Development of the synthesis technology of polyoxymethylene dimethyl ethers

doi:10.16085/j.issn.1000-6613.2016.07.050

Abstract

Abstract: Polyoxymethylene dimethyl ethers is a new product of coal chemical industry. As a good additive for diesel fuel, it has advantage in environmental protection. The latest advances on the synthesis technology of polyoxymethylene dimethyl ethers were reviewed. According to the starting materials, the synthesis technologies can be divided into four types, using ① methanol and trioxane, ② methylal and paraformaldehyde, ③ methylal and formaldehyde gas, and ④ methanol and formaldehyde. The four mainstream techniques and the industrialization status were briefly introduced, respectively. Lacking of policy support and facing opposition from the oil industry are the two major issues for polyoxymethylene dimethyl ethers which should be solved before it enters the market. Finally, this article especially points out that we should put the emphasis of future research of polyoxymethylene dimethyl ethers on reducing the costs. What we need to do is to take effective measures to remove negative influence of water for the methanol and formaldehyde route. Meanwhile, the performance of the catalyst should be further optimized to control the proper distribution of products and improve the efficiency of the synthetic reaction.

Key words: polyoxymethylene dimethyl ethers, diesel fuel additives, methylal, paraformaldehyde, trioxane

摘要： 聚甲氧基二甲醚是煤化工行业中的一个新兴产品,该产品作为车用燃料调和组分具有诸多环保优势,已受到了国内外各行业的极大关注。本文综述了近年来聚甲氧基二甲醚合成技术的最新进展,根据聚甲氧基二甲醚反应原料的不同,分别简要介绍了以甲醇和三聚甲醛为原料、以甲缩醛和多聚甲醛为原料、以甲缩醛和甲醛气体为原料、以甲醇和甲醛为原料的4种主流技术的特色和国内产业化动态;对聚甲氧基二甲醚进入市场所需的支持性政策以及将面临来自于石油行业的抵制等问题进行了评述。最后对聚甲氧基二甲醚的下一步研究方向进行了展望,指出应该围绕"降低产品成本"来开展工作,重点解决以甲醇和甲醛为原料时反应体系中水的负面影响,同时还应该进一步优化催化剂的性能,控制产物分布,提升反应效率。

关键词: 聚甲氧基二甲醚, 柴油添加组分, 甲缩醛, 多聚甲醛, 三聚甲醛

CLC Number:

TQ426.94

ZHANG Xinwei, LI Jie, NI Xiangqian, YIN Zequn, LIU Quanjie. Development of the synthesis technology of polyoxymethylene dimethyl ethers[J]. Chemical Industry and Engineering Progree, 2016, 35(07): 2293-2298.

张信伟, 李杰, 倪向前, 尹泽群, 刘全杰. 聚甲氧基二甲醚合成技术的产业化进展[J]. 化工进展, 2016, 35(07): 2293-2298.

References

[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(4):91-96.
[2] AN G J,WANG X D,LU C B,et al. Research progress on polyoxymethylene dimethyl ethers as the additive component of diesel fuel[J]. Applied Mechanics and Materials,2014,672-674:676-679.
[3] BURGER J,SIEGERT M,STRÖFER E,et al. Poly(oxymethylene) dimethyl ethers as components of tailored diesel fuel:properties,synthesis and purification concepts [J]. Fuel,2010,89:3315-3319.
[4] BURGER J,HASSE H. Multi-objective optimization using reduced models in conceptual design of a fuel additive production process [J]. Chemical Engineering Science,2013,99:118-126.
[5] 陈静,宋河远,夏春谷,等. 离子液体催化合成聚甲氧基甲缩醛的方法:101665414A[P]. 2010-03-10.
[6] 夏春谷,宋河远,陈静,等. 连续制备聚甲氧基二甲基醚的反应系统和工艺方法:103772163A[P]. 2014-05-07.
[7] 赵峰,李华举,宋焕玲,等. 三聚甲醛与甲醇在SO₄^2-/Fe₂O₃固体超强酸上的开环缩合反应研究[J]. 天然气化工(C1化学与化工),2013,38(1):1-6.
[8] WANG F,ZHU G L,LI Z,et al. Mechanistic study for the formation of polyoxymethylene dimethyl ethers promoted by sulfonic acid-functionalized ionic liquids[J]. Journal of Molecular Catalysis A:Chemical,2015,408:228-236.
[9] 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:103848730[P]. 2014-06-11.
[10] 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:103360224[P]. 2013-10-23.
[11] 谢忠设,张建民. 阻击雾霾,化企攻坚PODE助柴油升级[N]. 中国化工报,2015-01-13.
[12] 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:104971667[P]. 2015-10-14.
[13] 王金福,郑妍妍,王胜伟,等. 一种生产聚甲氧基二甲醚的方法:104974025[P]. 2015-10-14.
[14] ZHENG Y Y,TANG Q,WANG T F,et al. Kinetics of synthesis of polyoxymethylene dimethyl ethers from paraformaldehyde and dimethoxymethane catalyzed by ion-exchange resin[J]. Chemical Engineering Science,2015,134:758-766.
[15] 李化毅,方勇,方世壁,等. 一种制备聚甲醛二甲醚的方法:102617305A[P]. 2012-08-01.
[16] 叶子茂,向家勇,张鸿伟,等. 一种气体甲醛合成聚甲氧基二甲醚及脱酸的工艺装置及方法:104725203A[P]. 2015-06-24.
[17] 叶子茂,向家勇,张鸿伟. 一种用于聚甲氧基二甲醚原料生产的工艺装置及工艺方法:104725202A[P]. 2015-06-24.
[18] 叶子茂,向家勇,张鸿伟,等. 一种气体甲醛合成聚甲氧基二甲醚及脱酸的工艺装置及方法:104725203A[P]. 2015-06-24.
[19] 叶子茂,向家勇,张鸿伟. 一种用于聚甲氧基二甲醚合成的多段式反应塔及聚甲氧基二甲醚合成工艺装置:104722249A[P]. 2015-06-24.
[20] 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:103626640A[P]. 2014-03-12.
[21] 向家勇,张鸿伟,许引,等. 一种聚甲氧基二甲醚的制备工艺方法及装置:103880615A[P]. 2014-06-25.
[22] 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:104341279A[P]. 2015-02-11.
[23] 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:103848729A[P]. 2014-06-11.
[24] 刘殿华,房鼎业,罗万明,等. 一种由甲醇和甲醛制备聚甲氧基二甲醚的方法:103508860A[P]. 2014-01-15.
[25] 刘殿华,房鼎业,张建强,等. 改性酸性阳离子交换树脂及其用途:103506171A[P]. 2014-01-15.
[26] 刘殿华,房鼎业,张建强,等. 一种制备聚甲氧基二甲醚的方法:103508859A[P]. 2014-01-15.
[27] ZHANG J Q,SHI M H,FANG D Y,et al. Reaction kinetics of the production of polyoxymethylene dimethyl ethers from methanol and formaldehyde with acid cation exchange resin catalyst[J]. Reaction Kinetics Mechanisms and Catalysis,2014,113:459-470.
[28] ZHANG J Q,FANG D Y,LIU D H. Evaluation of Zr-alumina in production of polyoxymethylene dimethyl ethers from methanol and formaldehyde:performance tests and kinetic investigations[J]. Industrial & Engineering Chemistry Research,2014,53:13589-13597.
[29] 王建国,武建兵,吴志伟,等. 高硅铝比分子筛催化制备聚甲醛二甲醚的方法:104292084A[P]. 2015-01-21.
[30] 曹健,朱华青,王辉,等. 分子筛催化剂催化合成聚甲氧基二甲醚[J]. 燃料化学学报,2014,42(8):986-993.
[31] WU J B,ZHU H Q,WU Z W,et al. High Si Al ratio HZSM-5 zeolite an efficient catalyst for the synthesis of polyoxymethylene dimethyl ethers from dimethoxymethane and trioxymethylene[J]. Green Chemistry,2015,17:2353-2357.
[32] 张朝峰,陈树伟,张海新,等. 一种分子筛负载离子液体催化剂及其催化合成聚甲醛二甲醚的方法:103381372A[P]. 2013-11-06.
[33] 张朝峰,张海新,陈树伟,等. 吡啶甲磺酸盐离子液体的固载化及其在聚甲醛二甲醚合成中的催化作用[J]. 燃料化学学报,2014,42(5):609-615.
[34] ZHAO Y P,XU Z,CHEN H,et al. Mechanism of chain propagation for the synthesis of polyoxymethylene dimethyl ethers[J]. Journal of Energy Chemistry,2013,22:833-836.
[35] 雷艳华,孙清,陈兆旭,等. 合成聚甲醛二甲基醚反应热力学的理论计算[J]. 化学学报,2009,67(8):767-772.
[36] 闫卫林. 端甲氧基聚氧亚甲基醚的合成[D]. 青岛:青岛科技大学,2013.
[37] 高晓晨,杨为民,刘志成,等. HZSM-5分子筛用于合成聚甲醛二甲基醚[J]. 催化学报,2012,33(8):1389-1394.
[38] 刘奕,高晓晨,高焕新,等. 合成聚甲醛二甲醚的反应动力学[J]. 化学反应工程与工艺,2014,30(4):365-370.
[39] 何欣,刘志成,高焕新. 制备聚甲氧基二甲醚的方法:103664546A[P]. 2014-03-26.
[40] 蔡依进,蔡依超,孟祥波,等. 一种制备聚甲氧基二甲醚的反应装置和方法:104174344A[P]. 2014-12-03.
[41] 蔡依进,蔡依超,孟祥波,等. 反应系统和装置及使用该装置制备聚甲氧基二甲醚的方法:104177236A[P]. 2014-12-03.
[42] 商红岩,洪正鹏,薛真真,等. 一种浆态床和固定床联合制备聚甲氧基二甲醚的方法:104119210A[P]. 2014-10-29.
[43] 肖隆平. 世界首套30万吨/年聚氧甲基二甲醚装置将于2015年投产[N]. 财经国家周刊,2014-12-08.
[44] 王志,刘浩业,张俊,等. 聚甲氧基二甲醚与柴油混合燃料的燃烧与排放特性[J]. 汽车安全与节能学报,2015,6(2):191-197.
[45] LIU H Y,WANG Z,WANG J X,et al. Performance,combustion and emission characteristics of a diesel engine fueled with polyoxymethylene dimethyl ethers (PODE3-4)/diesel blends[J]. Energy,2015,88:793-800.
[46] 王旭东,熊春华,安高军,等. 高原环境柴油机燃用聚醚型含氧燃料燃烧特性[J]. 内燃机学报,2015,33(5):407-412.
[47] AN G J,XIONG C H,WANG X D,et al. Study on the effects of oxygenated fuels on diesel engine performance[J]. Applied Mechanics and Materials,2014,672-674:1580-1583.