镧硅磷酸铝分子筛的合成及表征
|
摘要
多孔晶状的硅磷酸铝系列分子筛是由AlO4、PO4及SiO4四面体构成的三维非中性骨架结构,具有离子交换性和一定的酸性。本论文中,用镧原子同晶取代SAPO-n分子筛骨架中的部分铝或磷,进入骨架中的氧负离子四面体结构单元,得到具有一定酸性的杂原子硅磷酸铝分子筛。LaSAPO分子筛的出现,开拓了分子筛材料合成和应用的一个新领域,可用作分离和纯化分子物种的吸附剂、催化剂或催化剂载体以及离子交换剂等。本文主要开展了以下几方面的工作:
1.系统考察了模板剂用量、反应体系的初始pH值、晶化时间、晶化温度、搅拌速度、SiO2/Al2O3以及添加晶种对LaSAPO合成的影响。实验结果表明,采用水热合成法在TMAOH-Al2O3-P2O5-SiO2-La2(CO3)3-H2O-CTAB体系中可合成结晶度较高的新型镧硅磷酸铝分子筛纯相。较为适宜的原料配比为n(TMAOH)∶n(Al2O3)∶n(P2O5)∶n(SiO2)∶n(CTAB)∶n(La2O3)∶n(H2O)=3.83∶1.0∶1.0∶0.6∶0.35∶0.4∶335 (摩尔比),对应的优化实验条件为:晶化温度170℃,晶化时间36小时,搅拌速度780rpm,pH值为6～7。在分子筛的合成过程中,陈化前后添加晶种能有效的促进LaSAPO分子筛生成,提高结晶度。
2.通过X射线粉末衍射、红外光谱、X射线荧光光谱、差热-热重分析、BET、透射电镜等方法对所合成LaSAPO分子筛样品进行表征,证明合成了热稳定性好的纯LaSAPO分子筛。
3.将所合成的LaSAPO分子筛样品用于乙酸与正丁醇的酯化反应,考察了其催化性能,结果表明,LaSAPO分子筛具有较高的催化活性,乙酸的转化率最高可达84.52%。
Porous crystalline silicoaluminophosphate molecular sieves possess three-dimensional framework structure of tetrahedral units AlO4, PO4 and SiO4, and ion-exchange properties and acidity. In this dissertation, Lanthanum is used to substitute part of Phosphorus or Aluminium in the framework and enter into the tetrahedron structure unit of oxygen negative ion for obtaining a kind of heteroatom molecular sieve with acidity. LaSAPO molecular sieve expands the realms of synthesis and application of molecular sieve materials, which can be used as sorbent of separating and purifying molecular species, catalyst or catalyst’s carrier and ions exchanger etc. The main studies of this dissertation are summarized as follows:
1. The effect of using template amounts, starting pH value of reaction system, crystalloid temperature and time, stirring speed, the SiO2/Al2O3 ratio and adding seed on synthesis of LaSAPO molecular sieve were systematically investigated. The experiment results show that a new type of pure lanthanum silicoaluminophosphate molecular sieve (LaSAPO) with higher crytal degree was synthesized by hydrothermal synthesis in TMAOH-Al2O3-P2O5-SiO2-La2(CO3)3-H2O-CTAB system. the optimal conditions are as follows: n(TMAOH)∶n(Al2O3)∶n(P2O5)∶n(SiO2)∶n(CTAB)∶n(La2O3)∶n(H2O)=3.83∶1.0∶1.0∶0.6∶0.35∶0.4∶335(mol ratio), crystallization is at 170℃for 36 hours, stirring speed is 780 rpm and the pH is 6.0~7.0. In the process of molecular sieve synthesis the formation of LaSAPO molecular sieve was effectively promoted and crystal degree was increased by adding seed before or behind stilling.
2. The LaSAPO sample was characterized by XRD, FTIR, XRF, DTA-TG, TEM and so on, and the results shows that pure LaSAPO molecular sieve with better heat stability was obtained.
3. The LaSAPO sample was used as esterification of acetic acid and butanol to investigate its catalytic activity The result shows LaSAPO molecular sieve possess better catalytic activity and the percent conversion of acetic acid is up to 84.52%.
1.系统考察了模板剂用量、反应体系的初始pH值、晶化时间、晶化温度、搅拌速度、SiO2/Al2O3以及添加晶种对LaSAPO合成的影响。实验结果表明,采用水热合成法在TMAOH-Al2O3-P2O5-SiO2-La2(CO3)3-H2O-CTAB体系中可合成结晶度较高的新型镧硅磷酸铝分子筛纯相。较为适宜的原料配比为n(TMAOH)∶n(Al2O3)∶n(P2O5)∶n(SiO2)∶n(CTAB)∶n(La2O3)∶n(H2O)=3.83∶1.0∶1.0∶0.6∶0.35∶0.4∶335 (摩尔比),对应的优化实验条件为:晶化温度170℃,晶化时间36小时,搅拌速度780rpm,pH值为6～7。在分子筛的合成过程中,陈化前后添加晶种能有效的促进LaSAPO分子筛生成,提高结晶度。
2.通过X射线粉末衍射、红外光谱、X射线荧光光谱、差热-热重分析、BET、透射电镜等方法对所合成LaSAPO分子筛样品进行表征,证明合成了热稳定性好的纯LaSAPO分子筛。
3.将所合成的LaSAPO分子筛样品用于乙酸与正丁醇的酯化反应,考察了其催化性能,结果表明,LaSAPO分子筛具有较高的催化活性,乙酸的转化率最高可达84.52%。
Porous crystalline silicoaluminophosphate molecular sieves possess three-dimensional framework structure of tetrahedral units AlO4, PO4 and SiO4, and ion-exchange properties and acidity. In this dissertation, Lanthanum is used to substitute part of Phosphorus or Aluminium in the framework and enter into the tetrahedron structure unit of oxygen negative ion for obtaining a kind of heteroatom molecular sieve with acidity. LaSAPO molecular sieve expands the realms of synthesis and application of molecular sieve materials, which can be used as sorbent of separating and purifying molecular species, catalyst or catalyst’s carrier and ions exchanger etc. The main studies of this dissertation are summarized as follows:
1. The effect of using template amounts, starting pH value of reaction system, crystalloid temperature and time, stirring speed, the SiO2/Al2O3 ratio and adding seed on synthesis of LaSAPO molecular sieve were systematically investigated. The experiment results show that a new type of pure lanthanum silicoaluminophosphate molecular sieve (LaSAPO) with higher crytal degree was synthesized by hydrothermal synthesis in TMAOH-Al2O3-P2O5-SiO2-La2(CO3)3-H2O-CTAB system. the optimal conditions are as follows: n(TMAOH)∶n(Al2O3)∶n(P2O5)∶n(SiO2)∶n(CTAB)∶n(La2O3)∶n(H2O)=3.83∶1.0∶1.0∶0.6∶0.35∶0.4∶335(mol ratio), crystallization is at 170℃for 36 hours, stirring speed is 780 rpm and the pH is 6.0~7.0. In the process of molecular sieve synthesis the formation of LaSAPO molecular sieve was effectively promoted and crystal degree was increased by adding seed before or behind stilling.
2. The LaSAPO sample was characterized by XRD, FTIR, XRF, DTA-TG, TEM and so on, and the results shows that pure LaSAPO molecular sieve with better heat stability was obtained.
3. The LaSAPO sample was used as esterification of acetic acid and butanol to investigate its catalytic activity The result shows LaSAPO molecular sieve possess better catalytic activity and the percent conversion of acetic acid is up to 84.52%.
引文
[1] 高滋,何鸣元,戴逸云等.沸石催化与分离技术[M].北京:中国石化出版社,1999:1～5
[2] 马丙丽,淳远,周炜等.新型两亲性 HZSM-5 沸石催化剂对环己烯水合相界面反应的催化研究[J].高等学校化学学报.2005,26 (4) :731～736
[3] 王辉,张汉军,孔德金等.ZSM-5 催化剂水蒸汽处理对甲苯选择性歧化性能的影响[J].石油化工.2000,29(6) :401～404
[4] 徐静莉,孙国富.固体酸催化剂在酯化反应中的应用研究进展[J].吉林化工学院学报.2001,18(4 ) :87～90
[5] 宋伟明,邓启刚,赵德丰等.CaX 分子筛负载过氯酸镁催化剂的制备及其催化性能[J].应用化学.2003,20 (8 ) :740～743
[6] Wilson S T,Lok B M,Messina C A,etc.[J].Am.Chem.Soc.1982,104:1146
[7] FlanigenE M,Lok B M,Patton R L,et al.New Developments in Zeolite Science and Technology[J]. Elsevier. 1986,103:28～32
[8] 武克瑞.金属磷酸铝分子筛进展[J].陕西师大学报.1989,17(4):71～74
[9] Lewis B Young,Skillman N J.US 4447642.1984
[10] Lewis B Young,Skillman N J.US 4448983.1984
[11] 张怀彬,庄孟芙等.酯化反应中 HZSM-5 的催化性能焙烧温度对催化剂性能的影响[J] .燃料化学学报[J].1988,15(2) :171～180
[12] 赵振华,赵瑞兰,申振.新型磷酸铝分子筛催化合成丙酸丙酯的研究[J].湖南师范大学自然科学学报.1993,16(4):332～337
[13] 赵瑞兰.用磷酸铝分子筛和硅磷酸铝分子筛作催化剂合成丙酸戊酯的研究[J].湖南师范大学自然科学学报.1992,15(3):246～251
[14] 黄奇伟, 张世英.硅磷酸铝分子筛催化羧酸的酯化反应研究[J].分子催化.2003,17(6):417～420
[15] 郭星翠,张杰,孟宪涛.ZrBSAPO-5 的制备及其催化合成三醋酸甘油酯[J].工业催化.2004,12(8):33～36
[16] 武宝萍,袁兴东,开玉台等.介孔分子筛 P-SBA-15 催化合成+一碳烯酸异丙酯[J].石油化工.2003,32(11):937～940
[17] 武宝萍,亓玉台,袁兴东等.介孔分子筛 B-SBA-15 催化合成柠檬酸三丁酯[J].工业催化.2004,12(1):32～35
[18] 苏建明,吴莱萍等.磷酸铝系列分子筛合成及应用前景[J].齐鲁石油化工.2002,30(4):317～320
[19] Helmkamp M,Davis M.Synthesis of poroussilicates[J].Ann.Rev. Mater. Sci. 1995,(25):161～192
[20] Barrer R M.Hydrothermal Chemistry of Zeolites. Academic Press. 1982:106～108
[21] Lok B M,Messina C A,Pat ton R,et al. Crystalline silicoalum inopho sphates[P ]. U S 4440871, 1984
[22] 董涛.高纯相 SAPO-5 分子筛的微波合成及其表征[D].陕西师范大学硕士毕业论文 2005
[23] 张立群.新型镧磷酸铝 LaAPO-5 的合成.内蒙古工业学硕士论文[D].2006.2～3
[24] 肖天存,安立敦.晶化时间及硅源对SAPO-5分子筛的结构及模板剂状态的影响[J].波谱学杂志.1995,12 (2):14～8-154
[25] 李宏愿,梁 娟,汪荣慧. 硅磷酸铝分子筛SAPO-34 的合成[J ] . 石油化工,1987 ,16 (5) :340～346
[26] Wilson S T. Crystalline silicoalum inophosphates : SAPO-36 and SAPO-56[ P] . US:5370851 ,1994-12-06
[27] Jianmin Xiong, Yunjie Ding, Hejun Zhu. Nitrogen-Incorporated SAPO-11 Molecular Sieve,Synthesis,Characterization,Properties[J]. J Phys.Chem.B 2003,(107):1366～1369
[28] 汪哲明, 阎子峰. SAPO-11 分子筛的合成[J].燃料化学学报.2003,8(4):361～366.
[29] Tapp N J , Milestone N B , Bibby D M. Synthesis of AlPO4-11[J ]. Zeolites , 1988 , 8 (1) : 183～188
[30] Lok B M, Cannan T R , Messina C A. The role of organic molecular in molecular sieve synthesis [J ].Zeolites , 1983 , 3(1) : 282～291
[31] 李宏愿,梁娟.磷酸硅铝分子筛的合成与应用[J].石油化工.1989,18(8): 503～507
[32] 谢素娟,李宏愿,赵修松,等. 磷酸硅铝SAPO25 的合成 [J ] . 石油化工,1995 ,24 (2) :82～85
[33] 须沁华. SAPO 分子筛[ J ] . 石油化工, 1988 , 17 (3) : 186～192
[34] 谭涓,何常青,刘中民. SAPO-34 分子筛研究进展 [J ] . 天然气化工,1999 ,24 (2) :47～53
[35] Vomscheid R , Briend M , Peltre M T , et al. The role of the template in directing the Si distribution in SAPO zeolites[J ] . J Phys Chem ,1994 ,98 :9614～9618
[36] 肖天存,王海涛,陈 方,等. 硅源及晶化时间对SAPO-5 分子筛模板剂、酸性及催化性能的影响[J ].催化学报,1998 ,19 (2) :144～148
[37] 江祖成,蔡汝秀,张华山.稀土元素分析化学[M].北京:科学出版社,2000:1～12
[38] 霍明远,肖纯美,中国稀土理论与应用研究[M].北京高等教育出版社.1998:34～35
[39] Pujado P R, Rabo J A ,A ntos G J. Industrial Catalytic App lications of Molecular Sieves[J ]. Catal Today, 1992, 13 (1) : 113
[40]须沁华. SAPO 分子筛. 石油化工[J], 1988, (17) : 186
[41] 付晔,王乐夫等.SAPO 分子筛的研究现状及应用前景[J].化学反应工程与工艺.2000,16(1):55～59
[42] Watanabe Y , Koiwai A . Multinuclear NMR Studies on the Thermal Stability of SAPO-34[J] .Journal of Catalysis.1993,143(2) :430～440
[43] Chu,W.yang,X. Ye,and Wu.Y. Appl.Catal.A [J]1996,145:125-140
[44] 廖世军.固体酸催化剂催化酯化反应研究.吉林化工学院学报[J].2002,18(4):87～90
[45] Santacesaria.E etal.P23795 A/80.1989
[46] 蒋登高主编.精细有机合成反应及工艺[M].北京.化学工业出版社.2002:237～249
[47] 刘新河.活性炭固载杂多酸催化合成乳酸正丁酯[J].精细石油化工.2001,3:16～18
[48] 支青,刘芸.合成乳酸正丁酯的新型催化剂-固体酸 NH4Fe(SO4)2/C[J].山地农业生物学报.2001,20(3) :196～199
[49] 解从霞,于世涛.复合固体酸 SnO2-Al2O3 催化合成柠檬酸酯的研究[J].精细石油化工进展.2001,2(7) :18～20
[50] 龙德清,宋秀坤.固体超强酸 SO42-/TiO2催化合成肉桂酸乙酯的研究[J].化学世界.2003,5:250～252
[51] 林绮纯,郭锡坤,林维明.ZrO2- Dy2O3/SO42-沸石分子筛催化合成柠檬酸三丁酯的研究[J].天然气化工.1999,24(6) :54～57
[52] 陈洪,符史良,龙翔.固体超强酸 SO42-/Fe2O3催化合成乙酸异戊酯的研究[J].化学与生物工程.2004,3 :26～28
[53] Yan-hua Xu,Tsunenori Nakajima,Akira Ohki.Adsorption and removal of arsenic from drinking water by aluminium-loaded Shirasu-zeolite[J]. Journal of Hazardous Materials.2002,B92: 275～287
[54] Xianhui Bu,Pingyun Feng,Thurman E.Gier,Galen D. Stucky.Synthesis and crystal structure of feldspar analogist in beryllosilicate and aluminium-cobalt phosphate systems[J]. Microporousand Mesoporous Materials.1998,23:323～330
[55] F.Cora,C.R.A.Catlow,A.D’Ercole.Acid and red ox properties of Co-substituted aluminium phosphates[J] . Journal of Molecular Catalysis A:Chemical .2001,166:87～99
[56] A.R.Brough,A.Katz,G-K.Sun,L.J.Struble,R.J.Kirkpatrick,J.F.Young.Adiabatically cured,alkali-activated cement-based waste forms containing high levels of fly ash Formation of zealots and Al-substituted C-S-H[J]. Cement and Concrete Research.2001,31 : 1437～1447
[57] K.Kedarnath,AmitavaChoudhury,and Srinivasan Natarajan.A Hybrid Open-Framework Aluminium Phosphate-Oxalate Possessing Large Circular 12-Membered Channels[J]. Journal of Solid State Chemistry.2000,150: 324～329
[58] J.S.Notario,J.E.Garcia,J.M.Caceres,I.J.Arteaga,M.M.Gonzalez.Characterization of natural philistine modified with orthophosphoric acid[J]. Applied Clay Science.1995,10 : 209～217
[59] K.Sakadevan ,H.J.Bavor.Phosphate adsorption characteristic of soils,sl-ags and zeolite to be used as substrates in constructed wetland systems[J]. Journal of Hazardous Materials.1998, 32(2):393～399
[60] J.Santamaria Gonzalez,A.Jimenez-Lopez,and Maria Martinez Lara. Preparation of Zeolite-like Pillared Metal (Ⅳ ) Phosphate Materials[J] . Journal of solid state chemistry.1995, 120:381～387
[61] Kezhan Yang,Barry D.Batts,Michael A.Wilson,Martin L.Gorbaty,Peter S,Maa,Mervyn A.Long,Simon X.J.He and Moetaz I.Attalla. Reaction of methane with coal[J]. Journal of solid state chemistry.1997, 76(12): 1105～1115
[62] 徐本静,钱岭.SAPO-11 分子筛合成技术研究进展[J].石油与天然气化工 2003,(28):37-46
[63] Yining Huang, David Machado, and Christopher W. Kirby. A Study of the Formation of Molecular Sieve SAPO-44[J]. J. Phys. Chem. B 2004, 108, 1855-1865
[64] 施尔畏,陈之战,元如林等.水热结晶学[M].北京:科学出版社,2005:98～99
[65] 林深,颜桂炀.CdAPO-5 的合成、结构及催化性能(J).结构化学.1999,5(3):213-217
[66] 张术跟,申少华.廉价矿物原料沸石分子筛合成研究[M].湖南:中南大学出版社.2003,11:12-29
[67] 汪哲明, 阎子峰. 新型取代型磷酸铝分子筛的合成与表征[J] 燃料化学学报, 2001 , 29 (增刊) :92111
[68] 段淑娥.NiAPO-11 分子筛的合成与结构研究[J] .西安工业学院学报.2003,20(1):62～65
[69] 辛勤.固体催化剂研究方法(上册) [M].北京:科学出版社,2005:248～261
[70] 马德里.用分子筛催化剂液相合成乙酸正丁醋[J].石油化工.1989,18(7):431
[71] 俞善信,文瑞明.丁酸异戊酯合成中的催化剂研究[J].应用化工.2002,31(1):5
[72] 自爱民,杨水金.合成乙酸异戊酯的催化剂研究[J].应用化工.2002,31(3):5～6
[73] 俞善信.固体酸催化合成乳酸正丁酯[J].石油化工.1989,18(7):431
[74] 陈丹云,张福连,.丁酸异戊酯催化合成研究进展[J].河北化工.2002,3:8～9
[75] Sinha A K,Sainkar S,Sivasankera S.An improved method for the synthesis of the silicoaluminophosphate molecular sieves, SAPO-5,SAPO-11 and SAPO-31[J] . Microporous Mater .1999,31(3) :321～331
[76] 徐如人,庞文琴.分子筛与多孔材料化学[M].北京:科学出版社,2004:528～529
[2] 马丙丽,淳远,周炜等.新型两亲性 HZSM-5 沸石催化剂对环己烯水合相界面反应的催化研究[J].高等学校化学学报.2005,26 (4) :731～736
[3] 王辉,张汉军,孔德金等.ZSM-5 催化剂水蒸汽处理对甲苯选择性歧化性能的影响[J].石油化工.2000,29(6) :401～404
[4] 徐静莉,孙国富.固体酸催化剂在酯化反应中的应用研究进展[J].吉林化工学院学报.2001,18(4 ) :87～90
[5] 宋伟明,邓启刚,赵德丰等.CaX 分子筛负载过氯酸镁催化剂的制备及其催化性能[J].应用化学.2003,20 (8 ) :740～743
[6] Wilson S T,Lok B M,Messina C A,etc.[J].Am.Chem.Soc.1982,104:1146
[7] FlanigenE M,Lok B M,Patton R L,et al.New Developments in Zeolite Science and Technology[J]. Elsevier. 1986,103:28～32
[8] 武克瑞.金属磷酸铝分子筛进展[J].陕西师大学报.1989,17(4):71～74
[9] Lewis B Young,Skillman N J.US 4447642.1984
[10] Lewis B Young,Skillman N J.US 4448983.1984
[11] 张怀彬,庄孟芙等.酯化反应中 HZSM-5 的催化性能焙烧温度对催化剂性能的影响[J] .燃料化学学报[J].1988,15(2) :171～180
[12] 赵振华,赵瑞兰,申振.新型磷酸铝分子筛催化合成丙酸丙酯的研究[J].湖南师范大学自然科学学报.1993,16(4):332～337
[13] 赵瑞兰.用磷酸铝分子筛和硅磷酸铝分子筛作催化剂合成丙酸戊酯的研究[J].湖南师范大学自然科学学报.1992,15(3):246～251
[14] 黄奇伟, 张世英.硅磷酸铝分子筛催化羧酸的酯化反应研究[J].分子催化.2003,17(6):417～420
[15] 郭星翠,张杰,孟宪涛.ZrBSAPO-5 的制备及其催化合成三醋酸甘油酯[J].工业催化.2004,12(8):33～36
[16] 武宝萍,袁兴东,开玉台等.介孔分子筛 P-SBA-15 催化合成+一碳烯酸异丙酯[J].石油化工.2003,32(11):937～940
[17] 武宝萍,亓玉台,袁兴东等.介孔分子筛 B-SBA-15 催化合成柠檬酸三丁酯[J].工业催化.2004,12(1):32～35
[18] 苏建明,吴莱萍等.磷酸铝系列分子筛合成及应用前景[J].齐鲁石油化工.2002,30(4):317～320
[19] Helmkamp M,Davis M.Synthesis of poroussilicates[J].Ann.Rev. Mater. Sci. 1995,(25):161～192
[20] Barrer R M.Hydrothermal Chemistry of Zeolites. Academic Press. 1982:106～108
[21] Lok B M,Messina C A,Pat ton R,et al. Crystalline silicoalum inopho sphates[P ]. U S 4440871, 1984
[22] 董涛.高纯相 SAPO-5 分子筛的微波合成及其表征[D].陕西师范大学硕士毕业论文 2005
[23] 张立群.新型镧磷酸铝 LaAPO-5 的合成.内蒙古工业学硕士论文[D].2006.2～3
[24] 肖天存,安立敦.晶化时间及硅源对SAPO-5分子筛的结构及模板剂状态的影响[J].波谱学杂志.1995,12 (2):14～8-154
[25] 李宏愿,梁 娟,汪荣慧. 硅磷酸铝分子筛SAPO-34 的合成[J ] . 石油化工,1987 ,16 (5) :340～346
[26] Wilson S T. Crystalline silicoalum inophosphates : SAPO-36 and SAPO-56[ P] . US:5370851 ,1994-12-06
[27] Jianmin Xiong, Yunjie Ding, Hejun Zhu. Nitrogen-Incorporated SAPO-11 Molecular Sieve,Synthesis,Characterization,Properties[J]. J Phys.Chem.B 2003,(107):1366～1369
[28] 汪哲明, 阎子峰. SAPO-11 分子筛的合成[J].燃料化学学报.2003,8(4):361～366.
[29] Tapp N J , Milestone N B , Bibby D M. Synthesis of AlPO4-11[J ]. Zeolites , 1988 , 8 (1) : 183～188
[30] Lok B M, Cannan T R , Messina C A. The role of organic molecular in molecular sieve synthesis [J ].Zeolites , 1983 , 3(1) : 282～291
[31] 李宏愿,梁娟.磷酸硅铝分子筛的合成与应用[J].石油化工.1989,18(8): 503～507
[32] 谢素娟,李宏愿,赵修松,等. 磷酸硅铝SAPO25 的合成 [J ] . 石油化工,1995 ,24 (2) :82～85
[33] 须沁华. SAPO 分子筛[ J ] . 石油化工, 1988 , 17 (3) : 186～192
[34] 谭涓,何常青,刘中民. SAPO-34 分子筛研究进展 [J ] . 天然气化工,1999 ,24 (2) :47～53
[35] Vomscheid R , Briend M , Peltre M T , et al. The role of the template in directing the Si distribution in SAPO zeolites[J ] . J Phys Chem ,1994 ,98 :9614～9618
[36] 肖天存,王海涛,陈 方,等. 硅源及晶化时间对SAPO-5 分子筛模板剂、酸性及催化性能的影响[J ].催化学报,1998 ,19 (2) :144～148
[37] 江祖成,蔡汝秀,张华山.稀土元素分析化学[M].北京:科学出版社,2000:1～12
[38] 霍明远,肖纯美,中国稀土理论与应用研究[M].北京高等教育出版社.1998:34～35
[39] Pujado P R, Rabo J A ,A ntos G J. Industrial Catalytic App lications of Molecular Sieves[J ]. Catal Today, 1992, 13 (1) : 113
[40]须沁华. SAPO 分子筛. 石油化工[J], 1988, (17) : 186
[41] 付晔,王乐夫等.SAPO 分子筛的研究现状及应用前景[J].化学反应工程与工艺.2000,16(1):55～59
[42] Watanabe Y , Koiwai A . Multinuclear NMR Studies on the Thermal Stability of SAPO-34[J] .Journal of Catalysis.1993,143(2) :430～440
[43] Chu,W.yang,X. Ye,and Wu.Y. Appl.Catal.A [J]1996,145:125-140
[44] 廖世军.固体酸催化剂催化酯化反应研究.吉林化工学院学报[J].2002,18(4):87～90
[45] Santacesaria.E etal.P23795 A/80.1989
[46] 蒋登高主编.精细有机合成反应及工艺[M].北京.化学工业出版社.2002:237～249
[47] 刘新河.活性炭固载杂多酸催化合成乳酸正丁酯[J].精细石油化工.2001,3:16～18
[48] 支青,刘芸.合成乳酸正丁酯的新型催化剂-固体酸 NH4Fe(SO4)2/C[J].山地农业生物学报.2001,20(3) :196～199
[49] 解从霞,于世涛.复合固体酸 SnO2-Al2O3 催化合成柠檬酸酯的研究[J].精细石油化工进展.2001,2(7) :18～20
[50] 龙德清,宋秀坤.固体超强酸 SO42-/TiO2催化合成肉桂酸乙酯的研究[J].化学世界.2003,5:250～252
[51] 林绮纯,郭锡坤,林维明.ZrO2- Dy2O3/SO42-沸石分子筛催化合成柠檬酸三丁酯的研究[J].天然气化工.1999,24(6) :54～57
[52] 陈洪,符史良,龙翔.固体超强酸 SO42-/Fe2O3催化合成乙酸异戊酯的研究[J].化学与生物工程.2004,3 :26～28
[53] Yan-hua Xu,Tsunenori Nakajima,Akira Ohki.Adsorption and removal of arsenic from drinking water by aluminium-loaded Shirasu-zeolite[J]. Journal of Hazardous Materials.2002,B92: 275～287
[54] Xianhui Bu,Pingyun Feng,Thurman E.Gier,Galen D. Stucky.Synthesis and crystal structure of feldspar analogist in beryllosilicate and aluminium-cobalt phosphate systems[J]. Microporousand Mesoporous Materials.1998,23:323～330
[55] F.Cora,C.R.A.Catlow,A.D’Ercole.Acid and red ox properties of Co-substituted aluminium phosphates[J] . Journal of Molecular Catalysis A:Chemical .2001,166:87～99
[56] A.R.Brough,A.Katz,G-K.Sun,L.J.Struble,R.J.Kirkpatrick,J.F.Young.Adiabatically cured,alkali-activated cement-based waste forms containing high levels of fly ash Formation of zealots and Al-substituted C-S-H[J]. Cement and Concrete Research.2001,31 : 1437～1447
[57] K.Kedarnath,AmitavaChoudhury,and Srinivasan Natarajan.A Hybrid Open-Framework Aluminium Phosphate-Oxalate Possessing Large Circular 12-Membered Channels[J]. Journal of Solid State Chemistry.2000,150: 324～329
[58] J.S.Notario,J.E.Garcia,J.M.Caceres,I.J.Arteaga,M.M.Gonzalez.Characterization of natural philistine modified with orthophosphoric acid[J]. Applied Clay Science.1995,10 : 209～217
[59] K.Sakadevan ,H.J.Bavor.Phosphate adsorption characteristic of soils,sl-ags and zeolite to be used as substrates in constructed wetland systems[J]. Journal of Hazardous Materials.1998, 32(2):393～399
[60] J.Santamaria Gonzalez,A.Jimenez-Lopez,and Maria Martinez Lara. Preparation of Zeolite-like Pillared Metal (Ⅳ ) Phosphate Materials[J] . Journal of solid state chemistry.1995, 120:381～387
[61] Kezhan Yang,Barry D.Batts,Michael A.Wilson,Martin L.Gorbaty,Peter S,Maa,Mervyn A.Long,Simon X.J.He and Moetaz I.Attalla. Reaction of methane with coal[J]. Journal of solid state chemistry.1997, 76(12): 1105～1115
[62] 徐本静,钱岭.SAPO-11 分子筛合成技术研究进展[J].石油与天然气化工 2003,(28):37-46
[63] Yining Huang, David Machado, and Christopher W. Kirby. A Study of the Formation of Molecular Sieve SAPO-44[J]. J. Phys. Chem. B 2004, 108, 1855-1865
[64] 施尔畏,陈之战,元如林等.水热结晶学[M].北京:科学出版社,2005:98～99
[65] 林深,颜桂炀.CdAPO-5 的合成、结构及催化性能(J).结构化学.1999,5(3):213-217
[66] 张术跟,申少华.廉价矿物原料沸石分子筛合成研究[M].湖南:中南大学出版社.2003,11:12-29
[67] 汪哲明, 阎子峰. 新型取代型磷酸铝分子筛的合成与表征[J] 燃料化学学报, 2001 , 29 (增刊) :92111
[68] 段淑娥.NiAPO-11 分子筛的合成与结构研究[J] .西安工业学院学报.2003,20(1):62～65
[69] 辛勤.固体催化剂研究方法(上册) [M].北京:科学出版社,2005:248～261
[70] 马德里.用分子筛催化剂液相合成乙酸正丁醋[J].石油化工.1989,18(7):431
[71] 俞善信,文瑞明.丁酸异戊酯合成中的催化剂研究[J].应用化工.2002,31(1):5
[72] 自爱民,杨水金.合成乙酸异戊酯的催化剂研究[J].应用化工.2002,31(3):5～6
[73] 俞善信.固体酸催化合成乳酸正丁酯[J].石油化工.1989,18(7):431
[74] 陈丹云,张福连,.丁酸异戊酯催化合成研究进展[J].河北化工.2002,3:8～9
[75] Sinha A K,Sainkar S,Sivasankera S.An improved method for the synthesis of the silicoaluminophosphate molecular sieves, SAPO-5,SAPO-11 and SAPO-31[J] . Microporous Mater .1999,31(3) :321～331
[76] 徐如人,庞文琴.分子筛与多孔材料化学[M].北京:科学出版社,2004:528～529