催化裂化油浆固含量测定及组成分析

doi:10.16085/j.issn.1000-6613.2018-2220

摘要/Abstract

摘要：

采用灰分法、过滤法、离心法测量了某重油催化裂化装置外甩油浆的固体颗粒含量，对几种方法在固含量测定方面的结果差异进行对比分析。实验结果表明，离心法测量的固含量约为2850μg/g，介于灰分法和过滤法之间。离心法结果显示，油浆中重组分与细粉颗粒存在较强的吸附作用，分离中能否准确得到焦粉是造成结果差异的主要原因。离心法耦合后续焙烧能够分离获得油浆中一定量的催化剂细粉颗粒，通过激光粒度仪、元素分析仪、XRD、BET、SEM-EDS等手段对分离得到的固体颗粒以及初始FCC催化剂进行了表征。FCC催化剂粒径集中在32～120μm之间，为规则的球形分布，油浆中的固体颗粒呈不规则的块状分布，粒径在0.4～40μm之间，其中催化剂细粉的粒径在1～30μm之间；催化裂化油浆中的固体颗粒组成主要有催化剂细粉、焦粉和碱金属K、Ca、无机盐和金属元素Sb、Fe等。

关键词: 固含量, 测量, 粒度分布, 聚集, 颗粒组成

Abstract:

Ash analysis, filtration and centrifugation analysis were adopted to measure the content of solid particles in the FCC slurry oil from a residue fluid catalytic cracking (RFCC) unit in CNPC. The solid content measured by centrifugation method was about 2850μg/g, which was between those by the ash analysis and filtration methods. The centrifugation method results indicated that the strong adsorption between fine particles and the heavy components in the slurry oil was the key factor to obtain coke powder. Centrifugal method coupled with subsequent calcination could isolate and obtain certain amount of solid particles from the slurry oil. Then the solid particles and the original FCC catalyst were characterized by means of laser particle size analyzer, elemental analyzer, X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), scanning electron microscopy & energy spectrum analysis (SEM-EDS), etc. The fresh FCC catalyst was regular spherical and showed a size distribution in the range of 32－120μm, while the solid particles in the oil slurry were scattered and irregular with the particle size of 0.4－40μm, in which the fine catalysts were mostly between 1－30μm. The solid particles in FCC slurry oil mainly consisted of catalyst powder, coke powder, inorganic metal salts, such as alkali metal (K, Ca), antimony (Sb), and iron (Fe).

Key words: solid content, measurement, particle size distribution, aggregation, particle composition

中图分类号:

TE624.41

张亮,张玉明,张浩然,杨行,温宏炎,高士秋. 催化裂化油浆固含量测定及组成分析[J]. 化工进展, 2019, 38(9): 4052-4059.

Liang ZHANG,Yuming ZHANG,Haoran ZHANG,Hang YANG,Hongyan WEN,Shiqiu GAO. Determination and composition analysis of solid contentsin FCC slurry oil[J]. Chemical Industry and Engineering Progress, 2019, 38(9): 4052-4059.

图/表 10

图1 典型的原油加工及催化裂化油浆利用流程

图2 不同方法测量得到的固含量

图3 焙烧前后油浆中固体物的形貌

图4 FCC-C、FCC-S和FCC-M的粒度分布和筛下累计积分曲线

表1 FCC-C与FCC-S的BET分析对比

样品	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
FCC-C	112.28	0.03	9.65
FCC-S	15.18	0.0056	29.75

图5 FCC-C、FCC-S和FCC-M颗粒的XRD分析

图6 FCC-C、FCC-S和FCC-M的SEM分析

表2 FCC-C、FCC-M和FCC-S颗粒的C、H、N、S元素

样品	N/%	C/%	H/%	S/%
FCC-C	0.036	0.280	0.113	1.629
FCC-M	1.066	18.29	2.778	0.660
FCC-S	0.140	0.400	0.084	0.360

图7 FCC-S和FCC-M的EDS谱图和元素分布图

表3 FCC-M和FCC-S的EDS元素质量分数分析结果（单位：%）

样品	O	Al	Si	K	P	Fe	Ni	Sb	La
FCC-M	56.75	21.65	16.12	1.02	0.66	1.10	0.31	1.20	1.19
FCC-S	53.63	23.89	17.92	0.22	0.87	1.08	0.51	0.14	1.61

参考文献 24

1	王曼霞 . 催化裂化油浆分离工艺的研究[D]. 青岛: 青岛化工学院, 2000.
	WANG M X . Separation and utilization of aromatic hydrocarbons in FCC slurry oil[D]. Qingdao: Qingdao Institute of Chemical Industry, 2000.
2	赵晓隆, 李会鹏, 赵华, 等 . 两种催化油浆的热重反应动力学研究[J]. 石油与天然气化工, 2014, 43(4): 357-361.
	ZHAO X L , LI H P , ZHAO H , et al . Study on thermogravimetric reaction kinetics of two kinds of FCC slurry[J]. Petroleum and Natural Gas Chemical Industry, 2014, 43(4): 357-361.
3	魏淑珍 . 油综合利用[J]. 催化裂化, 1993, 2(2): 8-13.
	WEI S Z . Comprehensive utilization of oil[J]. FCC, 1993, 2(2): 8-13
4	张晓方, 卜亿峰, 门卓武 . 过滤技术在油浆分离中的应用[J]. 化工进展, 2016, 35(12): 3746-3754.
	ZHANG X F , BU Y F , MEN Z W . Application of filtration technology in slurry oil clarification[J]. Chemical Industry and Engineering Progress, 2016, 35(12): 3746-3754.
5	林秀丽, 卢春燕, 马诲桐, 等 . 催化裂化油浆综合利用的发展趋势[J]. 广东石油化工学院学报, 2011, 21(3): 8-11.
	LIN X L , LU C Y , MA H T, et al . Development for integrated utilization of FCC slurry oil[J]. Journal of Guangdong University of Petro-Chemical Technology, 2011, 21(3): 8-11.
6	李锋林, 韩忠祥, 孙昱东 . 催化裂化油浆的综合利用[J]. 山东化工, 2007(9): 6-9, 23.
	LI F L , HAN Z X , SUN Y D . Comprehensive utilization of FCC slurry[J]. Shandong Chemical, 2007(9): 6-9, 23.
7	郭爱军, 龚黎明, 赵娜, 等 . 添加剂改性对催化裂化油浆静电分离的影响[J]. 化工进展, 2017, 36(9): 3266-3272.
	GUO A J , GONG L M , ZHAO N , et al . The influence of additive modification on electrostatic separation of FCC slurry oil[J]. Chemical Industry and Engineering Progress, 2017, 36(9): 3266-3272.
8	鲍景波, 张险峰 . 重油催化裂化装置中油浆过滤系统的改进[J]. 化学工程师, 2006, 129(6): 45-46.
	BAO J B , ZHANG X F . Improvement of slurry oil filtration system in catalytic cracking heavy oil device[J]. Chemical Engineer, 2006, 129(6): 45-46.
9	常泽军, 刘熠斌, 杨朝合, 等 . 催化裂化油浆利用研究进展[J]. 炼油技术与工程, 2016, 46(8): 1-5.
	CHANG Z J , LIU Y B , YANG Z H , et al . Research progress of utilization of fluid catalytic cracking slurry[J]. Petroleum Refinery Engineering, 2016, 46(8): 1-5.
10	刘国荣, 左海强 . 关于催化裂化油浆固含量分析的几点见解[J]. 炼油技术与工程, 2005(9): 22-23.
	LIU G R , ZUO H Q . Analysis of sediment content in FCC slurry[J]. Refining Technology and Engineering, 2005(9): 22-23.
11	林存辉, 陈坤, 郭爱军, 等 . 催化裂化油浆固含量测定方法的研究[J]. 化工进展, 2016, 35(9): 2699-2706.
	LIN C H , CHEN K , GUO A J , et al . Study on determination methods of solids content in catalytic cracking slurry oil[J]. Chemical Industry and Engineering Progress, 2016, 35(9): 2699-2706.
12	边玲 . 油浆内颗粒测定及分离的研究[D]. 上海: 华东理工大学, 2011.
	BIAN L . Study on determination and separation of particles in slurry oil[D]. Shanghai: East China University of Science and Technology, 2011.
13	GUO A J , WEI Z X , ZHAO B , et al . Separation of toluene-insoluble solids in the slurry oil from a residual fluidized catalytic cracking unit: determination of the solid content and sequential selective separation of solid components[J]. Energy & Fuels, 2014, 28(5): 3053-3065.
14	赵娜, 于传瑞, 赵波, 等 . 静电分离催化裂化油浆中固体颗粒及其组成的研究[J]. 石油化工, 2015, 44(10): 1218-1223.
	ZHAO N , YU C R , ZHAO B , et al . Removing solid particles in FCC slurry by electrostatic separation and their composition[J]. Petrochemical Industry, 2015, 44(10): 1218-1223.
15	中国石油化工总公司 . 石油产品灰分测定法: GB/T 508—85[S]. 北京: 中国标准出版社, 1986.
	China National Petrochemical Corporation . Determination of ash content in petroleum products: GB/T 508—85[S]. Beijing: China Standard Press, 1986.
16	刘存柱, 李胜昌, 孙玉虎, 等 . 重油催化装化油浆连续过滤技术的应用[J]. 炼油设计, 200l, 31(1): 32-34.
	LIU C Z , LI S C , SUN Y H , et al . Application of continuous filtration technique for slurry from RFCCU[J]. Petroleum Refinery Engineering, 2001, 31(1): 32-34.
17	SONG X N , LIU D , LOU B , et al . Removal of catalyst particles from fluid catalytic cracking slurry oil by the simultaneous addition of a flocculants and a weighting agent[J]. Chemical Engineering Research and Design, 2018, 132(4): 686-696.
18	周复昌 . 应用催化剂颗粒显微观察诊断FCC装置操作. 中国石油和石化工程研究会. 第二届全国炼油化工工程技术与装备发展研讨会论文集[C]. 中国石油和石化工程研究会: 中国石油和石化工程研会, 2013: 9.
	ZHOU F C . Application of catalyst particle microscopic observation to diagnose FCC plant operation. China petroleum and petrochemical engineering research association. Proceedings of the second national symposium on the development of petrochemical engineering technology and equipment[C]//China Petroleum and Petrochemical Engineering Research Association: China Petroleum and Petrochemical Engineering Research Association, 2013: 9.
19	蔺玉贵, 田松柏 . 催化裂化油浆及回炼油中固体物类型的分析[J]. 石油炼制与化工, 2012, 43(12): 83-86.
	LIN Y G , TIAN S B . Type of solid matter in FCC slurry oil and recycle stock[J]. Petroleum Refining and Chemical Industry, 2012, 43(12): 83-86.
20	罗辉, 常增明, 陈文龙, 等 . 催化裂化跑损催化剂的激光粒度及SEM分析[J]. 炼油技术与工程, 2009, 39(10): 53-56.
	LUO H , CHANG Z M , CHEN W L , et al . Study on catalyst loss in FCC by laser particle size and SEM analysis[J]. Refining Technology and Engineering, 2009, 39(10): 53-56.
21	ALVAREZ A G , MARTÍNEZ-ESCANDELL M , MOLINA-SABIO M , et al . Pyrolysis of petroleum residues: analysis of semi-cokes by X-ray diffraction[J]. Carbon, 1999, 37(10): 1627-1632.
22	徐春明, 杨朝合, 林世雄 . 石油炼制工程[M]. 北京: 石油工业出版社, 2009.
	XU C M , YANG Z H , LIN S X . Petroleum refining engineering[M]. Beijing: Petroleum Industry Press, 2009.
23	程爱珠, 陈宜俍, 张勤堂, 等 . 锑对FCC催化剂上镍的脱氢活性钝化机理的研究[J]. 郑州工学院学报, 1990(2): 86-91.
	CHENG A Z , CHEN Y L , ZHANG Q T , et al . Study on mechanism of passivation of dehydrogenation activity of nickel on FCC catalyst by passivation agent containing antimony[J]. Journal of Zhengzhou Institute of Technology, 1990(2): 86-91.
24	刘小鹏, 张永明, 王立成, 等 . 镧铈比对FCC催化剂性能的影响[J]. 硅酸盐通报, 2016, 35(2): 410-415.
	LIU X P , ZHANG Y M , WANG L C , et al . Effect of La-Ce ratio on the performance of FCC catalysts[J]. Bulletin of the Chinese Ceramic Society, 2016, 35(2): 410-415.

[1]	赵健, 卓泽文, 董航, 高文健. 含蜡原油及其乳状液体系微观结构观测的新方法[J]. 化工进展, 2023, 42(8): 4372-4384.
[2]	王兰江, 梁瑜, 汤琼, 唐明兴, 李学宽, 刘雷, 董晋湘. 快速热解铂前体合成高分散的Pt/HY催化剂及其萘深度加氢性能[J]. 化工进展, 2023, 42(8): 4159-4166.
[3]	吴展华, 盛敏. 绝热加速量热仪在反应安全风险评估应用中的常见问题[J]. 化工进展, 2023, 42(7): 3374-3382.
[4]	裴强, 胡文静, 聂丽珠, 史亚楠, 丁爱祥. 刺激响应性聚集诱导发光凝胶因子的设计、合成及性能[J]. 化工进展, 2023, 42(6): 3105-3113.
[5]	张芳, 郭鹍鹏, 梁春平, 尤雪瑞, 张志超. 一种具有聚集诱导发光效应有机荧光小分子的设计合成及功能应用[J]. 化工进展, 2023, 42(6): 3097-3104.
[6]	吴霞, 蒋勋涛, 张余晓, 吕慧园, 黄方, 于筱溪. 基于液滴微流控技术的蛋白质结晶[J]. 化工进展, 2023, 42(4): 2024-2030.
[7]	李娟娟, 张天永, 李祥高. 电泳显示用高质量铁锰黑纳米分散系的构建[J]. 化工进展, 2022, 41(6): 3178-3185.
[8]	申琪, 薛雨源, 杨涛伟, 张妍, 李胜任. 木质素荧光研究进展[J]. 化工进展, 2022, 41(5): 2672-2685.
[9]	韩芬, 杨娜, 孙永利, 姜斌, 肖晓明, 张吕鸿. 玻璃纤维聚结器脱除油中乳化水[J]. 化工进展, 2022, 41(12): 6723-6732.
[10]	张爽, 赵立新, 刘洋, 宋民航, 刘琳. 脱气除油旋流系统流场分布及分离特性[J]. 化工进展, 2022, 41(1): 75-85.
[11]	朱晓, 沈来宏, 沈天绪, 闫景春. 塔式化学链燃烧反应器系统的气固流动特性[J]. 化工进展, 2021, 40(8): 4144-4151.
[12]	刘梅华, 刘雪东, 徐晓东, 彭涛, 顾宇彤, 蒋威. 固定床反应器催化剂密相装填过程床层料面监测系统构建与研究[J]. 化工进展, 2021, 40(7): 3617-3625.
[13]	李金, 王军锋, 徐惠斌, 郑高杰, 孟新. 电晕放电喷雾荷电特性[J]. 化工进展, 2021, 40(3): 1300-1306.
[14]	田昌, 苏明旭, 蒋瑜, 夏多兵. 超声法在线测量烟气脱硫浆液粒度分布、密度方法和装置[J]. 化工进展, 2021, 40(12): 6516-6522.
[15]	徐日辛, 周骛, 张翔云. 基于深度学习的显微离焦图像法颗粒深度测量[J]. 化工进展, 2021, 40(12): 6499-6504.