供氢剂辅助重油热改质技术研究进展

doi:10.16085/j.issn.1000-6613.2017-1160

摘要/Abstract

摘要： 重油高黏度和高密度的特点给重油开采、集输和加工带来极大不便，一般都要先对其进行降黏处理。供氢热裂化是在传统减黏裂化基础上加入供氢剂，以改善减黏裂化加工深度不大、装置易生焦、产品安定性差等问题的一种高效重油改质降黏技术。文章首先介绍了重油管输技术基本类型，然后从供氢剂的供氢机理、供氢剂加入的作用、供氢剂的基本类型、供氢剂可供氢量的计算方法和供氢剂的运用等方面进行了综述。对于供氢剂的选择需要根据工艺条件和供氢剂性质等方面综合分析。指出在不生焦的前提下，尽可能提高改质苛刻度可有效提升重油改质效果，而影响生焦和抑制结焦的关键在于来自供氢剂的活泼氢能否及时封闭沥青质自由基。

关键词: 供氢剂, 重油, 黏度, 可供氢量, 测定方法

Abstract: Due to high viscosity and high density of heavy oil, the viscosity reduction had firstly to be done to ensure heavy oil extraction, gathering, and processing. The hydrogen donated visbreaking process, which the hydrogen donor was added into the conventional visbreaking process to solve the problem of low processing depth,coking,and poor stability,was an efficient thermal viscosity reduction technology. This review first introduced the basic types of heavy oil pipeline transportations. Then the hydrogen donating mechanism,the effect of hydrogen donor,the species of hydrogen donor,determination of donatable hydrogen concentration and application of hydrogen donor were summarized. The selection of hydrogen donors should be determined according to process conditions and the properties of hydrogen donor. The key issue of affecting the coking and inhibiting coking is whether the active hydrogen can be timely closed the asphaltic free radicals.

Key words: hydrogen donors, heavy oil, viscosity, donatable hydrogen, determination methods

中图分类号:

TE624-31

龚旭, 薛鹏, 刘贺, 陈坤, 郭爱军, 王宗贤. 供氢剂辅助重油热改质技术研究进展[J]. 化工进展, 2018, 37(04): 1374-1380.

GONG Xu, XUE Peng, LIU He, CHEN Kun, GUO Aijun, WANG Zongxian. Progress on the use of hydrogen donors for upgrading of heavy oil[J]. Chemical Industry and Engineering Progress, 2018, 37(04): 1374-1380.

参考文献

[1] 乔明,任静,聂光华. 非常规原油的加工利用进展——以委内瑞拉超重原油和加拿大油砂沥青为例[J]. 石化技术,2012,19(4):57-61. QIAO M,REN J,NIE G H. The progress of processing and utilization in unconventional crude oils——extra heavy crude oil and oil sands from Venezuela and Canada[J]. Petrochemical Industry Technology,2012,19(4):57-61.
[2] 王明进,童凤丫. 浆态床渣油加氢催化剂研究进展[J]. 工业催化,2015,23(9):659-665. WANG M J,TONG F Y. Development in the catalysts for residual oil hydrocraking in slurry-bed[J]. Industrial Catalysis,2015,23(9):659-665.
[3] 柳云骐,陈艳巨,刘赟,等. 废润滑油的临氢热处理及宽馏分产物的加氢精制[J]. 润滑油,2017,32(1):42-46. LIU Y Q,CHEN Y J,LIU Y,et al. The heat treatment with hydrogen of waste lubricating oil and hydro-refining of width fraction from distillate processing[J]. Lubricating Oil,2017,32(1):42-46.
[4] 孟科全,唐晓东,邹雯炆,等. 稠油降黏技术研究进展[J]. 天然气与石油,2009,27(3):30-34. MENG K Q,TANG X D,ZHOU W W,et al. Progress in research on heavy oil viscosity reduction technology[J]. Natural Gas and Oil,2009,27(3):30-34.
[5] 金鸣林,冯安祖. 煤沥青筑路油受氢改质[J]. 燃料化学学报,2000,28(1):85-88. JIN M L,FENG A Z. Hydrogen-accepting modification of coal tar pitch road binder[J]. Journal of Fuel Chemistry and Technology,2000,28(1):85-88.
[6] 王光耀,张晓静,陈贵锋,等. 煤油共处理中原料油结构对供氢性能影响研究[J]. 洁净煤技术,2015,4(3):83-87. WANG G Y,ZHANG X J,CHEN G F,et al. InfIuence of raw oil structure on hydrogen donation capacity during coal oil co-processing[J]. Clean Coal Technology,2015,4(3):83-87.
[7] SPEIGHT J G. Petroleum asphaltenes partⅠ:asphaltenes,resins and the structure of petroleum[J]. Oil & Gas Science & Technology,2004,59(5):467-477.
[8] FURLONG L E,EFFRON E,VERNON L W,et al. Coal processing:the exxon donor solvent process[J]. Chemical Engineering Progress,1976,72:8-10.
[9] HART A. A review of technologies for transporting heavy crude oil and bitumen via pipelines[J]. Journal of Petroleum Exploration and Production Technology,2014,4(3):327-336.
[10] 施雯,王淳. 盘锦输油管道降黏增输模拟试验[J]. 当代化工,2012,26(10):1094-1097. SHI W,WANG C. Simulation of viscosity-reduction and flowrate-enhancement for panjin pipelines[J]. Contemporary Chemical Industry,2012,26(10):1094-1097.
[11] 王青,王蓓. 电加热对低温情况下重油管线输送的几点研究[J]. 化工管理,2014,16(29):4. WANG Q,WANG B. Studies on the transmission of heavy oil pipeline under low temperature by electric heating[J]. Chemical Enterprise Management,2014,16(29):4.
[12] 沐俊,沐利彬. 劣质重质稠油改质工艺技术进展[J]. 炼油与化工,2015,26(5):1-5. MU J,MU L B. Process technology progress of inferior heavy viscous oil upgrading[J]. Refining and Chemical Industry,2015,26(5):1-5.
[13] 郭磊,王齐,李凤绪,等. 重油供氢减黏改质技术概述[J]. 化工进展,2014,33(s1):128-132. GUO L,WANG Q,LI F X,et al. Heavy oil hydrogen-donated visbreaking upgrading process[J]. Chemical Industry and Engineering Progress,2014,33(s1):128-132.
[14] CURRAN G P,STRUCK R T,GORIN E. Mechanism of hydrogen-transfer process to coal and coal extract[J]. Industrial & Engineering Chemistry Process Design and Development,1967,6(2):166-173.
[15] CANEL M,HEDDEN K,WILHELM A. Hydrogenating supercritical coal extraction with toluene,tetralin,molecular hydrogen and their mixtures[J]. Fuel,1990,69(4):471-475.
[16] MCMILLEN D F,MALHOTRA R,CHANG S J,et al. Mechanisms of hydrogen transfer and bond scission of strongly bonded coal structures in donor-solvent systems[J]. Fuel,1987,66(12):1611-1620.
[17] 李振芳,赵翔鵾,王宗贤,等. 加拿大油砂沥青常压渣油供氢热裂化改质基础研究[J]. 石油炼制与化工,2016,47(8):53-57. LI Z F, ZHAO X K,WANG Z X,et al. Fundamental study on thermal upgrading with hydrogen donor for Canadian oil sands bitumen atmospheric residue[J]. Petroleum Processing and Petrochemicals,2016,47(8):53-57.
[18] 尹依娜,谢传欣,纪晔,等. 辽河欢喜岭减压渣油供氢剂减黏裂化反应的研究[J]. 石油与天然气化工,2003,32(1):31-32. YIN Y N,XIE C X,JI H,et al. Research of hydro-donor visbreaking of liaohe huanxiling vacuum residue[J]. Chemical Engineering of Oil and Gas,2003,32(1):31-32.
[19] 李锐. 减压渣油掺兑沥青的减黏裂化[J]. 石油炼制与化工,1997,12(4):29-33. LI R. Visbreaking of the vacuum residue with deoiling asphalt[J]. Petroleum Processing and Petrochemicals,1997,12(4):29-33.
[20] 郭爱军,王宗贤,张会军,等. 减压渣油掺炼工业供氢剂缓和热转化的基础研究[J]. 燃料化学学报,2007,35(6):667-672. GUO A J,WANG Z X,ZHANG H J,et al. Fundamental study on mild thermal cracking of vacuum residue with industrial hydrogen donors[J]. Journal of Fuel Chemistry and Technology,2007,35(6):667-672.
[21] 邓文安,刘东,周家顺,等. 加供氢剂的减压渣油减黏裂化工艺的开发[J]. 炼油技术与工程,2006,36(12):7-10. DENG W A,LIU D,ZHOU J S,et al. Development of vacuum residue visbreaking process with hydrogen donors[J]. Petroleum Refinery Engineering,2006,36(12):7-10.
[22] ISA K M,ABDULLAH T A T,ALI U F M. Hydrogen donor solvents in liquefaction of biomass:a review[J]. Renewable and Sustainable Energy Reviews,2017,54(8):16-25.
[23] NIU B,JIN L,LI Y,et al. Mechanism of hydrogen transfer and role of solvent during heating-up stage of direct coal liquefaction[J]. Fuel Processing Technology,2017,160(13):130-135.
[24] 王治卿,王宗贤. 减压渣油供氢剂减黏裂化研究[J]. 燃料化学学报,2006,34(6):745-748. WANG Z Q,WANG Z X. Roles of hydrogen donor in visbreaking of vacuum residue[J]. Journal of Fuel Chemistry and Technology,2006,34(6):745-748.
[25] 石斌,文萍,王宗贤,等. 供氢剂及其前身物在渣油加氢裂化中的作用[J]. 中国石油大学学报(自然科学版),2003,27(1):84-87. SHI B,WEN P,WANG Z X,et al. Effect of hydrogen donor and precursor of donor on catalytic hydro-cracking reaction of residue oil[J]. Journal of China University of Petroleum (Edition of Natural Science),2003,27(1):84-87.
[26] 郭爱军,王宗贤,阙国和. 利用供氢剂探讨石油渣油的热转化机理[J]. 燃料化学学报,2002,30(1):1-5. GUO A J,WANG Z X,QUE G H. Investigation on thermal treatment mechanism of petroleum residue using H donor as a probe[J]. Journal of Fuel Chemistry and Technology,2002,30(1):1-5.
[27] 王齐,王宗贤,沐宝泉,等. 委内瑞拉常压渣油供氢热转化研究[J]. 燃料化学学报,2012,40(10):1200-1205. WANG Q,WANG Z X,MU B Q,et al. Hydrogen donor visbreaking of Venezuelan atmospheric residue[J]. Journal of Fuel Chemistry and Technology,2012,40(10):1200-1205.
[28] 宋育红,阎金城,虞琦,等. 辽河渣油供氢减黏裂化研究[J]. 石油炼制与化工,1994,31(12):15-19. SONG Y H,YAN J C,YU Q,et al. Visbreaking of liaohe vacuum residuum in the presence of hydrogen donor[J]. Petroleum Processing and Petrochemicals,1994,31(12):15-19.
[29] 邓文安,刘东,周家顺,等. 加供氢剂的减压渣油减黏裂化工艺的开发[J]. 炼油技术与工程,2006,36(12):7-10. DENG W A,LIU D,ZHOU J S,et al. Development of vacuum residue visbreaking process with hydrogen donors[J]. Petroleum Refinery Engineering,2006,36(12):7-10.
[30] 张钦希,韩志勇. 重质稠油供氢剂减黏裂化试验研究[J]. 齐鲁石油化工,2007,35(2):80-82. ZHANG Q X,HAN Z Y. Studies on dense oil visbreaking with hydrogen donors[J]. Qilu Petrochemical Technology,2007,35(2):80-82.
[31] 王宗贤,耿亚平,郭爱军,等. 馏分循环对延迟焦化加热炉管结焦规律影响的实验研究[J]. 石油炼制与化工,2010,41(9):65-69. WANG Z X,GEN Y P,GUO A J,et al. Experimental study on the effect of fractions circulation on the coking of furnace tube in delayed coking unit[J]. Petroleum Processing and Petrochemicals,2010,41(9):65-69.
[32] LANGER A W,STEWART J,THOMPSON C E,et al. Hydrogen donor diluent visbreaking of residua[J]. Industrial and Engineering Chemistry Research,1962,11(4):21-26.
[33] 迟春红,张道光,严易明. 浅析减黏裂化工艺应用与技术发展[J]. 石油化工设计,2010,27(2):25-27. CHI C H,ZHANG D G,YAN Y M. Application and development of visbreaking technology[J]. Petrochemical Design,2010,27(2):25-27.
[34] MARZIN R,PEREIRA P,MCGRATH M J,et al. New residue process increases conversion-produces stable residue in curacao refinery[J]. Oil and Gas Journal,1998,96(44):32-38.
[35] 樊泽霞,赵福麟,王杰祥,等. 超稠油供氢水热裂解改质降黏研究[J]. 燃料化学学报,2006,34(3):315-318. FAN Z X,ZHAO F L,WANG J X,et al. Upgrading and viscosity reduction of super heavy oil by aqua-thermolysis with hydrogen donor[J]. Journal of Fuel Chemistry and Technology,2006,34(3):315-318.
[36] HART A,LEWIS C,WHITE T,et al. Effect of cyclohexane as hydrogen-donor in ultradispersed catalytic upgrading of heavy oil[J]. Fuel Processing Technology,2015,13(8):724-733.
[37] COSTELLO C A,WRIGHT P J,SCHULZ D N,et al. Hydrogenation process for unsaturated homo and copolymers:US5399632[P]. 1995-06-12.
[38] 亓玉台,谢传欣,李会鹏,等. 减黏裂化工艺技术及其进展[J]. 炼油技术与工程,2000,30(10):1-6. QI Y T,XIE C X,LI H P,et al. Progress in visbreaking thchnology[J]. Petroleum Refinery Engineering,2000,30(10):1-6.
[39] AIURA M,MASUNAGA T,MORIYA K,et a1. Chemistry of solvents in coal liquefaction quantification of transferable hydrogen in coal derived solvents[J]. Fuel,1984,63(8):1138-1142.
[40] CURTIS C W,GUIN J A,HALE M A,et a1. Contribution of transferable hydrogen to coal conversion[J]. Fuel,1985,64(4):46l-469.
[41] LI Q,LIU D,SONG L,et al. Investigation of solvent effect on the hydro-liquefaction of sawdust:an innovative reference approach using tetralin as chemical probe[J]. Fuel,2016,16(4):94-98.
[42] AWADALLA A A,COOKLON D J,SMITH B E. Coal hydrogenation:quality of start-up solvents and partially process-derived recycle solvents[J]. Fuel,1985,64(8):1097-1107.
[43] AIURA M,MASUNAGA T,MORIYA K,et al. Chemistry of solvents in coal liquefaction:quantification of transferable hydrogen in coal-derived solvents[J]. Fuel,1984,63(8):1138-1142.
[44] 王宗贤. 渣油悬浮床加氢裂化生焦及抑焦机制[D]. 北京:中国石油大学,1999. WANG Z X. Coking and coking mechanism of residual oil suspended bed hydrocracking[D]. Beijing:China University of Petroleum,1999.
[45] GOULD K A,WIEHE I A. Natural hydrogen donors in petroleum resids[J]. Energy and Fuels,2006,21(3):1199-1204.
[46] RANA M S,SAMANO V,ANCHEYTA J,et al. A review of recent advances on process technologies for upgrading of heavy oils and residua[J]. Fuel,2007,86(9):1216-1231.
[47] ALEMAN L O,CANO J L,GARCIA J L. Effect of tetralin,decalin and naphthalene as hydrogen donors in the upgrading of heavy oils[J]. Procedia Engineering,2012,42(11):532-539.
[48] YI Y F,LI S Y,DIGN F C,et al. Change of asphaltene and resin properties after catalytic aquathermolysis[J]. Pet. Sci.,2009,6(2):194-200.
[49] FAN Z X,WANG T F,HE Y H. Upgrading and viscosity reducing of heavy oils by[BMIM] [AlCl₄] ionic liquid[J]. Journal of Fuel Chemistry and Technology,2009,37(6):690-693.
[50] LI W,ZHU J H,QI J H. Application of nano-nickel catalyst in the viscosity reduction of liaohe extra-heavy oil by aqua-thermolysis[J]. Journal of Fuel Chemistry and Technology,2007,35(2):176-180.