金属改性多级孔HZSM-5分子筛催化甲醇制芳烃反应研究

采用双模板剂水热合成的HZSM-5分子筛为纳米多级孔分子筛,用超声的方法将金属M1和M2负载在分子筛上,负载后的催化剂催化甲醇制芳烃MTA反应,并对合成的HZSM-5分子筛和金属负载后的HZSM-5进行了XRD、TEN、BET、NH_3-TPD表征分析。研究表明:采用上述方法合成的催化剂催化MTA反应,在反应温度400℃,反应压力0.5 MPa,反应空速1.0h~(-1),产物中芳烃的选择性提高了16.8%。催化剂表征分析表明:采用双金属同时负载ZSM-5分子筛催化剂,金属粒子均匀分散在HZSM-5分子筛表面,分子筛双金属同时负载时,部分弱酸以及强酸性位都会向中强酸性位转变,催化剂的稳定性大大地提高了。     

不同硅铝比HZSM-5催化正己烷耦合甲醇芳构化

在温度为400℃,压力为0.50 MPa,质量空速为1 h~(-1),甲醇与正己烷质量比为7/3的条件下,在50 mL固定床反应器中考察了5种不同硅铝比HZSM-5分子筛催化正己烷耦合甲醇芳构化反应的活性和稳定性,并对HZSM-5分子筛进行了X射线衍射(XRD)、N_2吸-脱附、NH_3程序升温脱附(NH_3-TPD)、扫描电镜(SEM)和吡啶吸附红外光谱(Py-IR)表征。研究结果表明:硅铝比低的HZSM-5分子筛作为催化剂时,产物中芳烃的选择性较大;硅铝比高的HZSM-5分子筛作为催化剂时,其反应稳定性较好。硅铝比为15时,芳烃选择性为49.7%,催化剂寿命为144 h;硅铝比为75时,芳烃选择性为27.7%,催化剂寿命为384 h。表征结果显示:不同硅铝比HZSM-5分子筛是由纳米尺寸的小晶粒构成,均具有MFI晶型结构,比表面积和孔体积相近;高硅铝比HZSM-5分子筛的中强酸量和Br?nsted酸量较小,反应温和,催化剂稳定性较好,不同硅铝比HZSM-5分子筛的酸量差异可能是造成催化性能不同的主要原因。     

稀土改性ZSM-5分子筛催化乙苯合成的研究

在ZSM-5分子筛水热合成过程中引入适量的稀土氧化物,制备了系列分子筛催化剂,并对其进行了XRD,NH3-TPD表征,考察了其在苯与乙醇反应过程中的催化性能。结果表明:适量稀土氧化物的引入,对于分子筛的骨架结构无明显影响,可以合成出较高结晶度的ZSM-5分子筛;催化剂酸强度无显著影响,总酸量降低;苯与乙醇的反应活性稍有下降,但乙苯选择性明显提高,并表现出优于HZSM-5的催化活性,具备一定的工业应用前景。     

不同晶粒尺寸HZSM-5载Pt催化剂上氢气选择催化还原氮氧化物的研究

将微晶和纳晶HZSM-5分子筛作为催化剂载体应用于富氧条件下氢气选择催化还原氮氧化物(H_2-SCR)反应。研究发现,微晶HZSM-5载Pt催化剂表现出较好的H_2-SCR反应活性,100℃时NO_x转化率高达90%,N_2选择性也明显高于纳晶HZSM-5载Pt催化剂。利用XRD、SEM、NH_3-TPD、XPS和IR对纳晶和微晶HZSM-5及其载Pt催化剂晶型结构、表面形态、表面酸性以及原位反应表面物种进行表征。结果表明,Pt在纳晶和微晶HZSM-5载体上均高度分散,微晶HZSM-5载体上的总酸量多、酸强度强,有利于催化剂上Pt保持活性金属位,使得催化剂上活性金属Pt位数目较多,进而促进了还原剂H_2的活化及重要活性中间物种氨物种的生成和稳定,从而提高了NO_x转化率和N_2选择性。     

复合分子筛催化剂上C9芳烃脱烷基的研究

将Ni负载在H-ZSM-5和H-MOR分子筛催化剂上，以异丙苯为模型化合物对分子筛催化剂加氢脱烷基性能进行评价。考察了分子筛复配比例、金属含量和酸浓度对催化剂活性的影响。结果表明，酸处理后的分子筛催化剂，异丙苯转化率和苯、甲苯、二甲苯(BTX)的收率有明显提高。当反应温度为340 ℃、压力0.8 MP和空速1 h^-1时，其转化率为81.5％，BTX收率为72.8％，选择性可达89.2％。     

催化裂化汽油裂解制丙烯

以催化裂化汽油为原料,水热处理后的HZSM-5分子筛为催化剂,催化裂解制丙烯。比较了水热处理后的HZSM-5分子筛催化剂上负载镧和未负载镧的催化裂化性能,并考察了镧的最佳负载量。结果表明,水热处理后负载镧提高了催化剂活性、稳定性和丙烯选择性,负载镧质量分数为8%时,催化裂化性能最佳。当反应温度550 ℃和空速4 h-1时,丙烯收率12.51%。     

正己烷在HZSM-5分子筛上的催化裂解研究

为筛选反应活性和烯烃选择性相对较高的催化剂用于研究吸热型碳氢燃料的催化裂解,以正己烷的催化裂解作为探针反应,探讨其在不同硅铝物质的量比HZSM-5［n(Si)∶n(Al)=25、36、100］分子筛上催化裂解的反应活性和产物分布。结果表明,正己烷在HZSM-5分子筛上的裂解转化率随温度的升高和分子筛中硅铝物质的量比的减小而增大;裂解产物中乙烯、丙烯和总烯烃的选择性均随裂解温度的升高和分子筛中硅铝物质的量比的增加而增加,在（300~550） ℃,HZSM-5［n（Si)∶n(Al)=36］上的总烯烃收率最高,芳烃含量随分子筛中硅铝物质的量比的增加而减小;基于裂解转化率、烯烃和芳烃收率等因素综合考虑,HZSM-5 n(Si)∶n(Al)=36］分子筛为优选催化剂。     

稀土改性HZSM-5催化乙醇脱水制乙烯

采用浸渍法制备La、Ce、Sm、Eu等稀土（RE）金属改性的HZSM-5分子筛催化剂（RE/HZSM-5）,考察它们在乙醇脱水制乙烯反应中的催化性能.通过X射线衍射（XRD）、N2吸附-脱附（BET）和氨程序升温脱附（NH3-TPD）等手段对其物化性能进行表征,并讨论反应温度对La/HZSM-5催化性能的影响.结果表明：少量稀土引入不破坏HZSM-5分子筛的骨架结构,只对表面酸性产生了较大的影响;表面酸量决定RE/HZSM-5催化乙醇脱水制乙烯的性能,酸量的增大有利于乙醇转化率的提高;在不同稀土改性的催化剂中,2%La/HZSM-5的催化性能最佳,在反应温度240℃、55%原料乙醇、进料质量空速（WHSV）2.5h^-1的条件下,乙醇转化率和乙烯选择性分别达到99.3%和98.6%.     

高温水蒸汽处理对HZSM-5分子筛催化甲醇制丙烯的影响

考察不同硅铝比的HZSM-5分子筛催化剂和经过高温水蒸汽处理后的HZSM-5分子筛催化剂在甲醇制丙烯反应中的催化性能,考察温度和空速对催化反应的影响。结果表明,随着HZSM-5分子筛硅铝比的增加,产物中丙烯选择性增大,可能是分子筛的酸性降低所致;经过高温水蒸汽处理后的HZSM-5分子筛表面酸性降低,提高了催化剂的催化性能。在反应温度450 ℃和空速1.0 h^-1条件下,600 ℃高温水蒸汽处理后的催化剂HT-600的丙烯选择性从改性前的26.8%提高到33.5%。     

纳米Zn/HZSM-5分子筛催化丙烷芳构化

采用低温老化、高温晶化两步法在Na2O-Al2O3-SiO2-四丙基氢氧化铵(TPAOH)-H2O体系中水热合成了纳米ZSM-5分子筛。用BET、N2吸/脱附曲线和NH3-TPD等手段对负载Zn的纳米HZSM-5分子筛结构和酸性进行了表征。结果表明,与微米Zn/HZSM-5分子筛催化剂相比,所制备的纳米Zn/HZSM-5催化剂比表面积明显增大,总酸量和弱酸量增加;在丙烷芳构化反应中,纳米Zn/HZSM-5分子筛具有更佳的催化活性、稳定性和芳烃选择性。     

Methane and ethane activation without adding oxygen: promotional effect of W in Mo-W/HZSM-5

The conversions of methane and ethane over Mo/HZSM-5 and W/HZSM-5 catalysts are compared. A reaction model for hydrocarbon formation over Mo/HZSM-5 catalysts is proposed, which involves heterolytic splitting of methane and a molybdenum-carbene intermediate. Ethene is shown to be the initial product of methane conversion, and it undergoes further reaction to form aromatics in a solid acid environment. The promotional effect of addition of tungsten in the Mo-W/HZSM-5 catalyst in methane conversion reaction suggests the formation of Mo-W mixed oxide. The product selectivity patterns of Mo/HZSM-5 and W/HZSM-5 catalysts in ethane conversion reaction are consistent with a dual-path model involving dehydrogenation and cracking (or hydrogenolysis) of ethane. The rates of both these reactions over Mo/HZSM-5 are higher than over W/HZSM-5.     

金属负载HZSM-5催化剂上乙烯芳构化反应研究

报道了15种负载不同金属的HZSM-5催化剂对乙烯芳构化的催化效果,以Ga(Zn)/HZSM-5催化剂为例,研究了载体酸性、金属含量、反应温度等因素对催化剂催化性能的影响。并对金属负载的HZSM-5催化剂在乙烯芳构化反应中的作用进行了深入研究讨论。     

纳米HZSM-5分子筛催化剂制备及其在乙酸丁醇酯化反应中的应用

以四丙基氢氧化铵为模板剂,碱性有机生物分子L-Lysine为添加剂,水热合成系列不同硅铝物质的量比的纳米HZSM-5分子筛,结合XRD、SEM、Py-FTIR和N2吸附-脱附技术,探讨分子筛结构形态、酸性与其在乙酸和丁醇酯化反应中的催化性能关系。结果表明,纳米HZSM-5分子筛催化剂的酸性位与比表面积、孔径和孔容等结构形态间存在协同作用,共同决定最终的催化效果;在反应温度125℃、乙酸用量0.125 mol、醇酸物质的量比2∶1、带水剂苯用量为10 m L、催化剂用量0.4 g和反应时间4.5 h条件下,乙酸转化率93.65%,乙酸丁酯选择性大于97%。催化剂重复使用6次,乙酸转化率仍大于90%,重复使用性能较好。     

Selective formation of light olefin by n-heptane cracking over HZSM-5 at high temperatures

The catalytic cracking of n-heptane has been performed over HZSM-5 catalysts with various Si/Al ratios at 723-923 K to form light olefins selectively. The HZSM-5 zeolites with various acid site densities exhibited almost the same selectivity at the same conversion. The ethylene + propylene selectivity increased, while the propylene/ethylene ratio decreased with an increase in reaction temperatures. It is found that a high temperature is required to obtain a high ethylene + propylene yield. The highest ethylene + propylene yield obtained in this study was 59.7 C-% with a propylene/ethylene ratio of ca. 0.72 at 99.6% conversion over HZSM-5 (Si/Al = 31) at 923 K. Moreover, it is concluded from the selectivities and activation energies that the monomolecular cracking is predominant at a high temperature as 923 K.     

SYNTHESIS OF ZSM-5 FROM MODIFIED CLINOPTILOLITE AND ITS CATALYTIC ACTIVITY IN ALKYLATION OF BENZENE TO ETHYLBENZENE

ZSM-5 catalysts were prepared by utilizing clinoptilolite found in Western Anatolia in abundant amounts as a type of natural zeolite. Hydrothermal reaction was conducted with HCl-treated clinoptilolite at 180°C. After characterizing the solid products obtained by this reaction as ZSM-5 by means of XRD, IR, TGA, surface area analyzer, and chemical analysis they were tested as catalysts in benzene alkylation reaction with ethylene leading to ethylbenzene. Catalytic performance of samples prepared in this study was investigated for benzene conversion, ethylbenzene yield, and selectivity. It was found that ZSM-5(A) sample showed performance similar to that of the reference sample (ZSM-5(C)) synthesized by using patented literature information in terms of benzene conversion. When the reaction temperature was increased from 400° to 425°C ethylbenzene yield and selectivity results of ZSM-5(A) sample were improved but coke formation increased. Catalyst test results indicated the possibility of using clinoptilolite as a raw material in the synthesis of ZSM-5 catalyst for alkylation of benzene with ethylene reaction.     

High effective dehydration of bio-ethanol into ethylene over nanoscale HZSM-5 zeolite catalysts

Nanoscale and microscale HZSM-5 zeolite catalysts were prepared and characterized by using SEM, XRD, IR, TPD and modified Hammett indicator method. Their performances in the dehydration of bio-ethanol into ethylene were compared in a fixed-bed reactor at 240 °C under atmospheric pressure. The results show that nanoscale HZSM-5 zeolite catalyst exhibits better stability than microscale HZSM-5 zeolite catalyst. When the 95(v) % bio-ethanol is used as the reactant, over nanoscale HZSM-5 catalyst, the conversion of bio-ethanol and the selectivity for ethylene almost keep constant during 630 h reaction, while over microscale HZSM-5 zeolite catalyst, the conversion of bio-ethanol decreases after 60 h reaction; in the case of the 45(v) % bio-ethanol employed as the feedstock, over nanoscale HZSM-5 catalyst, the conversion of bio-ethanol and the selectivity for ethylene almost keep constant during 320 h reaction, while over microscale HZSM-5 zeolite catalyst, both the conversion of bio-ethanol and the selectivity for ethylene decrease almost at the beginning of the reaction.     

Liquid-Phase Oxidation of Benzene to Phenol by Molecular Oxygen over La Catalysts Supported on HZSM-5

The liquid-phase oxidation of benzene to phenol over lanthanum oxide catalysts (LaOx/HZSM-5) supported on HZSM-5 was studied in the presences of oxygen as an oxidant and ascorbic acid as a reducing regent. LaO_x/HZSM-5 effectively catalyzes the formation of phenol at 353 K under the pressurization of oxygen. The LaO_x/HZSM-5 catalysts take place no leaching of lanthanum species from the catalysts to acidic solvent. Therefore, it is demonstrated that the supported lanthanum catalysts are stable and reusable for the benzene oxidation even in the acidic reaction solution.     

Study of W/HZSM-5-Based Catalysts for Dehydro-aromatization of CH4 in Absence of O2. I. Performance of Catalysts

With incorporation of Zn (or Mn, La, Zr ) into the W/HZSM-5 catalyst, highly active and heat-resisting W/HZSM-5-based catalysts were developed and studied. Under reaction conditions of 0.1 MPa, 1073 K, GHSV of feed-gas CH₄+10% Ar at 960 h^–1, the conversion of methane reached 18–23% in the first 2 h of reaction, and the corresponding selectivity to benzene, naphthalene, ethylene and coke was 56–48, 18, 5 and 22%, respectively. Addition of a small amount of CO₂ (2%) to the feed-gas was found to significantly enhance the conversion of methane and the selectivity of benzene, and to improve the performance of coke-resistance of the W/HZSM-5-based catalysts. Heavy deposition of carbon on the surface of the functioning catalyst was the main reason leading to deactivation of the catalyst. Reoxidation by air may regenerate the deactivated catalyst effectively. In comparison with the Mo/HZSM-5 catalyst, the promoted W/HZSM-5-based catalyst can operate under reaction temperature of 1073 K, and gain a methane conversion approximately two times as high as that of the Mo/HZSM-5 catalyst operating at 973 K. It can also operate at 973 K and have about the same methane conversion as that of the Mo/HZSM-5 catalyst at the same reaction temperature. Its main advantage is its heat-resistant performance; the high reaction temperature did not lead to loss of W component by sublimation.     

Ga2O3/HSSZ-13 for dehydrogenation of ethane: Effect of pore geometry of support

Dehydrogenation of ethane to ethylene in the presence of CO₂ was investigated over gallium oxide supported on HSSZ-13 with different Si/Al ratios. These catalysts exhibited higher activity as well as higher selectivity in comparison to HZSM-5 supported ones. 34% ethane conversion with 86.9% selectivity to ethylene could be obtained. The enhanced catalytic performance of Ga₂O₃/HSSZ-13 can be attributed to unique pore geometry of SSZ-13 support. However, the stability is not as good as that of Ga₂O₃/HZSM-5, owing to easy coking in channel with smaller pore-opening size.     

The study of methanol aromatization on transition metal modified ZSM-5 catalyst

In this article, transition metals of Cu, La and Zn were used as adjuvant to prepare modified HZSM-5 by impregnation method. The catalysts were characterized by XRD, BET, NH₃-TPD and Py-IR to reveal the microstructure and acid property. The catalysis performances of methanol aromatization of catalysts were investigated in a fixed-bed reactor. The results show that the strength and distribution of acid center of these catalysts are significantly influenced by the species of transition metal. There are more mediate strong Lewis acid center in Zn modified HZSM-5 catalyst and therefore exhibits higher selectivity to aromatic, benzene, toluene and xylenes in the MTA reaction..