Abstract
Methanol, the simplest aliphatic molecule of the alcohol family, finds diverse range of applications as an industrial solvent, a precursor for producing other chemicals (e.g., dimethyl ether, acetic acid and formaldehyde), and a potential fuel. There are conventional chemical routes for methanol production such as, steam reforming of natural gas to form syngas, followed by catalytic conversion into methanol; direct catalytic oxidation of methane, or hydrogenation of carbon dioxide. However, these chemical routes are limited by the requirement for expensive catalysts and extreme process conditions, and plausible environmental implications. Alternatively, methanotrophic microorganisms are being explored as biological alternative for methanol production, under milder process conditions, bypassing the requirement for chemical catalysts, and without imposing any adverse environmental impact. Methanotrophs possess inherent metabolic pathways for methanol production via biological methane oxidation or carbon dioxide reduction, thus offering a surplus advantage pertaining to the sequestration of two major greenhouse gases. This review sheds light on the recent advances in methanotrophic methanol production including metabolic pathways, feedstocks, metabolic engineering, and bioprocess engineering approaches. Furthermore, various reactor configurations are discussed in view of the challenges associated with solubility and mass transfer limitations in methanotrophic gas fermentation systems.
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References
Ali S, Sørensen K, Nielsen MP (2020) Modeling a novel combined solid oxide electrolysis cell (SOEC) - Biomass gasification renewable methanol production system. Renew Energy 154:1025–1034. https://doi.org/10.1016/J.RENENE.2019.12.108
AlSayed A, Fergala A, Khattab S et al (2018) Optimization of methane bio-hydroxylation using waste activated sludge mixed culture of type I methanotrophs as biocatalyst. Appl Energy 211:755–763. https://doi.org/10.1016/J.APENERGY.2017.11.090
Amulya K, Kopperi H, Venkata Mohan S (2020) Tunable production of succinic acid at elevated pressures of CO2 in a high pressure gas fermentation reactor. Bioresour Technol 309:123327. https://doi.org/10.1016/J.BIORTECH.2020.123327
Baxter NJ, Hirt RP, Bodrossy L et al (2002) The ribulose-1,5-bisphosphate carboxylase/oxygenase gene cluster of Methylococcus capsulatus (bath). Arch Microbiol 177:279–289. https://doi.org/10.1007/S00203-001-0387-X
Bennett RK, Dzvova N, Dillon M et al (2021) Expression of soluble methane monooxygenase in Escherichia coli enables methane conversion. bioRxiv 2021.08.05.455234. https://doi.org/10.1101/2021.08.05.455234
Cantera S, Estrada JM, Lebrero R et al (2016) Comparative performance evaluation of conventional and two-phase hydrophobic stirred tank reactors for methane abatement: Mass transfer and biological considerations. Biotechnol Bioeng 113:1203–1212. https://doi.org/10.1002/BIT.25897
Cattaneo CR, Rodríguez Y, Rene ER et al (2022) Biogas bioconversion into poly(3-hydroxybutyrate) by a mixed microbial culture in a novel Taylor flow bioreactor. Waste Manag 150:364–372. https://doi.org/10.1016/J.WASMAN.2022.07.017
Chidambarampadmavathy K, Obulisamy PK, Heimann K (2015) Role of copper and iron in methane oxidation and bacterial biopolymer accumulation. Eng Life Sci 15:387–399. https://doi.org/10.1002/ELSC.201400127
Cho S, Lee YS, Chai H et al (2022) Enhanced production of ectoine from methane using metabolically engineered Methylomicrobium alcaliphilum 20Z. Biotechnol Biofuels Bioprod 15:1–13. https://doi.org/10.1186/s13068-022-02104-2
Crombie A, Murrell JC (2011) Development of a system for genetic manipulation of the Facultative Methanotroph Methylocella silvestris BL2. Methods Enzymol 495:119–133. https://doi.org/10.1016/B978-0-12-386905-0.00008-5
Dalena F, Senatore A, Marino A et al (2018) Methanol production and applications: an overview. Methanol: Sci Eng 3–28. https://doi.org/10.1016/B978-0-444-63903-5.00001-7
Dedysh SN, Horz HP, Dunfield PF, Liesack W (2001) A novel pmoA lineage represented by the acidophilic methanotrophic bacterium Methylocapsa acidophila B2. Arch Microbiol 177:117–121. https://doi.org/10.1007/S00203-001-0362-6
Dedysh SN, Khmelenina VN, Suzina NE et al (2002) Methylocapsa acidiphila gen. nov., sp. nov., a novel methane-oxidizing and dinitrogen-fixing acidophilic bacterium from Sphagnum bog. Int J Syst Evol Microbiol 52:251–261. https://doi.org/10.1099/00207713-52-1-251
Doran PM (1995) Bioprocess Engineering principles, second edn. Elsevier
Duan Z, Mao S (2006) A thermodynamic model for calculating methane solubility, density and gas phase composition of methane-bearing aqueous fluids from 273 to 523 K and from 1 to 2000 bar. Geochim Cosmochim Acta 70:3369–3386. https://doi.org/10.1016/J.GCA.2006.03.018
Duan C, Luo M, Xing X (2011) High-rate conversion of methane to methanol by Methylosinus trichosporium OB3b. Bioresour Technol 102:7349–7353. https://doi.org/10.1016/J.BIORTECH.2011.04.096
Fei Q, Guarnieri MT, Tao L et al (2014) Bioconversion of natural gas to liquid fuel: opportunities and challenges. Biotechnol Adv 32:596–614. https://doi.org/10.1016/J.BIOTECHADV.2014.03.011
Ge X, Yang L, Sheets JP et al (2014) Biological conversion of methane to liquid fuels: Status and opportunities. Biotechnol Adv 32:1460–1475. https://doi.org/10.1016/J.BIOTECHADV.2014.09.004
Ghaz-Jahanian MA, Khoshfetrat AB, Hosseinian Rostami M, Haghighi M (2018) An innovative bioprocess for methane conversion to methanol using an efficient methane transfer chamber coupled with an airlift bioreactor. Chem Eng Res Des 134:80–89. https://doi.org/10.1016/J.CHERD.2018.03.039
Global Methane Tracker (2023) International Energy Agency. https://www.iea.org/news/methane-emissions-remained-stubbornly-high-in-2022-even-as-soaring-energy-prices-made-actions-to-reduce-them-cheaper-than-ever. Accessed 10 October 2023
Gregory GJ, Bennett RK, Papoutsakis ET (2022) Recent advances toward the bioconversion of methane and methanol in synthetic methylotrophs. Metab Eng 71:99–116. https://doi.org/10.1016/J.YMBEN.2021.09.005
Han B, Su T, Wu H et al (2009) Paraffin oil as a methane vector for rapid and high cell density cultivation of Methylosinus trichosporium OB3b. Appl Microbiol Biotechnol 83:669–677. https://doi.org/10.1007/S00253-009-1866-2
Han JS, Ahn CM, Mahanty B, Kim CG (2013) Partial oxidative conversion of methane to methanol through selective inhibition of methanol dehydrogenase in methanotrophic consortium from landfill cover soil. Appl Biochem Biotechnol 171:1487–1499. https://doi.org/10.1007/S12010-013-0410-0
Hanson RS, Hanson TE (1996) Methanotrophic bacteria. Microbiol Rev 60:439–471. https://doi.org/10.1128/MR.60.2.439-471.1996
Henard CA, Akberdin IR, Kalyuzhnaya MG, Guarnieri MT (2019) Muconic acid production from methane using rationally-engineered methanotrophic biocatalysts. Green Chem 21:6731–6737. https://doi.org/10.1039/C9GC03722E
International Energy Agency (2023) https://www.iea.org/news/global-co2-emissions-rose-less-than-initially-feared-in-2022-as-clean-energy-growth-offset-much-of-the-impact-of-greater-coal-and-oil-use. Accessed 10 October 2023
Ito H, Yoshimori K, Ishikawa M et al (2021) Switching between methanol Accumulation and Cell growth by Expression Control of Methanol Dehydrogenase in Methylosinus trichosporium OB3b mutant. Front Microbiol 12:639266. https://doi.org/10.3389/FMICB.2021.639266
Jeong J, Kim TH, Jang N et al (2023) A highly efficient and versatile genetic engineering toolkit for a methanotroph-based biorefinery. Chem Eng J 453:139911. https://doi.org/10.1016/J.CEJ.2022.139911
Kalyuzhnaya MG (2016) Methane Biocatalysis: Selecting the Right Microbe. Biotechnology for Biofuel Production and Optimization 353–383. https://doi.org/10.1016/B978-0-444-63475-7.00013-3
Kalyuzhnaya MG, Puri AW, Lidstrom ME (2015) Metabolic engineering in methanotrophic bacteria. Metab Eng 29:142–152. https://doi.org/10.1016/J.YMBEN.2015.03.010
Keller M, Sharma A (2022) Reverse Boudouard reforming produces CO directly suitable for the production of methanol from CO2 and CH4. Chem Eng J 431:134127. https://doi.org/10.1016/J.CEJ.2021.134127
Kim HG, Han GH, Kim SW (2010) Optimization of lab scale methanol production by Methylosinus trichosporium OB3b. Biotechnol Bioprocess Eng 15:476–480. https://doi.org/10.1007/S12257-010-0039-6
Kim IT, Yoo YS, Yoon YH et al (2018) Bio-Methanol Production Using Treated Domestic Wastewater with Mixed Methanotroph Species and Anaerobic Digester Biogas. Water 2018, Vol 10, Page 1414 10:1414. https://doi.org/10.3390/W10101414
Kim HJ, Huh J, Kwon YW et al (2019) Biological conversion of methane to methanol through genetic reassembly of native catalytic domains. Nat Catal 2019 2(4):342–353. https://doi.org/10.1038/s41929-019-0255-1
Koo CW, Rosenzweig AC (2021) Biochemistry of aerobic biological methane oxidation. Chem Soc Rev 50:3424–3436. https://doi.org/10.1039/D0CS01291B
Le HTQ, Nguyen AD, Park YR, Lee EY (2021) Sustainable biosynthesis of chemicals from methane and glycerol via reconstruction of multi-carbon utilizing pathway in obligate methanotrophic bacteria. Microb Biotechnol 14:2552–2565. https://doi.org/10.1111/1751-7915.13809
Li Y, Hu Y, Chu J et al (2023) Investigation of renewable methanol production from CO2 hydrogeneration based on spectral splitting and heat integration. Fuel 352:129041. https://doi.org/10.1016/J.FUEL.2023.129041
Mai DHA, Nguyen TT, Lee EY (2021) The ethylmalonyl-CoA pathway for methane-based biorefineries: a case study of using Methylosinus trichosporium OB3b, an alpha-proteobacterial methanotroph, for producing 2-hydroxyisobutyric acid and 1,3-butanediol from methane. Green Chem 23:7712–7723. https://doi.org/10.1039/D1GC02866A
Mardina P, Li J, Patel SKS et al (2016) Potential of immobilized whole-cell Methylocella tundrae as a biocatalyst for methanol production from methane. J Microbiol Biotechnol 26:1234–1241. https://doi.org/10.4014/JMB.1602.02074
Nguyen LT, Lee EY (2019) Biological conversion of methane to putrescine using genome-scale model-guided metabolic engineering of a methanotrophic bacterium Methylomicrobium alcaliphilum 20Z. Biotechnol Biofuels 12:1–12. https://doi.org/10.1186/S13068-019-1490-Z
Nguyen AD, Hwang IY, Lee OK et al (2018) Systematic metabolic engineering of Methylomicrobium alcaliphilum 20Z for 2,3-butanediol production from methane. Metab Eng 47:323–333. https://doi.org/10.1016/J.YMBEN.2018.04.010
Nguyen TT, Lee OK, Naizabekov S, Lee EY (2020) Bioconversion of methane to cadaverine and lysine using an engineered type II methanotroph, Methylosinus trichosporium OB3b. Green Chem 22:7803–7811. https://doi.org/10.1039/D0GC02232B
Park Syeong, Kim Cgyun (2019) Application and development of methanotrophs in environmental engineering. J Mater Cycles Waste Manag 21:415–422. https://doi.org/10.1007/S10163-018-00826-W
Patel SKS, Jeong JH, Mehariya S et al (2016a) Production of methanol from methane by Encapsulated Methylosinus sporium. J Microbiol Biotechnol 26:2098–2105. https://doi.org/10.4014/JMB.1608.08053
Patel SKS, Mardina P, Kim D et al (2016b) Improvement in methanol production by regulating the composition of synthetic gas mixture and raw biogas. Bioresour Technol 218:202–208. https://doi.org/10.1016/J.BIORTECH.2016.06.065
Patel SKS, Mardina P, Kim SY et al (2016c) Biological methanol production by a type II Methanotroph Methylocystis bryophila. J Microbiol Biotechnol 26:717–724. https://doi.org/10.4014/JMB.1601.01013
Patel SKS, Selvaraj C, Mardina P et al (2016d) Enhancement of methanol production from synthetic gas mixture by Methylosinus sporium through covalent immobilization. Appl Energy 171:383–391. https://doi.org/10.1016/J.APENERGY.2016.03.022
Patel SKS, Singh RK, Kumar A et al (2017) Biological methanol production by immobilized Methylocella tundrae using simulated biohythane as a feed. Bioresour Technol 241:922–927. https://doi.org/10.1016/J.BIORTECH.2017.05.160
Patel SKS, Kondaveeti S, Otari SV et al (2018a) Repeated batch methanol production from a simulated biogas mixture using immobilized Methylocystis bryophila. Energy 145:477–485. https://doi.org/10.1016/J.ENERGY.2017.12.142
Patel SKS, Kumar V, Mardina P et al (2018b) Methanol production from simulated biogas mixtures by co-immobilized Methylomonas methanica and Methylocella tundrae. Bioresour Technol 263:25–32. https://doi.org/10.1016/J.BIORTECH.2018.04.096
Patel SKS, Jeon MS, Gupta RK et al (2019) Hierarchical macroporous particles for efficient whole-cell immobilization: application in Bioconversion of Greenhouse gases to methanol. ACS Appl Mater Interfaces 11:18968–18977. https://doi.org/10.1021/ACSAMI.9B03420
Patel SKS, Gupta RK, Kondaveeti S et al (2020a) Conversion of biogas to methanol by methanotrophs immobilized on chemically modified chitosan. Bioresour Technol 315. https://doi.org/10.1016/j.biortech.2020.123791
Patel SKS, Gupta RK, Kumar V et al (2020b) Biomethanol Production from methane by immobilized co-cultures of Methanotrophs. Indian J Microbiol 60:318–324. https://doi.org/10.1007/S12088-020-00883-6
Patel SKS, Kalia VC, Joo JB et al (2020c) Biotransformation of methane into methanol by methanotrophs immobilized on coconut coir. Bioresour Technol 297:122433. https://doi.org/10.1016/J.BIORTECH.2019.122433
Patel SKS, Shanmugam R, Kalia VC, Lee JK (2020d) Methanol production by polymer-encapsulated methanotrophs from simulated biogas in the presence of methane vector. Bioresour Technol 304:123022. https://doi.org/10.1016/J.BIORTECH.2020.123022
Patel SKS, Gupta RK, Kalia VC, Lee JK (2021a) Integrating anaerobic digestion of potato peels to methanol production by methanotrophs immobilized on banana leaves. Bioresour Technol 323:124550. https://doi.org/10.1016/J.BIORTECH.2020.124550
Patel SKS, Shanmugam R, Lee JK et al (2021b) Biomolecules Production from Greenhouse gases by Methanotrophs. Indian J Microbiol 2021 61(4):449–457. https://doi.org/10.1007/S12088-021-00986-8
Patel SKS, Gupta RK, Kalia VC, Lee JK (2022) Synthetic design of methanotroph co-cultures and their immobilization within polymers containing magnetic nanoparticles to enhance methanol production from wheat straw-based biogas. Bioresour Technol 364:128032. https://doi.org/10.1016/J.BIORTECH.2022.128032
Patel SKS, Gupta RK, Kim I-W, Lee J-K (2023a) Encapsulation of Methanotrophs within a polymeric matrix containing copper- and Iron-based nanoparticles to enhance methanol production from a simulated Biogas. Polymers 15:3667. https://doi.org/10.3390/POLYM15183667
Patel SKS, Kalia VC, Lee JK (2023b) Integration of biogas derived from dark fermentation and anaerobic digestion of biowaste to enhance methanol production by methanotrophs. Bioresour Technol 369:128427. https://doi.org/10.1016/J.BIORTECH.2022.128427
Pen N, Soussan L, Belleville MP et al (2014) An innovative membrane bioreactor for methane biohydroxylation. Bioresour Technol 174:42–52. https://doi.org/10.1016/J.BIORTECH.2014.10.001
Razumovsky SD, Efremenko EN, Makhlis TA et al (2008) Effect of immobilization on the main dynamic characteristics of the enzymatic oxidation of methane to methanol by bacteria Methylosinus sporium B-2121. Russ Chem Bull 57:1633–1636. https://doi.org/10.1007/S11172-008-0211-8
Rocha-Rios J, Bordel S, Hernández S, Revah S (2009) Methane degradation in two-phase partition bioreactors. Chem Eng J 152:289–292. https://doi.org/10.1016/J.CEJ.2009.04.028
Rocha-Rios J, Muñoz R, Revah S (2010) Effect of silicone oil fraction and stirring rate on methane degradation in a stirred tank reactor. J Chem Technol Biotechnol 85:314–319. https://doi.org/10.1002/JCTB.2339
Rocha-Rios J, Quijano G, Thalasso F et al (2011) Methane biodegradation in a two-phase partition internal loop airlift reactor with gas recirculation. J Chem Technol Biotechnol 86:353–360. https://doi.org/10.1002/JCTB.2523
Rocha-Rios J, Kraakman NJR, Kleerebezem R et al (2013) A capillary bioreactor to increase methane transfer and oxidation through Taylor flow formation and transfer vector addition. Chem Eng J 217:91–98. https://doi.org/10.1016/J.CEJ.2012.11.065
Rodríguez Y, Firmino PIM, Pérez V et al (2020) Biogas valorization via continuous polyhydroxybutyrate production by Methylocystis hirsuta in a bubble column bioreactor. Waste Manag 113:395–403. https://doi.org/10.1016/j.wasman.2020.06.009
Sahoo KK, Goswami G, Das D (2021) Biotransformation of methane and Carbon Dioxide Into High-Value products by Methanotrophs: current state of art and future prospects. Front Microbiol 12. https://doi.org/10.3389/FMICB.2021.636486
Sahoo KK, Datta S, Goswami G, Das D (2022) Two-stage integrated process for bio-methanol production coupled with methane and carbon dioxide sequestration: kinetic modelling and experimental validation. J Environ Manage 301:113927. https://doi.org/10.1016/J.JENVMAN.2021.113927
Sahoo KK, Sinha A, Das D (2023) Process engineering strategy for improved methanol production in Methylosinus trichosporium through enhanced mass transfer and solubility of methane and carbon dioxide. Bioresour Technol 371:128603. https://doi.org/10.1016/J.BIORTECH.2023.128603
Sheets JP, Lawson K, Ge X et al (2017) Development and evaluation of a trickle bed bioreactor for enhanced mass transfer and methanol production from biogas. Biochem Eng J 122:103–114. https://doi.org/10.1016/J.BEJ.2017.03.006
Su Z, Ge X, Zhang W et al (2017) Methanol production from Biogas with a thermotolerant Methanotrophic Consortium isolated from an anaerobic digestion system. Energy Fuels 31:2970–2975. https://doi.org/10.1021/ACS.ENERGYFUELS.6B03471
Taylor A, Molzahn P, Bushnell T et al (2018) Immobilization of Methylosinus trichosporium OB3b for methanol production. J Ind Microbiol Biotechnol 45:201–211. https://doi.org/10.1007/S10295-018-2010-Z
Torre A, Metivier A, Chu F et al (2015) Genome-scale metabolic reconstructions and theoretical investigation of methane conversion in Methylomicrobium buryatense strain 5G(B1). Microb Cell Fact 14:1–15. https://doi.org/10.1186/S12934-015-0377-3
Van Hecke W, Bockrath R, De Wever H (2019) Effects of moderately elevated pressure on gas fermentation processes. Bioresour Technol 293:122129. https://doi.org/10.1016/J.BIORTECH.2019.122129
Verhelst S, Turner JW, Sileghem L, Vancoillie J (2019) Methanol as a fuel for internal combustion engines. Prog Energy Combust Sci 70:43–88. https://doi.org/10.1016/j.pecs.2018.10.001
Xin JY, Cui JR, Niu JZ, Hua SF, Xia CG, Li SB, Zhu LM (2004) Production of methanol from methane by methanotrophic bacteria. Biocatal Biotransform 22:225–229. https://doi.org/10.1080/10242420412331283305
Xin JY, Zhang YX, Zhang S et al (2007) Methanol production from CO2 by resting cells of the methanotrophic bacterium Methylosinus trichosporium IMV 3011. J Basic Microbiol 47:426–435. https://doi.org/10.1002/JOBM.200710313
Yan X, Chu F, Puri AW et al (2016) Electroporation-based genetic manipulation in type I methanotrophs. Appl Environ Microbiol 82:2062–2069. https://doi.org/10.1128/AEM.03724-15
Yu Y, Ramsay JA, Ramsay BA (2009) Production of soluble methane monooxygenase during growth of Methylosinus trichosporium on methanol. J Biotechnol 139:78–83. https://doi.org/10.1016/J.JBIOTEC.2008.09.005
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Krishna Kalyani Sahoo is thankful to Ministry of Education, Government of India for her research fellowship.
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Sahoo, K.K., Katari, J.K. & Das, D. Recent advances in methanol production from methanotrophs. World J Microbiol Biotechnol 39, 360 (2023). https://doi.org/10.1007/s11274-023-03813-y
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DOI: https://doi.org/10.1007/s11274-023-03813-y