俄罗斯渣油加氢处理技术开发与工业应用

doi:10.16085/j.issn.1000-6613.2022-0179

摘要/Abstract

摘要：

俄罗斯是我国最大原油供应国之一，俄罗斯渣油中硫、氮、残炭、金属含量均较高，无法直接进入催化裂化装置加工，需要进行渣油加氢处理。本文利用核磁、傅里叶变换高分辨质谱等技术手段对俄罗斯渣油分子结构进行了详细表征，并根据其性质和分子结构特点，对PHR系列催化剂及级配进行适应性优化改进，开发形成了俄罗斯渣油加氢处理技术。工业应用结果表明，开发的俄罗斯渣油加氢处理技术具有非常出色的原料适应性和活性稳定性，能够实现俄罗斯渣油中S、N、Ni、V深度脱除和残炭深度转化，催化剂运行时间达到19416h，1t催化剂加工处理原料油达到6000t，均比设计值高62%。通过分析加氢渣油中未被脱除的氮化物分子形态，提出了实现技术持续优化改进的方向。

关键词: 俄罗斯渣油, PHR系列催化剂, 加氢处理, 加氢脱氮

Abstract:

The sulfur, nitrogen, residual carbon and metal contents of Russian residue are higher than the feed requirements of catalytic cracking unit, so hydrotreating is required. The molecular structure of Russian residue was characterized by FT-ICR, MS and NMR. PHR series catalysts and their grading were optimized according to the characterized properties and molecular structure of Russian residue, and the Russian residue hydrotreating technology was then developed. The commercial application has realized the deep removal of S, N, Ni and V and the deep conversion of carbon residue in Russian residue. The catalyst running time reaches 19416h, and the processing of feed oil reaches 6000 tons per ton catalyst, both 62% higher than the design value. Through analyzing the molecular morphology of remaining nitrides in the hydrogenated residue, we proposed the future technical optimization and improvement direction.

Key words: Russia residue, PHR series catalyst, hydrogenation, hydrodenitrogenation

中图分类号:

TE624

赵愉生, 崔瑞利, 牛贵峰, 赵元生, 程涛, 何盛宝, 宋俊男, 张霖宙. 俄罗斯渣油加氢处理技术开发与工业应用[J]. 化工进展, 2022, 41(7): 3582-3588.

ZHAO Yusheng, CUI Ruili, NIU Guifeng, ZHAO Yuansheng, CHENG Tao, HE Shengbao, SONG Junnan, ZHANG Linzhou. Development and commercial application of Russian residue hydrotreating technology[J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3582-3588.

图/表 13

参考文献 17

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参数	俄罗斯渣油	沙轻渣油
密度（20℃）/g·cm^-3	0.9662	0.9752
平均分子量	770	647
S（质量分数）/%	1.04	3.46
N（质量分数）/%	0.42	0.26
C（质量分数）/%	86.23	85.02
H（质量分数）/%	11.53	11.12
MCR（质量分数）/%	10.62	13.05
Ni/μg·g^-1	17.28	20.24
V/μg·g^-1	22.77	37.35
MCR/S值	10.21	3.77
Ni/V值	0.76	0.54

参数	俄罗斯渣油	沙轻渣油
密度（20℃）/g·cm^-3	0.9662	0.9752
平均分子量	770	647
S（质量分数）/%	1.04	3.46
N（质量分数）/%	0.42	0.26
C（质量分数）/%	86.23	85.02
H（质量分数）/%	11.53	11.12
MCR（质量分数）/%	10.62	13.05
Ni/μg·g^-1	17.28	20.24
V/μg·g^-1	22.77	37.35
MCR/S值	10.21	3.77
Ni/V值	0.76	0.54

项目	俄罗斯渣油	沙轻渣油
与芳碳直接相连的氢个数（H_A）	10.04	7.47
与芳环α碳相连的氢个数（H _α ）	16.92	11.69
芳环β位及β位以远的CH₂、CH₃上的	63.91	70.4
氢个数（H _β ）
芳环γ位及γ位以远的CH₃上的氢个数（H _γ ）	9.13	10.44
芳碳率f_a	0.26	0.27
环烷碳率f_n	0.01	0.11
链烷碳率f_p	0.72	0.62
烷基侧链平均碳链长度（AV_L）	14.8	13.3

项目	俄罗斯渣油	沙轻渣油
与芳碳直接相连的氢个数（H_A）	10.04	7.47
与芳环α碳相连的氢个数（H _α ）	16.92	11.69
芳环β位及β位以远的CH₂、CH₃上的	63.91	70.4
氢个数（H _β ）
芳环γ位及γ位以远的CH₃上的氢个数（H _γ ）	9.13	10.44
芳碳率f_a	0.26	0.27
环烷碳率f_n	0.01	0.11
链烷碳率f_p	0.72	0.62
烷基侧链平均碳链长度（AV_L）	14.8	13.3

催化剂	沙轻渣油	俄罗斯渣油
脱金属剂（体积分数）/%	基准	基准 - 8
脱硫剂（体积分数）/%	基准	基准 - 4
脱氮脱残炭剂（体积分数）/%	基准	基准 + 12