New energy: Fuel resources from kraft pulping

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1 New energy: Fuel resources from kraft pulping Máté Nagy, MátyM tyás s Kosa, Arthur J. Ragauskas, Hans Theliander Georgia Institute of Technology Chalmers University

2 verview Fossil fuels vs. Biofuels Lignin as a feedstock for biofuel production LignoBoost process Analysis of the process products Composition of the lignin fractions Structural changes thought the process Catalytic pyrolysis/liquidification

3 The Carbon Cycle Biomass Fossils Closed cycle Broken cycle

4 International Energy verview Fossil fuels accounted for 86 % of all energy produced worldwide. World crude oil production totaled 73 million barrels per day in Need for Renewable Biofuels: Energy security (Local) Carbon neutral/climate change Sustainability Energy Information Administration.

5 Potential Biofuel Precursors Produced Needs biofuels Bio-renewable resources 460 quadrillion Btu annual consumption Ethanol (Bioethanol) 73 million barrels per day Economically Alkali fatty viable esters (Biodiesel) High energy content High volume Easily accessible Low cost Starch Carbohydrates Cellulose Hemicelluloses Lignin Plant: Fat Hydrocarbons (Fatty(PV, acids) UV) il (Triglycerides) Animal: Animal fat Yellow Grease

6 Biomass as a Raw Material From total annual biomass produced biosynthetically on Earth: 170 x 10 9 metric tons: Carbohydrates: ~70% Lignin: ~20% Cellulose is the most abundant renewable biomaterial on Earth, with a 100 x 10 9 metric tons annual biosynthesis rate H Lignin is the second most abundant biopolymer on Earth. Biosphere has an estimated 300 x 10 9 metric tons of lignin with a 20 x 10 9 metric tons annual biosynthesis rate Hemicelluloses H Ac Ac H H Ac Ac H H 3C H Ac H H H H H CH 3 CH 3 CH 3 H H 3C H H H H CH 3 H H H H CH 3 Ac CH 3 H H H CH 3 H CH 3 CH 3 H H CH 3 -Xylan H CH 3 CH 3 H H H H H H H H H H H H H H H H H H H H H H 3 C H DP Ragauskas A.J,, et. al. Science (2006), 311,

7 Lignocellulosic Feedstock Most abundant biopolymers are available in the form of lignocellulose matrix wood. US agriculture and forestry reserves have the potential to address at least 30% of the nation s s current petroleum demand. US timberland inventory is dry tons, with an annual production of dry tons and consumption of dry tons. US Pulp and Paper industry collects and processes dry tons annually. 7

8 Today s Industrial Process Chemical Pulping Kraft Typical kraft pulp mill will utilize 650,000 tons of wood/year Approximately ~ 200,000 tons of lignin/year are degraded Máté Nagy,, et. al. Industrial Biotechnology, (2006), 2(1),

9 Today- Tomorrow s Forest Products BioRefiner Current Products: Future Products: Pulp, Tall il, Turpentine Select Hemicellulose, Wood Extractives, Lignin Máté Nagy,, et. al. Industrial Biotechnology, (2006), 2(1),

10 Today s Industrial Process Chemical Pulping Kraft Wood Components Kraft Pulp Components Cellulose Component Pine Birch Pine Birch As a % of riginal Wood Glucomannan Xylan ther carbohydrates Lignin Extraneous compounds < Máté Nagy,, et. al. Industrial Biotechnology, (2006), 2(1),

11 Tomorrow s Industrial Process Cellulosic Ethanol More than enough for thermal biorefinery requirements Kim K.H,, J. Sci. Food Agr. (2005), 85(14), Value Added Chemicals Fuels from Lignin Wayman C.E. and Goodman B.J, Appl. Biochem. Biotechnol.. (1993), 39-40,

12 Lignin as a feedstock for biofuel production Lignin is the second most abundant biopolymer on Earth With a 20 x 10 9 annual biosynthesis rate Shift from Starch-Based Biorefinery to Lignocellulosics Biorefinery is due to cost, availability and efficiency The world will become awash with lignin Now from Chemical Pulp Mills Shortly from Cellulosic Ethanol Structure and chemistry of lignin is species/processing dependent nt Lignin chemistry can be manipulated Reductively, Enzymatically, xidatively,, Alkylation 12

13 Problem statement Chemical Pulping Kraft, Chemical Recovery Several US mills currently recovery furnace limited!!!! Too Much Lignin!!! 13

14 LignoBoost Process Evaporators Weak black liquor tank To recovery boiler Black liquor Washed lignin Solid content C 2 Precipitation vessel Dewatering Re-slurry tank Wash liquor 65-70% Heating value 26 GJ/ton ph ~10 ph A. Moosavifar, et. al. Nordic Pulp & Paper Research Journal (2006), 21(2),

15 LignoBoost Process Current objective Further develop LignoBoost applications and develop the use of lignin as a starting feedstock for a controlled catalytic conversion to precursors for biofuels and/or biomaterials; - Determine the composition of the final fractions at different ph - Understand the structural changes in the lignin structure on the molecular level through the LignoBoost process. 15

16 Composition of The Final Fractions Material balances for the LignoBoost Elemental lignin Analysis samples' purification process % 90% % Fraction Percentage weight (g) 70% % 50% % 30% % PURIFIED Leftover I. H2S4 CRUDE % 0% BL P 10.5 F 10.5 P 9.5 F 9.5 BL/E BL-L BL P 10.5 F 10.5Samples P 9.5 F 9.5 Samples H C S NM 16

17 Changes in the lignin structure Changes in the degree of polymerization Weight average molar mass distribution and polydispersity data Mw [g/mol] Polydispesity [Mw/Mn] 0.0 BL P 10.5 F 10.5 P 9.5 F 9.5 Sample 0.00 Mw PD 17 S. Baumberger,, et. al. Holzforschung (2007), 61(4),

18 Changes in the molecular composition Quantitative 1 H-NMR H CH 3 H Hydrogen content H 3 C H H H H CH 3 CH 3 H H H CH 3 1 H-NMR: TSP Percentage 35 H H H CH 3 H CH 3 CH 3 H H Black Liquor P 9.5 P 10.5 F 9.5 F H 3 C H H CH 3 H H CH 3 H CH ppm 0 Carboxylic ac. H Formyl HCH 3 Phenolic Arom. & Vinyl Aliphatic (C,H,) CH 3 Chemical group Aliphatic (C,H) -Me 18 Runge, T.M. and Ragauskas, A.J. Holzforschung (1999), 53:

19 Changes in the molecular composition Quantitative 31 P-NMR Phosphitylation of hydroxyl groups with: 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane Cyclohexanol as the internal standard (144.9 ppm) 19 Pu, Y. and Ragauskas, A.J. Can. J. Chem. (2005) 83:

20 Changes in the molecular composition Quantitative 31 P-NMR Total -H content Aliphatic H Conjug. Phen. H Guaiacyl Phen. H Carboxyl H Sample name [mmol/g] [mmol/mg] [mmol/mg ] [mmol/mg] [mmol/mg] Black liquor P P F F

21 Ligninocellulose vs. Fossil Fuels Gasoline Gasoil /diesel Carbohydrate Lignin Carbon chain length [6-5] n [9-10] n /C molar ratio H/C molar ratio 1-2 ~ Phase behavior (ambient T) liquid liquid solid liquid-solid Polarity a-polar a-polar polar a-polar Preferred structure branched/aromatic /cyclic/unsaturated linear/saturated linear/cyclic branched (3D) 21

22 LignoBoost Lignin Pyrolysis/Liquidification 22

23 LignoBoost Lignin Pyrolysis/Liquidification Pyrolysis oil yield Solid yield (Char) Unaccounted (Gas) LignoBoost sample [wt%] [wt%] [wt%] Black liquor (crude) P 9.5 (crude) P 9.5 (extracted)

24 LignoBoost Lignin Pyrolysis/Liquidification Measured Element Hydrogen Carbon xygen Sulfur Not Det. Sample name [wt%] [wt%] [wt%] [wt%] [wt%] Black Liquor BL Solid BL Pyr.. il P 9.5 Crude P 9.5 Crude Solid P 9.5 Crude Pyr.. il P 9.5 Extracted P 9.5 E. Solid P 9.5 E. Pyr.. il

25 LignoBoost Pyrolysis oil vs. Fossil Fuels Gasoline Gasoil /diesel LignoBoost lignin (P9.5) LignoBoost lignin (P9.5) Pyr.. il Carbon chain length [9-10] n --- /C molar ratio H/C molar ratio 1-2 ~ Phase behavior (ambient T) liquid liquid solid liquid Polarity a-polar a-polar a-polar a-polar Preferred structure branched/ aromatic /cyclic/ unsaturated linear/ saturated Branched (3D) --- Fundamental chemistry of Deoxygenation/Decarboxylation 25

26 Conclusions Composition of the LignoBoost fractions BL phase separation; P contains more lignin and F is enriched in salts. Precipitation yields; P 9.5 contains more PURIFIED material than P Molecular composition of the lignin fractions P contains more carboxylic and phenolic groups while F is enriched in methoxyl moieties. Total lignin hydroxyl content (solubility) of F at ph9.5: 56% at ph10.5: 45% higher than in the P fraction. Lower ph resulted in higher lignin hydroxyl content by F: +69% and a P +35%. LignoBoost lignin pyrolysis/liquidification Pyrolysis oil yield from extracted sample is 43%, that is 36% higher than the crude sample yield. Pyrolysis oil /C decreased by 24%, H/C increased by 20%. Pyrolysis oil composition, physical-chemical chemical properties Fundamental chemistry. 26

27 Acknowledgements Arthur J. Ragauskas Mátyás s Kosa Kasi David Georgia Institute of Technology Hans Theliander Chalmers University 27

28 Thank You!