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Liquid hydrocarbon production via ethylene oligomerization over Ni-Hβ
Fuel Processing Technology ( IF 7.5 ) Pub Date : 2018-10-01 , DOI: 10.1016/j.fuproc.2018.07.004
Oliver Jan , Fernando L.P. Resende

Abstract We carried out oligomerization of ethylene using nickel supported on an acidic zeolite β (Ni-Hβ) catalyst in a laboratory-scale packed bed reactor for the synthesis of liquid hydrocarbons in milliliter quantities. We evaluated the effect of several process variables (temperature, pressure, weight hourly space velocity (WHSV), and nickel loading) on the ethylene conversion, liquid hydrocarbon/coke yield, and oligomeric product selectivity. Increases in pressure resulted in higher ethylene conversion, leading to a liquid yield of 13.0 wt%, with 10.0 wt% coke at 65 bar. As the pressure increased to 65 bar, the selectivity towards octenes reached 10%, along with a decrease in C4 to 34%, which suggested that higher pressures promoted butene dimerization. Under the conditions studied, a minimum temperature of 120 °C was required to produce liquid hydrocarbons. The liquid yield increased with temperature, with a maximum of 17.0 wt% at 190 °C. Higher temperatures led to the formation of odd-numbered oligomers primarily due to acid-catalyzed cracking reactions. In the range of WHSV tested, a moderate 2.0 h −1 resulted in a local maximum of 10.6 wt% of liquid hydrocarbon yield. A moderate nickel loading of 3.4 wt% also resulted in the highest liquid yield (10.6 wt%) out of the three loadings tested. The results strongly suggest that the ionic form of nickel is much more active catalytically than the NiO form. The variation in nickel loading revealed the importance of having a synergistic balance of nickel and acid sites on the catalyst to maximize ethylene conversion and maintain high liquid hydrocarbon yield. The results from this work formed the basis for pilot scale runs carried out at the Southwest Research Institute (SWRI) for the Advanced Hardwood Biofuels (AHB) project. The pilot runs highlighted the need for efficient removal of ethanol from the ethylene feed after the dehydration process.

中文翻译:

Ni-Hβ上乙烯齐聚制液态烃

摘要 我们在实验室规模的填充床反应器中使用负载在酸性沸石 β (Ni-Hβ) 催化剂上的镍进行乙烯低聚反应,以合成毫升数量的液态烃。我们评估了几个工艺变量(温度、压力、重时空速 (WHSV) 和镍负载量)对乙烯转化率、液态烃/焦炭产率和低聚物产品选择性的影响。压力增加导致更高的乙烯转化率,导致液体产率为 13.0 wt%,在 65 bar 下焦炭为 10.0 wt%。随着压力增加到 65 bar,对辛烯的选择性达到 10%,同时 C4 减少到 34%,这表明更高的压力促进了丁烯二聚。在研究的条件下,生产液态碳氢化合物所需的最低温度为 120 °C。液体产率随温度增加,在 190 °C 时最大为 17.0 wt%。较高的温度导致奇数低聚物的形成,主要是由于酸催化裂化反应。在测试的 WHSV 范围内,适度的 2.0 h -1 导致局部最大值为 10.6 wt% 的液态烃产率。3.4 重量%的中等镍负载也导致测试的三种负载中最高的液体产率(10.6 重量%)。结果强烈表明,镍的离子形式比 NiO 形式的催化活性高得多。镍负载量的变化揭示了催化剂上镍和酸位协同平衡的重要性,以最大限度地提高乙烯转化率并保持高液态烃产率。这项工作的结果构成了在西南研究所 (SWRI) 进行的高级硬木生物燃料 (AHB) 项目中试规模运行的基础。试点运行强调了在脱水过程后从乙烯进料中有效去除乙醇的必要性。
更新日期:2018-10-01
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