固定床渣油加氢脱残炭催化剂的再生表征及性能评价

doi:10.16085/j.issn.1000-6613.2022-2206

化工进展 ›› 2023, Vol. 42 ›› Issue (10): 5200-5204.DOI: 10.16085/j.issn.1000-6613.2022-2206

固定床渣油加氢脱残炭催化剂的再生表征及性能评价

崔瑞利¹(), 程涛¹, 宋俊男¹(), 牛贵峰², 刘圆元³, 张涛¹, 赵愉生¹, 王路海¹

^1.中国石油石油化工研究院，北京 102206
^2.中国石油大连石化公司，辽宁大连 116023
^3.中国石油四川石化公司，四川彭州 611930

收稿日期:2022-11-29 修回日期:2023-03-09 出版日期:2023-10-15 发布日期:2023-11-11
通讯作者: 宋俊男
作者简介:崔瑞利（1983—），男，高级工程师，研究方向为渣油加氢技术开发与应用。E-mail：cuiruili@petrochina.com.cn。

Regeneration characterization and performance evaluation of the fixed-bed residue hydrotreating catalyst for microcarbon reduction

CUI Ruili¹(), CHENG Tao¹, SONG Junnan¹(), NIU Guifeng², LIU Yuanyuan³, ZHANG Tao¹, ZHAO Yusheng¹, WANG Luhai¹

^1.PetroChina Petrochemical Research Institute, Beijing 102206, China
^2.PetroChina Dalian Petrochemical Company, Dalian 116032, Liaoning, China
^3.PetroChina Sichuan Petrochemical Company, Pengzhou 611930, Sichuan, China

Received:2022-11-29 Revised:2023-03-09 Online:2023-10-15 Published:2023-11-11
Contact: SONG Junnan

摘要/Abstract

摘要：

利用BET、ICP、EPMA、TPR等分析手段对工业渣油加氢装置运转后脱残炭剂和再生剂进行了分析，并在中试装置上对运转后的催化剂和再生剂进行了活性评价。结果表明，运转后脱残炭催化剂沉积了一定量的积炭和一定量Ni、V，催化剂孔容、比表面积大幅减小。经过再生，积炭得到了有效烧除，再生剂孔容、比表面积分别恢复至新鲜剂87%、84%左右，H₂还原温度比新鲜剂提高了60℃左右，脱硫、脱残炭、脱金属（Ni+V）活性分别恢复至新鲜剂的72.2%、84.1%、86.4%。今后需开发新的技术去除沉积的金属，以进一步恢复催化剂孔道结构，提高再生剂的脱杂质活性。

关键词: 固定床, 渣油加氢, 催化剂, 失活, 再生, 脱残炭

Abstract:

The spent catalyst for microcarbon reduction from the industrial residue hydrotreating unit and the regenerated catalyst were characterized by means of BET, ICP, EPMA, TPR and other analysis methods, and their activities were evaluated on a pilot plant. The results showed that, carbon, Ni and V were deposited on the spent catalyst, and the pore volume and specific surface area decreased significantly. After regeneration, the carbon deposit was effectively burned off. The pore volume and specific surface area of the regenerant were respectively restored to about 87% and 84% of that of the freshener. The reduction temperature of H₂ was about 60℃ higher than that of the freshener. The desulfurization, microcarbon removal and Ni+V removal activities were respectively restored to 72.2%, 84.1% and 86.4% of those of the freshener. New technologies need to be developed to remove the deposited metal, so as to further restore the catalyst pore structure and improve the activity of the regenerant.

Key words: fixed-bed, residue hydrotreating, catalyst, deactivation, regeneration, microcarbon reduction

中图分类号:

TE624

崔瑞利, 程涛, 宋俊男, 牛贵峰, 刘圆元, 张涛, 赵愉生, 王路海. 固定床渣油加氢脱残炭催化剂的再生表征及性能评价[J]. 化工进展, 2023, 42(10): 5200-5204.

CUI Ruili, CHENG Tao, SONG Junnan, NIU Guifeng, LIU Yuanyuan, ZHANG Tao, ZHAO Yusheng, WANG Luhai. Regeneration characterization and performance evaluation of the fixed-bed residue hydrotreating catalyst for microcarbon reduction[J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5200-5204.

图/表 8

参考文献 14

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参数	数值
密度（20℃）/g·cm^-3	0.9692
S质量分数/%	1.79
N质量分数/%	0.35
MCR质量分数/%	11.61
（Ni+V）/μg·g^-1	56.11

参数	数值
密度（20℃）/g·cm^-3	0.9692
S质量分数/%	1.79
N质量分数/%	0.35
MCR质量分数/%	11.61
（Ni+V）/μg·g^-1	56.11

催化剂	杂质沉积量/g·(100g新鲜剂)^-1
催化剂	C	Ni^①	V	Fe	Ca
新鲜剂	0	0	0	0	0
HDMCR-1	17.3	3.48	3.92	0.91	0.18
HDMCR-2	18.4	1.54	1.37	0.35	0.10
HDMCR-3	21.5	1.21	1.19	0.40	0.10

催化剂	杂质沉积量/g·(100g新鲜剂)^-1
催化剂	C	Ni^①	V	Fe	Ca
新鲜剂	0	0	0	0	0
HDMCR-1	17.3	3.48	3.92	0.91	0.18
HDMCR-2	18.4	1.54	1.37	0.35	0.10
HDMCR-3	21.5	1.21	1.19	0.40	0.10

运转后催化剂	孔容损失/%	比表面积减小/%	孔径减小/%
HDMCR-1	46.3	38.2	15.4
HDMCR-2	46.3	38.7	15.4
HDMCR-3	50.0	44.7	16.7

固定床渣油加氢脱残炭催化剂的再生表征及性能评价

Regeneration characterization and performance evaluation of the fixed-bed residue hydrotreating catalyst for microcarbon reduction

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参考文献 14

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Metrics

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再生剂	孔径恢复比例/%
再生剂	孔容	比表面积	可几孔径
HDMCR-1r	86.8	83.7	99.2
HDMCR-2r	87.3	84.9	99.5
HDMCR-3r	87.4	83.0	99.6

催化剂	相对杂质脱除率/%
催化剂	脱硫活性	脱残炭活性	脱金属（Ni+V）活性
新鲜剂	100	100	100
运转后催化剂	66.7	75.0	55.6
再生剂	72.2	84.1	86.4

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催化剂牌号	炭质量分数/%
HDMCR-1r	0.15
HDMCR-2r	0.34
HDMCR-3r	0.14

催化剂牌号	炭质量分数/%
HDMCR-1r	0.15
HDMCR-2r	0.34
HDMCR-3r	0.14

催化剂	H₂还原温度/℃
HDMCR-1r	+57
HDMCR-2r	+56
HDMCR-3r	+65
新鲜剂	基准

催化剂	H₂还原温度/℃
HDMCR-1r	+57
HDMCR-2r	+56
HDMCR-3r	+65
新鲜剂	基准