Beta分子筛晶种法合成及其加氢脱氧性能
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摘要
采用晶种法制备一系列Beta分子筛,考察了晶化温度和时间等因素对合成Beta分子筛的影响,并采用XRD、 XRF、 SEM、 N_2物理吸附、 TG-DSC等手段对产物进行表征,结果显示合成的Beta分子筛具有良好的结晶度、孔道结构、热稳定性和相近的硅铝比;通过对初始凝胶进行老化处理可加快Beta分子筛的晶化速率,产物晶粒尺寸变小、比表面积和孔容变大;在晶种-凝胶体系中加入少量有机模板剂, Beta分子筛的收率和热稳定性均有提升. NH_3-TPD和Pyridine-FTIR分析结果表明不存在有机模板剂的晶种-凝胶体系中合成的Beta分子筛催化剂有更多的总酸量和Br?nsted酸的数量,使其在苯甲醚加氢脱氧反应中表现出高活性和环己烷选择性.
The seed-directed synthesis of zeolite Beta were successfully synthesized and characterized using a wide range of characterization techniques such as XRD, XRF, SEM, TG-DSC and BET. These as-synthesized zeolite Beta samples from different initial reactant gels have similar relative crystallinity, Si/Al ratios and thermal stability. The effect of synthesis conditions such as crystallization temperature, crystallization time, impurity of MOR zeolite and the composition of initial reactant gel were investigated in detail. It is found that aging treatment or introduce low content of TEAOH to the initial reactant gel could accelerate the crystallization rate, and obtain Beta zeolites with smaller average crystal size, larger surface area and more micro pores. It is also found that the yield and thermal stability of zeolite Beta were improved when a small amount of TEAOH was added. NH_3-TPD and pyridine-IR results indicate that zeolite Beta synthesized in the absence of TEOAH possess abundant acidic sites, in particular Br?nsted sites, and show good catalytic properties as catalysts for the hydrodeoxygenation of anisole to a range of hydrocarbons, such as cyclohexane and toluene.
The seed-directed synthesis of zeolite Beta were successfully synthesized and characterized using a wide range of characterization techniques such as XRD, XRF, SEM, TG-DSC and BET. These as-synthesized zeolite Beta samples from different initial reactant gels have similar relative crystallinity, Si/Al ratios and thermal stability. The effect of synthesis conditions such as crystallization temperature, crystallization time, impurity of MOR zeolite and the composition of initial reactant gel were investigated in detail. It is found that aging treatment or introduce low content of TEAOH to the initial reactant gel could accelerate the crystallization rate, and obtain Beta zeolites with smaller average crystal size, larger surface area and more micro pores. It is also found that the yield and thermal stability of zeolite Beta were improved when a small amount of TEAOH was added. NH_3-TPD and pyridine-IR results indicate that zeolite Beta synthesized in the absence of TEOAH possess abundant acidic sites, in particular Br?nsted sites, and show good catalytic properties as catalysts for the hydrodeoxygenation of anisole to a range of hydrocarbons, such as cyclohexane and toluene.
引文
[1] Higgins J B,Lapierre R B,Schlenker J L,et al.The framework topology of zeolite beta[J].Zeolites,1988,8(6):446-452.
[2] Tomlinson S M,Jackson R A,Catlow C R A.et al.A computational study of zeolite beta[J].J Chem Soc Chem Commun,1990,11:813-816.
[3] Tarach K,Góra-Marek K,Tekla J,et al.Catalytic crac- king performance of alkaline-treated zeolite Beta in the terms of acid sites properties and their accessibility[J].J Catal,2014,312(2):46-57.
[4] LI Gui-xian(李贵贤),Sun Lie-dong(孙烈东),JI Dong(季东),et al.Study on the reaction of benzene and methanol to toluene by modified beta molecular sieve(改性beta分子筛催化苯和甲醇制甲苯反应的研究)[J].J Mol Catal(China) (分子催化),2017,31(1):74-81.
[5] Batalha N,Morisset S,Pinard L,et al.BEA zeolite nanocrystals dispersed over alumina for n-hexadecane hydroisomerization[J].Micro Mes Mater,2013,166(2):161-166.
[6] Yihui W U,Tian F,Liu J,et al.Enhanced catalytic isomerization of α-pinene over mesoporous zeolite beta of low Si/Al ratio by NaOH treatment[J].Micro Mes Mater,2012,162(162):168-174.
[7] a.HU Yun-feng(胡云峰),Su Xun-ming(苏寻明),KANG Qi-qi(康琪琪),et al.Catalytic performance of molecular sieves with different structures in 1-butene cracking(不同结构的分子筛在1-丁烯中催化裂解性能的研究)[J].J Mol Catal(China) (分子催化),2017,31(1):38-45.b.Wang Gai(王改),Yang Dong-hua(杨冬花),Bo Qiong(薄琼),et al.Synthesis and characterization of a multichanne porous MCM-41/Y composite zeolites(具有多级孔 MCM-41/Y复合分子筛的合成及表征) [J].J Mol Catal(China)(分子催化),2018,32(4):325-333.c.Ren Rong-xin(任容欣),Song Wan-cang(宋万仓),Liu Guan-feng(刘冠锋),et al.Recent research in pre- paration 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.
[8] Tingfang H U,Chen J,Wang H,et al.Influence of shaped and modified Hβ zeolite on etherification of FCC light gasoline[J].Micro Mes Mater,2006,94(1):283-287.
[9] Camblor M A,PérezPariente J.Crystallization of zeolite beta:Effect of Na and K ions[J].Zeolites,1991,11(3):202-210.
[10] Lohse U,Altrichter B,Donath R,et al.Synthesis of zeolite beta.Part1.-Using tetraethylammonium hydroxide/bromide with addition of chelates as templating agents[J].J Am Chem Soc Faraday Trans,1996,92(1):159-165.
[11] Wadlinger R L,Kerr G T,Rosinski E J.US[P],3308069.1967.
[12] Xie B,Song J ,Ren L ,et al.Organotemplate-free and fast route for synthesizing beta zeolite[J].Chem Mater,2008,20(14):4533-4535.
[13] Majano G,Delmotte L,Valtchev V,et al.Al-rich zeolite beta by seeding in the absence of organic template[J].Chem Mater,2009,21(18):4184-4191.
[14] Kamimura Y,Chaikittisilp W,Itabashi K,et al.Critical factors in the seed-assisted synthesis of zeolite beta and “Green Beta” from OSDA-Free Na+-aluminosilicate gels[J].Chem Asian J,2010,5(10):2182-2219.
[15] Kamimura Y,Tanahashi S,Itabashi K,et al.Crystallization behavior of zeolite beta in OSDA-free,seed-assisted synthesis[J].J Phys Chem C,2011,115:744-750.
[16] De Baerdemaeker T,Yilmaz B,Müller U,et al.Cataly- tic applications of OSDA-free Beta zeolite[J].J Catal,2013,308:73-81.
[17] Xie B,Zhang H ,Yang C ,et al.Seed-directed synthesis of zeolites with enhanced performance in the absence of organic templates[J].Chem Commun,2011,47(13):3945-3947.
[18] Ye G,Sun Y,Guo Z,et al.Effects of zeolite particle size and internal grain boundaries on Pt/Beta catalyzed isomerization of n-pentane[J].J Catal,2018,360:152-159.
[19] Zhang H,Xie B,Meng X,et al.Rational synthesis of beta zeolite with improved quality by decreasing crystallization temperature in organotemplate-free route[J].Micro Mes Mater,2013,180(9):123-129.
[20] Bajpai P K.Synthesis of mordenite type zeolite[J].Zeolites,1986,6(1):2-8.
[21] Kerr G T.Chemistry of crystalline aluminosilicates.I.Factors affecting the formation of zeolite A[J].J Phys Chem,1966,70(4):1047-1050.
[22] Ren N,Bronic J,Subotic B,et al.Controllable and SDA-free synthesis of sub-micrometer sized zeolite ZSM-5.Part 2:Influence of sodium ions and ageing of the reaction mixture on the chemical composition,crystallinity and particulate properties of the products[J].Micro Mes Mater,2012,147(1):229-241.
[23] Zheng B ,Wan Y ,Yang W ,et al.Mechanism of seeding in hydrothermal synthesis of zeolite beta with organic structure-directing agent-free gel[J].Chin J Catal,2014,35(11):1800-1810.
[24] Szostak R,Lillerud K P,Stocker M,et al.Properties of tschernichite,the aluminum-rich mineral analog of zeolite beta[J].J Catal,1994,148(1):91-99.
[25] Modhera B,Chakraborty M,Parikh P A,et al.Synthesis of nano-crystalline zeolite β:Effects of crystallization parameters[J].Cryst Res Technol,2009,44(4):379-385.
[26] Kamimura Y,Iyoki K,Elangovan S P,et al.OSDA-free synthesis of MTW-type zeolite from sodium aluminosilicate gels with zeolite beta seeds[J].Micro Mes Mater,2012,163:282-290.
[27] Wang Xing-yi(王幸宜).Catalyst characterization(催化剂表征)[M].Beijing:East China University of Science and Technology Press(华东理工大学出版社),2008.
[28] Emeis C A.Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts[J].J Catal,1993,141(2):347-354.
[29] Ouyang Qian(欧阳仟),Yang Ni(杨妮),Yao Jing-wen(姚静雯),et al.Research on the catalytic performance of supported Pt catalyst for hydrodeoxygenation of biodiesel(负载Pt催化生物柴油加氢脱氧性能研究)[J].J Fuel Chem Technol(燃料化学学报),2018,46(10) :1202-1209.
[30] Lee H,Kim H ,Yu M J ,et al.Catalytic hydrodeoxygenation of Bio-oil model compounds over Pt/HY catalyst[J].Sci Rep,2016,6:28765.
[31] Yang Y,Ochoa-Hernández C,Víctor A,et al.Effect of metal-support interaction on the selective hydrodeoxyge- nation of anisole to aromatics over Ni-based catalysts[J].Appl Catal B Environ,2014,145:91-100.
[32] Zhu X,Lobban L L ,Mallinson R G ,et al.Bifunctional transalkylation and hydrodeoxygenation of anisole over a Pt/HBeta catalyst[J].J Catal,2011,281(1):21-29.
[33] Zanuttini M S,Lago C D ,Gros M S ,et al.Hydrodeo- xygenation of anisole with Pt catalysts[J].Ind Eng Chem Res,2017,56(22):6419-6431.
[2] Tomlinson S M,Jackson R A,Catlow C R A.et al.A computational study of zeolite beta[J].J Chem Soc Chem Commun,1990,11:813-816.
[3] Tarach K,Góra-Marek K,Tekla J,et al.Catalytic crac- king performance of alkaline-treated zeolite Beta in the terms of acid sites properties and their accessibility[J].J Catal,2014,312(2):46-57.
[4] LI Gui-xian(李贵贤),Sun Lie-dong(孙烈东),JI Dong(季东),et al.Study on the reaction of benzene and methanol to toluene by modified beta molecular sieve(改性beta分子筛催化苯和甲醇制甲苯反应的研究)[J].J Mol Catal(China) (分子催化),2017,31(1):74-81.
[5] Batalha N,Morisset S,Pinard L,et al.BEA zeolite nanocrystals dispersed over alumina for n-hexadecane hydroisomerization[J].Micro Mes Mater,2013,166(2):161-166.
[6] Yihui W U,Tian F,Liu J,et al.Enhanced catalytic isomerization of α-pinene over mesoporous zeolite beta of low Si/Al ratio by NaOH treatment[J].Micro Mes Mater,2012,162(162):168-174.
[7] a.HU Yun-feng(胡云峰),Su Xun-ming(苏寻明),KANG Qi-qi(康琪琪),et al.Catalytic performance of molecular sieves with different structures in 1-butene cracking(不同结构的分子筛在1-丁烯中催化裂解性能的研究)[J].J Mol Catal(China) (分子催化),2017,31(1):38-45.b.Wang Gai(王改),Yang Dong-hua(杨冬花),Bo Qiong(薄琼),et al.Synthesis and characterization of a multichanne porous MCM-41/Y composite zeolites(具有多级孔 MCM-41/Y复合分子筛的合成及表征) [J].J Mol Catal(China)(分子催化),2018,32(4):325-333.c.Ren Rong-xin(任容欣),Song Wan-cang(宋万仓),Liu Guan-feng(刘冠锋),et al.Recent research in pre- paration 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.
[8] Tingfang H U,Chen J,Wang H,et al.Influence of shaped and modified Hβ zeolite on etherification of FCC light gasoline[J].Micro Mes Mater,2006,94(1):283-287.
[9] Camblor M A,PérezPariente J.Crystallization of zeolite beta:Effect of Na and K ions[J].Zeolites,1991,11(3):202-210.
[10] Lohse U,Altrichter B,Donath R,et al.Synthesis of zeolite beta.Part1.-Using tetraethylammonium hydroxide/bromide with addition of chelates as templating agents[J].J Am Chem Soc Faraday Trans,1996,92(1):159-165.
[11] Wadlinger R L,Kerr G T,Rosinski E J.US[P],3308069.1967.
[12] Xie B,Song J ,Ren L ,et al.Organotemplate-free and fast route for synthesizing beta zeolite[J].Chem Mater,2008,20(14):4533-4535.
[13] Majano G,Delmotte L,Valtchev V,et al.Al-rich zeolite beta by seeding in the absence of organic template[J].Chem Mater,2009,21(18):4184-4191.
[14] Kamimura Y,Chaikittisilp W,Itabashi K,et al.Critical factors in the seed-assisted synthesis of zeolite beta and “Green Beta” from OSDA-Free Na+-aluminosilicate gels[J].Chem Asian J,2010,5(10):2182-2219.
[15] Kamimura Y,Tanahashi S,Itabashi K,et al.Crystallization behavior of zeolite beta in OSDA-free,seed-assisted synthesis[J].J Phys Chem C,2011,115:744-750.
[16] De Baerdemaeker T,Yilmaz B,Müller U,et al.Cataly- tic applications of OSDA-free Beta zeolite[J].J Catal,2013,308:73-81.
[17] Xie B,Zhang H ,Yang C ,et al.Seed-directed synthesis of zeolites with enhanced performance in the absence of organic templates[J].Chem Commun,2011,47(13):3945-3947.
[18] Ye G,Sun Y,Guo Z,et al.Effects of zeolite particle size and internal grain boundaries on Pt/Beta catalyzed isomerization of n-pentane[J].J Catal,2018,360:152-159.
[19] Zhang H,Xie B,Meng X,et al.Rational synthesis of beta zeolite with improved quality by decreasing crystallization temperature in organotemplate-free route[J].Micro Mes Mater,2013,180(9):123-129.
[20] Bajpai P K.Synthesis of mordenite type zeolite[J].Zeolites,1986,6(1):2-8.
[21] Kerr G T.Chemistry of crystalline aluminosilicates.I.Factors affecting the formation of zeolite A[J].J Phys Chem,1966,70(4):1047-1050.
[22] Ren N,Bronic J,Subotic B,et al.Controllable and SDA-free synthesis of sub-micrometer sized zeolite ZSM-5.Part 2:Influence of sodium ions and ageing of the reaction mixture on the chemical composition,crystallinity and particulate properties of the products[J].Micro Mes Mater,2012,147(1):229-241.
[23] Zheng B ,Wan Y ,Yang W ,et al.Mechanism of seeding in hydrothermal synthesis of zeolite beta with organic structure-directing agent-free gel[J].Chin J Catal,2014,35(11):1800-1810.
[24] Szostak R,Lillerud K P,Stocker M,et al.Properties of tschernichite,the aluminum-rich mineral analog of zeolite beta[J].J Catal,1994,148(1):91-99.
[25] Modhera B,Chakraborty M,Parikh P A,et al.Synthesis of nano-crystalline zeolite β:Effects of crystallization parameters[J].Cryst Res Technol,2009,44(4):379-385.
[26] Kamimura Y,Iyoki K,Elangovan S P,et al.OSDA-free synthesis of MTW-type zeolite from sodium aluminosilicate gels with zeolite beta seeds[J].Micro Mes Mater,2012,163:282-290.
[27] Wang Xing-yi(王幸宜).Catalyst characterization(催化剂表征)[M].Beijing:East China University of Science and Technology Press(华东理工大学出版社),2008.
[28] Emeis C A.Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts[J].J Catal,1993,141(2):347-354.
[29] Ouyang Qian(欧阳仟),Yang Ni(杨妮),Yao Jing-wen(姚静雯),et al.Research on the catalytic performance of supported Pt catalyst for hydrodeoxygenation of biodiesel(负载Pt催化生物柴油加氢脱氧性能研究)[J].J Fuel Chem Technol(燃料化学学报),2018,46(10) :1202-1209.
[30] Lee H,Kim H ,Yu M J ,et al.Catalytic hydrodeoxygenation of Bio-oil model compounds over Pt/HY catalyst[J].Sci Rep,2016,6:28765.
[31] Yang Y,Ochoa-Hernández C,Víctor A,et al.Effect of metal-support interaction on the selective hydrodeoxyge- nation of anisole to aromatics over Ni-based catalysts[J].Appl Catal B Environ,2014,145:91-100.
[32] Zhu X,Lobban L L ,Mallinson R G ,et al.Bifunctional transalkylation and hydrodeoxygenation of anisole over a Pt/HBeta catalyst[J].J Catal,2011,281(1):21-29.
[33] Zanuttini M S,Lago C D ,Gros M S ,et al.Hydrodeo- xygenation of anisole with Pt catalysts[J].Ind Eng Chem Res,2017,56(22):6419-6431.