稠油的甲酸供氢催化水热裂解改质实验研究  

Study on Upgrading Heavy Oil by Catalytic Aquathermolysis Using Formic Acid as Hydrogen Donor

作　　者：刘永建[1] 赵法军[1] 赵国[1] 胡绍彬[1] 林仲[2] 

机构地区：[1]大庆石油学院教育部重点实验室,黑龙江大庆163318 [2]中国石油辽河油田分公司曙光采油厂,辽宁盘锦124109

出　　处：《油田化学》2008年第2期133-136,161,共5页Oilfield Chemistry

基　　金：国家级重大基础研究前期研究专项“稠油中沥青质井下裂解机理研究及应用”(项目编号2005CCA06200);黑龙江省教育厅基金项目“大庆外围稠油油藏催化降粘机理及开采技术研究”(项目编号10551z0002)

摘　　要：在0．3升高温高压反应釜中，以甲酸为供氢体、以油溶性有机镍盐为催化剂，研究了辽河稠油的水热裂解反应，考察了水热裂解前后稠油的黏度、族组成及硫含量变化。所用催化剂为绿色黏稠液体，nD（25℃）=1．4737，由环烷酸和硫酸镍制成，介绍了制备方法。所用稠油黏度的温敏性强．50℃、44．11／s黏度为3716mPa·s。水热裂解反应条件如下：油水质量比4：1，催化剂加量以稠油质量计为0．1％，反应温度280℃，时间24h，初始充氮压力8.1MPa。催化水热裂解的降黏率为64．69％，使饱和烃、芳香烃由24．32％、36．89％增至26．12％、38．08％，使胶质、沥青质及硫含量由30．27％、8．52％及0．5650％减至28．27％、7．53％及0．3365％；加入1％～7％甲酸使降黏率增至69．16％-87．02％，使饱和烃、芳香烃增至27、73％～31．12％、39．68％-41．26％，使胶质、沥青质及硫含量减至26．29％-24．12％、6．66％～3．50％及0．3095％～0．0742％。红外光谱分析结果表明，稠油组分在供氢催化水热裂解中发生了脱羧反应且芳环数减少。讨论了甲酸作为供氢体在稠油催化水热裂解中的作用及其机理。图4表2参8。The aquathermolysis （AqTh） of Liaohe heavy crude oil （HOD） in a 0.3 liter autoclave is investigated at oil to water mass ratio 4：1 with an oil soluble catalyst added at dosage 0.1% HOD mass and formic acid as hydrogen donor added at dosage 0-7% HOD mass at 28012 in 24 hrs in N2 atmosphere of initial pressure 8.1 MPa. The catalyst is a green colored viscous liquid of nD = 1.4737 and prepared from naphthenic acid and nickel sulfate by a procedure described. The viscosity of HO3 is temperature sensitive, being of 3716 mPa＇s at 5012 and shear rate 44.1 1/s. The plain catalytic AqTh of HOD leads to a percentage viscosity reduction （PVR） of 64.69%, to an increase in saturates and aromatics contents from 24.32% and 36.89% to 26.12% and 38.08%, and to a decrease in resins, asphaltenes, and sufur contents from 30.27 %, 8.52 %, and 0. 5650 % to 28.27 %, 7.53 %, and 0. 3365 %,respectively; when formic acid is introduced at dosage of 1-7 % HCO mass, the PVR is continuously raised to 69.16-87.02 %, the saturates and aromatics contents increased to27.73-31.12% and39.68-41.26% and the resins, asphaltenes, and sulfur contents decreased to 26.29-24.12 %, 6.66-3.50 %, and 0. 3095-0. 0742 %, respectively. The IR-spectrometry shows that decarboxylation is conducted and number of aromatic tings is lessened in hydrogen donor catalytic AqTh. The role of formic acid and the functioning mechanisms involved in catalytic AqTh of HCO are discussed.

关 键 词：甲酸 供氢体 稠油 水热裂解 催化裂解 改质 有机镍盐催化剂 

分 类 号：TE624.41[石油与天然气工程—油气加工工程] TE357.44