聚甲氧基二甲醚合成工艺及产业化述评

doi:10.16085/j.issn.1000-6613.2020-0717

摘要/Abstract

摘要：

聚甲氧基二甲醚（DMM_n）作为一种新型绿色环保柴油添加剂，因其具有较高的十六烷值和含氧量，能有效减轻燃烧后的污染物排放，同时完善以煤基甲醇为源头的煤化工产业结构，这使得其合成工艺及产业化进程受到国内外学者的广泛关注。本文对国内外DMM_n合成工艺、国内工业化布局以及未来发展前景进行综述。在现有工艺基础上，归纳总结了由甲醇出发经不同中间产物合成DMM_n的各类合成路线的特点。通过分析制约DMM_n工业化进程的关键因素，特别是结合当前全球性新冠肺炎疫情导致的石油价格断崖式下跌，给煤化工产业带来巨大的冲击，认为反应精馏工艺将成为未来DMM_n产品推广和工业应用最具有竞争潜力的工艺技术路线。

关键词: 聚甲氧基二甲醚, 柴油添加剂, Schulz-Flory分布, 工艺路线, 反应精馏

Abstract:

Polyoxymethylene dimethyl ethers (DMM_n), as a new type of green and environmentally friendly diesel fuel additive, can effectively reduce the emission of pollutants after combustion and improve the industrial structure of coal chemical industry with coal-based methanol as the source because of its high cetane number and oxygen content. Therefore, the synthesis process and industrialization process of DMM_n are widely concerned by scholars at home and abroad. The domestic and foreign DMM_n synthesis process, industrial layout and future development prospects are reviewed. Based on the existing process, the characteristics of various synthesis routes of methanol to DMM_n through different intermediate products are summarized. Through the analysis of the key factors restricting the DMM_n industrialization process, especially the sharp drop in oil price caused by the global COVID-19, which has brought a huge impact on the coal chemical industry, reactive distillation is considered as the most competitive technology route for DMM_n product promotion and industrial application in the future.

Key words: polymethoxy dimethyl ether, diesel fuel additives, Schulz-Flory distribution, process route, reactive distillation

中图分类号:

耿雪丽, 孟莹, 从海峰, 李洪, 高鑫, 李鑫钢. 聚甲氧基二甲醚合成工艺及产业化述评[J]. 化工进展, 2020, 39(12): 4993-5008.

Xueli GENG, Ying MENG, Haifeng CONG, Hong LI, Xin GAO, Xingang LI. Review on the synthesis process and industrialization of polyoxymethylene dimethyl ethers[J]. Chemical Industry and Engineering Progress, 2020, 39(12): 4993-5008.

参考文献

1	时米东, 王云芳, 王巨龙, 等. 聚甲氧基二甲醚合成工艺介绍[J]. 天然气化工(C₁化学与化工), 2015, 40: 91-96.
1	SHI M D, WANG Y F, WANG J L, et al. A review on processes for synthesis of polyoxymethylene dimethyl ethers[J]. Natural Gas Chemical Industry, 2015, 40: 91-96.
2	张信伟, 李杰, 倪向前, 等. 聚甲氧基二甲醚合成技术的产业化进展[J].化工进展, 2016, 35(7):2293-2298.
2	ZHANG X W, LI J, NI X Q, et al. Development of the synthesis technology of polyoxymethylene dimethyl ethers[J]. Chemical Industry and Engineering Progress, 2016, 35(7):2293-2298.
3	韩红梅. 聚甲氧基二甲醚合成技术进展及产业化建议[J]. 煤炭加工与综合利用, 2014, 4: 30-32.
3	HAN H M. Progress of PODE synthetictechnology and suggestions on industrialization[J]. Coal Processing & Comprehensive Utilization, 2014, 4: 30-32.
4	SANFILIPPO D, PATRINI R, MARCHIONNA M. Use of an oxygenated product as a substitute of gas oil in diesel engines: US7235113[P]. 2007-06-26.
5	刘奕. 柴油添加剂聚甲醛二甲醚的合成研究[D]. 上海: 华东理工大学, 2014.
5	LIU Y. Synthesis of polyoxymethylene dimethly ethers as novel diesel additives[D]. Shanghai: East China University of Science and Technology, 2014.
6	HUANG H, CHEN Y, ZHU J, et al. Construction of a reduced PODE₃/nature gas dual-fuel mechanism under enginelike conditions[J]. Energy & Fuels, 2019, 33: 3504-3517.
7	李燊, 袁梦, 张燕鹏, 等. 聚甲氧基二甲醚合成工艺现状分析[J]. 应用化工, 2020, 49(4): 951-957.
7	LI S, YUAN M, ZHANG Y P, et al. Analysis of current status synthesis of polymethoxy dimethyl ether[J]. Applied Chemical Industry, 2020, 49(4): 951-957.
8	韩红梅．聚氧醚技术进展与产业化前景探析[J]. 煤炭加工与综合利用, 2015(10): 4-6.
8	HAN H M. Analysis of polyoxyether technology progress and industrialization prospect[J]. Coal Processing & Comprehensive Utilization, 2015(10): 4-6.
9	李丰，刘志成，李宗耀，等．柴油添加剂聚甲醛二甲醚的研究进展[J]. 工业催化, 2016, 24(6) : 31-34.
9	LI F, LIU Z C, LI Z Y, et al. Research progress in diesel additive polyoxymethylene dimethyl ethers[J]. Industrial Catalysis, 2016, 24 (6): 31-34.
10	QI J, HU Y, JIANG S, et al. Lewis acids promote the catalytic selectivity to polyoxymethylene dimethyl ethers PODE_3,4[J]. Fuel, 2019, 245: 521-527.
11	GAO X J, WANG W F, GU Y Y, et al. Synthesis of polyoxymethylene dimethyl ethers from dimethyl ether direct oxidation over carbon-based catalysts[J]. ChemCatChem, 2018, 10: 273-279.
12	WANG B, YAN X, ZHANG X, et al. Citric acid-modified beta zeolite for polyoxymethylene dimethyl ethers synthesis: the textural and acidic properties regulation[J]. Applied Catalysis B: Environmental, 2020, 266:118645.
13	WILLIAM F, RICHARD E. Preparation of polyformals: US2449469[P]. 1948-09-14.
14	HAGEN G P, SPANGLER M J. Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of dimethyl ether with formaldehyde formed by oxy-dehydrogenation of dimethyl ether: US6160186A[P]. 2000-12-12.
15	HAGEN G P, SPANGLER M J. Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of dimethyl ether with formaldehyde formed by oxy-dehydrogenation of methanol: US0616017[P]. 2000-12-12.
16	HAGEN G P, SPANGLER M J. Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of dimethyl ether with formaldehyde formed by dehydrogenation of dimethyl ether: US06160186[P]. 2000-12-12.
17	HAGEN G P, SPANGLER M J. Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of dimethyl ether with formaldehyde formed by oxidation of methanol: US06166266[P]. 2000 -12-26.
18	HAGEN G P, SPANGLER M J. Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of formaldehyde formed by oxidation of dimethyl ether: US06392102B1[P]. 2002-05-21.
19	HAGEN G P, SPANGLER M J. Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of formaldehyde formed by oxy-dehydrogenation of dimethyl ether: US20030171534A1[P]. 2003-09-11.
20	HAGEN G P, SPANGLER M J. Preparation of polyoxymethylene dimethyl ethers by acid-activated catalytic conversion of methanol with formaldehyde formed by oxy-dehydrogenation of dimethyl ether: US6265528B1[P]. 2001-07-24.
21	HAGEN G P, SPANGLER M J. Preparation of polyoxymethylene dimethyl ethers by acid-activated catalytic conversion of methanol with formaldehyde formed by dehydrogenation of methanol: US6437195B2[P]. 2002-08-20.
22	STR?FER E, HASSE H, BLAGOV S. Method for producing polyoxymethylene dimethyl ethers from methanol and formaldehyde: US07671240B2[P]. 2010-03-02.
23	STR?FER E, HASSE H, BLAGOV S. Process for preparing polyoxymethylene dimethyl ethers from methanol and formaldehyde: US07700809B2[P]. 2010-04-20.
24	ECKHARD S, HASSE H, BLAGOV S. Method for producing polyoxymethylene dimethyl ethers from methanol and formaldehyde:US20080207954A1[P]. 2008-09-28.
25	BARRO C, PARRAVICINI M, BOULOUCHOS K, et al. Neat polyoxymethylene dimethyl ether in a diesel engine; part 2: Exhaust emission analysis[J]. Fuel, 2018, 234: 1414-1421.
26	AWAD O I, MA X, KAMIL M, et al. Overview of polyoxymethylene dimethyl ether additive as an eco-friendly fuel for an internal combustion engine: current application and environmental impacts[J]. Sci. Total Environ., 2020, 715: 136849.
27	LIU J, SUN P, HUANG H, et al. Experimental investigation on performance, combustion and emission characteristics of a common-rail diesel engine fueled with polyoxymethylene dimethyl ethers-diesel blends[J]. Applied Energy, 2017, 202: 527-536.
28	张晓宇. 聚甲氧基二甲醚的合成与精制研究[D]. 天津: 天津大学, 2017.
28	ZHANG X Y. Study on synthesis and refining of polyoxymethylene dimethyl ethers[D]. Tianjin: Tianjin University, 2017.
29	孙育成, 刘秦, 罗明, 等. 甲醇为初始反应原料连续制备聚甲氧基二甲醚的系统: CN104003855A[P]. 2014-08-27.
29	SUN Y C, LIU Q, LUO M, et al. The system for continuously preparing polyoxymethylene dimethyl ethers by using methanol as the initial reaction raw material: CN104003855A[P]. 2014-08-27.
30	孙育成, 刘秦, 罗明, 等. 采用离子液体催化剂连续制备聚甲氧基二甲醚的多反应系统: CN104016838A[P]. 2014-09-03.
30	SUN Y C, LIU Q, LUO M, et al. The multi-reaction system for continuously preparing polyoxymethylene dimethyl ethers using ionic liquid catalyst: CN104016838A[P]. 2014-09-03.
31	孙育成, 刘秦, 罗明, 等. 采用负载型离子液体催化剂连续制备聚甲氧基二甲醚的系统: CN104045530A[P]. 2014-09-17.
31	SUN Y C, LIU Q, LUO M, et al. The system for continuously preparing polyoxymethylene dimethyl ethers by using supported ionic liquid catalyst: CN104045530A[P]. 2014-09-17.
32	上海盘马化工工程技术有限公司.服务供应网页[EB/OL]. 2020-04-30..,
32	Ltd. Service Supply Website[EB/OL]. 2020-04-30..
33	韦先庆, 王清洋, 黄小科, 等. 一种制备聚甲氧基二甲醚的系统装置及工艺: CN102701923A[P]. 2012-10-03.
33	WEI X Q, WANG Q Y, HUANG X K, et al. The system device and process for preparing polyoxymethylene dimethyl ethers: CN102701923A[P]. 2012-10-03.
34	韦先庆, 王清洋, 黄小科, 等. 一种制备聚甲氧基二甲醚的系统装置: CN202808649U[P]. 2013-03-20.
34	WEI X Q, WANG Q Y, HUANG X K, et al. The system device for preparing polyoxymethylene dimethyl ethers: CN202808649U[P]. 2013-03-20.
35	邓少年. 一种聚甲氧基二甲醚的生产装置: CN206337196U[P]. 2017-07-18.
35	DENG S N. A production device of polyoxymethylene dimethyl ethers: CN206337196U[P]. 2017-07-18.
36	邓少年. 一种聚甲氧基二甲醚生产中的反应装置: CN206337194U[P]. 2017-07-18.
36	DENG S N. A reaction device of polyoxymethylene dimethyl ethers production: CN206337194U[P]. 2017-07-18.
37	邓少年. 一种生产聚甲氧基二甲醚的生产装置: CN206337198U[P]. 2017-07-18.
37	DENG S N. A production device for polyoxymethylene dimethyl ethers: CN206337198U[P]. 2017-07-18.
38	邓少年. 一种生产聚甲氧基二甲醚的装置: CN206337195U[P]. 2017-07-18.
38	DENG S N. A device for producing polyoxymethylene dimethyl ethers: CN206337195U[P]. 2017-07-18.
39	邓少年. 一种用于制备聚甲氧基二甲醚的装置: CN206337193U[P]. 2017-07-18.
39	DENG S N. A device for preparing polyoxymethylene dimethyl ethers: CN206337193U[P]. 2017-07-18.
40	邓少年. 一种制备聚甲氧基二甲醚的装置: CN206337197U[P]. 2017-07-18.
40	DENG S N. A device for preparing polyoxymethylene dimethyl ethers: CN206337197U[P]. 2017-07-18.
41	夏春谷, 宋河远, 陈静, 等. 甲醛与甲醇缩醛化反应制备聚甲氧基二甲醚的工艺过程: CN102249868A[P]. 2011-11-23.
41	XIA C G, SONG H Y, CHEN J, et al. A process for preparing polyoxymethylene dimethyl ethers by acetalization reaction of formaldehyde and methanol: CN102249868A[P]. 2011-11-23.
42	SCHMITZ N, STR?FER E, BURGER J, et al. Conceptual design of a novel process for the production of poly(oxymethylene) dimethyl ethers from formaldehyde and methanol[J]. Industrial & Engineering Chemistry Research, 2017, 56: 11519-11530.
43	刘殿华, 房鼎业, 李毛, 等. 一种由甲醇和甲醛制备聚甲氧基甲缩醛的方法: CN103848729A[P]. 2014-06-11.
43	LIU D H, FANG D Y, LI M, et al. A method of preparing polyoxymethylene dimethyl ethers from methanol and formaldehyde: CN103848729A[P]. 2014-06-11.
44	刘殿华, 张建强, 房鼎业. 一种由甲醇和甲醛制备聚甲氧基二甲醚的方法: CN110028391A[P]. 2019-07-19.
44	LIU D H, ZHANG J Q, FANG D Y. A method of preparing polyoxymethylene dimethyl ethers from methanol and formaldehyde: CN110028391A[P]. 2019-07-19.
45	HAGEN G P, SPANGLER M J. Preparation of polyoxymethylene dimethyl ethers by reaction of dimethyletger with formaldehyde over heterogeneous catalysts.BP AMOCO CORPORATION: US005959156A[P]. 1999-09-28.
46	STR?FER E, SCHELLING H, HASSE H, et al. Method for the production of polyoxymethylene dimethyl ethers from trioxan and dialkylethers. BASF AG: CA20062610936[P]. 2006-06-12.
47	赵强, 李为民, 陈清林. Br?nsted酸性离子液体催化合成聚甲醛二甲醚的研究[J]. 燃料化学学报, 2013 (4): 463-468.
47	ZHAO Q, LI W M, CHEN Q L. Synthesis of poly( oxymethylene) dimethy ethers catalyzed by Br?nsted acid ionic liquids[J]. Journal of Fuel Chemistry and Technology, 2013(4): 463-468.
48	梁旭, 孙维毅. 一种聚甲氧基二甲醚合成与分离的精馏塔及其使用方法: CN110559678A[P]. 2019-12-13.
48	LIANG X, SUN W Y. A distillation column for the synthesis and separation of polyoxymethylene dimethyl ethers and its application: CN110559678A[P]. 2019-12-13.
49	梁旭, 孙维毅. 一种聚甲氧基二甲醚合成与分离系统： CN110496576A[P]. 2019-11-26.
49	LIANG X, SUN W Y. A system for synthesis and separation of polyoxymethylene dimethyl ethers. CN110496576A[P]. 2019-11-26.
50	梁旭, 孙维毅. 一种用于聚甲氧基二甲醚的合成装置及其合成工艺: CN110642687A[P]. 2020-01-03.
50	LIANG X, SUN W Y. A synthesis device and process for polyoxymethylene dimethyl ethers: CN110642687A[P]. 2020-01-03.
51	邓青, 桑练. 一种共沸精馏热耦合聚甲氧基二甲醚合成反应系统: CN108276257A[P]. 2018-07-13.
51	DENG Q, SANG L. A reaction system for the synthesis of polyoxymethylene dimethyl ethers by azeotropic distillation: CN108276257A[P]. 2018-07-13.
52	邓青, 桑练. 一种聚甲氧基二甲醚合成鼓泡式外挂反应系统: CN207646097U[P]. 2018-07-24.
52	DENG Q, SANG L. A bubbling plug-in reaction system for synthesizing polymethoxy dimethyl ether: CN207646097U[P]. 2018-07-24.
53	邓青, 桑练. 一种聚甲氧基二甲醚合成鼓泡式外挂反应系统及合成方法: CN107721831A[P]. 2018-02-23.
53	DENG Q, SANG L. A bubbling plug-in reaction system and synthesis method for polymethoxy dimethyl ether synthesis: CN107721831A[P]. 2018-02-23.
54	邓青, 桑练. 一种聚甲氧基二甲醚合成系统: CN207468522U[P]. 2018-06-08.
54	DENG Q, SANG L. A synthesis system of polyoxymethylene dimethyl ethers: CN207468522U[P]. 2018-06-08.
55	邓青, 桑练. 一种聚甲氧基二甲醚合成系统及工艺: CN107739301A[P]. 2018-02-27.
55	DENG Q, SANG L. A synthesis system and process of polyoxymethylene dimethyl ethers: CN107739301A[P]. 2018-02-27.
56	向家勇, 许引, 杨科歧, 等. 一种聚甲氧基二甲醚的制备工艺装置及方法: CN103626640A[P]. 2014-03-12.
56	XIANG J Y, XU Y, YANG K Q, et al. A process device and method for preparing polyoxymethylene dimethylethers: CN103626640A[P]. 2014-03-12.
57	叶子茂, 向家勇, 黄隆君. 一种浓甲醛制备聚甲氧基二甲醚的工艺方法和装置: CN106146266A[P]. 2016-11-23.
57	YE Z M, XIANG J Y, HUANG L J, et al. A process and device for preparing polyoxymethylene dimethyl ethers from concentrated formaldehyde: CN106146266A[P]. 2016-11-23.
58	叶子茂, 向家勇, 黄隆君. 一种浓甲缩醛制备聚甲氧基二甲醚的工艺装置: CN205953887U[P]. 2017-02-15.
58	YE Z M, XIANG J Y, HUANG L J, et al. A process device for preparing polyoxymethylene dimethyl ethers from concentrated methylal: CN205953887U[P]. 2017-02-15.
59	叶子茂, 向家勇. 一种气体甲醛制备聚甲氧基二甲醚的专用工艺装置: CN205575963U[P]. 2016-09-14.
59	YE Z M, XIANG J Y. A special equipment for the preparation of polyoxymethylene dimethyl ethers from formaldehyde: CN205575963U[P]. 2016-09-14.
60	刘红喜, 陈华, 卢建华, 等. 甲醇经缩合、氧化、缩聚和醚化合成聚甲氧基二甲醚的方法: CN104058940A[P]. 2014-09-24.
60	LIU H X, CHEN H, LU J H, et al. The synthesis of polyoxymethylene dimethyl ethers by condensation, oxidation, polycondensation and etherification of methanol: CN104058940A[P]. 2014-09-24.
61	刘红喜, 陈华, 卢建华, 等. 一种固定床反应精馏制备聚甲氧基二甲醚的方法: CN104355973A[P]. 2015-02-18.
61	LIU H X, CHEN H, LU J H, et al. A fixed bed reactive distillation method for the preparation of polyoxymethylene dimethyl ethers: CN104355973A[P]. 2015-02-18.
62	王金福, 郑妍妍, 王胜伟, 等. 一种生产聚甲氧基二甲醚的方法: CN104974025A[P]. 2015-10-14.
62	WANG J F, ZHENG Y Y, WANG S W, et al. A method of producing polyoxymethylene dimethyl ethers: CN104974025A[P]. 2015-10-14.
63	王金福, 唐强, 王胜伟, 等. 一种由甲缩醛和多聚甲醛制备聚甲氧基二甲醚的流化床装置及方法: CN104971667A[P]. 2015-10-01.
63	WANG J F, TANG Q, WANG S W, et al. A fluidized bed device and method for preparing polyoxymethylene dimethyl ethers from methanal and paraformaldehyde: CN104971667A[P]. 2015-10-01.
64	李化毅, 方勇, 方世壁, 等. 一种制备聚甲醛二甲醚的方法: CN102617305A[P]. 2012-08-01.
64	LI H Y, FANG Y, FANG S B, et al. A method of preparing polyoxymethylene dimethyl ether: CN102617305A[P]. 2012-08-01.
65	王云芳, 陈建国, 邢金仙, 等. 一种聚甲氧基二甲醚的生产装置系统及生产工艺: CN103848730A[P]. 2014-06-11.
65	WANG Y F, CHEN J G, XING J X, et al. A production system and process of polyoxymethylene dimethyl ethers: CN103848730A[P]. 2014-06-11.
66	王云芳, 陈建国, 邢金仙, 等. 一种制备聚甲氧基二甲醚的组合工艺: CN103360224A[P].2013-10-23.
66	WANG Y F, CHEN J G, XING J X, et al. A combined process for the preparation of polyoxymethylene dimethyl ethers: CN103360224A[P].2013-10-23.
67	毛进池, 刘文飞, 郭为磊, 等. 一种甲醇氧化制取聚甲氧基二甲醚的装置: CN206814664U[P]. 2017-12-29.
67	MAO J C, LIU W F, GUO W L, et al. A device for preparing polyoxymethylene dimethyl ethers by methanol oxidation: CN206814664U[P]. 2017-12-29.
68	毛进池, 刘文飞, 郭为磊, 等. 一种生产聚甲氧基二甲醚DMM的装置: CN205556511U[P]. 2016-09-07.
68	MAO J C, LIU W F, GUO W L, et al. A device for producing DMM: CN205556511U[P]. 2016-09-07.
69	毛进池, 刘文飞, 郭为磊, 等. 一种生产聚甲氧基二甲醚DMM的装置及方法: CN105622366A[P]. 2016-06-01.
69	MAO J C, LIU W F, GUO W L, et al. A device and method for producing DMM: CN105622366A[P]. 2016-06-01.
70	刘文飞, 毛进池, 高永林. 一种制备聚甲氧基二甲醚的工艺方法: CN105566077A[P]. 2016-05-11.
70	LIU W F, MAO J C, GAO Y L, et al. A process for preparation of polyoxymethylene dimethyl ethers: CN105566077A[P]. 2016-05-11.
71	刘文飞, 张长胜, 李运来, 等. 一种制备聚甲氧基二甲醚的工艺方法: CN106800500A[P]. 2017-06-06.
71	LIU W F, ZHANG C S, LI Y L, et al. A process for preparation of polyoxymethylene dimethyl ethers: CN106800500A[P]. 2017-06-06.
72	刘文飞, 毛进池, 高永林. 制备聚甲氧基二甲醚DMM的工艺装置: CN205556509U[P]. 2016-09-07.
72	LIU W F, MAO J C, GAO Y L, et al. Process device for preparing polyoxymethylene dimethylethers DMM: CN205556509U[P]. 2016-09-07.
73	毛进池, 刘文飞, 郭为磊, 等. 一种制备聚甲氧基二甲醚DMM的气相耦合方法: CN105566078A[P]. 2016-05-11.
73	MAO J C, LIU W F, GUO W L, et al. A gas phase coupling method for the preparation of polyoxymethylene dimethylethers DMM: CN105566078A[P]. 2016-05-11.
74	毛进池, 刘文飞, 郭为磊, 等. 一种制备聚甲氧基二甲醚DMM的气相耦合装置: CN205556510U[P]. 2016-09-07.
74	MAO J C, LIU W F, GUO W L, et al. A gas phase coupling device for the preparation of polyoxymethylene dimethylethers DMM: CN205556510U[P]. 2016-09-07.
75	白教法. 甲醇为原始反应物料连续生产聚甲氧基二甲醚的方法: CN104447239A[P]. 2015-03-25.
75	BAI J F. The method for continuously producing polyoxymethylene dimethylethers by using methanol as the original reaction material: CN104447239A[P]. 2015-03-25.
76	高鑫, 孟莹, 李洪, 等. 一种用于聚甲氧基二甲醚合成的反应精馏工艺装置及方法: CN110078600A[P]. 2019-08-02.
76	GAO X, MENG Y, LI H, et al. A device and method of reactive distillation process for the synthesis of polyoxymethylene dimethyl ethers: CN110078600A[P]. 2019-08-02.
77	高鑫, 孟莹, 李洪, 等. 用于聚甲氧基二甲醚合成的反应精馏-蒸汽渗透耦合工艺: CN110156575A[P]. 2019-08-23.
77	GAO X, MENG Y, LI H, et al. A coupling process of reactive distillation-steam permeation for synthesis of polyoxymethylene dimethylethers: CN110156575A[P]. 2019-08-23.
78	高鑫, 孟莹, 李洪, 等. 用于聚甲氧基二甲醚合成的分隔壁反应精馏方法及装置: CN210237495U[P]. 2020-04-03.
78	GAO X, MENG Y, LI H, et al. A method and device of dividing wall reactive distillation for polyoxymethylene dimethylethers ether synthesis: CN210237495U[P]. 2020-04-03.
79	李鑫钢, 孟莹, 李洪, 等. 一种聚甲氧基二甲醚的多段反应精馏合成工艺方法及装置: CN110078598A[P]. 2019-08-02.
79	LI X G, MENG Y, LI H, et al. A method and device for the synthesis of polyoxymethylene dimethyl ethers by multistage reactive distillation: CN110078598A[P]. 2019-08-02.
80	王佳臻, 韩艳辉, 胡慧敏, 等. 我国聚甲氧基二甲醚技术现状和产业化进展[J]. 现代化工, 2017, 37:15-18.
80	WANG J Z, HAN Y H, HU H M, et al. China’s status and industrialization progress of polyoxymethylene dimethyl ethers technology[J]. Modern Chemical Industry, 2017, 37:15-18.
81	山东辰信新能源有限公司.公司简介[EB/OL]. [2020-04-30]. .
81	Shandong Chenxin New Energy Co., Ltd. Company profile[EB/OL]. [2020-04-30]. .
82	中国塑料行业网新闻网页.又一化工巨头暴雷！山东玉皇化工“担保圈”债务危机引关注[EB/OL]. [2020-04-30]. .
82	China Plastics Industry Net. Another chemical giant thunder! Shandong Yuhuang Chemical “Guarantee Circle” debt crisis attracts attention[EB/OL]. [2020-04-30]. .
83	山东玉皇化工集团有限公司. 产品展示[EB/OL]. [2020-04-30]. .
83	Shandong Yuhuang Chemical Group Co., Ltd. Product display[EB/OL]. [2020-04-30]. .
84	东营市润成碳材料科技有限公司. 生产营销[EB/OL]. [2020-04-30]. .
84	Dongying Runcheng Carbon Materials Technology Co., Ltd. Production and marketing[EB/OL]. [2020-04-30]..
85	淄博津昌助燃材料科技有限公司.生产营销[EB/OL]. [2020-04-30]. .
85	Zibo Jinchang Combustion Supporting Material Technology Co., Ltd. Production and marketing[EB/OL]. [2020-04-30]. .
86	四川鑫达新能源科技有限公司.新闻中心. 首批聚甲氧基二甲醚样品出口海外[EB/OL]. [2020-04-30]. .
86	Sichuan Xinda New Energy Technology Co., Ltd. News Center. The first batch of polyoxymethylene dimethyl ethers samples exported to overseas webpage[EB/OL]. [2020-04-30]. .
87	四川鑫达新能源科技有限公司.新闻中心. 首批聚甲氧基二甲醚销售合同正式签约[EB/OL]. [2020-04-30]. .
87	Sichuan Xinda New Energy Technology Co., .Ltd. Center News. Official signing page of sales contract of the first batch of polyoxymethylene dimethyl ethers [EB/OL]. [2020-04-30]..
88	陕西省发展和改革委员会.发改文件. 陕西省发展和改革委员会关于陕西中润新能源有限公司15万吨/年聚甲氧基二甲醚项目节能报告的审查意见[EB/OL]. [2020-04-30]. .
88	Shaanxi Provincial development and Reform Commission. Development file. Review comments of Shaanxi Provincial development and Reform Commission on energy saving report of 150000 t/a polyoxymethylene dimethyl ethers project of Shaanxi Zhongrun New Energy Co.,Ltd.[EB/OL].[2020-04-30]. .
89	榆林市榆阳区人民政府. 政务公开. 兖州煤业榆林能化有限公司50万吨/年DMMn项目[EB/OL]. [2020-04-30]. .
89	People’s Government of Yuyang District, City Yulin. Open government affairs. 500000 t/a DMMn project of Yanzhou Coal Yulin Energy and Chemical Co., Ltd[EB/OL]. [2020-04-30]..
90	山东能源集团有限公司.新闻中心. 【过硬力量