Extraction, Purification and Catalytic Upgrading of Algae ...algaebiomass.org/wp-content/gallery/2012-algae-biomass-summit/201… · Extraction, Purification and Catalytic Upgrading

Extraction, Purification and Catalytic Upgrading of Algae Lipids to Fuel-

like Hydrocarbons

Eduardo Santillan-JimenezTonya MorganRyan LoeRobert PaceSarah MarquesMark Crocker

Washington, D.C.October 2, 2015

Rationale for Hydrocarbon Biofuels

•  Oxygenated fuel

•  Good cetane number

•  Good lubricity

•  Compatibility issues

•  Poor cold flow properties

•  Low storage stability

•  Deoxygenated fuel

•  Fungible with fossil fuels

•  Diesel, gasoline or jet fuel

•  Full compatibility

•  Better performance

•  Lower emissions

Hydrocarbons

A number of advantages make hydrocarbon biofuels preferable to biodiesel

http://www.nesteoil.com/default.asp?path=1,41,11991,12243,12335http://www.uop.com/processing-solutions/biofuels/green-diesel/#green-diesel-biodiesel

http://dynamicfuelsllc.com/wp-news/frequently-ask-questions/

Biodiesel (FAMEs)

2

Comparison of HDO and DeCOx

Hydrodeoxygenation (HDO)

Decarboxylation/decarbonylation (deCOx)

DeCOx represents an interesting alternative to HDO

•  Simple supported metal catalysts•  Lower pressures of hydrogen and hydrogen utilization

•  Problematic sulfided catalysts•  High pressures of hydrogen and hydrogen utilization

E. Santillan-Jimenez, M. Crocker, J. Chem. Technol. Biotechnol. 87 (2012) 1041 3

Pd vs. Ni-Catalyzed DeCOx of Lipids

Ni is a promising replacement for Pd in deCOx catalysts, particularly because its cost is ~1,550 times lower

Catalyst Conversion (%)

Selectivity to [Yield of] C10-C17 (%)

Selectivity to [Yield of] C17 (%)

5 wt.% Pd/C 86 86 [74] 33 [28]

20 wt.% Ni/C 81 75 [61] 30 [24]

Conversion of tristearin under N2 atmosphere

360 °C, 40 bar, 6 h, semi-batch reactor

•  Ni affords near-comparable hydrocarbon yields to Pd•  Negligible amounts of C18 are produced

•  The reaction proceeds in the absence of hydrogen

W.F. Maier, W. Roth, I. Thies, P.V.R. Schleyer, Chem. Ber. 115 (1982) 808M. Sna re, I. Kubickova , P. Ma ki-Arvela, K. Era nen, D.Y. Murzin, Ind. Eng. Chem. Res. 45 (2006) 5708

T. Morgan, D. Grubb, E. Santillan-Jimenez, M. Crocker, Top. Catal. 53 (2010) 820 4

Effect of Hydrogen on DeCOx of Lipids

High C-C bond hydrogenolysis activity of Ni relative to Pd leads to lower yields of long chain hydrocarbons

Catalyst Gas Conversion (%)

Selectivity to [Yield of]

C10-C17 (%)

Selectivity to [Yield of] C17 (%)

5 wt.% Pd/C 10% H2/N2 98 95 [93] 81 [79]

5 wt.% Pd/C H2 95 84 [80] 67 [64]

20 wt.% Ni/C 10% H2/N2 88 75 [66] 53 [47]

20 wt.% Ni/C H2 99 77 [76] 55 [54]

Conversion of tristearin under different H2 atmospheres

360 °C, 40 bar, 6 h, semi-batch reactor; standard deviation (conversion & selectivity) < 4.3%

•  The presence of H2 was found to be beneficial•  Best results over Pd and Ni were obtained with dilute and pure H2,

respectively

E. Santillan-Jimenez, T. Morgan, J. Lacny, S. Mohapatra, M. Crocker, Fuel 103 (2013) 1010 5

Screening of Ni Catalysts

Lipids can be efficiently converted to fuel-like hydrocarbons at temperatures as low as 260 °C

Conversion of tristearin over Ni-based catalysts under H2

•  Lower temperatures lead to higher selectivity to C10-C17•  This is indicative of decreased hydrogenolysis/cracking

40 bar, 6 h, semi-batch reactor

Catalyst Reaction temp. (°C)

Conversion (%)

Selectivity to [Yield of]

C10-C17 (%)

Selectivity to [Yield of] C17 (%)

20% Ni/Al2O3 260 30 89 [26] 59 [17]

20% Ni/ZrO2 260 100 91 [91] 50 [50]

Ni-Al LDH 260 100 98 [98] 42 [42] Ni-Al LDH 360 100 81 [81] 8 [8]

6

Structure and Formula of Ni-Al LDH

Structure of Layered Double Hydroxides

Layered Double Hydroxides have been observed to have interesting catalytic properties

•  Positively charged layers are weakly bound – and charge-balanced by – anions in the interlayer region

•  Formula: [Ni0.67Al0.33(OH)2][CO3]0.17⋅H2O

7

Effect of Reaction Temperature

Higher temperatures favor the occurrence of cracking reactions and the formation of lighter hydrocarbons

0.5 g of catalyst, 1.33 wt.% triolein in C12 fed at 0.2 mL/min, 40 bar H2 fed at 50 mL/min

Conversion of triolein over Ni-Al LDH in a fixed-bed reactor

B. Peng, X. Yuan, C. Zhao, J.A. Lercher, J. Am. Chem. Soc. 134 (2012) 9400

0

100

200

300

400

500

600

700

800

0 20 40 60 80 100

Boi

ling

Poin

t (°C

)

Mass (%)

Diesel range

260 °C0

100

200

300

400

500

600

700

800

0 20 40 60 80 100

Boi

ling

Poin

t (°

C)

Mass (%)

Diesel range

300 °C

8

Decreasing H2 partial pressure causes a slight drop in conversion and selectivity shifts from lighter to heavier hydrocarbons during the course of

the reaction

260 °C, 0.5 g of cat., 1.33 wt.% triolein/C12 (0.2 mL/min), 40 bar gas (50 mL/min)

Conversion of triolein over Ni-Al LDH in a fixed-bed reactor

0

100

200

300

400

500

600

700

800

0 20 40 60 80 100

Boi

ling

Poin

t (°C

)

Mass (%)

Diesel range

100% H20

100

200

300

400

500

600

700

800

0 20 40 60 80 100

Boi

ling

Poin

t (°C

)Mass (%)

Diesel range

10% H2/N2

Effect of Hydrogen Partial Pressure

9

Simulated Distillation GC for the Simultaneous Analysis of Lipid Feedstocks and Hydrocarbon Deoxygenation

Products

•  GC-FID based method based on ASTM D2887 •  Able to analyze polar oxygenates and

hydrocarbons •  Able to quantify triglycerides •  No sample derivitization required

10 T. Morgan, E. Santillan-Jimenez, M. Crocker, Energy & Fuels 28 (2014) 2654

GC analysis of (a) tristearin and (b) product mixture resulting from its catalytic deoxygenation

Boiling point calibration plots for various functional groups (C14, C16 and C18)

(a)

(b)

Lipids from Scenedesmus Acutus (UTEX B72) Grown using Flue Gas

M.H. Wilson, J. Groppo, E. Santillan-Jimenez, M. Crocker et al., Appl. Petrochem. Res. 4 (2014) 41E.G. Bligh, W.J. Dyer, Can. J. Biochem. Physiol. 37 (1959) 911

Flue gas from East Bend Station (coal-fired power plant)

Algae cultivation in a low cost photobioreactor

Flocculation & sedimentation

Gravity filtrationBligh-Dyer lipids extractionColumn chromatography

10

Column Chromatography: Chlorophyll Elimination

Both K10 montmorillonite and activated carbon can effectively rid the algae extract of chlorophyll

300 400 500 600 700

Abs

orba

nce

(a.u

.)Wavelength (nm)

Chlorophyll Crude algae oil Fraction 1 Fraction 2 Fraction 3Fraction 4 Fraction 5 Fraction 6 Fraction 7 Fraction 8Fraction 9 Fraction 10 Fraction 11

300 400 500 600 700

Abs

orba

nce

(a.u

.)

Wavelength (nm)

Crude algae oil Crude algae oil

Chlorophyll Chlorophyll

Activated carbon columnK10 montmorillonite column

11

Column Chromatography: Component Separation

Fraction 1 of the K10 column (~40% yield) contains both lipids and sterols and fractions 1-5 of the activated carbon column (~53% yield) contains

only lipids

100 100

K10 montmorillonite column Activated carbon column

12

0

10

20

30

40

50

60

70

80

90

Con

cent

ratio

n (w

t%)

Raw Algae

Residual Solids

Crude Lipids

AC-Purified Lipids

Elemental Analysis

!  N, P, S and Mg are effectively removed by the activated carbon treatment

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

Magnesium Phosphorus

Con

cent

ratio

n (w

t%)

Raw Algae

Residual Solids

Crude Lipids

AC-Purified Lipids

Error bars represent the st. dev. of 3 measurements

13

0

10

20

30

40

50

Con

tent

(wt%

)

Fatty Acid Chains

Raw AlgaeCrude LipidsResidual SolidsAC-Purified LipidsK10-Purified Lipids

Fatty Acid Profile

•  Fatty acid profile determined by GC/MS (after conversion to methyl esters)

•  Lipids rich in palmitic and linolenic fatty acid chains

•  No significant change in fatty acid profile during lipid extraction/ purification

14

Gas chromato

260 °C, 580 psi H2, fixed bed reactor, dodecane as solvent, algae oil WHSV = 0.25 h-1

T. Morgan, D. Grubb, E. Santillan-Jimenez, M. Crocker, Top. Catal. 53 (2010) 820; B. Peng, X. Yuan, C. Zhao, J.A. Lercher, J. Am. Chem. Soc. 134 (2012) 9400; T. Morgan, E. Santillan-Jimenez, A.E. Harman-Ware, M. Crocker, Chem. Eng. J. 189-190 (2012) 346; E. Santillan-Jimenez, T. Morgan, J. Lacny, S. Mohapatra, M. Crocker, Fuel 103 (2013) 1010.

Conversion of Algal Lipids to Fuel-Like HydrocarbonsVia Decarboxylation/Decarbonylation

Simulated-distillation GC: Boiling point distribution plot

Gas chromatogram

(C20)

15

Diesel range

Conclusions

•  Acidic adsorbents such as K10 MM and activated carbon are effective for the removal of chlorophyll and phospholipids from crude algae lipids

•  A Ni-Al LDH catalyst can quantitatively convert lipids to diesel-like hydrocarbons at 260 °C

•  Temperature, hydrogen partial pressure and feed to catalyst ratio were found to affect catalyst performance

•  Good diesel yields were obtained using lipids extracted from Scenedesmus acutus

•  For lipid streams with low heteroatom content, catalytic DeCOx represents an attractive alternative to conventional hydrotreating

16

Acknowledgements

•  KY Department of Energy Development and Independence

•  Duke Energy

•  Department of Energy: U.S.-China Clean Energy Research Center

•  The UK algae team: Michael Wilson Dr. Czarena Crofcheck Dr. Jack Groppo Aubrey Shea Stephanie Kesner Daniel Mohler Thomas Grubbs

18 17