KDI系列异丁烷流化床脱氢铬-氧化铝催化剂的研制与应用经验

S. Egorova, A. Lamberov
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摘要

本文总结了根据Yarsintez公司设计的技术开发异丁烷脱氢制异丁烯微球铬-氧化铝催化剂的经验。研究了以新型薄水铝石为载体的KDI系列工业催化剂的开发。建立了催化剂的元素组成和相组成与性能的相互关系。采用水热法对三水铝石团聚体热分解产物进行两步法制备薄水铝石载体,使其具有理想的尺寸,可以控制其相组成、催化剂的物理力学特性及其催化性能,从而获得一系列KDI、KDI- m和KDI- m1催化剂。指出了PJSC Nizhnekamskneftekhim催化剂商业化实施的最重要步骤。商用KDI-M催化剂在异丁烷脱氢过程中异丁烯的收率稳定在33 - 37%,在异戊烷脱氢过程中甲基丁烯的收率稳定在30%。催化剂用量为每吨异丁烯2 ~ 3公斤。对催化剂的运行进行了监测,提出了改进和优化反应器仪表的方法。经实验室测试,经含硅无机络合物修饰的KDI-M1催化剂的商业样品比该系列以前的催化剂具有更高的活性和选择性,可以工业化实施。
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Experience in the Development and Implementation of Chromium-Alumina Catalysts of the KDI Series for Isobutane Dehydrogenation in a Fluidized Bed
The paper summarizes the experience in the development of a microspherical chromium-alumina catalyst for isobutane dehydrogenation to isobutylene according to the technology devised at Yarsintez. The development of commercial catalysts of the KDI series based on a new boehmite support was considered. Interrelations of elemental and phase composition of the catalysts with their performance were established. A new two-step scheme for producing the boehmite support by hydrothermal treatment of the thermal decomposition product of gibbsite agglomerates with a desired size makes it possible to control its phase composition as well as the physico-mechanical characteristics of the catalysts and their catalytic properties, which allowed obtaining a series of KDI, KDI-M, and KDI-M1 catalysts. The most important steps in commercial implementation of the catalyst at PJSC Nizhnekamskneftekhim were noted. The commercial KDI-M catalyst provided a stable 33–37 % yield of isobutylene in isobutane dehydrogenation and a 30 % yield of methylbutenes in isopentane dehydrogenation. The catalyst consumption was 2–3 kg per ton of the produced isobutylene. The catalyst operation was monitored to propose a way for its improvement and optimization of the reactor instrumentation. According to the laboratory testing, a commercial sample of the KDI-M1 catalyst modified with a silicon-containing inorganic complex compound has higher activity and selectivity than previous catalysts of this series and is ready to industrial implementation.
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