Direct conversion of natural gas to higher hydrocarbons: A review

Direct conversion of methane to higher hydrocarbons is an effective process to solve the problem of natural gas utilization. Although remarkable progress has been achieved on the dehydro-aromatization of methane (DAM), low conversion caused by severe thermodynamic limitations, coke formation, and catalysis deactivation remain important drawbacks to the direct conversion process. Molybdenum catalysts supported on HZSM-5 type zeolite support are among the most promising catalysts. This review focuses on the aspects of direct methane conversion, in terms of catalysts containing metal and support, reaction conditions, and conversion in different types of reactors. The reaction mechanism for this catalytic process is also discussed.     

Direct conversion of natural gas to higher hydrocarbons:A review

Direct conversion of methane to higher hydrocarbons is an effective process to solve the problem of natural gas utilization. Although remarkable progress has been achieved on the dehydro-aromatization of methane (DAM), low conversion caused by severe thermodynamic limitations,coke formation, and catalysis deactivation remain important drawbacks to the direct conversion process. Molybdenum catalysts supported on HZSM-5 type zeolite support are among the most promising catalysts. This review focuses on the aspects of direct methane conversion, in terms of catalysts containing metal and support, reaction conditions, and conversion in different types of reactors. The reaction mechanism for this catalytic process is also discussed.     

Effect of doping fulllerene soots with metals on the conversion of methane into higher hydrocarbons

We have previously demonstrated that fullerene soots catalyze hydrogen-transfer reactions that are useful for hydrocarbon processing, including conversion of methane into higher hydrocarbons. In this paper we describe the effect of doping fullerene soot with alkali and transition metals for converting methane and other light hydrocarbons. The fullerene soot was found to lower the temperature threshold for methane activation compared to other carbons; however, the selectivity to C₂ hydrocarbons was quite low (20%). In contrast, when the soot was doped with metals such as Mn or K, the overall yield of hydrocarbons increased and selectivities as high as 80% were achieved. When potassium was used as a dopant, the selectivity to C₃ and C₄ hydrocarbons also increased.     

The conversion of natural gas to higher hydrocarbons using a microwave plasma and catalysts

Methane, the major constituent of natural gas, had been converted to higher hydrocarbons by a microwave plasma. The yield of C2+ products increased from 29.2% to 42.2% with increasing the plasma power and decreasing the flow rate of methane. When the catalysts were used in the plasma reactor, the selectivities of ethylene and acetylene increased while the yield of C2+ remained constant. Among the various catalysts used, the Fe catalyst showed the highest ethylene selectivity of 30%. When we introduced the actual natural gas, more C2+ products were obtained (46%). This is due to the ethane and propane in the natural gas. When an electric field inductance for evolving the high plasma was applied, a high yield in C2+ products of 63.7% was obtained for the Pd-Ni bimetal catalyst.     

核壳结构催化剂Cr-Zn@SiO2@SAPO-34催化合成气直接转化制低碳烃的性能

合成气直接转化高选择性制烃类产物仍是巨大的挑战.本文合成了以Cr-Zn氧化物为核, SiO2为中间过渡层,再通过原位水热合成覆盖一层SAPO-34分子筛为壳的核壳结构催化剂.合成气转化反应结果显示,与纯Cr-Zn金属氧化物相比,核壳结构催化剂将产物分布由甲醇和甲烷移动至C2–C4烃(所有烃类产物中占66.9%).这表明核壳结构催化剂用于合成气一步法直接转化制液化石油气的反应具有可行性,但是催化剂结构和组成有待于进一步优化,以提高其催化反应性能.     

Continuous conversion of methanol to higher hydrocarbons at ambient pressure

An iodozincate ionic liquid solvent and catalyst is used to convert methanol continuously to a wide variety of hydrocarbons at atmospheric pressure.     

Membranes for separation of higher hydrocarbons from methane

In the search for a membrane material capable of separating higher hydrocarbons from methane about 40 different polymers were tested. The most promising two, polyoctylmethylsiloxane (POMS) and polytrimethylsilylpropyne (PTMSP), are compared in this article to the standard material polydimethylsiloxane (PDMS).     

单原子催化甲烷直接转化的研究进展

将甲烷直接转化(DMC)为高附加值化学品(如甲醇等化合物),是实现天然气高效利用的有效途径.因甲烷结构非常稳定,使其在温和条件下(反应温度≤150℃的非强酸介质体系)的高效活化极具挑战性.近年来,单原子催化剂(SACs)因其活性物种的高利用率和高选择性,已引起国内外研究者的广泛关注,并被尝试应用于多种反应.研究表明,S...     

Direct methane conversion to methanol by ionic liquid-dissolved platinum catalysts

Ternary systems of inorganic Pt salts and oxides, ionic liquids and concentrated sulfuric acid are effective at catalyzing the direct, selective oxidation of methane to methanol and appear to be more water tolerant than the Catalytica reaction.     

Non-oxidative dehydro-oligomerization of methane to higher molecular weight hydrocarbons at low temperatures

The non-oxidative dehydro-oligomerization of methane to higher molecular weight hydrocarbons such as aroma tics and C2 hydrocarbons in a low temperature range of 773-973 K with Mo/HZSM-5,Mo-Zr/HZSM-5 and Mo-W/HZSM-5 catalysts is studied.The means for enhancing the activity and stability of the Mo-containing catalysts under the reaction conditions is reported.Quite a stable methane conversion rate of over 10% with a high selectivity to the higher hydrocarbons has been obtained at a temperature of 973 K.Pure methane conversions of about 5.2% and 2.0% have been obtained at 923 and 873 K,respectively.In addition,accompanied by the C2-C3 mixture,tht- methane reaction can be initiated even at a lower temperature and the conversion rate of methane is enhanced by the presence of tne initiator of C2-C3 hydrocarbons.Compared with methane oxidative coupling to ethylene,the novel way for methane transformation is significant and reasonable for its lower reaction temperatures and high selectivity to the desired prod     

High temperature catalytic synthesis of higher hydrocarbons from methane

It has been revealed that methane conversion to higher hydrocarbons over MgO catalyst involves the direct participation of heterogeneous catalyst at contact times of up to 3s and is a homogeneous reaction at 10s.

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Direct conversion of synthesis gas to light hydrocarbons on heterogeneous catalysts

Six catalysts consisting of mixtures of catalysts for methanol synthesis and its conversion to hydrocarbons were prepared by mechanical mixing, impregnation, and coprecipitation, followed by extrusion. Phase changes occurring during various stages of preparation and after use were followed by x-ray diffraction. The catalysts were found to be nontrivial bifunctional catalysts which selectively convert synthesis gas directly to low molecular weight hydrocarbons in the range of C₁ to C₄. Methanol and dimethylether were detected as intermediates. Olefins were formed, and their further hydrogenation yielded products with high paraffinic content. Carbon dioxide retards the conversion of synthesis gas to hydrocarbons, whereas steam retards the hydrogenation of olefins. On heating the commercial zinc chromite catalyst, dehydration, reduction, and solid-state reactions occur with the formation of ZnO-ZnCr₂O₄ solid solution. Exchanging cations within the zeolite component did not affect the space lattice, but these ions tend to occupy special sites, and during service more order was detected. Copper ions tend to diffuse in ZnO, forming a solid solution, and during service metallic copper was produced.     

Nonoxidative methane conversion into aromatic hydrocarbons on tungsten-containing pentasils

The effects of the tungsten concentration and of the method of tungsten introduction into ZSM-5 pentails with different SiO₂/Al₂O₃ molar ratios on the acidity and the activity of the resulting catalysis in nonoxidative methane conversion into aromatic hydrocarbons are considered. The catalysts obtained from the SiO₂/Al₂O₃ = 40 pentasil and a nanosized tungsten powder are the most active and the most stable. The maximum methane conversion and the highest yield of aromatic hydrocarbons are achieved on the zeolite containing 8.0 wt % tungsten nanopowder.     

SO2-4/MxOy固体超强酸催化合成烷基吡嗪类化合物研究

以乙二胺为唯一原料,在常压气相条件下经固体超强酸、固定床催化合成以乙基吡嗪为主要产品的烷基吡嗪系列化合物;并对反应温度、进料流速、原料配比和水等条件对产品产率的影响,进行了较为深入的讨论,得到最佳反应条件:温度340°C,原料配比乙二胺:水=0.9∶1,进料流速1.2 cm3/m in。     

Highly effective methane conversion to aromatic hydrocarbons by means of microwave and rf-induced catalysis

Conversion of methane to higher hydrocarbon products, in particular, aromatic hydrocarbons has been achieved with good methane conversion and selectivity to aromatic products over heterogeneous catalysts using both high power pulsed microwave and rf energy. For example, under microwave irradiation > 85% conversion of methane and 60% selectivity to aromatics could be achieved. Cu, Ni, Fe and Al metallic materials are highly effective catalysts for the aromatization of methane via microwave heating; however, with a variety of supported catalysts the major products were C₂ hydrocarbons and the conversion of methane was low. The use of sponge, wire and net forms of these metal catalysts was found advantageous in effective methane conversion. The reactions are considered to be free radical in nature and to proceed through an intermediate stage involving formation of acetylene. The influence of catalyst nature and configuration, as well as the microwave and rf irradiation parameters on the reaction efficiency and product selectivity has been examined in both batch and continuous flow conditions.     

Selective conversion of methane to aromatic hydrocarbons on large crystallite zeolite catalysts with mesoporous structure

Large crystallite mesoporous MFI (ZSM-5) zeolite was synthesized by using carbon nano-powder as a secondary template. The surface properties, morphological and phase composition of the synthesized material and of the commercial ZSM-5 (Zeolyst) zeolite were studied by nitrogen porosimetry, XRD and scanning electron microscopy. The results showed that the volume of mesopores volume increases with development of a secondary mesoporosity in the structure of zeolite. The obtained zeolite supports were used to prepare molybdenum-containing catalysts for the methane aromatization by solid phase preparation technique. Based on the XPS data, molybdenum particles in these catalysts are characterized by more uniform size distribution. The formation of a secondary pore structure restrains the carbon deposit formation as well as increases the methane conversion and the yield of the aromatic compounds.     

反应器型式对甲烷低温等离子体转化制C2烃的影响

就不同反应器对甲烷常压低温等离子体转化制C2烃的影响进行了研究。结果表明,相同的甲烷停留时间和相同甲烷流率下,反应器A和B中反应的主要产物是乙炔,乙烯和乙烷的含量较少,积炭量较多;而反应器C和D中反应的主要产物为乙烷和丙烷,乙烯和乙炔含量较少,积炭量很少。反应积炭对反应器A中甲烷转化率影响很大,对于产物选择性影响不大,而对反应器C中的反应影响较小。根据产物分布可知,在反应器A和B中,由于电子具有很高的能量和密度,甲烷主要解离为碳原子;而在反应器C及D中,由于电子能量和密度较低,甲烷主要解离为CH3自由基。     

Conversion of ethylene to butadiene and higher hydrocarbons in the absence of a catalyst

The conversion of ethylene to butadiene and higher hydrocarbons in the absence of a catalyst in the temperature range 973–1023 K, an ethylene partial pressure of 2–15 kPa and a flow rate of 30–150 cm³/min. The effect of the reactor free space on the overall conversion of ethylene and its selectivity has been studied. The probable steps in the formation of the principal products is discussed.Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 31, No. 2, pp. 95–99, March–April, 1995.This work was carried out with a grant from the Ukraine State Committee on Science and Technology.