兖州煤业榆林能化提升甲醇合成催化剂效能总结

兖州煤业榆林能化有限公司600 kt/a甲醇装置合成系统采用鲁奇“气冷串水冷反应器甲醇合成工艺”,迄今已使用七炉甲醇合成催化剂，前五炉甲醇合成催化剂使用期间均出现水冷反应器催化剂活性衰减过快、气冷反应器催化剂活性依然良好的状况；2018年10月甲醇装置大检修期间，更换为第六炉甲醇合成催化剂，并新增新鲜气调节副线以适度降低水冷反应器负荷、提高气冷反应器负荷。分析认为，铜基甲醇合成催化剂使用寿命主要受催化剂床层热点温度、新鲜气硫和氯含量、空速、催化剂升温还原控制优劣、工艺流程等因素的影响。新鲜气调节副线投用后，既不影响甲醇产量，又能降低水冷反应器的负荷；同时，部分新鲜气直接进入气冷反应器，减少了毒物对水冷反应器催化剂的毒害，水冷反应器催化剂使用寿命大致可由1.5 a延长至2 a,由此可降低甲醇合成催化剂整体更换费用。此举可有效解决“气冷串水冷反应器甲醇合成工艺”应用中普遍存在的问题，并带来较好的经济效益，具有良好的推广应用价值。     

LBC407型合成甲醇催化剂的制备与应用

介绍新型LBC407型合成甲醇催化剂的制备与性能，并对已实现工业化生产的LBC407型合成甲醇催化剂使用性能进行评价，使用结果表明，其性能优于同类催化剂，具有活性高，选择性好，耐毒性强，使用寿命长等特点，是一种优良的合成甲醇催化剂。     

甲醇合成催化反应机理及活性中心研究进展

甲醇不仅是一种重要的有机化工原料，而且可以单独或与汽油混合作为汽车燃料，具有节能与环保的双重优势。甲醇合成反应研究尽管有四十多年的历史，但有关甲醇合成反应机理及催化剂活性中心类型等方面的问题仍存在争议。本文综述了近几年来在铜基催化剂上甲醇合成催化反应机理及催化剂活性中心的研究进展，以期提高人们对甲醇合成反应催化本质的认...     

半月要闻

低压合成甲醇催化剂小试成功 一项新型低压合成甲醇催化剂科研项目，最近在上海焦化研究院研制成功并通过技术鉴定。 近几年来，研制开发活性高、寿命长、强度高和热稳定性能好的新型合成催化剂，一直是国内甲醇生产工业十分关注的一个重要课题。上海焦化研究院催化剂室经过一年多的努力终于取得成功。这种被命名为ＳＪＣ——ＸＸ的甲醇合成催化剂活性、选择性、热稳定性、强度和使用寿命均达到或超过了国内同类产品的水平。 据介绍，这种新型甲醇催化剂的投入工业性生产，将大大降低甲醇生产成本，对提高甲醇的市场竞争能力具有重要意义。 …     

甲醇合成催化剂在生产过程中的保护

讲述了甲醇合成反应机理，在甲醇生产过程中影响甲醇合成催化剂使用周期的因素分析；保护和延长甲醇合成铜催化剂使用周期的方法。对甲醇的生产具有一定的指导意义。     

甲醇合成过程的热力学探讨

借助Excel的功能，应用物理化学和催化理论知识，对甲醇合成过程进行了热力学分析，讨论了温度，压力，气源，催化剂等条件对甲醇合成过程中主副反应的影响，为甲醇合成催化剂的制备及优化甲醇合成条件提供了热力学方面的参考意见。     

甲醇合成催化剂技术的发展与展望

目前，甲醇在工业生产中变得越来越为重要，需求量也越来越大。因此，对于甲醇的合成也就成为了一项课题。现如今，国内外都积极开展利用甲醇合成过程中所需催化剂的研究，本文也将针对此项技术的发展进行一等的探讨，并对以后甲醇合成催化剂的前景进行了分析，找到催化剂技术发展的最佳途径。     

C307型催化剂使用过程中结蜡原因分析及处理

我厂甲醇生产系统采用的是先进的低压合成、三塔精馏流程，年生产能力为150kt，催化剂采用南化集团研究院研制生产的C307型低压甲醇合成催化剂。在系统合成粗甲醇过程中，常伴有石蜡（C20-C40高级脂肪族烷烃混合物）生成，造成合成系统结蜡。结蜡无论是对催化剂还是对设备运行的危害都是比较严重的。我厂在用的C307型甲醇合成催化剂是2004年12月30日投用的，     

论甲醇合成催化剂技术的发展与展望

近年来甲醇合成催化技术凭借强大的自身优势，占领了广大的市场，为工业生产等带来重大的影响。本文主要阐述甲醇合成催化剂的具体定义，分析甲醇合成催化剂技术的发展情况，并对其未来前景做出展望。     

合成甲醇催化剂组成和制法对催化性能的影响

讨论了合成甲醇催化剂的组成和制备方法对催化性能的影响，同时比较了国内外目前合成甲醇催化剂的各种制法和催化性能，对各种催化剂的组成也进行了探讨。     

关于180万吨/年DAVY甲醇合成工艺应用KATACO 51-9甲醇合成催化剂钝化工作总结

叙述了神华包头煤化工有限责任公司180万吨/年DAVY甲醇合成系统应用KATACO 51-9系列甲醇合成催化剂的钝化方法、具体钝化过程以及在钝化过程中出现的问题,并且针对钝化期间出现的问题进行了探讨,通过切实有效地对甲醇合成催化剂进行钝化操作,从而有效地解决了其它甲醇合成生产单位甲醇合成催化剂在卸出过程中出现大量结块、粘结、冒烟的问题。     

XNC-98甲醇合成催化剂升温还原简介

介绍贵州金赤化工有限责任公司300kt/a甲醇装置XNC-98甲醇合成催化剂升温还原过程、注意事项及其运行状况。应用结果表明,XNC-98甲醇合成催化剂是一种高活性的铜基催化剂,具有极高的选择性和低温活性。     

On the junction effect theory of activity in methanol synthesis catalysts

The junction effect theory which has been propounded to account for the activity in methanol synthesis of oxide supported copper catalysts has been examined in the light of published data on the mechanism of methanol synthesis on copper/zinc oxide/alumina catalysts. The absence of a formate species on the surface of the zinc oxide component of the catalyst after methanol synthesis (the formate species has been shown to be the pivotal intermediate in methanol synthesis on zinc oxide) precludes its involvement in the reaction and negates the applicability of the theory to the copper/zinc oxide/alumina system.     

Z型甲烷蒸汽转化催化剂用于补碳制合成甲醇合成气的研究

选择工业应用效果较好的CNYQ、Z-2和Z-3型催化剂，并补加CO₂,对在其上的甲烷水蒸汽转化制合成气催化反应过程进行了测试研究。结果表明，在适当补加CO₂、反应温度600～850 ℃下，制得的合成气适合于甲醇合成。Z型催化剂用于CH₄-H₂O-CO₂转化制合成甲醇合成气，在当前情况下可满足某些合成甲醇厂的需要。     

NC306催化剂使用总结

介绍了NC306催化剂在兖矿鲁南化肥厂100kt/a低压甲醇合成装置上的应用,分析了入塔气体成分及氢碳比对甲醇合成反应的影响,并通过采取触媒的保护措施,取得了良好的效果。文中列举相关事例及数据,使读者对NC306催化剂强度高、工艺适应强、低温活性好、低消耗、高寿命等特点有一个全面的认识。     

C306型甲醇催化剂在我公司的应用

我公司低压(5MPa)合成甲醇装置采用C306型催化剂后,甲醇产量高,催化剂使用寿命长,生产强度分别为其它两种型号催化剂的1.85倍和1.47倍,应用获得巨大成功。     

Fischer-Tropsch synthesis and the generation of DME in situ

Ternary physical mixtures comprised a Fischer-Tropsch catalyst, a methanol synthesis catalyst and a zeolite employed in the hydrocarbon synthesis from syngas. Two Fe-based catalysts (i.e., one promoted by K and the other by Ru), two HY zeolites with different acidities, a commercial HZSM-5 and Cu/ZnO/Al₂O₃ (methanol synthesis catalyst) were used in these systems. The main products obtained were dimethyl ether, methanol and hydrocarbons. First of all, it was observed that by adding Cu/ZnO/Al₂O₃ catalyst to a binary physical mixture comprised of a Fischer-Tropsch catalyst and HZSM-5, the CO conversion increases more than 20 times. Second, during the reaction transient period the dimethyl ether selectivity decreases as the conversion increases. Third, the hydrocarbons synthesized followed the ASF distribution in the C₁-C₁₂ range and finally, it was also verified that the Y zeolites and the Fischer-Tropsch synthesis catalyst promoted by Ru generated the most active physical mixtures. The results showed that the role of zeolites in the ternary physical mixture is only associated with the dimethyl ether synthesis. The following reaction pathway was suggested: first, methanol is synthesized from syngas using Cu/ZnO/Al₂O₃ catalyst; after that, this alcohol is dehydrated by an acid catalyst generating DME; and lastly, DME initiates Fischer-Tropsch synthesis, which is then propagated by CO.     

外购氢气进行甲醇催化剂还原技术的研究及应用

阐述了外购氢气进行甲醇催化剂还原的相关技术特点,并对该技术在大唐内蒙古多伦煤化工公司1680kt／a甲醇装置的应用情况进行了介绍,指出该技术能有效保证催化剂的还原活性,同时可以实现催化剂的预还原,缩短装置开车时间4d以上,应用于大型生产装置可降低开车费用2000万元以上。     

Development of sulfur tolerant catalysts for the synthesis of high quality transportation fuels

In this paper, results concerning the development of sulfur tolerant catalysts for Fischer–Tropsch synthesis (FTS), C₂₊ alcohol synthesis, methanol and/or DME synthesis are presented. In the FTS reaction on Fe using H₂-rich syngas such as the biomass-derived syngas, the composition of catalyst pretreatment gas and the addition of MnO on Fe had strong impacts on its sulfur resistance as well as activity. Especially the Fe/MnO catalyst pretreated with CO showed a much lower deactivation rate and a higher FTS activity than an Fe/Cu/K catalyst in the presence of H₂S. For C₂₊ alcohol synthesis a novel preparation method was developed for a highly active MoS₂-based catalyst that is well known as the sulfur tolerant catalyst. Besides some metal sulfides were found to show higher CO hydrogenation activities than MoS₂. In particular, both Rh and Pd sulfides were active and selective for the methanol synthesis. Modified Pd sulfide catalyst, i.e. sulfided Ca/Pd/SiO₂, showed an activity that was about 60% of that of a Cu/ZnO/Al₂O₃ catalyst in the absence of H₂S. This catalyst preserved 35% of the initial activity even in the presence of H₂S. The sulfided Ca/Pd/SiO₂ mixed with γ-Al₂O₃ was also available for in situ DME synthesis in the presence of H₂S.     

An in situ high pressure FT-IR study of CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol synthesis catalysts

In situ FT-IR spectroscopy allows the methanol synthesis reaction to be investigated under actual industrial conditions of 503 K and 10 MPa. On Cu/SiO₂ catalyst formate species were initially formed which were subsequently hydrogenated to methanol. During the reaction a steady state concentration of formate species persisted on the copper. Additionally, a small quantity of gaseous methane was produced. In contrast, the reaction of CO₂ and H₂ on ZnO/SiO₂ catalyst only resulted in the formation of zinc formate species: no methanol was detected. The interaction of CO₂ and H₂ with Cu/ZnO/SiO₂ catalyst gave formate species on both copper and zinc oxide. Methanol was again formed by the hydrogenation of copper formate species. Steady-state concentrations of copper formate existed under actual industrial reaction conditions, and copper formate is the pivotal intermediate for methanol synthesis. Collation of these results with previous data on copper-based methanol synthesis catalysts allowed the formulation of a reaction mechanism.