Progress 03/15/16 to 03/14/19

Outputs
Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Post-docs, studets and junior scholars involved in this project were able to present at conferences. This provided important professional development and soft skill development for them. 1. Posmanik, R., Angenent, L.T., Usack, J.G., Moore, M.C., Overton, T.R., Tester, J.W. (2015) Integrating anaerobic and hydrothermal treatment of dairy and food biowastes: a sustainable systems approach for biofuel and animal feed production and nutrient recovery. The Annual Meeting of Atkinson Center for sustainable Future (ACSF), Cornell University, Ithaca, NY. 2. Posmanik, R., Angenent, L.T., Usack, J.G., Moore, M.C., Overton, T.R., Tester, J.W. (2015) Coupling anaerobic digestion and hydrothermal liquifaction for sustainable energy generation and waste recovery in dairy operations. The Dairy Environmental Systems and Climate Adaptation Conference, Cornell University, Ithaca, NY. 3. Posmanik R., Labatut R.A., Kim A.H., Usack J.G., Tester J.W., Angenent L.T. (2016) Integrating hydrothermal liquefaction and anaerobic digestion for sustainable energy generation from food waste. Food Waste-to-Low Carbon Energy Conference, New Brunswick, NJ. 4. Posmanik R., Cantero D.A. Martinez C.M., Cantero-Tubilla B, Tester J. W. (2016) SmartWaste­­­­­­­­­­­­: ­biomass conversion into low oxygenated hydrocarbons in subcritical water. AIChE Annual Meeting, San Francisco, CA. 5. Sills D.L., Posmanik, R., Usack J.G., Moore M.C., Overton T.R., Angenent L. T., Tester J. W. (2016) Process integration of anaerobic digestion and hydrothermal liquifaction for sustainable energy generation and waste recovery in dairy operations. NYSAWWA/NYWEA Joint Energy Specialty Conference, Albany NY. 6. Posmanik, R., Gerber Van Doren L., Tester J.W., Sills D.L. (2016) Prospects for heat recovery and techno-economic analysis for energy generation using biological and hydrothermal processing of biomass. NYSAWWA/NYWEA Joint Energy Specialty Conference, Albany NY. 7. Martínez C.M., Posmanik R.,Cantero D.A. Cantero-Tubilla B., Cocero, M.J., Tester J.W. (2017)biomass conversion into low oxygenated hydrocarbons by hydrothermal liquefaction.The 10th World Congress of Chemical Engineering, Barcelona, Spain. 8. Cantero-Tubilla, B., Posmanik, R., Tester, J.W. (2017) Thermochemical approach for valorization of waste streams from food, dairy and water treatment industries using subcritical water. The 21st Annual Green Chemistry & Engineering Conference (GC&E), Reston, VA. 9. Posmanik, R., (2017) Sustainable resource recovery from dairy waste streams. The International Workshop for Nitrogen Transformation, Application and Challenges, Nazareth, Israel. 10. Usack J.G., Hafenbradl, D., Posmanik, R., Tester, J.W., Angenent, L.T. (2018) Integrating electrochemical, biological, physical, and thermochemical process units to expand the applicability of anaerobic digestion. The5thInternational Conference on Renewable Energy Gas Technology, Toulouse, France. How have the results been disseminated to communities of interest?Seven articles were produced from this work. Additionally 10 presentations were made around the world on the findings. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? In this phase of the project, digested dairy manure was experimentally treated using hydrothermal liquefaction (HTL) by the Tester group at Cornell. A range of valuable products including bio-oil and hydrochar were recovered as a result of HTL processing . Following determination of the optimized operational conditions as reported by Posmanik et al (2017a, 2017b), HTL reactions on model wastes were conducted at 300 °C for 60 min, with and without the addition of acid or base. We measured the quantity and characterized the quality of the three main HTL products: a liquid oil phase , an aqueous phase containing soluble products, and solid hydro char. Results and Discussion Acidic and basic conditions affected the carbon yields in the oil, aqueous, and solid fractions produced from digested dairy manure by HTL. The bio-crude oil yield with the addition of acid was 58±2 wt% (carbon basis), higher by 59% than the yield without acid. Under alkali conditions, the bio-crude oil yield was 42±4 wt% (carbon basis), higher by only 15% than the yield without base. The use of acid or base decreased the production hydro-char from digested dairy manure at 300 ?C. Hydro-char yields were 22±3 and 18±3 wt% (carbon basis) under acidic and alkali conditions, respectively, lower by 10% and 25% compared to the yield without acid or base added, respectively. The aqueous product yield was 12±3 wt% (carbon basis) under acidic conditions, lower by 35% compared to the yield without acid added. On the other hand, the addition of base, increased the aqueous product yield to 27±8 wt%, higher by 39% compared to the yield without base. The distribution of carbon among the HTL product phases (oil, aqueous, and hydro-char) from manure is largely controlled by the reaction chemistry. Manure has high alkalinity due to high ammonia content. Therefore, the reaction media without additives had a high pH (9.1±0.3). The addition of acid to lower reaction pH had a notable effect on bio-crude oil yield. Manure is dominantly consists of lignocellulosic biomass, rich in cellulose, hemicellulose and lignin. Cellulose, the major structural component of plant cell walls, is apolysaccharideconsisting of a linear chain of 6-carbon glucoseunits.Hemicellulose, the second major component of lignocellulosic biomass, is a hetero-polymer formed by 5-carbon pentoses (xylose and arabinose) and hexoses (glucose, galactose and mannose). Lignin is a highly amorphous polymer formed by phenolic units in a complex cross-linked structure. Cellulose and hemicellulose are hydrolyzed mainly to hexoses and pentoses; lignin forms mainly phenols, alcohols, aldehydes, catechols, and organic acids. The primary product of HTL, bio-crude oil, is rich in carbon (70-79 wt%) and hydrogen (7-10%) and contains minimal amounts of oxygen (12-18 wt%) and nitrogen (1-5 wt%). Negligible amounts of ash (0-0.5 wt%) and sulfur (0-0.4 wt%) were detected in bio-crude oil samples. Digested dairy manure, a feedstock with 34 wt% carbon and 26 wt% oxygen, was valorized via HTL, by producing a bio-crude oil with a carbon content higher by 100% and oxygen content lower by more than 40%, compared to the feedstock. This was also demonstrated by the increased HHV of the bio-crude oil, 140% higher than the raw feedstock. Our results suggest that HTL can generate a bio-crude oil with a HHV of 32-36 MJ kg−1 from digested dairy manure, similar to HHVs from HTL of woody biomass, algae, and anaerobic sludge. The removal of oxygen in HTL occurs by decarboxylation, which removes oxygen in the form of carbon dioxide, and by dehydration, which removes oxygen in the form ofwater. A decrease in the atomic oxygen to carbon ratio (O/C) indicates decarboxylation, whereas a decrease in hydrogen to carbon ratio (H/C) indicates dehydration reactions. Our results showed that the atomic O/C ratio was reduced from 0.5-0.6 to 0.1-0.2 after HTL while the H/C ratios for the feedstock and its oil product was similar. This suggests that for manure, decarboxylation was the main mechanism for oxygen removal. Moreover, we found that decarboxylation was enhanced by either acid or base addition, as both bio-crude oils had lower O/C ratios than for bio-crude oil produced by HTL without additives. A decrease in the O/C ratio (i.e., enhanced decarboxylation) with less reductions in the H/C (i.e., reduced dehydration) ratio represents an advantage with respect to the oil quality and its downstream upgrading to fuel. ?

Publications

• Type: Journal Articles Status: Published Year Published: 2017 Citation: 1. Posmanik, R., Cantero, D.A., Malkani, A., Sills, D.L., Tester, J.W. (2017) Biomass conversion to bio-oil using sub-critical water: study of model compounds for food processing waste. Journal of Supercritical Fluids 119, 26-35.
• Type: Journal Articles Status: Published Year Published: 2017 Citation: 2. Gerber Van Doren, L., Posmanik, R., Tester, J.W., Sills, D.L. (2017) Prospects for heat recovery during biological and hydrothermal processing of biomass. Bioresource Technology 225, 67⿿74.
• Type: Journal Articles Status: Published Year Published: 2017 Citation: 3. Posmanik, R., Labatut, R.A, Kim, A., Usack, J.G., Tester, J.W., Angenent, L.T. (2017) Coupling hydrothermal liquefaction and anaerobic digestion for sustainable energy generation from food waste. Bioresource Technology 223, 134⿿143.
• Type: Journal Articles Status: Published Year Published: 2018 Citation: 4. Cantero-Tubilla B., Cantero, D., Martinez, C.M., Tester, J.W., Walker, L.P., Posmanik, R. (2018) Characterization of the solid products from hydrothermal liquefaction of waste feedstocks from food and agricultural industries. Journal of Supercritical Fluids 133, 665-673.
• Type: Journal Articles Status: Published Year Published: 2018 Citation: 5. Angenent, L.T., Usack J.G., Xu, J., Hafenbradl, D., Posmanik, R., Tester, J.W. (2018) Integrating electrochemical, biological, physical, and thermochemical process units to expand the applicability of anaerobic digestion. Bioresource Technology 247, 1085-1094.
• Type: Journal Articles Status: Published Year Published: 2018 Citation: 6. Posmanik, R., Martinez, C.M., Cantero-Tubilla B., Cantero, D., Sills, D.L., Cocero, M.J., Tester, J.W. (2018) Acidity and alkalinity effects on the hydrothermal liquefaction of dairy manure and food waste. Sustainable Chemistry and Engineering 6 (2), 2724⿿2732.
• Type: Journal Articles Status: Published Year Published: 2018 Citation: 7. Rao, U., Posmanik, R., Hatch, L.E., Tester, J.W., Walker, S.L., Barsanti, K.C., Jassby, D. (2018) Coupling hydrothermal liquefaction and membrane distillation to treat anaerobic digestate from food and dairy farm waste. Bioresource Technology 267, 408⿿415.

Progress 03/15/17 to 03/14/18

Outputs
Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest?One publication was recently accepted by ACS Sustainable Chemistry and Engineering. Other manuscripts are in earlier stages of preparation. This work has been presented in multiple venues as listed below: Conference talks: Posmanik R., Labatut R.A., Kim A.H., Usack J.G., Tester J.W., Angenent L.T. (2016) Integrating hydrothermal liquefaction and anaerobic digestion for sustainable energy generation from food waste. Food Waste-to-Low Carbon Energy Conference. New Brunswick, NJ. Angenent L.T., Usack J.G., Daly S.E., Posmanik R., Tester J.W. (2016) Resource recovery from food waste: from storage to biorefineries. Food Waste-to-Low Carbon Energy Conference. New Brunswick, NJ. Posmanik R., Cantero D.A., Martinez C.M., Cantero-Tubilla B., Tester J. W. (2016) SmartWaste­­­­­­­­­­­­: ­biomass conversion into low oxygenated hydrocarbons in subcritical water. AIChE Annual Meeting.San Francisco, CA. Sills D.L., Posmanik, R., Usack J.G., Moore M.C., Overton T.R., Angenent L.T., Tester J.W. (2016) Process integration of anaerobic digestion and hydrothermal liquefaction for sustainable energy generation and waste recovery in dairy operations. NYSAWWA/NYWEA Joint Energy Specialty Conference. Albany NY. Posmanik, R., Gerber Van Doren L., Tester J.W., Sills D.L. (2016) Prospects for heat recovery and techno-economic analysis for energy generation using biological and hydrothermal processing of biomass. NYSAWWA/NYWEA Joint Energy Specialty Conference. Albany NY. Martinez C.M., Posmanik R.,Cantero D.A. Cantero-Tubilla B., Cocero, M.J., Tester J.W. (2017)biomass conversion into low oxygenated hydrocarbons by hydrothermal liquefaction.The 10th World Congress of Chemical Engineering. Barcelona, Spain. Cantero-Tubilla, B., Posmanik, R., Tester, J.W. (2017) Thermochemical approach for valorization of waste streams from food, dairy and water treatment industries using subcritical water. The 21st Annual Green Chemistry & Engineering Conference (GC&E), Reston, VA. Sela, S., Sills, D.L van Es, H, McCann, M.S, Posmanik, R. (2017) From waste management to a valuable resource: Nitrogen footprint of manure applications, state incentives and potential farmer revenues. The 45th annual conference of the Israel Society of Ecology and Environmental Sciences, Herzliya, Israel. Invited talks Posmanik, R., Tester, J.W. (2016) Energy recovery from dairy wastes. Cornell Dairy Center of Excellence Seminar Series, Ithaca, NY. Posmanik, R. (2017) Sustainable resource recovery from agricultural waste: Biological and thermochemical processes. Cornel Energy Engineering Seminar Series, Ithaca, NY. Posmanik, R. (2017) Sustainable Resource Recovery from Dairy Waste Streams. The International Workshop for Nitrogen Transformation, Application and Challenges, Nazareth, Israel. What do you plan to do during the next reporting period to accomplish the goals?During this next reporting period, two PhD students (one jointly with UCR and UCLA and one at Cornell) will be actively working on this project. At this point we will have training, experimental results, and additional dissemination to report on.

Impacts
What was accomplished under these goals? Progress at both UCR and Cornell was made on experimental set-up development, solidification of the collaborative relationship (i.e. sharing of samples and data exchange), and a first publication has culminated. The researchers working on this project to date were covered by other funds and therefore, the project will continue next year funding two graduate students. Additional information on the findings from the two institutions are below: UCR: In this project, we evaluated the coupling of HTL (a method used to valorize organics in anaerobic digestate into usable crude oil) with MD (a water desalination method that uses thermal energy to recover water from concentrated waste stream). In this process, hot effluent from the HTL chamber was used as feed for the MD, with the goal of recovering water and nutrients from the HTL effluent. The MD system was operated using a PTFE porous membrane (made by 3M) in a cross-flow configuration. Water and volatiles from the feed pass into the permeate stream, leaving behind non-volatile compounds. We measured membrane flux as a function of % water recovery and observed that, as expected, membrane flux declined with increasing recovery due to the increased concentration of residual foulants in the feed. Importantly, membrane wetting was not observed during this process, and the membrane continued to operate effectively up to 75% water recovery. However, it was determined that there were some volatile organic compounds remaining in the HTL effluent, which passed with the water into the permeate stream. Using TOF-MS we identified these volatiles as primarily fatty acids. The concentrations of these volatiles was quite high: 250 mg/L when the HTL was fed manure and 35 mg/L when the HTL was fed food waste. The retentate was analyzed for its organic load, as well as the species of N and P nutrients. In terms of organics, the majority of organics remained in the retentate, as expected, resulting in a highly concentrated stream. Phosphorous was found only in the retentate, with the majority of phosphorous in the form of reactive P (orthophosphorous), which is an excellent fertilizer. Nitrogen was primarily found in the retentate, with the majority of nitrogen found in the form of ammonia. Very small amounts of nitrate were found in the permeate (<1 mg/L). In conclusion, MD is an excellent method to concentrate nutrients in HTL effluent, while producing a water stream that contains large concentrations of volatile fatty acids. These fatty acids are readily consumed by bacteria, indicating that this stream can be safely disposed of in a wastewater treatment plant. Cornell: The study explained the role of temperature, time and pH on hydrothermal liquefaction of complex biomass such as dairy manure digestate. The formation of bio-crude oil from dairy manure digestate increased with temperature, bringing the carbon recoveries in the oil product from 10% of the initial feedstock TOC at 200ºC to ca. 40% at 300ºC. The addition of acid to the hydrothermal media increased the bio-crude oil yield by 59% compared to the yield without acid. Our experimental data showed that increased bio-crude oil yield is associated with alternative chemical pathways such as dehydration reactions that were enhanced by the acidification of the reaction media. In addition, we characterized the aqueous and solid phase products and provided information necessary to advance the utilization of hydrothermal co-products. Increasing the fundamental understanding of the catalytic effect for acid on chemical pathways to yield higher recovery of quality bio-crude, as well as the properties of hydrothermal co-products generated, is essential for adjusting the conditions for valorization strategies.

Publications

• Type: Journal Articles Status: Published Year Published: 2017 Citation: Posmanik et al. "Acid and Alkali Catalyzed Hydrothermal Liquefaction of Dairy Manure Digestate and Food Waste" ACS Sustainable Chemistry and Engineering DOI: 10.1021/acssuschemeng.7b04359

Progress 03/15/16 to 03/14/17

Outputs
Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?One PhD student at UCR has been supported by this project. How have the results been disseminated to communities of interest?One paper has been produced from this work thus far. Posmanik et al. "Coupling hydrothermal liquefaction and anaerobic digestion for energy valorization from model biomass feedstocks" Bioresource Technology (2017) 233:134-143 (Cover article) What do you plan to do during the next reporting period to accomplish the goals?Our project is ongoing. We are still actively working on our primary project goals to test the feasibility of hydrothermal processing and membrane distillation for the recovery of energy, water, and nutrients. Specific activities by the Cornell team include efforts to determine the forces controlling the fate of nitrogen and phosphorous in the combined anaerobic digestion-hydrothermal liquefaction (AD-HTL) process; specifically, test the hydrolysis rates of carbohydrates, protein and lipids from dairy manure under a range of operating conditions (temperature, pressure, pH and residence time). The UCR team is testing the feasibility of the combined AD-HTL-MD process to produce distilled water using waste heat from the HTL.

Impacts
What was accomplished under these goals? This project has been investigating the combination of two processes - hydrothermal liquefaction (HTL) and membrane distillation (MD). To date the ability of a small-scale HTL reactor to reduce COD from liquid AD effluent was confirmed. The actual removal of COD was found to be highly sensitive to temperature with the lowest COD removal of 10-20% at 200-225?C, moderate levels of 50-60% for 250-300?C and highest levels of 80-90% for 325-350?C. Once an optimal thermal condition was identified, it was found that 67% of the organic carbon from a model feedstock was converted to oil (20% as soluble carbon in the aqueous phase) and there was a small amount of gas. This HTL approach produced bio-oil with a higher high heating value compared to the higher heating value of the feedstock. Additional experiments with dairy manure digestate as a feedstock were also conducted with HTL and demonstrated the potential of both acid and base catalysts to improve the oil production. These findings suggest that for manure, acidic conditions during HTL are more advantageous than and alkali conditions, in terms of minimizing char and gas production. A critical finding of this work is that there is ample residual heat available to facilitate the following MD process. Effluent from the HTL process has been extensively characterized in terms of nitrogen, phosphorus, and other relevant organic species. This effluent is being run through a MD system that has been fabricated using electrically conducting membranes. 75% recovery of water has been achieved with no significant fouling or membrane wetting observed. The permeate and retentate of the MD system is currently being characterized in terms of carbon, nitrogen, and phosphorous species to identify the quality of the nutrient recovery and organic species removal.

Publications

• Type: Journal Articles Status: Published Year Published: 2017 Citation: Posmanik et al. Coupling hydrothermal liquefaction and anaerobic digestion for energy valorization from model biomass feedstocks Bioresource Technology (2017) 233:134-143 (Cover article)