Producing “green” methanol from syngas, derived from anaerobic digestion biogas

Abstract

An anaerobic digester of sewage sludge or agro-industrial waste produces biogas and ammonia-rich digestate. Three H₂-producing processes exist: dry reforming of methane (from biogas), catalytic decomposition of methane (from biogas after CO₂ capture), and catalytic decomposition of ammonia (from digestate). Dry reforming of methane offers the best syngas yield at 700 °C and for a 50–50 vol % CH₄/CO₂ biogas. Catalytic decomposition of methane achieved a H₂ yield of 95%. Finally, the digestate was stripped and NH₃ was further completely decomposed into H₂ and N₂, for a complete NH₃ conversion at 650 °C. A methanol valorization case study of a wastewater treatment plant of 300000 person equivalents with an anaerobic digester is examined. The methanol production from syngas (H₂/CO) and H₂ product streams is simulated using Aspen Plus^®. This anaerobic digester process will daily generate 4485 m³ CH₄, 2415 m³ CO, and 320 kg NH₃. The methanol production will be 183 kg·h^–1 (1600 t·y^–1). The additional H₂ from ammonia’s catalytic decomposition (631 m³·d^–1) can be valorized with excess biogas in the anaerobic digester-associated combined heat and power unit. Due to a significantly higher ammonia concentration in manure, catalytic decomposition of ammonia will produce more H₂ if manure would be co-digested.

Graphical abstract

Keywords

bio-methanol / biogas / catalysis / reforming / syngas / simulation

References

[1] Zhang C , Su H , Baeyens J , Tan T . Reviewing the anaerobic digestion of food waste for biogas production. Renewable & Sustainable Energy Reviews, 2014, 38: 383–392

[2] Yang M , Vander Elst M , Smets I , Zhang H L , Li S , Baeyens J , Deng Y M . Reviewing improved anaerobic digestion by combined pre-treatment of waste-activated sludge (WAS). Sustainability, 2024, 16(15): 19

[3] JolaosoL AZamanS F. Catalytic ammonia decomposition for hydrogen production: utilization of ammonia in a fuel cell. In: Sustainable Ammonia Production: Green Energy and Technology. Cham: Springer, 2020, 81–105

[4] Deng Y , Dewil R , Appels L , Van Tulden F , Li S , Yang M , Baeyens J . Hydrogen-enriched natural gas in a decarbonization perspective. Fuel, 2022, 318: 123680

[5] Shao B , Wang Z Q , Gong X Q , Liu H , Qian F , Hu P , Hu J . Synergistic promotions between CO₂ capture and in-situ conversion on Ni-CaO composite catalyst. Nature Communications, 2023, 14(1): 996

[6] Zhao Y X , Zhai R R , Liu S Y , Xu Y , Liu L T . Low carbon economic scheduling of integrated energy system with concentrating solar power and multi-stage hydrogen utilization based on ladder-type carbon trading. International Journal of Green Energy, 2025, 22(4): 722–739

[7] Deng Y , Li S , Dewil R , Appels L , Yang M , Zhang H , Baeyens J . Water splitting by MnFe₂O₄/Na₂CO₃ reversible redox reactions. RSC Advances, 2022, 12(48): 31392–31401

[8] Eggemann L , Escobar N , Peters R , Burauel P , Stolten D . Life cycle assessment of a small-scale methanol production system: a power-to-fuel strategy for biogas plants. Journal of Cleaner Production, 2020, 271: 122476

[9] Bayraktar M , Yuksel O , Pamik M . An evaluation of methanol engine utilization regarding economic and upcoming regulatory requirements for a container ship. Sustainable Production and Consumption, 2023, 39: 345–356

[10] Iaquaniello G , Centi G , Salladini A , Palo E , Perathoner S , Spadaccini L . Waste-to-methanol: process and economics assessment. Bioresource Technology, 2017, 243: 611–619

[11] Bellotti D , Rivarolo M , Magistri L , Massardo A F . Feasibility study of methanol production plant from hydrogen and captured carbon dioxide. Journal of CO₂ Utilization, 2017, 21: 132–138

[12] Baena-Moreno F M , Pastor-Pérez L , Wang Q , Reina T R . Bio-methane and bio-methanol co-production from biogas: a profitability analysis to explore new sustainable chemical processes. Journal of Cleaner Production, 2020, 265: 121909

[13] Iaquaniello G , Centi G , Salladini A , Palo E , Perathoner S . Waste to chemicals for a circular economy. Chemistry, 2018, 24(46): 11831–11839

[14] Borgogna A , Salladini A , Spadacini L , Pitrelli A , Annesini M C , Iaquaniello G . Methanol production from refuse derived fuel: influence of feedstock composition on process yield through gasification analysis. Journal of Cleaner Production, 2019, 235: 1080–1089

[15] Gautam P . Neha, Upadhyay S N, Dubey S K. Bio-methanol as a renewable fuel from waste biomass: current trends and future perspective. Fuel, 2020, 273: 117783

[16] Giulia B , Flavio M . Efficient methanol synthesis: perspectives, technologies, and optimization strategies. Progress in Energy and Combustion Science, 2016, 56: 71–105

[17] Sheldon D . Methanol production: a technical history. Johnson Matthey Technology Review, 2017, 61(3): 172–182

[18] SepahiSRahimpourM R. Chapter 5 Methanol Production from Syngas. In: Advances in Synthesis Gas: Methods, Technologies and Applications. Amsterdam: Elsevier, 2023, 111–146

[19] Liu G , Hagelin-Weaver H , Welt B . A concise review of catalytic synthesis of methanol from synthesis gas. Waste, 2023, 1(1): 228–248

[20] Van-Dal É S , Bouallou C . Design and simulation of a methanol production plant from CO₂ hydrogenation. Journal of Cleaner Production, 2013, 57: 38–45

[21] Mucci S, Mitsos A, Bongartz D. Cost-optimal power-to-methanol: flexible operation or intermediate storage? Journal of Energy Storage, 2023, 72: 108614

[22] Bisotti F , Fedeli M , Prifti K , Galeazzi A , Dell’Angelo A , Manenti F . Impact of kinetic models on methanol synthesis reactor predictions: in silico assessment and comparison with industrial data. Industrial & Engineering Chemistry Research, 2022, 61(5): 2206–2226

[23] PalmaVMeloniERuoccoCMartinoMRiccaA. Chapter 2 State of the Art of Conventional Reactors for Methanol Production. In: Methanol. Amsterdam: Elsevier, 2018, 29–51

[24] Bisotti F, Fedeli M, Prifti K, Galeazzi A, Dell’Angelo A, Barbieri M, Pirola C, Bozzano G, Manenti F. Century of technology trends in methanol synthesis: any need for kinetics refitting? Industrial & Engineering Chemistry Research, 2021, 60(44): 16032–16053

[25] Villa P , Forzatti P , Buzzi-Ferraris G , Garone G , Pasquon I . Synthesis of alcohols from carbon oxides and hydrogen. 1. Kinetics of the low-pressure methanol synthesis. Industrial & Engineering Chemistry Process Design and Development, 1985, 24(1): 12–19

[26] Klier K , Chatikavanij V , Herman R G , Simmons G W . Catalytic synthesis of methanol from COH₂: IV. The effects of carbon dioxide. Journal of Catalysis, 1982, 74(2): 343–360

[27] McNeil M A , Schack C J , Rinker R G . Methanol synthesis from hydrogen, carbon monoxide, and carbon dioxide over a CuO/ZnO/Al₂O₃ catalyst: II. Development of a phenomenological rate expression. Applied Catalysis, 1989, 50(1): 265–285

[28] Ma H F , Ying W Y , Fang D Y . Study on methanol synthesis from coal-based syngas. Journal of Coal Science and Engineering, 2009, 15(1): 98–103

[29] Takagawa M , Ohsugi M . Study on reaction rates for methanol synthesis from carbon monoxide, carbon dioxide, and hydrogen. Journal of Catalysis, 1987, 107(1): 161–172

[30] Graaf G H , Stamhuis E J , Beenackers A A C M . Kinetics of low-pressure methanol synthesis. Chemical Engineering Science, 1988, 43(12): 3185–3195

[31] Seidel C , Jörke A , Vollbrecht B , Seidel-Morgenstern A , Kienle A . Kinetic modeling of methanol synthesis from renewable resources. Chemical Engineering Science, 2018, 175: 130–138

[32] Park N , Park M J , Lee Y J , Ha K S , Jun K W . Kinetic modeling of methanol synthesis over commercial catalysts based on three-site adsorption. Fuel Processing Technology, 2014, 125: 139–147

[33] Lim H W , Park M J , Kang S H , Chae H J , Bae J W , Jun K W . Modeling of the kinetics for methanol synthesis using Cu/ZnO/Al₂O₃/ZrO₂ catalyst: influence of carbon dioxide during hydrogenation. Industrial & Engineering Chemistry Research, 2009, 48(23): 10448–10455

[34] Skrzypek J , Lachowska M , Moroz H . Kinetics of methanol synthesis over commercial copper/zinc oxide/alumina catalysts. Chemical Engineering Science, 1991, 46(11): 2809–2813

[35] Askgaard T S , Norskov J K , Ovesen C V , Stoltze P . A kinetic model of methanol synthesis. Journal of Catalysis, 1995, 156(2): 229–242

[36] Kubota T , Hayakawa I , Mabuse H , Mori K , Ushikoshi K , Watanabe T , Saito M . Kinetic study of methanol synthesis from carbon dioxide and hydrogen. Applied Organometallic Chemistry, 2001, 15(2): 121–126

[37] Bussche K M V , Froment G F . A steady-state kinetic model for methanol synthesis and the water gas shift reaction on a commercial Cu/ZnO/Al₂O₃ catalyst. Journal of Catalysis, 1996, 161(1): 1–10

[38] Tripodi A , Compagnoni M , Martinazzo R , Ramis G , Rossetti I . Process simulation for the design and scale up of heterogeneous catalytic process: kinetic modelling issues. Catalysts, 2017, 7(5): 159

[39] Kiss A A , Pragt J J , Vos H J , Bargeman G , de Groot M T . Novel efficient process for methanol synthesis by CO₂ hydrogenation. Chemical Engineering Journal, 2016, 284: 260–269

[40] Graaf G H , Scholtens H , Stamhuis E J , Beenackers A A C M . Intra-particle diffusion limitations in low-pressure methanol synthesis. Chemical Engineering Science, 1990, 45(4): 773–783

[41] Deng Y , Baeyens J , Elst Margot V , Liu H . Renewable electricity and “green” feedstock-based chemicals will foster industrial sustainability. Innovation Energy, 2024, 1(2): 100016

RIGHTS & PERMISSIONS

Higher Education Press