Upgrading Hydrothermal Liquefaction Biocrude Oil from Wet Biowaste into Transportation Fuel

Transcription

1 Upgrading Hydrothermal Liquefaction Biocrude Oil from Wet Biowaste into Transportation Fuel Wan-Ting (Grace) Chen Agricultural and Biological Engineering

2 How much crude oil is consumed by the U.S. every year?

3 Let s think about More food, water, and energy is needed! 3

4 A new paradigm Environment-Enhancing Energy Bio-waste Liquid Algae production Clean water Biomass from algae to HTL Solids Multi-cycle nutrients & water reuse Wastewater & nutrients from Post HTL to algae Bio-crude oil Hydrothermal liquefaction (HTL) Chen et al., Biorecource Technology 2014, 152,

5 Energy consumption (MJ/kg fuel produced) Algal Biofuel Bottlenecks: Energy Balance Drying and oil extraction are energy intensive steps (>75% energy) (Lardon et. al, 2009; Sander & Murthy, 2010 ) Culturing Harvesting Dewatering Slide Credit: C.T. Kuo, Y. Zhou, L. Schideman, & Y. Zhang (2015) Drying Oil transesterification Oil Extraction Drying Algae culture and harvesting Nomal/Dry Normal/Wet Low N/Dry Low N/Wet Oil Extraction Wet Extraction Conversion (adapted from Lardon et. al, 2009) Biodiesel Energy Content 5

6 Comparison of Thermochemical Conversion (TCC) Technologies Cons: High Pressure Unstable oil Complex Hydrothermal Liquefaction (HTL) Pros: Wet feedstocks Similar to crude oil Higher energy density Pyrolysis Gasification Slide Credit: C.T. Kuo, Y. Guo, & Y. Zhang (2015) 6

7 Research Question: How much crude oil is consumed by the U.S. every year and how to reduce/replace it with renewable energy? Proposed Solutions: Utilizing wet biowaste Hydrothermal Liquefaction (HTL) 7

8 Challenge 1 Feedstock -- Would it be feasible to convert mixed-culture algal biomass grown in wastewater into biocrude oil? Wet biomass contains 80~98 % moisture content Would this bioenergy conversion technique reach a net positive energy balance? 8

9 Hydrothermal liquefaction (HTL) of mixed-culture algal biomass from wastewater treatment plants Demonstrated HTL Feedstocks Animal Manure Microalgae Food waste Reactor Gas Product Post-HTL WW Solid Residue Oil Product Reaction Temp: o C Reaction Time: hr Slide Credit: Y. Zhang (2011) 9

10 Biocrude Oil Yield Optimization Chen et al., Biorecource Technology 2014, 152,

11 Energy Consumption Ratio (-) Chen et al., Applied Energy, 128: , 2014 HTL Results in a Positive Net Energy Gain % heat recovery No heat recovery ECR <1 Produce Net Positive Energy ECR E E input output 0.0 AW:SW=1:0 AW:SW=3:1 AW:SW=1:1 AW:SW=1:3 AW:SW=0:1 AW: Wastewater Algae SW: Swine Manure Feedstock Combination Ratios (-) 11

12 Challenge 1 Produce Enough Biofuel to Replace Fossil Fuel! Would it be feasible to convert mixed-culture algal biomass grown in wastewater into biocrude oil? Yes. The reaction temperature and time are determined. Be able to achieve a net positive energy gain 12

13 Challenge 2 HTL Biocrude -- How to obtain a large quantity of biocrude oil for downstream analysis and upgrading? A 1 L batch reactor can only produce 48 g of biocrude oil (with a 40 wt.% yield) Development of high pressure reactor is very challenging (e.g., feedstock pumping and clogging) 13

14 The first spiral PFR that can processes 6 ton of wet biowaste per day 14

15 Goal 1 Goal 2 Produce Enough Biofuel for the U.S. annual consumption! Would it be feasible to convert mixed-culture algal biomass grown in wastewater into biocrude oil? Yes. The reaction temperature and time is optimized. Be able to achieve a net positive energy gain How to obtain a large quantity of biocrude oil for further analysis and upgrading? Developed an up-scaled continuous reactor Address plugging issues 15

16 Challenge 3 Upgrading the HTL Biocrude --Since the composition of the biocrude oil is so complex, how to properly upgrade it? High ash content in the mixed-culture algae harvested from wastewater (AW) negatively affect the bio-crude oil quality How ash content interacts with volatile components in the feedstock under the HTL processes remains unknown 16

17 Pretreat Mixed-culture Algal Biomass from Wastewater Treatment Plants Harvest algae Wash with tap water (1 h) Pulverize Garbage entrained with algae Screen Ultrasonic Centrifuge Centrifuge + Ultrasonic Test Ash Content Thermogravimetric Analysis (TGA) Scanning Electric Microscope (SEM) 17

18 Ash Contents of Pretreated Algae Reduced by 7-10 wt.% Pretreatment condition Ash content Weight percentage centrifugation Pulverized 27.6 ± 0.07 % N/A S ± 1.9 % 100 % C-1 Upper 32.5 ± 1.2 % 26.4 ± 4.27 % Middle 18.6 ± 0.8 % 29.0 ± 0.73 % C-2 Upper 36.7 ± 3.1 % 24.5 ± 2.15 % Middle 21.8 ± 0.8 % 27.0 ± 0.50 % C-3 Upper 34.1 ± 3.5 % 24.4 ± 0.18 % Middle 21.0 ± 0.04 % 33.0 ± 7.35 % C-4 Upper 34.4 ± 1.7 % 26.7 ± 0.63 % Middle 19.2 ± 1.9 % 33.5 ± 1.38 % C1 & C2: Centrifuge at 3000 rpm with 15 min and 25 min, respectively; C3 & C4: Centrifuge at 3000 rpm with 15 min and 25 min, respectively; S2: Before Centrifuge. 18

19 Decomposition Kinetics Analysis of Pretreated Algal Biomass 105.0% Pulverize Screen#2 C-1-upper C-1-middle Ultrasonic C-upper+U-0.5h C-upper+U-1h C-middle+U-0.5h C-middle+U-1h Stage % 85.0% Weight Loss(%) Stage % 65.0% Stage.3 dx k (1 X ) dt 55.0% 45.0% k A exp( 35.0% Ea ) RT 25.0% Temperate(ºC) 19

20 Apparent Activation Energy (E a ) of Algae Decreased after Pretreatments of Centrifugation Plus Ultrasonication Sample Pretreatment method E a (kj/ mol) Algae from a waste-water treatment plant E a1 E a2 Pulverize S C-1-upper C-1-midddle U C+U-1-upper C+U-2-upper C+U-1-middle C+U-2-middle Chlorella a N/A a Adopted from (Gai et al., 2013), which was operated at the same condition under TGA. 20

21 Biocrude Oil Yield of Pretreated Algae Significantly Improved by wt.% Sample Pretreatment Method E a (kj/ mol) E a1 E a2 Biocrude Oil Yields from HTL (%) b Higher Heating Value (MJ/kg) Algae from a wastewater treatment plant Pulverize ± 1.87 % 28.2 S ± 3.35% 28.4 C-1-midddle ± 4.32 % 29.9 U ± 5.13 % 30.9 C+U-2-middle ± 1.54 % 32.4 Chlorella a N/A ± 0.79 % c 37.8 c a Adopted from (Gai et al., 2013), which was operated at the same condition under TGA. b HTL processes were conducted with 25 % total solids content of feedstocks at reaction temperature of 300 C with reaction time of 1 hour c Adopted from (Gai et al., 2014), which was operated at the same condition under HTL. 21

22 Goal 1 Goal 2 Goal 3 Produce Enough Biofuel for the U.S. annual consumption! Would it be feasible to convert mixed-culture algal biomass grown in wastewater into biocrude oil? Yes. The reaction temperature and time is optimized. Be able to achieve a net positive energy gain How to obtain a large quantity of biocrude oil for further analysis and upgrading? Developed an up-scaled continuous reactor Address plugging issues How to properly upgrade HTL Biocrude Oil? Remove excessive amounts of ash contents Understand the role of ash content under HTL 22

23 The composition of biocrude oil would be different from feedstock to feedstock Simple separation methods such as extraction was not able to fractionate biocrude oil into transportation fuel Catalytic upgrading of biocrude oil with hydroprocessing has not been effective to improve the fuel properties 23

24 Pretreatment of Biowaste Liquid Sun light CO 2 Clean water Chen et al., Nature Energy, in preparation Solids Algae production Phenols Fatty Acids Hydrocarbon s Continuous Hydrothermal liquefaction (producing 5 gallons biocrude oil /day) Biocrude oil Nitrogen-doped Carbonaceous Material Aviation Biofuel Biodiesel Engine Test Functional Materials 24

25 Weight of Biocrude ( wt.%) Chen et al., Nature Energy, in preparation 70% of the Distillates of Biocrude Oil are in the Diesel Range 80.0% 70.0% 60.0% 50.0% 40.0% Diesel Range: C* 30.0% Test % Test % Test 3 Test 4 0.0% Test Temperature ( C) *According to ASTM-D7467 and D975 25

26 Distillates from FPW-derived Biocrude Contains Alkanes and Fatty Acids % of Total Relative Peak Areas (%) Hydrocarbons Cyclic Hydrocarbons Fatty Acids Derivatives Fatty Nitriles N-Heterocyclic cmpds. Phenols Amino Acids Chen et al., Nature Energy, in preparation A B C D E F G H Distillate Fractions 26

27 Acidity (mg KOH/g sample) Yield (wt.%) Acidity of Different FPW-Distillates % % 60% % Acidity 40% Distillation Yield % % ASTM: % % A B C D E F G H Distillation Fraction (-) Chen et al., Nature Energy, in preparation 27 27

28 Mild Upgrading Esterification for FPW (food processing waste)- derived distillates to reduce their acidity Neutralization with NaOH for SW (Swine Manure)-derived distillates to reduce gum contents that caused by phenolic compounds Chen et al., Nature Energy, in preparation 28

29 Energy Consumption Ratio and Process Severity (R o ) of Different Upgrading Approaches Log R o Energy Consumption Ratio Severity 50% heat recovery No heat recovery Distillation of HTL biocrude oil is competitive to other available upgrading strategies, without the consumption of H 2 29 Chen et al., Nature Energy, in preparation Zeolite (425 C) SCW (400 C) HDT (400 C) DL of SW DL of FPW Different Upgrading Strategies (-) DL of SP 0

30 Chen et al., Nature Energy, in preparation Fuel Specification of Drop-in Biodiesel Prepared with Upgraded HTL Distillates meets ASTM Fuel Spec Property Bio-diesel (B5-20) Diesel HTL 10 HTL20 Viscosity f (mm 2 /s) a Acidity <0.3 d <0.3 d (mgkoh/g) b Gross Heat of Cumbustion (MJ/kg) c Cetane Number (min) f > d 40 e Lubricity (µm) <520 d <460 g e Oxidation Stability (hr) 6 > d N/A 48> 48> a Measured by ASTM D445; b Measured by ASTM D664; c Measured by bomb Calorimeter (ASTM D4809); d ASTM D7467; e ASTM D975; f Lin et al., Fuel, 2012 g Engine Manufacture Association recommendation High Cetane number refers to low ignition delay before combustion Lower lubricity than biodiesel implies to a better ability to reduce wear and friction Superior oxidation stability for long-term storage 30

31 Fuel Specification and Engine Test of Drop-in Biodiesel Prepared with Upgraded HTL Distillates Engine Test a HTL10 HTL20 Diesel/ Biodiesel Power Output (kw) CO emission (ppm) CO 2 emission (ppm) NO x emission (ppm) Unburnthydrocarbons (ppm) Soot (FSN) a Operated at rpm with injection timing of 0-12 BTDC under medium loading of fuel (20 mg/stroke); b filter smoke number (FSN) Competitive power output of HTL drop-in fuel to petroleum diesel Lower pollutant emissions of CO, CO 2, NO x, and unburned hydrocarbons Chen et al., Nature Energy, in preparation 31

32 Injection Timing (CA BTDC) HTL 10 and 20 Leads to a Higher Power Enigne Speed (1000*RPM) Output in Diesel Engine Power-HTL10 (%) Enigne Speed (1000*RPM) HTL 10 can achieve a higher power output than regular diesel at 0-4 CA BTDC and 2000rpm. HTL 20 can lead to a superior power output to diesel at 4-8 CA BTDC and 1500 rpm. Injection Timing (CA BTDC) Power-HTL20 (%)

33 HTL 10 and 20 Leads to a lower NOx emission in Diesel Engine Injection Timing (CA BTDC) NOx-HTL10 (%) Enigne Speed (1000*RPM) Injection Timing (CA BTDC) NOx-HTL20 (%) Enigne Speed (1000*RPM) HTL 10 can achieve a 6% lower NOx emission than diesel at 1500rpm for all tested crank angle, due to lower EGT. HTL 20 can lead to a 13% lower NOx emission than diesel at rpm for all tested crank angel. 33

34 Goal 1 Goal 2 Goal 3 Produce Enough Biofuel for the U.S. annual consumption! Would it be feasible to convert mixed-culture algal biomass grown in wastewater into biocrude oil? Yes. The reaction temperature and time is optimized. Be able to achieve a net positive energy gain How to obtain a large quantity of biocrude oil for further analysis and upgrading? Developed an up-scaled continuous reactor Address plugging issues How to properly upgrade HTL Biocrude Oil? Remove excessive amounts of ash contents Understand the role of ash content under HTL 34 How to properly upgrade HTL Biocrude Oil? Fractionate Biocrude oil by distillation Mildly upgrading HTL distillates (esterification) Fuel Spec and Diesel Engine Test is conducted

35 More food, water, and energy is needed! US consumed 1.1 billion tons of crude oil annually 35

36 Relevant Publication List 10. Wan-Ting Chen, Yuanhui Zhang, Timothy Lee, Zhenwei Wu, B.K. Sharma, Chia-Fon Lee, Lance Schideman, Renewable Transportation Biofuel Production Converted from Wet Biowaste via Hydrothermal Liquefaction, Nature Energy, in preparation, Mar, Wan-Ting Chen, Wanyi Qian, Yuanhui Zhang, Zachary Mazur, Karalyn Scheppe, Chih-Ting Kuo, Hydrothermal Liquefaction of High-Ash Algal Biomass: the Effect of Ash Contents in HTL Reactions, Algal Research, submitted, Dec Peng Zhang, Yuanhui Zhang, Wan-Ting Chen, Lance Schideman, B.K. Sharma, Hydrothermal Liquefaction of Diatom Skeletonema costatum and the Effect of Frustules on Biocrude Oil Production, International Journal of Agricultural and Biological Engineering, accepted, Dec, Wan-Ting Chen, Liyin Tang, Wanyi Qian, Karalyn Scheppe, Ken Nair, Zhenwei Wu, Chao Gai, Peng Zhang, Yuanhui Zhang, Extract Nitrogen-Containing Compounds in Biocrude Oil Converted from Wet Biowaste via Hydrothermal Liquefaction, ACS Sustainable Chemistry & Engineering, 4 (4): , Chao Gai, Yuanhui Zhang, Wan-Ting Chen, Peng Zhang, Yuping Dong, An Investigation of Reaction Pathways of Hydrothermal Liquefaction Using Chlorella pyrenoidosa and Spirulina platensis, Energy Conversion & Management, 96: , Giovana Tommaso, Wan-Ting Chen, Peng Li, Lance Schideman, Yuanhui Zhang, Chemical Characterization and Anaerobic Biodegradability of Aqueous Products Generated from Hydrothermal Liquefaction of Mixed-Culture Algae from Wastewater Treatment System, Bioresource Technology, 178: , Wan-Ting Chen, Junchao Ma, Yuanhui Zhang, Gai Chao, Wanyi Qian, Physical Pretreatments of Wastewater Algae to Reduce Ash Content and Improve Thermal Decomposition Characteristics, Bioresource Technology, 169: , Wan-Ting Chen, Yuanhui Zhang, Jixiang Zhang, Lance Schideman, Guo Yu, Peng Zhang, Mitchell Minarick, Coliquefaction of Swine Manure and Mixed-culture Algal Biomass from a Wastewater Treatment System to Produce Biocrude Oil, Applied Energy, 128: , Wan-Ting Chen, Yuanhui Zhang, Jixiang Zhang, Peng Zhang, Guo Yu, Lance Schideman, Mitchell Minarick, Hydrothermal Liquefaction of Mixed-culture Algal Biomass from Wastewater Treatment System into Bio-crude Oil, Bioresource Technology, 152: , Jixiang Zhang, Wan-Ting Chen, Peng Zhang, Yuanhui Zhang, Zhongyang Luo, Hydrothermal Liquefaction of Chlorella pyrenoidosa in Sub- and Supercritical Ethanol with Heterogeneous Catalysts, Bioresource Technology, 133: ,

37 Q&A Produce Enough Biofuel for the U.S. annual consumption! Would it be feasible to convert mixed-culture algal biomass grown in wastewater into biocrude oil? Yes. The reaction temperature and time is optimized. Be able to achieve a net positive energy gain How to obtain a large quantity of biocrude oil for further analysis and upgrading? Developed an up-scaled continuous reactor Address plugging issues How to properly upgrade HTL Biocrude Oil? Remove excessive amounts of ash contents Understand the role of ash content under HTL Learn more at: wchen58@illinois.edu How to properly upgrade HTL Biocrude Oil? Fractionate Biocrude oil by distillation Mildly upgrading HTL distillates (esterification) Fuel Spec and Diesel Engine Test is conducted 37

38 Thank you Acknowledgments All the members in Prof. Yuanhui Zhang s Group T. Lee, K. Nithyanandan and Prof. Chia-Fon Lee K.C. Tsao and Prof. Hong Yang in Dept. of CHBE Dr. Lance Schideman & Dr. B.K. Sharma in ISTC Prof. Alan Hansen in Dept. of ABE (Fuel Spec Test) Dave and Tom Burtons in Snapshot Energy LLC Dedicated Support from my family and Dr. Mei-Hsiu Lai 38

39 References 39 W.-T. Chen, Y. Zhang, J. Zhang, L. Schideman, G. Yu, P. Zhang and M. Minarick, Applied energy, 2014, 128, B. J. He, Y. Zhang, T. L. Funk, G. L. Riskowski and Y. Yin, Transactions of the ASAE, 2000, 43, D. Cheng, L. Wang, A. Shahbazi, S. Xiu and B. Zhang, Fuel, 2014, 130, (International Air Transportation ssociation) ASTM standards MIT open course provided by Chemical Engineering Carbon, 48(13), Zhou, D., Zhang, L., Zhang, S., Fu, H., Chen, J Hydrothermal liquefaction of macroalgae Enteromorpha prolifera to bio-oil. Energy & Fuels, 24(7), Zhou, D., Zhang, S., Fu, H., Chen, J Liquefaction of macroalgae Enteromorpha prolifera in sub-/supercritical alcohols: direct production of ester compounds. Energy & Fuels, 26(4), Zhou, N., Huo, M., Wu, H., Nithyanandan, K., Chia-fon, F.L., Wang, Q Low temperature spray combustion of acetone butanol ethanol (ABE) and diesel blends. Applied Energy, 117, Zhou, Y., Schideman, L., Yu, G., Zhang, Y A synergistic combination of algal wastewater treatment and hydrothermal biofuel production maximized by nutrient and carbon recycling. Energy & Environmental Science, 6(12), Zhang, L., Champagne, P., Xu, C Bio-crude production from secondary pulp/paper-mill sludge and waste newspaper via co-liquefaction in hotcompressed water. Energy, 36(4), Zhang, P Characterization of biofuel from diatoms via hydrothermal liquefaction. in: Agricultural & Biological Engineering, Vol. Master of Science, University of Illinois at Urbana-Champaign. Urbana. Zhang, Y Hydrothermal liquefaction to convert biomass into crude oil. in: Biofuels from Agricultural Wastes and Byproducts, Wiley-Blackwell. Hoboken, NJ, pp Zhao, C., Camaioni, D.M., Lercher, J.A Selective catalytic hydroalkylation and deoxygenation of substituted phenols to bicycloalkanes. Journal of Catalysis, 288, Zhao, C., Kou, Y., Lemonidou, A.A., Li, X., Lercher, J.A Highly Selective Catalytic Conversion of Phenolic Bio Oil to Alkanes. Angewandte Chemie, 121(22), Zhao, C., Kou, Y., Lemonidou, A.A., Li, X., Lercher, J.A. 2010a. Hydrodeoxygenation of bio-derived phenols to hydrocarbons using RANEY Ni and Nafion/SiO 2 catalysts. Chemical Communications, 46(3), Zhao, L., Baccile, N., Gross, S., Zhang, Y., Wei, W., Sun, Y., Antonietti, M., Titirici, M.-M. 2010b. Sustainable nitrogen-doped carbonaceous materials from biomass derivatives. Carbon, 48(13),

40 Questions?... Learn more at: e2-energy.illinois.edu/ Photo Credit: Chih-Ting Kuo Department of Agricultural & Biological Engineering University of Illinois at Urbana-Champaign