An integrated process for partial oxidation of alkanes

Zhou, Xiaoping; Yılmaz, Ali Özgür; Yılmaz, Gürkan; Lorković, Ivan M.; Laverman, Leroy E.; Weiss, Michael J.; Sherman, Jeffrey H.; McFarland, Eric W.; Stucky, Galen D.; Ford, Peter C.

doi:10.1039/b307235e

Cited by 46 publications

(55 citation statements)

References 6 publications

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“…Monohalogenomethanes (CH 3 Cl or CH 3 Br) could be alternative platform molecules for the conversion of CH 4 to chemicals. Olah et al reported the catalytic monohalogenation of CH 4 by Cl 2 or Br 2 over supported superacids or noble metals, followed by hydrolysis of methyl halides to methanol and dimethyl ether.…”

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confidence: 99%

Transformation of Methane to Propylene: A Two‐Step Reaction Route Catalyzed by Modified CeO₂ Nanocrystals and Zeolites

et al. 2012

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The utilization of methane, which is the main constituent of natural gas, coal-bed gas, shale gas, and the vast gas hydrate resources, for the production of chemicals is one of the most important research targets in catalysis. The current technology for chemical utilization of methane involves high-temperature steam reforming to produce syngas, and the subsequent conversion of syngas to methanol, followed by methanol transformation. However, steam reforming of methane is an energy-and cost-intensive process. The direct transformation of methane to valuable chemicals would be the most desirable route, however, despite many efforts it remains difficult to achieve.[1] The development of novel catalytic routes for the transformation of methane is of high significance from both practical and fundamental points of view.Monohalogenomethanes (CH 3 Cl or CH 3 Br) could be alternative platform molecules for the conversion of CH 4 to chemicals. Olah et al. reported the catalytic monohalogenation of CH 4 by Cl 2 or Br 2 over supported superacids or noble metals, followed by hydrolysis of methyl halides to methanol and dimethyl ether.[2] Zhou et al. disclosed the conversion of CH 4 or C 2 H 6 to alkyl bromides by using Br 2 , and the subsequent conversion to oxygenates through stoichiometric reactions with metal oxides.[3] GRT, Inc. developed a technology for the transformation of CH 4 to various products, particularly liquid hydrocarbon fuels, through the reaction with Br 2 via methyl bromides, and claimed that this is a costeffective route.[4] In these processes, the generated HCl, HBr, or metal bromides must be oxidized to Cl 2 or Br 2 to complete the catalytic cycle. HBr was demonstrated to be useful for the oxidative bromination of CH 4 in the presence of O 2 instead of Br 2 over supported Ru or Rh catalysts, [5] but the high cost and limited availability of noble metals may hinder the large-scale application of this system. Zn-MCM-48-supported hydrated dibromo(dioxo)molybdenum(VI), which might generate Br 2 during reaction, catalyzed the oxidation of CH 4 to methanol and dimethyl ether, but the long-term stability of this system was not confirmed.[6] SiO 2 -supported FePO 4 was stable for the oxidative bromination of CH 4 , which provided CH 3 Br with a selectivity of approximately 50 %.[7] Only a few studies have been devoted to the oxidative chlorination of CH 4 to CH 3 Cl, although HCl is cheaper than HBr. Lercher and co-workers found that LaCl 3 was a superior catalyst for this reaction, which provided CH 3 Cl with a selectivity of around 55 % at a CH 4 conversion of 12 % at 748 K.[8]Herein, we present a novel catalytic route for the conversion of CH 4 to propylene via monohalogenomethane. Propylene is one of the most important bulk chemicals, and currently, it is mainly produced as a coproduct of ethylene through the cracking of naphtha. However, the demand for propylene is growing much faster than the demand for ethylene.[9] The development of novel routes for the production of propylene, for example, dehydrogenat...

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Transformation of Methane to Propylene: A Two‐Step Reaction Route Catalyzed by Modified CeO₂ Nanocrystals and Zeolites

et al. 2012

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“…[11] Lorkovic and co-workers proposed a process for the functionalization of methane and ethane by using bromine as the mediator. [12] The process was carried out in a sequential zone-flow reactor (SZFR) that consisted of two serial reactors. In this process, the three-step conversions are actually carried out separately, and it is difficult to recycle the halogens.…”

Section: Fengbo LI and Guoqing Yuan*mentioning

confidence: 99%

Hydrated Dibromodioxomolybdenum(VI) Supported on Zn‐MCM‐48 for Facile Oxidation of Methane

Yuan

2006

Angew Chem Int Ed

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Methane is the most abundant and low cost C 1 feedstock and is considered to be a clean substitute for dwindling petroleum resources. However, its efficient transformation to more valuable liquid products remains a great challenge.[1] The current route is a multistep and energy-intensive conversion that involves the incipient generation of syngas from methane.[2] With potentially many benefits, much effort has been directed towards the exploration of direct methods to partially oxidize and selectively functionalize one of the CÀH bonds of methane, to convert it into valuable oxygenated and unsaturated compounds more efficiently, economically, and cleanly. As methane is an unreactive molecule, it reacts only under extreme conditions. Some methyl derivatives such as methanol, [3] methane sulfonic acid, [4] methane sulfonyl chlorides, [5] methyl bisulfate, [6] and acetic acid, [7] can be synthesized through the activation of methane in strong acid solvents with oxidants and radicals. Methane can also be activated over some solid catalysts with oxygen at high temperature, but selectivity towards valuable oxygenated products is poor. Catalytic methane-activation systems under mild conditions are all based on intricate metal complexes [8] and enzymes, [9] and their applications are limited to very small-scale syntheses.Methane can be converted into oxygenates under mild conditions through a three-step catalytic recycling of the oxidation mediator by using oxygen as the ultimate oxidant: 1) oxidizing methane to methyl derivatives by an oxidation mediator; 2) converting the methyl derivatives into oxygenated compounds; 3) regenerating the oxidation mediator. We have reported a series of catalysts for the low-temperature vapor-phase conversion of methane to methanol via methyl bisulfate with supported concentrated sulfuric acid as the oxidation mediator.[10] Others have considered halogens as the oxidation mediator. Olah et al. described selective monohalogenation of methane over supported acid and platinum-metal catalysts followed by hydrolysis of methyl halides over g-alumina-supported metal-oxide/hydroxide catalysts to convert methane into methanol and dimethyl ether.[11] Lorkovic and co-workers proposed a process for the functionalization of methane and ethane by using bromine as the mediator.[12] The process was carried out in a sequential zone-flow reactor (SZFR) that consisted of two serial reactors. In this process, the three-step conversions are actually carried out separately, and it is difficult to recycle the halogens.Herein, we report the design and preparation of a novel multifunction methane-activation catalyst, hydrated dibromodioxomolybdenum(VI) supported on Zn-MCM-48 (a zincmodified mesoporous silica), which integrates the three catalytic steps to transform methane into oxygenated products at a relatively low temperature (< 250 8C). Bromine is derived from dibromodioxomolybdenum and can be recycled in the catalyst bed through bromine metathesis of metal bromide/metal oxide pairs. Bromine acts as the ...

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“…Zhou and Lorkovic described the bromine-mediated process for the production of higher hydrocarbons through oxidative coupling of methane using O 2 as oxidant [12][13][14][15][16][17][18]. In the first step, CH 4 reacted with Br 2 giving a mixture of CH 4 , bromomethane, and HBr, and then this mixture passed over a metal oxide supported zeolite catalyst which condensed bromo with 100% conversion to products, and neutralized HBr to form the metal bromide.…”

Section: From Methane To Higher Hydrocarbons: the State Of The Artmentioning

confidence: 99%

Methyl Halide to Olefins and Gasoline over Zeolites and SAPO Catalysts: A New Route of MTO and MTG

Wei

Zhang

Liu

et al. 2012

Chinese Journal of Catalysis

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An integrated process for partial oxidation of alkanes

Abstract: The partial oxidation of alkanes via bromination followed by the reaction with solid metal oxide mixtures (MO) is shown to give an array of products that can be tuned by varying the MO and the reaction conditions.

Cited by 46 publications

References 6 publications

Transformation of Methane to Propylene: A Two‐Step Reaction Route Catalyzed by Modified CeO₂ Nanocrystals and Zeolites

Transformation of Methane to Propylene: A Two‐Step Reaction Route Catalyzed by Modified CeO₂ Nanocrystals and Zeolites

Hydrated Dibromodioxomolybdenum(VI) Supported on Zn‐MCM‐48 for Facile Oxidation of Methane

Methyl Halide to Olefins and Gasoline over Zeolites and SAPO Catalysts: A New Route of MTO and MTG

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An integrated process for partial oxidation of alkanes

Abstract: The partial oxidation of alkanes via bromination followed by the reaction with solid metal oxide mixtures (MO) is shown to give an array of products that can be tuned by varying the MO and the reaction conditions.

Cited by 46 publications

References 6 publications

Transformation of Methane to Propylene: A Two‐Step Reaction Route Catalyzed by Modified CeO2 Nanocrystals and Zeolites

Transformation of Methane to Propylene: A Two‐Step Reaction Route Catalyzed by Modified CeO2 Nanocrystals and Zeolites

Hydrated Dibromodioxomolybdenum(VI) Supported on Zn‐MCM‐48 for Facile Oxidation of Methane

Methyl Halide to Olefins and Gasoline over Zeolites and SAPO Catalysts: A New Route of MTO and MTG

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Transformation of Methane to Propylene: A Two‐Step Reaction Route Catalyzed by Modified CeO₂ Nanocrystals and Zeolites

Transformation of Methane to Propylene: A Two‐Step Reaction Route Catalyzed by Modified CeO₂ Nanocrystals and Zeolites