固定床渣油加氢脱残炭剂的深度再生

doi:10.16085/j.issn.1000-6613.2024-0137

摘要/Abstract

摘要：

分别通过焙烧、酸洗和浸渍等方式逐步再生固定床渣油加氢运行后的脱残炭剂，使再生剂的物性和活性最大程度接近新鲜剂水平。在最优焙烧条件下去除积炭，使再生剂孔容和比表面积分别恢复到新鲜剂的90.4%和89.4%，NiO沉积量为1.17%，V₂O₅沉积量为2.56%；在最优酸洗条件下去除沉积的金属杂质，恢复孔结构，金属杂质V₂O₅质量分数降至1.03%，NiO含量恢复至新鲜剂水平，但是活性金属MoO₃损失4.16%；采用等体积浸渍法补充MoO₃，使再生剂的MoO₃含量与新鲜剂基本相同，同时再生剂的比表面积和孔容分别恢复至新鲜剂的102.6%和107.7%。通过X射线衍射（XRD）检测确定再生剂的物相与新鲜剂基本相同，通过H₂-TPR（温度程序还原）检测发现再生剂的还原温度较新鲜剂升高，通过NH₃-TPD（温度程序脱附）检测发现再生剂的酸性比新鲜剂强，通过高分辨透射电子显微镜（HRTEM）分析发现再生剂的MoS₂片晶较新鲜剂增长且层数变少；采用高压釜对催化剂初活性进行对比评价，再生剂的脱金属活性、脱硫活性和脱残炭活性分别为新鲜剂的99.9%、91.0%和106.6%；采用固定床对催化剂稳定性进行对比评价，显示再生剂的稳定性与新鲜剂基本相当。

关键词: 固定床, 渣油加氢, 脱残炭剂, 失活, 再生

Abstract:

This paper gradually regenerates the spent HDCCR catalyst through calcination, acid washing, and impregnation, so that the physical properties and activity of the regenerant are as close as possible to the level of fresh catalyst. Under the optimal roasting conditions, carbon deposition was removed, resulting in the recovery of the pore volume and the surface area of the regenerant to 90.4% and 89.4% of those of the fresh catalyst, respectively; the deposition of NiO was 1.17%, and the deposition of V₂O₅ was 2.56%. Under the optimal acid washing conditions, the deposited metal impurities were removed to restore the pore structure; the content of metal impurities V₂O₅ reached 1.03%, NiO content restored to that of fresh catalyst, but the active metal MoO₃ lost 4.16%. The active metals were supplemented using equal volume impregnation method, making the active metal content of the regenerant basically the same as that of the fresh catalyst, while restoring the specific surface area and pore volume of the regenerant to 102.6% and 107.7% of the fresh catalyst, respectively. Through XRD detection, it was determined that the phase of the regenerant was basically the same as that of the fresh catalyst. Through H₂-TPR detection, it was found that the reduction temperature of the regenerant was higher than that of the fresh catalyst. NH₃-TPD detection showed the acidity of the regenerant was stronger than that of the fresh catalyst. Through HRTEM analysis, it was found that the MoS₂ crystal of the regenerant was longer and the number of layers decreased compared to the fresh catalyst. The initial activity of the regenerant was evaluated by a high-pressure reactor, and it was found that the demetallization activity, desulfurization activity, and residual carbon removal activity of the regenerant were 99.9%, 91.0%, and 106.6% of those of the fresh catalyst, respectively. The stability of the regenerant was evaluated by a fixed bed, and it was found that the stability of the regenerant was equivalent to that of the fresh catalyst.

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

中图分类号:

TE624

苏良健, 肖俊岩, 张春光, 赵元生, 杨旭. 固定床渣油加氢脱残炭剂的深度再生[J]. 化工进展, 2025, 44(2): 728-734.

SU Liangjian, XIAO Junyan, ZHANG Chunguang, ZHAO Yuansheng, YANG Xu. Deep regeneration of fixed-bed HDCCR catalyst[J]. Chemical Industry and Engineering Progress, 2025, 44(2): 728-734.

图/表 10

参考文献 16

1	严吉国, 邓强. 渣油加氢技术应用现状及发展前景[J]. 化工设计通讯, 2018, 44(12): 81.
	YAN Jiguo, DENG Qiang. Application status and development prospect of residue hydrotreating technology[J]. Chemical Engineering Design Communications, 2018, 44(12): 81.
2	宋官龙, 赵德智, 张志伟, 等. 渣油加氢工艺的现状及研究前景[J]. 石化技术, 2017, 24(7): 1-3, 7.
	SONG Guanlong, ZHAO Dezhi, ZHANG Zhiwei, et al. Current situation and research prospect of residue hydrogenation technology[J]. Petrochemical Industry Technology, 2017, 24(7): 1-3, 7.
3	廖有贵, 薛金召, 肖雪洋, 等. 固定床渣油加氢处理技术应用现状及进展[J]. 石油化工, 2018, 47(9): 1020-1030.
	LIAO Yougui, XUE Jinzhao, XIAO Xueyang, et al. Application situation and progress of fixed-bed residue hydrotreating technology[J]. Petrochemical Technology, 2018, 47(9): 1020-1030.
4	姚远, 张涛, 于双林, 等. 渣油加氢技术进展与发展趋势[J]. 工业催化, 2021, 29(2): 24-27.
	YAO Yuan, ZHANG Tao, YU Shuanglin, et al. Development and application trend of residuum hydroprocessing technologies[J]. Industrial Catalysis, 2021, 29(2): 24-27.
5	Victor GARCIA-MONTOTO, VERDIER Sylvain, MAROUN Zeina, et al. Understanding the removal of V, Ni and S in crude oil atmospheric residue hydrodemetallization and hydrodesulfurization[J]. Fuel Processing Technology, 2020, 201: 106341.
6	MARAFI A, STAINSLAUS A, HAUSER A, et al. An investigation of the deactivation behavior of industrial Mo/Al₂O₃ and Ni-Mo/Al₂O₃ catalysts in hydrotreating kuwait atmospheric residue[J]. Petroleum Science and Technology, 2005, 23(3/4): 385-408.
7	JURADO Javier, ANCHEYTA Jorge. Reactor model for heavy oil hydrotreating with catalyst deactivation based on vanadium and coke deposition[J]. Energy & Fuels, 2022, 36(18): 11132-11141.
8	ROCHA NOVAES Leandro DA, PACHECO Marcelo Edral, SALIM Vera Maria Martins, et al. Accelerated deactivation studies of hydrotreating catalysts in pilot unit[J]. Applied Catalysis A: General, 2017, 548: 114-121.
9	ZHANG Di, LIU Yunqing, HU Qizhao, et al. Sustainable recovery of nickel, molybdenum, and vanadium from spent hydroprocessing catalysts by an integrated selective route[J]. Journal of Cleaner Production, 2020, 252: 119763.
10	王振, 杨清河, 胡大为, 等. 柴油加氢废催化剂再生后梯级应用于渣油加氢脱硫反应的研究[J]. 石油炼制与化工, 2023, 54(5): 36-41.
	WANG Zhen, YANG Qinghe, HU Dawei, et al. Study on regeneration of spent diesel hydrogenation catalyst and its application in residue hydrodesulfurization[J]. Petroleum Processing and Petrochemicals, 2023, 54(5): 36-41.
11	隋宝宽, 刘文洁, 王刚, 等. Ni和Co物种对渣油加氢脱金属催化剂性能的影响[J]. 石油化工, 2022, 51(10): 1161-1166.
	SUI Baokuan, LIU Wenjie, WANG Gang, et al. Effect of Ni and Co species on the performance of catalysts in residue hydrodemetallization[J]. Petrochemical Technology, 2022, 51(10): 1161-1166.
12	程涛, 崔瑞利, 宋俊男, 等. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
	CHENG Tao, CUI Ruili, SONG Junnan, et al. Analysis of impurity deposition and pressure drop increase mechanisms in residue hydrotreating unit[J]. Chemical Industry and Engineering Progress,2023, 42(9): 4616-4627.
13	ZHANG Cen, BRORSON Michael, LI Ping, et al. CoMo/Al₂O₃ catalysts prepared by tailoring the surface properties of alumina for highly selective hydrodesulfurization of FCC gasoline[J]. Applied Catalysis A: General, 2019, 570: 84-95.
14	LIANG Jilei, WU Mengmeng, WEI Pinghe, et al. Efficient hydrodesulfurization catalysts derived from strandberg P-Mo-Ni polyoxometalates[J]. Journal of Catalysis, 2018, 358: 155-167.
15	郑爱国. 加氢催化剂的透射电子显微研究[J]. 石油学报(石油加工), 2014, 30(4): 707-711.
	ZHENG Aiguo. TEM studies of hydrotreating catalyst[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2014, 30(4): 707-711.
16	MAITY S K, ANCHEYTA J, ALONSO F, et al. Hydrodesulfurization activity of used hydrotreating catalysts[J]. Fuel Processing Technology, 2013, 106: 453-459.

编辑推荐 0

Metrics

阅读次数

全文

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	1	0	0	11

来源	本网站	其他网站

次数	10	2
比例	83%	17%

摘要

最新录用	在线预览	正式出版

0	0	32

来源	本网站	其他网站

次数	7	25
比例	22%	78%

样品	Al₂O₃/%	NiO/%	MoO₃/%	P₂O₅/%	V₂O₅/%	C/%
FJ	基准A	基准B+1.17	基准C-0.98	基准D-0.73	2.56	21.5
FJ-500	基准A	基准B+1.17	基准C-0.98	基准D-0.73	2.56	0
CSJ	基准A	基准B+0.04	基准C-4.16	基准D-0.73	1.03	0
ZSJ	基准A	基准B+0.04	基准C+0.05	基准D-0.73	0.92	0
XXJ	基准A	基准B	基准C	基准D	0	0

样品	Al₂O₃/%	NiO/%	MoO₃/%	P₂O₅/%	V₂O₅/%	C/%
FJ	基准A	基准B+1.17	基准C-0.98	基准D-0.73	2.56	21.5
FJ-500	基准A	基准B+1.17	基准C-0.98	基准D-0.73	2.56	0
CSJ	基准A	基准B+0.04	基准C-4.16	基准D-0.73	1.03	0
ZSJ	基准A	基准B+0.04	基准C+0.05	基准D-0.73	0.92	0
XXJ	基准A	基准B	基准C	基准D	0	0

样品	比表面积 /m²·g^-1	孔容 /cm³·g^-1	可几孔径 /nm	颗粒强度 /N·mm^-1
FJ	107.5	0.17	3.8	34.1
FJ-500	173.8	0.47	7.8	34.4
CSJ	191.1	0.53	7.8	29.0
ZSJ	199.5	0.56	7.8	33.9
XXJ	194.4	0.52	7.8	34.9

样品	比表面积 /m²·g^-1	孔容 /cm³·g^-1	可几孔径 /nm	颗粒强度 /N·mm^-1
FJ	107.5	0.17	3.8	34.1
FJ-500	173.8	0.47	7.8	34.4
CSJ	191.1	0.53	7.8	29.0
ZSJ	199.5	0.56	7.8	33.9
XXJ	194.4	0.52	7.8	34.9

样品	弱酸量 /cm³·g^-1	中强酸量 /cm³·g^-1	强酸量 /cm³·g^-1	总酸量 /cm³·g^-1	弱酸占比/%	中强酸占比/%	强酸占比/%
FJ-500	29.1	4.9	140.9	174.9	16.6	2.8	80.6
CSJ	30.4	9.5	35.0	74.9	40.6	12.7	46.7
ZSJ	45.9	15.5	22.5	83.9	54.7	18.5	26.8
XXJ	40.4	11.8	47.8	100.0	40.4	11.8	47.8