以天然矿物为全部硅铝源低成本绿色合成ZSM-5分子筛的研究
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摘要
ZSM-5分子筛被广泛地应用于催化、吸附分离、离子交换和绿色化工等领域,但目前其合成主要是以无机化学品为硅铝源,从源头来看是非绿色化的过程.我们以热活化的硅藻土和亚熔盐活化的累托土为全部硅铝源,通过调变两种矿物的加入比例调变合成体系的硅铝比,在水热合成体系中制备ZSM-5分子筛.系统地考察模板剂用量、碱度、投料硅铝比、晶化时间等合成条件对产物结构和性质的影响,并对在最优条件下合成的ZSM-5分子筛的物化性质进行了详细地表征,结果表明:以天然矿物为全部硅铝源可以合成出具有较高结晶度、晶粒尺寸约为4μm的六面体挛晶形貌的ZSM-5分子筛,该分子筛比商业ZSM-5分子筛具有更高的水热稳定性和更优的加氢异构性能.
ZSM-5 zeolite is widely used in catalysis, adsorption and separation, ion exchange and green chemical industry, but its synthesis is mainly based on inorganic chemicals as silicon-aluminum source, which is a non-green process from the source. In this paper, ZSM-5 zeolite was prepared in hydrothermal synthesis system by adjusting the ratio of silicon to aluminum in the synthesis system by using thermally activated diatomite and submolten salt activated rectorite as all silicon-aluminum sources. The effects of synthesis conditions such as template dosage, basicity, ratio of silicon to aluminum and crystallization time on the structure and properties of ZSM-5 zeolite were systematically investigated. The physical and chemical properties of ZSM-5 zeolite synthesized under the optimum conditions were characterized in detail. The results showed that hexahedral crystalline morphology with high crystallinity and grain size of about 4 microns could be synthesized by using natural minerals as all sources of silicon and aluminum. ZSM-5 zeolite has higher hydrothermal stability than commercial ZSM-5 zeolite.
ZSM-5 zeolite is widely used in catalysis, adsorption and separation, ion exchange and green chemical industry, but its synthesis is mainly based on inorganic chemicals as silicon-aluminum source, which is a non-green process from the source. In this paper, ZSM-5 zeolite was prepared in hydrothermal synthesis system by adjusting the ratio of silicon to aluminum in the synthesis system by using thermally activated diatomite and submolten salt activated rectorite as all silicon-aluminum sources. The effects of synthesis conditions such as template dosage, basicity, ratio of silicon to aluminum and crystallization time on the structure and properties of ZSM-5 zeolite were systematically investigated. The physical and chemical properties of ZSM-5 zeolite synthesized under the optimum conditions were characterized in detail. The results showed that hexahedral crystalline morphology with high crystallinity and grain size of about 4 microns could be synthesized by using natural minerals as all sources of silicon and aluminum. ZSM-5 zeolite has higher hydrothermal stability than commercial ZSM-5 zeolite.
引文
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[16] Ding J,Liu H,Yuan P,et al.Catalytic properties of a hierarchical zeolite synthesized from a natural aluminosilicate mineral without the use of a secondary mesoscale template[J].Chem Cat Chem,2013,5(8):2258-2269.
[17] Lok B M,Cannan T R,Messina C A.The role of organic molecules in molecular sieve synthesis[J].Zeolites,1983,3(4):282-291.
[18] Yoshikawa M,Wagner P,Lovallo M,et al.Synthesis,characterization,and structure solution of CIT-5,a new,high-silica,extra-large-pore molecular sieve[J].J Phys Chem B,1998,102(37):7139-7147.
[19] Treacy M M J,Higgins J B.MFI-tetrapropylammonium ZSM-5[M].Amsterdam:Elsevier Science B V,2007.
[20] Kang N Y,Song B S,Lee C W,et al.The effect of Na2SO4 salt on the synthesis of ZSM-5 by template free crystallization method[J].Micro Mes Mater,2009,118(1/3):361-372.
[21] Shirazi L,Jamshidi E,Ghasemi M R.The effect of Si/Al ratio of ZSM-5 zeolite on its morphology,acidity and crystal size[J].Crys Res Technol,2008,43(12):1300-1306.
[22] Zhu X,Liu S,Song Y,et al.Catalytic cracking of C4 alkenes to propene and ethene:Influences of zeolites pore structures and Si/Al2 ratios[J].Appl Catal A:Gener,2005,288(1/2):134-142.
[23] Zhu J,Cui Y,Wang Y,et al.Direct synthesis of hierarchical zeolite from a natural layered material[J].Chem Commun,2009,45(22):3282-3284.
[24] Zhu J,Cui Y,Wang Y,et al.Direct synthesis of hierarchical zeolite from a natural layered material[J].Chem Commun,2009,45(22):3282-3284.
[25] Jung J S,Park J W,Seo G.Catalytic cracking of n-octane over alkali-treated MFI zeolites[J].Appl Catal A:Gener,2005,288(1/2):149-157.
[2] a.Corma A.From microporous to mesoporous molecular sieve materials and their use in catalysis[J].Chem Rev,1997,97(6):2373-2420.b.Bo Qiong(薄琼),Wang Gai(王改),Yang Dong-hua(杨冬花),et al.Synthesis and characterization of nanowired ZSM-5 / L composite molecula sieves (具有纳米线镶嵌结构 ZSM-5 / L 复合分子筛的合成及表征) [J].J Mol Catal(China)(分子催化),2018,32(6):555-564.c.Fan Zong-liang(范宗良),Bian Jie(边杰),Ji Dong(季东),et al.The catalytic performance evaluation of acid-base modified nano-ZSM-11 zeolite on alkylation of benzene with methanol to prepare toluene (改性纳米 ZSM-11 分子筛及其催化苯与甲醇烷基化反应的性能) [J].J Mol Catal(China)(分子催化),2018,32(2):180-186 .d.Ji Dong(季东),Du Zhi-song(杜知松),Wang Dong-liang(王东亮),et al.Study on the reaction of benzene and methanol by Nd/HZSM-5 molecular sieve(Nd/ HZSM-5分子筛催化苯与甲醇烷基化的研究) [J].J Mol Catal(China)(分子催化),2018,32(1):27-34.
[3] a.Arandes J M,Torre I,Azkoiti M J,et al.HZSM-5 zeolite as catalyst additive for residue cracking under FCC conditions[J].Energy & Fuels,2009,23(9):4215-4223.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.Zhao Geng-xiang(赵庚香),Liu Hua-yan(刘华彦),Zhu qiu-lian(朱秋莲),et al.Deactivation behavior of ZSM-5 zeolites modified by LiNO3 in dehydration of lactic acid to acrylic acid (LiNO3改性ZSM-5分子筛催化乳酸制丙烯酸的失活行为研究) [J].J Mol Catal(China)(分子催化),2017,31(2):152-158.
[4] Schipper P H,Dwyer F G,Sparrell P T,et al.Zeolite ZSM-5 in fluid catalytic cracking:Performance,benefits,and applications[M].American Chemical Society,1988.64-86.
[5] Meng X,Xiao F S.Green routes for synthesis of zeolites[J].Chem Rev,2014,114(2):1521-1543.
[6] Coronas J.Present and future synthesis challenges forzeolites[J].Chem Engineer J,2010,156(2):236-242.
[7] Fawer M,Concannon M,Rieber W.Life cycle inventories for the production of sodium silicates[J].Inter J Life Cycle Assess,1999,4(4):207-212.
[8] Balomenos E,Panias D,Paspaliaris I.Energy and exergy analysis of the primary aluminum production processes:A review on current and future sustainability[J].Miner Proce Extra Metal Rev,2011,32(2):69-89.
[9] Chen Nian-yi(陈念怡).Physicochemistry of Alumina Production(氧化铝生产的物理化学)[M].Shanghai:Shanghai Science and Technology Publishing House(上海:上海科学技术出版社),1962.
[10] Vachon P,Tyagi R D,Auclair J C,et al.Chemical and biological leaching of aluminum from red mud[J].Environ Sci & Technol,1994,28(1):26-30.
[11] Atasoy A.The comparison of the bayer process wastes on the base of chemical and physical properties[J].J Therm Analy Calor,2007,90(1):153-158.
[12] Kovo A S,Hernandez O,Holmes S M.Synthesis and characterization of zeolite Y and ZSM-5 from Nigerian Ahoko kaolin using a novel,lower temperature,metakaolinization technique[J].J Mater Chem,2009,19:6207-6212.
[13] Anderson M W,Holmes S M,Hanif N,et al.Hierarchical pore structures through diatom zeolitization[J].Angew Chem Inter Ed,2000,39(15):2707-2710.
[14] Holmes S M,Plaisted R J,Crow P,et al.The zeolitisation of diatoms to create hierarchical pore structures[M].FFFDRA Galarneau and J Vedrine Elsevier,2001.296.
[15] Wei B,Liu H,Li T,et al.Natural rectorite mineral:A promising substitute of kaolin for in-situ synthesis of fluid catalytic cracking catalysts[J].AIChE J,2010,56(11):2913-2922.
[16] Ding J,Liu H,Yuan P,et al.Catalytic properties of a hierarchical zeolite synthesized from a natural aluminosilicate mineral without the use of a secondary mesoscale template[J].Chem Cat Chem,2013,5(8):2258-2269.
[17] Lok B M,Cannan T R,Messina C A.The role of organic molecules in molecular sieve synthesis[J].Zeolites,1983,3(4):282-291.
[18] Yoshikawa M,Wagner P,Lovallo M,et al.Synthesis,characterization,and structure solution of CIT-5,a new,high-silica,extra-large-pore molecular sieve[J].J Phys Chem B,1998,102(37):7139-7147.
[19] Treacy M M J,Higgins J B.MFI-tetrapropylammonium ZSM-5[M].Amsterdam:Elsevier Science B V,2007.
[20] Kang N Y,Song B S,Lee C W,et al.The effect of Na2SO4 salt on the synthesis of ZSM-5 by template free crystallization method[J].Micro Mes Mater,2009,118(1/3):361-372.
[21] Shirazi L,Jamshidi E,Ghasemi M R.The effect of Si/Al ratio of ZSM-5 zeolite on its morphology,acidity and crystal size[J].Crys Res Technol,2008,43(12):1300-1306.
[22] Zhu X,Liu S,Song Y,et al.Catalytic cracking of C4 alkenes to propene and ethene:Influences of zeolites pore structures and Si/Al2 ratios[J].Appl Catal A:Gener,2005,288(1/2):134-142.
[23] Zhu J,Cui Y,Wang Y,et al.Direct synthesis of hierarchical zeolite from a natural layered material[J].Chem Commun,2009,45(22):3282-3284.
[24] Zhu J,Cui Y,Wang Y,et al.Direct synthesis of hierarchical zeolite from a natural layered material[J].Chem Commun,2009,45(22):3282-3284.
[25] Jung J S,Park J W,Seo G.Catalytic cracking of n-octane over alkali-treated MFI zeolites[J].Appl Catal A:Gener,2005,288(1/2):149-157.