Abstract
As described in Chapter 2, biological systems can accomplish the conversion of methane to methanol via direct oxidation of methane with molecular oxygen at ambient temperature and pressure. Such systems have inspired scientists to attempt to establish artificial, energy-efficient, one-step processes for methanol production from methane using molecular oxygen as the oxidant. However, methanol production in such artificial systems remains highly challenging. In this chapter, the systems for the direct conversion of methane to methanol over homogeneous or heterogeneous catalysts developed so far are reviewed. Important examples of synthetic homogeneous and heterogeneous catalytic systems for the oxidation of methane to methanol are described. In heterogeneous catalysis, materials based on several metals have been found capable of catalytically producing methanol from methane. The methanol yields obtained in these reactions were low, mainly due to the high reactivity of methanol under the reaction conditions for the activation of methane. The highly selective synthesis of methanol via methane conversion by homogeneous metal catalysts remains difficult, with far fewer successful examples than heterogeneous catalysts. On the other hand, reactions in which methanol is obtained as its more stable ester derivatives have been devised. These reactions achieved very high product selectivity even at high methane conversion, and allow the production of methyl esters with higher concentrations than can be achieved in the production of methanol. However, approaches for methanol production from methane via methanol derivatives and those for direct conversion of methane to methanol should be considered separately.
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References
Spencer ND (1988) Partial oxidation of methane to formaldehyde by means of molecular oxygen. J Catal 109:187–197
Spencer ND, Pereira CJ (1989) V2O5-SiO2-catalyzed methane partial oxidation with molecular oxygen. J Catal 116:399–406
Liu HF, Li RS, Liew KY, Johnson RE, Lunsford JH (1984) Partial oxidation of methane by nitrous oxide over molybdenum on silica. J Am Chem Soc 106:4117–4121
Caceres CV, Fierro JLG, Lopez Agudo A, Blanco MN, Thomas HJ (1985) Preparation and characterization of equilibrium adsorption-prepared molybdena-alumina catalysts. J Catal 95:501–511
Kobayashi T, Guilhaume N, Miki J, Kitamura N, Haruta M (1996) Oxidation of methane to formaldehyde over FeSiO2 and Sn-W mixed oxides. Catal Today 32:171–175
Michalkiewicz B (2004) Partial oxidation of methane to formaldehyde and methanol using molecular oxygen over Fe-ZSM-5. Appl Catal A: Gen 277:147–153
Zhang Q, Li Y, An D, Wang Y (2009) Catalytic behavior and kinetic features of FeOx/SBA-15 catalyst for selective oxidation of methane by oxygen. Appl Catal A: Gen 356:103–111
Arena F, Gatti G, Martra G, Coluccia S, Stievano L, Spadaro L, Famulari P, Parmaliana A (2005) Structure and reactivity in the selective oxidation of methane to formaldehyde of low-loaded FeOx/SiO2 catalysts. J Catal 231:365–380
He J, Li Y, An D, Zhang Q, Wang Y (2009) Selective oxidation of methane to formaldehyde by oxygen over silica-supported iron catalysts. J Nat Gas Chem 18:288–294
Otsuka K, Wang Y (2001) Direct conversion of methane into oxygenates. Appl Catal A: Gen 222:145–161
Wang Y (2006) Selective oxidation of hydrocarbons catalyzed by iron-containing heterogeneous catalysts. Res Chem Intermed 32:235–251
McCormick RL, Alptekin GO (2000) Comparison of alumina-, silica-, titania-, and zirconia-supported FePO4 catalysts for selective methane oxidation. Catal Today 55:269–280
Alptekin GO, Herring AM, Williamson DL, Ohno TR, McCormick RL (1999) Methane partial oxidation by unsupported and silica supported iron phosphate catalysts: influence of reaction conditions and co-feeding of water on activity and sectivity. J Catal 181:104–112
Wang X, Wang Y, Tang Q, Guo Q, Zhang Q, Wan H (2003) MCM-41-supported iron phosphate catalyst for partial oxidation of methane to oxygenates with oxygen and nitrous oxide. J Catal 217:457–467
Wang Y, Wang X, Su Z, Guo Q, Tang Q, Zhang Q, Wan H (2004) SBA-15-supported iron phosphate catalyst for partial oxidation of methane to formaldehyde. Catal Today 93–95:155–161
Brown MJ, Parkyns ND (1991) Progress in the partial oxidation of methane to methanol and formaldehyde. Catal Today 8:305–335
Fajardo CAG, Niznansky D, Guyen YN, Courson C, Roger A-C (2008) Methane selective oxidation to formaldehyde with Fe-catalysts supported on silica or incorporated into the support. Catal Commun 9:864–869
Štolcová M, Litterscheid C, Hronec M, Glaum R (2007) Bimetallic orthophosphate and pyrophosphate catalysts for direct oxidation of methane to formaldehyde. Stud Surf Sci Catal 167:37–42
Polnišer R, Štolcová M, Hronec M, Mikul M (2011) Structure and reactivity of copper iron pyrophosphate catalysts for selective oxidation of methane to formaldehyde and methanol. Appl Catal A Gen 400:122–130
Sobolev VI, Dubkov KA, Panna OV, Panov GI (1995) Selective oxidation of methane to methanol on a FeZSM-5 surface. Catal Today 24:251–252
Snyder BER, Vanelderen P, Bols ML, Hallaert SD, Böttger LH, Ungur L, Pierloot K, Schoonheydt RA, Sels BF, Solomon EI (2016) The active site of low-temperature methane hydroxylation in iron-containing zeolites. Nature 536:317–321
Starokon EV, Parfenov MV, Pirutko LV, Abornev SI, Panov GI (2011) Room-temperature oxidation of methane by α-oxygen and extraction of products from the FeZSM-5 surface. J Phys Chem C 115:2155–2161
Göltl F, Michel C, Andrikopoulos PC, Love AM, Hafner J, Hermans I, Sautet P (2016) Computationally exploring confinement effects in the methane-to-methanol conversion over iron-oxo centers in zeolites. ACS Catal 6:8404–8409
Zhen KJ, Khan MM, Mak CH, Lewis KB, Somorjai GA (1985) Partial oxidation of methane with nitrous oxide over V2O5-SiO2 catalyst. J Catal 94:501–507
Chen SY, Willcox D (1993) Effect of vanadium oxide loading on the selective oxidation of methane over vanadium oxide (V2O5)/silica. Ind Eng Chem Res 32:584–587
Otsuka K, Hatano M (1992) Boron, phosphorus, and alkaline earth-metal mixed oxides as active catalysts in partial oxidation of methane into formaldehyde. Chem Lett 21:2397–2400
Weng T, Wolf EE (1993) Partial oxidation of methane on Mo/Sn/P silica supported catalysts. Appl Catal A 96:383–396
Tabata K, Teng Y, Takemoto T, Suzuki E, Banares MA, Pena MA, Fierro JL (2002) Activation of methane by oxygen and nitrogen oxide. Catal Rev 44:1–58
Aoki K, Ohmae M, Nanba T, Takeishi K, Azuma N, Ueno A, Ohfune H, Hayashi H, Udagawa Y (1998) Direct conversion of methane into methanol over MoO3/SiO2 catalyst in anexcess amount of water vapor. Catal Today 45:29–33
Kasztelan S, Payen E, Moffat JB (1988) The formation of molybdosilicic acid on Mo/SiO2 catalysts and its relevance to methane oxidation. J Catal 112:320–324
Barbaux Y, Elamrani A, Bonnelle JP (1987) Catalytic oxidation of methane on MoO3-SiO2: mechanism of oxidation with O2 and N2O studied by surface potential measurements. Catal Today 1:147–156
Smith MR, Ozkan US (1993) The partial oxidation of methane to formaldehyde: role of different crystal planes of MoO3. J Catal 141:124–139
Grzybowska-Swierkosz B (2000) Thirty years in selective oxidation on oxides: what have we learned? Top Catal 11:23–42
Fu G, Xu X, Lu X, Wan H (2005) Mechanisms of methane activation and transformation on molybdenum oxide based catalysts. J Am Chem Soc 127:3989–3996
Kihlborg L (1963) Least squares refinement of the crystal structure of molybdenum trioxide. Ark Kemi 21:357–364
Spencer ND, Pereira CJ (1987) Partial oxidation of CH4 to HCHO over a MoO3-SiO2 catalyst: a kinetic study. AIChE J 33:1808–1812
Kuba S, Heydorn PC, Grasselli RK, Gates BC, Che M, Kno¨zinger H (2001) Redox properties of tungstated zirconia catalysts: relevance to the activation of n-alkanes. Phys Chem Chem Phys 3:146–154
Busca G, Finocchio E, Lorenzelli V, Ramis G, Baldi M (1999) IR studies on the activation of C-H hydrocarbon bonds on oxidation catalysts. Catal Today 49:453–465
Limberg C (2003) The role of radicals in metal-assisted oxygenation reactions. Angew Chem Int Ed 42:5932–5954
Mayer JM (1998) Hydrogen atom abstraction by metal−oxo complexes: understanding the analogy with organic radical reactions. Acc Chem Res 31:441–450
Soper JD, Mayer JMJ (2003) Slow hydrogen atom self-exchange between Os(IV) anilide and Os(III) aniline complexes: relationships with electron and proton transfer self-exchange. J Am Chem Soc 125:12217–12229
Roberts BP (1999) Polarity-reversal catalysis of hydrogen-atom abstraction reactions: concepts and applications in organic chemistry. Chem Soc Rev 28:25–35
Fornés V, López C, López HH, Mart´ınez A (2003) Catalytic performance of mesoporous VOx/SBA-15 catalysts for the partial oxidation of methane to formaldehyde. Appl Catal A: Gen 249:345–354
Kartheuser B, Hodnett BK (1993) Relationship between dispersion of vanadia on silica catalysts and selectivity in the conversion of methane into formaldehyde. J Chem Soc Chem Commun 1093–1094
Koranne MM, Goodwin JG Jr, Marcelin G (1994) Partial oxidation of methane over silica- and alumina-supported vanadia catalysts. J Catal 148:388–391
Irusta S, Cornaglia LM, Miró EE, Lombardo EA (1995) The role of V=O sites on the oxidation of methane to formaldehyde over V/SiO2. J Catal 156:167–170
Irusta S, Marchi AJ, Lombardo EA, Miró EE (1996) Characterization of surface species on V/SiO2 and V, Na/SiO2 and their role in the partial oxidation of methane to formaldehyde. Catal Lett 40:9–16
Das N, Eckert H, Hu H, Wachs IE, Walzer JF, Feher FJ (1993) Bonding states of surface vanadium(V) oxide phases on silica: structural characterization by 51V NMR and Raman spectroscopy. J Phys Chem 97:8240–8243
Wang CB, Herman RG, Shi C, Sun Q, Roberts JE (2003) V2O5-SiO2 xerogels for methane oxidation to oxygenates: preparation, characterization, and catalytic properties. Appl Catal A 247:321–333
Groothaert MH, Smeets PJ, Sels BF, Jacobs PA, Schoonheydt RA (2005) Selective oxidation of methane by the bis(μ-oxo)dicopper core stabilized on ZSM-5 and mordenite zeolites. J Am Chem Soc 127:1394–1395
Li Y, An D, Zhang Q, Wang Y (2008) Copper-catalyzed selective oxidation of methane by oxygen: studies on catalytic behavior and functioning mechanism of CuOx/SBA-15. J Phys Chem C 112:13700–13708
Panov GI, Sobolev VI, Dubkov KA, Parmon VN, Ovanesyan NS, Shilov AE, Shteinman AA (1997) Iron complexes in zeolites as a new model of methane monooxygenase. React Kinet Catal Lett 61:251–258
Smeets PJ, Groothaert MH, Schoonheydt RA (2005) Cu based zeolites: a UV-vis study of the active site in the selective methane oxidation at low temperatures. Catal Today 110:303–309
Woertink JS, Smeets PJ, Groothaert MH, Vance MA, Sels BF, Schoonheydt RA, Solomon EIA (2009) [Cu2O]2+ core in Cu-ZSM-5, the active site in the oxidation of methane to methanol. Proc Natl Acad Sci USA 106:18908–18913
Grundner S, Markovits MAC, Li G, Tromp M, Pidko EA, Hensen EJM, Jentys A, Sanchez-Sanchez M, Lercher JA (2015) Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol. Nat Commun 6:1–8
Markovits MAC, Jentys A, Tromp M, Sanchez-Sanchez M, Lercher JA (2016) Effect of location and distribution of Al sites in ZSM-5 on the formation of Cu-oxo clusters active for direct conversion of methane to methanol. Top Catal 59:1554–1563
Raja R, Ratnasamy P (1997) Direct conversion of methane to methanol. Appl Catal A Gen 158:L7–L15
Hammond C, Forde MM, Ab Rahim MH, Thetford A, He Q, Jenkins RL, Dimitratos N, Lopez-Sanchez JA, Dummer NF, Murphy DM, Carley AF, Taylor SH, Willock DJ, Stangland EE, Kang J, Hagen H, Kiely CJ, Hutchings GJ (2012) Direct catalytic conversion of methane to methanol in an aqueous medium by using copper-promoted Fe-ZSM-5. Angew Chem Int Ed 51:5129–5133
Panov GI, Uriarte AK, Rodkin MA, Sobolev VI (1998) Generation of active oxygen species on solid surfaces. Opportunity for novel oxidation technologies over zeolites. Catal Today 41:365–385
Sushkevich VL, Palagin D, Ranocchiari M, van Bokhoven JA (2017) Selective anaerobic oxidation of methane enables direct synthesis of methanol. Science 356:523–527
Wang W, Hunger M (2008) Reactivity of surface alkoxy species on acidic zeolite catalysts. Acc Chem Res 41:895–904
Benlounes O, Mansouri S, Rabia C, Hocine S (2008) Direct oxidation of methane to oxygenates over heteropolyanions. J Nat Gas Chem 17:309–312
Mansouri S, Benlounes Q, Rabia C, Thouvenot R, Bettahar MM, Hocine S (2013) Partial oxidation of methane over modified Keggin-type polyoxotungstates. J Mol Catal A: Chem 379:255–262
Khokhar MD, Shukla RS, Jasra RV (2009) Selective oxidation of methane by molecular oxygen catalyzed by a bridged binuclear ruthenium complex at moderate pressures and ambient temperature. J Mol Catal A: Chem 299:108–116
Shilov AE, Shul’pin GB (1997) Activation of C–H bonds by metal complexes. Chem Rev 3:2879–2932
Yamanaka I, Soma M, Otsuka K (1995) Oxidation of methane to methanol with oxygen catalysed by europium trichloride at room temperature. J Chem Soc Chem Commun 2235–2236
Yamanaka I (2002) Reductive activation of O2 and monooxygenation of hydrocarbons by Eu catalyst. Catal Surv Asia 6:63–72
Yamanaka I, Soma M, Otsuka K (1996) Enhancing effect of titanium(II) for the oxidation of methane with O2 by an EuCl3-Zn-CF3CO2H-catalytic system at 40 °C. Chem Lett 25:565–566
Piao D, Inoue K, Shibasaki H, Taniguchi Y, Kitamura T, Fujiwara Y (1999) An efficient partial oxidation of methane in trifluoroacetic acid using vanadium-containing heteropolyacid catalysts. J Organomet Chem 574:116–120
Periana RA, Taube DJ, Evitt ER, Lӧffler DG, Wentrcek PR, Voss G, Masuda T (1993) A mercury-catalyzed, high-yield system for the oxidation of methane to methanol. Science 259:340–343
Sen A, Benvenuto MA, Lin M, Hutson AC, Basickes N (1994) Activation of methane and ethane and their selective oxidation to the alcohols in protic media. J Am Chem Soc 116:998–1003
Jones CJ, Taube D, Ziatdinov VR, Periana RA, Nielsen RJ, Oxgaard J, Goddard WA (2004) Selective oxidation of methane to methanol catalyzed, with C-H activation, by homogeneous, cationic gold. Angew Chem Int Ed 43:4626–4629
Periana RA, Taube DJ, Gamble S, Taube H, Satoh T, Fujii H (1998) Platinum catalysts for the high-yield oxidation of methane to a methanol derivative. Science 280:560–564
Zimmermann T, Soorholtz M, Bilke M, Schueth F (2016) Selective methane oxidation catalyzed by platinum salts in oleum at turnover frequencies of large-scale industrial processes. J Am Chem Soc 138:12395–12400
Hashiguchi BG, Konnick MM, Bischof SM, Gustafson SJ, Devarajan D, Gunsalus N, Ess DH, Periana RA (2014) Main-group compounds selectively oxidize mixtures of methane, ethane, and propane to alcohol esters. Science 343:1232–1237
Gretz E, Oliver TF, Sen A (1987) Carbon-hydrogen bond activation by electrophilic transition-metal compounds. Palladium(II)-mediated oxidation of arenes and alkanes including methane. J Am Chem Soc 109:8109–8111
Sen A (1991) Homogeneous palladium(II) mediated oxidation of methane. Plat Metal Rev 35:126–132
Muehlhofer M, Strassner T, Herrmann WA (2000) New catalyst systems for the catalytic conversion of methane into methanol. Angew Chem Int Ed 41:1745–1747
Munz D, Myyer D, Strassner T (2013) Methane CH activation by palladium complexes with chelating bis(NHC) ligands: a DFT study. Organometal 32:3469–3480
Vargaftik MN, Stolarov IP, Moiseev II (1990) Highly selective partial oxidation of methane to methyl trifluoroacetate. J Chem Soc Chem Commun 1049–1050
Strassner T, Ahrens S, Muehlhofer M, Munz D, Zeller A (2013) Cobalt-catalyzed oxidation of methane to methyl trifluoroacetate by dioxygen. Eur J Inorg Chem 21:3659–3663
An Z, Pan X, Liu X, Han X, Bao X (2006) Combined redox couples for catalytic oxidation of methane by dioxygen at low temperatures. J Am Chem Soc 128:16028–16029
Yuan J, Wang L, Wang Y (2011) Direct oxidation of methane to a methanol derivative using molecular oxygen. Ind Eng Chem Res 50:6513–6516
Riess JG (2001) Oxygen carriers (“Blood substitutes”)-raison d’etre, chemistry and some physiology. Chem Rev 101:2797–2920
Riess JG (2002) Fluorous micro- and nanophases with a biomedical perspective. Tetrahedron 58:4113–4131
Elibol M, Mavituna F (1999) A remedy to oxygen limitation problem in antibiotic production addition of perfluorocarbon. Biochem Eng J 3:1–7
Kozhevnikov IV (1997) PMo12-nVnO(3+n)- 40 heteropolyanions as catalysts for aerobic oxidation. J Mol Catal A: Chem 117:151–158
Palkovits R, von Malotki C, Baumgarten M, Müllen K, Baltes C, Antonietti M, Kuhn P, Weber J, Thomas A, Schüth F (2010) Development of molecular and solid catalysts for the direct low-temperature oxidation of methane to methanol. Chemsuschem 22:277–282
Palkovits R, Antonietti M, Kuhn P, Thomas A, Schüth F (2009) Solid catalysts for the selective low-temperature oxidation of methane to methanol. Angew Chem Int Ed 48:6909–6912
Ravi M, Ranocchiari M, van Bokhoven JA (2017) The direct catalytic oxidation of methane to methanol—a critical assessment. Angew Chem Int Ed 22:16464–16483
Conley BL, Tenn WJ, Young KJH, Ganesh SK, Meier SK, Ziatdinov VR, Mironov O, Oxgaard J, Gonzales J (2006) Goddard III WA, Periana RA. J Mol Catal A 251:8–23
Periana RA, Bhalla G, Tenn WJ, Young KJH, Liu XY, Mironov O, Jones CJ, Ziatdinov VR (2004) J Mol Catal A 220:7–25
Furuto T, Takeguchi M, Okura I (1999) Semicontinuous methanol biosynthesis by Methylosinus trichosporium OB3b. J Mol Catal A: Chem 144:257–261
Lee SG, Goo JH, Kim HG, Oh JI, Kim YM, Kim SW (2004) Optimization of methanol biosynthesis from methane using Methylosinus trichosporium OB3b. Biotechnol Lett 26:947–950
Duan C, Luo M, Xing X (2011) High-rate conversion of methane to methanol by Methylosinus trichosporium OB3b. Bioresour Technol 102:7349–7353
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Baba, T., Miyaji, A. (2020). Heterogeneous and Homogeneous Catalytic Partial Oxidations of Methane to Methanol and Its Derivatives. In: Catalysis and the Mechanism of Methane Conversion to Chemicals. Springer, Singapore. https://doi.org/10.1007/978-981-15-4132-2_3
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