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.     

甲烷催化部分氧化制合成气催化剂的研究进展

叙述了甲烷催化部分氧化制合成气催化剂的最新研究进展,包括含钴的钙钛矿、碳化钼、碳化、Ｎｉ／α－Ａｌ２Ｏ３,Ｐｔ－Ｎｉ／α－Ａｌ２Ｏ３、ｌａＯ３＿ＮｉＯ／Ａｌ２Ｏ３等。     

甲烷空气催化部分氧化制含氮合成气的研究

采用常规的浸渍法制备镍基催化剂,研究了甲烷空气催化部分氧化制备含氮合成气的催化性能,得到了镍含量在8％时部分氧化活性最佳;加入镧助剂使催化剂的活性和选择性达到95．3％和97．5％,通过向体系加入H2O和CO2,可以提高加压条件下甲烷的转化率并抑制催化剂积炭,可以获得n(H2):n(CO）接近２的合成气;催化剂连续使用500h性能稳定。     

甲烷空气催化部分氧化制含氮合成气的研究

采用常规的浸渍法制备了镍基催化剂和经过镧改性的镍基催化剂,研究了甲烷催化部分氧化制备含氮合成气的催化功能,结果说明,镍含量在8％时催化活性达到最好,同时加入镧进行改性后催化剂的活性和选择性有所提高;该催化剂对甲烷空气催化部分氧化制合成气在常压下具有较高的转化率,随压力升高,转化率明显下降,并且积极严重,通过向体系加入H2O和CO2可以提高加压条件下甲烷的转化率并抑制催化剂积碳,还可以获得H2／CO接近2的合成气,满足合成液体燃料的要求。     

甲烷部分氧化制合成气的研究进展

综述了近年来甲烷部分氧化制合成气的催化剂，反应机理及活性中心的研究进展及反应中存在的主要问题。     

甲烷常压非催化部分氧化制合成气研究

考察了常压下甲烷非催化部分氧化制合成气过程中,甲烷转化率、气体产物产率以及积炭率随反应器温度、进气配比、原料气流量变化的影响。通过考察反应器温度对制备合成气过程的影响结果,分析了甲烷非催化部分氧化制合成气过程的反应机理。     

甲烷催化部分氧化制合成气催化剂的研究进展

天然气是一种前景广阔的清洁燃料,甲烷作为天然气的主要成分,其高效利用具有重要的现实意义。在众多甲烷转化途径中,甲烷催化部分氧化（CPOM）具有能耗低、合成气组分适宜、反应迅速等优势。本文简要介绍了CPOM反应机理,即直接氧化机理和燃烧-重整机理;重点综述了过渡金属、贵金属、双金属和钙钛矿这四类CPOM催化剂的研究现状;分析了反应温度、反应气体碳氧比和反应空速对CPOM反应特性的影响;阐述了积炭和烧结这两种催化剂失活的主要原因及应对措施。根据研究结果可知,通过选取合适的催化剂组分、采用优化的制备方法、精确控制催化剂活性组分分布和微观结构等措施,可以保证更多的有效活性位更稳定地暴露在催化剂表面,以此提高催化性能（包括甲烷转化率、合成气选择性、合成气生成率、反应稳定性等）。最后指出了对CPOM催化剂微观结构的合理设计与可控制备以及对CPOM反应机理的深入研究仍将是今后关注的重点。     

甲烷部分氧化制合成气催化剂的研究进展

甲烷部分氧化（POM）反应制合成气是化学利用甲烷的有效途径之一。研究表明,甲烷部分氧化反应的工艺有能耗低和反应速率较快等优点,而且所得的H2和CO的比例适于合成甲醇等工业化学品。在该工艺过程中,所需反应容器体积小,反应效率高,可大幅度降低制备合成气的成本。开发POM反应的高效催化剂是进一步提高反应效率、实现工业化的关键途径,因此,是当前国际催化领域研究的热门课题之一。本文主要介绍了传统的金属负载型催化剂和金属氧化物催化剂用于POM反应的研究进展。     

天然气甲烷部分氧化制合成气的研究进展

甲烷部分氧化制合成气是高转化率、高选择性、高空速、低H2/CO、温和的放热反应,综述了近几年来甲烷部分氧化制合成气的催化剂、反应机理及活性中心的研究进展及反应中的存在问题。     

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.     

甲烷空气部分氧化制合成气喷动床反应器的研究

On the basis of hydrodynamic and scaling-up studies, a pilot-plant-scale thermal spouted bed reactor (50 mm in ID and 1500 mm in height) was designed and fabricated by scaling-down cold simulators. It was tested for making syngas via catalytic partial oxidation (CPO) of methane by air. The effects of various operating conditions such as operating pressure and temperature, feed composition, and gas flowrate etc. on the CPO process were investigated. CH4 conversion of 92.20％ and selectivity of 92.3% and 83.30/0 to CO and H2, respectively, were achieved at the pressure of 2.1 MPa. It was found that when the spouted bed reactor was operated within the stable spouting flow regime, the temperature profiles along the bed axis were much more uniform than those operated within the fixed-bed regime. The CH4 conversion and syngas selectivity were found to be close to thermodynamic equilibrium limits. The results of the present investigation showed that spouted bed could be considered as a potential type of chemical reactor for the CPO process of methane.     

甲烷部分氧化制合成气反应的研究

用粒度为5mm的α－Al2O3、β-Al2O3、γ-Al2O3为载体，用浸渍法制备了10％（质量）Ni基催化剂。在固定床流动反应器中，在反应温度500－850℃，大空速和不同的CH4／O2摩尔比下，测定了该催化剂用于甲烷部分氧化制合成气的活性和CO选择性。500℃用H2对催化剂还2h后，进行活性测试结果,10%Ni／β-Al2O3、Ni／γ-Al2O3对POM反应无活性，只有10％Niα－Al2O3对POM反应有活性。TPR测试结果表明，这是由于10％Ni／β-Al2O3和Ni／γ-Al2O3催化剂在700℃以下未被还原所致。另外，合成气的生成速率和CO选择尾均随反应温度和空速的增大而增大，并在CH4／O2摩尔比2时有最大值。     

甲烷部分氧化制合成气催化剂的研究进展

综述了甲烷部分氧化制合成气的研究意义和现状，从金属活性组分，载体效应，载量选择，助剂添加和制备方法等因素对催化剂活性的影响及研究进行了系统。结合本课题组的研究结果及文献报道，分析了Ni基催化剂的失活特性，并提出使用等离子体技术对Ni基催化剂进行改笥处理，以提高其催化稳定性的技术展望。     

Novel and Ideal Zirconium-Based Dense Membrane Reactors for Partial Oxidation of Methane to Syngas

A novel and ideal dense catalytic membrane reactor for the reaction of partial oxidation of methane to syngas (POM) was constructed from the stable mixed conducting perovskite material of BaCo_0.4Fe_0.4Zr_0.2O_3– and the catalyst of LiLaNiO/-Al₂O₃. The POM reaction was performed successfully. Not only was a short induction period of 2 h obtained, but also a high catalytic performance of 96–98% CH₄ conversion, 98–99% CO selectivity and an oxygen permeation flux of 5.4–5.8 mlcm^–2min^–1 (1.9–2.0 molm^–2S^–1Pa^–1) at 850°C were achieved. Moreover, the reaction has been steadily carried out for more than 2200 h, and no interaction between the membrane material and the catalyst took place.     

Sonochemically Prepared high Dispersed Ru/TiO2 Mesoporous Catalyst for Partial Oxidation of Methane to Syngas

Highly dispersed Ru nanoparticles on mesoporous TiO₂ have been synthesized by a one-step ultrasound assisted polyol reduction procedure. The catalysts have been characterized by XRD, TEM and HR-TEM, EDX, BET and TPR methods. It has been demonstrated that the sonochemical method reduces the Ru⁺³ ions creating a narrow size distribution of metallic nanoparticles deposited on the mesoporous support without damaging its pore structure. The nanoparticles of Ru are highly dispersed and stable because of their incorporation into the mesopores, and the strong metal-support interaction. The catalytic properties of Ru/TiO₂(MSP) have been tested in the partial oxidation of methane, and high activity and selectivity towards CO and H₂ have been demonstrated.     

焦炉气非催化部分氧化与催化部分氧化制合成气工艺比较

提出了一种可用于焦炉气转化的非催化部分氧化工艺,并进行了研究;同时对焦炉气非催化部分氧化和催化部分氧化制合成气工艺进行了比较,结果表明,催化部分氧化需要大量的外加蒸汽,其总体能耗并不比非催化部分氧化法低。     

Partial Oxidation of Methane to Syngas in a Packed Bed Catalyst Membrane Reactor

The planar membrane reactor configuration was explored for partial oxidation of methane (POM) to syngas. A supported membrane composed of yttria‐stabilized zirconia and La_0.8Sr_0.2Cr_0.5Fe_0.5O_3‐δ was sealed to a stainless holder, and a Ni/Al₂O₃ catalyst bed was placed under the membrane plane with a small slit between them. This reactor configuration would facilitate the POM reaction via oxidation‐reforming mechanism: the oxidation reaction occurring at the membrane surface and the reforming reaction taking place in the catalyst bed. At 800°C and a methane feed rate of 32 mL min^?1, the reactor attained methane throughput conversion over 90%, CO and H₂ selectivity both over 95%, and an equivalent oxygen permeation rate 1.4 mL cm^?2 min^?1. The membrane and catalyst remained intact after the POM testing. The planar membrane reactor configuration explored in this study may lead to the development of a compact reactor for syngas production. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2170–2176, 2016     

甲烷非催化部分氧化制乙炔和合成气过程的实验研究

通过探头取样和四极杆质谱在线测量甲烷、氧气和乙炔等组分的浓度分布,考察了氧气/甲烷(甲烷+乙烷/丙烷)摩尔比、气体预热温度及原料气中添加乙烷和丙烷对甲烷非催化部分氧化制乙炔和合成气的影响. 结果表明,随轴向距离增加,乙炔浓度先增大后减小,存在最大值;随氧气/甲烷(甲烷+乙烷/丙烷)摩尔比增加,乙炔选择性下降;升高混合气体预热温度产物中乙炔浓度增大,620℃时最大乙炔浓度为4.52%;添加乙烷和丙烷时产物中乙炔浓度基本不变,但甲烷消耗量下降. 在实验条件下,生成最大乙炔浓度的激冷位置距烧嘴出口的距离约为80 mm.