典型石油热加工技术发展现状及展望

doi:10.16085/j.issn.1000-6613.2024-0441

摘要/Abstract

摘要：

石油热加工技术是在热量作用下使石油及其产物发生热裂化和缩合反应生成不同产品，涉及石油炼制与化工生产的绝大多数加工过程，属于“热化学反应工程”分支之一。随着第三次能源转型持续推进，石油炼制行业正面临“油转化”的重大生产结构调整，促使以热化学反应为核心的石油热加工技术不断发展，包括以重油轻质化为主要目标的减黏裂化、延迟焦化、重油流化热裂化技术以及以低碳烯烃为主要目标的蒸汽裂解技术。为了更为高效地将石油转化为低碳烯烃，将热化学反应进一步与催化反应耦合，发展出含催化热载体的轻油催化热裂解和重油催化热裂解两类热化学-催化耦合热加工技术。本文对上述六种典型石油热加工技术的演变历程、技术特点、发展现状与前景进行了纵向梳理，并从不同维度对其进行横向对比分析。对比发现，热加工中热载体循环再生能够有效解决工艺过程焦炭处理问题，且能与催化反应相耦合，使得重油流化热裂化、轻油催化热裂解和重油催化热裂解等热加工技术在原料适应性、产物灵活性、环保性方面具有突出优势。此外，将电气化技术进一步与蒸汽裂解及以外的其他热加工技术相结合，可有效提升石油热加工领域未来的整体环保性和节能性。

关键词: 石油热加工, 重油轻质化, 低碳烯烃, 热化学-催化耦合热加工

Abstract:

Petroleum thermal processing technology employs heat that indues thermal cracking and condensation of petroleum and its derivatives, resulting in the formation of various products. This technology includes a wide range of processes involved in petroleum refining and chemical synthesis and belongs to one of the branches of “thermochemical reaction engineering”. The ongoing third energy transition has led to a significant restructuring of the petroleum refining industry with a shift from producing fuel oil to manufacturing chemicals. This has driven continuous advancements in petroleum thermal processing technology, which is primarily based on thermochemical reactions. The main objectives of petroleum processing technology are heavy oil upgrading and low-carbon olefins production. The former includes processes such as visbreaking, delayed coking and heavy oil fluidized thermal cracking, while the latter involves steam cracking technology. In order to more efficiently convert petroleum into low-carbon olefins, researchers have further coupled thermochemical reactions with catalytic reactions, leading to the development of thermochemical-catalytic coupling thermal processing technology. This technology can be divided into light oil catalytic pyrolysis and heavy oil catalytic pyrolysis techniques. This article comprehensively analyzed the evolution process, technical characteristics, current situation and prospects of the above six typical petroleum thermal processing technologies, and conducted a comprehensive comparison. Through comparison, it was found that different petroleum thermal processing technologies can be distinguished based on whether there was recycling of heat carrier. The use of heat carrier recycling can effectively solve the coking problem and can also combine catalytic reactions to significantly enhance the adaptability of raw materials, flexibility of products and environmental friendliness in various technologies such as heavy oil fluidized thermal cracking, light oil catalytic pyrolysis, and heavy oil catalytic cracking. Therefore, future development would focus on these areas. In addition, by further integrating electrification technology with steam cracking and other related thermal processing technologies, the environmental friendliness and energy efficiency of the entire field can be effectively improved.

Key words: petroleum thermal processing, heavy oil upgrading, low-carbon olefins production, thermochemical-catalytic coupling thermal processing

中图分类号:

TQ175

刘文津, 张玉明, 李家州, 张炜, 陈哲文. 典型石油热加工技术发展现状及展望[J]. 化工进展, 2024, 43(7): 3534-3550.

LIU Wenjin, ZHANG Yuming, LI Jiazhou, ZHANG Wei, CHEN Zhewen. State of the art and prospect of typical petroleum thermal processing technology[J]. Chemical Industry and Engineering Progress, 2024, 43(7): 3534-3550.

图/表 19

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技术名称	研发单位	反应器	热载体	裂化器温度/℃	压力 /MPa	裂化停留时间/s	裂化器气氛
延迟焦化^[37]	美国标准石油公司率先研发	管式炉+焦炭塔	无	500	0.1~0.35	≤60	H₂O
流化焦化^[39-40]	Exxon Mobile率先研发	流化床裂化器+燃烧器	热焦粉	480~550	0.07~0.09	1~2	H₂O
灵活焦化^[44]	Exxon Mobile率先研发	流化床裂化器+加热器+气化器	热焦粉	480~550	0.07~0.09	1~2	H₂O、H₂、CO
ART^[51]	恩格尔哈德&凯洛格公司	流化床裂化器+燃烧器	惰性颗粒	450~530	0.1~0.3	<2	H₂O、NH₃
KKI^[52-53]	日本神户制钢&兴亚石油&出光兴产	流化床裂化器+加热器+气化器+还原器	铁矿石粉	500~560	0.5~1	0.3~0.8	H₂O
OSI^{[47, 49]}	中国石油大学（北京）	流化床裂化-气化耦合反应器	混合热载体	450~700	0.1	1~20	H₂O、H₂、CO

技术名称	研发单位	反应器	热载体	裂化器温度/℃	压力 /MPa	裂化停留时间/s	裂化器气氛
延迟焦化^[37]	美国标准石油公司率先研发	管式炉+焦炭塔	无	500	0.1~0.35	≤60	H₂O
流化焦化^[39-40]	Exxon Mobile率先研发	流化床裂化器+燃烧器	热焦粉	480~550	0.07~0.09	1~2	H₂O
灵活焦化^[44]	Exxon Mobile率先研发	流化床裂化器+加热器+气化器	热焦粉	480~550	0.07~0.09	1~2	H₂O、H₂、CO
ART^[51]	恩格尔哈德&凯洛格公司	流化床裂化器+燃烧器	惰性颗粒	450~530	0.1~0.3	<2	H₂O、NH₃
KKI^[52-53]	日本神户制钢&兴亚石油&出光兴产	流化床裂化器+加热器+气化器+还原器	铁矿石粉	500~560	0.5~1	0.3~0.8	H₂O
OSI^{[47, 49]}	中国石油大学（北京）	流化床裂化-气化耦合反应器	混合热载体	450~700	0.1	1~20	H₂O、H₂、CO

研发单位	技术特点	应用现状
中国石油大学（北京）^[65]	电磁感应加热供能	2022年工业示范
Lummus公司^[69]	蒸汽裂解炉主要压缩机的蒸汽涡轮部分更换为电动驱动，可实现CO₂零排放	2022年首次工业化应用
BASF公司、沙特基础工业公司和Linde公司^[70]	直接加热，电流直接应用于反应器内的管道；间接加热，利用放置在管道周围加热电气元件的辐射加热	2023年启动建设工业化装置
中石化上海工程公司和华东理工大学^[71]	新型高收率、低排放SH-III型裂解炉	2023年完成技术包开发
Coolbrook公司和Linde公司^[66]	通过旋转叶片流的空气动力，转化为可再生能源电力给蒸汽裂解炉供能	2024年建成首批工业装置
Shell公司和Dow公司^[72]	基于理论电气化模型改造现有燃气蒸汽裂解炉	2025年开始建造中试装置

研发单位	技术特点	应用现状
中国石油大学（北京）^[65]	电磁感应加热供能	2022年工业示范
Lummus公司^[69]	蒸汽裂解炉主要压缩机的蒸汽涡轮部分更换为电动驱动，可实现CO₂零排放	2022年首次工业化应用
BASF公司、沙特基础工业公司和Linde公司^[70]	直接加热，电流直接应用于反应器内的管道；间接加热，利用放置在管道周围加热电气元件的辐射加热	2023年启动建设工业化装置
中石化上海工程公司和华东理工大学^[71]	新型高收率、低排放SH-III型裂解炉	2023年完成技术包开发
Coolbrook公司和Linde公司^[66]	通过旋转叶片流的空气动力，转化为可再生能源电力给蒸汽裂解炉供能	2024年建成首批工业装置
Shell公司和Dow公司^[72]	基于理论电气化模型改造现有燃气蒸汽裂解炉	2025年开始建造中试装置

技术名称	乙烯	丙烯	尾气（主要是甲烷）	丁二烯	C₄抽余油	粗汽油	焦炭	酸性气	丙烯/乙烯	总烯烃
蒸汽裂解	36.25	16.56	16.98	5.11	4.58	18.49	1.77	0.17	0.46	52.81
ACO催化热裂解	31.93	29.44	15.14	0	0	21.62	1.75	0.12	0.92	61.37