Etherification Performance of Transition Metals Modified β-Zeolite Catalyst

Abstract

The etherification experiment for FCC light gasoline on transition metals modified Hβ zeolite was studied in a fixed-bed reactor. The effect of preparation condition of catalyst on the catalyst's activity, stability, and the effect of reaction temperature, methanol/tert-olefin molar ratio, and liquid hour space velocity on the etherification reaction were discussed. The experimental results showed that the different metals modified Hβ zeolite had different etherification performances. And the conversion of tertiary carbon-olefins of the molybdenum modified Hβ zeolite, which was loaded 3%, was higher 6.0% than the Hβ zeolite. The optimal reaction conditions were temperature 70–80°C, liquid hour space velocity 1.0 h^?1 and methanol/tert-olefin molar ratio 1.05. The modified Hβ zeolite catalysts possessed favorable prospect for its higher stability.     

Etherification of FCC Light Gasoline over Mo-Modified β Zeolite Catalyst

Etherification activity of several molecular sieve catalysts for FCC light gasoline was studied in a fixed-bed reactor. H-Beta zeolite was found to be high active than that of others and close to cation exchanged resin catalyst. H-Beta zeolite also showed good activity and selectivity and could not be deactivated easily, and could be easily regenerated after deactivation. In order to further improve etherification activity, the surface acidity and pore structure of zeolite could be modified, by loading different metal oxides. The result showed that the highest conversion of tert-olefin was obtained over Mo/Hβ (1%). The influence of reaction temperature, methanol and tert-olefin molar ratio, reaction pressure, and LHSV on the conversion was investigated. At optimized reaction conditions, tert-olefin conversion of 57.42% had been reached with Mo/Hβ (1%).     

Etherification of FCC Light Gasoline over Mo-Modified β Zeolite Catalyst

Abstract

Etherification activity of several molecular sieve catalysts for FCC light gasoline was studied in a fixed-bed reactor. H-Beta zeolite was found to be high active than that of others and close to cation exchanged resin catalyst. H-Beta zeolite also showed good activity and selectivity and could not be deactivated easily, and could be easily regenerated after deactivation. In order to further improve etherification activity, the surface acidity and pore structure of zeolite could be modified, by loading different metal oxides. The result showed that the highest conversion of tert-olefin was obtained over Mo/Hβ (1%). The influence of reaction temperature, methanol and tert-olefin molar ratio, reaction pressure, and LHSV on the conversion was investigated. At optimized reaction conditions, tert-olefin conversion of 57.42% had been reached with Mo/Hβ (1%).     

Synthesis of Tert-amyl Methyl Ether with Methanol and C5 Hydrocarbons

The reaction system and mechanism of etherification of C5 cut with methanol were analyzed theoretically. Experiments were carried out in a tubular reactor at temperatures of 50°C-80°C in the presence of a strong cation-exchange resin, QRE. In the reaction system, two types of reactions took place: etherification and isomerization. At lower temperature, the reaction rates were controlled by kinetic factors, but at temperature above 60°C, both reactions were affected by thermodynamic equilibrium. The appropriate operating conditions were: T at 60°C-65°C, molar ratio of methanol and isoamylenes 1.0-1.2, and liquid hourly space velocity (LHSV) 1.0-1.5.     

正戊烷与甲醇制芳烃工艺条件的优化

以负载ZnO的ZSM-5为催化剂,利用固定床微型反应装置系统地考察了反应温度、反应空速、投料摩尔比对甲醇与正戊烷共芳构化反应的影响。结果表明：与单独芳构化相比,正戊烷与甲醇共芳构化可提高芳烃的选择性,抑制干气的生成;随着甲醇与正戊烷摩尔比的增大,正戊烷的转化率下降;正戊烷与甲醇在ZSM-5分子筛上进行芳构化反应的适宜反应条件为：温度475℃,烃基质量空速2 h^-1,甲醇与正戊烷摩尔比3∶1;在优化工艺条件下,正戊烷与甲醇共芳构化反应中芳烃的选择性可达31.68%。     

Mn改性Cu/ZnO/Al_2O_3催化剂上甲醇水蒸气重整制氢研究

研究了Mn改性Cu/ZnO/Al2O3催化剂上的甲醇水蒸气重整制氢反应。考察了催化剂组成、反应温度和水醇比对反应的影响。研究结果表明,当催化剂的组成为Cu45Zn45Al5Mn5,反应温度为220～240℃,n(H2O)/n(CH3OH)=1～1 2,液体空速为3 0h-1左右时,反应具有较好的甲醇转化率、氢气产率和较低的出口CO含量,同时催化剂表现出较好的稳定性。     

磷改性ZSM-5/磷酸铝复合分子筛在甲醇制丙烯反应中的应用

以磷酸二氢铵对ZSM-5/磷酸铝 (ZSM-5/AlPO₄-m) 复合分子筛进行P改性,得到wP-ZSM-5/AlPO₄-m催化剂,采用XRD、N₂吸附-脱附、NH₃-TPD和FT-IR表征其物化性能,并系统地考察了在甲醇制丙烯(MTP)反应中,wP-ZSM-5/AlPO₄-m中P质量分数,反应温度、空速(MHSV)等反应条件对该复合分子筛催化性能的影响。结果表明,P改性可以有效地调节ZSM-5/AlPO₄-m的比表面积及酸性分布,3%P-ZSM-5/AlPO₄-m催化剂中B酸与L酸中心数的最大比达到3.03。当反应温度为500℃、MHSV为1 h-^-1时,3%P-ZSM-5/AlPO₄-m催化剂表现出最佳的MTP活性和稳定性;反应持续73 h,甲醇转化率保持100%,丙烯的单程选择性和产物中丙烯/乙烯摩尔比分别保持在50.0%和5。     

低硅/铝比介孔USY分子筛的制备及其VGO加氢裂化性能

以低硅/铝摩尔比((n(Si)/n(Al)=7.0))USY分子筛为原料,通过低浓度碱溶液浸渍结合热处理的方法制备了介孔增强的MUSY分子筛.通过X射线衍射(XRD)、扫描电镜(SEM)、N2吸附-脱附曲线等手段对改性前后分子筛进行表征.结果表明,MUSY分子筛的介孔体积和介孔比表面积分别为0.31 cm3/g和150...     

镁改性ZSM-5分子筛的制备及其催化苯与甲醇烷基化反应性能

制备了不同镁负载量的镁改性多级孔ZSM-5催化剂,采用X射线衍射、N₂吸附-脱附、NH₃程序升温脱附等分析手段对镁改性ZSM-5催化剂进行表征,考察了反应温度、质量空速、原料配比、镁负载量对镁改性ZSM-5催化剂催化苯与甲醇烷基化反应性能的影响,并对催化剂稳定性进行评价。结果表明：镁改性ZSM-5催化剂催化苯与甲醇烷基化反应最佳的工艺条件为：反应温度470 ℃,质量空速2.0 h^-1,苯与甲醇摩尔比1∶1;在最佳工艺条件下,镁负载量（w）为3%的改性ZSM-5催化剂可连续运行1 300 h,苯平均转化率大于54%,甲苯和二甲苯的平均选择性大于90%,乙苯平均选择性低于1.5%;催化剂再生后的反应活性和稳定性与新鲜催化剂相当;催化剂经过了工业试验验证,具备工业应用前景。     

甲醇耦合抽余油芳构化反应催化剂制备及其催化性能研究

采用简单、快速、易工业化的一步法水热合成制备了ZSM-5/ZSM-11共晶分子筛,采用XRD、N₂吸附-脱附、NH₃-TPD、Py-IR、SEM和TEM等分析手段对ZSM-5/ZSM-11共晶分子筛进行了表征,并首次将成型催化剂应用于催化甲醇耦合抽余油芳构化反应体系中。结果表明：通过一系列表征手段证实了合成的分子筛为ZSM-5/ZSM-11共晶分子筛,具有多级孔结构,其比表面积为358 m²/g,孔体积0.35 cm³/g;具有B酸和L酸,B/L酸量比为2.07,晶体是由棒状的六方柱体插接而成的规则、棱角清晰的球体构成。在反应温度为380 ℃、反应压力为0.5 MPa、甲醇/抽余油质量比为1∶1、质量空速为1 h^-1的条件下,ZSM-5/ZSM-11共晶分子筛成型催化剂催化甲醇耦合抽余油芳构化反应时,C₅+收率大于81%,芳烃收率最高为38%。ZSM-5/ZSM-11共晶分子筛催化剂催化甲醇耦合抽余油芳构化反应具有良好的工业应用前景。     

Influence of Shaping Condition on Etherification Performance of Hβ Zeolite

Etherification reaction of FCC light gasoline over Hβ zeolite was investigated to decrease the light olefins in motor gasoline while enhancing octane. Etherification activity of several molecular sieve catalysts for FCC light gasoline was studied in a fixed-bed reactor. The influence of pore-enlarging agent (PEG) with different molecular weight, binder (γ-Al₂O₃), and peptizing agent (HNO₃) in the shaping process on etherification activity of Hβ zeolite was studied. The impregnating ways of precursor of oxides and the order of extruding and impregnating were also investigated. The results show that the activity of extruded Hβ zeolite before impregnating precursor of oxides is higher than the reverse order. The best shaping condition obtained was PEG-4000 10%, γ-Al₂O₃ 20%, and HNO₃ 10%. At the optimal reaction condition, the conversion of tert-olefins reached the peak. 62.93%, the yield of TAME, is also high and the technology can be applied to industry as well.     

NiLaLiPt/γ-Al_2O_3催化剂煤油水重整制氢的反应行为

以γ-Al2O3为载体,Ni为活性组分,稀土元素La、碱金属Li和贵金属Pt为助剂,采用等体积分步浸渍法制备催化剂NiLaLiPt/γ-Al2O3。研究了催化剂的催化活性和稳定性,考察了NiLaLiPt/γ-Al2O3上煤油液空速、温度、水碳比等因素对煤油水重整制氢的影响。在优化的工艺条件温度700℃、水碳比20、煤油液空速0.06h-1下,氢产率为33.057mol/mol。     

ZSM-5分子筛用于甲醇制低碳烯烃的反应条件研究

以ZSM-5分子筛(n(Si)/n(Al)=360)为催化剂,在固定床反应器上考察了反应温度、水醇比、原料空速和反应时间对甲醇制低碳烯烃(MTO)各产物选择性的影响。结果表明:随反应时间增加,丙烯的选择性逐渐增大,乙烯的选择性先增大后减小,所有产物的选择性均在6.5h后趋于稳定;随反应温度升高,低碳烯烃的选择性先增大后减小;原料中适量掺杂水对反应有利,n(水)/n(醇)为2时,低碳烯烃的选择性最高;空速增加,低碳烯烃的选择性逐渐下降,但空速过低催化剂易积炭失活。最佳反应条件确定为:430℃,LHSV=2.2h-1,n(水)/n(醇)=2,此时乙烯+丙烯的选择性达69.36%,其中丙烯的选择性为53.54%。     

催化裂解制丙烯新型催化剂的研究

以催化重整石脑油为原料,水热处理磷改性HZSM-5分子筛为催化剂,考察了改性催化剂的催化裂解性能。结果表明,催化剂最佳改性条件为:水热处理温度700℃,处理时间1 h,处理空速2 h-1。最佳反应条件为:温度650℃,液体空速4 h-1,水/原料油(体积比)0.75,压力0.2 MPa。在此条件下,与未改性HZSM-5分子筛催化剂相比,改性者水热稳定性增强,丙烯收率提高;在磷负载质量分数为3%时,丙烯收率最高,达到22.62%。     

晶种诱导合成FER分子筛催化1-丁烯骨架异构化反应

采用晶种诱导的方法,在无有机结构导向剂的条件下合成了高结晶度的FER分子筛,考察了晶种用量和晶化时间对分子筛结晶度的影响,并在较优条件下对合成的分子筛进行催化1-丁烯骨架异构化反应性能评价。结果表明：在初始投料摩尔比n(Na₂O)∶n(Al₂O₃)∶n(SiO₂)∶n(H₂O)为0.18∶0.033∶1∶30、晶化温度为160 ℃的条件下,随着晶种加入量增加和晶化时间的延长,分子筛样品相对结晶度增加;在较优晶种添加质量分数为15%、晶化时间为72 h条件下,合成的分子筛相对晶种结晶度达100.1%。以最优条件下晶种合成分子筛为催化剂, 1-丁烯为原料,在反应温度350 ℃、质量空速2.0 h^-1、常压的反应条件下,连续运行600 h,1-丁烯平均转化率大于38%,异丁烯平均选择性大于90%,催化剂反应活性和稳定性均良好。     

正丁烷异构化制异丁烷反应热力学分析及试验研究

在分析正丁烷异构化制异丁烷反应特点的基础上,通过系统的热力学计算,获得了不同反应温度下目标反应的标准摩尔焓变、标准摩尔吉布斯自由能变、标准平衡常数及正丁烷平衡转化率,并以Pt/Al₂O₃-Cl为催化剂进行了正丁烷异构化反应试验研究。结果表明,正丁烷异构化属微放热反应,降低反应温度可提高正丁烷的平衡转化率;对于Pt/Al₂O₃-Cl催化正丁烷异构化反应,反应温度、反应压力、正丁烷进料空速和氢/烃摩尔比均对正丁烷转化率有较明显的影响,选择合适的反应温度和压力,并适当降低进料空速和氢/烃摩尔比,有利于提高正丁烷转化率;在优化的反应条件下,正丁烷的试验转化率与热力学平衡转化率基本吻合,验证了热力学分析结果的可靠性。     

苯与乙烯气相烷基化制乙苯用分子筛催化剂的研制

考察了ZSM-5沸石的硅铝比、晶粒尺寸和改性方法对催化剂活性和稳定性的影响。结果表明,以较高硅铝比和较小晶粒的ZSM-5分子筛为活性组元,再进行适当的水蒸汽改性,可制得具有高活性、高选择性和高稳定性的烷基化催化剂。     

CuZnAlZr整体式催化剂上甲醇氧化重整制氢的研究

制备和筛选出用于甲醇氧化重整制氢的CuZnAlZr整体式催化剂,并考察了水醇比、氧醇比和液体空速等条件对该催化剂上甲醇氧化重整制氢反应的影响,结合对该反应所做的理论计算,得到反应的最佳条件为水醇摩尔比1,氧醇摩尔比0.22,液体空速0.96h-1。     

One-step synthesis of N-methylaniline by hydroalkylation of nitrobenzene over oxide catalysts

The reaction of nitrobenzene hydroalkylation with methanol forming N-methylaniline as the main product has been studied. Alumina modified with copper and chromium compounds deposited by incipient wetness impregnation has been examined as the catalyst. It has been shown that the reductive alkylation of nitrobenzene with methanol is preferable to conduct at a temperature of 250°C, a feed weight hourly space velocity of 1 to 2 h^?1, a methanol: nitrobenzene molar ratio of 3 to 4, and hydrogen: nitrobenzene molar ratio of 3–6. It has been found that promotion of the copper-containing catalyst with chromium leads to enhancement of the catalyst activity and facilitates an increase in selectivity for N-methylaniline.     

NiP/Hβ催化正己烷异构化反应性能及机理

以氯化镍为镍源,次磷酸钠为磷源,合成活性组分NiP,再通过干混法制备出正己烷异构化新型催化剂NiP/Hβ;采用XRD、FT-IR、NH3-TPD以及H2-TPR等手段分析该催化剂的表面性质及NiP在载体上的分散程度.在温度为280℃、正己烷质量空速为1 h-1、氢压为2 MPa、氢/油摩尔比为3条件下,考察了4％NiP...