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ACS omega2026; 11(21); 31510-31520; doi: 10.1021/acsomega.6c01555

Alkaline-Promoted Hydrothermal Liquefaction of Polo Horse Manure for Biocrude Production.

Abstract: Horse manure (collected as pure feces) is a high-moisture, nutrient-dense organic waste stream with potential for valorization via hydrothermal liquefaction (HTL). However, catalyst selection is often reported without direct catalyst-class comparisons under identical conditions. In this study, manure collected in Thailand was characterized and converted via noncatalytic and catalytic HTL in a batch reactor at 300 °C for 40 min (feedstock/water = 1:10, w/w; heating rate 10 °C min). Four catalysts (KOH, NaOH, HPO, NH·HO) were evaluated at 10 and 20 wt % (dry feed basis), with biocrude recovered by dichloromethane extraction and quantified gravimetrically (mean ± SD, = 3). Noncatalytic HTL produced 15.4 wt % biocrude, whereas alkali promotion substantially increased yield: KOH produced 42.8 wt % (10 wt %) and 51.1 wt % (20 wt %), and NaOH produced 39.1 wt % (10 wt %) and 55.1 wt % (20 wt %), the highest yield obtained. In contrast, HPO (10.7-11.3 wt %) and NH·HO (4.6-11.7 wt %) did not improve yields relative to the baseline. Chemical characterization via FTIR revealed mixed aliphatic and oxygenated functionalities in both biocrudes. Furthermore, GC-MS analysis of the highest-yield condition (20 wt % NaOH) showed a dominance of lipid-like ester species (75.85% peak area). Ultimate analysis indicated that CAT-HTL increased the estimated higher heating value (HHV) of the product. Overall, alkali promotion particularly 20 wt % NaOH was the most effective strategy among tested catalysts for maximizing biocrude yield from horse manure under fixed reaction severity.
Publication Date: 2026-05-16 PubMed ID: 42255545PubMed Central: PMC13235218DOI: 10.1021/acsomega.6c01555Google Scholar: Lookup
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  • Journal Article

Summary

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Overview

  • This study investigates the conversion of horse manure into biocrude oil using hydrothermal liquefaction (HTL), comparing the effects of different alkaline catalysts on biocrude yield and quality under identical reaction conditions.

Background and Motivation

  • Horse manure is a nutrient-rich, high-moisture organic waste often considered for renewable energy production.
  • Hydrothermal liquefaction (HTL) is a thermochemical process that converts wet biomass into biocrude, a crude oil-like substance that can be refined into fuels.
  • Previous studies lack direct comparisons of different catalysts for HTL under the same experimental conditions.
  • This research aims to fill that gap by evaluating several catalysts for HTL of horse manure to maximize biocrude yield and enhance energy content.

Materials and Methods

  • Horse manure was collected from Thailand and analyzed for key characteristics such as moisture content and nutrient density.
  • HTL experiments were conducted in a batch reactor at 300 °C for 40 minutes with a feedstock-to-water ratio of 1:10 (weight basis) and a heating rate of 10 °C per minute.
  • Four catalysts were tested at two loadings (10 wt% and 20 wt% relative to dry feed): potassium hydroxide (KOH), sodium hydroxide (NaOH), hypophosphorous acid (HPO), and ammonium hydroxide (NH₄OH).
  • Biocrude oil was extracted using dichloromethane and quantified gravimetrically to assess yield.
  • Three replicates per condition ensured statistical reliability (mean ± standard deviation reported).

Results: Biocrude Yield

  • Noncatalytic HTL (no catalyst) yielded 15.4 wt% biocrude from dry manure.
  • Alkali catalysts greatly increased biocrude yields:
    • KOH at 10 wt% gave 42.8 wt%, and at 20 wt% gave 51.1 wt% biocrude.
    • NaOH at 10 wt% produced 39.1 wt%, and at 20 wt% produced the highest yield of 55.1 wt% biocrude.
  • Non-alkali catalysts did not significantly improve yield:
    • HPO produced 10.7-11.3 wt% biocrude.
    • NH₄OH produced 4.6-11.7 wt% biocrude.
  • This shows that alkali catalysts, particularly NaOH at higher loading, are highly effective for promoting HTL biocrude production.

Chemical Characterization

  • Fourier-transform infrared spectroscopy (FTIR) analysis revealed biocrudes contained a mix of aliphatic (hydrocarbon-like) and oxygenated functional groups.
  • Gas chromatography-mass spectrometry (GC-MS) of biocrude from 20 wt% NaOH HTL showed a dominance (75.85% peak area) of lipid-like ester compounds, typical molecules derived from fats and oils.
  • Ultimate (elemental) analysis indicated that catalytic HTL increased the higher heating value (HHV), meaning biocrude from catalyzed runs has higher energy content compared to raw manure or noncatalytic processes.

Conclusions and Implications

  • The study conclusively demonstrates that alkaline catalysts significantly enhance biocrude yield from horse manure under hydrothermal liquefaction conditions at 300 °C.
  • Among tested catalysts, 20 wt% NaOH yielded the most biocrude, suggesting strong base catalysis facilitates breakdown and conversion of manure components into energy-rich oils.
  • The chemical makeup of the biocrude is favorable for use as a biofuel precursor due to high ester content and increased heating value.
  • This research informs catalyst selection for sustainable valorization of nutrient-rich agricultural wastes like horse manure into renewable liquid fuels.

Cite This Article

APA
Namsiri P, Pianthong K, Thanakijkasem P. (2026). Alkaline-Promoted Hydrothermal Liquefaction of Polo Horse Manure for Biocrude Production. ACS Omega, 11(21), 31510-31520. https://doi.org/10.1021/acsomega.6c01555

Publication

ISSN: 2470-1343
NlmUniqueID: 101691658
Country: United States
Language: English
Volume: 11
Issue: 21
Pages: 31510-31520

Researcher Affiliations

Namsiri, Pongthep
  • Program of Energy Technology, School of Energy, Environment and Materials, King Mongkut's University of Technology Thonburi, 126 Pracha Uthit Rd, Bang Mod, Thung Khru, Bangkok 10140, Thailand.
Pianthong, Kulachate
  • Faculty of Engineering, Ubon Ratchathani University, 85 Sathonlamak Rd, Mueang Si Khai, Warin Chamrap District, Ubon Ratchathani 34190, Thailand.
Thanakijkasem, Purit
  • Program of Energy Technology, School of Energy, Environment and Materials, King Mongkut's University of Technology Thonburi, 126 Pracha Uthit Rd, Bang Mod, Thung Khru, Bangkok 10140, Thailand.

References

This article includes 58 references
  1. Kabeyi MJB, Akanni O. Dimensions of Energy Sustainability Measurement. Proceedings of the International Conference on Industrial Engineering and Operations Management IEOM Society International, 2023.
    doi: 10.46254/in03.20230164google scholar: lookup
  2. Kabeyi MJB, Olanrewaju OA. Sustainable Energy Transition for Renewable and Low Carbon Grid Electricity Generation and Supply. Frontiers in Energy Research 2022;9:743114.
    doi: 10.3389/fenrg.2021.743114google scholar: lookup
  3. Ermakova D, Bae JW, Wainwright H, Vujić J. Remining and Restoring Abandoned US Mining Sites: The Case for Materials Needed for Zero-Carbon Transition. 2022.
    doi: 10.2172/1888913google scholar: lookup
  4. Yu X, Manthiram A. Sustainable Battery Materials for Next-Generation Electrical Energy Storage. Adv. Energy Sustain. Res. 2021;2(5):2000102.
    doi: 10.1002/aesr.202000102google scholar: lookup
  5. Jena MC, Mishra SK, Moharana HS. Shifting Towards Renewable Energy: A Sustainable Solution to Pollution. Sustainable Social Development 2024;2(6):2905.
    doi: 10.54517/ssd2905google scholar: lookup
  6. Nasir MN, Bengi KS. The Energy Mix Dilemma in Indonesia in Achieving Net Zero Emissions by 2060. Asean Natural Disaster Mitigation and Education Journal 2024, 2(1).
  7. Li W, Dumortier J, Dokoohaki H, Miguez FE, Brown RC, Laird DA, Wright MM. Regional Techno-economic and Life-cycle Analysis of the Pyrolysis-bioenergy-biochar Platform for Carbon-negative Energy. Biofuel Bioprod. Biorefining 2019;13(6):1428–1438.
    doi: 10.1002/bbb.2043google scholar: lookup
  8. Wang Y, Wang J, Zhang X, Grushecky ST. Environmental and Economic Assessments and Uncertainties of Multiple Lignocellulosic Biomass Utilization for Bioenergy Products: Case Studies. Energies 2020;13(23):6277.
    doi: 10.3390/en13236277google scholar: lookup
  9. Benavides PT, Bartling A, Phillips S, Hawkins TR, Singh A, Zaimes GG, Wiatrowski M, Harris K, Burli P, Hartley D. Identification of Key Drivers of Cost and Environmental Impact for Biomass-Derived Fuel for Advanced Multimode Engines Based on Techno-Economic and Life Cycle Analysis. ACS Sustainable Chem. Eng. 2022;10(32):10465–10475.
  10. Woertz I, Benemann JR, Du N, Unnasch S, Mendola D, Mitchell BG, Lundquist T. Life Cycle GHG Emissions From Microalgal Biodiesel – A CA-GREET Model. Environ. Sci. Technol. 2014;48(11):6060–6068.
    doi: 10.1021/es403768qpubmed: 24779347google scholar: lookup
  11. Mathanker A, Das S, Pudasainee D, Khan M, Kumar A, Gupta R. A Review of Hydrothermal Liquefaction of Biomass for Biofuels Production with a Special Focus on the Effect of Process Parameters, Co-Solvents, and Extraction Solvents. Energies 2021;14:4916.
    doi: 10.3390/en14164916google scholar: lookup
  12. Nonchana T, Pianthong K. Bio-oil synthesis from cassava pulp via hydrothermal liquefaction: Effects of catalysts and operating conditions. Int. J. Renewable Energy Dev. 2020;9:329–337.
  13. Nonchana T, Pianthong K, Milton BE, Takayama K. Effect of reaction temperature and ethanol-to-water ratio on bio-oil yield from catalytic hydrothermal liquefaction of sugarcane leaves. Journal of Research and Applications in Mechanical Engineering 2021;9(2):021.
  14. Ocampo E, Beltrán VV, Gómez EA, Ríos LA, Ocampo D. Hydrothermal liquefaction process: Review and trends. Curr. Res. Green Sustainable Chem. 2023;7:100382.
  15. Usman M, Cheng S, Boonyubol S, Cross JS. From biomass to biocrude: Innovations in hydrothermal liquefaction and upgrading. Energy Convers. Manage. 2024;302:118093.
  16. Alherbawi M, Parthasarathy P, Al-Ansari T, Mackey H, McKay G. Potential of drop-in biofuel production from camel manure by hydrothermal liquefaction and biocrude upgrading: A Qatar case study. Energy 2021;232:121027.
  17. dos Passos J S, Matayeva A, Biller P. Synergies during hydrothermal liquefaction of cow manure and wheat straw. J. Environ. Chem. Eng. 2022;10(5):108181.
  18. Kwakye J M, Ekechukwu D E, Ogundipe O B. Systematic Review of the Economic Impacts of Bioenergy on Agricultural Markets. Int. J. Adv. Manag. Econ. 2024;6(7):306–318.
    doi: 10.51594/ijae.v6i7.1342google scholar: lookup
  19. Çetinkaya A Y, Yılmaz F, Bilgili L. Life Cycle Assessment and Thermodynamic Performance of Biomass-Based Combined Cogeneration. Eng. Res. Express 2024;6(4):045009.
    doi: 10.1088/2631-8695/ad9982google scholar: lookup
  20. Harrison B P, Moo Z, Perez-Agredano E, Gao S, Zhang X, Ryals R. Biochar-Composting Substantially Reduces Methane and Air Pollutant Emissions From Dairy Manure. Environ. Res. Lett. 2024;19(1):014081.
    doi: 10.1088/1748-9326/ad1ad2google scholar: lookup
  21. dos Passos J S, Matayeva A, Biller P. Synergies During Hydrothermal Liquefaction of Cow Manure and Wheat Straw. J. Environ. Chem. Eng. 2022;10(5):108181.
  22. Jha S, Okolie J A, Nanda S, Dalai A K. A Review of Biomass Resources and Thermochemical Conversion Technologies. Chem. Eng. Technol. 2022;45(5):791–799.
    doi: 10.1002/ceat.202100503google scholar: lookup
  23. Jiang J, Lopez-Ruiz J A, Leininger A, Du L, Yan Y, May H D, Ren Z J. Molecular Transformation and Metabolic Insights of Microbial Electrolysis Treatment and Valorization of Post-Hydrothermal Liquefaction Wastewater. Green Chem. 2023;25(22):9115–9125.
    doi: 10.1039/D3GC02252Hgoogle scholar: lookup
  24. Lu J, Liu Z, Zhang Y, Savage P E. Synergistic and Antagonistic Interactions During Hydrothermal Liquefaction of Soybean Oil, Soy Protein, Cellulose, Xylose, and Lignin. ACS Sustainable Chem. Eng. 2018;6(11):14501–14509.
  25. Ding X, Mahadevan Subramanya S, Fang T, Guo Y, Savage P E. Effects of Potassium Phosphates on Hydrothermal Liquefaction of Triglyceride, Protein, and Polysaccharide. Energy Fuels 2020;34(12):15313–15321.
  26. Vadlamudi D P, Pecchi M, Sudibyo H, Tester J W. Direct and Two-Stage Hydrothermal Liquefaction of Chicken Manure: Impact of Reaction Parameters on Biocrude Oil Upgradation. ACS Sustainable Chem. Eng. 2024;12(10):4300–4313.
  27. Motavaf B, Savage P E. Effect of Process Variables on Food Waste Valorization via Hydrothermal Liquefaction. ACS ES&T Eng. 2021;1(3):363–374.
  28. Sudibyo H, Tester J W. Sustainable Resource Recovery From Dairy Waste: A Case Study of Hydrothermal Co-Liquefaction of Acid Whey and Anaerobic Digestate Mixture. Energy Fuels 2023;37(4):2897–2911.
  29. Okolie J A, Jimoh T, Akande O, Okoye P U, Ogbaga C C, Adeleke A A, Ikubanni P P, Güleç F, Amenaghawon A N. Pathways for the Valorization of Animal and Human Waste to Biofuels, Sustainable Materials, and Value-Added Chemicals. Environments 2023;10(3):46.
  30. Matsumura Y, Suganuma Y, Ichikawa T, Kim W, Nakashimada Y, Nishida K. Reaction Rate of Hydrothermal Ammonia Production From Chicken Manure. Acs Omega 2021;6(36):23442–23446.
    doi: 10.1021/acsomega.1c03418pmc: PMC8444327pubmed: 34549142google scholar: lookup
  31. Zhu C, Gutiérrez OY, Santosa DM, Kutnyakov IV, Weindl R, Shi H, Wang H. Impact of Coprocessing Biocrude With Petroleum Stream on Hydrotreating Catalyst Stability. Energy Fuels 2022;36(16):9133–9146.
  32. Rojas-Pérez A, Diaz-Diestra D, Frias-Flores CB, Beltran-Huarac J, Das KC, Weiner BR, Morell G, Díaz-Vázquez LM. Catalytic Effect of Ultrananocrystalline Fe3 O4 on Algal Bio-Crude ProductionviaHTL Process. Nanoscale 2015;7(42):17664–17671.
    doi: 10.1039/c5nr04404apubmed: 26465090google scholar: lookup
  33. Zhang L, Wang J, Ming H, Hu H, Dou X, Xiao Y, Cheng L, Hu Z. Investigation of Cotton Stalk-Derived Hydrothermal Bio-Oil: Effects of Mineral Acid/Base and Oxide Additions. Energies 2024;17(19):4854.
    doi: 10.3390/en17194854google scholar: lookup
  34. Shah AA, Sharma K, Seehar TH, Toor SS, Sandquist J, Saanum I, Pedersen TH. Sub-Supercritical Hydrothermal Liquefaction of Lignocellulose and Protein-Containing Biomass. Fuels 2024;5(1):75–89.
    doi: 10.3390/fuels5010005google scholar: lookup
  35. Chen WT, Jin K, Linda Wang NH. Use of Supercritical Water for the Liquefaction of Polypropylene Into Oil. ACS Sustainable Chem. Eng. 2019;7(4):3749–3758.
  36. Zhu Z, Toor SS, Rosendahl L, Chen G. Analysis of Product Distribution and Characteristics in Hydrothermal Liquefaction of Barley Straw in Subcritical and Supercritical Water. Environ. Prog. Sustainable Energy 2014;33(3):737–743.
    doi: 10.1002/ep.11977google scholar: lookup
  37. Posmanik R, Martinez C, Cantero-Tubilla B, Cantero DA, Sills DL, Cocero MAJ, Tester JW. Acid and Alkali Catalyzed Hydrothermal Liquefaction of Dairy Manure Digestate and Food Waste. ACS Sustainable Chem. Eng. 2018;6(2):2724–2732.
  38. Madsen RB, Bernberg RZK, Biller P, Becker J, Iversen BB, Glasius M. Hydrothermal Co-Liquefaction of Biomasses – Quantitative Analysis of Bio-Crude and Aqueous Phase Composition. Sustainable Energy & Fuels 2017;1(4):789–805.
    doi: 10.1039/C7SE00104Egoogle scholar: lookup
  39. Shende A, Tungal R, Jaswal R, Shende RV. A Novel Integrated Hydrothermal Liquefaction and Solar Catalytic Reforming Method for Enhanced Hydrogen Generation From Biomass. Am. J. Energy Res. 2015;3(1):1–7.
    doi: 10.12691/ajer-3-1-1google scholar: lookup
  40. Liu Q, Kong G, Zhang G, Cao T, Wang K, Zhang X, Han L. Recent advances in hydrothermal liquefaction of manure wastes into value-added products. Energy Convers. Manage. 2023;292:117392.
  41. Toor SS, Rosendahl L, Rudolf A. Hydrothermal liquefaction of biomass: A review of subcritical water technologies. Energy 2011;36(5):2328–2342.
  42. Gollakota ARK, Kishore N, Gu S. A review on hydrothermal liquefaction of biomass. Renew. Sustain. Energy Rev. 2018;81:1378–1392.
  43. Castello D, Haider MS, Rosendahl LA. Catalytic upgrading of hydrothermal liquefaction biocrudes: Different challenges for different feedstocks. Renewable Energy 2019;141:420–430.
  44. Hadin Å, Eriksson O, Hillman K. A review of potential critical factors in horse keeping for anaerobic digestion of horse manure. Renew. Sustain. Energy Rev. 2016;65:432.
  45. Mong GR, Chong CT, Ng J-H, Chong WWF, Lam SS, Ong HC, Ani FN. Microwave pyrolysis for valorisation of horse manure biowaste. Energy Convers. Manage. 2020;220:113074.
  46. Kaewtrakulchai N, Putta A, Pasee W, Fuangnawakij K, Panomsuwan G, Eiad-ua A. Magnetic Carbon Nanofibers from Horse Manure via Hydrothermal Carbonization for Methylene Blue Adsorption. IOP Conference Series: Materials Science and Engineering 2019, 540, 012006.
  47. Kaewtrakulchai N, Chanpee S, Pasee W, Putta A, Chutipaijit S, Kaewpanha M, Suriwong T, Puengjinda P, Panomsuwan G, Fuji M. Valorization of horse manure conversion to magnetic carbon nanofiber for dye adsorption by hydrothermal treatment coupled with carbonization. Case Stud. Chem. Environ. Eng. 2024;9:100563.
  48. Shah A A, Sharma K, Haider M S, Toor S S, Rosendahl L, Pedersen T H, Castello D. The Role of Catalysts in Biomass Hydrothermal Liquefaction and Biocrude Upgrading. Processes 2022;10(2):207.
    doi: 10.3390/pr10020207google scholar: lookup
  49. Ghosh S, Rana M, Park J H. Catalyst-Free Depolymerization of Methanol-Fractionated Kraft Lignin to Aromatic Monomers in Supercritical Methanol. Energies 2024;17(24):6482.
    doi: 10.3390/en17246482google scholar: lookup
  50. Margellou A, Torofias S, Iakovou G, Triantafyllidis K S. Valorization of Chlorella Microalgae Residual Biomass via Catalytic Acid Hydrolysis/Dehydration and Hydrogenolysis/Hydrogenation. Catalysts 2024;14(5):286.
    doi: 10.3390/catal14050286google scholar: lookup
  51. Alper K, Tekin K, Karagöz S. Hydrothermal Liquefaction of Lignocellulosic Biomass Using Potassium Fluoride-Doped Alumina. Energy Fuels 2019;33(4):3248–3256.
  52. Chia S R, Chew K W, Show P L, Yap Y J, Ong H C, Ling T C, Chang J S. Analysis of Economic and Environmental Aspects of Microalgae Biorefinery for Biofuels Production: A Review. Biotechnol. J. 2018:1700618.
    doi: 10.1002/biot.201700618pubmed: 29356369google scholar: lookup
  53. Aman A M N, Selvarajoo A, Lau T L, Chen W H. Biochar as Cement Replacement to Enhance Concrete Composite Properties: A Review. Energies 2022;15(20):7662.
    doi: 10.3390/en15207662google scholar: lookup
  54. Ding X, Subramanya S M, Wang Y, Savage P E. Effects of Potassium Phosphates and Other Additives on Biocrude Production and Composition From Hydrothermal Liquefaction of Pectin and Chitin. Ind. Eng. Chem. Res. 2021;60(24):8642–8648.
    doi: 10.1021/acs.iecr.1c00913google scholar: lookup
  55. Chao C L V, Carpio R B, Yap K J R, Leon R L d. Influence of Potassium Carbonate (K2CO3) as Catalyst on Biocrude Oil Yield and Properties via Hydrothermal Liquefaction of Spirulina. International Journal of Smart Grid and Clean Energy 2018;7(1):42–47.
    doi: 10.12720/sgce.7.1.42-47google scholar: lookup
  56. Sánchez-Bayo A, Rodríguez R a, Morales V, Nasirian N, Bautista L F, Vicente G. Hydrothermal Liquefaction of Microalga Using Metal Oxide Catalyst. Processes 2019;8(1):15.
    doi: 10.3390/pr8010015google scholar: lookup
  57. Chen W T, Tang L, Qian W, Scheppe K, Nair K, Wu Z, Gai C, Zhang P, Zhang Y. Extract Nitrogen-Containing Compounds in Biocrude Oil Converted From Wet Biowaste via Hydrothermal Liquefaction. ACS Sustainable Chem. Eng. 2016;4(4):2182–2190.
  58. Lu J, Li H, Zhang Y, Liu Z. Nitrogen Migration and Transformation During Hydrothermal Liquefaction of Livestock Manures. ACS Sustainable Chem. Eng. 2018;6(10):13570–13578.

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