环丁砜处理磺酸树脂高效催化聚甲氧基二甲醚合成
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摘要
聚甲氧基二甲醚(DMM3～7)作为柴油添加剂可提高柴油十六烷值和燃料利用率,具有广阔应用前景。以环丁砜处理后的磺酸树脂为催化剂,用于甲缩醛(DMM)和三聚甲醛(TOX)合成DMM3～7反应,系统地研究了不同条件因素对反应过程中原料转化率和产物选择性的影响,并推断了反应机理。发现:反应体系中含有不同微量(mg/kg级) H_2O对原料转化率和产物选择性影响较大;当H_2O含量超过一定值时,有白色沉淀多聚甲醛(PF)生成,PF选择性随H_2O含量增加而增大,同时生成大量甲醇,导致目标产物DMM3～7选择性降低。创新地采用环丁砜对酸性磺酸树脂NKC-9进行脱水处理,使固体催化剂表面及孔道吸附H_2O含量从2154 mg/kg显著降至198 mg/kg;同时使用13X分子筛对原料DMM进行吸附脱水处理,使DMM中H_2O含量从710 mg/kg明显降至54mg/kg。当反应温度313 K (40℃)、反应2 h、压力1.0 MPa、DMM与TOX质量比2/1时,DMM和TOX转化率以及DMM3～7质量选择性分别从48.27%、88.41%以及45.27%显著提升至52.91%、93.34%和61.58%。与文献报道的数据相比,改性后的磺酸树脂在低温下即表现出极佳的催化效果,DMM3～7质量选择性突破60%。
Polymethoxy dimethylether(DMM3—7) as a diesel additive can improve diesel cetane number and fuel utilization rate, and has broad application prospects. For the synthesis of DMM3—7from dimethoxymethane(DMM) and trioxymethylene(TOX), this work systematically studied the effects of different conditional parameters on the conversions and products selectivity with the sulfolane-treated sulfonic acid as the catalyst and the reaction routes were proposed according to the results of products analysis by GC-MS. It was observed that trace amounts(mg/kglevel) of H_2O left in the reaction system significantly influenced the reactants conversions and products selectivity.With raising H_2O content, more white precipitation paraformaldehyde(PF) was gradually produced, while methanolwas substantially generated to lower the selectivity of DMM3—7. The sulfolane-treated method was first proposed and sulfolane solvent was acted as dehydration and pore-forming reagent, that resulted in the absorbed H_2O in thesurface/pores of NKC-9sulfolaneobvious decrease from 2154 mg/kg to 198 mg/kg. Meanwhile, 13 X molecular sieve wasapplied to significantly reduce H_2O content of DMM from 710 mg/kg to 54 mg/kg. When the reaction temperature is313 K(40℃), the reaction is 2 h, the pressure is 1.0 MPa, and the mass ratio of DMM to TOX is 2/1, the DMM andTOX conversion rates and the DMM3-7mass selectivity increase from 48.27%, 88.41% and 45.27% to 52.91%,93.34% and 61.58%, respectively. Comparing to literatures reports, the mass selectivity to DMM3-7 was higher than60% that makes it promising for industrial applications.
Polymethoxy dimethylether(DMM3—7) as a diesel additive can improve diesel cetane number and fuel utilization rate, and has broad application prospects. For the synthesis of DMM3—7from dimethoxymethane(DMM) and trioxymethylene(TOX), this work systematically studied the effects of different conditional parameters on the conversions and products selectivity with the sulfolane-treated sulfonic acid as the catalyst and the reaction routes were proposed according to the results of products analysis by GC-MS. It was observed that trace amounts(mg/kglevel) of H_2O left in the reaction system significantly influenced the reactants conversions and products selectivity.With raising H_2O content, more white precipitation paraformaldehyde(PF) was gradually produced, while methanolwas substantially generated to lower the selectivity of DMM3—7. The sulfolane-treated method was first proposed and sulfolane solvent was acted as dehydration and pore-forming reagent, that resulted in the absorbed H_2O in thesurface/pores of NKC-9sulfolaneobvious decrease from 2154 mg/kg to 198 mg/kg. Meanwhile, 13 X molecular sieve wasapplied to significantly reduce H_2O content of DMM from 710 mg/kg to 54 mg/kg. When the reaction temperature is313 K(40℃), the reaction is 2 h, the pressure is 1.0 MPa, and the mass ratio of DMM to TOX is 2/1, the DMM andTOX conversion rates and the DMM3-7mass selectivity increase from 48.27%, 88.41% and 45.27% to 52.91%,93.34% and 61.58%, respectively. Comparing to literatures reports, the mass selectivity to DMM3-7 was higher than60% that makes it promising for industrial applications.
引文
[1]洪正鹏,商红岩,薛真真,等.聚甲氧基二甲醚作为环保型溶剂油的新用途:104031194[P]. 2014-09-10.Hong Z P, Shang H Y, Xue Z Z, et al. Polymethoxy dimethyl ether as a new use of environmentally friendly solvent oil:104031194[P]. 2014-09-10.
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[11]许云风.柴油添加剂聚甲醛二甲醚的酸催化合成研究[D].上海:上海师范大学, 2013.Xu Y F. Study on acid catalytic synthesis of diesel oil additive polyoxymethylene dimethyl ether[D]. Shanghai:Shanghai Normal University, 2013.
[12] Secordel X, Berrier E, Capron M, et al. TiO2-supported rhenium oxide catalysts for methanol oxidation:effect of support texture on the structure and reactivity evidenced by an operando Raman study[J]. Catalysis Today, 2010, 155(3):177-183.
[13] Schmitz N, Burger J, Hasse H, Reaction kinetics of the formation of poly(oxymethylene)dimethyl ethers from formaldehyde and methanol in aqueous solutions[J]. Industrial&Engineering Chemistry Research, 2015, 54:12553-12560.
[14] Schmitz N, Strofer E, Burger J. 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.
[15]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氧基二甲醚[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.
[16]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.
[17]王云芳,歩长娟,邢金仙.合成聚甲氧基二甲醚催化剂研究进展[J].现代化工, 2015, 35(4):38-43.Wang Y F, Bu C J, Xing J X. Research progress in catalyst for polyoxymethylene dimethyl ethers[J]. Modern Chemical Industry,2015, 35(4):38-43.
[18]陈建国,王云芳,邢金仙,等.制备聚甲氧基二甲醚的组合系统装置:203582765U[P]. 2014-05-07.Chen J G, Wang Y F, Xing J X, et al. Composite system device for preparing polymethoxy dimethyl ether:203582765U[P]. 2014-05-07.
[19]李晓云,于海斌,孙彦民,等.一种连续生产聚甲醛二甲醚的方法:102786397A[P]. 2012-11-21.Li X Y, Yu H B, Sun Y M, et al. Method for continuously producing polyoxymethylene dimethyl ether:102786397A[P].2012-11-21
[20]张也贤,商红岩,洪正鹏,等.用于合成聚甲氧基二烷基醚的液相反应装置:202962442U[P]. 2013-06-05.Zhang Y X, Shang H Y, Hong Z P, et al. Liquid phase reaction device for synthesizing polymethoxy dialkyl ether:202962442U[P]. 2013-06-05.
[21]张英伟,秦少鹏,王耀红,等.制备聚甲氧基二甲醚的系统:203820659U[P]. 2014-09-10.Zhang W Y, Qin S P, Wang Y H, et al. System for preparing polymethoxy dimethyl ether:203820659U[P]. 2014-09-10.
[22] Zheng Y Y, Tang Q, Wang T F, et al. Molecular size distribution in synthesis of polyoxymethylene dimethyl ethers and process optimization using response surface methodology[J]. Chemical Engineering Journal, 2015, 278:183-189
[23] Li H J, SONG H L, Xia C G, et al. Designed SO42-/Fe2O3-SiO2solid acids for polyoxymethylene dimethyl ethers synthesis:the acid sites control and reaction pathways[J]. Applied Catalysis B:Environmental, 2014, 165:466-476.
[24] Wu Q, Wang M, Hao Y, et al. Synthesis of polyoxymethylene dimethyl ethers catalyzed by Br?nsted acid ionic liquids with alkane sulfonic acid group[J]. Royal Society of Chemistry, 2014, 5(71):57968-57974.
[25]钟禄平,肖剑.聚甲醛二甲醚的生产方法:102372614A[P].2012-03-14.Zhong L P, Xiao J. Method for polyoxymethylene dimethyl ether production:102372614A[P]. 2012-03-14.
[26] 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].Industrial&Engineering Chemistry Research, 2012, 51(39):12751-12761.
[27] Gresham W F, Brooks R E. Preparation of polyformals:US2449469[P]. 1948-09-14.
[28] Patrini R, Marchionna M. Liquid mixture consisting of diesel gas oils and oxygenated compounds:US6534658[P]. 2003-03-18.
[29] Chen J, Song H Y, Xia C, et al. Method for synthesizing polyxymethylene dimethyl ethers by liquid catalysis:US20100056830 A1[P]. 2010-03-04.
[30] 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.
[31]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:103360224A[P]. 2013-10-23.Wang Y F, Chen J G, Xing J X, et al. A combined process for preparing polymethoxy dimethyl ether:103360224A[P]. 2013-10-23.
[32] Liu F, Wang T F, Zheng Y Y, et al. Synergistic effect of Br?nsted and Lewis acid sites for the synthesis of polyoxymethylene dimethyl ethers over highly efficient SO42-/TiO2catalysts[J].Journal of Catalysis, 2017, 255:17-25.
[33] Zheng Y Y, Tang Q, Wang T F, et al. Synthesis of a green diesel fuel additive over cation resins[J]. Chemical Engineering&Technology, 2013, 36(11):1951-1956.
[34]石磊,姚杰,朱文良,等.磺酸树脂催化甲缩醛一步羰化制高附加值甲氧基乙酸甲酯[J].化工学报, 2017, 68(10):3739-3746.Shi L, Yao J, Zhu W L, et al. Efficient sulfonic acid resin catalysts for carbonylation of dimethoxymethane to value-added methyl methoxyacetate[J]. CIESC Journal, 2017, 68(10):3739-3746.
[35] Chen F, Shi L, Yao J, et al. A highly efficient sulfonic acid resin for liquid phase carbonylation of dimethoxymethane[J]. Catalysis Science&Technology, 2018, 8(2):580-590.
[36]杨科岐,郭兵.最新喷雾干燥法制多聚甲醛工艺[J].煤炭加工与综合利用, 2016, 4(199):52-56.Yang K Q, Guo B. Latest spray-drying process for making paraformaldehyde[J]. Coal Processing&Comprehensive, 2016, 4(199):52-56.
[37] Wang F, Zhu G L, Li Z, et al. Mechanistic study for the formation of polyoxymethylene dimethyl ethers promoted by sulfonic acidfunctionalized ionic liquids[J]. Journal of Molecular Catalysis A:Chemical, 2015, 408:228-236
[38] Celik F E, Kim T, Mlinara N, et al. An investigation into the mechanism and kinetics of dimethoxymethane carbonylation over FAU and MFI zeolites[J]. Journal of Catalysis, 2010, 274(2):150-162
[39] Zhang D X, Shi L, Wang Y, et al. Effect of mass-transfer control on HY zeolites for dimethoxymethane carbonylation to methyl methoxyacetate[J]. Catalysis Today, 2018, 316:114-121.
[40] 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.
[41] Ma W T, Hu Y F, Wang H Y, et al. The effects of typical salts,acids and ionic liquids on the solubility of formaldehyde in aqueous solutions[J]. Fluid Phase Equilibria, 2018, 460(5):51-56.
[42]石磊,孙东,张婉莹,等.一种合成聚甲氧基二甲醚的磺酸树脂催化剂改性方法:201610223149.5[P]. 2018-05-04.Shi L, Sun D, Zhang W Y, et al. Method for modifying sulfonic acid resin catalyst for synthesizing polymethoxy dimethyl ether:201610223149.5[P]. 2018-05-04.
[43] 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.
[44] Liu Y, Wang Y, Cai W F. A synthesis, process optimization and mechanism investigation for the formation of polyoxymethylene dimethyl ethers[J]. Transactions of Tianjin University, 2018. https://doi. org/10. 1007/s12209-018-0131-0.
[2] Boyd R H. Some physical properties of polyoxymethylene dimethyl ethers[J]. Journal of Polymer Science, 1961, 50(153):133-141.
[3] Li H J, Song H L, Zhao F, et al. Chemical equilibrium controlled synthesis of polyoxymethylene dimethyl ethers over sulfated titania[J]. Journal of Energy Chemistry, 2015, 24(2):239-244.
[4] Arvidson M, Fakley M E, Spencer M S. Lithium halide-assisted formation of polyoxymethylene dimethyl ethers from dimethoxymethane and formaldehyde[J]. Journal of Molecular Catalysis, 1987, 41(2):39l-393.
[5] 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.
[6] Fleisch T H, Sills R A. Large-scale gas conversion through oxygenates:beyond GTL-FT[J]. Studies in Surface Science and Catalysis, 2004, 147:31-36.
[7] Sanfilppo D, Patrini R, Marchionna M. Use of an oxygenated product as a substitute of gas oil in diesel engines:US20040187380A1[P]. 2004-09-30.
[8]申威,张阿玲,韩维建.车用合成燃料能源消费和温室气体排放对比分析[J].清华大学学报(自然科学版), 2007, 47(3):441-444.Shen W, Zhang A L, Han W J. Well-to-wheel analysis of energy use and greenhouse gas emissions for synthesized vehicle fuels[J].Journal of Tsinghua University(Science and Technology), 2007, 47(3):441-444.
[9] 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:US6160186A[P]. 2000-12-30.
[10] 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(6):833-836.
[11]许云风.柴油添加剂聚甲醛二甲醚的酸催化合成研究[D].上海:上海师范大学, 2013.Xu Y F. Study on acid catalytic synthesis of diesel oil additive polyoxymethylene dimethyl ether[D]. Shanghai:Shanghai Normal University, 2013.
[12] Secordel X, Berrier E, Capron M, et al. TiO2-supported rhenium oxide catalysts for methanol oxidation:effect of support texture on the structure and reactivity evidenced by an operando Raman study[J]. Catalysis Today, 2010, 155(3):177-183.
[13] Schmitz N, Burger J, Hasse H, Reaction kinetics of the formation of poly(oxymethylene)dimethyl ethers from formaldehyde and methanol in aqueous solutions[J]. Industrial&Engineering Chemistry Research, 2015, 54:12553-12560.
[14] Schmitz N, Strofer E, Burger J. 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.
[15]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氧基二甲醚[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.
[16]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.
[17]王云芳,歩长娟,邢金仙.合成聚甲氧基二甲醚催化剂研究进展[J].现代化工, 2015, 35(4):38-43.Wang Y F, Bu C J, Xing J X. Research progress in catalyst for polyoxymethylene dimethyl ethers[J]. Modern Chemical Industry,2015, 35(4):38-43.
[18]陈建国,王云芳,邢金仙,等.制备聚甲氧基二甲醚的组合系统装置:203582765U[P]. 2014-05-07.Chen J G, Wang Y F, Xing J X, et al. Composite system device for preparing polymethoxy dimethyl ether:203582765U[P]. 2014-05-07.
[19]李晓云,于海斌,孙彦民,等.一种连续生产聚甲醛二甲醚的方法:102786397A[P]. 2012-11-21.Li X Y, Yu H B, Sun Y M, et al. Method for continuously producing polyoxymethylene dimethyl ether:102786397A[P].2012-11-21
[20]张也贤,商红岩,洪正鹏,等.用于合成聚甲氧基二烷基醚的液相反应装置:202962442U[P]. 2013-06-05.Zhang Y X, Shang H Y, Hong Z P, et al. Liquid phase reaction device for synthesizing polymethoxy dialkyl ether:202962442U[P]. 2013-06-05.
[21]张英伟,秦少鹏,王耀红,等.制备聚甲氧基二甲醚的系统:203820659U[P]. 2014-09-10.Zhang W Y, Qin S P, Wang Y H, et al. System for preparing polymethoxy dimethyl ether:203820659U[P]. 2014-09-10.
[22] Zheng Y Y, Tang Q, Wang T F, et al. Molecular size distribution in synthesis of polyoxymethylene dimethyl ethers and process optimization using response surface methodology[J]. Chemical Engineering Journal, 2015, 278:183-189
[23] Li H J, SONG H L, Xia C G, et al. Designed SO42-/Fe2O3-SiO2solid acids for polyoxymethylene dimethyl ethers synthesis:the acid sites control and reaction pathways[J]. Applied Catalysis B:Environmental, 2014, 165:466-476.
[24] Wu Q, Wang M, Hao Y, et al. Synthesis of polyoxymethylene dimethyl ethers catalyzed by Br?nsted acid ionic liquids with alkane sulfonic acid group[J]. Royal Society of Chemistry, 2014, 5(71):57968-57974.
[25]钟禄平,肖剑.聚甲醛二甲醚的生产方法:102372614A[P].2012-03-14.Zhong L P, Xiao J. Method for polyoxymethylene dimethyl ether production:102372614A[P]. 2012-03-14.
[26] 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].Industrial&Engineering Chemistry Research, 2012, 51(39):12751-12761.
[27] Gresham W F, Brooks R E. Preparation of polyformals:US2449469[P]. 1948-09-14.
[28] Patrini R, Marchionna M. Liquid mixture consisting of diesel gas oils and oxygenated compounds:US6534658[P]. 2003-03-18.
[29] Chen J, Song H Y, Xia C, et al. Method for synthesizing polyxymethylene dimethyl ethers by liquid catalysis:US20100056830 A1[P]. 2010-03-04.
[30] 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.
[31]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:103360224A[P]. 2013-10-23.Wang Y F, Chen J G, Xing J X, et al. A combined process for preparing polymethoxy dimethyl ether:103360224A[P]. 2013-10-23.
[32] Liu F, Wang T F, Zheng Y Y, et al. Synergistic effect of Br?nsted and Lewis acid sites for the synthesis of polyoxymethylene dimethyl ethers over highly efficient SO42-/TiO2catalysts[J].Journal of Catalysis, 2017, 255:17-25.
[33] Zheng Y Y, Tang Q, Wang T F, et al. Synthesis of a green diesel fuel additive over cation resins[J]. Chemical Engineering&Technology, 2013, 36(11):1951-1956.
[34]石磊,姚杰,朱文良,等.磺酸树脂催化甲缩醛一步羰化制高附加值甲氧基乙酸甲酯[J].化工学报, 2017, 68(10):3739-3746.Shi L, Yao J, Zhu W L, et al. Efficient sulfonic acid resin catalysts for carbonylation of dimethoxymethane to value-added methyl methoxyacetate[J]. CIESC Journal, 2017, 68(10):3739-3746.
[35] Chen F, Shi L, Yao J, et al. A highly efficient sulfonic acid resin for liquid phase carbonylation of dimethoxymethane[J]. Catalysis Science&Technology, 2018, 8(2):580-590.
[36]杨科岐,郭兵.最新喷雾干燥法制多聚甲醛工艺[J].煤炭加工与综合利用, 2016, 4(199):52-56.Yang K Q, Guo B. Latest spray-drying process for making paraformaldehyde[J]. Coal Processing&Comprehensive, 2016, 4(199):52-56.
[37] Wang F, Zhu G L, Li Z, et al. Mechanistic study for the formation of polyoxymethylene dimethyl ethers promoted by sulfonic acidfunctionalized ionic liquids[J]. Journal of Molecular Catalysis A:Chemical, 2015, 408:228-236
[38] Celik F E, Kim T, Mlinara N, et al. An investigation into the mechanism and kinetics of dimethoxymethane carbonylation over FAU and MFI zeolites[J]. Journal of Catalysis, 2010, 274(2):150-162
[39] Zhang D X, Shi L, Wang Y, et al. Effect of mass-transfer control on HY zeolites for dimethoxymethane carbonylation to methyl methoxyacetate[J]. Catalysis Today, 2018, 316:114-121.
[40] 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.
[41] Ma W T, Hu Y F, Wang H Y, et al. The effects of typical salts,acids and ionic liquids on the solubility of formaldehyde in aqueous solutions[J]. Fluid Phase Equilibria, 2018, 460(5):51-56.
[42]石磊,孙东,张婉莹,等.一种合成聚甲氧基二甲醚的磺酸树脂催化剂改性方法:201610223149.5[P]. 2018-05-04.Shi L, Sun D, Zhang W Y, et al. Method for modifying sulfonic acid resin catalyst for synthesizing polymethoxy dimethyl ether:201610223149.5[P]. 2018-05-04.
[43] 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.
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