载钯C5/C6烷烃异构化催化剂研究及工业应用
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摘要
C5/C6异构化是通过异构化反应将正构烃原料转化为相应的异构烃，提高汽油辛烷值，使汽油具有均匀的抗爆性能。异构化汽油不含硫、烯烃及芳烃，是最洁净的高辛烷值汽油组份。目前我国异构化油尚未真正形成生产能力，异构化技术今后将成为我国石化企业生产清洁汽油的最有效手段之一。
异构化技术的核心是催化剂制造，目前世界上工业应用的异构化催化剂主要有低温及中温型两类，均以铂（Pt）作为活性金属组份，虽然中温催化剂活性略低于低温催化剂，但对原料要求不高，可再生，装置投资小，操作费用低，在我国具有广泛的应用前景。
本文在国内外学者对中温异构化催化剂及工艺研究的基础上，以钯（Pd）作为金属组份，氢型丝光沸石（HM）作为酸性载体，系统研究了工业制备过程中各种因素对催化剂性能的影响，以及催化剂失活的原因及再生方法，进行了丝光沸石及催化剂的放大生产，并在10万吨/年工业装置上考察了催化剂的稳定性，为制备载Pd异构化催化剂及工业应用提供了重要依据。
丝光沸石对催化剂活性有较大影响，试验结果表明：以水玻璃为主要原料，加入晶种可缩短晶化时间，合成的丝光沸石具有较高的比表面积及小晶粒大孔径结构，经铵交换及酸交换后适于制备异构化催化剂。
采用混捏法载钯制备的Pd/HM催化剂比离子交换法具有更高的异构化性能，异构化反应按正碳离子机理进行，Pd提供加氢脱氢中心，HM提供酸性中心，在Pd含量0.25-0.5%范围内，催化剂具有较好稳定性，C5异构化率>62%，C6异构化率>82%，C6选择性>18%。
采用微反-在线色谱活性评价、X-RF、X-RD、FT-IR、BET、NH3-TPD及元
素分析等手段，研究了催化剂的失活原因及再生方法，对催化剂的孔结构、晶相及表面酸性进行了表征。结果表明：结焦是造成Pd/HM催化剂失活的主要原因， 焦炭在Pd中心及酸性中心上的沉积不仅使B酸及L酸数量减少，而且覆盖催化剂表面，使微孔数量减少；而硫是造成Pd/HM催化剂中毒的主要毒物，原料中的硫与Pd结合，覆盖催化剂活性中心，使催化剂活性下降。失活催化剂在550℃烧焦再生，活性可基本恢复。再生温度高于550℃，催化剂比表面、孔容及晶胞常数减少，金属颗粒增大，分散度降低，酸中心数量减少。
工业放大生产的0.5%Pd/HM催化剂具有较好的稳定性及抗硫性能，寿命试验结果表明，以含硫近50ppm的工业重整拔头油为原料，运行1000小时催化剂活性没有下降。
Pd/HM是世界上首次进行工业放大及应用的载钯中温型异构化催化剂，成本比Pt/分子筛催化剂低40万元/吨，具有广泛的应用前景。
10万吨/年工业装置运转结果表明，Pd/HM催化剂具有比较好的活性、稳定性及抗水性能，累积运行4个多月，一次通过辛烷值（RON）达到80-82，提高8-10个单位，异构化油产品RON达83-85，已作为调合组份掺入汽油，取得了明显的经济和社会效益。
C5/C6 isomerization process is used to convert normal paraffin feedstock into corresponding iso-paraffins so as to improve the octane number of gasoline and make gasoline have uniform antiknock performance. Isomerized gasoline is the cleanest high-octane gasoline component, which is free of sulfur, olefin and aromatics. There is no actual ability of producing isomerized oil up to now, but the isomerization technology will become the most effective means of producing clean gasoline for our petrochemical enterprise.
The core of isomerization technology is catalyst production. The commercialized catalysts in the world are divided into two groups, i.e. low-temperature and moderate temperature types, with Pt as their active metal components. Although the activity of moderate temperature catalyst is less than that of low temperature catalyst, it demands not too much on feedstock and can be regenerated. This catalyst can find wide application in China since both the investment of plant and its operation cost are low.
Based on the studies of moderate temperature isomerization catalysts carried out by domestic and foreign researchers, the paper systematically discussed the influence of a variety of factors in process of commercial preparation on the performance of catalyst which applied Pd as its metal component and HM as its acid carrier. The paper also explored the deactivated reasons of catalyst and its regenerating measure. Preparation of mordenite and scaled up production of catalyst, stability of catalyst was demonstrated in a 100kt/a commercial plant. The findings provide important basis for preparing Pd isomerization catalyst and industrial application.
Mordenite has a significant effect on the activity of catalyst, results of test showed: with soluble glass as main feedstock and addition of crystal precursor, the
crystalization time can be reduced, and the synthesized mordenite has higher surface area and structure of small crystal particulate and big pore diameter. Through ion exchange with ammonium and acid, the synthesized mordenite is suitable to prepare isomerization catalyst.
The Pd/HM catalyst prepared through mixed pinching method has higher isomerization feature. With the use of this kind of catalyst, the isomerization reaction is carried out as the mechanism of carbocation，because Pd offers site for hydrogenation and de-hydrogenation, HM provides acid site. Within the range of 0.25-0.5% Pd content, the catalyst has good stability, isomerization rates of C5 and C6 are >62% and >82%, and selectivity of C6 is >18%, respectively.
Applying activity evaluation of micro-reaction test and online chromatography analysis, X-RF、X-RD、FT-IR、BET、NH3-TPD and element analysis, the deactivated reasons and regeneration method of the prepared catalyst were investigated, and the pore structure, crystal phase, surface acid were characterized. The results showed: coking was the main reason of deactivation of Pd/HM catalyst，the deposition of coke on Pd site and acid site not only reduced the quantities of Bronsted acid sites and Lewis acid sites，but also covered the surface of catalyst resulted in reduction of micropore；while sulfur was the main factor poisoning Pd/HM catalyst since the sulfur in the feedstock combined with Pd so that active site of catalyst was covered and causing the decrease of catalyst activity. The deactivated catalyst was regenerated at 550℃ by coke-burning，and its majority of activity could recover. If the regeneration temperature was over 550℃，the surface area, pore volume, cell constant of catalyst would decreased, and the metal particulate became bigger, dispersion and number of acid site were weaken.
The 0.5%Pd/HM catalyst produced through commercial scale-up possesses have better stability and sulfur-resistant characteristics. Results of life test indicated that the activity had not decreased with reforming topped oil containing near 50ppm sulfur as feedstock after 1000 hours' operation.
Pd/HM catalyst was the first moderate-temperature isomerization catalys
异构化技术的核心是催化剂制造，目前世界上工业应用的异构化催化剂主要有低温及中温型两类，均以铂（Pt）作为活性金属组份，虽然中温催化剂活性略低于低温催化剂，但对原料要求不高，可再生，装置投资小，操作费用低，在我国具有广泛的应用前景。
本文在国内外学者对中温异构化催化剂及工艺研究的基础上，以钯（Pd）作为金属组份，氢型丝光沸石（HM）作为酸性载体，系统研究了工业制备过程中各种因素对催化剂性能的影响，以及催化剂失活的原因及再生方法，进行了丝光沸石及催化剂的放大生产，并在10万吨/年工业装置上考察了催化剂的稳定性，为制备载Pd异构化催化剂及工业应用提供了重要依据。
丝光沸石对催化剂活性有较大影响，试验结果表明：以水玻璃为主要原料，加入晶种可缩短晶化时间，合成的丝光沸石具有较高的比表面积及小晶粒大孔径结构，经铵交换及酸交换后适于制备异构化催化剂。
采用混捏法载钯制备的Pd/HM催化剂比离子交换法具有更高的异构化性能，异构化反应按正碳离子机理进行，Pd提供加氢脱氢中心，HM提供酸性中心，在Pd含量0.25-0.5%范围内，催化剂具有较好稳定性，C5异构化率>62%，C6异构化率>82%，C6选择性>18%。
采用微反-在线色谱活性评价、X-RF、X-RD、FT-IR、BET、NH3-TPD及元
素分析等手段，研究了催化剂的失活原因及再生方法，对催化剂的孔结构、晶相及表面酸性进行了表征。结果表明：结焦是造成Pd/HM催化剂失活的主要原因， 焦炭在Pd中心及酸性中心上的沉积不仅使B酸及L酸数量减少，而且覆盖催化剂表面，使微孔数量减少；而硫是造成Pd/HM催化剂中毒的主要毒物，原料中的硫与Pd结合，覆盖催化剂活性中心，使催化剂活性下降。失活催化剂在550℃烧焦再生，活性可基本恢复。再生温度高于550℃，催化剂比表面、孔容及晶胞常数减少，金属颗粒增大，分散度降低，酸中心数量减少。
工业放大生产的0.5%Pd/HM催化剂具有较好的稳定性及抗硫性能，寿命试验结果表明，以含硫近50ppm的工业重整拔头油为原料，运行1000小时催化剂活性没有下降。
Pd/HM是世界上首次进行工业放大及应用的载钯中温型异构化催化剂，成本比Pt/分子筛催化剂低40万元/吨，具有广泛的应用前景。
10万吨/年工业装置运转结果表明，Pd/HM催化剂具有比较好的活性、稳定性及抗水性能，累积运行4个多月，一次通过辛烷值（RON）达到80-82，提高8-10个单位，异构化油产品RON达83-85，已作为调合组份掺入汽油，取得了明显的经济和社会效益。
C5/C6 isomerization process is used to convert normal paraffin feedstock into corresponding iso-paraffins so as to improve the octane number of gasoline and make gasoline have uniform antiknock performance. Isomerized gasoline is the cleanest high-octane gasoline component, which is free of sulfur, olefin and aromatics. There is no actual ability of producing isomerized oil up to now, but the isomerization technology will become the most effective means of producing clean gasoline for our petrochemical enterprise.
The core of isomerization technology is catalyst production. The commercialized catalysts in the world are divided into two groups, i.e. low-temperature and moderate temperature types, with Pt as their active metal components. Although the activity of moderate temperature catalyst is less than that of low temperature catalyst, it demands not too much on feedstock and can be regenerated. This catalyst can find wide application in China since both the investment of plant and its operation cost are low.
Based on the studies of moderate temperature isomerization catalysts carried out by domestic and foreign researchers, the paper systematically discussed the influence of a variety of factors in process of commercial preparation on the performance of catalyst which applied Pd as its metal component and HM as its acid carrier. The paper also explored the deactivated reasons of catalyst and its regenerating measure. Preparation of mordenite and scaled up production of catalyst, stability of catalyst was demonstrated in a 100kt/a commercial plant. The findings provide important basis for preparing Pd isomerization catalyst and industrial application.
Mordenite has a significant effect on the activity of catalyst, results of test showed: with soluble glass as main feedstock and addition of crystal precursor, the
crystalization time can be reduced, and the synthesized mordenite has higher surface area and structure of small crystal particulate and big pore diameter. Through ion exchange with ammonium and acid, the synthesized mordenite is suitable to prepare isomerization catalyst.
The Pd/HM catalyst prepared through mixed pinching method has higher isomerization feature. With the use of this kind of catalyst, the isomerization reaction is carried out as the mechanism of carbocation，because Pd offers site for hydrogenation and de-hydrogenation, HM provides acid site. Within the range of 0.25-0.5% Pd content, the catalyst has good stability, isomerization rates of C5 and C6 are >62% and >82%, and selectivity of C6 is >18%, respectively.
Applying activity evaluation of micro-reaction test and online chromatography analysis, X-RF、X-RD、FT-IR、BET、NH3-TPD and element analysis, the deactivated reasons and regeneration method of the prepared catalyst were investigated, and the pore structure, crystal phase, surface acid were characterized. The results showed: coking was the main reason of deactivation of Pd/HM catalyst，the deposition of coke on Pd site and acid site not only reduced the quantities of Bronsted acid sites and Lewis acid sites，but also covered the surface of catalyst resulted in reduction of micropore；while sulfur was the main factor poisoning Pd/HM catalyst since the sulfur in the feedstock combined with Pd so that active site of catalyst was covered and causing the decrease of catalyst activity. The deactivated catalyst was regenerated at 550℃ by coke-burning，and its majority of activity could recover. If the regeneration temperature was over 550℃，the surface area, pore volume, cell constant of catalyst would decreased, and the metal particulate became bigger, dispersion and number of acid site were weaken.
The 0.5%Pd/HM catalyst produced through commercial scale-up possesses have better stability and sulfur-resistant characteristics. Results of life test indicated that the activity had not decreased with reforming topped oil containing near 50ppm sulfur as feedstock after 1000 hours' operation.
Pd/HM catalyst was the first moderate-temperature isomerization catalys
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