ZnZr/HZSM-5双功能催化剂在合成气与苯烷基化反应中的催化性能

将系列锌锆金属氧化物与HZSM-5分子筛耦合制备成双功能复合催化剂,并将其应用于合成气与苯烷基化反应。研究结果表明,ZnO是合成甲醇的主要活性组分,ZrO₂的加入能够促进ZnO分散,同时其表面具有的氧空位可促进CO的活化,二者结合方式显著影响反应活性。SEM、XPS、CO-TPD等表征结果表明,ZnO与ZrO₂相结合不仅能够提高ZnO的分散度,而且能调控氧化物表面的氧空位浓度,当二者形成固溶体时,锌在氧化锆中的分散度最大,表面氧空位浓度最高,CO吸附量最大,催化活性最高。锌锆结合方式一定时,锌含量是影响催化活性的另一重要因素,n(Zr)/n(Zn)=2的锌锆固溶体与HZSM-5以质量比1∶2耦合表现出最高的催化活性,CO和苯的转化率为34.65%和35.82%时,甲苯和二甲苯的总选择性高达85.24%。     

双功能催化剂在合成气一步法制低碳烯烃中的研究进展

双功能催化剂能够有效地突破费托合成中烯烃选择性限制,实现了高的低碳烯烃选择性,成为合成气一步法制低碳烯烃的研究热点。详细综述了近五年来金属氧化物/分子筛双功能催化剂的制备、构效关系、催化机理的研究进展,并对双功能催化剂的进一步发展方向进行了展望。     

双功能催化剂在合成气一步法制低碳烯烃中的研究进展

双功能催化剂能够有效地突破费托合成中烯烃选择性限制,实现了高的低碳烯烃选择性,成为合成气一步法制低碳烯烃的研究热点.详细综述了近五年来金属氧化物/分子筛双功能催化剂的制备、构效关系、催化机理的研究进展,并对双功能催化剂的进一步发展方向进行了展望.     

合成气一步法制低碳烯烃工艺及催化剂研究进展

综述合成气一步法制低碳烯烃工艺及催化剂的研究进展,总结一步法制低碳烯烃的不同种类催化剂,包括铁基催化剂、钴基催化剂和双功能OX-ZEO金属氧化物-分子筛催化剂。对催化剂活性组分、载体、助剂等的相互作用关系进行分析,介绍目前两项最新完成的工业侧线试验结果。     

合成气制二甲醚双功能催化剂的研究进展

综述了二甲醚的物化特性以及其作为新型替代能源的广阔应用前景.对现有的几种不同的合成气一步法合成二甲醚的反应机理及动力学模型进行了概述.并分别介绍了双功能催化剂中的甲醇合成催化组分、甲醇脱水催化组分的研发现状及进展.CuO/ZnO/Al2O3作为甲醇合成组分技术已经比较成熟,甲醇脱水活性组分以γ-Al2O3、分子筛及其改性后产物最为常用.探讨了双功能催化剂的制备方法及改性方法的研究,这也将成为今后合成气一步法制二甲醚技术的研究热点.     

合成气一步法制二甲醚催化剂研究进展

简述了二甲醚的物化特性及其应用前景,对现有的几种合成气一步法合成二甲醚的反应机理及动力学模型进行了概述。分别研究了双功能催化剂中的甲醇合成活性组分和甲醇脱水活性组分,CuO/ZnO/Al₂O₃ 作为甲醇合成组分,活性和稳定性较好,甲醇脱水活性组分以γ-Al₂O₃ 、分子筛及其改性后产物较为常用。探讨了双功能催化剂的制备方法及改性方法。     

合成气一步法制二甲醚催化剂

正BASF公司提出一种合成气一步法制二甲醚催化剂。该催化剂由甲醇合成催化剂和酸性脱水催化剂经物理混合、压片而成,质量分数分别为70%~90%和10%~30%,粒径分布为:D-10粒径5~140μm,D-50粒径40~300μm、D-90粒径180~800μm。在具体实施例中,采用共沉淀法制备甲醇合成催化剂,金属氧化物含量为:CuO48%(w)、ZnO17%(w)、ZrO12%(w)、Al2O323%(w);酸性催化剂通过喷雾法将磷酸     

合成气一步法制二甲醚工艺条件研究

研究了三相床反应器中合成气一步法制二甲醚的工艺条件,催化剂是由甲醇合成催化剂与甲醇脱水催化剂均匀混合组成的双功能催化剂.在温度220～265℃、压力4～5MPa、空速1～2 L/(g·h)的条件下,分别考察了温度、压力和空速对二甲醚合成反应中CO转化率及二甲醚选择性的影响.结果表明,在上述各因素相应的范围内,,随着反应温度的升高,CO转化率、DME选择性逐渐增加;随着压力的升高,CO转化率、DME选择性逐渐增加;CO转化率、DME选择性随空速的提高而逐渐减小.与固定床实验结果相比,三相床反应器中CO转化率略低于固定床反应器.     

合成气一步法制二甲醚工艺及催化剂研究进展

二甲醚在车用燃料和民用燃料方面具有良好发展前景。合成气一步法制二甲醚工艺分气相法和浆态床法。综述了合成气一步法制取二甲醚的工艺和催化剂的研究进展以及工业化前景。     

苯与合成气烷基化催化剂的研究进展

对二甲苯（PX）是制备聚酯材料的重要原料,随着我国经济快速发展,对二甲苯的需求日益增长。目前PX主要通过石化路线生产,由于我国石油资源短缺,迫切需要开发基于煤化工路线的PX生产技术。通过苯与合成气烷基化制备PX是一条新的煤化工路线,近年来受到关注。本文综述了苯与合成气烷基化的最新进展,讨论了贵金属（Pt）、铜基氧化物、锌基氧化物（ZnZr、ZnCr）与沸石的复合以及负载和机械混合两类复合方式对催化效果的影响,分析了甲醇合成与烷基化反应的耦合机制以及反应条件的匹配关系;并与其他三种煤制芳烃技术,即合成气制芳烃、甲醇制芳烃以及苯与甲醇烷基化制烷基苯做了对比分析,表明该技术路线具有成本较低和工艺路线短的优势。     

Alkylation of benzene with carbon dioxide to low-carbon aromatic hydrocarbons over bifunctional Zn-Ti/HZSM-5 catalyst

Alkylation of benzene to value-added,high octane number and low toxic toluene and xylenes provides a way to lower benzene content in gasoline pool,and is hence a method to promote fuel quality.On the other hand,CO₂ accumulation in the atmosphere causes global warming and requires effective route for its valorization.Utilization of CO₂ as a carbon source for benzene alkylation could achieve both goals.Herein,alkylation of benzene with CO₂ and H2 was realized by a series of low-cost bifunctional catalysts containing zinc/titanium oxides(Zn/Ti oxides)and HZSM-5 molecular sieves in a fixed-bed reactor.By regulating and controlling oxygen vacancies of Zn/Ti oxides and the acidities of HZSM-5,benzene conversion and CO₂ conversion reached 28.7%and 29.9%respectively,along with a total selectivity of toluene and xylene higher than 90%.In this process,more than 25%CO₂ was effectively utilized and incorporated into the target products.Moreover,the mechanism of the reaction was analyzed and the course was simultaneously traced.CO₂ was transformed into methanol firstly,and then methanol reacted with benzene generating toluene and xylene.The innovation provides a new method for upgrading of fuels and upcycling the emissions of CO₂,which is of great environmental and economic benefits.     

Efficient conversion of benzene and syngas to toluene and xylene over ZnO-ZrO2&H-ZSM-5 bifunctional catalysts

A series of ZnO-ZrO₂ solid solutions with different Zn contents were synthesized by the urea co-precipitation method, which were coupled with H-ZSM-5 zeolite to form bifunctional catalysts. As a new benzene alkylation reagent, syngas was used instead of methanol to realize the efficient conversion of syngas and benzene into toluene and xylene. A suitable ratio of ZnO-ZrO₂ led to the significant improvement in the catalytic performance, and a suitable amount of acid helped to increase the selectivity of toluene/xylene and reduce the selectivity of the by-products ethylbenzene and C₉⁺ aromatics. The highest benzene conversion of 89.2% and toluene/xylene selectivity of 88.7% were achieved over 10% ZnO-ZrO₂&H-ZSM-5 (Si/Al = 23) at a pressure of 3 MPa and a temperature of 450 ℃. In addition, the effect of the zeolite framework structure on product distribution was examined. Similar to the molecular dynamics of aromatic hydrocarbons, H-ZSM-5 zeolites comprise 10-membered-ring pores, which are beneficial to the activation of benzene; hence, the conversion of benzene is higher. H-ZSM-35 and H-MOR zeolites exhibited small eight-membered-ring channels, which were not conducive to the passage of benzene; hence, the by-product ethylbenzene exhibits a higher selectivity. The distance between the active centers of the bifunctional catalysts was the main factor affecting the catalytic performance, and the powder mixing method was more conducive to the conversion of syngas and benzene.     

Effect of the operating conditions on the conversion of syngas into liquid hydrocarbons over a Cr2O3–ZnO/ZSM5 bifunctional catalyst

The effect of the operating conditions (pressure, temperature, space time, CO/H₂ ratio in the feed and time on stream) on the conversion of syngas into liquid hydrocarbons over a Cr₂O₃–ZnO/ZSM5 bifunctional catalyst has been studied by means of experimentation in an integral fixed bed reactor. On the basis of the results, the global stoichiometry of the process is established and the relative importance of the operating variables in order to reach a good compromise between catalyst activity and gasoline quality is analysed. © 1998 SCI     

ZnxZr/HZSM-5 as efficient catalysts for alkylation of benzene with carbon dioxide

Alkylation of benzene with carbon dioxide and hydrogen to produce toluene and xylene could increase the added-value of surplus benzene as well as relieve environmental problems like green-house effect. In this work, the alkylation benzene with carbon dioxide and hydrogen reaction was proceeded by using the mixture of zinc-zirconium oxide and HZSM-5 as bifunctional catalyst. The equivalent of Zn/Zr = 1 displays the best catalytic performance at 425 °C and 3.0 MPa, and benzene conversion reaches 42.9% with a selectivity of 90% towards toluene and xylene. Moreover, the carbon dioxide conversion achieves 23.3% and the carbon monoxide selectivity is lower than 35%, indicating that more than 50% carbon dioxide has been effectively incorporated into the target product, which is the best result as far as we know. Combined with characterizations, it indicated that the Zn and Zr formed a solid solution under specific conditions (Zn/Zr = 1). The as-formed solid solution not only possesses a high surface area but also provides a large amount of oxygen vacancies. Additionally, the bifunctional catalyst has excellent stabilities that could keep operating without deactivation for at least 80 h. This work provides promising industrial applications for the upgrading of aromatics.     

生物质合成气合成二甲醚的研究

在加压固定床反应装置上进行了生物质合成气合成二甲醚(DME)的研究.采用机械混合法制备二甲醚合成双功能催化剂.考察了组成为V(H_2):V(CO):V(CO_2):V(CH_4)=52:24:23:1的生物质合成气在不同反应温度、空速、压力下对合成二甲醚反应的影响.同时进行了102 h的催化剂的稳定性实验.结果表明,在260-300℃范围内,随反应温度的升高,CO转化率和二甲醚的选择性均先增大后减小;随反应压力的升高,CO转化率和二甲醚选择性都随之升高;原料气中高浓度的CO_2可导致铜基催化剂较快的失活.     

反应压力对HZSM-5分子筛催化剂上合成气经二甲醚制取芳烃反应的影响

在2个等压串联连续流动同定床反应器内考察了合成气经由二甲醚制取芳烃的反应性能.一段合成二甲醚反应采用Cu/Zn/Al_2O_3和γ-Al_2O_3复合催化剂;二段合成芳烃反应采用HZSM-5(Si/Al=38)催化剂.考察了反应压力对合成芳烃反应的影响,并分析了产物的分布规律.结果表明:在T_1=270℃,T_2=360℃,GHSV=500 h~(-1)条件下,反应压力由2 NPa增加到4 MPa时,芳烃选择性轻微降低,由86.75%降低到83.67%,同时CO转化率从72.47%升高到84.34%,产物中均四甲苯的选择性增加不明显.而当压力增加到5 NPa时,芳烃选择性降低到63.51%,而异构烷烃选择性提高5倍多.反应压力增加,反应平衡倾向于加氢异构化反应;反应压力在2～4 NPa时,有利于芳烃的合成.     

改性HZSM-5上焦化苯与乙醇烷基化制乙苯

通过离子交换法制备硼改性的分子筛,并在连续固定床反应器上对其进行焦化苯与乙醇烷基化反应催化性能和脱硫性能的考察。通过XRD和BET方法对催化剂进行表征,结果表明,改性后催化剂的比表面积、微孔孔容和孔径均减少。反应评价结果显示,改性后乙苯选择性略有降低,苯转化率增加。最佳反应条件：温度（350～400） ℃,n(苯)∶n(乙醇)=(3∶1)～(5∶1),空速（4～6） h^-1。