Advances in acetalization synthesis of polyoxymethylene dimethyl ethers

doi:10.11949/j.issn.0438-1157.20170706

Abstract

Abstract:

Polyoxymethylene dimethyl ether compounds have high oxygen contents and cetane numbers (CN), low condensation point and cold filtration point, are promising environmental protection diesel additive to improve diesel combustibility, enhance combustion efficiency, and reduce emission of NO_x and carbon smog pollutants. In this review, latest achievement in catalyst system, reaction mechanism and synthesis kinetics of polyoxymethylene dimethyl ether by acetalization reaction was summarized. The catalyst systems included liquid acid, solid acid, and ionic liquid systems in literature. The reaction materials contained end-group (-CH₃, -OCH₃) provider such as methanol, methylal and dimethyl ether, which were downstream products of methanol, and chain segment (-CH₂O-) provider such as 1,3,5-trioxane (TOX), paraformaldehyde (PF) or formaldehyde (FA). Synthesis kinetic models and parameters of polyoxymethylene dimethyl ethers were reviewed briefly. The acetalization and kinetics research are moving towards the direction that benefits large scale commercial production.

Key words: polyoxymethylene dimethyl ethers, catalyst, liquid acid, solid acid, molecular sieves, ionic liquid, kinetics

摘要：

聚甲氧基二甲基醚具有很高的十六烷值和含氧量，低冷凝点和冷滤点，能显著改善柴油的燃烧特性，有效地提高热效率，大幅度减少NO_x和碳烟的排放，被认为是一种优良的环保型燃油组分。综述了近年来缩醛化反应合成聚甲氧基二甲基醚催化剂体系、反应机理、反应动力学研究进展，已报道的催化剂体系包括液体酸催化剂、固体酸催化剂及离子液体催化剂体系，涉及的反应原料包括可提供亚甲氧基的化合物，如甲醛水溶液、多聚甲醛、三聚甲醛，以及提供封端甲基的化合物，如甲醇、甲缩醛、二甲醚等甲醇下游产品。另外，综述了国内外缩醛化反应合成聚甲氧基二甲基醚反应动力学研究进展，及所建立的反应动力学模型和得到的动力学参数。缩醛化反应及动力学研究正朝着更有利于工业化生产的方向发展，将对工业化生产具有一定的参考意义。

关键词: 聚甲氧基二甲基醚, 催化剂, 液体酸, 固体酸, 分子筛, 离子液体, 动力学

CLC Number:

JIN Fuxiang, SONG Heyuan, KANG Meirong, XIA Chungu, CHEN Jing. Advances in acetalization synthesis of polyoxymethylene dimethyl ethers[J]. CIESC Journal, 2017, 68(12): 4471-4485.

金福祥, 宋河远, 康美荣, 夏春谷, 陈静. 缩醛化反应合成聚甲氧基二甲基醚研究进展[J]. 化工学报, 2017, 68(12): 4471-4485.

References 84

[1]	VIGIER F, COUTANCEAU C, LEGER J M, et al. Polyoxymethylenedimethylether (CH3O(CH2O)nCH3) oxidation on Pt and Pt/Ru supported catalysts[J]. J. Power Sources, 2008, 175(1):82-90.
[2]	MOULTON D S, NAEGELI D W. Diesel fuel having improved qualities and method of forming:US5746785[P]. 1998-5-5.
[3]	SANFILIPPO D, PATRINI R, MARCHIONNA M. Use of oxygenated product as a substitute of gas oil in diesel engines:EP1422285 B1[P]. 2004-5-26.
[4]	SANFILIPPO D, PATRINI R, MARCHIONNA M. Use of an oxygenated product as a substitute of gas oil in diesel engines:US7235113 B2[P]. 2007-6-26.
[5]	TEBBEN G D, SCHELING H, STROEFER E, et al. Biodiesel fuel mixture containing polyoxymethylene dialkyl ether:US20080216390 A1[P]. 2008-9-11.
[6]	PATRINI R, MARCHIONNA M. Liquid mixture consisting of diesel gas and oxygenated compounds:EP1070755 B1[P]. 2001-1-24.
[7]	VLASENKO N V, KOCHKIN Y N. Direct single-stage conversion of synthesis gas to dimethoxymethane:influence of the sequence of metal introduction into Cu, Pd-zeolite catalysts on the degree of Cu and Pd reduction and catalyst acidity[J]. Russ. J. Appl. Chem., 2003, 76(10):1615-1619.
[8]	YUAN Y Z, LIU H C, IMOTO H, et al. Performance and characterization of a new crystalline SbRe2O6 catalyst for selective oxidation of methanol to methylal original research article[J]. J. Catal., 2000, 195(1):51-61.
[9]	YUAN Y Z, IWASAWA Y. Performance and characterization of supported rhenium oxide catalysts for selective oxidation of methanol to methylal[J]. J.Phys. Chem.B, 2002, 106(17):4441-4449.
[10]	ZHANG Q D, TAN Y S, YANG C H, et al. Catalytic oxidation of dimethyl ether to dimethoxymethane over Cs modified H3PW12O40/SiO2 catalysts[J]. J. Nat. Gas. Chem., 2007, 16(3):322-325.
[11]	LIU H C, IGLESIA E. Selective one-step synthesis of dimethoxymethane via methanol or dimethyl ether oxidation on H3+nVnMo12-nPO40 Keggin structures[J]. J. Phys. Chem. B, 2003, 107(39):10840-10847.
[12]	STAUDINGER H, LUTHY M. Uber die konstitution der poly-oxymethylene[J]. Helv. Chim. Acta, 1925, 8(1):41-64.
[13]	WILLIAN F, RICHARD E. Preparation of polyformals:US2449469[P]. 1948-9-14.
[14]	STROEFER E, SCHELLING H, HASSE H, et al. Method for production of polyoxymethylene dimethyl ethers from trioxan and dialkylethers:EP1902009[P]. 2008-3-26.
[15]	STROEFER E, SCHELLING H, HASSE H, et al.Method for producing of polyoxymethylene dimethyl ethers:CA2581502 A1[P]. 2006-5-4.
[16]	SCHELLING H, STROEFER E, PINKOS R, et al.Method for producing of polyoxymethylene dimethyl ethers:WO2006045506 A1[P]. 2006-5-4.
[17]	SCHELLING H, STROEFER E, PINKOS R, et al.Method for producing of polyoxymethylene dimethyl ethers:US20070260094 A1[P]. 2007-11-8.
[18]	STROEFER E, HASSE H, BLAGOV S. Method for producing of polyoxymethylene dimethyl ethers from methanol and formaldehyde:US20080207954 A1[P]. 2008-8-28.
[19]	ZHAO Y P, XU Z, CHENH, et al. Mechanism of chain propagation for the synthesis of polyoxymethylene dimethyl ethers[J]. J. Energy Chem., 2013, 22(6):833-836.
[20]	HAGEN G P, SPANGLER M J. Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of dimethyl ether with formaldehyde formed by oxydehydrogenation of dimethyl ether:US5959156[P]. 1999-9-28.
[21]	HAGEN G P, SPANGLER M J. Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of dimethyl ether with formaldehyde formed by oxydehydrogenation of methanol:US6160174[P]. 2000-12-12.
[22]	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:US6160186[P]. 2000-12-12.
[23]	HAGEN G P, SPANGLER M J. Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of dimethyl ether with formaldehyde formed by oxidation of methanol:US6166266[P]. 2000-12-26.
[24]	HAGEN G P, SPANGLER M J. Preparation of polyoxymethylene dimethyl ethers by acid-activated catalytic conversion of methanol with formaldehyde formed by oxydehydrogenation of dimethyl ether:US6265528[P]. 2001-7-24.
[25]	HAGEN G P, SPANGLER M J. Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of formaldehyde formed by oxidation of dimethyl ether:US6392102[P]. 2002-5-21.
[26]	HAGEN G P, SPANGLER M J. Preparation of polyoxymethylene dimethyl ethers by acid-catalytic conversion of methanol with formaldehyde formed by dehydrogenation of methanol:US6437195[P]. 2002-8-20.
[27]	ARVIDSON M, FAKLEY M E, SPENCER M S. Lithium halide-assisted formation of polyoxymethylene dimethyl ethers from dimethoxymethane and formaldehyde[J]. J. Mol. Catal., 1987, 41(3):391-393.
[28]	CLARISSE D, LAURENT G, JEANLUC C, et al. Mixtures of symmetrical and unsymmetrical polyoxymethylene dialkyl ethers, used in fuel compositions based on hydrocarbon distillates, especially diesel fuel:FR2906815A1[P]. 2008-12-12.
[29]	BURGER J, SIEGERT M, STROFER E, et al. Poly(oxymethylene) dimethyl ethers as components of tailored diesel fuel:properties, synthesis and purification concepts[J]. Fuel, 2010, 89(11):3315-3319.
[30]	刘现立, 田恒水, 王贺玲, 等. 甲醛低聚反应研究[J]. 广东化工, 2009, 36:23. LIU X L, TIAN H S, WANG H L, et al. Study on polymerization of formaldehyde[J]. Guangdong Chemical Industry, 2009, 36:23.
[31]	陈婷, 王亮, 陈群, 等. 大孔强酸性阳离子交换树脂催化甲缩醛和三聚甲醛合成聚甲醛二甲醚的研究[J]. 离子交换与吸附, 2012, 28(5):456-462. CHEN T, WANG L, CHEN Q, et al. Synehesis of polyoxymethylene dimethyl ethers from dimethoxymethane and trioxymethylene with cation resin as catalyst[J]. Ion Exchange and Adsorption, 2012, 28(5):456-462.
[32]	ZHENG Y Y, TANG Q, WANG T F, et al. Synthesis of a green diesel fuel additive over cation resins[J]. Chem. Eng. Technol., 2013, 36(11):1951-1956.
[33]	隆宽燕, 王涛, 田恒水, 等. 聚甲醛二甲醚的绿色合成工艺研究[J]. 天然气化工, 2016, 41(5):1-5. LONG K Y, WANG T, TIAN H S, et al. Environment-friendly process for synthesis of polyoxymethylene dimethyl ethers[J]. Natural Gas Chemical Industry, 2016, 41(5):1-5.
[34]	施敏浩, 刘殿华, 赵光, 等. 甲醇和甲醛催化合成聚甲氧基二甲醚[J]. 化工学报, 2013, 64(3):931-935. SHI M H, LIU D H, ZHAO G, et al. Catalytic synthesis of polyoxymethylene dimethyl ethers from methanol and formaldehyde[J]. CIESC Journal, 2013, 64(3):931-935.
[35]	刘显科, 夏成良, 张建强, 等.甲缩醛和甲醛催化合成柴油添加剂聚甲氧基二甲醚[J]. 石油化工, 2015, 44(7):888-892. LIU X K, XIA C L, ZHANG J Q, et al. Synthesis of polyoxymethylene dimethyl ethers as fuel additives from methylal and formaldehyde[J]. Petrochemical Technology, 2015, 44(7):888-892.
[36]	时米东, 何高银, 代方方, 等. 氯化锌催化甲醇和甲醛合成聚甲氧基二甲醚[J]. 化工学报, 2016, 67(7):2824-2831. SHI M D, HE G Y, DAI F F, et al. Synthesis of polyoxymethylene dimethyl ethers from methanol and formaldehyde catalyzed by ZnCl2[J]. CIESC Journal, 2016, 67(7):2824-2831.
[37]	冯伟樑, 李丰, 高焕新, 等. 聚甲醛二甲醚的制备方法:101768058 A[P]. 2010-07-07. FENG W L, LI F, GAO H X, et al. The preparation method of polyoxymethylene dimethyl ether:101768058 A[P]. 2010-07-07.
[38]	李丰, 冯伟樑, 高焕新, 等. 分子筛催化合成聚甲醛二甲醚的方法:102040491 A[P]. 2011-05-04. LI F, FENG W L, GAO H X, et al. The method of polyoxymethylene dimethyl ether by molecular sieve catalysis:102040491 A[P]. 2011-05-04.
[39]	李丰, 刘志成, 高焕新, 等.催化合成聚甲醛二甲醚的方法:102295539 A[P]. 2011-11-28. LI F, LIU Z C, GAO H X, et al. The method of catalytic synthesis of polyoxymethylene dimethyl ether:102295539 A[P]. 2011-11-28.
[40]	ZHAO Q, WANG H, QIN Z F, et al. Synthesis of polyoxymethylene dimethyl ethers from methanol and trioxymethylene with molecular sieves as catalysts[J]. J. Fuel Chem. Technol., 2011, 39(12):918-923.
[41]	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. CAO J, ZHU H Q, WANG H, et al. Synthesis of polyoxymethylene dimethyl ethers over zeolite catalysts[J]. Journal of Fuel Chemistry and Technology, 2014, 42(8):986-993.
[42]	张向京, 武朋涛, 张云, 等. HMCM-22分子筛负载磷钨酸催化合成聚甲醛二甲醚[J]. 化学反应工程与工艺, 2014, 30(2):140-144. ZHANG X J, WU P T, ZHANG Y, et al. Synthesis of polyoxymethylene dimethyl ethers with HMCM-22 zeolite loading phosphotungstic acid as catalyst[J]. Chemical Reaction Engineering and Technology, 2014, 30(2):140-144.
[43]	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 Chem., 2015, 17:2353-2357.
[44]	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. GAO X C, YANG W M, LIU Z C, et al. Catalytic performance of HZSM-5 molecular sieve for synthesis of polyoxymethylene dimethyl ethers[J]. Chinese Journal of Catalysis, 2012, 33(8):1389-1394.
[45]	何欣, 袁志庆, 腾加伟. 聚甲氧基甲缩醛的制备方法:103539645 A[P]. 2014-01-29. HE X, YUAN Z Q, TENG J W. The preparation method of polyoxymethylene dimethyl ether:103539645 A[P]. 2014-01-29.
[46]	刘志成, 许云风, 高晓晨, 等. 聚甲醛二甲醚催化剂及其应用:104549443 A[P]. 2015-04-29. LIU Z C, XU Y F, GAO X C, et al. Catalyst for polyoxymethylene dimethyl ether and its application:104549443 A[P]. 2015-04-29.
[47]	李丰, 冯伟樑, 高焕新, 等. 聚甲醛二甲醚的合成方法:101768057[P]. 2010-07-07. LI F, FENG W L, GAO H X, et al. The method for synthesizing polyoxymethylene dimethyl ethers:101768057[P]. 2010-07-07.
[48]	洪正鹏, 商红岩. 一种合成聚甲醛二甲基醚的方法:101898943 A[P]. 2010-12-01. HONG Z P, SHANG H Y. A method for synthesizing polyoxymethylene dimethyl ethers:101898943 A[P]. 2010-12-01.
[49]	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]. Ind. Eng. Chem. Res., 2014, 53:13589-13597.
[50]	赵峰, 李华举, 宋焕玲, 等. 三聚甲醛与甲醇在SO42-/Fe2O3固体超强酸上的开环缩合反应研究[J]. 天然气化工, 2013, 38(1):1-6. ZHAO F, LI H J, SONG H L, et al. Ring-opening and condensation of trioxane with methanol over SO42-/Fe2O3 solid superacid[J]. Natural Gas Chemical Industry, 2013, 38(1):1-6.
[51]	LI H J, SONG H L, CHEN L W, et al. Designed SO42-/Fe2O3-SiO2 solid acids for polyoxymethylene dimethyl ethers synthesis:the acid sites control and reaction pathways[J]. Appl. Catal. B:Environ., 2015, 165:466-476.
[52]	LI H J, SONG H L, ZHAO F, et al. Chemical equilibrium controlled synthesis of polyoxymethylene dimethyl ethers over sulfated titania[J]. J. Energy Chem., 2015, 24(2):239-244.
[53]	沈俭一, 赵宇培, 徐铮, 等. 一种合成聚甲醛二甲基醚的方法:102775284A[P]. 2012-11-14. SHEN J Y, ZHAO Y P, XU Z, et al. A method for synthesis of polyoxymethylene dimethyl ether:102775284A[P]. 2012-11-14.
[54]	高晓晨, 杨为民, 刘志成, 等. 聚甲醛二甲醚的合成方法:103880614 A[P]. 2014-06-25. GAO X C, YANG W M, LIU Z C, et al. The synthesis method of polyoxymethylene dimethyl:103880614 A[P]. 2014-06-25.
[55]	王一萌, 付文华, 梁筱敏, 等. 一种聚甲醛二甲醚的合成方法:104177237 A[P]. 2014-12-03. WANG Y M, FU W H, LIANG X M, et al. A method for synthesis of polyoxymethylene dimethyl ether:104177237 A[P]. 2014-12-03.
[56]	FU W H, LIANG X M, ZHANG H D, et al. Shape selectivity extending to ordered supermicroporous aluminosilicates[J]. Chem. Commun., 2015, 51(8):1449-1452.
[57]	FANG X L, CHEN J, YE L M, et al. Efficient synthesis of poly(oxymethylene) dimethyl ethers over PVP-stabilized heteropolyacids through self-assembly[J]. Sci. China Chem., 2015, 58(1):131-138.
[58]	王建国, 王瑞义, 吴志伟, 等. 聚甲氧基二甲醚的制备方法:104086380 A[P]. 2014-10-08. WANG J G, WANG R Y, WU Z W, et al. The preparation method of polyoxymethylene dimethyl ether:104086380 A[P]. 2014-10-08.
[59]	WANG R Y, WU Z W, QIN Z F, et al. Graphene oxide:an effective acid catalyst for the synthesis of polyoxymethylene dimethyl ethers from methanol and trioxymethylene[J].Catal. Sci. Technol., 2016, 6:993-997.
[60]	陈静, 唐中华, 夏春谷, 等. 聚甲氧基甲缩醛的制备方法:200710018474.9[P]. 2008-05-21. CHEN J, TANG Z H, XIA C G, et al. Method for preparing polymethoxymethylal:200710018474.9[P]. 2008-05-21.
[61]	CHEN J, TANG Z H, XIA C G, et al. Method for preparing polymethoxymethylal:US 7560599B2[P]. 2009-07-14.
[62]	CHEN J, TANG Z H, XIA C G, et al. Process for synthesizing trioxymethylene using ionic liquid:US7598402B2[P]. 2008-11-27.
[63]	陈静, 唐中华, 夏春谷, 等. 离子液体催化合成聚甲氧基甲缩醛的方法:101665414B[P]. 2010-03-10. CHEN J, TANG Z H, XIA C G, et al. Method for synthesizing polyoxymethylene dimethyl ethers by ionic liquid catalysis:101665414B[P]. 2010-03-10.
[64]	CHEN J, SONG H Y, XIA C G, et al. Method for synthesizing polyoxymethylene dimethyl ethers by ionic liquid catalysis:US8344183 B2[P]. 2013-01-01.
[65]	CHEN J, SONG H Y, XIA C G, et al. Method for synthesizing polyoxymethylene dimethyl ethers catalyzed by an ionic liquid:US8816131B2[P]. 2014-8-26.
[66]	XIA C G, SONG H Y, CHEN J, et al. Method for preparing polyoxymethylene dimethyl ethers by acetalation reaction of formaldehyde with methanol:US8987521B2[P]. 2016-02-26.
[67]	CHEN J, SONG H Y, XIA C G, et al. System and method for continuously producing polyoxymethylene dialkyl ethers:US 9067188B2[P]. 2016-02-26.
[68]	XIA C G, SONG H Y, CHEN J, et al. System and method for continuously producing polyoxymethylene dimethyl ethers:US 9169186B2[P]. 2015-10-27.
[69]	CHEN J, SONG H Y, XIA C G, et al. Reaction system and process for prepaing polymethoxy dimethyl ether:US 9168503B2[P]. 2016-02-26.
[70]	夏春谷, 宋河远, 陈静, 等. 连续制备聚甲氧基二甲醚的反应系统和工艺方法:103772163B[P]. 2014-05-07. XIA C G, SONG H Y, CHEN J, et al. System and method for continuously producing polyoxymethylene dimethyl ethers:103772163B[P]. 2014-05-07.
[71]	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].J. Mol. Catal. A-Chem., 2015, 408:228-236.
[72]	WU Y J, LI Z, XIA C G. Silica-gel-supported dual acidic ionic liquids as efficient catalysts for the synthesis of polyoxymethylene dimethyl ethers[J].Ind. Eng. Chem. Res., 2016, 55(7):1859-1865.
[73]	赵变红, 刘康军, 张朝峰, 等. 聚甲醛二甲醚合成反应中离子液体催化性能的比较[J]. 化工学报, 2013, 64(S1):98-103. ZHAO B H, LIU K J, ZHANG C F, et al. Comparison of catalytic properties of ionic liquids in polyoxymethylene dimethyl ethers synthesis reaction[J].CIESC Journal, 2013, 64(S1):98-103.
[74]	WU Q, WANG M, HAO Y, et al. Synthesis of polyoxymethylene dimethyl ethers catalyzed by Brønsted acid ionic liquids with alkanesulfonic acid groups[J].Ind. Eng. Chem. Res., 2014, 53(42):16254-16260.
[75]	WU Q, LIW J, WANG M, et al. Synthesis of polyoxymethylene dimethyl ethers from methylal and trioxane catalyzed by Brønsted acid ionic liquids with different alkyl groups[J]. RSC Adv., 2015, 5(71):57968-57974.
[76]	赵强, 李为民, 陈清林. Brønsted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, 41(4):463-468. ZHAO Q, LI W M, CHEN Q L. Synthesis of polyoxymethylene dimethy ethers catalyzed by Brønsted acid ionic liquids[J]. Journal of Fuel Chemistry and Technology, 2013, 41(4):463-468.
[77]	李为民, 赵强, 左同梅, 等. 酸功能化离子液体催化合成聚缩醛二甲醚[J]. 燃料化学学报, 2014, 42(4):501-506. LI W M, ZHAO Q, ZUO T M, et al. Synthesis of polyoxymethylene dimethy ethers catalyzed by acidic functionalized ionic liquids[J]. Journal of Fuel Chemistry and Technology, 2014, 42(4):501-506.
[78]	邓小丹, 曹祖宾, 韩冬云, 等. 复合催化剂合成聚甲氧基二甲醚的工艺研究[J].化学试剂, 2014, 36(7):651-655. DENG X D, CAO Z B, HAN D Y, et al. Preparation of polyoxymethylene dimethyl ethers catalyzed by composite catalyst[J]. Chemical Reagents, 2014, 36(7):651-655.
[79]	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. ZHANG C F, ZHANG H X, CHEN S W, et al. Immobilization of N-(3-sulfopropyl) pyridinium methanesulfonate ionic liquid and its catalytic performance in the synthesis of polyoxymethylene dimethyl ethers[J]. Journal of Fuel Chemistry and Technology, 2014, 42(5):609-615.
[80]	BURGER J, STROFER E, HASSE H. Chemical equilibrium and reaction kinetics of the heterogeneously catalyzed formation of poly(oxymethylene) dimethyl ethers from methylal and trioxane[J]. Ind. Eng. Chem. Res., 2012, 51(39):12751-12761.
[81]	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. LIU Y, GAO X C, GAO H X, et al. Kinetics of synthesis of polyoxymethylene dimethyl ethers[J]. Chemical Reaction Engineering and Technology, 2014, 30(4):365-370.
[82]	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]. Reac. Kinet. Mech. Cat., 2014, 113(2):459-470.
[83]	张建强, 唐斌, 夏成良, 等. 甲缩醛与三聚甲醛合成聚甲氧基二甲醚反应速率研究[J]. 化学反应工程与工艺, 2015, 31(1):69-76. ZHANG J Q, TANG B, XIAN C L, et al. Kinetics of polyoxymethylene dimethyl ethers synthesis from methylal and trioxymethylene[J]. Chemical Reaction Engineering and Technology, 2015, 31(1):69-76.
[84]	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]. Chem. Eng. Sci., 2015, 134:758-766.