过氧化氢及其基本有机化学品绿色合成技术

doi:10.16085/j.issn.1000-6613.2020-1411

摘要/Abstract

摘要：

烃类氧化与氮化反应是生产基础有机化学品和高附加值产品的主要反应，在满足和丰富人类物质需求方面贡献巨大，传统的工业氧化与氮化工艺导致严重的环境问题，亟需绿色化转型。作为公认的绿色氧化剂，过氧化氢在烃类氧化和氮化的绿色生产工艺中应用广泛。文章简要介绍了国内外过氧化氢生产现状，重点介绍了中国石化石油化工科学研究院浆态床过氧化氢生产技术，以己内酰胺、环氧丙烷和环氧氯丙烷为例，介绍了过氧化氢在绿色烃类氧化和氮化反应中的应用，汇报了石油化工科学研究院近年来在绿色化工方面的主要研究进展及工业实践结果。多个成套绿色化工技术的成功开发突破了国外对我国的技术封锁，为多个化工生产基地提供全流程绿色生产技术，有力保障了我国化工行业的绿色化转型。

关键词: 绿色化工, 过氧化氢, 烃氧化, 烃氮化, 己内酰胺, 环氧丙烷, 环氧氯丙烷

Abstract:

Hydrocarbon oxidation and nitridation are widely used to produce basic organic chemicals and high value-added products. Though the traditional industrial oxidation and nitridation processes have made outstanding contributions in enriching human life, they also cause serious environmental issues, which urges them to be more environmentally friendly. As a well-known green oxidant, hydrogen peroxide has been widely used in green chemical production, such as oxidation or nitridation of hydrocarbon. The article here briefly introduces the current status of hydrogen peroxide industry in China and foreign countries, with the focus on the slurry reactor technology for hydrogen peroxide production exploited by Research Institute of Petroleum Processing (RIPP), SINOPEC. Specifically, the article, by taking caprolactam, propylene oxide and epichlorohydrin as examples, introduces the applications of hydrogen peroxide in oxidation or nitridation of hydrocarbon, and reports the research progresses and industrial experimental results of RIPP in green chemical industry. The successful exploitation of several green chemical technologies have broken through the technical blockade of foreign countries against China, provided the whole process of green chemical technologies to a plurality of chemical industrial bases, and effectively ensured the green transformation of the chemical industry in China.

Key words: green chemical industry, hydrogen peroxide, hydrocarbon oxidation, hydrocarbon nitridation, caprolactam, propylene oxide, epichlorohydrin

中图分类号:

TQ21

史延强, 夏玥穜, 温朗友, 郜亮, 徐广通, 宗保宁. 过氧化氢及其基本有机化学品绿色合成技术[J]. 化工进展, 2021, 40(4): 2048-2059.

SHI Yanqiang, XIA Yuetong, WEN Langyou, GAO Liang, XU Guangtong, ZONG Baoning. Hydrogen peroxide and its green synthesis of basic organic chemicals[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2048-2059.

图/表 9

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聚合物	能耗 /MJ·(kg产品）^-1	碳排放 /MJ·(kg产品）^-1
尼龙-6	129.1	6.7
尼龙-66	139.5	6.4
聚碳酸酯（PC）	104.3	3.4
高抗冲聚苯乙烯（HIPS）	86.4	2.4
通用聚苯乙烯（GPPS）	82.3	2.3
涤纶树脂（PET）	69.6	2.2
低密度聚乙烯（LDPE）	81.5	1.9
高密度聚乙烯（HDPE）	79.4	1.8
线型低密度聚乙烯（LLDPE）	78.3	1.8
聚丙烯（PP）	77.1	1.6

聚合物	能耗 /MJ·(kg产品）^-1	碳排放 /MJ·(kg产品）^-1
尼龙-6	129.1	6.7
尼龙-66	139.5	6.4
聚碳酸酯（PC）	104.3	3.4
高抗冲聚苯乙烯（HIPS）	86.4	2.4
通用聚苯乙烯（GPPS）	82.3	2.3
涤纶树脂（PET）	69.6	2.2
低密度聚乙烯（LDPE）	81.5	1.9
高密度聚乙烯（HDPE）	79.4	1.8
线型低密度聚乙烯（LLDPE）	78.3	1.8
聚丙烯（PP）	77.1	1.6

项目	工作液组成	蒽醌溶解度/g·L^-1	Pd质量分数/%	催化剂	氢化反应器	氢化效率/g·L^-1	萃取液H₂O₂质量分数/%
国内技术	AR+TOP+EAQ	125~140	0.3	Pd/Al₂O₃	固定床	7~8	27.5~35
FMC	AR+TOP+EAQ	160~180	0.3	—	固定床	10~12	27.5~35
MGC	AR+TBU+AAQ	250~300	1~2	Pd/SiO₂	浆态床	15~18	45~48
Solvay	AR+TBU+EAQ	160~180	1~2	Pd/Al₂O₃-ZrO₂	浆态床	12~15	43~46
Degussa	AR+TOP+EAQ	160~180	1~2	Pd	浆态床	11~15	40~45
Arkema	AR+2-MCHA+EAQ	160~180	1~2	—	浆态床	11~14	40~45

项目	工作液组成	蒽醌溶解度/g·L^-1	Pd质量分数/%	催化剂	氢化反应器	氢化效率/g·L^-1	萃取液H₂O₂质量分数/%
国内技术	AR+TOP+EAQ	125~140	0.3	Pd/Al₂O₃	固定床	7~8	27.5~35
FMC	AR+TOP+EAQ	160~180	0.3	—	固定床	10~12	27.5~35
MGC	AR+TBU+AAQ	250~300	1~2	Pd/SiO₂	浆态床	15~18	45~48
Solvay	AR+TBU+EAQ	160~180	1~2	Pd/Al₂O₃-ZrO₂	浆态床	12~15	43~46
Degussa	AR+TOP+EAQ	160~180	1~2	Pd	浆态床	11~15	40~45
Arkema	AR+2-MCHA+EAQ	160~180	1~2	—	浆态床	11~14	40~45

技术商	甲醇/双氧水（摩尔比）	丙烯/双氧水（摩尔比）	反应温度/℃	反应压力/MPa	H₂O₂转化率/%	环氧丙烷选择性/%
中国石化	7.0	2.0	40	2.0	98.8	96.0
国外技术1	9.6	2.0	40	2.1	96.0	95.0
国外技术2	15.6	2.0	65	1.6	96.8	94.5