FIG. 8, the catalytic performance of the reference Catalyst H shows good stability and methanol utilization, but no enhanced para-selectivity. High initial benzene formation (7percent), due to toluene disproportionation reaction, was obtained. The toluene conversion declines with the time on stream. This decline is mainly due to the loss of catalyst activity on the toluene disproportionation reaction. The benzene formation decreased from 7percent to less than 2percent within 24 hours. With hydrogen, zeolite bound zeolite ZSM-5 (Catalyst H), Time= 25h, T= 500 °C , p= 1535.79 - 8517.48Torr , Product distribution / selectivity Patent; Dakka, Jihad Mohammed; Buchanan, John Scott; Crane, Robert Andrew; Elia, Christine Nicole; Feng, Xiaobing; Iaccino, Larry Lee; Mohr, Gary David; Raich, Brenda Anne; Santiesteban, Jose Guadalupe; Zhang, Lei; US2005/143613; (2005); (A1) English View in Reaxys

Rx-ID: 23225165 View in Reaxys 69/165 Yield

Conditions & References EXAMPLE; [00033] An increased selectivity to A8s at the expense of light ends has been demonstrated in pilot plant tests and is shown in the following material balance comparison. The prior art, gas-phase transalkylation process, is compared against the present invention, which combines a liquid-phase transalkylation process with a gas-phase process. This comparison shows the benefits of the present invention as increased xylenes and ethylbenzene, and concomitantly decreased benzene and light-end gas (especially ethane). By reducing the production of ethane by de-ethylation in gas-phase reactions within an aromatics complex, the invention provides improved total retention of aromatics relative to prior art transalkylation units used in complexes that produce xylenes. [00034] With reference to the FIGURE, showing the flow scheme of the present invention, a simulated material balance is shown below. The liquid-phase transalkylation process unit is combined with the gas-phase transalkylation process unit, and results in the following changes over a prior art single gas-phase transalkylation unit. Hydrogen feed to the flow scheme decreases. Feed of toluene and A9 + remains constant. Production of A8s increases, while benzene production decreases. Heavies production remains constant. Most importantly, light-end gas production decreases. With hydrogen Patent; UOP LLC; US6855854; (2005); (B1) English View in Reaxys

(v2)

H N O

(v2) (v4)

H 2N

(v3) (v4) HN H2 N Rh 2+ (v6) Rh 2+ O– (v2) (v6) O O– (v2) O(v3) (v3)

–O –O

O (v3)

(v3) O HN N O (v3) (v4) OO N 2+ 2+Rh – Rh (v6) (v2) N (v6) O –O (v4) (v3) O O (v2)

(v2) (v2)

5 N

–

(v3)

NH O

Rx-ID: 27512868 View in Reaxys 70/165

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Yield

Conditions & References

65 %

in benzene, dissolving of Rh2(Me3CCOO)4(NH2C6H4NHPh)2 in benzene under Ar; addn. of pyrrole-2,5-dialdehyde; heating at 80°C for 20 min; concn., cooling to 20°C, crystn. for 48 h; filtration, washing with cold hexane, drying in vac., elem. anal. Sidorov; Aleksandrov; Pakhmutova; Chernyad'ev; Eremenko; Moiseev; Russian Chemical Bulletin; vol. 54; nb. 3; (2005); p. 588 - 599 ; (from Gmelin) View in Reaxys

(v3)

H N

H 2O (v6)O (v3)Rh O O(v6) O Rh (v3) OH 2 OO

NH 2 5

(v3)

(v3) O HN N O –O (v3) (v4) O –O 2+N Rh Rh 2+ – (v2) (v6) N (v6) O –O (v4)O(v3) O (v2) (v3)

(v2) (v2)

NH O

Rx-ID: 32389802 View in Reaxys 71/165 Yield

Conditions & References Reaction Steps: 2 1: toluene 2: benzene in toluene, benzene Sidorov; Aleksandrov; Pakhmutova; Chernyad'ev; Eremenko; Moiseev; Russian Chemical Bulletin; vol. 54; nb. 3; (2005); p. 588 - 599 View in Reaxys

Rx-ID: 10226728 View in Reaxys 72/165 Yield

Conditions & References With silica-supported tantalum hydride, Time= 60h, T= 250 °C , Product distribution, Further Variations: Pressures Kimura, Takumi; Kawai, Kiyohiko; Fujitsuka, Mamoru; Majima, Tetsuro; Chemical Communications; nb. 12; (2004); p. 1438 - 1439 View in Reaxys

Rx-ID: 23138418 View in Reaxys 73/165 Yield

Conditions & References 1,3,5,1-2 : [0035] Examples 1 to 4 Toluene and the raw material enriched in C9A were subjected to toluene disproportionation and transalkylation reactions. The reactions were carried out in a fixed bed reactor in the presence of hydrogen and bismuth-containing macropore zeolite catalyst. The reactor used had a diameter of 25 mm and a length of 1000 mm, made of stainless steel. Glass beads 3 mm in diameter were evenly filled at both the top and the bottom of the bed for the purpose of gas distribution and support. 20 g of bismuth-containing marcoporous zeolite catalyst was loaded into the reactor. Aromatics raw materials and hydrogen were, after mixing up, passed downflow through the catalyst bed, in which toluene disproportionation and transalkylation of toluene and C9A occurred. Benzene and C8A were produced. EXAMPLES 5 TO 7 [0036] Toluene and the raw material enriched in C10+ hydrocarbons were subjected to transalkylation reaction. The reaction was carried out in a fixed bed reactor in the presence of hydrogen and molybdenum-containing macropore zeolite catalyst. The reactor used had a diameter of 25 mm and a length of 1000 mm, made of stainless steel. Glass beads 3 mm in diameter were evenly filled at both the top and the bottom of the catalyst bed for the purpose of gas distribution and support. 20 g of molybdenum-containing macropore zeolite catalyst was loaded into the reactor. Aromatics raw materials and hydrogen were, after mixing up, passed downflow through the catalyst bed, in which transalkylation occurred. Benzene, C8A and C9A were formed by the reaction between toluene and C10+ hydrocarbons. COMPARATIVE EXAMPLE 1 [0037] Based on the data described in example 1, a typical disproportionation and transalkylation reaction between tol-

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uene and C9A was conducted. In the reactor feed, a ratio of toluene/C9A of 60:40 was used. When a feed flow rate of 100 W/T (unit weight unit time) was used, consumed amount of toluene (?Tol) and consumed amount of C9A (?C9A) in the reaction (i.e., fresh feed materials) are as follows: [0038] ?Tol=57.16-36.10=21.06(W/T) [0039] ?C9A=38.16-13.06=25.10(W/T) [0040] ? Tol/?CgA=1/1.2 [0041] The amounts above correspond to those consumed in a unit of the disproportionation and transalkylation of a typical combined aromatics plant. [0042] The amounts of the products are as the following: [0043] the amount of benzene formed: ?Ben=11.41-0.02=11.39(WIT) [0044] the amount of benzene formed: ?C8A=33.96-0.56=33.40(WIT) [0045] Thus, in a typical toluene disproportionation and transalkylation process, when feed flow rates of fresh toluene and fresh C9A are 21.06 W/T and 25.10 W/T respectively, 11.39 W/T benzene and 33.40 W/T C8A were produced after complete reaction. COMPARATIVE EXAMPLE 2 [0046] In this example, the formations of benzene and C8A are investigated using the same feed flow rates of fresh toluene and fresh C9A, that is, 21.06 W/T and 25.10 W/T respectively. [0047] A portion of toluene and all C9A coming from outside the unit, and the C9A formed in the second reaction zone, as the fresh feedstock, underwent toluene disproportionation and transalkylation in the first reaction zone. Another portion of toluene coming from outside the unit and the C10+ hydrocarbons formed in the first reaction zone as well as C10+ hydrocarbons from C8+A raw material, as the fresh feedstock, underwent transalkylation between toluene and C10+ in the second reaction zone. Composition of feed of the first reaction zone was the same as in example 2: the toluene/C9A ratio was 55:45; composition of feed of the second reaction zone was the same as in example 6: the toluene/C10+ ratio was 70:30. The total of fresh toluene feed of both the first and second reaction zones was 21.06 WIT. C9A feed to first reaction zone was equal to the fresh C9A feed plus withdrawal of C9A from the second reaction zone. Results from computer simulation are summarized in table 3. [0048] It can be seen from the above that the shortcomings existing with an combined aromatics plant of the prior art, including low utilization of heavy aromatics, restricted C8A yield and higher formation of lighter hydrocarbons and less flexibility or stringent requirement on the selection of raw materials are all solved by the present invention. This process achieves ample latitude in selecting raw materials, less formation of lighter hydrocarbons and complete utilization of heavy aromatics and an increased C8A yield. From the comparative examples 1 and 2, it can be concluded that given the same amount of toluene and C9A consumed, 11.67 W/T of benzene and 36.62 W/T of C8A are produced in the process of the present invention, representing increases of 2.5percent and 9.6percent respectively compared with conventional process for toluene disproportionation and transalkylation. With hydrogen, 2.5percent molybdenum-containing mordenite, T= 340 - 430 °C , p= 15001.5 - 26252.6Torr Patent; China Petroleum and Chemical Corporation; Shanghai Research Institute of Petrochemical Technology Sinopec; US2004/186332; (2004); (A1) English View in Reaxys 2,4,6-7 : [0035] Examples 1 to 4 Toluene and the raw material enriched in C9A were subjected to toluene disproportionation and transalkylation reactions. The reactions were carried out in a fixed bed reactor in the presence of hydrogen and bismuth-containing macropore zeolite catalyst. The reactor used had a diameter of 25 mm and a length of 1000 mm, made of stainless steel. Glass beads 3 mm in diameter were evenly filled at both the top and the bottom of the bed for the purpose of gas distribution and support. 20 g of bismuth-containing marcoporous zeolite catalyst was loaded into the reactor. Aromatics raw materials and hydrogen were, after mixing up, passed downflow through the catalyst bed, in which toluene disproportionation and transalkylation of toluene and C9A occurred. Benzene and C8A were produced. EXAMPLES 5 TO 7 [0036] Toluene and the raw material enriched in C10+ hydrocarbons were subjected to transalkylation reaction. The reaction was carried out in a fixed bed reactor in the presence of hydrogen and molybdenum-containing macropore zeolite catalyst. The reactor used had a diameter of 25 mm and a length of 1000 mm, made of stainless steel. Glass beads 3 mm in diameter were evenly filled at both the top and the bottom of the catalyst bed for the purpose of gas distribution and support. 20 g of molybdenum-containing macropore zeolite catalyst was loaded into the reactor. Aromatics raw materials and hydrogen were, after mixing up, passed downflow through the catalyst bed, in which transalkylation occurred. Benzene, C8A and C9A were formed by the reaction between toluene and C10+ hydrocarbons. With hydrogen, 1.8percent molybdenum-containing φ-zeolite, T= 380 - 450 °C , p= 22502.3 - 37503.8Torr Patent; China Petroleum and Chemical Corporation; Shanghai Research Institute of Petrochemical Technology Sinopec; US2004/186332; (2004); (A1) English View in Reaxys

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(v3)

LiO+ O (v3) (v4)O (v3) (v3)

NH –

(v5) (v5) (v5)(v5) –

(v6)

H H C Si B BB(v6) (v6) (v4) BH BH (v4) (v6) N Yb3+ –C(v6)BH BH (v10)(v6) B B B (v6) (v2) –Cl H(v6)H (v6) (v6) Cl – H –Cl (v6) H (v2) H (v6) H(v6) (v2) (v10) (v6) BB B (v6) 3+ – (v6) N Yb C BH BH (v6) (v4) BHBH (v4) C –Si B BB(v6) (v6) (v5)(v5) H HH (v5)(v5)

Na +

(v6)

(v5) (v5) (v4)(v5) C–

(v6) H (v6)

(v4) (v5)

0.5

H (v6) H(v6) B B BH (v6) Si (v6)(v6) (v6) H H B B 3+ – H (v6) Yb C B BH (v8) (v6) (v6) B B B H(v6)H H NH – (v6) (v6) (v3)

(v6)(v6)

Rx-ID: 27428557 View in Reaxys 74/165 Yield

Conditions & References

65 %

in tetrahydrofuran, byproducts: LiCl; under N2 atm. to soln. ((φ5:φ1:φ-Me2Si(C9H5CH2CH2NMe2)(C2B10H10))Yb(μCl)1.5)2(Li(THF)4) in THF soln. NaNHC6H3-2,6-Pr(i)2 in THF at room temp. and stirred overnight; solvent was removed, benzene was added and refluxed for 1 h, soln. was filtered, concd., and kept at room temp. for 4 days Wang, Shaowu; Li, Hung-Wing; Xie, Zuowei; Organometallics; vol. 23; nb. 16; (2004); p. 3780 - 3787 ; (from Gmelin) View in Reaxys

B– P

(v4)

(v4) Ni 2+ P

Cl – (v1)

Cl Cl

B–

P (v4)

P 2

(v5)

Ni 2+ (v2) O SP-5 (v3) Cl – O O(v3) Cl – (v5)(v3) P (v3) (v2) Ni 2+O SP-5 P (v4)

B–

Rx-ID: 27428602 View in Reaxys 75/165 Yield 94 %

Conditions & References in benzene, soln. of Ni-complex in benzene was treated with O2, stirred at room temp. for 6 h; volatiles were removed under reduced pressure, extd. into benzene, filtered, petroleum ether was slow diffused into benzene soln. at room temp.;elem. anal. MacBeth, Cora E.; Thomas, J. Christopher; Betley, Theodore A.; Peters, Jonas C.; Inorganic Chemistry; vol. 43; nb. 15; (2004); p. 4645 - 4662 ; (from Gmelin) View in Reaxys

(v1)

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N 2H

N –HC

(v4) Cu + Cu +(v4) (v4) (v4) N (v4) (v4) N

CH –

H 2H

Cu (v1)

Rx-ID: 32386115 View in Reaxys 76/165 Yield

Conditions & References Reaction Steps: 2 1: diethyl ether 2: benzene-d6 in diethyl ether, benzene-d6 Dai, Xuliang; Warren, Timothy H.; Journal of the American Chemical Society; vol. 126; nb. 32; (2004); p. 10085 - 10094 View in Reaxys

N Si

3 O

N– Si

Eu3+

Cl –

Li+

0.5

N (v4) (v5) (v2)H – (v5) (v5) (v12) (v4) Si(v5) Eu 2+ Cl C –N Si C– Eu2+ (v4) (v4) (v5) (v6) – (v6) (v10) (v5) N Si C H (v5) (v5) H (v5) (v4) – CH (v5) (v5) (v5) H (v5)(v6) (v10) Si N 2+ (v4) (v6) (v5) (v5) (v6) (v5) (v4) Eu C(v4) – – C Eu2+ Si N Cl – (v12) (v5) Si (v5)H (v5) (v2) N (v4)

Rx-ID: 27679744 View in Reaxys 77/165 Yield 61 %

Conditions & References in toluene, (inert atm.); slow addn. of toluene soln. of ligand to a toluene soln. of europium complex, stirring at room temp. for 6 h, reflux for 12 h; evapn., washing with n-hexane, extn. with toluene, concn., addn. of a drop of benzene, cooling to 0°C; elem. anal. Wang, Shaowu; Zhou, Shuangliu; Sheng, Enhong; Xie, Meihua; Zhang, Kehua; Cheng, Lin; Feng, Yan; Mao, Lili; Huang, Zixiang; Organometallics; vol. 22; nb. 17; (2003); p. 3546 - 3552 ; (from Gmelin) View in Reaxys

C+

Rx-ID: 9149405 View in Reaxys 78/165 Yield

Conditions & References With H3(+), T= 26.85 °C , Kinetics Milligan, Daniel B.; Wilson, Paul F.; Freeman, Colin G.; Meot-Ner (Mautner), Michael; McEwan, Murray J.; Journal of Physical Chemistry A; vol. 106; nb. 42; (2002); p. 9745 - 9755 View in Reaxys

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H O

Rx-ID: 9149407 View in Reaxys 79/165 Yield

Conditions & References With oxygen, T= 726.85 - 1101.85 °C , p= 760Torr , Product distribution Dagaut; Pengloan; Ristori; Physical Chemistry Chemical Physics; vol. 4; nb. 10; (2002); p. 1846 - 1854 View in Reaxys

(v1)

HO HO

Rx-ID: 22834162 View in Reaxys 80/165 Yield

Conditions & References 5 : Example 5 Catalyst prepared as in Example 1 is loaded into a 1-cm3 reactor (particle size 1-2 mm). Toluene is delivered at V=0.25 h-1 at a molar ratio of N2O:toluene=1:1. The reaction temperature is 425° C., the yield of a mixture of o-, m-, p-cresols is 21.1percent with selectivity for cresol of 75percent. Benzene, xylene, and phenol are the major by-products. The ratio of o-, m-, and p-cresols is 30:40:30. With 2percent ZnO/HZSM-5 (Si/Al=21), T= 425 °C , Product distribution / selectivity Patent; General Electric Company; US6388145; (2002); (B1) English View in Reaxys

xylene; mixture of Rx-ID: 23138420 View in Reaxys 81/165 Yield 16 %Chromat., 1 %Chromat.

Conditions & References , Time= 5h, T= 124 - 160 °C , p= 6750.68Torr Patent; UOP LLC; US6355852; (2002); (B1) English View in Reaxys

Cl (v3) (v4) Si– O

(v4) –

(v4)

0.33

Os (v4)

2+ (v5)

(v4)

SiH N

Os 2+(v4)(v6)N Si–

Cl –

(v1)

(v4)

(v3)

Rx-ID: 26296588 View in Reaxys 82/165 Yield 45 %

Conditions & References in benzene, Si compound condensed under vac. to a soln. of Os complex in dry benzenein the Schlenk tube; after sealing the tube, mixt. allowed to warm to r oom temp., then heated in an oil bath at 90°C for 24 h; the solvent volume concd., dry hexane added to give solid; elem. anal. Choo, Tong N.; Kwok, Wai-Him; Rickard, Clifton E.F.; Roper, Warren R.; Wright, L.James; Journal of Organometalic Chemistry; vol. 645; nb. 1-2; (2002); p. 235 - 245 ; (from Gmelin) View in Reaxys

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Cl (v3) (v4) Si– O

Os 2+

0.33

(v4)

SiH N

(v5)

Os 3+(v4)(v6)N Si–

Cl –

(v4)

(v4) (v1)– Si– Cl

(v4)

(v1)

(v4)

(v3)

Rx-ID: 26296589 View in Reaxys 83/165 Yield

Conditions & References

40 %

in benzene, Si compound condensed under vac. to a soln. of Os complex in dry benzenein the Schlenk tube; after sealing the tube, mixt. allowed to warm to r oom temp., then heated in an oil bath at 75°C for 21 h; the solvent volume concd., dry hexane added to give solid; elem. anal. Choo, Tong N.; Kwok, Wai-Him; Rickard, Clifton E.F.; Roper, Warren R.; Wright, L.James; Journal of Organometalic Chemistry; vol. 645; nb. 1-2; (2002); p. 235 - 245 ; (from Gmelin) View in Reaxys

(v4) (v5)–H C (v5) 2 (v4)– – (v5) (v5) N 4+ O– HCHC Fe 2+(v4) Zr – (v2) (v4) (v10) N(v4) OC-6 (v5) (v6) O (v2) (v5) (v5) (v5) – H 2C (v4)

(v4) – (v5) H C (v5) 2 2H (v5) (v5) (v4) –HC –HC 2+ N (v6)O– Fe (v4)(v4) Zr 4+ (v4) N (v10) OC-6 (v5) O– (v2) (v2) (v5) (v5) 2H (v5) –H C 2 (v4)

1.5 2H

Rx-ID: 27261014 View in Reaxys 84/165 Yield

Conditions & References in benzene-d6 Shafir, Alexandr; Fiedler, Dorothea; Arnold, John; Journal of the Chemical Society, Dalton Transactions; nb. 4; (2002); p. 555 - 560 ; (from Gmelin) View in Reaxys N

(v2) – O

O– Al3+

O–

1.33

1.5

– 3+ (v4) (v2)(v3) O Fe O– (v3) O(v2) –– (v3)O– O (v6) O(v3) (v3) 3+(v6) O O Fe 3+2– (v3) O Fe (v6) O3+ (v2) (v6)O2(v3) (v3) (v2) –O 3+ (v3) O (v3)Fe– (v3)OFe O – O(v3) O– O –O (v3) (v2) 3+ – Fe O (v3) (v2) (v4)

O– (v2)

Fe 4O2( 8+)

Rx-ID: 27262233 View in Reaxys 85/165 Yield

Conditions & References

59 %

in benzene, under N2, standard Schlenk techniques; Al compd. added to suspn. of Fe complex (molar ratio 3.5:1) in benzene; stirred for 24 h; supernatant decanted; evapd. under N2; crystd. over several wk; recrystd. from benzene Ammala, Paul S.; Batten, Stuart R.; Cashion, John D.; Kepert, Christopher M.; Moubaraki, Boujemaa; Murray, Keith S.; Spiccia, Leone; West, Bruce O.; Inorganica Chimica Acta; vol. 331; nb. 1; (2002); p. 90 - 97 ; (from Gmelin) View in Reaxys

-1 F

N (v4)

N F

B (v4)

Cu + (v4) N (v4) N (v4) (v4)

H O

N N

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(v1) F–

(v4)

B3+– – FF

–F

(v1)

(v1) (v1)

N N (v4)

N 2 (v2)

(v4)

Cu + N

N Cu + (v4) (v2)

(v4)

N H

Cu + (v2) (v4)

N N

Rx-ID: 27655843 View in Reaxys 86/165 Yield

Conditions & References in methanol, acetonitrile, benzene, further solvents; mixed in CH3OH:CH3CN:C6H6:C6H5CH3=3:2:1:1; elem. anal. Su, Cheng-Yong; Cai, Yue-Peng; Chen, Chun-Long; Lissner, Falk; Kang, Bei-Sheng; Kaim, Wolfgang; Angewandte Chemie - International Edition; vol. 41; nb. 18; (2002); p. 3371 - 3375 ; (from Gmelin) View in Reaxys

O– Ag+

O N N

3– O

F F O S O

N N (v4)

N (v2)

(v4)

Ag+ N

Ag+ (v4)(v2) (v4)

(v4)

Ag+

(v4)

(v2)

N N

Rx-ID: 27668821 View in Reaxys 87/165 Yield

Conditions & References in methanol, acetonitrile, benzene, further solvents; mixed in CH3OH:CH3CN:C6H6:C6H5CH3=3:2:1:1; elem. anal., NMR Su, Cheng-Yong; Cai, Yue-Peng; Chen, Chun-Long; Lissner, Falk; Kang, Bei-Sheng; Kaim, Wolfgang; Angewandte Chemie - International Edition; vol. 41; nb. 18; (2002); p. 3371 - 3375 ; (from Gmelin) View in Reaxys

Rx-ID: 3537711 View in Reaxys 88/165 Yield

Conditions & References With hydrogen, nickel tetrahydridoaluminate, T= 300 - 350 °C , Kinetics

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Villemin, Bernard Louis; Hoang-Van, Can; Teichner, Stanislas Jean; Bulletin de la Societe Chimique de France; vol. 1; nb. 1-2; (1980); p. 15 - 19 View in Reaxys With hydrogen, Time= 0.000972222h, T= 909.85 °C , p= 18751.5Torr , Kinetics, Further Variations: Temperatures, Pressures Van Scheppingen, Wibo B.; Cieplik, Mariusz K.; Louw, Robert; European Journal of Organic Chemistry; nb. 11; (2001); p. 2101 - 2106 View in Reaxys

Rx-ID: 8960660 View in Reaxys 89/165 Yield

Conditions & References With boron trioxide, sodium hydroxide, T= 720 °C , Product distribution, Further Variations: Temperatures, Reagents Chekryshkin; Tetenova; Fedorov; Petroleum Chemistry; vol. 41; nb. 4; (2001); p. 272 - 276 View in Reaxys

(v5) (v5) (v5) (v5)

(v5)

(v5)(v5) (v5)

(v2)

(v5)

(v10)

(v11)

C –4 C–

(v5)

(v5)(v5) (v5)

(v5) (v5)(v5)

2 Sm3+

Rx-ID: 27245072 View in Reaxys 90/165 Yield

Conditions & References

in toluene, the mixt. in tolueneirred Castillo; Tilley; Journal of the American Chemical Society; vol. 123; nb. 43; (2001); p. 10526 - 10534 ; (from Gmelin) View in Reaxys N

O 8 O– (v3)

O (v3) FeO O O (v3) (v6)N(v6) (v3) (v6) O (v4) O Zr O O Zr O O (v3) (v6) (v3) O O O NFe (v3) O (v4) O O O

4 1.5

Zr 4+ –O

(v3)

Fe 4O2( 8+)

Rx-ID: 31994877 View in Reaxys 91/165 Yield

Conditions & References

71 %

in benzene, under N2, Schlenk technique; dissolving withing 24 h; soln. was evapd., washing with benzene; elem. anal. Ammala, Paul S.; Cashion, John D.; Kepert, Christopher M.; Murray, Keith S.; Moubaraki, Boujemaa; Spiccia, Leone; West, Bruce O.; Journal of the Chemical Society. Dalton Transactions; nb. 13; (2001); p. 2032 - 2041 ; (from Gmelin) View in Reaxys

Rx-ID: 8832520 View in Reaxys 92/165 Yield

Conditions & References With MnAPO-46, Time= 5h, T= 350 °C , Product distribution, Further Variations: Catalysts, Temperatures Cheralathan; Kannan; Palanichamy; Murugesan; Indian Journal of Chemistry - Section A Inorganic, Physical, Theoretical and Analytical Chemistry; vol. 39; nb. 9; (2000); p. 921 - 927 View in Reaxys

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Cl N

0.43

0.33 O

Cl Ti Cl N N

(v6) (v4) (v4) OC-6

(v4)

Cl Ti Cl Cl

Rx-ID: 27096829 View in Reaxys 93/165 Yield

Conditions & References in benzene, under N2; 1 equiv. of ligand in light petroleum-benzene added to stirred soln. of Ti complex in light petroleum; stirred for 1 h; filtered; solid washed with light petroleum; dried in vac. for 1 h; elem. anal. Nielson, Alastair J.; Schwerdtfeger, Peter; Waters, Joyce M.; Journal of the Chemical Society, Dalton Transactions; nb. 4; (2000); p. 529 - 537 ; (from Gmelin) View in Reaxys

H O

Rx-ID: 3537655 View in Reaxys 94/165 Yield

Conditions & References With air, aluminum oxide, vanadia, T= 400 °C , activity of catalysts, mechanism of catalysts, Product distribution Jonson, Bo; Rebenstorf, Bernd; Larsson Ragnar; Andersson, S. Lars T.; Lundin, Sten T.; Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases; vol. 82; (1986); p. 767 - 784 View in Reaxys With aluminum oxide, silica gel, catalytic oxidation, Product distribution Jonson, Bo; Rebenstorf, Bernd; Larsson, Ragnar; Andersson, S. Lars T.; Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases; vol. 84; nb. 10; (1988); p. 3363 - 3376 View in Reaxys With oxygen, aluminum oxide, chromium(III) oxide, T= 270 °C , various temp., various toluene and O2 pressure, Rate constant, Product distribution, Mechanism Younes, M. K.; Ghorbel, A.; Naccache, C.; Journal de Chimie Physique et de Physico-Chimie Biologique; vol. 92; nb. 7-8; (1995); p. 1472 - 1485 View in Reaxys With oxygen, T= 250 - 400 °C , variation of the catalyst; ΔH(excit.), Kinetics, Product distribution Younes; Ghorbel; Naccache; Journal de Chimie Physique et de Physico-Chimie Biologique; vol. 94; nb. 11-12; (1997); p. 1993 - 2006 View in Reaxys

H H 2C

Rx-ID: 4614409 View in Reaxys 95/165 Yield 77 % Spectr., 23 % Spectr.

Conditions & References With nitrate radical, Time= 6.94444E-07h, T= 26.9 °C , p= 2Torr , var. of reagent, energy profile, Product distribution, Rate constant, Mechanism Hoyermann; Seeba; Olzrnann; Viskolcz; Berichte der Bunsengesellschaft/Physical Chemistry Chemical Physics; vol. 101; nb. 3; (1997); p. 538 - 544 View in Reaxys

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CH + C+ H

Rx-ID: 4737830 View in Reaxys 96/165 Yield

Conditions & References T= 26.9 °C , ΔH(excit.), ΔS(excit.), Rate constant, Kinetics, Thermodynamic data Szulejko; Hrusak; McMahon; Journal of Mass Spectrometry; vol. 32; nb. 5; (1997); p. 494 - 506 View in Reaxys

Rx-ID: 5217300 View in Reaxys 97/165 Yield

Conditions & References With Na-X zeolite, T= 425 °C , p= 760Torr , other zeolite catalysts; var. temp. and molecular ratios, Product distribution Das; Pramanik, Krishna; Journal of the Indian Chemical Society; vol. 74; nb. 9; (1997); p. 701 - 704 View in Reaxys

B–

–H (v4) (v3)

(v5) (v3)

(v2) O

CH –2

2C (v6)4+ (v2) Zr – O OO–

CH –2 (v4) Zr 4+ – (v2) OO– O (v3)

C–

(v4)

O(v2)

(v3)

(v4) (v6) (v2) O (v3)

–– (v3) (v2) O– OO4+ O (v2) Zr Zr 4+ (v3) (v3)– (v6) OO–– O(v2) (v4) C–

Rx-ID: 27193793 View in Reaxys 98/165 Yield

Conditions & References in dichloromethane-d2, (N2); 1 h, 90°C Giannini, Luca; Caselli, Alessandro; Solari, Euro; Floriani, Carlo; Chiesi-Villa, Angiola; Rizzoli, Corrado; Re, Nazzareno; Sgamellotti, Antonio; Journal of the American Chemical Society; vol. 119; nb. 39; (1997); p. 9198 - 9210 ; (from Gmelin) View in Reaxys

Rx-ID: 4581127 View in Reaxys 99/165 Yield

Conditions & References With aluminum oxide, manganese, silica gel, Time= 5h, T= 479.9 °C , other cycloalkanes and aromatics, Product distribution, Mechanism Marczewski; Marczewska; Mufid; Golcbiewska; Polish Journal of Chemistry; vol. 70; nb. 12; (1996); p. 1562 - 1572 View in Reaxys

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CH 3

H 2C

Rx-ID: 4182411 View in Reaxys 100/165 Yield

Conditions & References in gaseous matrix, Irradiation, relative reaction efficiencies, product translational energies Froechtenicht, Ralf; Journal of Chemical Physics; vol. 102; nb. 12; (1995); p. 4850 - 4859 View in Reaxys

Rx-ID: 4272119 View in Reaxys 101/165 Yield

Conditions & References With dealuminated H-ZSM-5 zeolite (D1ex), T= 346.9 °C , various catalysts under different conditions, Product distribution Cejka, Jiri; Vondrova, Alena; Wichterlova, Blanka; Jerschkewitz, Hans G.; Lischke, Guenter; Schreier, Ellen; Collection of Czechoslovak Chemical Communications; vol. 60; nb. 3; (1995); p. 412 - 420 View in Reaxys

(v3)

O(v3) O (v3) OO Mn O O (v6) Mn OH (v4) (v6) O Mn HO (v4) (v6) O O Mn (v3)O (v3) H O (v4) O (v3)(v3) O

(v3)

(v4) (v3) H (v6)

(v4)

(v4) (v3) –

(v3)

H (v6) (v3) Mn+ O–O (v6) HO +Mn O (v3) O (v6) (v4) – HO Mn+O (v3) (v3) O O Mn+ O– (v3) (v6) H O O(v3) O (v4) (v3)

(v3)

Rx-ID: 27130029 View in Reaxys 102/165 Yield

Conditions & References With C6H6 in acetonitrile, dropwise addn. of C6H6 to Mn-complex soln. (room temp.), boiling; crystn. on slow cooling Copp, Steven B.; Holman, K. Travis; Sangster, Jeffrey O. S.; Subramanian, S.; Zaworotko, Michael J.; Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999); nb. 13; (1995); p. 2233 - 2244 ; (from Gmelin) View in Reaxys

(v3)

(v4)

(v3)

(v4)

H (v6) (v3) Mn+ O–O

–HO (v6) (v3) +Mn O (v3) (v6) (v4) O– HO Mn+O (v3) (v3) O O Mn+ O– (v3) (v6) H O O(v3) O (v4) (v3) (v3)

Rx-ID: 31800794 View in Reaxys 103/165 Yield

Conditions & References Reaction Steps: 2 1: toluene 2: C6H6 / acetonitrile With C6H6 in toluene, acetonitrile Copp, Steven B.; Holman, K. Travis; Sangster, Jeffrey O. S.; Subramanian, S.; Zaworotko, Michael J.; Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999); nb. 13; (1995); p. 2233 - 2244 View in Reaxys

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Rx-ID: 3536936 View in Reaxys 104/165 Yield 0.065 %, 13.2 %, 0.040 %, 2.26 %, 0.046 %, 0.112 %

Conditions & References T= 490 °C , various temp., also with 14C-labelled ester, Rate constant, Product distribution Shi, Buchang; Ji, Ying; Dabbagh, Hossein A.; Davis, Burtron H.; Journal of Organic Chemistry; vol. 59; nb. 4; (1994); p. 845 - 849 View in Reaxys

Rx-ID: 3537688 View in Reaxys 105/165 Yield

Conditions & References With dealuminated Y zeolite, T= 399.9 °C , p= 760Torr , several, in different way prepared zeolite catalyst; activation energy, Product distribution, Thermodynamic data, Mechanism Rhodes, Nigel P.; Rudham, Robert; Journal of the Chemical Society, Faraday Transactions; vol. 90; nb. 5; (1994); p. 809 - 814 View in Reaxys 2H 2H

2H 2H

Rx-ID: 3960130 View in Reaxys 106/165 Yield

Conditions & References With hydrogen, Time= 0.333333h, T= 450 °C , deuterium content in reaction products Guthrie, Robert D.; Shi, Buchang; Rajagopal, Venkatsubramanian; Ramakrishnan, Sreekumar; Davis, Burtron H.; Journal of Organic Chemistry; vol. 59; nb. 24; (1994); p. 7426 - 7432 View in Reaxys

Rx-ID: 3536845 View in Reaxys 107/165 Yield

Conditions & References With oxygen, Na+ + 5percent Cs+, magnesium oxide, Time= 3h, T= 750 °C , p= 760Torr , other catalysts, Product distribution Khan, Ashraf Z.; Ruckenstein, Eli; Journal of the Chemical Society, Chemical Communications; nb. 7; (1993); p. 587 - 589 View in Reaxys

Rx-ID: 3537648 View in Reaxys 108/165 Yield

Conditions & References With oxygen, V-ZSM5, T= 299.9 °C , other reaction temperatures, other vanadium catalysts; activation energies, Rate constant, Product distribution, Mechanism

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Whittington, B. I.; Anderson, J. R.; Journal of Physical Chemistry; vol. 97; nb. 5; (1993); p. 1032 - 1041 View in Reaxys

(v5)(v5)(v5) (v5) (v2)

Y(v12) (v12)Y

(v5) (v5) (v5) (v5)

H (v2)

(v5) (v5) (v5)

(v5) (v5)(v5)

(v5)(v5) (v5) (v5)

(v5)

(v5) (v5) (v5) (v5)

(v5)(v5) (v5) (v5) (v2)

0.5

(v5) (v11)

(v12)

(v11) (v5)(v5) (v5)

(v5)(v5) (v5)(v5)

(v5)(v5) (v5)(v5)(v5)

Rx-ID: 26903293 View in Reaxys 109/165 Yield

Conditions & References in toluene, byproducts: H2; N2-atmosphere; stirring (room temp., 0.5 h); evapn. to dryness; identification of product mixt. by (1)H-NMR spectroscopy Booij, Martin; Deelman, Berth-Jan; Duchateau, Rob; Postma, Djurre S.; Meetsma, Auke; Teuben, Jan H.; Organometallics; vol. 12; (1993); p. 3531 - 3540 ; (from Gmelin) View in Reaxys 2H

(v5)(v5)(v5) (v5) (v2)

(v5) (v5) (v5) (v5)

(v5) (v5) (v5)

Y(v12) (v12)Y

(v5)(v5) (v5) (v5)

0.5

(v5) (v2) (v5) (v5) (v5)

(v5)(v5)(v5) (v5) (v2) 2 H

(v5)(v5) (v5) (v5) (v2)

(v5) (v11)

(v12)

(v5)(v5) (v5)

(v5)(v5) (v5)(v5)(v5)

(v5) (v5) (v5) (v5)

Y(v12) (v12)Y 2H (v2)

(v5)(v5) (v5) (v5)

(v5) (v5) (v5) (v5)

Rx-ID: 26906180 View in Reaxys 110/165 Yield

Conditions & References in (2)H8-toluene, N2-atmosphere; stoichiometric amts.; not isolated, detd. by (1)H-NMR spectroscopy Booij, Martin; Deelman, Berth-Jan; Duchateau, Rob; Postma, Djurre S.; Meetsma, Auke; Teuben, Jan H.; Organometallics; vol. 12; (1993); p. 3531 - 3540 ; (from Gmelin) View in Reaxys

Rx-ID: 3537678 View in Reaxys 111/165 Yield

Conditions & References T= 1036.9 °C , var. temp. and diluent gases; also methane, Product distribution Kawakami, Shigenobu; Kanaguchi, Takeshi; Tagami, Hiroshi; Nakada, Masahiro; Yamaguchi, Tatsuaki; Bulletin of the Chemical Society of Japan; vol. 65; nb. 12; (1992); p. 3434 - 3438 View in Reaxys

Rx-ID: 3537693 View in Reaxys 112/165 Yield 6.6 % Chromat., 2.7 % Chromat., 2.5 % Chromat., 4.2 % Chromat., 4.7 % Chromat., 46.6 % Chromat.

Conditions & References Time= 2h, T= 1116.9 °C , var. temperature, flow rate, and inner diameter of a diffusion column., Product distribution, Mechanism Kawakami, Shigenobu; Gao, Zhiming; Nakada, Masahiro; Yamaguchi, Tatsuaki; Bulletin of the Chemical Society of Japan; vol. 65; nb. 2; (1992); p. 586 - 590 View in Reaxys

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2 N

N N

Rx-ID: 3537504 View in Reaxys 113/165 Yield

Conditions & References With butylsodium, 1.) hexane, RT, 1 h, 2.) hexane, 5 deg C, 30 min, Yield given. Multistep reaction Corbelin, Siegfried; Lorenzen, Nis Peter; Kopf, Juergen; Weiss, Erwin; Journal of Organometallic Chemistry; vol. 415; nb. 3; (1991); p. 293 - 313 View in Reaxys

H 2C

Rx-ID: 1978535 View in Reaxys 114/165 Yield

Conditions & References pyrolysis, Kinetics, Rate constant Hippler, H.; Reihs, C.; Troe, J.; Zeitschrift fuer Physikalische Chemie (Muenchen, Germany); vol. 167; nb. 1; (1990); p. 1 - 16 View in Reaxys

H Br

Rx-ID: 3536785 View in Reaxys 115/165 Yield

Conditions & References

280 %

With air, Time= 10h, Irradiation Nakada; Fukushi; Hirota; Bulletin of the Chemical Society of Japan; vol. 63; nb. 3; (1990); p. 944 - 946 View in Reaxys

Rx-ID: 3536844 View in Reaxys 116/165 Yield

Conditions & References With oxygen, yttrium(III) oxide, calcium oxide, lithium oxide, T= 699.9 °C , perdeuterated toluene and benzaldehyde as reactants, Product distribution, Mechanism Osada, Yo; Ogasawara, Sadao; Fukushima, Takakazu; Shikada, Tsutomu; Ikariya, Takao; Journal of the Chemical Society, Chemical Communications; nb. 20; (1990); p. 1434 - 1436 View in Reaxys

Rx-ID: 3537016 View in Reaxys 117/165 Yield 3.66 %

Conditions & References Time= 0.00125278h, T= 657.9 °C , other temperatures and times investigated, Kinetics, Rate constant, Mechanism

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Manion, Jeffrey A.; Louw, Robert; Journal of Physical Chemistry; vol. 94; nb. 10; (1990); p. 4127 - 4134 View in Reaxys

Rx-ID: 3537669 View in Reaxys 118/165 Yield 3 %, 14 %, 100 % Turnov.

3 % Turnov., 14 % Turnov., 83 % Turnov.

Conditions & References With hydrogen, aluminum oxide, Rh-Cu, T= 400 °C , p= 760Torr , dynamic differential reactor, 5percent conversion Hoang-Van, Can; Kachaya, Yann; Belaid, Ali; Ghorbel, Abdelhamid; Bulletin de la Societe Chimique de France; nb. 2; (1989); p. 267 - 271 View in Reaxys With hydrogen, Rh/Al2O3, T= 325 °C , in dynamic differential reactor at 5percent conversion; studied activity and selectivity of catalysts, activation energy; varied: reaction temp. 300-400 deg C, catalysts Cu content also in Ni base catalysts, Kinetics, Product distribution Hoang-Van, Can; Kachaya, Yann; Belaid, Ali; Ghorbel, Abdelhamid; Bulletin de la Societe Chimique de France; nb. 2; (1989); p. 267 - 271 View in Reaxys

Rx-ID: 3537710 View in Reaxys 119/165 Yield

Conditions & References With methane, oxygen, magnesium oxide, lead(II) oxide, T= 700 °C , Yield given. Yields of byproduct given Osada, Yo; Enomoto, Koichi; Fukushima, Takakazu; Ogasawara, Sadao; Shikada, Tsutomu; Ikariya, Takao; Journal of the Chemical Society, Chemical Communications; nb. 16; (1989); p. 1156 - 1157 View in Reaxys

CO, CO2, H2 Rx-ID: 6211586 View in Reaxys 120/165

Yield

Conditions & References With water, aluminum oxide, chromium(III) oxide, rhodium, T= 460 °C , p= 750.06Torr , other activity and selectivity of catalyst, Product distribution, Rate constant Zun, Ro Yong; Davidova, Helena; Polednova, Jaroslava; Jiratova, Kveta; Schneider, Petr; Collection of Czechoslovak Chemical Communications; vol. 53; nb. 3; (1988); p. 466 - 478 View in Reaxys

H O

CO, CO2 Rx-ID: 6211608 View in Reaxys 121/165

Yield

Conditions & References With vanadia, titanium(IV) oxide, Time= 1h, T= 219.9 °C , investigation of intermediates at various temperatures, Mechanism Miyata, Hisashi; Mukai, Tadashi; Ono, Takenhiko; Ohno, Takashi; Hatayama, Fumikazu; Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases; vol. 84; nb. 7; (1988); p. 2465 - 2476 View in Reaxys

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Ph3Bi

Rx-ID: 6218223 View in Reaxys 122/165 Yield

Conditions & References

0.40 mol

With (C6H5)3Bilt;OOC(CH3)3gt;2, Yields of byproduct given Dodonov, V. A.; Zinov'eva, T. I.; Osadchaya, N. N.; J. Gen. Chem. USSR (Engl. Transl.); vol. 58; nb. 3; (1988); p. 712,630 631 View in Reaxys

H 2C

Rx-ID: 3537709 View in Reaxys 123/165 Yield

Conditions & References p= 152 - 380Torr , thermal decomposition at 1550-2200 K by shock tube techniques; products were detected by MS; Ea, Product distribution, Kinetics, Thermodynamic data Pamidimukkala, K. M.; Kern, R. D.; Patel, M. R.; Wei, H. C.; Kiefer, J. H.; Journal of Physical Chemistry; vol. 91; nb. 8; (1987); p. 2148 - 2154 View in Reaxys

H O

methylanhracenes Rx-ID: 6215807 View in Reaxys 124/165 Yield

Conditions & References With aluminium trichloride, Time= 1h, T= 60 °C , other aldehydes and arenes; var. temp. and time; var. reagents, Product distribution, Mechanism Roberts, Royston M.; El-Khawaga, Ahmed M.; Sweeney, Kevin M.; El-Zohry, Maher F.; Journal of Organic Chemistry; vol. 52; nb. 8; (1987); p. 1591 - 1599 View in Reaxys

O O -1

-1

N N

O O

(v4) Pt (v4) SP-4 P (v4) I

0.25

O O

N N

(v4) Pt (v4) SP-4 P (v4) I

O O

Rx-ID: 26942272 View in Reaxys 125/165 Yield

Conditions & References With benzene in benzene, recrystn. from hot benzene at room temp.; elem. anal. Arduengo, Anthony J.; Stewart, Constantine A.; Davidson, Fredric; Dixon, David A.; Becker, James Y.; et al.; Journal of the American Chemical Society; vol. 109; nb. 3; (1987); p. 627 - 646 ; (from Gmelin) View in Reaxys

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P (v4) O O O O(v5) Pt S S

P (v4) (v5)

(v4)

Pt Pt (v4) P (v5) S (v5) P O O

(v4) Pt P (v5)

Pt (v4) S (v5) P

O O

O S

Rx-ID: 26959650 View in Reaxys 126/165 Yield 76 %

Conditions & References With carbon monoxide, benzene in benzene, 1/3 mol equiv. of PPh3 was added to a soln. of Pt3-cluster in benzene, CO was bubbled through the soln.; solvent was removed in vacuo, residue was recrystd. from Et2O-MeOH; elem. anal. Evans, David G.; Hallam, Malcolm F.; Mingos, D. Michael P.; Wardle, Robert W. M.; Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999); (1987); p. 1889 - 1896 ; (from Gmelin) View in Reaxys

Rx-ID: 3536829 View in Reaxys 127/165 Yield

Conditions & References T= 676.9 - 826.9 °C , p= 1520 - 3800Torr , Irradiation, in single-pulse shock, Rate constant, Kinetics, Mechanism Robaugh, D.; Tsang, W.; Journal of Physical Chemistry; vol. 90; nb. 17; (1986); p. 4159 - 4163 View in Reaxys O O Cl O O–

S–

(v2) (v5) – N N (v3) (v4)

N –(v4) (v3)

2 Na +

NFe 3+

0.5

E S–

(v3)

–N N (v4) (v3)– Fe N3+ N (v5) S– (v4)

(v2)

N E

(v2) S–

– (v5) N Fe 3+ (v3) N (v4)N (v4)

N– (v3)

Rx-ID: 27615956 View in Reaxys 128/165 Yield 89 %

Conditions & References With benzene in benzene, soln. of sodium trans-dicyanoethylenedithiolate and Fe-compound in benzene was stirred at reflux temp. for 6 h; soln. was cooled to room temp.; soln. was filtered; n-heptane was slowly added with stirring; soln. wasconcd.; pptn. by filtration and washing with n-heptane; elem. anal. Elliott, C. Michael; Akabori, Kozo; Anderson, Oren P.; Schauer, Cynthia K.; Hatfield, William E.; et al.; Inorganic Chemistry; vol. 25; (1986); p. 1891 - 1896 ; (from Gmelin) View in Reaxys

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Rx-ID: 3537689 View in Reaxys 129/165 Yield 1.64 %, 1.64 %, 7.36 %

Conditions & References With hydrogen, H-ZSM-5 zeolite, T= 400 °C , various time; different circumstances of adsorption, Product distribution Yatovt; Kotov; Bursian; Journal of applied chemistry of the USSR; vol. 58; nb. 2 pt 1; (1985); p. 268 - 272 View in Reaxys

C9 aromatics Rx-ID: 6210953 View in Reaxys 130/165 Yield

Conditions & References

7.61 %, 8.1 With Na mordenite-Al2O3, T= 399.9 °C , p= 22501.8Torr , Product distribution %, 17.97 %, Bursian, N.R.; Shavandin, Yu.A.; Tat'yanina, E.M.; Shimuk, N.P.; J. Appl. Chem. USSR (Engl. Transl.); vol. 57; nb. 6; 6.11 % (1984); p. 1244 - 1247,1151 - 1154 View in Reaxys

C9 aromatics Rx-ID: 6210954 View in Reaxys 131/165 Yield 4.81 %, 5.2 %, 0.24 %, 10.7 %, 19.39 %

Conditions & References With Na mordenite-Al2O3, T= 399.9 °C , p= 22501.8Torr , effect of dealuminization of catalyst (HNO3), Product distribution Bursian, N.R.; Shavandin, Yu.A.; Tat'yanina, E.M.; Shimuk, N.P.; J. Appl. Chem. USSR (Engl. Transl.); vol. 57; nb. 6; (1984); p. 1244 - 1247,1151 - 1154 View in Reaxys

H 2C

Rx-ID: 3536813 View in Reaxys 132/165 Yield

Conditions & References in 1,1,2-Trichloro-1,2,2-trifluoroethane, T= 24.9 °C , Irradiation, laser flash photolysis technique, Rate constant Scaiano; Stewart; Journal of the American Chemical Society; vol. 105; nb. 11; (1983); p. 3609 - 3614 View in Reaxys

O O O

H 2C

Rx-ID: 3537526 View in Reaxys 133/165 Yield

Conditions & References in 1,1,2-Trichloro-1,2,2-trifluoroethane, T= 24.9 °C , Irradiation, laser flash photolysis technique, Rate constant

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Scaiano; Stewart; Journal of the American Chemical Society; vol. 105; nb. 11; (1983); p. 3609 - 3614 View in Reaxys

Rx-ID: 3537626 View in Reaxys 134/165 Yield

Conditions & References With hydrogenchloride, oxygen, aluminum oxide, copper dichloride, Time= 0.001h, T= 460 - 470 °C , different ratio of reagents, 7 s, Product distribution Potapov, A. M.; Journal of Organic Chemistry USSR (English Translation); vol. 19; nb. 7; (1983); p. 1400; Zhurnal Organicheskoi Khimii; vol. 19; nb. 7; (1983); p. 1555 View in Reaxys

(v3)

O1N

(v2)

Rx-ID: 3537331 View in Reaxys 135/165 Yield

Conditions & References Thermodynamic data Stone, John A.; Splinter, Dena E.; Kong, Soon Yau; Canadian Journal of Chemistry; vol. 60; (1982); p. 910 - 915 View in Reaxys

+HC

Rx-ID: 3537359 View in Reaxys 136/165 Yield

Conditions & References T= 32 °C , Rate constant Sharma, D. K. Sen; Ikuta, S.; Kebarle, P.; Canadian Journal of Chemistry; vol. 60; (1982); p. 2325 - 2331 View in Reaxys

(v3)

O O

(v3)

H (v5)(v5) (v3)(v5)(v5) (v5)H (v5) H O H H

(v3)

O O

(v3)

(v6) Co (v7)

(v3)

Co Co Co (v7) (v4) P(v4) (v7) (v4)P O P

(v3)

(v4)

O Co (v9) O Co O P(v7) Co Co (v7) (v4) (v7) O(v4) P P

(v3)

Rx-ID: 27108300 View in Reaxys 137/165 Yield

Conditions & References

90 %

With benzene in toluene, Complex was refluxed in toluene for 6 h (inert atm.);; evapd. in vac. to dryness, recrystd. from benzene-hexane; elem. anal.; Bahsoun, A. A.; Osborn, J. A.; Voelker, C.; Bonnet, J. J.; Lavigne, G.; Organometallics; vol. 1; (1982); p. 1114 - 1120 ; (from Gmelin) View in Reaxys

Rx-ID: 3536897 View in Reaxys 138/165 Yield

Conditions & References gaseous plasma of glow discharge, Yield given. Further byproducts given. Yields of byproduct given

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So, Y. H.; Miller, Larry L.; Journal of the American Chemical Society; vol. 103; nb. 14; (1981); p. 4204 - 4209 View in Reaxys

O O O O

Rx-ID: 3537525 View in Reaxys 139/165 Yield

Conditions & References

1.19 %, 4.78 %, 22.2 %, 7.17 %, 62.8 %

Time= 15h, T= 80 °C , Heating, Product distribution

3.33 %, 2.19 %, 9.28 %, 3.06 %, 20.4 %

Time= 9h, Irradiation, other wave length, Product distribution

Ogata, Yoshiro; Tomizawa, Kohtaro; Furuta, Kyoji; Kato, Hiroshi; Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999); (1981); p. 110 - 112 View in Reaxys

CO; CO2; H2 Rx-ID: 6211709 View in Reaxys 140/165

Yield

Conditions & References With water, iridium, Time= 24h, T= 400 - 460 °C , p= 760 - 1520Torr , other catalysts, other time, Kinetics Duprez, Daniel; Pereira, Pedro; Grand, Michel; Maurel, Raymond; Bulletin de la Societe Chimique de France; vol. 1; nb. 1-2; (1980); p. 35 - 45 View in Reaxys

HCN Rx-ID: 6214237 View in Reaxys 141/165

Yield 4 %, 90 %

Conditions & References With ammonia, hydrogen faujasite zeolite, Time= 0.00111111h, T= 726.9 °C , p= 760Torr , var. time, temp., cat., Product distribution, Mechanism Weigert, Frank; Journal of the Chemical Society, Chemical Communications; nb. 3; (1980); p. 97 - 98 View in Reaxys

light hydrocarbons, xylenes, hydrogen, coke Rx-ID: 6215470 View in Reaxys 142/165 Yield

Conditions & References With aluminum oxide, T= 600 °C , p= 35.03Torr , Investigation of the formation of coke during the cracking of toluene on various samples of alumina in helium as a carrier gas. Investigation of the effect of the thickness of the catalyst bed, time and the inhibiting influence of hydrogen., Product distribution

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Miloudi, A.; Duprez, D.; Bastick, M.; Bastick, J.; Bulletin de la Societe Chimique de France; vol. 1; nb. 11-12; (1980); p. 443 - 450 View in Reaxys

Ag+

Rx-ID: 26295374 View in Reaxys 143/165 Yield

Conditions & References in benzene, ligand exchange in soln.; vol. Ag: MVol.B5; 1.3.3.2, page 96 - 97 View in Reaxys Krishnamurthy, V. N.; Soundararajan, S.; Proc. 1st Chem. Symp., Chandigarh, India, 1969 (1970), Nr. 2, S. 1/4; C. A.; vol. 74; (1971); p. 35941 ; (from Gmelin) View in Reaxys

hydrogen

Rx-ID: 6208121 View in Reaxys 144/165 Yield

Conditions & References auch in Gegenwart von Katalysatoren.Hydrogenation Anonymus; Industrial and Engineering Chemistry; vol. 54; nb. 2; (1962); p. 28 View in Reaxys Asinger,F.; View in Reaxys T= 426.9 - 726.9 °C , Hydrogenation, Equilibrium constant Matsui et al.; ; vol. 1; (1959); p. 67 View in Reaxys Doumani; Industrial and Engineering Chemistry; vol. 50; (1958); p. 1677 View in Reaxys Silsby; Sawyer; Journal of Applied Chemistry; vol. 6; (1956); p. 347,350 View in Reaxys T= 480 °C , p= 73550.8Torr Hall; Journal of the Society of Chemical Industry, London; vol. 54; (1935); p. 208 T, 212 T View in Reaxys

hydrogen Rx-ID: 6208093 View in Reaxys 145/165 Yield

Conditions & References T= 580 - 650 °C , Wasserstoff-Drucken bis 600 Torr, Kinetics Matsui et al.; ; vol. 1; (1959); p. 67 View in Reaxys T= 500 - 950 °C , und Drucken bis 250 at, Kinetics Betts et al.; Journal of Applied Chemistry; vol. 7; (1957); p. 497,498 View in Reaxys Silsby; Sawyer; Journal of Applied Chemistry; vol. 6; (1956); p. 347,350 View in Reaxys

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T= 455 - 490 °C , Drucke bis 1350 at, Kinetics Gonikberg; Nikitenkow; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; (1954); p. 936; engl. Ausg. S. 813 View in Reaxys

hydrogen

nickel / aluminium oxide

Rx-ID: 6208123 View in Reaxys 146/165 Yield

Conditions & References T= 460 °C , Hydrogenation Schuikin et al.; Zhurnal Obshchei Khimii; vol. 29; (1959); p. 2230; engl. Ausg. S. 2197 View in Reaxys

cobalt molybdate Al2O3

hydrogen

Rx-ID: 6208122 View in Reaxys 147/165 Yield

Conditions & References T= 566 °C , p= 51485.6Torr , Hydrogenation Doumani; Industrial and Engineering Chemistry; vol. 50; (1958); p. 1677 View in Reaxys O

C O

Ni(CO)4

O O

Rx-ID: 6208109 View in Reaxys 148/165 Yield

Conditions & References T= 325 °C , p= 73550.8Torr Prichard; Journal of the American Chemical Society; vol. 78; (1956); p. 6137 View in Reaxys

hydrogen

platinum /Al2O3

Rx-ID: 6208233 View in Reaxys 149/165 Yield

Conditions & References T= 460 °C , p= 14710.2Torr Schuikin; Berdnikowa; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; (1955); p. 109,110; engl. Ausg. S. 95, 96 View in Reaxys Schuikin; Berdnikowa; Research (London); vol. 6; (1956); p. 132,134 View in Reaxys

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Cl Al

tolylpentane/s

Rx-ID: 8288903 View in Reaxys 150/165 Yield

Conditions & References T= 25 °C Burwell; Shields; Journal of the American Chemical Society; vol. 77; (1955); p. 2766 View in Reaxys

S HO

(R)-2-phenyl-pentane

tolylpentane/s

Rx-ID: 8288904 View in Reaxys 151/165 Yield

Conditions & References T= 142 °C Burwell; Shields; Journal of the American Chemical Society; vol. 77; (1955); p. 2766 View in Reaxys

2H 2

H 2

hydrogen-atoms

hydrogen

Rx-ID: 7454679 View in Reaxys 152/165 Yield

Conditions & References Deuterium-Gehalt des Produkts Blades; Steacie; Canadian Journal of Chemistry; vol. 32; (1954); p. 1142 View in Reaxys

benzyl and tolyl and benzene and ethylene

butadiyne and methane and methyl and carbon Rx-ID: 6210732 View in Reaxys 153/165

Yield

Conditions & References T= 1150 °C , p= 1E-06Torr , und 1225grad und 1300grad.Pyrolysis, Product distribution Ingold; Lossing; Canadian Journal of Chemistry; vol. 31; (1953); p. 30,33 View in Reaxys

nickel silicon dioxide

Rx-ID: 6208124 View in Reaxys 154/165

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Yield

Conditions & References T= 420 °C , Hydrogenation Melander; Arkiv foer Kemi; vol. 21 A; nb. 18; (1946); p. 1,7 View in Reaxys

Cl Al

CuCl

Rx-ID: 6208173 View in Reaxys 155/165 Yield

Conditions & References T= 80 °C Norris; Arthur; Journal of the American Chemical Society; vol. 62; (1940); p. 874,876 View in Reaxys

O Al

2.4-dimethyl-acetophenone and 4-methyl-acetophenone

Rx-ID: 7066953 View in Reaxys 156/165 Yield

Conditions & References zuletzt bei Siedetemperatur Norris; Arthur; Journal of the American Chemical Society; vol. 62; (1940); p. 874,876 View in Reaxys

nickel

Rx-ID: 6208125 View in Reaxys 157/165 Yield

Conditions & References T= 255 - 350 °C , Hydrogenation Mailhe; Chimie et Industrie (Paris); vol. 28; (1932); p. 1263; Chem. Zentralbl.; vol. 104; nb. I; (1933); p. 1711 View in Reaxys Mailhe; Creusot; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 193; (1931); p. 176 View in Reaxys O

Na +

H –N

H 2N O

biphenyl-carboxylic acid-(4)-amide Rx-ID: 7069593 View in Reaxys 158/165

Yield

Conditions & References De Ceuster; ; vol. 14; (1932); p. 188,191 View in Reaxys

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(v2)

Br Hg

Rx-ID: 750139 View in Reaxys 159/165 Yield

Conditions & References Whitmore; Thurman; Journal of the American Chemical Society; vol. 51; (1929); p. 1500 View in Reaxys

sodium Rx-ID: 6208149 View in Reaxys 160/165

Yield

Conditions & References Bachmann; Clarke; Journal of the American Chemical Society; vol. 49; (1927); p. 2093 View in Reaxys

sodium

petroleum ether

Rx-ID: 6208155 View in Reaxys 161/165 Yield

Conditions & References White; Journal of the American Chemical Society; vol. 45; (1923); p. 781 View in Reaxys

H N

sodium

Rx-ID: 6208171 View in Reaxys 162/165 Yield

Conditions & References White; Journal of the American Chemical Society; vol. 45; (1923); p. 781 View in Reaxys O

Na +

H –N

φ.φ.φ-trimethyl-n-caproic acid amide

Rx-ID: 8265027 View in Reaxys 163/165 Yield

Conditions & References Haller; Cornubert; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 158; (1914); p. 304 View in Reaxys

Na +

H –N

φ.φ-dibenzyl-propionic acid amide

Rx-ID: 7920560 View in Reaxys 164/165 Yield

Conditions & References Haller; Bauer; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 149; (1909); p. 8; Annales de Chimie (Cachan, France); vol. <8> 28; (1913); p. 399

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View in Reaxys

Na +

H –

1-methyl-3-isopropyl-cyclopentane-carboxylic acid-(1)-amide Rx-ID: 8265042 View in Reaxys 165/165 Yield

Conditions & References Bouveault; Levallois; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 148; (1909); p. 1400,1525 View in Reaxys

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