具有纳米线镶嵌结构ZSM-5/L复合分子筛的合成及表征
|
摘要
采用两步晶化法,以四丙基氢氧化铵预处理ZSM-5为晶种,快速合成了纳米线镶嵌结构ZSM-5/L复合分子筛.通过XRD、SEM-EDX、TEM和N_2吸附-脱附等手段对合成样品的物理化学性质进行了表征.孔道性质表明复合分子筛具有微孔和介孔的多级孔道结构,椭球的L分子筛镶嵌在纳米线的ZSM-5分子筛周围.晶种预处理影响了溶胶的电荷及分子筛的形貌,当合成样品中ZSM-5的质量分数小于2%(重量百分比)时,凝胶的负电荷较多,易形成椭球状L分子筛;当合成样品中ZSM-5的质量分数大于2%(重量百分比)时,zeta电位在-39.822～-42.352mV之间波动,ZSM-5分子筛的形貌从长条状逐渐转变为纳米线状.阳离子比影响复合分子筛中L分子筛形成,当阳离子比R=n(K_2O)/(n(K_2O)+n(Na_2O))小于0.6时,不利于L型分子筛的形成;当阳离子比大于0.6,即K~+较多Na~+较少时,有利于L型分子筛中α-钙霞石笼的形成.
In this paper,the nanowire Mosaic structure ZSM-5/L composite molecular sieve was rapidly synthesized by a two-step crystallization method that pretreated ZSM-5 with tetrapropylammonium hydroxide to a seed crystal.The physicochemical properties of the synthesized samples were characterized by XRD,SEM,TEM and N_2 adsorption-desorption. The pore properties indicate that the composite molecular sieve has multi-stage pore structure composed of micropores and mesopores. The ellipsoidal L molecular sieves are embedded in the ZSM-5 molecular sieve around the nanowire. The pretreatment of the seed crystal affect the electric charge of the synthetic sol and the morphology of the molecular sieve. When the mass fraction of ZSM-5 in the synthetic sample is less than 2%,the gel has more negative charges,forming ellipsoidal L molecular sieve. When the mass fraction of ZSM-5 in the synthetic sample is greater than 2%,the zeta potential fluctuates between-39.822 m V and-42.352 m V,the morphology of ZSM-5 molecular sieve changes from strip to nanowire. The cation ratio affects the change of the L-type molecular sieve's morphology,When the cationic ratio is less than 0.6,it is not conducive to the formation of L-type molecular sieve. When the cationic ratio is greater than 0.6,in other words,K+gets more and Na+gets less,the formation of α-calcium nepheline cages in L-type molecular sieves is facilitated.
In this paper,the nanowire Mosaic structure ZSM-5/L composite molecular sieve was rapidly synthesized by a two-step crystallization method that pretreated ZSM-5 with tetrapropylammonium hydroxide to a seed crystal.The physicochemical properties of the synthesized samples were characterized by XRD,SEM,TEM and N_2 adsorption-desorption. The pore properties indicate that the composite molecular sieve has multi-stage pore structure composed of micropores and mesopores. The ellipsoidal L molecular sieves are embedded in the ZSM-5 molecular sieve around the nanowire. The pretreatment of the seed crystal affect the electric charge of the synthetic sol and the morphology of the molecular sieve. When the mass fraction of ZSM-5 in the synthetic sample is less than 2%,the gel has more negative charges,forming ellipsoidal L molecular sieve. When the mass fraction of ZSM-5 in the synthetic sample is greater than 2%,the zeta potential fluctuates between-39.822 m V and-42.352 m V,the morphology of ZSM-5 molecular sieve changes from strip to nanowire. The cation ratio affects the change of the L-type molecular sieve's morphology,When the cationic ratio is less than 0.6,it is not conducive to the formation of L-type molecular sieve. When the cationic ratio is greater than 0.6,in other words,K+gets more and Na+gets less,the formation of α-calcium nepheline cages in L-type molecular sieves is facilitated.
引文
[1] a. Zhang Rui-zhen(张瑞珍),Wen Shao-bo(温少波),Xing Pu(邢普),et al. Preparation and characterization of HZSM-5/SAPO-11 composite molecular sieves and their catalytic properties in isobutane aromatization(HZSM-5/SAPO-11复合分子筛的制备、表征及在异丁烷芳构化反应中的催化性能)[J]. Chem J Chin Univer(高等学校化学学报),2017,38(1):126-132.b. Li Heng-jie(李恒杰),Gao Peng-fei(高鹏飞),Xue Xiao-lu(薛晓璐),et al. Ionothermal synthesis of TAPO-5 molecular sieve by microwave irradiation in eutectic mixture(低共熔体中微波离子热法合成TAPO-5分子筛)[J]. J Mol Catal(China)(分子催化),2018,32(3):218-227.c. Ren Rong-xin(任容欣),Song Wan-cang(宋万仓),Liu Guan-feng(刘冠锋),et al. Recent research in preparation and application of hierarchical titanium silicalite-1 molecular sieve(多级孔钛硅分子筛的制备及应用进展)[J]. J Mol Catal(China)(分子催化),2017,31(6):594-604.
[2] a. Zhu Shu-jin(朱数金),Liu Su-yao(刘粟侥),Zhang Huai-ke(张怀科),et al. Investigation of synthesis and hydroisomerization performance of SAPO-11/Beta composite molecular sieve(SAPO-11/Beta复合分子筛的合成及其异构化性能研究)[J]. Chin J Catal(催化学报),2014,35(10):1676-1686.b. Zheng Bu-me(郑步梅),Fang Xiang-chen(方向晨),Guo Rong(郭蓉),et al. Hierarchical ZSM-5 zeolite:synthesis and application in oil refinery(多级孔ZSM-5分子筛的制备及其在炼油领域中的应用)[J]. J Mol Catal(China)(分子催化),2017,31(5):486-500.c. Ma Cun-cun(马存存),Hu Li(胡丽),Yang Donghua(杨冬花),et al. Synthesis and characterization of L/EU-1 composite zeolites with the tubular mosaic morphology(具有管状镶嵌结构L/EU-1复合分子筛的合成及表征)[J]. J Mol Catal(China)(分子催化),2017,31(1):82-91.
[3] Gao X,Zhang P,Yang J,et al. A novel approach for the removal of radiocesium from aqueous solution by ZSM-5molecular sieve[J]. Appl Radia Isoto,2018,139:231-237.
[4] Sadeghpour P,Haghighi M. High-temperature and shorttime hydrothermal fabrication of nanostructured ZSM-5catalyst with suitable pore geometry and strong intrinsic acidity used in methanol to light olefins conversion[J].Adv Pow Technol,2018,29(5):1175-1188.
[5] Breck D W, Acara N A. Crystalline zeolite L. US,3216789[P]. 1965.
[6] Zhang Ya-jing(张雅静),Deng Ju-lei(邓据磊),Zhang Su-juan(张素娟),et al. Investigation on Cu O-ZnO-Al2O3/HZSM-5 catalysts for synthesis of dimethyl ether from CO2hydrogenation(CO2加氢制备二甲醚Cu O-ZnO-Al2O3/HZSM-5催化剂的研究)[J]. J Mol Catal(China)(分子催化),2013,27(3):235-241.
[7] Du Jie(杜杰),Zhang Ya-jing(张雅静),Zhang Yu(张宇),et al. Effect of Si O2promoter on performance of Cu O-ZnO/HZSM-5 catalysts for synthesis of DME from CO2hydrogenation(Si O2助剂对Cu O-ZnO/HZSM-5催化CO2加氢制DME性能的影响)[J]. J Mol Catal(China)(分子催化),2016,30(4):346-353.
[8] Young D A,Linda Y,Calif. US,3867512[P]. 1975.
[9] Woltel T M. U.S.,4593133[P]. 1986.
[10] Wortel T M. U.S.,4701315[P]. 1987.
[11] Li S Gi,Xu R R. C.N.,85103013 A[P]. 1986.
[12] Ma Cun-cun(马存存). Synthetic study of L/ZSM-5 and L/EU-1 composite zeolite with the mosaic morphology(具有镶嵌结构L/ZSM-5和L/EU-1复合分子筛的合成研究)[D]. Taiyuan:Taiyuan University of Technology(太原:太原理工大学),2017.
[13] Liu Chang-jiang(刘昶江),Su Shang-qing(苏双青),Yang Jing(杨静),et al. Synthesis of L-type molecular sieve from potassium feldspar powder(钾长石粉体合成L型分子筛)[J]. J Chin Cera Soc(硅酸盐学报),2013,41(8):1151-1157.
[14] Lu Lu(陆璐),Zhang Hui-zhen(张会贞),Zhu Xuedong(朱学栋). Synthesis of hierarchical ZSM-5 and its application in benzene alkylation with methanol(多级孔ZSM-5分子筛的合成及催化苯、甲醇烷基化反应的研究)[J]. Acta Petro Sin(Petrol Proce Sec)(石油学报(石油加工)),2012,28(s1):111-115.
[15] He Ying-ping(何英萍),Liu Min(刘民),Dai Chengyi(代成义),et al. TPAOH modified nano HZSM-5 zeolite and the catalytic properties in methanol making gasoline(四丙基氢氧化铵改性纳米HZSM-5分子筛及其在甲醇制汽油中的催化性能)[J]. Chin J Catal(催化学报),2013,34(6):1148-1158.
[16] Huo Quan(霍全),Dou Tao(窦涛),Gong Yan-jun(巩雁军),et al. Synthesis and desulfurization performance of nanocrystal-assembled zeolite L with a hierarchical pore structure(纳米晶簇多级孔道L沸石的合成及其脱硫性能)[J]. Acta Phys-Chim Sin(物理化学学报),2010,26(2):378-384.
[17] Li Yu-ping(李玉平),Sun Cui-juan(孙翠娟),Jia Kun(贾坤),et al. Soft template-directed hierarchical mordenites and their performance in ben-zylation of benzene with benzyl alcohol(软模板导向合成多级孔丝光沸石及其苯的苄基化催化性能)[J]. J Inorg Mater(无机材料学报),2016,31(12):1355-1362.
[18] Mao Dong-sen(毛东森),Guo Qiang-sheng(郭强胜),Meng Tao(孟涛),et al. Effect of hydrothermal treatment on the acidity and catalytic performance of nanosized HZSM-5 zeolites for the conversion of methanol to propene(水热处理对纳米HZSM-5分子筛酸性及催化甲醇制丙烯反应性能的影响)[J]. Acta Phys-Chim Sin(物理化学学报),2010,26(2):338-344.
[19] Yang Dong-hua(杨冬花),Zhao Jun-fu(赵君芙),Zhang Jun-liang(张军亮),et al. Designed synthesis and crystallization of Fe-Al-EU-1 zeolites containing framework-iron(含铁骨架Fe-Al-EU-1分子筛的设计合成和晶化)[J]. Acta Phys-Chim Sin(物理化学学报),2012,28(3):720-728.
[20] Xiao Qi(肖奇),Wang Ping-hua(王平华),Ji Lingling(纪伶伶),et al. Dispersion of carbon nanotubes in aqueous solution with cationic surfactant CTAB(分散剂CTAB对碳纳米管悬浮液分散性能的影响)[J]. J Inorg Mater(无机材料学报),2007,22(6):1122-1126.
[21] Hu Li(胡丽),Yang Dong-hua(杨冬花),Zhao Yu(赵煜),et al. Synthesis of Ni Y zeolite and hydrogen evolution performance in cathode of a microbial electrolysis cell(Ni Y分子筛的合成及在微生物电解池阴极的析氢性能研究)[J]. J Fuel Chem Technol(燃料化学学报),2018,46(5):607-614.
[22] Li Qiang(李强),Dou Tao(窦涛),Huo Quan(霍全),et al. Physicochemical properties and activities of hydrocarbon catalytic cracking ofβ-zeolite with different silica-alumina ratios(不同硅铝比β沸石的理化性质及烃类催化裂化活性)[J]. Acta Phys-Chim Sin(物理化学学报),2008,24(7):1192-1198.
[23] Sun Na(孙娜),Wang Hai-yan(王海彦),Li Hao(李浩),et al. Synthesis of hierarchical pore SAPO-11 molecular sieve by sisal fiber and its hydrogen isomerization performance(剑麻纤维素合成多级孔SAPO-11分子筛及其临氢异构化性能)[J]. J Chin Cera Soc(硅酸盐学报),2018,46(1):108-115.
[24] Niu Jing-jing(牛静静),Guo Shi-ling(郭士岭),Chen Yi-liang(陈宜俍). Influencing factors for in-situ synthesis of zeolite l on calcined kaolin microspheres(高岭土微球原位合成L沸石过程中的影响因素)[J]. Acta Petro Sin(Petrol Proce Sec)(石油学报(石油加工)),2008,24(3):237-242.
[25] Fu Xian-cai(傅献彩),Shen Wen-xia(沈文霞),Yao Tian-yang(姚天扬),et al. Phys Chem(物理化学)[M]. Beijing:Higher Education Press(北京:高等教育出版社),2006,433-3445.
[26] Li Shou-gui(李守贵),Li Xi-kai(李锡凯),Xu Ru-ren(徐如人). Studies on the ageing mechanism for the directing agent of zeolite L(L沸石导向剂陈化机制的研究)[J]. Chem J Chin Univer(高等学校化学学报),1992,13(2):145-148.
[27] Sato M,Morikawa K,Kurosawa S. X-ray rietveld analysis of cation exchanged zeolite-L(LTL)[J]. Euro J Miner,1990,2(6):851-859.
[28] Lv Ai-ning(吕爱凝),Yang Dong-hua(杨冬花),Li Jian-hua(李建华),et al. Rapid Synthesis and characterization of hierarchical structured T-L composite zeolite with the mosaic morphology(具有镶嵌结构T-L多级孔道复合分子筛的快速合成与表征)[J]. J Mol Catal(China)(分子催化),2016,30(1):72-79.
[2] a. Zhu Shu-jin(朱数金),Liu Su-yao(刘粟侥),Zhang Huai-ke(张怀科),et al. Investigation of synthesis and hydroisomerization performance of SAPO-11/Beta composite molecular sieve(SAPO-11/Beta复合分子筛的合成及其异构化性能研究)[J]. Chin J Catal(催化学报),2014,35(10):1676-1686.b. Zheng Bu-me(郑步梅),Fang Xiang-chen(方向晨),Guo Rong(郭蓉),et al. Hierarchical ZSM-5 zeolite:synthesis and application in oil refinery(多级孔ZSM-5分子筛的制备及其在炼油领域中的应用)[J]. J Mol Catal(China)(分子催化),2017,31(5):486-500.c. Ma Cun-cun(马存存),Hu Li(胡丽),Yang Donghua(杨冬花),et al. Synthesis and characterization of L/EU-1 composite zeolites with the tubular mosaic morphology(具有管状镶嵌结构L/EU-1复合分子筛的合成及表征)[J]. J Mol Catal(China)(分子催化),2017,31(1):82-91.
[3] Gao X,Zhang P,Yang J,et al. A novel approach for the removal of radiocesium from aqueous solution by ZSM-5molecular sieve[J]. Appl Radia Isoto,2018,139:231-237.
[4] Sadeghpour P,Haghighi M. High-temperature and shorttime hydrothermal fabrication of nanostructured ZSM-5catalyst with suitable pore geometry and strong intrinsic acidity used in methanol to light olefins conversion[J].Adv Pow Technol,2018,29(5):1175-1188.
[5] Breck D W, Acara N A. Crystalline zeolite L. US,3216789[P]. 1965.
[6] Zhang Ya-jing(张雅静),Deng Ju-lei(邓据磊),Zhang Su-juan(张素娟),et al. Investigation on Cu O-ZnO-Al2O3/HZSM-5 catalysts for synthesis of dimethyl ether from CO2hydrogenation(CO2加氢制备二甲醚Cu O-ZnO-Al2O3/HZSM-5催化剂的研究)[J]. J Mol Catal(China)(分子催化),2013,27(3):235-241.
[7] Du Jie(杜杰),Zhang Ya-jing(张雅静),Zhang Yu(张宇),et al. Effect of Si O2promoter on performance of Cu O-ZnO/HZSM-5 catalysts for synthesis of DME from CO2hydrogenation(Si O2助剂对Cu O-ZnO/HZSM-5催化CO2加氢制DME性能的影响)[J]. J Mol Catal(China)(分子催化),2016,30(4):346-353.
[8] Young D A,Linda Y,Calif. US,3867512[P]. 1975.
[9] Woltel T M. U.S.,4593133[P]. 1986.
[10] Wortel T M. U.S.,4701315[P]. 1987.
[11] Li S Gi,Xu R R. C.N.,85103013 A[P]. 1986.
[12] Ma Cun-cun(马存存). Synthetic study of L/ZSM-5 and L/EU-1 composite zeolite with the mosaic morphology(具有镶嵌结构L/ZSM-5和L/EU-1复合分子筛的合成研究)[D]. Taiyuan:Taiyuan University of Technology(太原:太原理工大学),2017.
[13] Liu Chang-jiang(刘昶江),Su Shang-qing(苏双青),Yang Jing(杨静),et al. Synthesis of L-type molecular sieve from potassium feldspar powder(钾长石粉体合成L型分子筛)[J]. J Chin Cera Soc(硅酸盐学报),2013,41(8):1151-1157.
[14] Lu Lu(陆璐),Zhang Hui-zhen(张会贞),Zhu Xuedong(朱学栋). Synthesis of hierarchical ZSM-5 and its application in benzene alkylation with methanol(多级孔ZSM-5分子筛的合成及催化苯、甲醇烷基化反应的研究)[J]. Acta Petro Sin(Petrol Proce Sec)(石油学报(石油加工)),2012,28(s1):111-115.
[15] He Ying-ping(何英萍),Liu Min(刘民),Dai Chengyi(代成义),et al. TPAOH modified nano HZSM-5 zeolite and the catalytic properties in methanol making gasoline(四丙基氢氧化铵改性纳米HZSM-5分子筛及其在甲醇制汽油中的催化性能)[J]. Chin J Catal(催化学报),2013,34(6):1148-1158.
[16] Huo Quan(霍全),Dou Tao(窦涛),Gong Yan-jun(巩雁军),et al. Synthesis and desulfurization performance of nanocrystal-assembled zeolite L with a hierarchical pore structure(纳米晶簇多级孔道L沸石的合成及其脱硫性能)[J]. Acta Phys-Chim Sin(物理化学学报),2010,26(2):378-384.
[17] Li Yu-ping(李玉平),Sun Cui-juan(孙翠娟),Jia Kun(贾坤),et al. Soft template-directed hierarchical mordenites and their performance in ben-zylation of benzene with benzyl alcohol(软模板导向合成多级孔丝光沸石及其苯的苄基化催化性能)[J]. J Inorg Mater(无机材料学报),2016,31(12):1355-1362.
[18] Mao Dong-sen(毛东森),Guo Qiang-sheng(郭强胜),Meng Tao(孟涛),et al. Effect of hydrothermal treatment on the acidity and catalytic performance of nanosized HZSM-5 zeolites for the conversion of methanol to propene(水热处理对纳米HZSM-5分子筛酸性及催化甲醇制丙烯反应性能的影响)[J]. Acta Phys-Chim Sin(物理化学学报),2010,26(2):338-344.
[19] Yang Dong-hua(杨冬花),Zhao Jun-fu(赵君芙),Zhang Jun-liang(张军亮),et al. Designed synthesis and crystallization of Fe-Al-EU-1 zeolites containing framework-iron(含铁骨架Fe-Al-EU-1分子筛的设计合成和晶化)[J]. Acta Phys-Chim Sin(物理化学学报),2012,28(3):720-728.
[20] Xiao Qi(肖奇),Wang Ping-hua(王平华),Ji Lingling(纪伶伶),et al. Dispersion of carbon nanotubes in aqueous solution with cationic surfactant CTAB(分散剂CTAB对碳纳米管悬浮液分散性能的影响)[J]. J Inorg Mater(无机材料学报),2007,22(6):1122-1126.
[21] Hu Li(胡丽),Yang Dong-hua(杨冬花),Zhao Yu(赵煜),et al. Synthesis of Ni Y zeolite and hydrogen evolution performance in cathode of a microbial electrolysis cell(Ni Y分子筛的合成及在微生物电解池阴极的析氢性能研究)[J]. J Fuel Chem Technol(燃料化学学报),2018,46(5):607-614.
[22] Li Qiang(李强),Dou Tao(窦涛),Huo Quan(霍全),et al. Physicochemical properties and activities of hydrocarbon catalytic cracking ofβ-zeolite with different silica-alumina ratios(不同硅铝比β沸石的理化性质及烃类催化裂化活性)[J]. Acta Phys-Chim Sin(物理化学学报),2008,24(7):1192-1198.
[23] Sun Na(孙娜),Wang Hai-yan(王海彦),Li Hao(李浩),et al. Synthesis of hierarchical pore SAPO-11 molecular sieve by sisal fiber and its hydrogen isomerization performance(剑麻纤维素合成多级孔SAPO-11分子筛及其临氢异构化性能)[J]. J Chin Cera Soc(硅酸盐学报),2018,46(1):108-115.
[24] Niu Jing-jing(牛静静),Guo Shi-ling(郭士岭),Chen Yi-liang(陈宜俍). Influencing factors for in-situ synthesis of zeolite l on calcined kaolin microspheres(高岭土微球原位合成L沸石过程中的影响因素)[J]. Acta Petro Sin(Petrol Proce Sec)(石油学报(石油加工)),2008,24(3):237-242.
[25] Fu Xian-cai(傅献彩),Shen Wen-xia(沈文霞),Yao Tian-yang(姚天扬),et al. Phys Chem(物理化学)[M]. Beijing:Higher Education Press(北京:高等教育出版社),2006,433-3445.
[26] Li Shou-gui(李守贵),Li Xi-kai(李锡凯),Xu Ru-ren(徐如人). Studies on the ageing mechanism for the directing agent of zeolite L(L沸石导向剂陈化机制的研究)[J]. Chem J Chin Univer(高等学校化学学报),1992,13(2):145-148.
[27] Sato M,Morikawa K,Kurosawa S. X-ray rietveld analysis of cation exchanged zeolite-L(LTL)[J]. Euro J Miner,1990,2(6):851-859.
[28] Lv Ai-ning(吕爱凝),Yang Dong-hua(杨冬花),Li Jian-hua(李建华),et al. Rapid Synthesis and characterization of hierarchical structured T-L composite zeolite with the mosaic morphology(具有镶嵌结构T-L多级孔道复合分子筛的快速合成与表征)[J]. J Mol Catal(China)(分子催化),2016,30(1):72-79.