正丁烯骨架异构催化剂再生性能

采用小型固定床装置评价自制ZSM-35分子筛催化剂正丁烯骨架异构性能,在反应温度380℃、反应压力0.1 MPa和空速6.0 h-1条件下反应350 h,正丁烯转化率和异丁烯收率均大于35%,异丁烯选择性大于95%,副产物收率在反应进行至120 h时接近0,催化剂正丁烯骨架异构性能稳定。通过程序升温氧化表征研究催化剂积炭过程,采用程序升温氧化烧碳法对催化剂进行再生,采用XRD、NH3-TPD和BET等表征新鲜催化剂和三次再生催化剂的物化性能,结果表明,再生催化剂的物化性质几乎无变化,三次再生催化剂异构性能接近新鲜催化剂,催化剂再生性能良好。     

催化裂化轻汽油选择性加氢除二烯烃工艺研究

主要进行了催化裂化轻汽油选择性加氢除二烯烃工艺条件优化研究,从反应温度、氢/油体积比和反应压力等3个方面考察了其对选择性加氢和3-甲基-1-丁烯异构为2-甲基-1-丁烯的异构化率的影响,确定选择性加氢的较优工艺条件为反应温度60℃、氢/油体积比30、反应压力1.5 MPa。在此基础上进行了选择性加氢催化剂1500 h寿命试验。试验数据表明,在1500 h的考察期内,催化剂表现出良好的活性稳定性。     

硫改性镍催化剂丁烯-1双键临氢异构性能

将Ni/Al_2O_3催化剂浸渍于有机多硫化物(TPS-37)中制备得到硫改性Ni/Al_2O_3催化剂。采用X射线荧光光谱(XRF)、热重-质谱(TG-MS)联用、X射线光电子能谱仪(XPS)和程序升温还原(TPR)等方法对催化剂进行表征,并考察了硫改性Ni/Al_2O_3催化剂上丁烯-1双键临氢异构性能。结果表明,硫改性Ni/Al_2O_3催化剂经高温氢气活化及甲苯萃取后,催化剂上硫含量基本不变。硫与催化剂之间存在较强的相互作用,使氧化镍在相对较低的温度下被H2还原;硫改变了Ni金属周围电子环境,从而显著改善催化剂的双键临氢异构性能。在反应温度60℃,氢压1.6 MPa,氢气和碳四烃物质的量之比(氢烃比)为0.013的条件下,硫改性Ni/Al_2O_3催化剂催化丁烯-1双键临氢异构反应,丁烯-1转化率可达92.6%,丁烯-2选择性为97.5%。催化剂稳定性实验结果表明,硫改性催化剂催化性能好,稳定性优良。     

2-丁烯双键异构1-丁烯的研究进展

本文通过介绍国内外公开报道的几种2-丁烯双键异构生成1-丁烯的工艺技术,以及金属氧化物、分子筛、金属硫酸盐、阳离子交换树脂等几类催化剂的研究进展,对比各类催化剂的优缺点,为实际生产条件选择合适的催化剂提供了参考,实现增产高纯1-丁烯的目的。     

SAPO-11分子筛催化丁烯异构化反应的研究

在连续流动固定床反应装置上,考察了温度、空速及添加水蒸汽对混合丁烯在SAPO-11分子筛催化剂上骨架异构化的影响。结合催化剂的NH₃-TPD表征与Al₂O₃催化剂的评价结果,对催化剂酸性能和孔结构与丁烯骨架异构化进行了关联。结果表明,对于丁烯骨架异构,分子筛催化剂优于Al₂O₃催化剂,显示出催化剂孔结构的重要作用。SAPO-11分子筛酸量越小,转化率越低,酸量过小时催化剂基本没有活性,说明丁烯异构转化与表面酸量有密切关系。分子筛催化剂上,添加少量的水蒸汽使转化率有所降低,但异丁烯选择性明显增加。     

新型丁烯异构化催化剂在中原石化的应用

丁烯双键异构制取1-丁烯是中国石化上海石油化工研究院专利技术,介绍了装置工业试验和应用情况.总结了新型丁烯异构化催化剂工业化应用和第一代催化剂在工艺操作条件、1-丁烯收率、选择性及产品中关键组分含量的优化和提升.     

ZSM-35分子筛催化剂催化正丁烯骨架异构工艺条件研究

采用水热法合成了ZSM-35分子筛,并成型制备成品催化剂。在小型固定床反应器上考察了反应温度、重时空速和原料中正丁烯浓度等对该催化剂的正丁烯骨架异构催化性能的影响,确定最佳工艺条件为:温度380℃,压力0.1 MPa,重时空速6 h-1,原料中正丁烯浓度50%~70%。在最佳工艺条件下,正丁烯骨架异构反应运行600 h后,异丁烯收率仍保持在25%以上,异丁烯选择性反应在25 h后即保持在90%以上,丙烯和重组分收率在反应120 h后接近0,催化剂异构性能良好。     

ZSM－35分子筛催化剂催化正丁烯骨架异构工艺条件研究

采用水热法合成了ZSM－35分子筛,并成型制备成品催化剂。在小型固定床反应器上考察了反应温度、重时空速和原料中正丁烯浓度等对该催化剂的正丁烯骨架异构催化性能的影响,确定最佳工艺条件为：温度380℃,压力0．1 MPa,重时空速6 h^－1,原料中正丁烯浓度50％～70％。在最佳工艺条件下,正丁烯骨架异构反应运行600 h后,异丁烯收率仍保持在25％以上,异丁烯选择性反应在25 h后即保持在90％以上,丙烯和重组分收率在反应120 h后接近0,催化剂异构性能良好。     

原料杂质对ZSM-35分子筛正丁烯骨架异构反应的影响

采用实验室制备的H型ZSM-35分子筛催化剂在固定床反应器进行正丁烯骨架异构反应,原料为自行配制的不同甲醇和丁二烯含量的正丁烯,使用气相色谱仪检测产物中组分变化,研究原料杂质对反应的影响。结果表明,在异构条件下,甲醇促进正丁烯的裂解反应,而丁二烯的存在会与正丁烯竞争吸附。为得到较高的正丁烯转化率和异丁烯收率,原料中甲醇和丁二烯含量不超过50μg/g。     

正丁烯骨架异构化催化剂研究进展

论述了正丁烯骨架异构化活性位的性质、骨架异构化的主导机理和异构催化剂的最新进展。指出正丁烯骨架异构化的主导机理是单分子性的, B ronsted 酸 (OH) 活性位是必需的位点。沸石的形状选择性和沸石类型对催化剂的选择性和稳定性有很大影响。     

正丁烯异构化催化剂中国专利量化分析

异丁烯是重要的有机化工原料,可以用作多种化学品和聚合物的合成原料。增产异丁烯最好方法是正丁烯骨架异构化制异丁烯,正丁烯骨架异构化制异丁烯技术的核心是催化剂的研制,因此,有必要对正丁烯异构化制备异丁烯催化剂中国专利文献进行全面调研。对中国专利正丁烯异构化制备异丁烯催化剂领域相关专利进行检索,对检索到的专利文献进行量化分析,分析正丁烯异构化制备异丁烯用催化剂技术的发展趋势、中国专利申请人国别分布以及中国专利主要申请人情况,更好地了解正丁烯异构化制备异丁烯催化剂技术的研究进展。     

OXIDATION OF METHACROLEIN AND ISOMERIZATION OF n-BUTENE OVER HETEROPOLY COMPOUNDS

The various salts of 12-molybdophosphoric acid were used for the oxidation of methacrolein and the isomerization of n-butene. The structure of the heteropoly compounds was identified with the aid of infrared spectroscopy, x-ray diffraction, and thermal analysis. The catalytic activity, acidity, and the reaction rate for oxidation of methacrolein were determined by micro-reactor with gas chromatography. The oxidation rate was proportional to the partial pressure of methacrolein and independent of those of oxygen and steam. The catalytic activity of alkali and alkaline earth metal salts was inversely proportional to the electro-negativity of metal elements. It was also revealed that the acidity of catalysts was strongly correlated with the catalytic activities for the oxidation of methacrolein and the isomerization of n-butene.     

OXIDATION OF METHACROLEIN AND ISOMERIZATION OF n-BUTENE OVER HETEROPOLY COMPOUNDS

The various salts of 12-molybdophosphoric acid were used for the oxidation of methacrolein and the isomerization of n-butene. The structure of the heteropoly compounds was identified with the aid of infrared spectroscopy, x-ray diffraction, and thermal analysis. The catalytic activity, acidity, and the reaction rate for oxidation of methacrolein were determined by micro-reactor with gas chromatography. The oxidation rate was proportional to the partial pressure of methacrolein and independent of those of oxygen and steam. The catalytic activity of alkali and alkaline earth metal salts was inversely proportional to the electro-negativity of metal elements. It was also revealed that the acidity of catalysts was strongly correlated with the catalytic activities for the oxidation of methacrolein and the isomerization of n-butene.     

镁碱沸石分子筛催化剂的制备

采用自制镁碱沸石分子筛为活性组分,考察不同用量拟薄水铝石为黏结剂、不同用量田菁粉为助挤剂、不同温度下焙烧的催化剂径向抗压碎力和正丁烯骨架异构性能,并对比以乙酸和硝酸为胶溶剂时催化剂的物化性能。采用XRD和NH₃-TPD表征催化剂,分析其结构和酸性,测定径向抗压碎力,并在固定床反应器上进行正丁烯骨架异构化反应评价,对比采用不同成型条件制备的催化剂物化性能差异。结果表明,硝酸胶溶效果优于乙酸,在黏结剂拟薄水铝石质量分数为20%、助挤剂田菁粉质量分数为3%、胶溶剂质量分数为2%硝酸和柠檬酸（硝酸与柠檬酸物质的量比为2∶1）条件下,催化剂径向抗压碎力高于70 N·cm^-1,正丁烯异构化反应活性高,异丁烯选择性和稳定性良好。     

正丁烯异构化工艺技术及发展前景

我国炼厂及化工生产企业的碳四烃资源丰富,正丁烯存量过剩,但是异丁烯存量相对匮乏,无法满足市场需求。介绍了国内外正丁烯异构化工艺技术的发展历程,对正丁烯异构化与MTBE联合装置及异丁烯下游产品进行了市场需求分析,肯定了正丁烯异构化装置存在的必要性。针对市场对异丁烯的广泛需求,正丁烯异构化装置不仅为提供了所需的生产原料,而且有利于提高生产企业的经济效益。同时,异丁烯下游产品的需求量巨大,正丁烯异构化装置与下游装置联合生产高附加值产品的延伸技术的开发与利用,未来也具有较好的发展前景。     

Effect of Divalent Metal Component (MeII) on the Catalytic Performance of MeIIFe2O4 Catalysts in the Oxidative Dehydrogenation of n-Butene to 1,3-Butadiene

A series of metal ferrite (Me^IIFe₂O₄) catalysts were prepared by a co-precipitation method with a variation of divalent metal component (Me^II = Zn, Mg, Mn, Ni, Co, and Cu) for use in the oxidative dehydrogenation of n-butene to 1,3-butadiene. Successful formation of metal ferrite catalysts with a random spinel structure was confirmed by XRD, ICP-AES, and XPS analyses. The catalytic performance of metal ferrite catalysts in the oxidative dehydrogenation of n-butene strongly depended on the identity of divalent metal component. Acid properties of metal ferrite catalysts were measured by NH₃-TPD experiments, with an aim of correlating the catalytic performance with the acid property of the catalysts. It was revealed that the yield for 1,3-butadiene increased with increasing surface acidity of the catalyst. Among the catalysts tested, ZnFe₂O₄ catalyst with the largest surface acidity showed the best catalytic performance in the oxidative dehydrogenation of n-butene.     

正丁烯骨架异构化催化剂的研究

成功合成了YZ-2型正丁烯异构化催化剂。以醚后混合碳四为原料,无任何稀释气体,在固定床反应器装置上考察了催化剂对正丁烯异构化的催化性能,探讨了工艺条件对异构化产物分布的影响,考察了催化剂性能的稳定性。结果表明:YZ-2型催化剂在正丁烯骨架异构化上具有较好的催化性能和稳定性。     

直馏汽油异构催化剂的研究进展

主要介绍了直馏汽油异构改质催化剂的研究进展以及在国内的工业使用情况。目前,直馏汽油异构催化剂主要集中在多孔材料负载金属的催化剂上,尤其集中在分子筛负载金属的双功能催化剂的研发及应用上。如何选择最合适的催化剂载体,使负载金属与载体酸中心之间更匹配以促进异构反应的进行,如何对比表面积较大的多孔性材料进行改性以及以普通金属代替贵金属是当今比较热点的问题。直馏汽油异构改质催化剂的工业应用也呈现出多元化的局面,有多种不同的催化剂同时应用于不同的生产厂家,并彰显出各自的特色。     

Transformation of olefin over Ni/HZSM-5 catalyst

Olefins in the cracked naphtha can be transformed into aromatics and isoparaffin to reduce the olefin content as well as to improve the octane number. In this work, Ni/HZSM-5 bifunctional catalyst was prepared and was characterized by nitrogen adsorption, FT-IR analysis with adsorbed pyridine as well as by X-ray powder diffraction analysis. The activity of the catalyst was investigated with the transformation of 1-hexene. The experimental results show that the main reactions occurring over Ni/HZSM-5 at relatively low temperature are cracking and isomerization of 1-hexene, which results in the high concentration of olefin in the hydrotreated product. The double-bond isomerization of 1-hexene is dominant at low temperature (<220 °C) while the skeletal isomerization is elevated at high temperature, and the aromatization activity of the Ni/HZSM-5 catalyst is promoted by high temperature. The sulfided Ni/HZSM-5 catalyst shows higher aromatization activity than the reduced one and the zeolite supported Ni catalysts show comparatively better stability than that without metal components.