DL-Lactic acid (2-Hydroxypropanoic acid) to Propionic acid (Propanoic acid) by Asch

Query Query O

1. Query

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Date

34 reactions in Reaxys

2018-03-12 01h:50m:36s (EST)

Search as: As drawn, No salts, No mixtures

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HO O

Rx-ID: 101719 View in Reaxys 1/34 Yield

Conditions & References

5.5 %, 5.9 %

With cobalt in water, Time= 2h, T= 250 °C , Green chemistry, Concentration, Temperature, Reagent/catalyst Huo, Zhibao; Xiao, Jiefeng; Ren, Dezhang; Jin, Fangming; Wang, Tian; Yao, Guodong; Green Chemistry; vol. 19; nb. 5; (2017); p. 1308 - 1314 View in Reaxys Geschwindigkeit des aeroben und anaeroben Abbaus durch P.pentosaceum und P.zeae Fromageot; Bost; ; vol. 2; (1938); p. 232; Chem. Zentralbl.; vol. 109; nb. II; (1938); p. 1064 View in Reaxys

O OH

HO O

Rx-ID: 101722 View in Reaxys 2/34 Yield 58.79 %

Conditions & References 1 : Example 1 lactic acid(1.5 mmol, reaction concentration 200 mmol / L), Zn powder (10 mmol) and Co powder (4 mmol)Teflonlined reactor, the reactor was filled with water to a 25percent rate, and the reactor was purged with nitrogen to remove airThe reactor was placed in an oven to make the reaction temperature 250 ° C, the reaction time 120 min, and the reaction was taken outThe mixture was filtered to give a propionic acid solution.The reaction product, propionic acid, was analyzed by HPLC (see Fig. 1), and the results shown in Fig. 1 showed that propionic acid was the mainThe yield was 58.79percent. With cobalt, zinc in water, Time= 2h, T= 250 °C , Inert atmosphere, Temperature, Reagent/catalyst Patent; Shanghai Jiaotong University; Huo, Zhibao; Xiao, Jiefeng; Ren, Dezhang; Jin, Fangming; Jiang, Naimeng; Yao, Guodong; (9 pag.); CN106117035; (2016); (A) Chinese View in Reaxys

With titanium(IV) oxide, zinc in water, Time= 2h, T= 250 °C , Green chemistry, Reagent/catalyst Huo, Zhibao; Xiao, Jiefeng; Ren, Dezhang; Jin, Fangming; Wang, Tian; Yao, Guodong; Green Chemistry; vol. 19; nb. 5; (2017); p. 1308 - 1314 View in Reaxys Einw. von Propionilbacterium pentosaceum Delwiche; ; vol. 56; (1948); p. 815; ; (1949); p. 2277 View in Reaxys Fromageot; Bost; ; vol. 2; (1937); p. 225 View in Reaxys Einw. von Propionsaeurebakterien Erb,Wood,Werkman; ; vol. 31; p. 599; Chem. Zentralbl.; vol. 107; nb. II; (1936); p. 1188 View in Reaxys bei der Einw. von Bact.acidi propionici, Bact.acidi propionici a oder Bact.acidi propionici b v.Freudenreich; Jensen; ; vol. <II>17; (1907); p. 537,539 View in Reaxys bei der Einw. Bact.propionicum Maurer; Biochemische Zeitschrift; vol. 191; (1927); p. 83 View in Reaxys Virtanen; ; vol. 1; nb. 36; p. 11; Chem. Zentralbl.; vol. 95; nb. II; (1924); p. 64 View in Reaxys

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With hydrogen iodide Lautemann; Justus Liebigs Annalen der Chemie; vol. 113; (1860); p. 217 View in Reaxys With hydrogen iodide Freund; Journal fuer Praktische Chemie (Leipzig); vol. <2>5; (1872); p. 446 View in Reaxys als Zwischenprodukt bei der Vergaerung zu Methan durch Abwasserbakterien Tarvin; Buswell; Journal of the American Chemical Society; vol. 56; (1934); p. 1753 View in Reaxys With hydrogen, T= 199.84 °C , Gas phase Simonov; Simakova; Minyukova; Khassin; Russian Chemical Bulletin; vol. 58; nb. 6; (2009); p. 1114 - 1118 View in Reaxys 4 : Example 4 The activated alumina powder was placed in a muffle furnace and calcined at 500 ° C for 3 hours under static or flowing air,The rate of heating was 5 ° C / min to obtain the calcined alumina powder. Weigh 0.2 g of tin sulfate in a beaker, add 30 ml of deionized water, and weigh 1.0 g of calcined alumina powderWas added to the solution, treated with ultrasonic dipping, treated at room temperature for three hours, and then the resulting solution was placed in a microwaveAnd the resulting catalyst was dried in a drying oven at 130 ° C for 4 hours, followed by filtrationThe temperature is calcined at a temperature programmed temperature rise of 5-10 ° C / min, and the calcination temperature is set at 600 ° C and calcined at constant temperature for 3 hours to obtain20 wtpercent SnSO4 / Al2O3 supported catalyst, wherein SnSO4 corresponds to a supported amount of carrier Al2O3 of 20 wtpercent. The obtained 20 wtpercent SnSO4 / Al2O3 supported catalyst was 0.8-1.2 g, compressed, ground,Take 40-60 mesh particles as a catalyst. The prepared catalyst was placed at a diameter of 8 mm,A length of 45 cm in the middle of the tubular reactor,The upper and lower portions of the catalyst are filled with 40-60 mesh quartz sand.The tube reactor filled with the catalyst is then placed in a heating furnace,Open the carrier gas (N2) and access, access flow rate of 20ml / min,Open the heating device,The temperature was raised to 300 ° C by the temperature of the program (3-5 ° C / min)A constant temperature was passed through 10 wtpercent aqueous solution of lactic acid at a flow rate of 0.5 ml / min,After 3 hours of reaction, the product was collected and subjected to product analysis,To gas chromatography as a detection tool,Using n-butanol as internal standard, using FFAP capillary column,Hydrogen flame (FID) detection,The results showed that the conversion of lactic acid was 100percentThe selectivity of propionic acid was 82.6percent. in water, Time= 3h, T= 300 °C , Catalytic behavior, Reagent/catalyst, Temperature Patent; (11 pag.); CN106431890; (2017); (A) Chinese View in Reaxys

O OH

HO O

Rx-ID: 32222673 View in Reaxys 3/34 Yield

Conditions & References With calcium phosphate-calcium pyrophosphate composite catalyst in water, Time= 27h, T= 390 °C , Inert atmosphere Hong, Ju Hyeong; Lee, Jong-Min; Kim, Hyungrok; Hwang, Young Kyu; Chang, Jong-San; Halligudi, Shiva B.; Han, Yo-Han; Applied Catalysis A: General; vol. 396; nb. 1-2; (2011); p. 194 - 200 View in Reaxys [0146] Dehydroxylation of Lactic Acid in a Water Solvent - Lactic Acid Concentration Effect. Starting compositions with 50percent and 60percent initial concentrations of lactic acid ("LA") in water as listed in Table 9 were reacted in the vapor phase with a (7.1percent Na2HPO4)/Na3/K-L-type zeolite, according to Reaction Protocol III above, for 5 hours at varying temperatures as listed in Table 9. [0147] As shown in Table 9, increasing the temperature led to an increase in the conversion but the selectivity was minimally changed at the higher temperature. Further, increasing

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the initial lactic acid concentration has minimal effect, at least at these concentrations, on the conversion and selectivity at the corresponding temperatures With (7.1percentNa2HPO4)/Na3/K-L-type zeolite in water, Time= 5h, T= 350 °C , Temperature, Concentration, Reagent/catalyst Patent; MYRIANT CORPORATION; OZMERAL, A., Cenan; GLAS, Joseph P.; DASARI, Rajesh; TANIELYAN, Setrak; BHAGAT, Ramesh Deoram; KASIREDDY, Mohan Reddy; SINGH, Ramnik; GNANADESIKAN, Vijay; AUGUSTINE, Robert L.; MORE, Santosh; WO2013/134385; (2013); (A1) English View in Reaxys 7.9 %Chromat., 7.4 %Chromat., 18.5 %Chromat.

Catalyst evaluation General procedure: The dehydration of lactic acid to acrylic acid over the catalysts was carried out in a fixed-bed quartz reactor with a 4mm inner diameter operated at atmospheric pressure. The catalyst (0.50–0.60 g, 20–40 meshes) was placed in the middle of the reactor and quartz wool was placed in both ends. Before catalytic evaluation the catalyst was pretreated at the required reaction temperature (400 °C) for 1.0 hunder high purity N2 (0.1 MPa, 1.0 mL/min). The feedstock (20 wt.percent solution of lactic acid) was then pumped into the preheating zone (lactic acid aqueous solution flow rate, 1.0 mL/h) and driven through the catalyst bed by nitrogen. The liquid products were condensed using ice-water bath and analyzed off-line using an SP-6890 gas chromatograph with a FFAP capillary column connected to an FID. Quantitative analysis of the products was carried out by the internal standard method using n-butanol as the internal standard material. GC–MS analyses of the samples were performed using Agilent 5973N Mass Selective Detector attachment. With barium phosphate in water, T= 400 °C , Flow reactor Tang, Congming; Peng, Jiansheng; Fan, Guoce; Li, Xinli; Pu, Xiaoli; Bai, Wei; Catalysis Communications; vol. 43; (2014); p. 231 - 234 View in Reaxys

79 %Chromat., 5.5 %Chromat., 9.4 %Chromat.

With aluminum oxide in water, T= 400 °C , p= 760.051Torr , Flow reactor, Inert atmosphere, Gas phase, Reagent/ catalyst Peng, Jiansheng; Li, Xinli; Tang, Congming; Bai, Wei; Green Chemistry; vol. 16; nb. 1; (2014); p. 108 - 111 View in Reaxys

23 %Chro- With sodium sulfate in water, T= 400 °C , p= 760.051Torr , Flow reactor, Inert atmosphere, Gas phase mat., 24.1 Peng, Jiansheng; Li, Xinli; Tang, Congming; Bai, Wei; Green Chemistry; vol. 16; nb. 1; (2014); p. 108 - 111 %ChroView in Reaxys mat., 27 %Chromat. 20.5 With calcium sulfate in water, T= 400 °C , p= 760.051Torr , Flow reactor, Inert atmosphere, Gas phase, Time %ChroPeng, Jiansheng; Li, Xinli; Tang, Congming; Bai, Wei; Green Chemistry; vol. 16; nb. 1; (2014); p. 108 - 111 mat., 7.6 View in Reaxys %Chromat., 68.6 %Chromat. 20.3 %Chromat., 9.4 %Chromat., 65.7 %Chromat.

With barium sulfate in water, T= 400 °C , p= 760.051Torr , Flow reactor, Inert atmosphere, Gas phase, Reagent/ catalyst, Temperature, Concentration, Time Peng, Jiansheng; Li, Xinli; Tang, Congming; Bai, Wei; Green Chemistry; vol. 16; nb. 1; (2014); p. 108 - 111 View in Reaxys

General procedure: The typical catalytic conversions of lactic acid to acrylic acid werecarried in a fixed-bed continuous-flow reactor under atmosphericpressure. Before reaction, the pelletized catalysts (0.2–1.0 g) werepretreated at 773 K for 3 h in Ar flow and cooled to 623 K. 38 wt.percent lacticacid aqueous solution (1.2 mL h−1) was introduced into the reactor by amicrosyringe pump with 40 mL min−1 of Ar gas. The products werecondensed in an ice–water trap. The collected liquid products were analyzedon a GC-FID (Shimadzu GC14B) with a Stabilwax-DA column.And, after the dilutions of the collected liquid products with distilledwater into 50 mL, they were analyzed using an HPLC (HITACHI LC-2000withUVdetector)with a Shodex KC811 column, and a total organiccarbon analyzer (TOC2000, Shimadzu). The gas product of acetaldehydewas determined by on-line GC-TCD (Shimadzu GC8A) with aGaskuro-

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pack 54. CO and CO2 were non-quantitatively analyzed by onlineGC-TCD. The lactic acid conversion and product yieldwere calculatedbased on the following equations: With HAP-300 in water, Time= 6h, T= 349.84 °C , Inert atmosphere Matsuura, Yumiko; Onda, Ayumu; Yanagisawa, Kazumichi; Catalysis Communications; vol. 48; (2014); p. 5 - 10 View in Reaxys With lanthanum phosphate nanorods in water, T= 350 °C , Inert atmosphere Guo, Zhen; Theng, De Sheng; Tang, Karen Yuanting; Zhang, Lili; Huang, Lin; Borgna, Armando; Wang, Chuan; Physical Chemistry Chemical Physics; vol. 18; nb. 34; (2016); p. 23746 - 23754 View in Reaxys 1 : Example 1 [Synthesis 1 of acrylic acid from lactic acid] The reaction was carried out using a high temperature high pressure microreaction system. Figure 2 shows the reaction part of the high-temperature high-pressure microreaction system.The reaction was carried out using a 10 m long double tube (FIG. 3) obtained by lining a copper tube having an inner diameter of 0.5 mm inside the pipe made of SUS 316 having an outer shape of 1/8 inch. Using lactic acid as a raw material as 2-hydroxycarboxylic acid,The reaction was carried out using acrylic acid as an α, β-unsaturated carboxylic acid as an objective substance.Lactic acid aqueous solution (0.11 M, 0.5 mL / min)High temperature and high pressure water (distilled water or ion exchanged water,2.0 mL / min) with a micro mixer,From room temperature (25 ° C.) to a predetermined temperature (300, 320, 340, 360, 380, 400 ° C., 420,A pressure of 40 MPa).The temperature after the temperature rise is,The temperature of the oven was adjusted so that the temperature difference between the entrance and the exit was less than 0.1 ° C as observed with a thermocouple.After mixing and raising the temperature and reacting in a reaction tube under high temperature and high pressure conditions, After cooling to a predetermined temperature (40 ° C.) with a cooler (heat exchanger)Finally, pressure was released via a back pressure valve.Reaction time isConverting from the density of water,46.8 seconds at 300 ° C., 44.7 seconds at 320 ° C., 39.7 seconds at 360 ° C., 36.4 seconds at 380 ° C., 32.0 seconds at 400 ° C. and 25.9 seconds at 420 ° C. .In the obtained sample,With clear aqueous solution,Analysis,Without special treatment,The aqueous solution was analyzed by liquid chromatography and gas chromatography (GC), and the product was analyzed. FIG. 4 shows a GC chart of the obtained sample (reaction temperature 380 ° C., reaction pressure 40 MPa, reaction time 36.4 seconds).HP-INNOWAX was used for the column, and the product was detected using the FID detector for the detector.Compound identification of each peak was made from GCMS and standard sample, and the yield of each compound was obtained by preparing a calibration curve using a standard sample. FIG. 5 shows,When conducted at each temperature, acrylic acid,Hydroxyacetone,Acetic acid,Propionic acid,Acetaldehyde,The yields of 3-methyl-2 (5H) -furanone were determined and shown in the graph.At 40 MPa,It was found that the maximum value exists between 360 ° C. and 380 ° C.,It was found that the yield of acrylic acid was highest at 85percent. At the same time, it was also found that the yield of acetaldehyde decreased to 10percent.Incidentally, including the following Examples 2 to 5,In either case, the raw lactic acid was not left and the conversion was 100percent.Therefore, in Examples 1 to 5, the selectivity and yield values were the same. FIG. 5 shows,When conducted at each temperature, acrylic acid,Hydroxyacetone,Acetic acid,Propionic acid,Acetaldehyde,The yields of 3-methyl-2 (5H) -furanone were determined and shown in the graph.At 40 MPa,It was found that the maximum value exists between 360 ° C. and 380 ° C.,It was found that the yield of acrylic acid was highest at 85percent. At the same time, it was also found that the yield of acetaldehyde decreased to 10percent.Incidentally, including the following Examples 2 to 5,In either case, the raw lactic acid was not left and the conversion was 100percent.for that reason,In Examples 1 to 5, the selectivity and yield values were the same. With water, copper, Time= 0.0101111h, T= 300 °C , p= 300030Torr , Autoclave, Green chemistry Patent; NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY; KAWANAMI, HAJIME; HATAKEDA, KIYOTAKA; ISHIZAKA, TAKAYUKI; NAGAO, IKUHIRO; (12 pag.); JP2017/14144; (2017); (A) Japanese View in Reaxys With barium sulfate, ammonia in water, Time= 24h, T= 420 °C , Temperature Li, Xinli; Chen, Zhi; Cao, Ping; Pu, Wenjie; Zou, Weixin; Tang, Congming; Dong, Lin; RSC Advances; vol. 7; nb. 86; (2017); p. 54696 - 54705 View in Reaxys

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Rx-ID: 37504351 View in Reaxys 4/34 Yield 5.2 %, 5.1 %, 1.0 %, 74.3 %

Conditions & References With 12percent Na2HPO4-modified NaY-20.1 (H2O/SiO2 molar ratio) in water, Time= 2h, T= 340 °C , Catalytic behavior, Reagent/catalyst, Temperature Zhang, Junfeng; Zhao, Yuling; Feng, Xinzhen; Pan, Min; Zhao, Jing; Ji, Weijie; Au, Chak-Tong; Catalysis Science and Technology; vol. 4; nb. 5; (2014); p. 1376 - 1385 View in Reaxys

2.5 %, 13.6 %, 1.1 %, 42 %

With NaY-20.1 (H2O/SiO2 molar ratio) in water, Time= 2h, T= 340 °C , Catalytic behavior, Reagent/catalyst, Temperature Zhang, Junfeng; Zhao, Yuling; Feng, Xinzhen; Pan, Min; Zhao, Jing; Ji, Weijie; Au, Chak-Tong; Catalysis Science and Technology; vol. 4; nb. 5; (2014); p. 1376 - 1385 View in Reaxys General procedure: The typical catalytic conversions of lactic acid to acrylic acid werecarried in a fixed-bed continuous-flow reactor under atmosphericpressure. Before reaction, the pelletized catalysts (0.2–1.0 g) werepretreated at 773 K for 3 h in Ar flow and cooled to 623 K. 38 wt.percent lacticacid aqueous solution (1.2 mL h−1) was introduced into the reactor by amicrosyringe pump with 40 mL min−1 of Ar gas. The products werecondensed in an ice–water trap. The collected liquid products were analyzedon a GC-FID (Shimadzu GC14B) with a Stabilwax-DA column.And, after the dilutions of the collected liquid products with distilledwater into 50 mL, they were analyzed using an HPLC (HITACHI LC-2000withUVdetector)with a Shodex KC811 column, and a total organiccarbon analyzer (TOC2000, Shimadzu). The gas product of acetaldehydewas determined by on-line GC-TCD (Shimadzu GC8A) with aGaskuropack 54. CO and CO2 were non-quantitatively analyzed by onlineGC-TCD. The lactic acid conversion and product yieldwere calculatedbased on the following equations: With calcium phosphate hydroxyapatite, ammonia, sodium hydroxide in water, Time= 6h, T= 349.84 °C , Inert atmosphere Matsuura, Yumiko; Onda, Ayumu; Yanagisawa, Kazumichi; Catalysis Communications; vol. 48; (2014); p. 5 - 10 View in Reaxys 13 : Catalytic dehydration of lactic acid using modified NaZSM-5 zeolite In the first set of experiments, NaZSM-5 zeolite was modified by impregnating one of the five different potassium phosphate compounds as provided in Table 7 and each of the modified NaZSM-5 zeolites was tested for their efficiency in vapor phase dehydration reaction. The vapor phase dehydration reaction using lactic acid as a reactant was carried out using the following experimental parameters: Gas flow rate: 55cc/mm; Feed: Heat treated 20percent USP lactic acid; Feed flow rate: 0.1 cc/mi; Temp: 330°C; Catalyst volume: 3 cc. As the results shown in Table 7 indicate among the five different potassium phosphate compound tested, monobasic potassium phosphate (KH2PO4) at 2mmol/g of zeolite was found to be efficient doping agent in terms of resulting in the formation of acetaldehyde as the only major side product in the vapor phase dehydration reaction using lactic acid for the production acrylic acid. With dipotassium hydrogenphosphate, Time= 3h, Reagent/catalyst Patent; MYRIANT CORPORATION; OZMERAL, Cenan; DASARI, Rajesh; SINGH, Ramnik; NODA, Yu; RIOUX, Robert, M.; ROMAN-LESHKOV, Yuriy; (102 pag.); WO2016/201181; (2016); (A1) English View in Reaxys Stage 1: With Cs-doped hydroxyapatite in water, T= 300 °C , p= 760.051Torr , Inert atmosphere Stage 2:T= 700 °C , Calcination, Reagent/catalyst Li, Xinli; Sun, Liangwei; Zou, Weixin; Cao, Ping; Chen, Zhi; Tang, Congming; Dong, Lin; ChemCatChem; vol. 9; nb. 24; (2017); p. 4621 - 4627 View in Reaxys With 96 wtpercent sodium ion-4 wtpercent potassium ion-exchanged 46 molar SiO2/Al2O3 ratio ZSM-11 zeolite in water, T= 360 °C , p= 760.051Torr , Flow reactor, Inert atmosphere, Reagent/catalyst Yan, Bo; Tao, Li-Zhi; Mahmood, Azhar; Liang, Yu; Xu, Bo-Qing; ACS Catalysis; vol. 7; nb. 1; (2017); p. 538 - 550 View in Reaxys

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Rx-ID: 40660706 View in Reaxys 5/34 Yield

Conditions & References

72.3 %

Stage 1: With Cs-doped hydroxyapatite in water, T= 300 °C , p= 760.051Torr , Inert atmosphere Stage 2:T= 400 °C , Calcination, Reagent/catalyst Li, Xinli; Sun, Liangwei; Zou, Weixin; Cao, Ping; Chen, Zhi; Tang, Congming; Dong, Lin; ChemCatChem; vol. 9; nb. 24; (2017); p. 4621 - 4627 View in Reaxys 2.4. Catalyst evaluation The synthesis of acetaldehyde from LA over the catalysts is carried out in a fixed-bed quartz reactor with an 4 mm inner diameter operated at atmospheric pressure. The catalyst (ca. 0.3 g, 20–40 meshes) is placed in the middle of the reactor and quartz wool is placed in both ends. Firstly, the catalyst is pretreated at the required reaction temperature (ca. 380 C) for 1.0 h under N2 withhigh purity (0.1 MPa, 1.0 mL/min). The feedstock (20 wtpercent solutionof LA) is then pumped into the reactor (LA aqueous solution flowrate, 1.0 mL/h) and driven through the catalyst bed by nitrogen. The contact time of reactant over the catalyst is around 0.5 s, and the contact time is estimated according to Eq. (1) [32,49]. The liquid products are condensed using ice-water bath and analyzed off-line using a SP-6890 gas chromatograph with a FFAP capillary column connected to a FID. Quantitative analysis of the products is carried out by the internal standard method using n-butanol as the internal standard material. GC–MS analyses of the samples are performed using Agilent 5973N Mass Selective Detector attachment. The reaction tail gas is analyzed using GC with a packed column of TDX-01 connected to TCD detector. The conversion of LA and the selectivity toward acetaldehyde or other by-products are calculated according to Eqs. (2) and (3). With Mg0388Al2408O4, T= 380 °C , p= 760.051Torr , pH= 7 - 8, Gas phase, Reagent/catalyst, Concentration Tang, Congming; Zhai, Zhanjie; Li, Xinli; Sun, Liangwei; Bai, Wei; Journal of Catalysis; vol. 329; (2015); p. 206 217; Art.No: 11766 View in Reaxys

Rx-ID: 45933555 View in Reaxys 6/34 Yield

Conditions & References

15.6 %, 7.3 %, 6.4 %

With cobalt, zinc in water, Time= 1h, T= 300 °C , Green chemistry Huo, Zhibao; Xiao, Jiefeng; Ren, Dezhang; Jin, Fangming; Wang, Tian; Yao, Guodong; Green Chemistry; vol. 19; nb. 5; (2017); p. 1308 - 1314 View in Reaxys

Rx-ID: 45933556 View in Reaxys 7/34 Yield

Conditions & References

17.8 %, 47.3 %, 30.9 %

O OH

With cobalt, zinc in water, Time= 2h, T= 250 °C , Green chemistry, Concentration, Temperature, Reagent/catalyst Huo, Zhibao; Xiao, Jiefeng; Ren, Dezhang; Jin, Fangming; Wang, Tian; Yao, Guodong; Green Chemistry; vol. 19; nb. 5; (2017); p. 1308 - 1314 View in Reaxys

HO O

Rx-ID: 46854214 View in Reaxys 8/34

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Yield

Conditions & References 1 : compartive Example 1 [Synthesis of Acrylic Acid from Lactic Acid 4 - Influence Survey of the Type of Alloy 1] The reaction was carried out using a high temperature high pressure microreaction system. Figure 2 shows the reaction part of the high-temperature high-pressure microreaction system.The reaction was carried out using a 10 m long double tube (FIG. 3) obtained by lining a copper tube having an inner diameter of 0.5 mm inside the pipe made of SUS 316 having an outer shape of 1/8 inch. Using lactic acid as a raw material as 2-hydroxycarboxylic acid,The reaction was carried out using acrylic acid as an α, β-unsaturated carboxylic acid as an objective substance.Lactic acid aqueous solution (0.11 M, 0.5 mL / min)High temperature and high pressure water (distilled water or ion exchanged water,2.0 mL / min) with a micro mixer,From room temperature (25 ° C.) to a predetermined temperature (300, 320, 340, 360, 380, 400 ° C., 420,A pressure of 40 MPa).The temperature after the temperature rise is,The temperature of the oven was adjusted so that the temperature difference between the entrance and the exit was less than 0.1 ° C as observed with a thermocouple.After mixing and raising the temperature and reacting in a reaction tube under high temperature and high pressure conditions, After cooling to a predetermined temperature (40 ° C.) with a cooler (heat exchanger)Finally, pressure was released via a back pressure valve.Reaction time isConverting from the density of water,46.8 seconds at 300 ° C., 44.7 seconds at 320 ° C., 39.7 seconds at 360 ° C., 36.4 seconds at 380 ° C., 32.0 seconds at 400 ° C. and 25.9 seconds at 420 ° C. .In the obtained sample,With clear aqueous solution,Analysis,Without special treatment,The aqueous solution was analyzed by liquid chromatography and gas chromatography (GC), and the product was analyzed. FIG. 4 shows a GC chart of the obtained sample (reaction temperature 380 ° C., reaction pressure 40 MPa, reaction time 36.4 seconds).HP-INNOWAX was used for the column, and the product was detected using the FID detector for the detector.Compound identification of each peak was made from GCMS and standard sample, and the yield of each compound was obtained by preparing a calibration curve using a standard sample. FIG. 5 shows,When conducted at each temperature, acrylic acid,Hydroxyacetone,Acetic acid,Propionic acid,Acetaldehyde,The yields of 3-methyl-2 (5H) -furanone were determined and shown in the graph.At 40 MPa,It was found that the maximum value exists between 360 ° C. and 380 ° C.,It was found that the yield of acrylic acid was highest at 85percent. At the same time, it was also found that the yield of acetaldehyde decreased to 10percent.Incidentally, including the following Examples 2 to 5,In either case, the raw lactic acid was not left and the conversion was 100percent.Therefore, in Examples 1 to 5, the selectivity and yield values were the same. As the material of the reaction tube, SUS 316,Hastelloy (registered trademark) C-276,Alternatively, acrylic acid was synthesized under the same conditions as in Example 1 except that an alloy system of Inconel 625 was used.result,In any of the alloys, the yield of acrylic acid remained at only about 14percent at the maximum, and it turned out that there was not much effect.Also, in the case of using SUS 316, the breakdown of products at 400 ° C. and 40 MPa is as follows:49percent acetaldehyde,1.5percent of hydroxyacetone,8.2percent of acetic acid,Propionic acid is 29percent7.9percent acrylic acid,Other (furanone etc.) is 4.2percentBy-products other than acrylic acid, Especially propionic acid and acetaldehyde were found to be the main products. With water, copper, T= 400 °C , p= 300030Torr , Autoclave, Green chemistry Patent; NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY; KAWANAMI, HAJIME; HATAKEDA, KIYOTAKA; ISHIZAKA, TAKAYUKI; NAGAO, IKUHIRO; (12 pag.); JP2017/14144; (2017); (A) Japanese View in Reaxys

HO O

Rx-ID: 29898111 View in Reaxys 9/34 Yield 34 %, 8 %

Conditions & References With 20 wtpercent H4PVMo11O40 on CARiACT.(R). Q-15 supported in water, Time= 16h, T= 274.84 °C , Inert atmosphere Katryniok, Benjamin; Paul, Sebastien; Dumeignil, Franck; Green Chemistry; vol. 12; nb. 11; (2010); p. 1910 1913 View in Reaxys With iron(II) oxide, T= 390 °C , Inert atmosphere, Reagent/catalyst Li, Xinli; Zhai, Zhanjie; Tang, Congming; Sun, Liangwei; Zhang, Yu; Bai, Wei; RSC Advances; vol. 6; nb. 67; (2016); p. 62252 - 62262 View in Reaxys

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H HO

Rx-ID: 42413378 View in Reaxys 10/34 Yield

Conditions & References

44 %

With Cs beta zeolite, Time= 10h, T= 360 °C Yan, Bo; Mahmood, Azhar; Liang, Yu; Xu, Bo-Qing; Catalysis Today; vol. 269; (2016); p. 65 - 73 View in Reaxys

Rx-ID: 43026709 View in Reaxys 11/34 Yield

Conditions & References With iron(II,III) oxide, T= 390 °C , Inert atmosphere, Reagent/catalyst Li, Xinli; Zhai, Zhanjie; Tang, Congming; Sun, Liangwei; Zhang, Yu; Bai, Wei; RSC Advances; vol. 6; nb. 67; (2016); p. 62252 - 62262 View in Reaxys

O O

HO O

Rx-ID: 38453301 View in Reaxys 12/34 Yield

Conditions & References With nonstoichiometric calcium pyrophosphate in water, T= 375 °C , Flow reactor, Reagent/catalyst, Temperature Ghantani, Vidhya C.; Dongare, Mohan K.; Umbarkar, Shubhangi B.; RSC Advances; vol. 4; nb. 63; (2014); p. 33319 - 33326 View in Reaxys O

HO O

O O

Rx-ID: 38942332 View in Reaxys 13/34 Yield

Conditions & References 2.3 Catalytic testing General procedure: Dehydration of lactic acid was conducted in a fixed bed reactor (inner diameter 14 mm) operating at atmospheric pressure. A 20 weight percent aqueous solution of lactic acid was fed using 307 HPLC pump (Gilson), vaporized at 170 °C with home-made system and diluted with N2. The vaporization temperature was determined from liquid vapor equilibrium simulated by the ProSim plus software (ProSim S.A.). The feed composition was LA/H2O/N2: 3/66/31. Before addition of the vaporized LA solution, the reactor was heated at the reaction temperature under N2. The contact time was varied from 0.1 to 4.1 s (GHSV from 36,000 to 880 h−1). Condensable molecules were collected in a cold trap at −4 °C and analyzed off-line with a GC-2014 chromatograph (Shimadzu) equipped with AOC-20i auto injector, ZB-WAXplus (30 m, 0.32 mm) column and FID detector, while gas products, mainly CO, CO2 and N2 were analyzed online with the same chromatograph but using sampling valve, Carboxen 1000 column and TCD detector. With calcium pyrophosphate, nitrogen, water, T= 170 °C , Kinetics, Reagent/catalyst, Time Blanco; Delichere; Millet; Loridant; Catalysis Today; vol. 226; (2014); p. 185 - 191 View in Reaxys

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O O

Rx-ID: 38942333 View in Reaxys 14/34 Yield

Conditions & References 2.3 Catalytic testing General procedure: Dehydration of lactic acid was conducted in a fixed bed reactor (inner diameter 14 mm) operating at atmospheric pressure. A 20 weight percent aqueous solution of lactic acid was fed using 307 HPLC pump (Gilson), vaporized at 170 °C with home-made system and diluted with N2. The vaporization temperature was determined from liquid vapor equilibrium simulated by the ProSim plus software (ProSim S.A.). The feed composition was LA/H2O/N2: 3/66/31. Before addition of the vaporized LA solution, the reactor was heated at the reaction temperature under N2. The contact time was varied from 0.1 to 4.1 s (GHSV from 36,000 to 880 h−1). Condensable molecules were collected in a cold trap at −4 °C and analyzed off-line with a GC-2014 chromatograph (Shimadzu) equipped with AOC-20i auto injector, ZB-WAXplus (30 m, 0.32 mm) column and FID detector, while gas products, mainly CO, CO2 and N2 were analyzed online with the same chromatograph but using sampling valve, Carboxen 1000 column and TCD detector. With calcium pyrophosphate, nitrogen, water, T= 380 °C , Reagent/catalyst, Time Blanco; Delichere; Millet; Loridant; Catalysis Today; vol. 226; (2014); p. 185 - 191 View in Reaxys

H HO

HO OH

Rx-ID: 35746880 View in Reaxys 15/34 Yield

Conditions & References

8 %Spectr. With bis(acetylacetonato)dioxidomolybdenum(VI), sodium hydroxide in Triethylene glycol dimethyl ether, water, T= 220 - 270 °C , Inert atmosphere, Reagent/catalyst, Solvent, Pressure Korstanje, Ties J.; Kleijn, Hendrik; Jastrzebski, Johann T. B. H.; Klein Gebbink, Robertus J. M.; Green Chemistry; vol. 15; nb. 4; (2013); p. 982 - 988 View in Reaxys

H HO

O Na +

O–

Rx-ID: 35746881 View in Reaxys 16/34 Yield

Conditions & References

41 %Spectr.

With bis(acetylacetonato)dioxidomolybdenum(VI), sodium hydroxide in water, T= 200 - 270 °C , Inert atmosphere, Solvent, Temperature Korstanje, Ties J.; Kleijn, Hendrik; Jastrzebski, Johann T. B. H.; Klein Gebbink, Robertus J. M.; Green Chemistry; vol. 15; nb. 4; (2013); p. 982 - 988 View in Reaxys

HO 2

O– Ca 2+ O

O Na + O–

Rx-ID: 35746882 View in Reaxys 17/34 Yield Ca. 20 %

Conditions & References With bis(acetylacetonato)dioxidomolybdenum(VI) in water, T= 200 - 270 °C , Inert atmosphere

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Korstanje, Ties J.; Kleijn, Hendrik; Jastrzebski, Johann T. B. H.; Klein Gebbink, Robertus J. M.; Green Chemistry; vol. 15; nb. 4; (2013); p. 982 - 988 View in Reaxys

O OH

Rx-ID: 36232479 View in Reaxys 18/34 Yield

Conditions & References [0152]Dehydroxylation of Lactic Acid in a Solvent — Solvent Effect. A starting composition as listed in Table 12 was reacted in the vapor phase with a Na3/K-L-type zeolite, according to Reaction Protocol III above, for 4 hours at 340°C.[0153]As shown in Table 12, a Na3/K-L-type zeolite does catalyze esterificationreactions. Further, the addition of an alcohol in the starting composition appears to haveeffect on the conversion but does dramatically reduce the selectivity to acrylic acid. With Na3/K-L-type zeolite in water, Time= 4h, T= 340 °C Patent; MYRIANT CORPORATION; OZMERAL, A., Cenan; GLAS, Joseph P.; DASARI, Rajesh; TANIELYAN, Setrak; BHAGAT, Ramesh Deoram; KASIREDDY, Mohan Reddy; SINGH, Ramnik; GNANADESIKAN, Vijay; AUGUSTINE, Robert L.; MORE, Santosh; WO2013/134385; (2013); (A1) English View in Reaxys

Rx-ID: 36232480 View in Reaxys 19/34 Yield

O OH

HO O

Rx-ID: 29315702 View in Reaxys 20/34 Yield

Conditions & References With hydrogen, silica gel in water, T= 349.84 °C , p= 42754.3Torr , Mechanism, Reagent/catalyst Carlos Serrano-Ruiz, Juan; Dumesic, James A.; Green Chemistry; vol. 11; nb. 8; (2009); p. 1101 - 1104 View in Reaxys

Rx-ID: 30265869 View in Reaxys 21/34 Yield

Conditions & References With hydrogen, T= 199.84 °C , Gas phase

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Simonov; Simakova; Minyukova; Khassin; Russian Chemical Bulletin; vol. 58; nb. 6; (2009); p. 1114 - 1118 View in Reaxys

O C

Rx-ID: 4816920 View in Reaxys 22/34 Yield

Conditions & References

14 %, 9.1 With sodium nitrate, silica gel, sodium lactate, Time= 2.2h, T= 315 °C , p= 4500.4Torr , ΔE(excit.); var. temp. and %, 12.5 %, time, Product distribution, Rate constant, Thermodynamic data 1.6 %, 3.1 Wadley, Douglas C.; Tam, Man S.; Kokitkar, Prashant B.; Jackson, James E.; Miller, Dennis J.; Journal of Cat%, 7.8 % alysis; vol. 165; nb. 2; (1997); p. 162 - 171; Art.No: CA971484 View in Reaxys

Rx-ID: 1698292 View in Reaxys 23/34 Yield

Conditions & References

4.3 %, 1.9 %, 0.9 %, 0.6 %, 2.0 %

With aluminum oxide, silica gel, sodium phosphate, T= 300 °C , p= 3750.3Torr , mechanism, var. sodium phosphate salts, temp. and contact times, Product distribution, Thermodynamic data, Equilibrium constant Gunter, Garry C.; Miller, Dennis J.; Jackson, James E.; Journal of Catalysis; vol. 148; nb. 1; (1994); p. 252 - 260 View in Reaxys

O O

HO O

Rx-ID: 1698293 View in Reaxys 24/34 Yield

Conditions & References With water, sulfuric acid, Time= 0.00916667h, T= 385 °C , p= 258574Torr , other carboxylic acids; effects of pH, residence time, temperature, concentration, and solvent density, Product distribution, Mechanism Mok, William Shu-Lai; Antal, Michael Jerry; Jones, Maitland; Journal of Organic Chemistry; vol. 54; nb. 19; (1989); p. 4596 - 4602 View in Reaxys

OH O

Rx-ID: 3949021 View in Reaxys 25/34 Yield

Conditions & References

3 % Chromat., 43 % Chromat., 1 % Chromat., 1 % Chromat., 3.4 % Chromat., 24 % Chromat.

O OH

With lt;PtH(PEt3)3gt;OH in water, Time= 2h, T= 230 °C , pH = 2; investigated effect of reaction conditions and the effect of different catalysts, Product distribution Odell, Barbara; Earlam, George; Cole-Hamilton, David J.; Journal of Organometallic Chemistry; vol. 290; (1985); p. 241 - 248 View in Reaxys

HO O

OH O

Rx-ID: 3949022 View in Reaxys 26/34

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Yield

Conditions & References

6.3 % Chromat., 50.5 % Chromat., 1.1 % Chromat., 24 % Chromat.

With lt;PtH(PEt3)3gt;OH in water, Time= 0.25h, T= 250 °C , pH = 2 Odell, Barbara; Earlam, George; Cole-Hamilton, David J.; Journal of Organometallic Chemistry; vol. 290; (1985); p. 241 - 248 View in Reaxys

Rx-ID: 3949023 View in Reaxys 27/34 Yield

Conditions & References

19 % Chromat., 13.0 % Chromat., 1 % Chromat.

With lt;PtH(PEt3)3gt;OH in water, Time= 2h, T= 220 °C , pH = 7 Odell, Barbara; Earlam, George; Cole-Hamilton, David J.; Journal of Organometallic Chemistry; vol. 290; (1985); p. 241 - 248 View in Reaxys

O O

Rx-ID: 6681729 View in Reaxys 28/34 Yield

Conditions & References durch Clostridium propionicum Cardon; Barker; Archives of Biochemistry; vol. 12; (1947); p. 169 View in Reaxys

O O

Rx-ID: 6681790 View in Reaxys 29/34 Yield

Conditions & References aerobe Oxydation durch belueftete und gewaschene Kulturen von Propionibacterium arabinosum Erb,Wood,Werkman; ; vol. 31; (1936); p. 599; Chem. Zentralbl.; vol. 107; nb. II; (1936); p. 1188 View in Reaxys

O O

HO O

Rx-ID: 6681725 View in Reaxys 30/34 Yield

Conditions & References Vergaerung durch Abwasserbakterien Tarvin; Buswell; Journal of the American Chemical Society; vol. 56; (1934); p. 1753 View in Reaxys

O– Na +

water

hydrogen

nickel (II)-oxide

methylethylacetic acid (?) O

Rx-ID: 8427139 View in Reaxys 31/34

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Yield

Conditions & References T= 270 °C , p= 53200Torr , in Gegenwart Tonerde; Produkt 5: dl-Brenzweinsaeure Ipatjew; Rasuwajew; Chemische Berichte; vol. 59; (1926); p. 2032; Zhurnal Russkago Fiziko-Khimicheskago Obshchestva; vol. 58; (1926); p. 1347 View in Reaxys O–

HO 2

Ca 2+

O 5 H

H 2N 2

Rx-ID: 737774 View in Reaxys 32/34 Yield

Conditions & References bei der Einw. von Bac. propionicus Virtanen; ; vol. 1; nb. 36; p. 2,11; Chem. Zentralbl.; vol. 95; nb. II; (1924); p. 54 View in Reaxys

sodium hydroxide OH

OH H

HO O

Rx-ID: 6681730 View in Reaxys 33/34 Yield

Conditions & References T= 270 - 290 °C Nef; Justus Liebigs Annalen der Chemie; vol. 335; (1904); p. 323; Justus Liebigs Annalen der Chemie; vol. 357; (1907); p. 215,300 View in Reaxys

I OH

HO O

Rx-ID: 6681717 View in Reaxys 34/34 Yield

Conditions & References Lautemann; Justus Liebigs Annalen der Chemie; vol. 113; (1860); p. 217 View in Reaxys

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