磁性纳米颗粒负载离子液体催化合成聚甲醛二甲醚
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摘要
制备了磁性纳米颗粒负载离子液体催化剂,使用XRD、TEM、FT-IR等手段对催化剂进行分析表征,结果表明离子液体较好地负载在磁性纳米颗粒上。将其用于催化合成聚甲醛二甲醚(PODEn)的反应中,考察了催化剂用量、醇醛比、反应温度和时间等因素对催化活性的影响,得出了最佳工艺条件:催化剂的质量分数为2.0%,甲醇与三聚甲醛物质的量比2∶1,反应温度110℃,反应时间3h.在该条件下,三聚甲醛的转化率为99.8%,PODE3～5的选择性达到37.96%,催化剂重复使用4次后仍有较高催化活性。
Magnetic nanoparticle supported ionic liquid catalysts were prepared.XRD,TEM and FT-IR were used for the characterization of the catalysts.The results show that ionic liquid was well supported on magnetic nanoparticles.Polyoxymethylene dimethyl ethers(PODEn)was synthesized via the reaction catalyzed by the magnetic nanoparticle supported ionic liquid catalyst.The influences of catalyst dosage,the mole ratio of methanol to trioxane,reaction temperature and reaction time on catalytic activity were investigated.The optimum operating conditions were obtained:reaction temperature 110℃,reaction time 3 h,n(methanol)∶n(trioxane)=2∶1,catalyst dosage 2.0%.Under these conditions,the conversion rate of trioxane was 99.8% and selectivity of PODE3～8 reached 37.96%,catalyst still remained highly active even after being reused four times.
Magnetic nanoparticle supported ionic liquid catalysts were prepared.XRD,TEM and FT-IR were used for the characterization of the catalysts.The results show that ionic liquid was well supported on magnetic nanoparticles.Polyoxymethylene dimethyl ethers(PODEn)was synthesized via the reaction catalyzed by the magnetic nanoparticle supported ionic liquid catalyst.The influences of catalyst dosage,the mole ratio of methanol to trioxane,reaction temperature and reaction time on catalytic activity were investigated.The optimum operating conditions were obtained:reaction temperature 110℃,reaction time 3 h,n(methanol)∶n(trioxane)=2∶1,catalyst dosage 2.0%.Under these conditions,the conversion rate of trioxane was 99.8% and selectivity of PODE3～8 reached 37.96%,catalyst still remained highly active even after being reused four times.
引文
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[16]张朝峰,李静,陈树伟,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:CN103381372B[P].2015-08-19.ZHANG C F,LI J,CHEN S W,et al.Method for preparing polyoxymethylene dimethyl ethers by using molecular sieve load of ionic liquids as catalyst:CN103381372B[P].2015-08-19.
[17]张朝峰,邢俊德,刘康军,等.一种磁性纳米咪唑类离子液体催化剂及其催化合成聚甲醛二甲醚的方法:CN103381373B[P].2016-01-20.ZHANG C F,XING J D,LIU K J.Method for preparing polyoxymethylene dimethyl ethers by using magnetic nanometer imidazole ionic liquid as catalyst:CN103381373B[P].2016-01-20.
[18]谢成,刘志明,吴鹏.无惰性气体保护Fe3O4纳米球的超声法制备及表征[J].应用化工,2012,41(10):1697-1701.XIE C,LIU Z M,WU P.Ultrasonic preparation and characterization of Fe3O4nanospheres without inert gas protection[J].Applied Chemical Industry,2012,41(10):1697-1701.
[19]SAFARI J,ZARNEGAR Z.Immobilized ionic liquid on superparamagnetic nanoparticles as an effective catalyst for the synthesis of tetrasubstituted imidazoles under solvent-free conditions and microwave irradiation[J].Comptes Rendus Chimie,2013,16(10):920-928.
[20]张育红,彭振磊,王川.聚甲醛二甲基醚的分析方法[J].石油化工,2010,39(s1):581-583.ZHANG Y H,PENG Z L,WANG C.Analytical methods for polyoxymethylene dimethyl ethers[J].Petrochemical technology,2010,39(sl):581-583.
[21]张文学.酸洗废液资源化:纳米四氧化三铁的制备及性能研究[D].哈尔滨:哈尔滨师范大学,2015.ZHANG W X.Reclamation of acid picking waste:controllable preparation of nano Fe3O4and its properity study systemically[D].Harbin:Harbin Normal University,2015.
[2]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].Industrial&Engineering Chemistry Research,2016,55(7):1859-1865.
[3]MARCHIONNA M,PATRINI R,SANFILIPPO D,et al.From natural gas to oxygenates for cleaner diesel fuels[J].Studies in Surfaceence&Catalysis,2001,136:489-494.
[4]李晓云,李晨,于海斌.柴油添加剂聚甲醛二甲醚的应用研究进展[J].化工进展,2008,27(s1):317-319.LI X Y,LI C,YU H B.Applied research progress of diesel fuel additive polyoxymethylene dimethyl ethers[J].Chemical Industry and Engineering Progress,2008,27(s1):317-319.
[5]GRESHAM W F,BROOKS R E.Preparation of polyformals:US2449469[P].1948-09-14.
[6]SCHELLING H,STROEFER E,PINKOS R,et al.Method for producing polyoxymethylene dimethyl ethers:US20070260094A1[P].2007-11-08.
[7]BURGER J,STRFER 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,2016,51(39):12751-12761.
[8]HAGEN G P,SPANGLER M J.Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of formaldehyde formed by oxidation of dimethyl ether:US6392102[P].2002-03-21.
[9]PATRINI R,MARCHIONNA M.Liquid mixture consisting of diesel gas oils and oxygenated compounds:US6534685B1[P].2003-03-18.
[10]陈静,唐中华,夏春谷,等.聚甲氧基甲缩醛的制备方法:CN101182367A[P].2008-05-21.CHEN J,TANG Z H,XIA C G,et al.Method for preparing polyoxymethylene dimethyl ether:CN101182367A[P].2008-05-21.
[11]赵峰,李华举,宋焕玲,等.三聚甲醛与甲醇在SO2-4/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.ZHAO F,LI H J,SONG H L,et al.Ring-opening and condensation of trioxane with methanol over SO2-4/Fe2O3solid superacid[J].Natural Gas Chemical Industry,2013,38(1):1-6.
[12]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.
[13]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 poly(oxymethylene)dimethy ethers catalyzed by acidic functionalized ionic liquids[J].Journal of Fuel Chemistry and Technology,2014,42(4):501-506.
[14]郑明岩,刘康军,张朝峰,等.响应面法优化聚甲醛二甲醚的合成工艺[J].石油学报(石油加工),2013,29(5):830-835.ZHENG M Y,LIU K J,ZHANG C F,et al.Optimization of synthesis process for polyoxymethylene dimethyl ethers by response surface methodology[J].Acta Petrolei Sinica(Petroleum Processing Section),2013,29(5):830-835.
[15]刘康军,张朝峰,李瑞丰.聚甲氧基甲缩醛的最新研究进展[J].化工进展,2013,32(11):2593-2598.LIU K J,ZHANG C F,LI R F.Recent progress in polyoxymethylene dimethyl ethers[J].Chemical Industry and Engineering Progress,2013,32(11):2593-2598.
[16]张朝峰,李静,陈树伟,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:CN103381372B[P].2015-08-19.ZHANG C F,LI J,CHEN S W,et al.Method for preparing polyoxymethylene dimethyl ethers by using molecular sieve load of ionic liquids as catalyst:CN103381372B[P].2015-08-19.
[17]张朝峰,邢俊德,刘康军,等.一种磁性纳米咪唑类离子液体催化剂及其催化合成聚甲醛二甲醚的方法:CN103381373B[P].2016-01-20.ZHANG C F,XING J D,LIU K J.Method for preparing polyoxymethylene dimethyl ethers by using magnetic nanometer imidazole ionic liquid as catalyst:CN103381373B[P].2016-01-20.
[18]谢成,刘志明,吴鹏.无惰性气体保护Fe3O4纳米球的超声法制备及表征[J].应用化工,2012,41(10):1697-1701.XIE C,LIU Z M,WU P.Ultrasonic preparation and characterization of Fe3O4nanospheres without inert gas protection[J].Applied Chemical Industry,2012,41(10):1697-1701.
[19]SAFARI J,ZARNEGAR Z.Immobilized ionic liquid on superparamagnetic nanoparticles as an effective catalyst for the synthesis of tetrasubstituted imidazoles under solvent-free conditions and microwave irradiation[J].Comptes Rendus Chimie,2013,16(10):920-928.
[20]张育红,彭振磊,王川.聚甲醛二甲基醚的分析方法[J].石油化工,2010,39(s1):581-583.ZHANG Y H,PENG Z L,WANG C.Analytical methods for polyoxymethylene dimethyl ethers[J].Petrochemical technology,2010,39(sl):581-583.
[21]张文学.酸洗废液资源化:纳米四氧化三铁的制备及性能研究[D].哈尔滨:哈尔滨师范大学,2015.ZHANG W X.Reclamation of acid picking waste:controllable preparation of nano Fe3O4and its properity study systemically[D].Harbin:Harbin Normal University,2015.
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