生产未来的环境燃料

标准催化剂公司(Criterion Catalyst Company L.P)开发了三种不同于以往的Co-Mo和 Co-Ni新型加氢处理催化剂以满足各类深度或超深度脱硫工艺的应用,包括DC-185,DC-16 0,DC-2000.其中DC-2000是该公司的专利产品(Century).此外它还生产了Century Ni-Mo催化剂(DC-190).这些催化剂在超低硫柴油的生产中起了关键的作用.     

使用温度对B90催化剂催化性能的影响探讨

分析了丁烯氧化脱氢制丁二烯Ｂ９０催化剂的性能和使用条件，认为Ｂ９０催化剂使用温度过高是催化剂结碳和失活的主要原因，提出了将绝热式反应器改为换热式反应器的建议。     

乙二醇空气催化氧化制乙二醛

采用磷锡铜合金催化剂,考察了小试的反应规律,表明催化剂的活性、选择性和稳定性都较好。采用恒温式列管反应器进行放大,和用磷铜合金催化剂进行绝热式薄层反应器放大,都取得较好的效果。     

3996催化剂在上海石油化工股份有限公司工业应用一次开汽成功

2000年8月，由抚顺石油化工研究院研制开发的3996重质馏分油加氢精制催化剂,在上海石油化工股份有限公司首次工业应用,一次开汽成功。 3996催化剂是抚顺石油化工研究院继3936催化剂之后，新研制开发的重质馏分油加氢精制催化剂，主要设计用于一段串联加氢裂化过程的预精制段，也可用于焦化蜡油加氢处理和中压加氢改质等工艺过程。该催化剂具有比表面积大、孔容大、孔分布集中、金属分布均匀、堆积密度适中、强度好、活性高和使用寿命长等特点。该剂的中试研究结果已于2000年3月7日通过了由原中国石油化工集团公司技术开发中心主持的技术鉴定。鉴定专家一致认为:3996催化剂作为3936催化剂的换代产品，已达到目前国外同类催化剂的先进水平。 上海石油化工股份有限公司炼油化工部II套芳烃联合装置加氢裂化车间于8月20～29日装填催化剂，精制反应器DC-101共装填3996催化剂109.45 t,总装填密度为0.876 t/m3；裂化反应器DC-102用再生3825催化剂(补充了部分新鲜剂)，DC-102的底部装填3996催化剂13.5 t作为后精制催化剂，其装填密度为0.826 t/m3。 9月9日9：00，装置开始引进低氮开工油，22：00装置进料全部置换为VGO。9月11日2：00装置负荷达60%，VGO总进量为143.9 m3/h，其中DC-101进料量为81.1 m3/h，其平均反应温度为333℃，床层总温升34.9℃，DC-101出口生成油氮含量小于1 μg/g,完全满足裂化催化剂对其进料中氮含量小于10 μg/g的要求。9月12日装置负荷达到100%。9月15日装置VGO总进料量达200 t/h，其中DC-101进料量为114.5 t/h，高分压力14.2 MPa，氢油体积比1 013∶1，体积空速1.01 h-1，平均反应温度为369.6℃，床层总温升39.6℃，DC-101出口生成油氮含量为7.7 μg/g。 目前，装置在满负荷条件下运转平稳。 (抚顺石油化工研究院科管部供稿)     

工业反应过程的开发方法Ⅱ．负压法乙苯脱氢绝热反应器的开发

针对乙苯脱氢绝热反应器工程特点建立了有关转化率和选择性的数学模型。为进一步减少径向反应器阻力降，提出变截面Ｚ型中心分流流型设计计算式。根据本研究结果提出６万吨苯乙烯／年负压法绝热反应器的设计基础。     

气态烃预转化催化剂研制及工业应用

根据气态烃预转化工艺的特点设计了预转化催化剂研制方案,研制出用于预转化炉的CN-30型镍系催化剂。考察了催化剂的抗析炭和抗蒸汽氧化性能,以及水碳比、空速对催化剂性能的影响。结果表明,该催化剂活性和稳定性高,抗高烃能力强。与现有工业催化剂对比以及工业实际应用证实,CN-30型催化剂是一种优良的预转化催化剂,完全能够满足合成氨改造过程中转化反应的各项工艺条件,可广泛用于以天然气或其它气态烃为原料的合成氨厂和制氢厂的绝热反应器中。     

裂解汽油加氢装置的技术改造及工业试生产

介绍了在裂解汽油二段加氢工艺中,用国产3641催化剂代替进口钯催化剂,用塞式绝热反应器代替原列管恒温反应器,实践表明,3641催化剂可满足裂解汽油进行完全加氢,所得产品符合芳烃抽提装置要求的原料规格。同时还简介了自产一段加氢钯催化剂的运转情况。     

FX-01催化剂上苯与丙烯烷基化Ⅱ.反应器的模拟

利用已得到的FX -0 1沸石催化剂上苯与丙烯烷基化反应动力学模型 ,用内扩散有效因子校正内扩散影响 ;用有关关联式计算外扩散传质系数 ;对不同操作方式的反应器 ,如等温床、单段绝热床和多段绝热床进行模拟 ;并对多段绝热床操作条件进行优化设计。模拟结果与年产 1 0 0t异丙苯装置的实际运行情况接近。     

FX-01催化剂上苯与丙烯烷基化Ⅱ.反应器的模拟

利用已得到的FX -0 1沸石催化剂上苯与丙烯烷基化反应动力学模型 ,用内扩散有效因子校正内扩散影响 ;用有关关联式计算外扩散传质系数 ;对不同操作方式的反应器 ,如等温床、单段绝热床和多段绝热床进行模拟 ;并对多段绝热床操作条件进行优化设计。模拟结果与年产 1 0 0t异丙苯装置的实际运行情况接近。     

裂解汽油在Co-Mo/Al_2O_3催化剂上的加氢—脱硫工艺条件

叙述了350cm~3绝热反应器的结构参数、绝热保温方式、以及裂解汽油二段加氢和脱硫的主要化学反应。并以工业装置的工艺操作条件为基础,在350cm~3绝热反应器中,试验了裂解汽油在8602Co-Mo/Al_2O_3催化剂上加氢和脱硫时反应器的入口温度、氢油比、液时空速和反应压力等工艺操作条件对加氢和脱硫反应的影响。给出了8602催化剂于绝热型反应器上的最佳工艺操作条件。     

RIPP开发的催化重整技术

To meet the demands for high-octane gasoline and aromatics, catalytic reforming process has been advancing quickly in China. The reforming catalysts developed by RIPP have been used in more than 80% capacity of domestic CCR and SR units. This paper introduces the properties of PS-VI CCR catalyst developed by RIPP in recent years and also the result from commercial units. The PS-VI catalyst has high activity and good selectivity, under the same reaction conditions, the carbon on catalyst was lowered by 26% in mass as compared with that of the reference catalyst. Among the SR reforming catalysts, the new type of PRT series catalysts have excellent performance at low reaction pressure compared with the ref. Cat A. The aromatics and reformate mass yields of PRT catalyst were 2%～3% and 3%, respectively, higher than those of Cat A, and the run length was 30%～40% longer as well, which exhibits good prospect of application.     

低积炭半再生重整催化剂的研发

在铂铢催化剂卜引入助剂钇,采用新颖的制备方法,开发了三金属PRT重整催化剂。采用专用的制备方法,催化剂上的金属组元分布均匀。引入助剂钇后,可以明显提高铂金属组分的热稳定性。中型装置试验和工业应用试验表明,催化剂的积炭速率明显降低;催化剂具有较好的活性、选择性和稳定性。因此,催化剂具有较好的工业化应用效果。     

银催化剂的发展和EO／EG生产技术进步

简述了国内外银催化剂的发展及其对ＥＯ／ＥＧ工业生产发展的促进作用。银催化剂的发展,以提高选择性为中心经历了三个阶段。北京燕化公司研究院研究开发的ＹＳ－系列银催化剂成功地用于工业ＥＯ／ＥＧ生产装置,在提高选择性方面取得了新的进展。从催化剂活性,选择和稳定性综合考虑提出了ＥＯ／ＥＧ装置银催化剂的选型原则。     

Application of Thermal Analysis for Regeneration of Reforming Catalyst

Catalytic reforming of naphtha for improving its characteristics is one of the most important petroleum refining catalytic processes. Modern catalytic reformers utilize dual function platinum-based catalysts which during operation are exposed to the formation of carbonaceous deposits causing gradual deterioration of their activity and alteration of their selectivity. In-situ regeneration has proved to be adequate practice in restoring a catalyst's activity as well as its selectivity. Hence, optimization of regeneration is a vital step of the reforming process. This is usually done under conditions of a general nature that have been recommended by catalyst manufacturers and/or suppliers. Results of thorough laboratory investigations on the thermal behavior of used reforming catalyst (spent samples) revealed that the amount and complexity of the chemical nature of carbonaceous deposits on reforming catalysts are directly related to its life on stream and severity of operating conditions. Optimal regeneration of the catalyst requires specific conditions that take into consideration behavior and combustibility of carbonaceous deposits on its surface. Such information can easily be obtained by applying thermal analysis on catalyst samples which can be taken from the reformer during the production cycle.

The paper discusses this topic and presents results of detailed thermal analysis carried out on series of reforming catalyst samples taken from semi-regenerative reformers for two different commercial catalysts.     

FC-50中油型加氢裂化催化剂的研制

为满足市场对清洁燃料油及化工原料需求量不断增长的要求,中国石油化工股份有限公司抚顺石油化工研究院以无定型硅铝为主载体,改性Y型分子筛为主要酸性组分,W-Ni为活性组分,采用浸渍法制备了FC-50中油型加氢裂化催化剂,属多产中间馏分油兼产高质量重石脑油和尾油的催化剂。在试验装置上对该剂与国内同类先进催化剂进行了对比评价,并进行了工业放大。结果表明,FC-50催化剂具有较高的中间馏分油选择性、反应活性以及良好的稳定性,产品质量优良。以伊朗VGO-1为原料,使用FC-50催化剂,在反应温度380℃、空速1.5h-1条件下,单程转化率为65.8%,中间馏分油选择性79.90%。在相同条件下,FC-50与FC-26催化剂相比,反应温度低3℃,中油选择性比FC-26催化剂高近2%。结果表明,FC-50催化剂的反应性能完全达到了实验室定型催化剂的水平。     

Application of Thermal Analysis for Regeneration of Reforming Catalyst

ABSTRACT

Catalytic reforming of naphtha for improving its characteristics is one of the most important petroleum refining catalytic processes. Modern catalytic reformers utilize dual function platinum-based catalysts which during operation are exposed to the formation of carbonaceous deposits causing gradual deterioration of their activity and alteration of their selectivity. In-situ regeneration has proved to be adequate practice in restoring a catalyst's activity as well as its selectivity. Hence, optimization of regeneration is a vital step of the reforming process. This is usually done under conditions of a general nature that have been recommended by catalyst manufacturers and/or suppliers. Results of thorough laboratory investigations on the thermal behavior of used reforming catalyst (spent samples) revealed that the amount and complexity of the chemical nature of carbonaceous deposits on reforming catalysts are directly related to its life on stream and severity of operating conditions. Optimal regeneration of the catalyst requires specific conditions that take into consideration behavior and combustibility of carbonaceous deposits on its surface. Such information can easily be obtained by applying thermal analysis on catalyst samples which can be taken from the reformer during the production cycle.

The paper discusses this topic and presents results of detailed thermal analysis carried out on series of reforming catalyst samples taken from semi-regenerative reformers for two different commercial catalysts.     

Nb掺杂对Pd/Al2O3催化剂脱硝活性的影响

为了提高Pd基催化剂对HC-SCR反应的催化活性、选择性和稳定性,同时降低催化剂成本,采用非贵金属Nb掺杂来改善贵金属Pd基催化剂的织构、结构、氧化还原等性能。首先通过添加廉价的造孔剂对商业化Al2O3进行改性,制备出孔隙率高的Al2O3基底,然后通过浸渍法制备出Nb改性的Pd/Al2O3催化剂,采用XRD,BET,NH3-TPD,H2-TPR,XPS等手段对催化剂进行表征,并系统研究了Nb掺杂对 Pd/Al2O3催化剂的HC-SCR催化性能的影响。结果表明,适当的Nb掺杂可以提高Pd/Al2O3催化剂的催化活性,在Nb添加量为5%时催化剂活性最高并具有较好的稳定性,当NO转化率为90%时,转化温度仅为269 ℃。     

催化裂化催化剂及助剂的现状和发展

介绍了国内外催化裂化催化剂及助剂领域的最新动态.在全球范围内,许多催化剂企业进行了重组.在技术上,多种新的催化材料引入催化剂中.重油转化催化剂得到了越来越广泛的应用,降低汽油烯烃含量和硫含量催化剂的开发取得了实质进展.中国在特种催化裂化工艺专用催化剂技术方面明显处于国际领先水平,如CGP-1和CGP-2催化剂(MIP-CGP工艺专用催化剂)、MMC系列催化剂(DCC工艺专用催化剂),等等.受日益增长的丙烯市场需求影响,催化裂化催化剂对丙烯和液化石油气的选择性有了显著提高.今后,提高清洁汽油辛烷值的催化裂化催化剂以及减少催化裂化装置烟气污染排放的催化剂和助剂将成为研发的热点,催化剂低成本和清洁生产技术也将得到重视和发展.     

X-RAY DIFFRACTION CHARACTERIZATION OF Ag-Rh CATALYSTS FOR OXYGENATE AND HYDROCARBON SYNTHESIS

Ag-Rh/SiO₂ catalysts which exhibit activity and selectivity for oxygenate and hydrocarbon synthesis have been characterized by X-ray diffraction (XRD). XRD patterns show that the catalysts prepared using Rh chloride precursor contain Rh, Ag, AgCl, and AgClO₂ crystallites. The size of these crystallites varied with the amount of Ag in the catalyst. The variation in crystallite size of Rh, Ag, AgCl, and AgClO₂ with Ag/Rh ratio has an impact on the activity and selectivity for synthesis of oxygenates and hydrocarbons during CO hydrogenation and ethylene hydroformylation reactions. The selectivity towards oxygenates is decreased on the Ag-Rh catalysts due to the presence of AgCl and AgClO₂ crystallites on the catalyst surface. Ag-Rh catalyst with Ag/Rh ratio of 0.5 gives a higher activity and selectivity for ethanol and propanol during CO hydrogenation and ethylene hydroformylation than the other Ag-Rh catalysts. Ag-Rh catalysts prepared from Rh chloride and Ag nitrate precursors are less active and selective for oxygenate synthesis than those prepared from nitrate precursors. Ag-Rh catalysts for oxygenate synthesis should be prepared using nitrate precursors.     

催化裂化重汽油临氢脱砷剂的研制及性能评价

以大孔γ-Al₂O₃为载体,Mo-Ni为活性组元,采用等体积浸渍法制备了催化裂化重汽油临氢脱砷剂。考察了拟薄水铝石、胶溶剂、金属活性组元类型、金属原子比对临氢脱砷剂催化性能的影响,以及脱砷剂活性和长周期稳定性。结果表明：氧化铝孔径分布对脱砷剂性能影响较大,大孔径有利于提高临氢脱砷剂脱砷活性,有机酸作为胶溶剂可显著提高载体大孔比例;适宜的Ni/(Ni+Mo)原子比有利于改善金属分散性,提高催化剂的脱砷活性和脱砷选择性;临氢脱砷剂表现出较好的长周期运行稳定性,综合性能与商品临氢脱砷剂相当。