原油中有机氯化物分布转化情况及危害性研究进展  

Research progress on the distribution,transformation and hazards of organochloride compounds in crude oil

作　　者：胡渤 武本成[1] 朱建华[1] 丁康乐[2] HU Bo;WU Bencheng;ZHU Jianhua;DING Kange(College of Chemical Engineering and Environmental,China University of Petroleum,Beijing 102249,China;College of Chemistry&Environmental Engineering,Yangtze University,Wuhan,Hubei 434023,China)

机构地区：[1]中国石油大学(北京)化学工程与环境学院,北京102249 [2]长江大学化学与环境工程学院,湖北荆州434023

出　　处：《世界石油工业》2024年第3期90-99,共10页World Petroleum Industry

基　　金：国家自然科学基金“有机氯化物在原油蒸馏过程中的转移及转化规律研究”(21206194);国家重点研发计划课题“城镇垃圾废塑料高值化利用研究与工程示范”(2019YFC1906305)。

摘　　要：原油中天然存在的有机氯化物含量通常较低。随着油田进入开采中后期,原油重质化、劣质化加剧,为提高原油采收率使用了一些含氯化学助剂,导致原油中有机氯化物含量增加。了解有机氯化物在原油中的组成、分布、石油加工中的转移/转化以及危害机理至关重要。不同原油中的有机氯化物在馏分油中有着不同的分布规律,且轻馏分中的有机氯化物类型多为氯代烷烃、氯代烯烃、氯代苯及氯代苯胺等,随着原油重质化程度的增加,有机氯化物也逐渐富集于重质馏分油中,其形态也由此变得复杂。有机氯化物无法在原油脱盐脱水工段有效去除,会随着原油进入后续加工工段并产生不良影响。综述了有机氯化物在原油常减压蒸馏、催化裂化和催化加氢等加工过程中的转移和转化情况,其中发生的裂解、水解和加氢等反应会生成腐蚀性产物氯化氢,其在原油加工过程中会对设备造成腐蚀,也会导致管路堵塞及催化剂中毒等严重危害。本文对3个方面的危害进行了机理分析,并阐述了其研究现状。结果表明:有机氯化物会形成酸性腐蚀环境腐蚀设备、形成铵盐结晶堵塞管路、破坏催化剂金属活性位使催化剂失活,对炼油过程造成一定程度影响。The low content of naturally occurring OCCs and the relatively high content of artificially introduced OCCs,With the oil field entering the middle and late stage of exploitation,the heavy and inferior quality of crude oil is intensified,so some chlorination additives have to be used to improve oil recovery,which is the main reasons for the increase of OCCs in crude oil.It is vital important to understand the composition and distribution of OCCs in crude oil,the transfer/transformation in petroleum processing,and the harm mechanism.OCCs in different crude oil have different distribution rules in distillate oil,and the types of OCCs in light distillate are mostly chloro-alkanes,chloro-alkenes,chloro-benzene and chloro-aniline,etc.With the increase of crude oil heavy degree,OCCs are gradually enriched in heavy distillate oil,and their forms become complicated.Since OCCs cannot be effectively removed in the desalting and dehydrating stage of crude oil,they will enter the subsequent processing stage along with crude oil and produce adverse effects.This paper reviews the transfer and transformation of OCCs in the processing of crude oil such as atmospheric and vacuum distillation,catalytic cracking and catalytic hydrogenation.The reaction such as cracking,hydrolysis and hydrogenation will produce corrosive product HCl,which can cause corrosion to equipment,and can also lead to pipeline blockage and catalyst poisoning and other serious harms during crude oil processing.In this paper,the mechanism of these three aspects of harm is analyzed,and the current situation is described.The results show that OCCs can form acid corrosion environment to corrode equipment,form ammonium salt crystals to block pipelines,destroy the metal active sites of catalysts to inactivate catalysts,and affect the refining process to a certain extent.

关 键 词：有机氯化物 原油加工 转化情况 氯腐蚀 危害性 

分 类 号：TE624[石油与天然气工程—油气加工工程]