SO42-/ZrO2轻质烷烃异构化催化剂的制备和工业应用进展

doi:10.16085/j.issn.1000-6613.2019-0112

摘要/Abstract

摘要：

硫酸化氧化锆固体酸（SO₄^2-/ZrO₂）烷烃异构化催化剂兼具高活性、可再生和环境友好的优点，具有广阔的应用前景。本文综述了SO₄^2-/ZrO₂催化剂在轻质烷烃异构化中的工业应用进展，包括市场现状、现有技术、经济性等方面，并对专利和文献中报道的催化剂制备技术进行了论述总结。重点针对催化剂的关键制备参数以及对催化剂结构和异构化性能的影响进行了深入分析和探讨，包括氢氧化物前体的沉淀和焙烧条件、助剂的添加和改性作用、催化剂预处理条件和原料水含量的影响等。最后对催化剂开发和工业化中的难点给出了分析和建议，并展望了未来的催化剂发展方向，指出拓宽催化剂的原料适应性、发展新型制备技术和助剂体系、结合催化剂再生等工艺研究是未来的发展方向。

关键词: 轻质烷烃, 异构化, 催化剂, 制备, 工业应用

Abstract:

Sulfated zirconia solid acid (SO₄^2-/ZrO₂) provides the great potential as a new-generation catalyst for light paraffin isomerization, which combines the high catalytic activity, regenerability with the environmental-friendly character. The progresses of industrial application of light naphtha catalyzed by sulfated zirconia are summarized, including the current market situation, commercial technologies and technical economy. The research progresses on the catalyst preparation technologies reported in the patents and literature are also reviewed. The effects of crucial preparation parameters on their influences on the catalysts structure and isomerization performance are deeply discussed, including precipitation and calcination conditions of precursor, the addition and modification of promoters, pretreatment conditions of catalysts and influence of water content of raw materials. Finally, the challenges of catalyst preparation and industrialization are analyzed and the corresponding suggestions are given. We also propose the future direction of the catalysts development, that is to broaden the adoption of raw materials, develop the new synthesis techniques and promoters, and the catalyst regeneration technology.

Key words: light paffafin, isomerization, catalyst, preparation, industrial application

中图分类号:

TQ426.6

王锐,阳雪,缪平. SO₄^2-/ZrO₂轻质烷烃异构化催化剂的制备和工业应用进展[J]. 化工进展, 2019, 38(11): 4930-4940.

Rui WANG,Xue YANG,Ping MIAO. Progress in preparation research and industrial application of SO₄^2-/ZrO₂catalysts for light paraffin isomerization[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 4930-4940.

图/表 6

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序号	装置	产能 /万吨	技术来源/工艺名称	年份	说明
1	宁夏宝塔化纤	26	UOP/Par-Isom	2015	合同签约
2	庆阳石化	20	UOP/Par-Isom	2017	工程建设
3	中石油克拉玛依	15	UOP/Par-Isom	2017	工程建设
4	山东金诚石化	25	UOP/Par-Isom	2017	工程竣工
5	山东汇丰石化集团	22	UOP/Par-Isom	2018	工程竣工
6	湛江东兴石油	18	中国石化石油化工科学研究院	2016	开车运行
7	恒力石化	50	GTC/Isomalk-2	2015	合同执行
8	山东诚信化工	42	GTC/Isomalk-2	2018	合同执行
9	山东利丰达生物科技	8	GTC/Isomalk-2	2018	合同执行
10	山东东方华龙工贸集团	33	GTC/Isomalk-2	2018	合同执行
11	利华益集团股份	22	UOP/Par-Isom	2017	试车运行
12	珠海市虹彩精细化工	20	UOP/Par-Isom	2018	环评公示

序号	装置	产能 /万吨	技术来源/工艺名称	年份	说明
1	宁夏宝塔化纤	26	UOP/Par-Isom	2015	合同签约
2	庆阳石化	20	UOP/Par-Isom	2017	工程建设
3	中石油克拉玛依	15	UOP/Par-Isom	2017	工程建设
4	山东金诚石化	25	UOP/Par-Isom	2017	工程竣工
5	山东汇丰石化集团	22	UOP/Par-Isom	2018	工程竣工
6	湛江东兴石油	18	中国石化石油化工科学研究院	2016	开车运行
7	恒力石化	50	GTC/Isomalk-2	2015	合同执行
8	山东诚信化工	42	GTC/Isomalk-2	2018	合同执行
9	山东利丰达生物科技	8	GTC/Isomalk-2	2018	合同执行
10	山东东方华龙工贸集团	33	GTC/Isomalk-2	2018	合同执行
11	利华益集团股份	22	UOP/Par-Isom	2017	试车运行
12	珠海市虹彩精细化工	20	UOP/Par-Isom	2018	环评公示

参数	Penex OT 氯化型	Par-Isom OT SO₄^2-/ZrO₂	Penex DIH 氯化型	Par-Isom DIH SO₄^2-/ZrO₂
原料流量/桶·天^-1	10000	10000	10000	10000
辛烷值	83.4	83.4	88.0	88.0
辛烷桶	81040	81040	84520	84500
总CAPEX/×10⁶USD	36.5	32.7	56.9	47.5
公用消耗	基础	基础×0.56	基础×1.82	基础×1.36

参数	Penex OT 氯化型	Par-Isom OT SO₄^2-/ZrO₂	Penex DIH 氯化型	Par-Isom DIH SO₄^2-/ZrO₂
原料流量/桶·天^-1	10000	10000	10000	10000
辛烷值	83.4	83.4	88.0	88.0
辛烷桶	81040	81040	84520	84500
总CAPEX/×10⁶USD	36.5	32.7	56.9	47.5
公用消耗	基础	基础×0.56	基础×1.82	基础×1.36

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SO₄^2-/ZrO₂轻质烷烃异构化催化剂的制备和工业应用进展

Progress in preparation research and industrial application of SO₄^2-/ZrO₂catalysts for light paraffin isomerization

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