Synthesis of polyoxymethylene dimethyl ethers with shaped ZSM-5 catalysts in a fixed-bed reactor

doi:10.16085/j.issn.1000-6613.2021-0907

Abstract

Abstract:

The ZSM-5 zeolite powders with different silica/alumina ratios(SiO₂/Al₂O₃) were characterized by XRD, SEM, NH₃?TPD and Py-IR. The catalytic performance of the ZSM-5 zeolites was compared in the synthesis of polyoxymethylene dimethyl ethers (PODE) from trioxane and methylal in a batch reactor. The ZSM-5 catalyst with SiO₂/Al₂O₃molar ratio of 400 showed the highest yield and selectivity of PODE_2-8. Then, the extruded ZSM-5 catalyst were prepared from the ZSM-5 powder (SiO₂/Al₂O₃=400) by adding silica sol and methyl cellulose as binder. The mechanical strength of the extruded ZSM-5 catalyst was influenced by the adding amount of silica sol and the molecular weight of methyl cellulose. The extruded ZSM-5 catalyst were used to synthesize PODE in a fixed-bed reactor. Temperature and space velocity had little effect on the conversion of trioxane and the selectivity of PODE under the conditions examined. When the reaction temperature was 85℃ and space velocity was 5h^-1 in the fixed-bed reactor, the extruded ZSM-5 catalyst showed excellent stability in a 240h test, and the conversion of trioxane was higher than 90%, and the selectivity of PODE_2~8 was above 95%.

Key words: polyoxymethylene dimethyl ethers, synthesis, molecular sieves, catalysts, fixed-bed

摘要：

通过X射线衍射（XRD）、扫描电子显微镜（SEM）、氨气程序升温脱附（NH₃-TPD）和吡啶吸附-红外光谱（Py-IR）等对不同硅铝比（SiO₂/Al₂O₃）的ZSM-5分子筛粉末催化剂进行表征。在间歇反应器中，本文对比了不同硅铝比ZSM-5分子筛粉末催化三聚甲醛和甲缩醛合成聚甲氧基二甲醚（PODE）的催化活性，结果表明硅铝比为400的ZSM-5分子筛粉末具有最高的PODE_2~8的收率和选择性。然后，采用挤条成型法，在ZSM-5分子筛粉末（SiO₂/Al₂O₃=400）中加入硅溶胶黏结剂和甲基纤维素黏结剂，制备得到ZSM-5成型催化剂，硅溶胶添加量和甲基纤维素分子量影响成型催化剂强度。采用ZSM-5成型催化剂，以固定床为反应器，反应温度和反应空速在所考察的范围内对三聚甲醛（TOX）的转化率和PODE的选择性影响较小。在85℃、压力1MPa、空速为5h^-1的条件下进行了240h催化性能考察，成型催化剂催化性能稳定，三聚甲醛的转化率高于90%，PODE_2~8的选择性达到95%以上。

关键词: 聚甲氧基二甲醚, 合成, 分子筛, 催化剂, 固定床

CLC Number:

O643

LEI Qian, LIANG Linlin, LYU Gaomeng, CHEN Honglin. Synthesis of polyoxymethylene dimethyl ethers with shaped ZSM-5 catalysts in a fixed-bed reactor[J]. Chemical Industry and Engineering Progress, 2022, 41(4): 1908-1915.

雷骞, 梁琳琳, 吕高孟, 陈洪林. ZSM-5分子筛固定床催化合成聚甲氧基二甲醚[J]. 化工进展, 2022, 41(4): 1908-1915.

Figures/Tables 12

References 29

1	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(11): 3315-3319.
2	HAN D Y, CAO Z B, SHI W W, et al. Influence of polyoxymethylene dimethyl ethers on diesel fuel properties[J]. Energy Sources A: Recovery, Utilization, and Environmental Effects, 2016, 38(18): 2687-2692.
3	LI D H, GAO Y X, LIU S H, et al. Effect of polyoxymethylene dimethyl ethers addition on spray and atomization characteristics using a common rail diesel injection system[J]. Fuel, 2016, 186: 235-247.
4	YANG H, LI X H, WANG Y, et al. Pyrolysis characteristic analysis of particulate matter from diesel engine run on diesel/polyoxymethylene dimethyl ethers blends based on nanostructure and thermogravimetry[J]. Aerosol and Air Quality Research, 2016, 16(10): 2560-2569.
5	YANG H, LI X H, WANG Y, et al. Experimental investigation into the oxidation reactivity and nanostructure of particulate matter from diesel engine fuelled with diesel/polyoxymethylene dimethyl ethers blends[J]. Scientific Reports, 2016, 6: 37611.
6	LIU J L, WANG H, LI Y, et al. Effects of diesel/PODE (polyoxymethylene dimethyl ethers) blends on combustion and emission characteristics in a heavy duty diesel engine[J]. Fuel, 2016, 177: 206-216.
7	BURGER J, STRÖFER E, HASSE H. Chemical equilibrium and reaction kinetics of the heterogeneously catalyzed formation of poly(oxymethylene) dimethyl ethers from methylal and trioxane[J]. Industrial & Engineering Chemistry Research, 2012, 51(39): 12751-12761.
8	曹晨, 秦晓飞, 张旭斌, 等. 聚甲氧基二甲醚合成反应动力学研究进展[J]. 化工进展, 2020, 39(12): 5021-5028.
	CAO Chen, QIN Xiaofei, ZHANG Xubin, et al. Advances of formation kinetics of polymethoxy dimethyl ether[J]. Chemical Industry and Engineering Progress, 2020, 39(12): 5021-5028.
9	SONG H Y, KANG M R, JIN F X, et al. Brønsted-acidic ionic liquids as efficient catalysts for the synthesis of polyoxymethylene dialkyl ethers[J]. Chinese Journal of Catalysis, 2017, 38(5): 853-861.
10	WU Q, WANG M, HAO Y, et al. Synthesis of polyoxymethylene dimethyl ethers catalyzed by brønsted acid ionic liquids with alkanesulfonic acid groups[J]. Industrial & Engineering Chemistry Research, 2014, 53(42): 16254-16260.
11	YANG Z Y, HU Y F, MA W T, et al. Synthesis of polyoxymethylene dimethyl ethers catalyzed by pyrrolidinonium-based ionic liquids[J]. Chemical Engineering &Technology, 2017, 40(10): 1784-1791.
12	WANG D, ZHAO F, ZHU G L, et al. Production of eco-friendly poly(oxymethylene) dimethyl ethers catalyzed by acidic ionic liquid: a kinetic investigation[J]. Chemical Engineering Journal, 2018, 334: 2616-2624.
13	FU W H, LIANG X M, ZHANG H D, et al. Shape selectivity extending to ordered supermicroporous aluminosilicates[J]. Chemical Communications, 2015, 51(8): 1449-1452.
14	耿雪丽, 孟莹, 从海峰, 等. 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.
	GENG Xueli, MENG Ying, CONG Haifeng, et al. Review on the synthesis process and industrialization of polyoxymethylene dimethyl ethers[J]. Chemical Industry and Engineering Progress, 2020, 39(12): 4993-5008.
15	BARANOWSKI C J, ROGER M, BAHMANPOUR A M, et al. Nature of synergy between brønsted and lewis acid sites in Sn-beta zeolites for polyoxymethylene dimethyl ethers synthesis[J]. ChemSusChem, 2019, 12(19): 4421-4431.
16	周林. 改性MCM-22分子筛的制备及其在催化合成聚甲氧基二甲醚中的应用[D]. 西安: 西北大学, 2019.
	ZHOU Lin. Preparation of modified MCM-22 zeolites and its performance in synthesis of polyoxymethylene dimethyl ethers[D]. Xi’an: Northwest University, 2019.
17	李国斌, 徐彩霞, 陈立宇. Al-MCM-41分子筛的制备及其催化合成聚甲氧基二甲醚[J]. 石油化工, 2021, 50(2): 103-111.
	LI G B, XU C X, CHEN L Y. Preparation of Al-MCM-41 zeolite and its catalytic performance in the synthesis of polymethoxy dimethyl ether[J]. Petrochemical Technology, 2021, 50(2): 103-111.
18	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]. Catalysis Science & Technology, 2016, 6(4): 993-997.
19	SCHMITZ N, HOMBERG F, BERJE J, et al. Chemical equilibrium of the synthesis of poly(oxymethylene) dimethyl ethers from formaldehyde and methanol in aqueous solutions[J]. Industrial & Engineering Chemistry Research, 2015, 54(25): 6409-6417.
20	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.
21	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(4): 2353-2357.
22	BARANOWSKI C J, BAHMANPOUR A M, HÉROGUEL F, et al. Prominent role of mesopore surface area and external acid sites for the synthesis of polyoxymethylene dimethyl ethers (OME) on a hierarchical H-ZSM-5 zeolite[J]. Catalysis Science & Technology, 2019, 9(2): 366-376.
23	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.
24	赵启, 王辉, 秦张峰, 等. 分子筛催化剂上甲醇与三聚甲醛缩合制聚甲醛二甲醚[J]. 燃料化学学报, 2011, 39(12): 918-923.
	ZHAO Q, WANG H, QIN Z F, et al. Synthesis of polyoxymethylene dimethyl ethers from methanol and trioxymethylene with molecular sieves as catalysts[J]. Journal of Fuel Chemistry and Technology, 2011, 39(12): 918-923.
25	XUE Z Z, SHANG H Y, ZHANG Z L, et al. Efficient synthesis of polyoxymethylene dimethyl ethers on Al-SBA-15 catalysts with different Si/Al ratios and pore sizes[J]. Energy & Fuels, 2017, 31(1): 279-286.
26	BARANOWSKI C J, BAHMANPOUR A M, KRÖCHER O. Catalytic synthesis of polyoxymethylene dimethyl ethers (OME): a review[J]. Applied Catalysis B: Environmental, 2017, 217: 407-420.
27	SEKI T, NAKAJO T, ONAKA M. The tishchenko reaction: a classic and practical tool for ester synthesis[J]. ChemInform, 2007, 35(8): 824-829.
28	FREIDING J, PATCAS F C, KRAUSHAAR-CZARNETZKI B. Extrusion of zeolites: properties of catalysts with a novel aluminium phosphate sintermatrix[J]. Applied Catalysis A: General, 2007, 328(2): 210-218.
29	LEE K Y, LEE H K, IHM S K. Influence of catalyst binders on the acidity and catalytic performance of HZSM-5 zeolites for methanol-to-propylene (MTP) process: single and binary binder system[J]. Topics in Catalysis, 2010, 53(3/4): 247-253.

样品	SiO₂ /%	Al₂O₃ /%	Na₂O /%	SiO₂/Al₂O₃（摩尔比）	Al浓度 /mmol·g^-1	总酸量 /mmol·g^-1
ZSM-5-60	86.85	4.01	0.03	37	0.786	0.543
ZSM-5-100	93.68	1.50	0.20	106	0.295	0.463
ZSM-5-150	95.78	0.86	0.06	189	0.168	0.262
ZSM-5-200	95.47	0.64	0.07	254	0.126	0.272
ZSM-5-400	94.77	0.38	0.03	424	0.075	0.190

样品	SiO₂ /%	Al₂O₃ /%	Na₂O /%	SiO₂/Al₂O₃（摩尔比）	Al浓度 /mmol·g^-1	总酸量 /mmol·g^-1
ZSM-5-60	86.85	4.01	0.03	37	0.786	0.543
ZSM-5-100	93.68	1.50	0.20	106	0.295	0.463
ZSM-5-150	95.78	0.86	0.06	189	0.168	0.262
ZSM-5-200	95.47	0.64	0.07	254	0.126	0.272
ZSM-5-400	94.77	0.38	0.03	424	0.075	0.190

样品	总酸量（200℃脱附） /μmol·g^-1			中强酸量（350℃脱附） /μmol·g^-1
样品	L酸	B 酸	B/L	L酸	B 酸	B/L
ZSM-5-60	28.7	492.6	17.2	25.7	366.3	14.3
ZSM-5-100	39.6	153.2	3.9	19.3	112.4	5.8
ZSM-5-150	15.7	91.7	5.8	14.2	70.6	5.0
ZSM-5-200	8.6	49.4	5.7	6.4	36.7	5.7
ZSM-5-400	17.6	29.0	1.6	12.4	19.5	1.6

样品	总酸量（200℃脱附） /μmol·g^-1			中强酸量（350℃脱附） /μmol·g^-1
样品	L酸	B 酸	B/L	L酸	B 酸	B/L
ZSM-5-60	28.7	492.6	17.2	25.7	366.3	14.3
ZSM-5-100	39.6	153.2	3.9	19.3	112.4	5.8
ZSM-5-150	15.7	91.7	5.8	14.2	70.6	5.0
ZSM-5-200	8.6	49.4	5.7	6.4	36.7	5.7
ZSM-5-400	17.6	29.0	1.6	12.4	19.5	1.6

[1]	SHI Yongxing, LIN Gang, SUN Xiaohang, JIANG Weigeng, QIAO Dawei, YAN Binhang. Research progress on active sites in Cu-based catalysts for CO₂ hydrogenation to methanol [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 287-298.
[2]	ZHAO Wei, ZHAO Deyin, LI Shihan, LIU Hongda, SUN Jin, GUO Yanqiu. Synthesis and application of triazine drag reducing agent for nature gas pipeline [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 391-399.
[3]	WANG Zhengkun, LI Sifang. Green synthesis of gemini surfactant decyne diol [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 400-410.
[4]	XU Jiaheng, LI Yongsheng, LUO Chunhuan, SU Qingquan. Optimization of methanol steam reforming process [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 41-46.
[5]	GU Yongzheng, ZHANG Yongsheng. Dynamic behavior and kinetic model of Hg⁰ adsorption by HBr-modified fly ash [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 498-509.
[6]	XIANG Yang, HUANG Xun, WEI Zidong. Recent progresses in the activity and selectivity improvement of electrocatalytic organic synthesis [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4005-4014.
[7]	WANG Yaogang, HAN Zishan, GAO Jiachen, WANG Xinyu, LI Siqi, YANG Quanhong, WENG Zhe. Strategies for regulating product selectivity of copper-based catalysts in electrochemical CO₂ reduction [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4043-4057.
[8]	WANG Xiaohan, ZHOU Yasong, YU Zhiqing, WEI Qiang, SUN Jinxiao, JIANG Peng. Synthesis and hydrocracking performance of Y molecular sieves with different crystal sizes [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4283-4295.
[9]	CHEN Sen, YIN Pengyuan, YANG Zhenglu, MO Yiming, CUI Xili, SUO Xian, XING Huabin. Advances in the intelligent synthesis of functional solid materials [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3340-3348.
[10]	LI Jia, FAN Xing, CHEN Li, LI Jian. Research progress of simultaneous removal of NO _x and N₂O from the tail gas of nitric acid production [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3770-3779.
[11]	WANG Shuaiqi, WANG Congxin, WANG Xuelin, TIAN Zhijian. Solvent-free rapid synthesis of ZSM-12 zeolite [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3561-3571.
[12]	WANG Darui, SUN Hongmin, XUE Mingwei, WANG Yiyan, LIU Wei, YANG Weimin. Efficient synthesis of fully crystalline ZSM-5 zeolite catalyst by microwave method and its catalytic performance [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3582-3588.
[13]	YU Xixi, ZHANG Jinshuai, LEI Wen, LIU Chengguo. Research progress of self-healing photocuring polymeric materials based on dynamic covalent bonds [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3589-3599.
[14]	WANG Zhicai, LIU Weiwei, ZHOU Cong, PAN Chunxiu, YAN Honglei, LI Zhanku, YAN Jingchong, REN Shibiao, LEI Zhiping, SHUI Hengfu. Synthesis and performance of a superplasticizer based on coal-based humic acid [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3634-3642.
[15]	YIN Pengzhen, WU Qin, LI Hansheng. Advances in catalysts for liquid-phase selective oxidation of methyl aromatic hydrocarbons [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2916-2943.