Environment-Enhancing Energy Paradigm -- Integrated Approach for BioEnergy, Water and Carbon Capture Yuanhui Zhang, PhD, PE Innoventor Professor in Engineering Dept. Agricultural and Biological Engineering University of Illinois at Urbana-Champaign U NIVERSITY OF I LLINOIS 1 U NIVERSITY OF I LLINOIS AT U RBANA- C HAMPAIGN AT U RBANA- C HAMPAIGN
Environment-Enhancing Energy Road-Map Sun light CO 2 Biowaste Clean water Liquid Algae production Wastewater Multi-cycle Biomass and nutrients nutrient and from algae from Post HTL water reuse to HTL to algae Biocrude oil Hydrothermal liquefaction (HTL) Solids U NIVERSITY OF I LLINOIS 2 AT U RBANA- C HAMPAIGN
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Alternative Energy Generate electricity and heat: Solar energy Geothermal energy Wind farm Hydroelectric power Generate transportation fuel: Conversion Renewable resources Biofuel U NIVERSITY OF I LLINOIS 4 AT U RBANA- C HAMPAIGN
Why Low-Lipid Microalgae? Current approach: high-lipid microalgae for biodiesel. Oil Transesterification Harvest Drying Extraction Energy intensive (~75% of total) ( Rodolfi et al ., 2009 ) ( Williams & Laurens , 2010 ) U NIVERSITY OF I LLINOIS 5 AT U RBANA- C HAMPAIGN
滇池 太湖 High High-lipid Low Lipid The naturally Fast-grow Fast-grow occurring algal （ HTL ） Biomass (Extraction) bloom s are all Low-lipid, fast – grow species. High-lipid Low-lipid Slow-grow Slow-grow （ Pharmceuticals ） High Low Lipid Content (% ） U NIVERSITY OF I LLINOIS 6 青岛 AT U RBANA- C HAMPAIGN 巢湖
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Based on the biogenic hypothesis All fossil fuels found on earth – petroleum (including oil shale and tar sand), natural gas and coal, are formed through processes of ThermoChemical Conversion* from biomass buried beneath the ground and subjected to millions of years of high temperature and pressure. * ThermoChemical Conversion processes include pyrolysis, hydrothermasl liquefaction and gasification U NIVERSITY OF I LLINOIS 8 AT U RBANA- C HAMPAIGN
Hydrothermal Liquefaction (HTL) Mimicking Mother Nature’s millions -of-years process of turning deceased living matters buried beneath the ground into petroleum, swine manure and other bio-waste, have been converted into crude oil in minutes using hydrothermal liquefaction (HTL) technology in 10 – 40 minutes. U NIVERSITY OF I LLINOIS 9 AT U RBANA- C HAMPAIGN
1.8 min CHG HTL 1 billion yr Source: Hunt, John. 1996 U NIVERSITY OF I LLINOIS Petroleum Geochemistry and Geology 10 AT U RBANA- C HAMPAIGN
Algae to Biocrude Conversion Efficiency Microalgae Macroalgae Biowastes 40% 35% Bio-crude oil Yield Percentage (wt%) 30% Lipid Content 25% 20% 15% 10% 5% 0% Chlorella Spirulina Chlamydomonas Algae GOM Diatom Algae UCSD RT Algae KELP Red Algae Seaweed Sewage sludge Swine manure Algae SWP Initial lipid content and HTL oil conversion efficiency for different feedstocks. Energy recovery ratio is 3~11 to 1. Note that the HTL can convert the very low-lipid algae into crude oil – a paradigm shift from ‘extracting’ to ‘converting ’. (Yu et al., 2011) U NIVERSITY OF I LLINOIS 11 AT U RBANA- C HAMPAIGN
CSTR Commercial system (160 bbl/d) CSTR system PFR reactor system Licensed from UIUC (1 gallon/d) (2 gallon/d) Ochemia et al., 2005, Minarick et al. 1996 1999 2005 2007 2015 2011 2013 Hydro- thermal ? He et al., 2000, CSTR Pilot system 2001 (10 bbl/d) PFR pilot/commercial Licensed from UIUC system (12 bbl/d) Licensed from UIUC U NIVERSITY OF I LLINOIS 12 AT U RBANA- C HAMPAIGN
HTL Feedstock and Biocrude Food- Slaughter- Swine MWW processing house manure Algae Feedstook Properties: Ash Content (dry based) 1.5 8.38 16.3 47.5 Lipid content 52.3 23.8 20.3 1.7 C 60.7 59.5 41.1 27.9 H 8.49 8.77 5.42 3.01 N 3.33 5.44 3.36 3.9 O 27.5 26.3 50.1 65.2 Biocrude oil yield (% dw TS) 62.4 39 46.8** 72.1 High Heating Value (MJ/kg) 40.6 36.5 38.8 32.5 C 75.4 69.7 76.6 59.4 H 12 11.1 10.3 7.79 N 1.79 2.32 3.76 2.5 O 10.8 16.8 9.4 30.3 Energy Recovery (%)* 91.2 96.7 83.8 84.2** * ER not include 5-10% HTL process energy; ** For volatile solids U NIVERSITY OF I LLINOIS 14 AT U RBANA- C HAMPAIGN
Distillation of HTL Biocrude U NIVERSITY OF I LLINOIS 15 AT U RBANA- C HAMPAIGN
Fuel specification analysis and engine test of BD10-20 Fuel Spec Property Upgraded BD-10 Upgraded BD-20 Diesel (FPW) (FPW) Viscosity @20 ° C (mm 2 /s) a 3.050 i 3.737 3.746 Acidity (mg KOH/g) b 0.3 e 0.08-0.23 0.26-0.33 Existent Gum (mg/100ml) f 0.17 wt.% 0.21 wt.% 0.21 wt.% Net Heat of Combustion (MJ/kg) e 44.7 44.2 46.1 Cetane Number (min) f 40> e 44.2 43.6 Lubricity ( μ m) f <520 e 364 324 Oxidation Stability (hrs) f 6> e 48> 48> Engine Test Power Generated (ft-lb) 7.4 -13.5 6.0-13.7 7.3-13.5 EGT ( ° C) h 326.3- 569.6 303.7-554.1 334.9 -574.4 Thermal Efficiencies j TBA i TBA i TBA i CO emission (ppm) 0.04-1.82 0.05-1.66 0.05-2.12 CO 2 emission (ppm) 7.06-11.4 6.22-11.7 7.12-11.6 NOx emission (ppm) 606-1576 551-1456 540-1549 Unburnt hydrocarbons (ppm) 14-26 18-29 14-32 Particulate matter emission (Soot) TBD TBD TBD a Measured by Cannon-Fenske Viscometer (ASTM D7566-14a); b Measured by ASTM D664; c Measured by ASTM D93; d According to ASTM D7566-14a; e ASTM D7467-13; f Modified ASTM D381, heat the sample in the furnace from room temperature to 240 ° C for 30 minutes; g Not applied; h Exhaust Gas Temperature; Through the cooperation with Prof. Chia-Fon Lee; i To be analyzed; j check the reference papers on Biomass & Bioenergy U NIVERSITY OF I LLINOIS 16 AT U RBANA- C HAMPAIGN
Synergy of Algae and Wastewater Treatment National Algal Biofuels Technology Roadmap: ( DOE, 2010, pg. 83 ) “ Inevitably, wastewater treatment and recycling must be incorporated with algae biofuel production.” WHY? “ Nutrient recycling would be needed since wastewater flows in the United States are insufficient to support large-scale algae production on the basis of a single use of nutrients.” U NIVERSITY OF I LLINOIS 17 AT U RBANA- C HAMPAIGN
Nitrogen Balance of the HTL Process Chlorella Chlorella As temperature increased, more nitrogen was recovered by aqueous product. NR of bio-crude oil increased mainly due to the increase of its yield. About 75% of nitrogen remained in the aqueous phase after HTL. Yu et al., 2011 U NIVERSITY OF I LLINOIS 18 AT U RBANA- C HAMPAIGN
Destruction of Bio-active Compounds and Antibiotic Resistance Gene via HTL Process Liquid Scintillation 14 C-BPA/Estradiol HTL Treatment Counter + Swine Manure Temperature:250 – 300 o C Reaction Time: 15, 30, 60 min Flofernicol HPLC Analysis Certiofur Estrone Estradiol BPA U NIVERSITY OF I LLINOIS Distribution of 14 C from BPA and Estradiol in the HTL final products (300 0 C, 60 min RT) AT U RBANA- C HAMPAIGN
Destruction of Bisphenol A 100 % C14 in post HTL wastewater 300 C 80 a) 300 0 C-60 min 60 40 300 0 C-45 min b) 20 0 60 min 45 min 15 min Feedstock c) 300 0 C-15 min Figure 3: Percentage of 14 C in HTL wastewater. Detection of BPA and its breakdown products before and after HTL treatment at 300 o C and three different reaction times: a) 60 min, b) 45 min, and c) 15 min. (Pham et al., U NIVERSITY OF I LLINOIS 2013) AT U RBANA- C HAMPAIGN
Destruction of Plasmid DNA via HTL Treatment 1000 DNA concentration (ng/mL) o C E.Coli-250 o C E.Coli-300 100 o C Swine manure+E.Coli-250 10 1 0.1 0 15 30 45 60 75 Retention time (min) Left: DNA concentration pre- and post HTL treatment; Right: Agarose gel of plasmid DNA extracts from pure E. Coli culture before HTL treatment (Well 1) and after various HTL U NIVERSITY OF I LLINOIS treatments (Well 2-7) versus size standards (Well 8). AT U RBANA- C HAMPAIGN
HTL Pathway Analysis (Outputs Distribution) Gases Biocrude Aqueous Ⅲ Ⅱ Solids Ⅰ → Ⅰ : 3, 2+4(2-, 3-) → Ⅱ : 4(6)+(5, 2) → Ⅲ : 3(1, 2) U NIVERSITY OF I LLINOIS 22 AT U RBANA- C HAMPAIGN
Pathway Analysis -- Effect of FS Composition U NIVERSITY OF I LLINOIS 23 AT U RBANA- C HAMPAIGN
Model Construction STELLA Widely used in biological, ecological, and environmental sciences (Hannon and Ruth 1999, Ouyang 2008) U NIVERSITY OF I LLINOIS 24 AT U RBANA- C HAMPAIGN 1 2 3 4 5
Evaluate process improvements Improved Scenario: 10 Times Biosolids Amplification Q 1008 C 686 CO 2 TSS 20 C 314 C 38 N 9 Algal- Dilute Liquid Treated bacterial Q 999 Wastewater Cultivation TSS 63 C 75 Solids 1959 N 37 Waste TSS 942 C 992 Stream C 472 Waste N 147 Pretreatment Harvested Biomass CO 2 Q 1000 Oil 990 C 31 Solids 210 C 657 TSS 210 PHWW Q 0.7 N 23 C 132 Q 9.0 C 132 TSS 147 TSS 147 C 226 Biocrude Oil C 57 N 40 N 121 N 4 Residue 379 Hydrothermal C 123 + Liquefaction _________ Concentrated N 7 = 10 Biosolids Residue U NIVERSITY OF I LLINOIS 25 AT U RBANA- C HAMPAIGN Zhou, 2014 1 2 3 4 5
The combination system diagram CO 2 Microalgae N, P absorption and Biogas Membrane cultivation wastewater treatment The condensed effluent was used Raw for water soluble fertilizer materials The diluted Microalgae used as co- digestion to produce CH 4 Biocrude oil production U NIVERSITY OF I LLINOIS Fig. The diagram of anaerobic digestion and microalgae AT U RBANA- C HAMPAIGN cultivation
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