Pt-SO42-/ZrO_2固体超强酸异构化催化剂的失活与再生
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摘要
轻质烷烃异构化是生产高辛烷值汽油调和组分的重要工艺手段之一,硫酸化氧化锆(SZ)具有强酸或者超强酸性、良好的热稳定性以及高的低温异构化活性等优点,是异构化催化剂的重要发展研究方向。
本文考察了活化条件如活化温度、活化气氛、反应温度及氢油比等对Pt-SO42-/ZrO2-Al2O3(简称PSZA)催化剂的异构化反应活性及失活行为的影响,考察了催化剂的再生性能,探讨了PSZA低温反应的失活原因,同时,通过对比不同载体负载的Pt催化剂上的异构化行为,揭示了异构化反应历程。实验结果表明：反应温度与氢油比对催化剂的异构化初始活性没有明显影响,反应温度对PSZA催化剂的异构化反应稳定性有显著的影响。低温反应条件下催化剂在短时间内失活显著,相对较高的反应温度大大提高了催化剂的反应稳定性,在为200℃、1h-1及氢油比为3～6,反应200小时后异构化转化率高达83%,产物中二甲基丁烷的收率大于25%。催化剂的低温失活与PSZA上的异构化机理有关,并非来自积碳和硫物种的还原等因素。不同载体负载Pt上的正己烷异构化行为表明PSZA上的异构化反应并不遵循传统的酸功能-金属功能的双功能机理,PSZA上Pt起到解离氢气产生新的强酸中心的作用。短时间内失活后的催化剂通过空气高温再生完全恢复活性,空气活化或再生的作用除了脱水之外,对催化剂表面结构重排也起到一定作用。高温氮气气氛中活化或再生导致PSZA完全失去催化活性。
Sulfated zirconia had super acidity, good thermal stability and high isomerization activity at low reaction temperature, which attracted more and more attention from researchers. In this dissertion, the effects of process conditions such as activation temperature, the activation gas, reaction temperature and ration of hydrogen to n-hexane on the isomerization activity and deactivation behavior were investigated. The experiment results showed that the reaction temperature and ratio of hydrogen to n-hexane had no great influence on the initial isomerization activity. As for the reaction stability, the low reaction temperature led to the fast deactivation of the PSZA even in the presence of H2, while the enhancement of reaction temperature delayed greatly the deactivation velocity. The yield of iso-hexanes and di-methyl butanes was up to 83% and 25%. respectively after 200h of reaction under the reaction conditions of 200℃. the H2/Oil ratio of 3-6 and WHSV of 1h-1. The deactivation behavior of PSZA catalyst in hydro-isomerization reaction in short time could not be attributed to the coke deposit and the reduction of sulfated species. On the contrast, the deactivation was closely related to the isomerization reaction mechanism over PSZA. The isomerization behavior over Pt/zeolite and PSZA showed different reaction paths. The reaction over the former followed the traditional bi-functional mechanism. For reaction over PSZA, Pt played part in the dissociation of H2 and creation of new Bronsted acid sites by hydrogen atom spillover. The isomerization activity of the deactived PSZA catalyst in short time could be completely restored after regeneration in air at high temperature. However, the activation and regeneration in nitrogen led to the complete loss of catalytic activity. It was proposed that the air activation played not only in the removal of adsorbed water, but in the surface structure rearrangement of active species.
本文考察了活化条件如活化温度、活化气氛、反应温度及氢油比等对Pt-SO42-/ZrO2-Al2O3(简称PSZA)催化剂的异构化反应活性及失活行为的影响,考察了催化剂的再生性能,探讨了PSZA低温反应的失活原因,同时,通过对比不同载体负载的Pt催化剂上的异构化行为,揭示了异构化反应历程。实验结果表明：反应温度与氢油比对催化剂的异构化初始活性没有明显影响,反应温度对PSZA催化剂的异构化反应稳定性有显著的影响。低温反应条件下催化剂在短时间内失活显著,相对较高的反应温度大大提高了催化剂的反应稳定性,在为200℃、1h-1及氢油比为3～6,反应200小时后异构化转化率高达83%,产物中二甲基丁烷的收率大于25%。催化剂的低温失活与PSZA上的异构化机理有关,并非来自积碳和硫物种的还原等因素。不同载体负载Pt上的正己烷异构化行为表明PSZA上的异构化反应并不遵循传统的酸功能-金属功能的双功能机理,PSZA上Pt起到解离氢气产生新的强酸中心的作用。短时间内失活后的催化剂通过空气高温再生完全恢复活性,空气活化或再生的作用除了脱水之外,对催化剂表面结构重排也起到一定作用。高温氮气气氛中活化或再生导致PSZA完全失去催化活性。
Sulfated zirconia had super acidity, good thermal stability and high isomerization activity at low reaction temperature, which attracted more and more attention from researchers. In this dissertion, the effects of process conditions such as activation temperature, the activation gas, reaction temperature and ration of hydrogen to n-hexane on the isomerization activity and deactivation behavior were investigated. The experiment results showed that the reaction temperature and ratio of hydrogen to n-hexane had no great influence on the initial isomerization activity. As for the reaction stability, the low reaction temperature led to the fast deactivation of the PSZA even in the presence of H2, while the enhancement of reaction temperature delayed greatly the deactivation velocity. The yield of iso-hexanes and di-methyl butanes was up to 83% and 25%. respectively after 200h of reaction under the reaction conditions of 200℃. the H2/Oil ratio of 3-6 and WHSV of 1h-1. The deactivation behavior of PSZA catalyst in hydro-isomerization reaction in short time could not be attributed to the coke deposit and the reduction of sulfated species. On the contrast, the deactivation was closely related to the isomerization reaction mechanism over PSZA. The isomerization behavior over Pt/zeolite and PSZA showed different reaction paths. The reaction over the former followed the traditional bi-functional mechanism. For reaction over PSZA, Pt played part in the dissociation of H2 and creation of new Bronsted acid sites by hydrogen atom spillover. The isomerization activity of the deactived PSZA catalyst in short time could be completely restored after regeneration in air at high temperature. However, the activation and regeneration in nitrogen led to the complete loss of catalytic activity. It was proposed that the air activation played not only in the removal of adsorbed water, but in the surface structure rearrangement of active species.
引文
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