共查询到17条相似文献,搜索用时 140 毫秒
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甲醇制汽油(MTG)在生物质、合成气和煤制取高辛烷值汽油中应用广泛。MTG工艺技术既可以解决甲醇产能过剩问题,又可以降低对石油的依赖程度。MTG工艺的核心是HZSM-5分子筛催化剂,提高HZSM-5分子筛催化剂的汽油选择性和催化寿命是MTG工艺过程中的关键。对传统的HZSM-5分子筛改性是提高其催化性能的有效方式。综述了负载过渡金属、制备多级介孔、合成纳米颗粒以及复合其他材料等改性方法制备的HZSM-5分子筛对MTG反应催化性能的研究进展。着重说明了这些改性方法对HZSM-5分子筛酸性、孔径和表面积等性质的影响,同时对改性后的HZSM-5分子筛的汽油选择性和催化寿命进行了比较。指出了各种改性方法的优缺点和对汽油品质的影响,并对今后的研究方向进行了展望。 相似文献
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《现代化工》2017,(3)
在HZSM-5中引入金属元素进行改性,可以改变催化剂的酸性和孔结构,进而提高催化剂的抗积炭能力和选择性。选用金属铈改性前后的HZSM-5分子筛催化剂,在内径为16 mm的不锈钢管式反应器中考察反应温度、系统压力等条件对甲醇制汽油(MTG)反应的影响,并结合X射线衍射、FT-IR、低温氮吸附-脱附等对HZSM-5催化剂进行表征,分析了汽油收率、产物分布和产物组成的变化规律。结果表明,经铈改性后HZSM-5催化剂仍能保持完整的MFI结构,L酸强度增加。在反应温度为375℃,系统压力为2.0 MPa,进料空速为1.0 h~(-1)的条件下,甲醇转化率为100%,汽油的收率可达34%以上,反应效果和活性周期明显优于改性前。 相似文献
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Fe改性HZSM-5分子筛上甲醇耦合C4烃制低碳烯烃反应性能研究 总被引:1,自引:0,他引:1
用等体积浸渍法制备Fe改性HZSM-5分子筛催化剂(Fe/HZSM-5)。考察了Fe/HZSM-5在不同温度下对甲醇耦合C4烃制低碳烯烃反应性能的影响,并利用紫外-可见漫反射光谱对Fe/HZSM-5进行了表征。结果表明,在低铁含量条件下,Fe改性HZSM-5分子筛上Fe(Ⅲ)主要以高分散隔离的形式存在于HZSM-5分子筛的表面,Fe改性提高了催化剂上的原料转化率以及乙烯和丙烯选择性,从而获得了较高的乙烯和丙烯总收率。在反应温度为550 ℃时,在Fe(Ⅲ)处理的HZSM-5分子筛上,乙烯和丙烯总收率最高可达42.1%,比未改性的HZSM-5提高了7%。 相似文献
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采用水热法合成纳米和微米尺寸的HZSM-5分子筛,并用浸渍法负载Mg对纳米HZSM-5分子筛进行改性,通过XRD、SEM、N_2等温吸附-脱附、NH_3-TPD和TGA对分子筛进行表征,并将其用于甲醇与1-丁烯偶合制丙烯反应,考察分子筛晶粒尺寸、Mg负载量、反应温度、空时和甲醇与1-丁烯物质的量比对催化剂反应性能的影响。结果表明,纳米HZSM-5分子筛具有比表面积大、孔道短和孔口多等特点,表现出较好的活性和稳定性及较强的容碳能力。利用Mg对纳米HZSM-5进行改性,提高了HZSM-5分子筛上原料的转化率和丙烯收率,在反应温度550℃、反应压力0.1 MPa、空时1.6 gcat·(h·mol_(CH_2))~(-1)和甲醇与1-丁烯物质的量比为3的条件下,1%Mg/HZSM-5分子筛催化剂上的丙烯收率最高,达41.8%,比未改性的纳米HZSM-5分子筛催化剂提高9.7个百分点。 相似文献
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催化裂化轻汽油在ZSM-5分子筛催化剂上裂化反应的研究 总被引:2,自引:0,他引:2
以ZSM-5分子筛为催化剂,在小型固定床反应器上,进行了催化裂化轻汽油的裂化反应。考察了反应温度和空速对催化裂化轻汽油裂化反应气液相收率和产品分布的影响。实验结果表明,ZSM-5分子筛催化剂具有较强的裂化活性和氢转移活性。在保证裂化转化率的条件下,提高反应温度和空速可以抑制催化剂上氢转移反应的发生。以ZSM-5分子筛为催化剂上的催化裂化反应中,温度、空速是影响转化率和选择性的重要因素,因此可以通过改变温度、空速来提高目的产物的选择性。但是,单纯依靠改善反应条件,不能使目的产物的收率和选择性达到理想的程度,还必须对催化剂进行改性。ZSM-5分子筛催化剂上催化裂化反应的研究为ZSM-5分子筛催化剂的进一步改性,及ZSM-5分子筛催化剂在轻汽油催化裂解和汽油改质方面的进一步应用提供了试验依据。 相似文献
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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%。 相似文献
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《Microporous and mesoporous materials》2007,98(1-3):174-181
This article describes a novel citric acid treatment method for realuminating dealuminated HZSM-5 zeolite and its application in enhancing the performance of the zeolite derived FCC gasoline hydro-upgrading catalysts. A series of modified HZSM-5 zeolites were prepared by streaming and/or acid treatments and the influences of the different modification methods on the acidity, pore structure and catalytic performance of the modified HZSM-5 zeolite supported catalysts were compared in the present investigation. The results showed that compared with the single HCl or citric acid treatment, the steaming treatment, and the steaming/HCl treatments, the citric acid treatment after steaming exclusively increased the amount of framework Al species due to its realumination effect on the steamed HZSM-5 zeolite. This realumination effect of the citric acid treatment could optimize the ratio of framework Al to extra-framework Al in the steamed HZSM-5 zeolite and thus greatly improve the acidity distribution and pore structure of the corresponding catalyst. The catalytic performance assessments of the different zeolite supported catalysts for FCC gasoline hydro-upgrading revealed that the catalyst supported on the steaming/citric acid treated HZSM-5 zeolite had balanced initial and long-term activities in hydrodesulfurization, hydroisomerization and aromatization, high liquid yield and improved gasoline road octane number. The superior catalytic performance of the catalyst could be closely related to its suitable ratio of framework Al to extra-framework Al achieved by the combinational use of the steaming dealumination and the citric acid realumination, fully demonstrating the effectiveness of the steaming and citric acid treatments in optimizing the physicochemical properties and catalytic performance of HZSM-5 zeolite supported catalysts. 相似文献
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Nanoscale HZSM-5 zeolite was hydrothermally treated with ammonia water at different temperatures and then loaded with La2O3 and ZnO. The parent and the modified nanoscale HZSM-5 catalysts were characterized by SEM, NH3-TPD, IR and XRF. The performance of the modified HZSM-5 catalysts for FCC gasoline upgrading was evaluated in a fixed bed reactor in the presence of hydrogen. The results indicated that the modified catalyst which was hydrothermally treated at 400 °C exhibited excellent aromatization activity, isomerization activity and higher ability of reducing olefin content in FCC gasoline. Under the given reaction conditions, the olefin content in FCC gasoline could be decreased from 49.6 to 8.1 vol.%. The catalytic performance of the modified nanoscale ZSM-5 catalyst hardly changed within 300 h time on stream, and the research octane number (RON) of gasoline was preserved. 相似文献
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催化裂化汽油在多元沸石基催化剂上加氢改质研究 总被引:1,自引:0,他引:1
采用浸渍法分别制备了以丝光沸石(HM)、Hβ和HZSM-5及其组合为载体的沸石基Ni-Mo-P催化剂,考察了载体组成对催化裂化汽油加氢改质反应性能的影响。结果表明,由适宜比例的三者组合得到的沸石基Ni-Mo-P催化剂具有良好的加氢异构化、脱硫、芳构化活性及稳定性,可在催化裂化汽油脱硫降烯烃的同时保证产品的辛烷值不降低。考察了工艺条件对三元沸石基Ni-Mo-P催化剂反应性能的影响。在温度300 ℃、氢油体积比350、液相体积空速2.5 h-1和反应压力1.5 MPa反应条件下,催化裂化汽油异构烷烃收率、芳烃收率、脱硫率及液相收率分别达41.9%、31.7%、51.0%和98.3% 。 相似文献
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Zhang Peiqing Wang Xiangsheng Guo Xinwen Guo Hongchen Zhao Leping Hu Yongkang 《Catalysis Letters》2004,92(1-2):63-68
Nanoscale HZSM-5 zeolite was hydrothermally treated with steam containing 0.8 wt% NH3 at 773 K and then loaded with La2O3 and NiO. Both the parent nanoscale HZSM-5 and the modified nanoscale HZSM-5 zeolites catalysts were characterized by TEM, XRD, IR, NH3-TPD and XRF, and then the performance of olefins reduction in fluidized catalytic cracking (FCC) gasoline over the modified nanoscale HZSM-5 zeolite catalyst was investigated. The IR and NH3-TPD results showed that the amount of acids of the parent nanoscale HZSM-5 zeolite decreased after the combined modification, so did the strong acid sites deactivating catalysts. The stability of the catalyst was still satisfactory, though the initial activity decreased a little after the combined modification. The modification reduced the ability of aromatization of nanoscale HZSM-5 zeolite catalyst and increased its isomerization ability. After 300 h onstream, the average olefins content in the gasoline was reduced from 56.3 vol% to about 20 vol%, the aromatics (C7–C9 aromatics mainly) and paraffins contents in the product were increased from 11.6 vol% and 32.1 vol% to about 20 vol% and 60 vol% respectively. The ratio of i-paraffins/n-paraffins also increased from 3.2 to 6.6. The yield of gasoline was obtained at 97 wt%, while the Research Octane Number (RON) remained about 90. 相似文献
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To develop a novel catalyst system that has excellent olefin reduction capability for FCC gasoline without loss in octane number, different catalysts supported on multiple composite carriers consisting of SAPO-11, Hβ, HMOR and HZSM-5 were prepared and their catalytic performances for FCC gasoline upgrading were assessed in the present investigation. The pore structure and acidity of the catalysts were characterized by N2 adsorption and pyridine adsorption FTIR, respectively. Based on the results obtained over the catalysts supported on binary-zeolite carriers (Hβ/HZSM-5, HMOR/HZSM-5 and SAPO-11/HZSM-5) using FCC gasoline as the feedstock, various multiple-zeolite supported catalysts were developed from different combinations of the binary-zeolite systems. It was found that the SAPO-11/HMOR/β/ZSM-5 quadruple composite zeolite supported catalyst gave higher liquid yield, improved gasoline RON, and lower coke deposit amount for the hydro-upgrading of FCC gasoline and thus can be considered as a potential catalyst system. A comprehensive analysis based on the catalytic activities and acidity measurements revealed that acid strength and acid type were two very important factors influencing hydroisomerization and aromatization activities, and the difference in catalyst acid strength determined which factor predominates. 相似文献
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Various CuO/HZSM-5 catalysts were studied in a fixed bed reactor for the conversion of methanol to gasoline range hydrocarbons
at 673 K and at one atmospheric pressure. The catalysts were prepared by wet impregnation technique. Copper oxide loading
over HZSM-5 (Si/Al=45) catalyst was studied in the range of 0 to 9 wt%. XRD, BET surface area, metal oxide content, scanning
electron microscopy (SEM) and thermogravimetric (TGA) techniques were used to characterize the catalysts. Higher yield of
gasoline range hydrocarbons (C5-C12) was obtained with increased weight % of CuO over HZSM. Effect of run time on the hydrocarbon yields and methanol conversion
was also investigated. The activity of the catalyst decreased progressively with time on-stream. Hydrocarbon products’ yield
also decreased with the increase in wt% of CuO. Relatively lower coke deposition over HZSM-5 catalysts was observed compared
to CuO impregnated HZSM-5 catalyst. 相似文献