简化晶种导向液法合成低硅铝比SAPO-34分子筛
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摘要
用三乙胺为模板剂,采用简化晶种导向液法制备低硅铝比的SAPO-34分子筛,利用XRD、SEM、TPD和NMR等手段分析分子筛的性质,并与常规的晶种法进行对比。结果表明:晶种法需要在36 h内完成晶化,晶粒粒径约为2μm;而简化晶种导向法液法所需晶化时间仅为24 h,晶粒粒径约3. 5μm;与晶种法相比,简化晶种导向液法合成的分子筛具有相对较弱的酸性,其甲醇转化制乙烯和丙烯选择性高出4%。
The SAPO-34 molecular sieves with low ratio of Si/Al were synthesized using the trimethylamine as template by simplified seed induced agent method. The products were characterized using XRD,SEM,TPD and NMR,which were compared with samples by seed method. The results show that molecular sieve synthesized by seed method finishes crystallization at 36 h,and the sizes are about 2 μm; However,the simplified seed induced agent method only needs 24 h to finish crystallization,and the sizes are about 3. 5 μm. Compared with SAPO-34 synthesized by seed method,the SAPO-34 synthesized by simplified seed induced agent method present weaker acidity and its selections of the ethylene and propylene olefins in the conversion of methanol are increased by about 4%.
The SAPO-34 molecular sieves with low ratio of Si/Al were synthesized using the trimethylamine as template by simplified seed induced agent method. The products were characterized using XRD,SEM,TPD and NMR,which were compared with samples by seed method. The results show that molecular sieve synthesized by seed method finishes crystallization at 36 h,and the sizes are about 2 μm; However,the simplified seed induced agent method only needs 24 h to finish crystallization,and the sizes are about 3. 5 μm. Compared with SAPO-34 synthesized by seed method,the SAPO-34 synthesized by simplified seed induced agent method present weaker acidity and its selections of the ethylene and propylene olefins in the conversion of methanol are increased by about 4%.
引文
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[3] HEREIJGERS B P C,BLEKEN F,NILSEN M H,et al.Product shape selectivity dominates the methanol-to-olefins(MTO)reaction over H-SAPO-34 catalysts[J]. Journal of Catalysis,2009,264(1):77-87.
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[5]崔宇,王垚,魏飞.SAPO-34分子筛硅铝比对甲醇制烯烃反应性能及积炭组成的影响[J].化工学报,2015,66(8):2982-2989.CUI Yu,WANG Yao,WEI Fei. Effect of Si/Al ratio of SAPO-34 on reactivity and coke composition in methanol to olefins reaction[J]. CIESC Journal,2015,66(8):2982-2989.
[6] WILSON S. BARGER P. The characteristics of SAPO-34which influence the conversion of methanol to light olefins[J]. Microporous&Mesoporous Materials,1999,29(1/2):117-126.
[7]唐君琴,叶丽萍,应卫勇,等.硅铝比对SAPO-34催化剂在甲醇制烯烃反应中催化性能的影响[J].石油化工,2010,39(1):22-26.TANG Junqin,YE Liping,YING Weiyong,et al. Performances of SAPO-34 catalysts with different ratios of Si to Al in methanol-to-olefins[J]. Petrochemical Technology,2010,39(1):22-26.
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[10] XU L,DU A,WEI Y,et al. Synthesis of SAPO-34 with only Si(4Al)species:effect of Si contents on Si incorporation mechanism and Si coordination environment of SAPO-34[J]. Microporous&Mesoporous Materials,2008,115(3):332-337.
[11] ASKARI S,HALLDJ R. Ultrasonic pretreatment for hydrothermal synthesis of SAPO-34 nanocrystals[J]. Ultrasonic Sonochemistry,2012,19(3):554-559.
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[13] SHALMANI F M,HALLDJ R,ASKARI S. Effect of contributing factors on microwave-assisted hydrothermal synthesis of nanosized SAPO-34 molecular sieves[J].Powder Technology,2012,221(5):395-402.
[14]刘红星,谢在库,张成芳,等.用氟化氢-三乙胺复合模板剂合成SAPO-34分子筛的晶化历程[J].催化学报,2003,24(11):849-855.LIU Hongxing,XIE Zaiku,ZHANG Chengfang,et al.Crystallization process of SAPO-34 molecular sieve using hydrogen fluoride and triethylamine as composite template[J]. Chinese Journal of Catalysis,2003,24(11):849-855.
[15]管洪波,刘红星,赵昱,等.高活性SAPO-34分子筛的制备方法:CN201410455784. 7[P].2016-03-09.
[16]狄春雨,张贺,徐丹,等.导向剂法合成SAPO-34分子筛及其在甲醇制烯烃中的性能[J].工业催化,2012,20(2):33-36.DI Chunyu,ZHANG He,XU Dan,et al. Synthesis of SAPO-34 molecular sieves by seed gel method and their catalytic performance in methanol to olefins reaction[J].Industrial Catalysis,2012,20(2):33-36.
[17] TAN Juan,LIU Zhongmin,HE Changqing,et al. Study on the crystallization mechanism of molecular sieve SAPO-34[J]. Chinese Journal of Catalysis,1998,19(5):440-441.
[18]田树勋,岳国,李艺,等.晶种参与合成SAPO-34分子筛[J].石油化工,2009,38(12):1276-1280.TIAN Shuxun,YUE Guo,LI Yi,et al. The synthesis of SAPO-34 molecular sieve with the seed participate in[J]. Petroleum Chemical Industry,2009,38(12):1276-1280.
[19] ALIPOUR SM,HALLADJ R,ASKARI S. Effects of the different synthetic parameters on the crystallinity and crystal size of nanosized ZSM-5 zeolite[J]. Reviews in Chemical Engineering,2014,30(3):289-322.
[20] ASKARI S,HALLADJ R,SOHRABI M. An overview of the effects of crystallization time,template and silicon sources on hydrothermal synthesis of SAPO-34 molecular sieve with small crystals[J]. Reviews on Advanced Materials Science,2012,32(2):83-93.
[21] HEYDEN HV,MINTOVA S,BEIN T. Nanosized SAPO-34 synthesized from colloidal solutions[J]. Chemistry of Materials,2008,20(9):2956-2963.
[22] WANG Q,WANG L,WANG H,et al. Synthesis,characterization and catalytic performance of SAPO-34 molecular sieves for methanol-to-olefin(MTO)reaction[J]. Asia-pacific Journal of Chemical Engineering,2011,6(4):596-605.
[23]刘红星,谢在库,张成芳,等.不同模板剂合成SAPO-34分子筛的表征与热分解过程研究[J].化学物理学报,2003,16(6):521-527.LIU Hongxing,XIE Zaiku,ZHANG Chengfang,et al.Characterization and the thermal decomposition modes of SAPO-34 molecular sieves synthesized with different templates[J]. Chinese Journal of Chemical Physics,2003,26(6):521-527.
[24] VENNA S R,CARREON M A. Amino-functionalized SAPO-34 membranes for CO2/CH4and CO2/N2separation[J]. Langmuir the Acs Journal of Surfaces&Colloids,2011,27(6):2888-2894.
[25] TAN J,LIU Z,BAO X,et al. Crystallization and Si incorporation mechanisms of SAPO-34[J]. Microporous&Mesoporous Materials,2002,53(1):97-108.
[26]冯琦瑶,邢爱华,张新锋,等.硅溶胶原料对SAPO-34分子筛及其对MTO反应性能的影响[J].天然气化工(C1化学与化工),2016,41(3):11-42.FENG Qiyao,XING Aihua,ZHANG Xinfeng,et al.Effect of silica sol sources on properties of SAPO-34 molecular sieves and their methanol to olefins reaction performances[J].Natural Gas Chemical Industry,2016,41(3):11-42.
[27] GAO B B,FAN D,SUN L J,et al. Insights into the amino thermal crystallization process of SAPO-34 and its comparison with hydrothermal system[J]. Microporous&Mesoporous Materials,2017,248:204-213.
[28] BLACKWELL C S,PATTON R. Solid-state NMR of silicoaluminophosphate molecular sieves and aluminophosphate materials[J].The Journal of Physical Chemistry,1988,92(13):3965-3970.
[29] YAN Z M,CHEN B B,HUANG Y M. A solid-state NMR study of the formation of molecular sieve SAPO-34[J]. Solid State Nuclear Magnetic Resonance,2009,35(2):49-60.
[30] YAN Z M,ZHUANG J Q,XU L,et al. Direct observation of various Al sites in SAPO-34 by 27Al multiquantum(MQ)magic angle spinning(MAS)NMR[J].Chinese Chemical Letters,2003,14(1):87-90.
[31] BLEKEN F,BJ?RGEN M,PALUMBO L,et al. The effect of acid strength on the conversion of methanol to olefins over acidic microporous catalysts with the CHA topology[J]. Topics in Catalysis,2009,52(3):218-228.
[32] SUN Q,MA Y,WANG N,et al. High performance nanosheet-like silicoaluminophosphate molecular sieves:synthesis,3D EDT structural analysis and MTO catalytic studies[J]. Journal of Materials Chemistry A,2014,42(2):17828-17839.
[2] DAHL I M,KOLBOE S. On the reaction mechanism for propene formation in the MTO reaction over SAPO-34[J]. Catalysis Letters,1993,20(3/4):329-336.
[3] HEREIJGERS B P C,BLEKEN F,NILSEN M H,et al.Product shape selectivity dominates the methanol-to-olefins(MTO)reaction over H-SAPO-34 catalysts[J]. Journal of Catalysis,2009,264(1):77-87.
[4] DAHL I M,MOSTAD H,AKPORIAYE D,et al. Structural and chemical influences on the MTO reaction:a comparison of chabazite and SAPO-34 as MTO catalysts[J]. Microporous&Mesoporous Materials,1999,29(1/2):185-190.
[5]崔宇,王垚,魏飞.SAPO-34分子筛硅铝比对甲醇制烯烃反应性能及积炭组成的影响[J].化工学报,2015,66(8):2982-2989.CUI Yu,WANG Yao,WEI Fei. Effect of Si/Al ratio of SAPO-34 on reactivity and coke composition in methanol to olefins reaction[J]. CIESC Journal,2015,66(8):2982-2989.
[6] WILSON S. BARGER P. The characteristics of SAPO-34which influence the conversion of methanol to light olefins[J]. Microporous&Mesoporous Materials,1999,29(1/2):117-126.
[7]唐君琴,叶丽萍,应卫勇,等.硅铝比对SAPO-34催化剂在甲醇制烯烃反应中催化性能的影响[J].石油化工,2010,39(1):22-26.TANG Junqin,YE Liping,YING Weiyong,et al. Performances of SAPO-34 catalysts with different ratios of Si to Al in methanol-to-olefins[J]. Petrochemical Technology,2010,39(1):22-26.
[8]ALVARO-MUNOZ T,MARQUEZ-ALVAREZ C,SASTRE E. Use of different templates on SAPO-34 synthesis:effect on the acidity and catalytic activity in the MTO reaction[J]. Catalysis Today,2012,179(1):27-34.
[9] IZADBAKHSH A,FARHADI F,KHORASHEH F,et al.Key parameters in hydrothermal synthesis and characterization of low silicon content SAPO-34 molecular sieve[J]. Microporous&Mesoporous Materials,2009,126:1-7.
[10] XU L,DU A,WEI Y,et al. Synthesis of SAPO-34 with only Si(4Al)species:effect of Si contents on Si incorporation mechanism and Si coordination environment of SAPO-34[J]. Microporous&Mesoporous Materials,2008,115(3):332-337.
[11] ASKARI S,HALLDJ R. Ultrasonic pretreatment for hydrothermal synthesis of SAPO-34 nanocrystals[J]. Ultrasonic Sonochemistry,2012,19(3):554-559.
[12]吴磊.不同晶粒形貌的SAPO-34分子筛的可控合成、表征及其MTO催化性能研究[D].北京:中国科学院大学,2013.WU Lei. Controllable synthesis, characterization and MTO catalytic performance of SAPO-34 molecular sieve with different crystal morphology[D]. Beijing:University of Chinese Academy of Sciences,2013.
[13] SHALMANI F M,HALLDJ R,ASKARI S. Effect of contributing factors on microwave-assisted hydrothermal synthesis of nanosized SAPO-34 molecular sieves[J].Powder Technology,2012,221(5):395-402.
[14]刘红星,谢在库,张成芳,等.用氟化氢-三乙胺复合模板剂合成SAPO-34分子筛的晶化历程[J].催化学报,2003,24(11):849-855.LIU Hongxing,XIE Zaiku,ZHANG Chengfang,et al.Crystallization process of SAPO-34 molecular sieve using hydrogen fluoride and triethylamine as composite template[J]. Chinese Journal of Catalysis,2003,24(11):849-855.
[15]管洪波,刘红星,赵昱,等.高活性SAPO-34分子筛的制备方法:CN201410455784. 7[P].2016-03-09.
[16]狄春雨,张贺,徐丹,等.导向剂法合成SAPO-34分子筛及其在甲醇制烯烃中的性能[J].工业催化,2012,20(2):33-36.DI Chunyu,ZHANG He,XU Dan,et al. Synthesis of SAPO-34 molecular sieves by seed gel method and their catalytic performance in methanol to olefins reaction[J].Industrial Catalysis,2012,20(2):33-36.
[17] TAN Juan,LIU Zhongmin,HE Changqing,et al. Study on the crystallization mechanism of molecular sieve SAPO-34[J]. Chinese Journal of Catalysis,1998,19(5):440-441.
[18]田树勋,岳国,李艺,等.晶种参与合成SAPO-34分子筛[J].石油化工,2009,38(12):1276-1280.TIAN Shuxun,YUE Guo,LI Yi,et al. The synthesis of SAPO-34 molecular sieve with the seed participate in[J]. Petroleum Chemical Industry,2009,38(12):1276-1280.
[19] ALIPOUR SM,HALLADJ R,ASKARI S. Effects of the different synthetic parameters on the crystallinity and crystal size of nanosized ZSM-5 zeolite[J]. Reviews in Chemical Engineering,2014,30(3):289-322.
[20] ASKARI S,HALLADJ R,SOHRABI M. An overview of the effects of crystallization time,template and silicon sources on hydrothermal synthesis of SAPO-34 molecular sieve with small crystals[J]. Reviews on Advanced Materials Science,2012,32(2):83-93.
[21] HEYDEN HV,MINTOVA S,BEIN T. Nanosized SAPO-34 synthesized from colloidal solutions[J]. Chemistry of Materials,2008,20(9):2956-2963.
[22] WANG Q,WANG L,WANG H,et al. Synthesis,characterization and catalytic performance of SAPO-34 molecular sieves for methanol-to-olefin(MTO)reaction[J]. Asia-pacific Journal of Chemical Engineering,2011,6(4):596-605.
[23]刘红星,谢在库,张成芳,等.不同模板剂合成SAPO-34分子筛的表征与热分解过程研究[J].化学物理学报,2003,16(6):521-527.LIU Hongxing,XIE Zaiku,ZHANG Chengfang,et al.Characterization and the thermal decomposition modes of SAPO-34 molecular sieves synthesized with different templates[J]. Chinese Journal of Chemical Physics,2003,26(6):521-527.
[24] VENNA S R,CARREON M A. Amino-functionalized SAPO-34 membranes for CO2/CH4and CO2/N2separation[J]. Langmuir the Acs Journal of Surfaces&Colloids,2011,27(6):2888-2894.
[25] TAN J,LIU Z,BAO X,et al. Crystallization and Si incorporation mechanisms of SAPO-34[J]. Microporous&Mesoporous Materials,2002,53(1):97-108.
[26]冯琦瑶,邢爱华,张新锋,等.硅溶胶原料对SAPO-34分子筛及其对MTO反应性能的影响[J].天然气化工(C1化学与化工),2016,41(3):11-42.FENG Qiyao,XING Aihua,ZHANG Xinfeng,et al.Effect of silica sol sources on properties of SAPO-34 molecular sieves and their methanol to olefins reaction performances[J].Natural Gas Chemical Industry,2016,41(3):11-42.
[27] GAO B B,FAN D,SUN L J,et al. Insights into the amino thermal crystallization process of SAPO-34 and its comparison with hydrothermal system[J]. Microporous&Mesoporous Materials,2017,248:204-213.
[28] BLACKWELL C S,PATTON R. Solid-state NMR of silicoaluminophosphate molecular sieves and aluminophosphate materials[J].The Journal of Physical Chemistry,1988,92(13):3965-3970.
[29] YAN Z M,CHEN B B,HUANG Y M. A solid-state NMR study of the formation of molecular sieve SAPO-34[J]. Solid State Nuclear Magnetic Resonance,2009,35(2):49-60.
[30] YAN Z M,ZHUANG J Q,XU L,et al. Direct observation of various Al sites in SAPO-34 by 27Al multiquantum(MQ)magic angle spinning(MAS)NMR[J].Chinese Chemical Letters,2003,14(1):87-90.
[31] BLEKEN F,BJ?RGEN M,PALUMBO L,et al. The effect of acid strength on the conversion of methanol to olefins over acidic microporous catalysts with the CHA topology[J]. Topics in Catalysis,2009,52(3):218-228.
[32] SUN Q,MA Y,WANG N,et al. High performance nanosheet-like silicoaluminophosphate molecular sieves:synthesis,3D EDT structural analysis and MTO catalytic studies[J]. Journal of Materials Chemistry A,2014,42(2):17828-17839.