富甲烷气制合成油原料气技术发展现状

随着我国经济快速发展,石油需求量越来越大。我国煤炭资源丰富,开发高效煤制油技术是解决石油供需矛盾的一种有效途径。本文分析了富甲烷气制合成油合成气技术的国内外发展状况,指出催化部分氧化和高温非催化技术可较经济地用于富甲烷气合成油制合成气。其中,催化部分氧化技术对原料气S含量要求严格,而且产品气H_2含量高;高温非催化技术对原料气组成要求宽松,但转化温度和能耗较高,对反应器材质要求较高,投资大。     

国内外甲烷催化部分氧化技术进展

介绍了国内外甲烷催化部分氧化制合成气技术的研究进展。主要工艺包括固定床工艺、流化床工艺和陶瓷膜工艺。此外，在反应器方面，还对两项最新专利技术进行了讨论。最后，提出了甲烷催化部分氧化制合成气技术的发展趋势，为我国在天然气利用方面的技术开发提供了参考和依据。     

膜催化技术用于甲烷转化反应的研究进展

介绍了膜催化技术在甲烷转化反应中的应用,这些过程包括甲烷氧化偶联反应制乙烯,甲烷部分氧化制甲醇,甲烷水蒸气重整制合成气等,通过膜催化反应与传统催化反应的比较,揭示了膜催化技术的优点。     

甲烷催化部分氧化制合成气的研究进展

文章叙述了甲烷催化部分氧化制合成气研究的进展情况。介绍了两种主要的反应机理：间接反应机理和直接反应机理;对负载型镍系催化剂的研究现状进行了叙述,并简单介绍了非负载型催化剂;另外还对固定床、流化床、膜反应器以及一些新开发的反应器的特点进行了讨论。     

甲烷活化与转化的研究进展

甲烷活化与转化是当今催化研究领域的前沿课题。本文对甲烷氧化偶联制乙烯、甲烷芳构化、甲烷部分氧化制合成气的催化剂进行了介绍。     

甲烷催化部分氧化制甲醇在炼油厂的应用前景

简要介绍了各种正在研究开发中的天然气制合成气技术，催化部分氧化制合成气较好的工业化应用前景。对此过程中采用的催化剂和反应器也进行了介绍。     

管式致密透氧膜用于甲烷部分氧化制合成气的研究

采用钙钛矿型管式致密透氧膜反应器,在Ｎｉ／Ａｌ２Ｏ３催化剂上进行了甲烷部分氧化制合成气的实验研究,考察了进料气中甲烷的摩尔分数和反应温度对反应结果的影响,并对膜在反应条件下的稳定性作了分析     

流化床内生物质合成气制取甲烷的实验与宏观动力学

为了研究低温低压下流化床反应器中生物合成气催化制取甲烷过程,制备了Ni基甲烷化催化剂,对其进行表面形态分析,并考察了该催化剂催化合成气制备甲烷反应中操作条件对甲烷化过程的影响。实验结果表明,在低温低压的条件下,合成气甲烷化过程受到操作参数(反应温度、压力、空速和氢碳比等)的影响较大。较高的反应压力和氢碳比有利于甲烷的生成,反应温度存在最佳值,空速则有一折中值。根据实验结果,考虑到温度对甲烷生成的影响,引入了基于甲烷化反应温度的修正系数,建立了低温低压下合成气制备甲烷的宏观动力学模型。实验数据与模拟数据比较符合,验证了所建宏观动力学模型的正确性,从而为准确描述低温低压下合成气催化制取甲烷的过程奠定基础。     

甲烷部分氧化制合成气反应中床层热点问题研究进展

综述了甲烷部分氧化制合成气反应中催化剂床层热点问题,包括热点产生的原因,热点位置的测定,热点温度的影响因素,以及热点问题的解决方法,对于保护催化剂和反应器,降低反应的危险性起到借鉴作用.     

天然气部分氧化制合成气的研究进展

综述了天然气部分氧化制合成气的研究进展,包括天然气无催化部分氧化、固定床催化部分氧化、两段转化法、膜反应器新工艺、流化床反应工艺、氧化剂研究、微波辐射加热部分氧化、部分氧化的机理,以及部分氧化工艺的催化剂研究。     

Temperature profile in a two-stage fixed bed reactor for catalytic partial oxidation of methane to syngas

Detailed axial temperature distribution has been studied in a two-stage process for catalytic partial oxidation of methane to syngas, which consists of two consecutive fixed bed reactors with oxygen or air separately introduced. The first stage of the reactor, packed with a combustion catalyst, is used for catalytic combustion of methane at low initial temperature. While the second stage, filled with a partial oxidation catalyst, is used for the partial oxidation of methane to syngas. A pilot-scale reactor packed with up to 80 g combustion catalyst and 80 g partial oxidation catalyst was employed. The effects of oxygen distribution in the two sections, and gas hourly space velocity (GHSV) on the catalyst bed temperature profile, as well as conversion of methane and selectivities to syngas were investigated under atmospheric pressure. It is found that both oxygen splitting ratio and GHSV have significant influence on the temperature profile in the reactor, which can be explained by the synergetic effects of the fast exothermic oxidation reactions and the slow endothermic (steam and CO₂) reforming reactions. Almost no change in activity and selectivity was observed after a stability experiment for 300 h.     

焦炉煤气非催化部分氧化制合成气实验研究与数值模拟

在带有单孔喷嘴石英管反应器实验的基础上,对焦炉煤气非催化部分氧化工艺制合成气进行了研究,分析了O_2/GAS比对合成气各组分含量的影响,反应器中反应过程和温度分布及出口产品组成.实验结果表明CH4转化率随O_2/GAS比增大而增大,O_2/GAS比调节到0.22～0.26时,CH_4转化率达到95%～97%,此时合成气CH_4含量低于1%.利用CFD软件平台对转化反应器进行了数值模拟.模拟结果显示,流量一定时出口气体组分H_2与CH4分别随着进气氧气与焦炉煤气体积流量比值的增加而减少.CO和CO_2分别随着比值的增加而增加.出口气体有效组分摩尔分数随进气流量的变化不是非常明显.在壁面温度为1 100 K时转化效果最好.     

Rh负载的整体型催化剂甲烷催化部分氧化过程

采用负载Rh的泡沫独石整体型催化剂研究了甲烷催化部分氧化过程,考察了外界温度、空速和甲烷与氧气进料比例对反应转化率和选择性的影响,并对过程控制条件和调控参数进行了分析。研究结果表明该过程为毫秒级超短接触过程,反应可以在自热条件下进行,高空速条件下（8×10⁵ h^-1）,甲烷与氧气进料比（体积比）为1.8,甲烷转过率超过90%,CO选择性接近95%,H₂选择性超过90%。外界加热对过程有利,可获得更高的转化率和选择性。     

MODELING AND SIMULATION OF A NONISOTHERMAL CATALYTIC MEMBRANE REACTOR

A two-dimensional nonisothermal mathematical model has been developed to simulate a tube-and-shell configuration, catalytic membrane reactor. The three-layer membrane consists of an inert large-pore support, an o₂ semipermeable dense perovskite layer and a porous catalytic layer. The model is applied to the simulation of the partial oxidation or methane to syngas (oxyreforming). The membrane reactor simultaneously supplies oxygen to the catalytic reaction along the reactor length, and separates oxygen from the air feed, using a dense perovskite layer which is a mixed conductor, thus allowing rapid oxygen permeation without the use of an external circuit. Two configurations of catalytic membrane reactors are simulated, for both bench-scale and industrial-scale conditions. Comparisons are made to the conventional fixed-bed reactor, and to membrane reactors which are isothermal, adiabatic or wall-cooled. The simulation results imply that the temperature rise in exothermic partial oxidation reactions may be mitigated substantially by the use of a dense membrane reactor,     

SrFe0.6Cu0.3Ti0.1O3-δ透氧膜反应器中甲烷部分氧化反应工艺及膜稳定性考察

采用SrFe_0.6Cu_0.3Ti_0.1O_3-δ混合导体透氧膜组装成膜催化反应器,进行甲烷部分氧化制合成气反应,考察了反应温度、空速、催化剂粒径等条件的影响,并分析了反应气氛引起的透氧膜结构变化情况。结果表明,在膜反应器内,催化反应与透氧过程存在相互制约和相互促进的关系。在膜反应器内进行甲烷部分氧化反应后,透氧膜的两侧表面均发生蚀刻现象,结晶度显著降低,反应侧蚀刻现象较为严重,膜表面形成了疏松的多孔层,反应气氛使膜表面晶体结构发生了较大改变,Sr容易从钙钛矿结构中析出并与CO₂结合形成SrCO₃,Sr的析出导致组成不平衡,促进了钙钛矿结构分解及其他物相的产生。     

Conversion of hydrocarbon fuels to syngas in a short contact time catalytic reactor

Some results of the theoretical and experimental research on the oxidative production of syngas from hydrocarbon fuels in catalytic reactors which operate at high temperatures and short contact times are presented. Pilot scale tests of the partial oxidation of methane, isooctane and gasoline have been carried out in nearly adiabatic conditions on structured catalysts developed at the Boreskov Institute of Catalysis and characterized by a low (≤0.5 wt./wt.%) content of noble metals. High yield of syngas and stable performance of the catalysts were revealed in the experiments. The details of interaction between chemical and physical processes inside adiabatic monolith reactor have been elucidated by mathematical modeling of the partial oxidation reaction on the base of catalyst detailed chemistry. The problems that emerged from the short contact time reactor operating on a pilot scale are also discussed.     

催化部分氧化甲烷制合成气的平衡热力学研究

The catalytic partial oxidation of methane to syngas (CO H2) has been simulated thermodynamically with the advanced process simulator PRO/Ⅱ. The influences of temperature,pressure,CH4/O2 ratio and steam addition in feed gas on the conversion of CH4 selectively to syngas and heat duty required were investigated, and their effects on carbon formation were also discussed. The simulation results were in good agreement with the literature data taken from a spouted bed reactor.     

微波辐照引发甲烷部分氧化制合成气

考察用微波辐照方式引发反应后,１０％Ｎｉ／Ｌａ２Ｏ３催化氧化甲烷制合成气的反应行为。结果表明,当催化剂用量为０．１０ｇ,原料气空速为１５０～１８０Ｌ·ｇ－１·ｈ－ｌ,原料气中ＣＨ４与Ｏ２配比为２：ｌ,且原料气从催化床层的上端通入时,催化活性最佳