Fe-多级孔Hβ的制备及催化合成二苯甲烷性能
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摘要
用NaOH溶液对Hβ进行处理,得到多级孔Hβ分子筛。在0.10 mol/L碱浓度下,采用浸渍法制备Fe-多级孔Hβ分子筛(Fe-Hβ-B0.10)。通过XRD、XRF、N_2吸附-脱附、SEM-EDS、傅里叶变换红外光谱、NH_3-TPD和Py-FTIR对样品进行了表征。结果表明,适当的碱浓度处理在保持Hβ分子筛微孔骨架的同时,引入了介孔,Fe-多级孔Hβ分子筛仍能保持微介孔结构,活性组分Fe_2O_3能够很好地分散在载体表面。以苯和氯化苄为原料,考察其催化合成二苯甲烷的性能。与Fe-Hβ-B0催化剂相比,Fe-多级孔Hβ有效地提高了反应物和产物的扩散性能,氯化苄的转化率、二苯甲烷的选择性分别提高了9.4%和3.2%。Fe-多级孔Hβ催化剂重复使用3次后仍然保持较好的催化活性。
Hierarchical porous Hβ molecular sieve was obtained by treating Hβ molecular sieve with NaOH solution. Fe-hierarchical porous Hβ molecular sieve was prepared by impregnation method in 0.10 mol/L alkali solution. The samples were characterized by XRD, XRF, N_2 adsorption-desorption, SEM-EDS, FTIR,NH_3-TPD and Py-FTIR. The results showed that proper alkali concentration treatment could not only maintain the microporous framework of Hβ molecular sieve, but also introduce mesopores. Fe-hierarchical porous Hβ molecular sieve also could maintain the micro-mesoporous structure, and the active component Fe_2O_3 could be well dispersed on the surface of the carrier. The catalytic synthesis of diphenylmethane from benzene and benzyl chloride was studied. Compared with Fe-Hβ-B_0 catalyst, Fe-hierarchical porous Hβeffectively improved the diffusion performance of the reactants and products. The conversion of benzyl chloride and the selectivity of diphenylmethane were increased by 9.4% and 3.2%, respectively.Fe-hierarchical porous Hβ still maintained good catalytic activity after repeated use for 3 times.
Hierarchical porous Hβ molecular sieve was obtained by treating Hβ molecular sieve with NaOH solution. Fe-hierarchical porous Hβ molecular sieve was prepared by impregnation method in 0.10 mol/L alkali solution. The samples were characterized by XRD, XRF, N_2 adsorption-desorption, SEM-EDS, FTIR,NH_3-TPD and Py-FTIR. The results showed that proper alkali concentration treatment could not only maintain the microporous framework of Hβ molecular sieve, but also introduce mesopores. Fe-hierarchical porous Hβ molecular sieve also could maintain the micro-mesoporous structure, and the active component Fe_2O_3 could be well dispersed on the surface of the carrier. The catalytic synthesis of diphenylmethane from benzene and benzyl chloride was studied. Compared with Fe-Hβ-B_0 catalyst, Fe-hierarchical porous Hβeffectively improved the diffusion performance of the reactants and products. The conversion of benzyl chloride and the selectivity of diphenylmethane were increased by 9.4% and 3.2%, respectively.Fe-hierarchical porous Hβ still maintained good catalytic activity after repeated use for 3 times.
引文
[1]Zhan Jinyou(詹金友),Zhang Yaobing(张耀兵),Shen Jian(沈健),et al.Synthesis of diphenylmethane on Sb-SBA-15[J].Chemical Industry and Engineering Progress(化工进展),2016,35(5):1460-1465.
[2]Zhou Chunhui(周春晖),Luo Xiping(罗锡平),Ge Zhonghua(葛忠华),et al.Preparation of acid-treated clay-supported ZnCl2 and its catalytic properties for benzylation of benzene by benzyl chloride[J].Chinese Journal of Catalysis(催化学报),2003,24(8):579-584.
[3]Kun Y L,Zhang C,Li X L,et al.Iron-containing MIL-101(Cr)as highly active and stable heterogeneous catalysts for the benzylation of a romatics with benzyl chloride[J].Reaction Kinetics Mechanisms&Catalysis,2016,120(1):1-13.
[4]Ji Min(纪敏),Wu Haiwei(吴海鸣),He Min(贺民),et al.Kinetic study on catalytic synthesis of diphenylmethane by immobilized Al Cl3[J].Journal of Dalian University of Technology(大连理工大学学报),2008,48(2):168-172.
[5]Arafat A,Alhamed Y.Catalytic activity of mesoporous catalysts in Friedel-Crafts benzylation of benzene[J].Journal of Porous Materials,2009,16(5):565-572.
[6]Chuabe V D.Benzylation of benzene to diphenylmethane using zeolite catalysts[J].Catalysis Communications,2004,5(6):321-326.
[7]Liu Hui(刘惠),Zhang Shuang(张爽),Xie Sujuan(谢素娟),et al.Synthesis characterization and catalytic performance of hierarchical ZSM-11 zeolite synthesized via dual-template route[J].Chinese Journal of Catalysis(催化学报),2018,39(1):167-180.
[8]Liu Dongmei(刘冬梅),Jiang Hanbo(蒋涵博),Qu Shengtao(曲圣涛),et al.Study on the alkylation of thiophene and catalyst deactivation and regeneration with modified HZSM-5 zeolite[J].Journal of Fuel Chemistry and Technology(燃料化学学报),2018,46(3):355-364.
[9]Liu Wanrong(刘万荣),Liu Xinmei(刘欣梅),Xin Ying(辛颖),et al.Preparation of hierarchical Y/ZrO2 composite[J].Acta Petrolei Sinica(Petroleum Processing Section)(石油学报:石油加工),2018,34(4):689-695.
[10]Tarach K,Gora-marek K,Tekla J,et al.Catalytic cracking performance of acid sites properties and their accessibility[J].Journal of Catalysis,2014,312(2):46-57.
[11]Guo Yongle(郭永乐),Zhang Yu(张钰),Zhao Zhongkui(赵忠奎),et al.Ceria-modified hierarchical Hβzeolite as a robust solid acid catalyst for alkenylation of p-xylene with phenylacetylene[J].Chinese Journal of Catalysis(催化学报),2018,39(1):181-189.
[12]Bi Y,Lei X,Xu G,et al.Catalytic fast pyrolysis of kraft lignin over hierarchical HZSM-5 and Hβzeolites[J].Catalysts,2018,8(2):82-95.
[13]Zhang Kongyuan(张孔远),Zhao Xingtao(赵兴涛),Shi Shijie(史世杰),et al.Hydroisomerization of n-hexane over Pt/Hβ-HZSM-5catalyst[J].Acta Petrolei Sinica(Petroleum Processing Section)(石油学报:石油加工),2017,33(2):204-209.
[14]Khan A,Chen P,Boolchand P,et al.Modified nano-crystalline ferrites for high-temperature WGS membrane reactor applications[J].Journal of Catalysis,2008,253(1):91-104.
[15]Yang Jing(杨静),Ming Yang(明阳),Sun Yu(孙宇),et al.Preparation and adsorption desulfurization performance of Cu-β/SBA-15 composite molecular sieves[J].Acta Petrolei Sinica(Petroleum Processing Section)(石油学报:石油加工),2017,33(5):919-926.
[16]Liu J,Cui L,Wang L,et al.Alkaline-acid treated mordenite and beta zeolites featuring mesoporous dimensional uniformity[J].Materials Letters,2014,132(10):78-81.
[17]Li Yuping(李宇萍),Wang Tiejun(王铁军),Ma Longlong(马隆龙),et al.Hβmodified Co/SiO2 catalysts for Fischer-Tropsch synthesis of jet fuel-range hydrocarbons[J].Journal of Inorganic Materials(无机材料学报),2014,29(6):599-604.
[18]Zeng Maorong(曾茂荣),Luo Gang(罗刚),Wang Yu(王宇),et al.Quaternary ammonium surfactant assisted synthesis of hierarchical porous Hβzeolite for aniline catalytic condensation[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2017,31(5):1113-1119.
[19]He Jiajie(何嘉杰),Zhu Baokun(朱保昆),Wu Jiacan(吴家灿),et al.Effect of surface modification by H2 reduction on geranylacetone adsorption and desorption of modified Hβzeotiles[J].Ion Exchange and Adsorption(离子交换与吸附),2017,33(5):463-471.
[20]Guo Haiwei(郭海纬),Fei Zhaoyan(费兆阳),Wang Yu(王宇),et al.Effect of alkali treatment on the catalytic performance of Hβzeolites in condensation of aniline to diphenylamine[J].Acta Petrolei Sinica(Petroleum Processing Section)(石油学报:石油加工),2017,33(1):100-107.
[21]Yang C,Xu Q H.States of aluminum in zeoliteβand influence of acidic or basic medium[J].Zeolites,1997,19(5):404-410.
[22]Wang Junfeng(王俊丰),Shen Jian(沈健),Shi Weiwei(石薇薇),et al.Experimental study on the catalytic alkylation of phenol with methanol by Ce/USY modified molecular sieve[J].Acta Petrolei Sinica(Petroleum Processing Section)(石油学报:石油加工),2017,33(4):757-762.
[23]Xiang Shouhe(项寿鹤),Wang Jingzhong(王敬中),Gao Feng(高峰),et al.Study on L acid on Hβzeolite[J].Chinese Journal of Catalysis(催化学报),1991,12(5):404-408.
[24]Yang Juhong(杨菊红),Han Xiaoxiang(韩晓祥),Chen Qing(陈青),et al.Synthesis of diphenylmethane by alkylation of benzene with benzyl chloride by ionic liquid[J].Fine Chemicals(精细化工),2010,27(6):610-613.
[2]Zhou Chunhui(周春晖),Luo Xiping(罗锡平),Ge Zhonghua(葛忠华),et al.Preparation of acid-treated clay-supported ZnCl2 and its catalytic properties for benzylation of benzene by benzyl chloride[J].Chinese Journal of Catalysis(催化学报),2003,24(8):579-584.
[3]Kun Y L,Zhang C,Li X L,et al.Iron-containing MIL-101(Cr)as highly active and stable heterogeneous catalysts for the benzylation of a romatics with benzyl chloride[J].Reaction Kinetics Mechanisms&Catalysis,2016,120(1):1-13.
[4]Ji Min(纪敏),Wu Haiwei(吴海鸣),He Min(贺民),et al.Kinetic study on catalytic synthesis of diphenylmethane by immobilized Al Cl3[J].Journal of Dalian University of Technology(大连理工大学学报),2008,48(2):168-172.
[5]Arafat A,Alhamed Y.Catalytic activity of mesoporous catalysts in Friedel-Crafts benzylation of benzene[J].Journal of Porous Materials,2009,16(5):565-572.
[6]Chuabe V D.Benzylation of benzene to diphenylmethane using zeolite catalysts[J].Catalysis Communications,2004,5(6):321-326.
[7]Liu Hui(刘惠),Zhang Shuang(张爽),Xie Sujuan(谢素娟),et al.Synthesis characterization and catalytic performance of hierarchical ZSM-11 zeolite synthesized via dual-template route[J].Chinese Journal of Catalysis(催化学报),2018,39(1):167-180.
[8]Liu Dongmei(刘冬梅),Jiang Hanbo(蒋涵博),Qu Shengtao(曲圣涛),et al.Study on the alkylation of thiophene and catalyst deactivation and regeneration with modified HZSM-5 zeolite[J].Journal of Fuel Chemistry and Technology(燃料化学学报),2018,46(3):355-364.
[9]Liu Wanrong(刘万荣),Liu Xinmei(刘欣梅),Xin Ying(辛颖),et al.Preparation of hierarchical Y/ZrO2 composite[J].Acta Petrolei Sinica(Petroleum Processing Section)(石油学报:石油加工),2018,34(4):689-695.
[10]Tarach K,Gora-marek K,Tekla J,et al.Catalytic cracking performance of acid sites properties and their accessibility[J].Journal of Catalysis,2014,312(2):46-57.
[11]Guo Yongle(郭永乐),Zhang Yu(张钰),Zhao Zhongkui(赵忠奎),et al.Ceria-modified hierarchical Hβzeolite as a robust solid acid catalyst for alkenylation of p-xylene with phenylacetylene[J].Chinese Journal of Catalysis(催化学报),2018,39(1):181-189.
[12]Bi Y,Lei X,Xu G,et al.Catalytic fast pyrolysis of kraft lignin over hierarchical HZSM-5 and Hβzeolites[J].Catalysts,2018,8(2):82-95.
[13]Zhang Kongyuan(张孔远),Zhao Xingtao(赵兴涛),Shi Shijie(史世杰),et al.Hydroisomerization of n-hexane over Pt/Hβ-HZSM-5catalyst[J].Acta Petrolei Sinica(Petroleum Processing Section)(石油学报:石油加工),2017,33(2):204-209.
[14]Khan A,Chen P,Boolchand P,et al.Modified nano-crystalline ferrites for high-temperature WGS membrane reactor applications[J].Journal of Catalysis,2008,253(1):91-104.
[15]Yang Jing(杨静),Ming Yang(明阳),Sun Yu(孙宇),et al.Preparation and adsorption desulfurization performance of Cu-β/SBA-15 composite molecular sieves[J].Acta Petrolei Sinica(Petroleum Processing Section)(石油学报:石油加工),2017,33(5):919-926.
[16]Liu J,Cui L,Wang L,et al.Alkaline-acid treated mordenite and beta zeolites featuring mesoporous dimensional uniformity[J].Materials Letters,2014,132(10):78-81.
[17]Li Yuping(李宇萍),Wang Tiejun(王铁军),Ma Longlong(马隆龙),et al.Hβmodified Co/SiO2 catalysts for Fischer-Tropsch synthesis of jet fuel-range hydrocarbons[J].Journal of Inorganic Materials(无机材料学报),2014,29(6):599-604.
[18]Zeng Maorong(曾茂荣),Luo Gang(罗刚),Wang Yu(王宇),et al.Quaternary ammonium surfactant assisted synthesis of hierarchical porous Hβzeolite for aniline catalytic condensation[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2017,31(5):1113-1119.
[19]He Jiajie(何嘉杰),Zhu Baokun(朱保昆),Wu Jiacan(吴家灿),et al.Effect of surface modification by H2 reduction on geranylacetone adsorption and desorption of modified Hβzeotiles[J].Ion Exchange and Adsorption(离子交换与吸附),2017,33(5):463-471.
[20]Guo Haiwei(郭海纬),Fei Zhaoyan(费兆阳),Wang Yu(王宇),et al.Effect of alkali treatment on the catalytic performance of Hβzeolites in condensation of aniline to diphenylamine[J].Acta Petrolei Sinica(Petroleum Processing Section)(石油学报:石油加工),2017,33(1):100-107.
[21]Yang C,Xu Q H.States of aluminum in zeoliteβand influence of acidic or basic medium[J].Zeolites,1997,19(5):404-410.
[22]Wang Junfeng(王俊丰),Shen Jian(沈健),Shi Weiwei(石薇薇),et al.Experimental study on the catalytic alkylation of phenol with methanol by Ce/USY modified molecular sieve[J].Acta Petrolei Sinica(Petroleum Processing Section)(石油学报:石油加工),2017,33(4):757-762.
[23]Xiang Shouhe(项寿鹤),Wang Jingzhong(王敬中),Gao Feng(高峰),et al.Study on L acid on Hβzeolite[J].Chinese Journal of Catalysis(催化学报),1991,12(5):404-408.
[24]Yang Juhong(杨菊红),Han Xiaoxiang(韩晓祥),Chen Qing(陈青),et al.Synthesis of diphenylmethane by alkylation of benzene with benzyl chloride by ionic liquid[J].Fine Chemicals(精细化工),2010,27(6):610-613.