渣油加氢装置杂质沉积规律与压降升高机理分析

doi:10.16085/j.issn.1000-6613.2022-1963

摘要/Abstract

摘要：

反应器压降升高是影响固定床渣油加氢装置长周期运行的重要因素。选取三套加工不同典型原料的工业渣油加氢装置，分析不同位置不同种类运转后催化剂的杂质沉积和孔结构变化情况，采用扫描电子显微镜-二维元素分析方法对结块催化剂杂质沉积分布进行原位表征，获得渣油加氢装置杂质沉积规律。结合装置原料性质和运行工况，对反应器压降升高机理进行分析。结果表明，长周期运行过程中，前部反应器催化剂大量沉积金属杂质，积炭严重，催化剂孔结构发生显著变化；同时，在催化剂颗粒间隙沉积大量焦炭或含铁垢物，造成床层堵塞。Ni、V主要沉积在催化剂颗粒内部，Fe、Ca则沉积在催化剂颗粒之间或附着在催化剂外表面，结块催化剂颗粒间隙填堵大量焦炭。反应器压降升高遵循两种不同的机理或路径。原料Fe、Ca含量较低时，反应器下部脱金属催化剂因沉积金属Ni、V而失活，进而在催化剂颗粒之间形成大量积炭，导致床层板结、压降上升；原料Fe、Ca含量高时，Fe、Ca在床层上部保护剂颗粒间大量沉积，导致反应器堵塞，压降升高。在严格控制进料Fe、Ca含量的同时，还应针对性优化催化剂及其级配设计，延长运转周期。

关键词: 渣油加氢, 固定床, 反应器压降, 催化剂, 失活

Abstract:

The increase of reactor pressure drop is an important factor affecting the long-term operation of industrial residue hydrotreating unit. Three sets of industrial residue hydrotreating units processing different typical raw materials were selected to analyze the impurity deposition and pore structure changes at different locations of the catalysts after operation. The SEM-EDS Mapping method was used to in situ characterize the impurity deposition distribution of agglomerated catalysts, and the impurity deposition rules were obtained. The rise mechanism of reactor pressure drop was analyzed based on the properties of the raw materials and the operating conditions. The results showed that a large number of metal impurities and carbon deposits were deposited on the catalysts in the front of the reactor during the long period operation, and the pore structure of the catalysts changed significantly. At the same time, a large amount of coke or iron containing scale was deposited in the gap between catalyst particles, causing bed plugging. Ni and V were mainly deposited within the catalyst particles, while Fe and Ca were deposited between catalyst particles or attached to the external surface of the catalysts, and a large amount of coke was filled in the gap of caked catalyst particles. The increase of reactor pressure drop followed two different mechanisms. When the content of Fe and Ca in the raw materials was low, the demetallization catalyst at the lower part of the reactor would be deactivated due to the deposition of metal Ni and V, and thus formed a large amount of coke between catalyst particles, resulting in bed hardening and pressure drop increase. When the content of Fe and Ca in the raw materials was high, a large amount of Fe and Ca would deposit among the guard catalyst particles at the upper part of the bed, which led to reactor blockage and high pressure drop. Therefore, controlling the content of Fe and Ca in the feed should be strictly controlled, and the design and grading of the catalysts should also be optimized to extend the operating time.

Key words: residue hydrotreating, fixed bed, reactor pressure drop, catalyst, deactivation

中图分类号:

TE624

程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 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, ZHANG Tianqi, ZHANG Yunhe, LIANG Shijie, PU Shi. Analysis of impurity deposition and pressure drop increase mechanisms in residue hydrotreating unit[J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4616-4627.

图/表 21

图1 三套装置反应器压降随运行时间的变化

表1 装置原料平均性质对比

项目	装置A	装置B	装置C
密度/g·cm^-3	0.955	0.944	0.969
黏度（100℃）/mm²·S^-1	98.0	46.9	67.3
S（质量分数）/%	1.28	1.12	3.15
N（质量分数）/%	0.34	0.33	0.24
MCR（质量分数）/%	9.3	10.1	10.9
(Ni+V)/μg·g^-1	34.5	35.8	61.5
Fe/μg·g^-1	7.4	28.1	7.7
Ca/μg·g^-1	—	11.3	—

图2 装置B原料油及加氢渣油Fe、Ca含量

图3 装置A运转后催化剂剖析结果（床层位置指取样位置在全部催化剂床层的相对位置，第一反应器入口处为0，末反应器出口处为1）

图4 装置A一反脱金属剂运转前后孔径分布对比

图5 装置A一反结块催化剂SEM-EDS Mapping图像

图6 装置A二反结块催化剂SEM-EDS Mapping图像

图7 一反和二反床层焦粉组成

图8 装置A一反催化剂颗粒间焦粉微观形貌

表2 装置B一反催化剂剖析结果

催化剂	空高 /mm	杂质沉积量/g·(100g新鲜剂)^-1				孔体积损失 /%
催化剂	空高 /mm	Ni+V	Fe	Ca	C	孔体积损失 /%
HG-1	350	0.4	2.6	0.5	0.5	—
HG-2	700	1.6	1.7	0.3	1.1	—
HDM-1	1700	20.3	3.7	0.5	35.0	53.8
HDM-2	4000	34.7	6.4	0.9	30.8	56.2
HDM-3-1	7000	40.6	5.6	0.6	25.4	52.2
HDM-3-2	12000	33.8	3.9	0.5	27.8	46.1

图9 装置B一反HDM-2 SEM-EDS Mapping 图像

图10 装置B催化剂焦粉含量分布

图11 装置B一反焦粉样品C、S含量分布

图12 装置B一反焦粉样品元素组成

图13 装置B一反催化剂颗粒间焦粉微观形貌

图14 装置C运转后催化剂剖析结果

图15 装置C一反结块催化剂SEM-EDS Mapping图像

图16 不同运转时间脱金属催化剂积炭量和孔体积损失率

图17 装置A原料和加氢渣油Fe含量

图18 装置C原料和产品Fe含量

表3 装置B两列装置一反催化剂装填对比

催化剂粒径/mm	装填比例/%
催化剂粒径/mm	Ⅰ列	Ⅱ列
≥5.0	17.7	5.0
2.0~5.0	21.8	16.2

参考文献 19

1	方向晨. 国内外渣油加氢处理技术发展现状及分析[J]. 化工进展, 2011, 30(1): 95-104.
	FANG Xiangchen. Development of residuum hydroprocessing technologies[J]. Chemical Industry and Engineering Progress, 2011, 30(1): 95-104.
2	钟英竹, 靳爱民. 渣油加工技术现状及发展趋势[J]. 石油学报(石油加工), 2015, 31(2): 436-443.
	ZHONG Yingzhu, JIN Aimin. Present situation and progresses of residue processing technology[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2015, 31(2): 436-443.
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	李大东, 聂红, 孙丽丽. 加氢处理工艺与工程[M]. 2版. 北京: 中国石化出版社, 2016: 1276-1287.
	LI Dadong, NIE Hong, SUN Lili. Hydrotreating process and engineering[M]. 2nd ed. Beijing: China Petrochemical Press, 2016: 1276-1287.
5	邱开辉. 渣油加氢反应器床层压降升高原因及应对措施[J]. 化工管理, 2020(9): 157-158.
	QIU Kaihui. Causes and countermeasures of pressure drop rise in residue hydrogenation reactor bed[J]. Chemical Enterprise Management, 2020(9): 157-158.
6	杨刚, 隋宝宽, 张成, 等. Fe在固定床渣油加氢处理装置中的沉积及对装置操作的影响[J]. 当代化工, 2017, 46(7): 1326-1328, 1332.
	YANG Gang, SUI Baokuan, ZHANG Cheng, et al. Deposition of Fe in fixed bed residue hydrotreating unit and its effect on unit operation[J]. Contemporary Chemical Industry, 2017, 46(7): 1326-1328, 1332.
7	SUN Yudong, WANG Xue, WEI Cheng, et al. Research for structure and composition of coke on spent commercial residue hydrotreating catalysts along HDM bed[J]. Journal of Fuel Chemistry and Technology, 2019, 47(2): 167-173.
8	孙淑玲, 刁玉霞, 张进, 等. 组合SEM技术在渣油加氢失活催化剂表征中的应用[J]. 石油炼制与化工, 2015, 46(4): 97-102.
	SUN Shuling, DIAO Yuxia, ZHANG Jin, et al. Characterization of spent residue hydroprocessing catalyst by combined SEM techniques[J]. Petroleum Processing and Petrochemicals, 2015, 46(4): 97-102.
9	宋宇, 辛靖, 尉琳琳, 等. 工业渣油加氢失活催化剂上沉积金属及积炭研究[J]. 石油炼制与化工, 2021, 52(4): 33-44.
	SONG Yu, XIN Jing, WEI Linlin, et al. Study of coke and metallic impurities deposition on spent residue hydrotreating catalysts in industrial plant[J]. Petroleum Processing and Petrochemicals, 2021, 52(4): 33-44.
10	VOGELAAR Bas M, EIJSBOUTS Sonja, BERGWERFF Jaap A, et al. Hydroprocessing catalyst deactivation in commercial practice[J]. Catalysis Today, 2010, 154(3/4): 256-263.
11	邵志才, 贾燕子, 戴立顺, 等. 高铁钙原料渣油加氢装置长周期运行的工业实践[J]. 石油炼制与化工, 2015, 46(9): 20-23.
	SHAO Zhicai, JIA Yanzi, DAI Lishun, et al. Industrial practice of long-term running of hydroprocessing residue with high Fe and Ca content[J]. Petroleum Processing and Petrochemicals, 2015, 46(9): 20-23.
12	RANA Mohan S, ANCHEYTA J, SAHOO Sangram K, et al. Carbon and metal deposition during the hydroprocessing of Maya crude oil[J]. Catalysis Today, 2014, 220/221/222: 97-105.
13	赵愉生, 崔瑞利, 牛贵峰, 等. 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, et al. Development and commercial application of Russian residue hydrotreating technology[J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3582-3588.
14	郭大光, 戴立顺. 工业装置渣油加氢脱金属催化剂结块成因的探讨[J]. 石油炼制与化工, 2003, 34(4): 47-49.
	GUO Daguang, DAI Lishun. Discussion on agglomeration of commercial residue HDM catalyst[J]. Petroleum Processing and Petrochemicals, 2003, 34(4): 47-49.
15	孙谦, 杨清河, 聂红, 等. 工业固定床渣油加氢装置卸出剂颗粒间焦炭结构与组成[J]. 工业催化, 2021, 29(8): 50-55.
	SUN Qian, YANG Qinghe, NIE Hong, et al. Structureand composition of intergranular coke between spent catalyst of commercial fixed-bed residue hydrotreating unit[J]. Industrial Catalysis, 2021, 29(8): 50-55.
16	HAUSER Andre, STANISLAUS Anthony, MARAFI Abdulazem, et al. Initial coke deposition on hydrotreating catalysts. Part Ⅱ. Structure elucidation of initial coke on hydrodematallation catalysts[J]. Fuel, 2005, 84(2/3): 259-269.
17	王杰明, 徐茜, 邢丹静. 渣油中铁的形态分析方法研究[J]. 石油炼制与化工, 2018, 49(1): 79-82.
	WANG Jieming, XU Qian, XING Danjing. Determination of iron species in residuum[J]. Petroleum Processing and Petrochemicals, 2018, 49(1): 79-82.
18	孙谦, 杨清河, 韩伟, 等. FeS沉积量对渣油加氢过程中结焦行为及焦炭结构的影响[J]. 石油化工, 2021, 50(9): 899-904.
	SUN Qian, YANG Qinghe, HAN Wei, et al. Effects of FeS deposition on coking behavior and coke microstructure in residue hydrogenation process[J]. Petrochemical Technology, 2021, 50(9): 899-904.
19	谭青峰, 聂士新, 程涛, 等. PHR系列固定床渣油加氢催化剂的研制开发与工业应用[J]. 化工进展, 2018, 37(10): 3867-3872.
	TAN Qingfeng, NIE Shixin, CHENG Tao, et al. Development and application of PHR fixed-bed residue hydrotreating catalysts[J]. Chemical Industry and Engineering Progress, 2018, 37(10): 3867-3872.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	许家珩, 李永胜, 罗春欢, 苏庆泉. 甲醇水蒸气重整工艺的优化[J]. 化工进展, 2023, 42(S1): 41-46.
[6]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[7]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[8]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[9]	王晋刚, 张剑波, 唐雪娇, 刘金鹏, 鞠美庭. 机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展[J]. 化工进展, 2023, 42(9): 4636-4648.
[10]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[11]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[12]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[13]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[14]	向阳, 黄寻, 魏子栋. 电催化有机合成反应的活性和选择性调控研究进展[J]. 化工进展, 2023, 42(8): 4005-4014.
[15]	王耀刚, 韩子姗, 高嘉辰, 王新宇, 李思琪, 杨全红, 翁哲. 铜基催化剂电还原二氧化碳选择性的调控策略[J]. 化工进展, 2023, 42(8): 4043-4057.