Low temperature isomerizational transformation of gas gasoline on modified zeolite catalysts

M. T. Mamedova
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Abstract

New multicomponent catalytic systems synthesized by modifying zeolites (НМOR17 and HZSM-5) and γ-Al2O3 with metals (Co, Ni), zirconium dioxide and subsequent sulfation and tungestation of the obtained samples. It was shown that the introduction of zirconia into the M/MOR (where M = Co, Ni) system allows one to lower the isomerization temperature by 140-160°С, turning the medium-temperature skeletal-isomerisation catalyst M/MOR into a low-temperature M/MOR/ZrO2. It was found that sulfated Co/MOR/ZrO2/SO42- and Co/HZSM-5/ZrO2/SO42- have a higher isomerization activity, which makes it possible to increase the content of isomeric C5-C6 components with high octane numbers in gas gasoline from 43 to 66%. It was found that upon contacting the gas gasoline with the Co/MOR/ZrO2/SO42- or Co/HZSM-5/ZrO2/SO42- catalytic systems, efficient processing of higher molecular weight C7+ alkanes occurs not only into iso-C5 and C6, but also into n-pentane whose content in contact products rises from 19 to 40%. For the first time it was found that at temperatures of 160-200 °C, impurity gaseous C4- alkanes in the gas gasoline are consumed of when contacted with synthesized catalysts, turning into liquid alkanes. It was established that sulfated catalysts have more isomerizing activity in the low-temperature isomerization conversion of gas gasoline than volframated ones. The effect of the concentration of SO42- ions on the activity of the catalysts was studied and it was found that 2 wt.% is satisfactory for the studied catalysts. The temperature dependence of the activity of the most active of the synthesized catalysts in this process – Co/HZSM-5/ZrO2/SO42-, was studied. The results showed that the optimum temperature for the isomerization functioning of the selected catalyst is 180 oC. The change in the activity of the optimal catalyst (Co/HZSM-5/ZrO2/SO42-) depending on the reaction period was also studied. It was established that with the course of the process, the activity of the catalyst increases and reaches a maximum of 30 minutes work. After this, the activity of the catalyst gradually decreases. In this case, the total concentration of iso-C5 and iso-C6 increases by 22.9% and reaches 66.1%, and the conversion of C7+ components of gas gasoline is 69.2%.
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改性沸石催化剂对汽油低温异构化反应的影响
用金属(Co, Ni),二氧化锆对沸石(НМOR17和HZSM-5)和γ-Al2O3进行改性,并对所得样品进行磺化和钨化处理,合成了新的多组分催化体系。结果表明,在M/MOR (M = Co, Ni)体系中引入氧化锆可使异构化温度降低140 ~ 160°С,使中温骨架异构化催化剂M/MOR变为低温M/MOR/ZrO2。结果表明,Co/MOR/ZrO2/SO42-和Co/HZSM-5/ZrO2/SO42-磺化后具有较高的异构化活性,可将汽油中高辛烷值C5-C6异构组分的含量从43%提高到66%。结果表明,汽油与Co/MOR/ZrO2/SO42-或Co/HZSM-5/ZrO2/SO42-催化体系接触后,高分子量的C7+烷烃不仅能被高效加工成异c5和C6,还能被高效加工成正戊烷,正戊烷在接触产物中的含量从19%提高到40%。首次发现在160 ~ 200℃的温度下,汽油中的杂质气态C4-烷烃与合成的催化剂接触后被消耗,转化为液态烷烃。结果表明,硫酸化催化剂在汽油低温异构化转化中的异构化活性高于挥发化催化剂。研究了SO42-离子浓度对催化剂活性的影响,发现SO42-离子浓度为2 wt.%即可。研究了该工艺合成的活性最高的催化剂Co/HZSM-5/ZrO2/SO42-的活性与温度的关系。结果表明,所选催化剂的异构化功能的最佳温度为180℃。研究了最佳催化剂(Co/HZSM-5/ZrO2/SO42-)的活性随反应周期的变化。结果表明,随着工艺的进行,催化剂的活性增加,最大可达30分钟的工作时间。在此之后,催化剂的活性逐渐降低。在此情况下,iso-C5和iso-C6总浓度增加22.9%,达到66.1%,汽油中C7+组分转化率为69.2%。
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