Oilseed Fatty Acids Chemistry, Processing, and Conversion

Oilseed Fatty Acids Chemistry, Processing, and Conversion

Terry A. Isbell USDA-ARS Bio-Oils Research Unit National Center for Agricultural Utilization Research

UOP Renewable Jet Fuel Process™ Isomerization/ Product Selective Cracking Separation Reactor

Deoxygenation Reactor

Hydrogen Light Fuels

Acid Gas (to treating)

Feedstocks

Bio-SPK (HRJ)

Water (to treating)

Green Diesel (HRD)

 Feedstock flexible  Optimized for maximum distillate yield (SPK + Green Diesel)  Possible to achieve maximum conversion to SPK  Makes valuable hydrocarbon co-products - Green Diesel - Green Naphtha - Green LPG  Ability to swing SPK and Green Diesel production to meet market demands Diagram simplified for clarity

Commercial scale, proven technology

Cultivars for Stress Trials

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Habit Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring Winter Winter Winter Winter Winter Winter

Species B. napus B. napus B. napus B. napus B. carinata B. carinata B. carinata B. carinata B. juncea B. juncea C. sativa B. rapa S. alba S. alba B. napus B. napus B. napus B. napus C. sativa B. rapa

Type Canola Canola Industrial Industrial Industrial Industrial Industrial Industrial Industrial Industrial Industrial Industrial Industrial Industrial Canola Canola Industrial Industrial Industrial Industrial

Cultivar DK3042RR Cara Gem Hero #1 #2 #3 #4 P45J10 Pacific Gold Calena Goldrush Idagold Tilney Wichita Amanda Durola Dwarf Essex Joelle Salut

Source Dekalb UI UI UI Agrisoma Agrisoma Agrisoma Agrisoma Pioneer UI ARS Morris UI UI UI KSU UI UI UI ARS-Morris UI

Cultivar Oil Yield/Hectare 1800 1600

Oil Yield (Kg/Ha)

1400 1200 1000 800 600 400 200 0

Carinata

Juncea

Napus

Canola

Cultivar

Rapa

Camelina Sinapis

Canola Oil Yield/Hectare 1800 1600

DK3042RR Invigor SC28

Oil Yield (Kg/Ha)

1400 1200 1000 800 600 400 200 0

Ames

Mandan

Morris

Moscow

Location

Sidney

Temple

Chemical Diversity for Conversion Cultivar

Oil Yield Location Kg/Ha

Sat

Mono

Poly

18:1

18:2

18:3

Erucic

Carinata

Morris

1432

6.2

56.2

32.2

9.0

16.8

13.4

40.2

Juncea

Morris

1006

6.2

66.5

24.0

61.6

14.3

9.4

1.8

Juncea

Morris

1146

6.6

55.6

34.6

20.7

21.6

11.5

22.4

Napus

Morris

1090

5.8

68.3

22.3

14.7

12.7

8.9

45.6

Canola

Moris

1755

7.1

62.9

27.5

61.7

18.4

8.8

0.1

Camelina

Mandan

409

11.6

29.5

56.6

19.3

20.4

35.2

1.3

Sinapis

Morris

556

5.3

69.0

22.3

28.1

11.4

10.6

30.2

Screw Pressing

French Model 324 Seed Cooker/Conditioner

French Model L-250 Screw Press

Oil Extraction Cultivar

Seed MC (%)

Oil (%, db)

Oil Extraction

Seed Cooking

Oil in Meal (%)

B. carinata AAC A110

5.2

46.0

Scott Tech Screw Press

No

21.7

B. juncea Oasis

5.2

45.6

Scott Tech Screw Press

No

20.0

B. juncea Pacific Gold

9.5

39.9

French Screw Press

Yes

7.6

B. napus Gem

5.6

46.5

French Screw Press

Yes

10.8

B. napus Invigor L130

6.5

47.5

French Screw Press

Yes

14.3

C. sativa Joelle

11.9

36.9

French Screw Press

Yes

4.2

S. alba Tilney

5.4

26.5

Scott Tech & Hexane

No

0.5

T. arvense

9.2

32.0

French Screw Press

Yes

4.9

Oil Extraction Cold pressing leaves significant amount of oil in the cake. Oil yield may be improved by double pressing.

Full pressing oilseeds with oil content < 40% can be effectively extracted in one pass with good yields.

Oilseeds with oil content > 40% may require a screw press with different screw configuration.

Prepressing followed by hexane extraction provided the maximum oil yield. This process is only economically feasible when operated at large capacities.

Vegetable Oil Refining

X X

Steps

Contaminants removed

Degumming

Hydrated phospholipids Sulfur compounds

Chemical refining

Free fatty acids (Soap) Phospholipids Metals Sulfur compounds

Bleaching

Pigments Residual phospholipids Residual soap Metals

Winterization

Waxes Saturated TAGs

Deodorization

Oxidation products Free fatty acid Some tocopherols/sterols Other volatiles

Phosphorus and Sulfur Contents of Processed Oils (ppm) Cultivar

Crude

Degummed

Bleached

P

S

P

S

P

S

B. Carinata (AAC A110)

15.9

16.0

9.3

14.6

< DL

9.9

B. Juncea (Oasis)

-

-

16.2

4.8

< DL

4.1

B. Juncea Pacific Gold)

59.5

53.6

13.8

31.4

< DL

11.2

-

-

10.6

5.6

< DL

3.7

B. Napus Invigor L130)

93.4

10.0

< DL

4.8

< DL

4.3

C. Sativa Joelle)

110.0

19.7

0.4

13.7

< DL

5.6

S. Alba Tilney)

131.9

16.9

0.0

7.6

< DL

5.0

111

107

30

90

< DL

56

B. Napus Gem)

T. arvense

HRJ Product Yield (% of Total Distillate) Oil

Jet

Heavy Diesel

Soybean

60.3

18.0

Invigor

61.2

18.3

Pacific Gold

66.7

13.2

Gem

66.7

13.2

Product Yield (Soybean) Item H2 CO2 CO C1 C2 C3 iC4 nC4 iC5 nC5 C6—180°F 180°F—240°F 240°F—553°F (Jet) 553°F—EBP (Hvy. Diesel) H2O

SOR, vol * 402.6 12.8 0.1 1.5 1.0 31.0 1.52 3.03 4.47 1.53 8.22 7.68 60.30 18.03

SOR, %wt 3.92 2.72 0.01 0.12 0.15 6.61 0.92 1.91 3.02 1.04 5.82 5.70 49.30 15.22 8.27

EOR, vol * 359.2 28.4 0.1 1.9 1.2 31.1 2.23 3.19 4.99 1.64 8.67 8.07 59.08 17.59

EOR, %wt 3.50 6.05 0.01 0.15 0.18 6.63 1.36 2.01 3.37 1.12 6.15 6.00 48.30 14.85 9.03

* vol yields in nm3/m3 for gas products H2,CO2,CO,C1,C2,C3, in % for liquid products C4+

78 vol % total distillate yield, with 60 vol % Renewable Jet

Product Yield (Invigor) Item H2 CO2 CO C1 C2 C3 iC4 nC4 iC5 nC5 C6—180°F 180°F—240°F 240°F—553°F (Jet) 553°F—EBP (Hvy. Diesel) H2O

SOR, vol * 380.0 12.6 0.1 1.5 1.0 30.8 1.54 3.07 4.52 1.54

SOR, %wt 3.70 2.69 0.01 0.12 0.15 6.56 0.94 1.94 3.06 1.06

EOR, vol * 336.6 28.2 0.1 1.9 1.2 30.9 2.22 3.17 4.97 1.64

EOR, %wt 3.28 5.99 0.01 0.15 0.18 6.58 1.36 2.01 3.36 1.12

7.95 7.79 61.16 18.28

5.91 5.79 50.00 15.44 10.05

8.26 8.06 58.98 17.56

6.14 5.99 48.22 14.83 7.35

* vol yields in nm3/m3 for gas products H2,CO2,CO,C1,C2,C3, in % for liquid products C4+

79 vol % total distillate yield, with 61 vol % Renewable Jet

Product Yield (Pacific Gold) Item H2 CO2 CO C1 C2 C3 iC4 nC4 iC5 nC5 C6—180°F 180°F—240°F 240°F—553°F (Jet) 553°F—EBP (Hvy. Diesel) H2O

SOR, vol * 380.3 12.2 0.1 1.5 1.0 27.8 4.60 1.93 4.53 1.54 7.01 8.63 66.65 13.24

SOR, %wt 3.70 2.58 0.01 0.12 0.15 5.91 2.80 1.22 3.06 1.05 5.20 6.40 54.38 11.20 9.62

EOR, vol * 337.9 27.0 0.1 1.9 1.2 27.9 5.25 2.06 4.98 1.64 7.34 8.90 64.42 12.58

EOR, %wt 3.29 5.73 0.01 0.15 0.18 5.94 3.20 1.30 3.36 1.12 5.44 6.60 52.56 10.65 7.04

* vol yields in nm3/m3 for gas products H2,CO2,CO,C1,C2,C3, in % for liquid products C4+

~80

vol % total distillate yield, with 65.65 vol % Renewable

Jet Comparable total distillate yield with shift towards higher jet yield

Product Yield (Gem) Item H2 CO2 CO C1 C2 C3 iC4 nC4 iC5 nC5 C6—180°F 180°F—240°F 240°F—553°F (Jet) 553°F—EBP (Hvy. Diesel) H2O

SOR, vol * 363.9 11.9 0.1 1.6 1.0 27.8 4.60 1.94 4.53 1.55 7.02 8.64 66.70 13.25

SOR, %wt 3.54 2.53 0.01 0.12 0.15 5.91 2.80 1.22 3.06 1.05 5.20 6.40 54.42 11.21 9.45

EOR, vol * 323.6 26.5 0.1 1.9 1.2 27.9 5.26 2.06 4.99 1.64 7.35 8.91 64.49 12.60

EOR, %wt 3.15 5.63 0.01 0.15 0.18 5.94 3.20 1.30 3.37 1.12 5.45 6.61 52.62 10.66 6.91

* vol yields in nm3/m3 for gas products H2,CO2,CO,C1,C2,C3, in % for liquid products C4+

~80 vol % total distillate yield, with 66.7 vol % Renewable Jet Highest production of total distillate with highest jet yield

Summary • UOP Renewable Jet technology commercially proven, providing fuels for regular flights –Current commercial production based on first-generation feedstocks –Use of non-edible oils has been demonstrated in pilot plants • Lab processing of seed oil samples in progress, to be completed by May 2017 • Modeling indicates that oils with more long-chain carbon molecules are advantageous for jet fuel production –Hydrogen consumption dominated by degree of unsaturation

Acknowledgements The brassica HRJ work is funded under NIFA Biomass Research and Development Initiative Award # 2012-10008-19727 (August 1, 2012 â&#x20AC;&#x201C; July 31, 2017).

Brett Allen David Archer Jason Bergtold Rick Brenner Jack Brown David Buland Shawn Conners John Dyer Roque Evangelista Cornelia Flora Elodie Gazave Russ Gesch Michael Gore David Grant Jerry Hatfield Kim Hunter Jay Jarbo Jim Kiniry Dan Long Emily Oblath Lynn Shi David Shonnard Erica Tassone Terry Tomlinson Merle Vigil