Development of PHR fix-bed residue hydrodemetallization catalysts

doi:10.16085/j.issn.1000-6613.2016.10.029

Abstract

Abstract: In order to solve the diffusion,reaction and deposition problems of high molecular materials such as asphaltenes and resins,and to improve the catalyst's activity and metal capacity during the process of residue hydrodemetallization,we developed a series of key technologies and 4 grades residue hydrodemetallization catalysts(PHR-101,PHR-102,PHR-103,PHR-104)by optimized catalyst design. Non-acidic binder was employed to replace the traditional acids to prepare alumina support with substantially increased pore volume and size. Dual-peak-pore-structure support,with 16.4% pore size above 1000nm,was obtained through compound pore expanding method to improve catalysts' pore structure. And non-uniform distribution of active metal components was achieved to promote impurities to diffuse to and deposit on internal catalyst whose active-site distribution was refined. The results of a 2000h test on small-scale device showed that catalysts' activity and stability after removing the impurities(metal,sulfur,carbon residue)were significantly higher than that of conventional catalysts. A 1L-scale Pilot test,with 5500h long period running under the industrial operating conditions and products requirements,indicated that the prospective running life of catalysts reached more than 8000h which totally satisfied the industrial application requirement. A 14 months industrial hanging-basket test was carried out and the results showed that,compared with the commercial atalysts,the developed catalysts exhibited higher metal capacity and more uniform metal deposition.

Key words: residue hydrotreating, catalyst, diffusion, support, stability

摘要： 为有效解决渣油加氢脱金属过程中沥青质和胶质等大分子物质的扩散、反应和沉积难题，提高催化剂脱杂质活性和容金属能力，对催化剂设计进行了优化集成，开发出了一系列催化剂制备关键技术，研制成功4个牌号的脱金属催化剂（PHR-101、PHR-102、PHR-103、PHR-104）。以非酸性的黏结剂代替胶溶酸实现氧化铝的无酸成型，大幅提高了载体孔容和孔径；采用复合扩孔方法制备出双峰孔结构载体，大于1000nm孔比例达到16.4%，改善了催化剂孔道结构；实现活性金属组分的非均匀负载，优化活性分布，促进杂质向催化剂内部的扩散和沉积。小型装置2000h评价结果表明，催化剂脱杂质（脱金属、脱硫、脱残炭）活性与稳定性明显高于常规催化剂。模拟工业运转条件下，在1L中型装置上进行了5500h长周期试验，结果表明，加氢全馏分产品金属含量满足指标要求，催化剂预期寿命达到8000h以上，满足工业应用要求。14个月的挂篮试验表明，与工业催化剂相比，所开发催化剂的金属容纳能力更高，金属沉积更为均匀。

关键词: 渣油加氢, 催化剂, 扩散, 载体, 稳定性

CLC Number:

TE624

CHENG Tao, ZHAO Yusheng, TAN Qingfeng, CUI Ruili. Development of PHR fix-bed residue hydrodemetallization catalysts[J]. Chemical Industry and Engineering Progree, 2016, 35(10): 3219-3225.

程涛, 赵愉生, 谭青峰, 崔瑞利. PHR系列固定床渣油加氢脱金属催化剂的研制[J]. 化工进展, 2016, 35(10): 3219-3225.

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