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Methane to Methanol Through Heterogeneous Catalysis and Plasma Catalysis

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Methane to Methanol Through Heterogeneous Catalysis and Plasma Catalysis catalysts Review Methane to Methanol through Heterogeneous Catalysis and Plasma Catalysis Shangkun Li 1,2,†, Rizwan Ahmed 1,†, Yanhui Yi 1,2,* and Annemie Bogaerts 2 1 State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China; [email protected] (S.L.); [email protected] (R.A.) 2 Research Group PLASMANT, Department of Chemistry, University of Antwerp, Universiteitsplein 1, BE-2610 Wilrijk-Antwerp, Belgium; [email protected] * Correspondence: [email protected]; Tel.: +86-411-8498-6120 † These authors contributed equally. Abstract: Direct oxidation of methane to methanol (DOMTM) is attractive for the increasing industrial demand of feedstock. In this review, the latest advances in heterogeneous catalysis and plasma catalysis for DOMTM are summarized, with the aim to pinpoint the differences between both, and to provide some insights into their reaction mechanisms, as well as the implications for future development of highly selective catalysts for DOMTM. Keywords: methane conversion; direct oxidation; methanol production; heterogeneous catalysis; plasma catalysis 1. Introduction Methane (CH4), as one of the most important molecules in C1 chemistry, is widely Citation: Li, S.; Ahmed, R.; Yi, Y.; present in natural gas, shale gas, coalbed gas, combustible ice, etc. Noticeably, natural Bogaerts, A. Methane to Methanol gas, which consists of approximately 70% to 90% CH4, will be part of the energy system through Heterogeneous Catalysis and for decades [1]. Unfortunately, most of these CH4 reserves are located in remote areas, Plasma Catalysis. Catalysts 2021, 11, indicating the need of transportation for utilization of CH4 [1,2]. However, due to a very 590. https://doi.org/10.3390/ low boiling point (−161.6 ◦C at a pressure of 1 atm) and high flammability, compression of catal11050590 CH4(gas) into CH4(liquid) for transportation requires huge amounts of energy, making it economically infeasible [3]. In addition, another important issue is the rising global emis- Academic Editor: Leon Lefferts sion of CH4, mainly as by-product of oil production, and its global warming potential is ca. 30 times that of CO [1]. The International Energy Outlook 2019 (IEO2019) estimated that Received: 12 April 2021 2 140 billion cubic meters (bcm) were flared and 60 bcm released into the atmosphere in 2018, Accepted: 29 April 2021 Published: 1 May 2021 more than the annual LNG (Liquefied Natural Gas) imports of Japan and China combined. This enormous source of emissions accounts for 40% of the total indirect emissions from Publisher’s Note: MDPI stays neutral global oil supply. Therefore, the conversion of CH4 to value-added chemicals has attracted with regard to jurisdictional claims in intensive interests from both academic and industrial communities. published maps and institutional affil- In general, as shown in Figure1, the conversion of CH 4 into value-added chemicals iations. can be classified into indirect and direct routes [4]. As implemented in industry, indi- rect routes are, actually, initiated through a steam reforming (SR) and/or auto-thermal reforming (ATR) process to produce syngas (mixture of CO and H2), and then a variety of products such as olefins, gasoline, and diesel, as well as oxygenates, can be obtained using the well-established technology of Fischer-Tropsch synthesis (FTS) promoted by Fe-based Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. or Co-based catalysts [5,6]. Alternatively, using Cu-Zn-Al-based catalysts, syngas can This article is an open access article also be converted into methanol (CH3OH), which has been used as feedstock to produce distributed under the terms and light olefins, gasoline and aromatics through industrial technologies of methanol-to-olefins conditions of the Creative Commons (MTO), methanol-to-gasoline (MTG) and methanol-to-aromatics (MTA) conversion, re- Attribution (CC BY) license (https:// spectively [6]. Although the above indirect routes are carried out in industry to produce creativecommons.org/licenses/by/ value-added chemicals from CH4, the syngas production by SR and ATR is energy-intensive 4.0/). and costly, motivating researchers to develop direct routes (not syngas-based) [7]. Catalysts 2021, 11, 590. https://doi.org/10.3390/catal11050590 https://www.mdpi.com/journal/catalysts Catalysts 2021, 11, 590 2 of 35 Catalysts 2021, 11, 590 value‐added chemicals from CH4, the syngas production by SR and ATR is energy2 of 35‐inten‐ sive and costly, motivating researchers to develop direct routes (not syngas‐based) [7]. Figure 1. FigureSignificant 1. Significant pathways for pathways value‐added for value-added utilization of utilizationCH4. Commercial of CH (indirect)4. Commercial pathways (indirect) through pathways syngas are indicated throughin red. Direct syngas routes are to indicatedolefins, gasoline in red. or aromatics, Direct routes by various to olefins, processes, gasoline are in blue, or aromatics, while the direct by various oxidation to CH3OH is in green. processes, are in blue, while the direct oxidation to CH3OH is in green. Direct routes (Figure 1), including CH4 dehydroaromatization, CH4 coupling to hy‐ Direct routes (Figure1), including CH 4 dehydroaromatization, CH4 coupling to hy- drocarbons (both oxidative and non‐oxidative coupling), CH4 pyrolysis (high temperature drocarbons (both oxidative and non-oxidative coupling), CH4 pyrolysis (high temperature pyrolysis and catalytic pyrolysis) and direct oxidation of CH4 to methanol/formaldehyde, pyrolysis and catalytic pyrolysis) and direct oxidation of CH to methanol/formaldehyde, have also been developed and are still being improved4 [2–8]. However, CH4, a molecule have also beenwith developed tetrahedral and geometry are still and being four improved equivalent [ 2C–H–8]. bonds, However, is inert CH and4, difficult a molecule to activate with tetrahedraland geometry convert. The and absence four equivalentof a dipole moment C–H bonds, and a rather is inert small and polarizability difficult to (2.84 ac- × 10−40 tivate and convert.C2∙m2∙J− The1) imply absence that CH of4 aneeds dipole a relatively moment high and local a rather electric small field to polarizability be polarized and to −40 2 2 −1 (2.84 × 10 Callow·m ·electrophilicJ ) imply or that nucleophilic CH4 needs attack a relatively [2]. CH4 exhibits high local the highest electric C–H field bond to be strength −1 polarized andamong to allow all electrophilicalkanes, with the or first nucleophilic bond dissociation attack [energy2]. CH (BDE)4 exhibits of 493.3 the kJ highest mol (5.1 eV), C–H bond strengthmeaning among that CH all4 alkanes,is the least with reactive the alkane first bond [2]. Therefore, dissociation most energyof the direct (BDE) routes of must −1 be operated at ultra‐high temperature (973~1223 K), except for direct oxidation to metha‐ 493.3 kJ mol (5.1 eV), meaning that CH4 is the least reactive alkane [2]. Therefore, most of the direct routesnol/formaldehyde, must be operated which at ultra-high can be realized temperature at relatively (973~1223 low temperature K), except (300~700 for direct K), indi‐ oxidation to methanol/formaldehyde,cating low cost and high feasibility which can in beindustry realized [2,3]. at For relatively that reason, low temperaturedirect oxidation has attracted more attention, and in this review, we mainly focus on recent progress of direct (300~700 K), indicating low cost and high feasibility in industry [2,3]. For that reason, oxidation of methane to methanol (DOMTM). direct oxidation has attracted more attention, and in this review, we mainly focus on recent progress of direct oxidation of methaneCH4 + 0.5 to methanolO2 → CH3OH (DOMTM). ΔH (298K) = −126.4 kJ∙mol−1 (1) DOMTM by O2 (1) has been considered as a dream reaction− in1 chemical industry and aCH holy4 + grail 0.5 in O 2catalytic! CH 3chemistryOH D [9,10],H (298K) and it = has−126.4 attracted kJ·mol intensive interests from(1) both academic and industrial communities for more than 100 years. DOMTM has been studied DOMTM by Ohomogeneous2 (1) has been catalysis, considered in which as a noble dream metals reaction (Pt and in chemical Pd) are typically industry used and as the a holy grail in catalyticcentral atoms chemistry of the complex [9,10], and catalysts, it has and attracted the reaction intensive is usually interests carried from out both in strong academic and industrialacid media communities (sulfuric and trifluoroacetic for more than acid) 100 [11–13]. years. DOMTMAlternatively, has DOMTM been studied can also be by homogeneousrealized catalysis, by heterogeneous in which noble catalysis. metals In the (Pt 1980s, and a Pd) Mo are‐based typically catalyst used was developed as the for central atoms ofCH the4 oxidation. complex The catalysts, Mo=O species and the was reaction considered is usuallyto be the carriedactive site out for in the strong oxidation of acid media (sulfuricCH4 to andCH3OH, trifluoroacetic and at that time, acid) Mo [11 –was13]. considered Alternatively, to be the DOMTM most active can alsometal be catalyst realized by heterogeneousfor this reaction catalysis. [14,15]. However, In the 1980s, the biggest a Mo-based drawback catalyst of a Mo was‐based developed catalyst is for that Mo can be easily lost at high temperature through volatilization, which was not conducive for CH4 oxidation. The Mo=O species was considered to be the active site for the oxidation industrial application [16]. Compared with a Mo‐based catalyst, a V‐based catalyst is more of CH4 to CH3OH, and at that time, Mo was considered to be the most active metal stable, but the CH4 conversion was too low (less than 10%) [17,18]. At the beginning of catalyst for this reaction [14,15]. However, the biggest drawback of a Mo-based catalyst this century, inspired by the active sites of double iron and double copper in methane is that Mo can be easily lost at high temperature through volatilization, which was not conducive for industrial application [16].
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