以硅藻土为原料合成沸石分子筛的探索研究
摘要
沸石分子筛是一种结晶态的硅铝酸盐,可作为良好的吸附剂、离子交换剂和催化剂,用化学原料合成分子筛具有成本高、母液排放量大且污染环境等诸多弊端。本文在综合分析国内外有关沸石分子筛的合成与应用的大量文献的基础上,采用吉林敦化的硅藻土为主要原料成功合成出了NaP、NaA和NaY型分子筛,既提高了硅藻土的高层次开发利用,又为沸石分子筛的合成提供了一种来源丰富的新原料。本论文对硅藻土水热法合成分子筛结晶变化过程中的影响因素进行了全面系统的研究,主要内容如下:
探索以硅藻土为主要原料,不采用传统的高温焙烧,直接与碱液反应,水热合成系列低品位沸石分子筛(NaP、NaA和NaY型)。通过XRD、IR、SEM及CEC等测试手段对合成的产品进行了测试与表征,系统考察了合成过程中的影响因素,如反应体系配比、陈化条件、晶化温度及晶化时间等,从而确定了分子筛水热合成的最佳工艺参数。该合成方法工艺简单、反应条件易控制,而且原料来源丰富、合成成本低,可进行工业化生产。
探索以硅藻土为主要原料,采用碱熔、添加导向剂合成结晶度高的高品位NaY型沸石分子筛。以硅藻土为原料,采用优化的水热反应合成新工艺:碱焙烧硅藻土→添加导向剂→晶化合成→过滤、洗涤→烘干→NAY型分子筛产品。最佳工艺参数为:先将硅藻土与氢氧化钠按Na_2O/SiO_2=1∶1混合,在550℃焙烧1h,再将碱土与偏铝酸钠、水按照摩尔比6SiO_2∶Al_2O_3∶6Na_2O∶219.6H_2O配制,并加入少量的导向剂(组成为15SiO_2∶Al_2o_3∶21.6Na_2O∶569H_2O),在100℃下恒温晶化10h。所得产品的结晶度接近100%,饱和静态水吸附量可达到27.3%。研究发现,碱熔焙烧、导向剂和反应体系配比对合成产品晶相的影响起了决定性作用。
Zeolites are widely used as absorbents, ion exchanges and catalysts. There are many shortcomings in synthesizing zeolites from chemical materials, such as high cost, and serious pollution from reactant liquids and so on. Based on lots of literatures of zeolites synthesis, a series of zeolites are hydrothermally synthesized successfully from diatomite. Besides, the influence of treatment conditions is studied systematically.Using diatomite and alkali solution directly, this paper synthesizes a series of zeolite products (NaP, NaA and NaY type) through the hydrothermal method. It is discussed in depth the effects on synthesis of zeolites, including the composition of the reaction mixture and the hydrothermal conditions. Then the technical parameters of hydrothermal treatment of zeolites are optimized.In existing of the structure directing agent (SDA), Zeolite NaY of high crystallinity is hydrothermally synthesized by diatomite, which is calcined with alkali in advance. The crystal phase is identified by X-ray diffraction. And the static water absorption capacity data of zeolite NaY is gained. The reaction conditions are discussed and the results show that the alkali fusion, the action of SDA and the composition of reactant system are the main impacting factors on zeolite NaY synthesis. The optimum technical conditions are as follows. Diatomite is calcined with sodium hydroxide under the Na_2O/SiO_2 ratio of 1:1 at the temperature of 550℃. Afterwards, the composition of reactant mixture is 6SiO_2: Al_2O_3: 6Na_2O: 219.6H_2O, with adding little amounts of SDA composed of 15SiO_2:Al_2O_3:21.6Na_2O: 569H_2O. And then the reactants are crystallized 10h at the temperature of 100℃. The crystallinity of product reaches to the maximum, and its water absorption capacity comes to 27.3%.
探索以硅藻土为主要原料,不采用传统的高温焙烧,直接与碱液反应,水热合成系列低品位沸石分子筛(NaP、NaA和NaY型)。通过XRD、IR、SEM及CEC等测试手段对合成的产品进行了测试与表征,系统考察了合成过程中的影响因素,如反应体系配比、陈化条件、晶化温度及晶化时间等,从而确定了分子筛水热合成的最佳工艺参数。该合成方法工艺简单、反应条件易控制,而且原料来源丰富、合成成本低,可进行工业化生产。
探索以硅藻土为主要原料,采用碱熔、添加导向剂合成结晶度高的高品位NaY型沸石分子筛。以硅藻土为原料,采用优化的水热反应合成新工艺:碱焙烧硅藻土→添加导向剂→晶化合成→过滤、洗涤→烘干→NAY型分子筛产品。最佳工艺参数为:先将硅藻土与氢氧化钠按Na_2O/SiO_2=1∶1混合,在550℃焙烧1h,再将碱土与偏铝酸钠、水按照摩尔比6SiO_2∶Al_2O_3∶6Na_2O∶219.6H_2O配制,并加入少量的导向剂(组成为15SiO_2∶Al_2o_3∶21.6Na_2O∶569H_2O),在100℃下恒温晶化10h。所得产品的结晶度接近100%,饱和静态水吸附量可达到27.3%。研究发现,碱熔焙烧、导向剂和反应体系配比对合成产品晶相的影响起了决定性作用。
Zeolites are widely used as absorbents, ion exchanges and catalysts. There are many shortcomings in synthesizing zeolites from chemical materials, such as high cost, and serious pollution from reactant liquids and so on. Based on lots of literatures of zeolites synthesis, a series of zeolites are hydrothermally synthesized successfully from diatomite. Besides, the influence of treatment conditions is studied systematically.Using diatomite and alkali solution directly, this paper synthesizes a series of zeolite products (NaP, NaA and NaY type) through the hydrothermal method. It is discussed in depth the effects on synthesis of zeolites, including the composition of the reaction mixture and the hydrothermal conditions. Then the technical parameters of hydrothermal treatment of zeolites are optimized.In existing of the structure directing agent (SDA), Zeolite NaY of high crystallinity is hydrothermally synthesized by diatomite, which is calcined with alkali in advance. The crystal phase is identified by X-ray diffraction. And the static water absorption capacity data of zeolite NaY is gained. The reaction conditions are discussed and the results show that the alkali fusion, the action of SDA and the composition of reactant system are the main impacting factors on zeolite NaY synthesis. The optimum technical conditions are as follows. Diatomite is calcined with sodium hydroxide under the Na_2O/SiO_2 ratio of 1:1 at the temperature of 550℃. Afterwards, the composition of reactant mixture is 6SiO_2: Al_2O_3: 6Na_2O: 219.6H_2O, with adding little amounts of SDA composed of 15SiO_2:Al_2O_3:21.6Na_2O: 569H_2O. And then the reactants are crystallized 10h at the temperature of 100℃. The crystallinity of product reaches to the maximum, and its water absorption capacity comes to 27.3%.
引文
[1] 上海试剂五厂.分子筛制备与应用.上海:上海人民出版社,1976.
[2] 中国科学院大连化学物理研究所分子筛组.沸石分子筛.北京:科学出版社,1978.
[3] Barrer R M.见:徐如人,庞文琴等.分子筛与多孔材料化学.北京:科学出版社,1987:206.
[4] 杨立玲.以伊利石合成4A沸石分子筛的实验研究: (硕士学位论文).西安:西安科技大学,2005.
[5] 冯芳霞,窦涛等.干粉法合成中孔分子筛MCM-41.石油学报,1998,14(3):89-92.
[6] Bibby D. M., Dale M. P. Synthesis of silica-sodalite from non-aqueous systems. Nature, 1985, 347(Sept. 12):157-158.
[7] 申少华.廉价矿物原料水热法制备沸石分子筛的形成机理与晶体生长模型:(博士学位论文).长沙:中南大学,2001.
[8] Endres, Robert, Drave, Heinz, Mansmann, Manfred, Puppe, Lothar. Process for the preparation of zeolite A from kaolin. United States Patent: 4271130, Nov 19, 1979.
[9] Kwon Yeong Soo, Kim Myun Sup. Reaction mechanism for zeolite A synthesis from Hadong kaolin. Yo Op Hoe Chi, 1983, 20(3):255-9 (Korean).
[10] Al-Mashta Ferdos, Al-Daghistani Nadia, Al-Derzi Nidhal. Formation of zeolite type A from Iraqi kaolinite. J. Pet. Res., 1989, 8(1), 83-92.
[11] Alberti A., Colella C., Oggiano G., Pansini M., Vezzalini G. Zeolite production from waste kaolin-containing materials. Materials Engineering, 1994, 5(2): 145-58.
[12] Costa Enrique, de Lucas Antonio, Uguina M. Angeles, Ruiz Juan Carlos. Industrial & Engineering Chemistry Research, 1988, 27(7): 1291-1296.
[13] 吴棱,康遥,李兆基,覃业燕,姚元根.高岭土碱融法合成4A分子筛,中国专利CN1287971,2001.03.
[14] 陈泉水.用金溪膨润土合成4A分子筛及产品性能研究.非金属矿,2001,24(3):43-44.
[15] 刘德贡.珍珠岩高温碱溶合成4A分子筛实验研究,非金属矿,2002,25(6):13-14.
[16] 杨慧芬,杨华.纯化天然斜发沸石合成4A沸石工艺研究.建材地质,1997,(6):20-23.
[17] S. S. Rayalu, J. S. Udhoji, K. N. Munshi, M. Z. Hasan. Highly crystalline zeolite-a from flyash of bituminous and ligite coal combustion. Journal of Hazardous Materials, 2001, 88(1):107-121.
[18] Vernon S. Somerset, Leslie F. Petrik, Richard A. White, Michael J. Klink, David Key, Emmanuel I. Iwuoha. Alkaline hydrothermal zeolites synthesized from high SiO_2 and Al_2O_3 co-disposal fly ash filtrates. Fuel, 2005, 84(18):2324-2329.
[19] 马淑杰等.A型沸石的生成机理.高等化学学报,1984,(4):52-57.
[20] 王建等.偏高岭石合成4A沸石机理的研究.无机化学学报,2000,16(1):31-36.
[21] Lucas, Nadimi S. Nonaqueous synthesis of large zeolite and molecular sieve crystals. Stud. Sur. Sci. Catal., 1994, 84:319-321.
[22] Alkira Yoshida, Kouzou Inoue. Formation of faujasite-type zeolite from ground volcanic glass. Zeolites, 1986, 6:467-73.
[23] A. Molina, C. Poole. A comparative study two methods to produce zeolites from fly ash. Minerals Engineering, 2004, 17(2):167-173.
[24] 李酽.利用天然资源合成Y型分子筛.IM&P化工矿物与加工,2004,(2):11-14.
[25] 刘新锦,黄铁钢.用叶蜡石合成Y型沸石的研究.硅酸盐通报,1996,15(3):61-64.
[26] G. Steenbruggen, G. G. Hollman. The synthesis of zeolites from fly ash and the properties of the zeolite products. Journal of Geochemical exploration, 1998, 62(1-3):305-309.
[27] Miki Inada, Yukari Eguchi, Naoya Enomoto, Junichi Hojo. Synthesis of zeolite from coal fly ashes with different silica-alumina composition. Fuel, 2005, 84(2-3):299-304.
[28] 胡付欣,郭鹏.碱法活化膨润土合成洗涤用P型沸石研究.非金属矿,2005,28(5):28-30.
[29] 焦庆祝,庞文琴,霍启升.用英安岩和粉煤灰合成ZSM-5分子筛研究.硅酸盐通报,1996,(4):29-31.
[30] 马淑杰,李连生,刘新生,黄元夏.硅灰石直接合成ZSM-5分子筛.吉林大学自然科学学报,1995,(4):81-84.
[31] 第七届全国颗粒制备与处理学术暨应用研讨会论文集,2004年.
[32] 葛忠华,唐刚伟,陈银飞.国内外非金属矿资源的开发与应用.化工生产与技术,1995,(2):3-7.
[33] 吴荣庆,张燕如.硅藻土国内外市场形势分析和发展前景预测.中国矿业,1994,3(3):16-21,30.
[34] M. S. Hassan, I. A. Ibrahim, I.S. Ismael. Diatomaceous Deposits of Fayium, Egypt;Characterization and Evaluation for Industrial Application. Chinese journal of geochemistry, 1999, 18(3):233-241.
[35] 晓非.硅藻土开发利用技术专利信息.矿产保护与利用,1997,(1):38-46.
[36] 王泽民,马晓凡,王义,岳贵春,孙文田.硅藻土提纯研究(Ⅲ).非金属矿,1997,(6):20-23.
[37] 马崇勇,黄发政.硅藻土处理造纸等有机废水.CN86106871,1988,04,27.
[38] 生化工业株式会社,岩井重久,内田千寻,户田茂等.一种改善水域底层质量和水质的方法及用于该方法的一组加入剂.中国专利CN1085877,1994,04.
[39] 朱济成.新兴的工业资源硅藻土.百科知识,1995,(4):41-42.
[40] 朱志华,梁基照,杨卫国.硅藻土对聚合物的填充改性.上海塑料,2005,6(2):38-40.
[41] 陈荣三,杨宇翔,侯祺泰.国产硅藻土研究进展及其新应用.化工时刊,1997,11(5):54-56.
[42] William A., Pierre B., et al. Absorption of Streptococcus faecalis on diatomite carriers for use in biotransformations. J. Chem. Tech. Biotechnol., 1990, 47(2):93-100.
[43] Brennan, John F. Macroporous alumina/diatomaceous earth bio-supports. U. S. Pat. No. 4980334, Sep 13, 1989.
[44] Robertson, John S., LiPuma, Mildred M., Gross, Stephen E. Preparation of catalyst supports and materials produced thereby. U. S. Pat. No. 4581338, May 31, 1985.
[45] Jacques, Roland, Dupin, et al. Preparation of spheroidal alumina particulates. U. S. Pat. No. 4514511, May 19, 1983.
[46] 谢祖芳,黄锁义.国产硅藻土研究的进展及新应用.贵州化工,2002,27(1):5-7,16.
[47] 张若愚.用硅藻土制取四氯化硅.云南化工,1994,(4):44-46.
[48] Biswajit Ghosh, Dinesh C. Agrawal, Subhash Bhatia. Synthesis of zeolite A from calcined diatomaceous clay:optimization. Industrial & engineering chemistry research, 1994, 33(9):2107-2110.
[49] Vilma Sanhueza, Ursula Kelml, Ruby Cid. Synthesis of mordenite from diatomite: a case of zeolite synthesis from natural material. Journal of Chemical Technology and Biotechnology, 2003, 78(5): 485-488.
[50] A. Chaisena, K. Rangsriwatananon. Synthesis of sodium zeolites from natural and modified diatomite. Materials Letters, 2005, 59(12): 1474-1479.
[51] 中华人民共和国轻工行业标准—洗涤剂用4A沸石,QB/T1768-93.
[52] 国家标准GB 6287-86.
[53] 徐如人,庞文琴,屠昆刚等.沸石分子筛的结构与合成.长春:吉林大学出版社,1987.
[54] 赵善雷.新型P沸石的性能及应用前景.日用化学工业,2003,33(5):321-323.
[55] 董家禄,刘杨,姜斌臣,张骏.半合成法制备洗衣粉助剂4A沸石.江苏化工,1998,26(1):25-29.
[56] C. Poole et al. Synthesis of zeolite adsorbents by hydrothermal treatment of PFA waste: a comparative study. Minerals Engineering, 2000, 13(8-9):831-842.
[57] 申少华,张术根,王大伟.天然红辉沸石合成P型沸石工艺优化研究.非金属矿,2001,24(3):40-42.
[58] 王仰东,刘杨,董家禄,须沁华.小晶粒A型分子筛的合成及其晶貌.催化学报,1998,19(6):610-612.
[59] Leszek Gora, Robert W. Thompson. Controlled addition of aged mother liquor to zeolite NaA synthesis solutions. Zeolites, 1997, 18(2):132-141.
[60] Mathavee Sathupunya, Erdogan Gulari, Sujitra Wongkasemjit. Na-A(LTA) zeolite synthesis directly from alumatrane and silatrane by sol-gel microwave techniques. Journal of the European Ceramic Society, 2003, 23(8): 1293-1303.
[61] 申少华,张术根,王大伟.酸处理红辉石-碱-铝酸钠-水的水热反应体系A型沸石的晶化合成.硅酸学报,2001,29(5):451-454.
[62] 罗玉长,罗鹤鹏,魏召刚.4A沸石分子筛晶体生长过程.粉体技术,1995,1(3):21-25.
[63] S. Chandrasekhar, P. Raghavan, G. Sebastian, A. D. Damodaran. Brightness improvement studies on "kaolin based" zeolite 4A. Applied clay science, 1997, 12(3):221-231.
[64] K. Rajagopalan, A. W. Peters, G. C. Edwards. Influence of zeolite particle size on selectivity during fluid catalytic cracking. Appl. Catal., 1986, 23: 69-80.
[65] Navarro. Uriel, Trujillo. Carlos A., Oviedo. Alfredo, Lobo. Raul. Impact of deactivation conditions on the acidity of Y zeolites used in the formulation of FCC Catalysts, studied by FTIR of adsorbed CO. Journal of Catalysis, 2002, 211(1): 64-74.
[66] B. De Witte, J. Patarin, D. Le Nouen, et al. Cyclic polyols: a new class of structure-directing agents? Study of inositol in the synthesis of FAU-and LTA-type zeolites. Microporous and mesoporous materials, 1998, 23(1-2): 11-22.
[67] H. Gies, B. Marler. The structure-controlling role of organic templates for the synthesis of porosils in the system SiO_2/template/H_2O. Zeolites, 1992, 12: 42-49.
[68] F. Delprato, L. Delmotte, J. L. Guth, L. Huve. Synthesis of new silica-rich cubic and hexagonal faujasites using crown-ether-based supramolecules as templates. Zeolites, 1990, 10(6): 546-552.
[69] Sathy Chandrasekhar, P. N. Pramada. Kaolin-based zeolite Y, a precursor for cordierite ceramics. Applied Clay Science, 2004, 27(3-4): 187-198.
[70] Norihiro Murayama, Hideki Yamamoto, Junji Shibata. Mechanism of zeolite synthesis from coal fly ash by alkali hydrothermal reaction. International Journal of Mineral Processing, 2002, 64: 1-17.
[71] Ruiz R., Blanco C., Pesquera C., Gonzalez F., et al. Zeolitization of a bentonite and its application to the removal of ammonium ion from waste water. Applied Clay Science, 1997, 12(1-2): 73-83.
[72] B. R. Albert, A. K. Cheetham, J. A. Stuart, C. J. Adams. Investigations on P zeolites: synthesis, characterisation, andstructure of highly crystalline low-silica NaP. Microporous and mesoporous materials, 1998, 21(1-3): 133-142.
[73] H. Julide Koroglu, Alper Saroglan, et al. Effects of low-temperature gel ageing on the synthesis of zeolite Y at different alkalinities. Journal of Crystal Growth, 2002, 241(4): 481-488.
[74] 刘欣梅,阎子峰,王槐平.由煤系高岭土原位合成NaY分子筛.石油大学学报(自然科学版),2002,26(5):94-99.
[75] 马跃龙,陈诵英,彭少逸.小颗粒NaY分子筛透明液相导向剂的制备及其性能.催化学报,1995,16(5):410-414.
[76] 董家禄,鲍书林,须沁华.新型液相晶化导向剂.南京大学学报,1986,22(1):83-87.
[77] Wang Bo, Ma Hongzhu. Factors affecting the synthesis of microsized NaY zeolite, Microprous and mesoporous materials, 1998, (25):131-136.
[2] 中国科学院大连化学物理研究所分子筛组.沸石分子筛.北京:科学出版社,1978.
[3] Barrer R M.见:徐如人,庞文琴等.分子筛与多孔材料化学.北京:科学出版社,1987:206.
[4] 杨立玲.以伊利石合成4A沸石分子筛的实验研究: (硕士学位论文).西安:西安科技大学,2005.
[5] 冯芳霞,窦涛等.干粉法合成中孔分子筛MCM-41.石油学报,1998,14(3):89-92.
[6] Bibby D. M., Dale M. P. Synthesis of silica-sodalite from non-aqueous systems. Nature, 1985, 347(Sept. 12):157-158.
[7] 申少华.廉价矿物原料水热法制备沸石分子筛的形成机理与晶体生长模型:(博士学位论文).长沙:中南大学,2001.
[8] Endres, Robert, Drave, Heinz, Mansmann, Manfred, Puppe, Lothar. Process for the preparation of zeolite A from kaolin. United States Patent: 4271130, Nov 19, 1979.
[9] Kwon Yeong Soo, Kim Myun Sup. Reaction mechanism for zeolite A synthesis from Hadong kaolin. Yo Op Hoe Chi, 1983, 20(3):255-9 (Korean).
[10] Al-Mashta Ferdos, Al-Daghistani Nadia, Al-Derzi Nidhal. Formation of zeolite type A from Iraqi kaolinite. J. Pet. Res., 1989, 8(1), 83-92.
[11] Alberti A., Colella C., Oggiano G., Pansini M., Vezzalini G. Zeolite production from waste kaolin-containing materials. Materials Engineering, 1994, 5(2): 145-58.
[12] Costa Enrique, de Lucas Antonio, Uguina M. Angeles, Ruiz Juan Carlos. Industrial & Engineering Chemistry Research, 1988, 27(7): 1291-1296.
[13] 吴棱,康遥,李兆基,覃业燕,姚元根.高岭土碱融法合成4A分子筛,中国专利CN1287971,2001.03.
[14] 陈泉水.用金溪膨润土合成4A分子筛及产品性能研究.非金属矿,2001,24(3):43-44.
[15] 刘德贡.珍珠岩高温碱溶合成4A分子筛实验研究,非金属矿,2002,25(6):13-14.
[16] 杨慧芬,杨华.纯化天然斜发沸石合成4A沸石工艺研究.建材地质,1997,(6):20-23.
[17] S. S. Rayalu, J. S. Udhoji, K. N. Munshi, M. Z. Hasan. Highly crystalline zeolite-a from flyash of bituminous and ligite coal combustion. Journal of Hazardous Materials, 2001, 88(1):107-121.
[18] Vernon S. Somerset, Leslie F. Petrik, Richard A. White, Michael J. Klink, David Key, Emmanuel I. Iwuoha. Alkaline hydrothermal zeolites synthesized from high SiO_2 and Al_2O_3 co-disposal fly ash filtrates. Fuel, 2005, 84(18):2324-2329.
[19] 马淑杰等.A型沸石的生成机理.高等化学学报,1984,(4):52-57.
[20] 王建等.偏高岭石合成4A沸石机理的研究.无机化学学报,2000,16(1):31-36.
[21] Lucas, Nadimi S. Nonaqueous synthesis of large zeolite and molecular sieve crystals. Stud. Sur. Sci. Catal., 1994, 84:319-321.
[22] Alkira Yoshida, Kouzou Inoue. Formation of faujasite-type zeolite from ground volcanic glass. Zeolites, 1986, 6:467-73.
[23] A. Molina, C. Poole. A comparative study two methods to produce zeolites from fly ash. Minerals Engineering, 2004, 17(2):167-173.
[24] 李酽.利用天然资源合成Y型分子筛.IM&P化工矿物与加工,2004,(2):11-14.
[25] 刘新锦,黄铁钢.用叶蜡石合成Y型沸石的研究.硅酸盐通报,1996,15(3):61-64.
[26] G. Steenbruggen, G. G. Hollman. The synthesis of zeolites from fly ash and the properties of the zeolite products. Journal of Geochemical exploration, 1998, 62(1-3):305-309.
[27] Miki Inada, Yukari Eguchi, Naoya Enomoto, Junichi Hojo. Synthesis of zeolite from coal fly ashes with different silica-alumina composition. Fuel, 2005, 84(2-3):299-304.
[28] 胡付欣,郭鹏.碱法活化膨润土合成洗涤用P型沸石研究.非金属矿,2005,28(5):28-30.
[29] 焦庆祝,庞文琴,霍启升.用英安岩和粉煤灰合成ZSM-5分子筛研究.硅酸盐通报,1996,(4):29-31.
[30] 马淑杰,李连生,刘新生,黄元夏.硅灰石直接合成ZSM-5分子筛.吉林大学自然科学学报,1995,(4):81-84.
[31] 第七届全国颗粒制备与处理学术暨应用研讨会论文集,2004年.
[32] 葛忠华,唐刚伟,陈银飞.国内外非金属矿资源的开发与应用.化工生产与技术,1995,(2):3-7.
[33] 吴荣庆,张燕如.硅藻土国内外市场形势分析和发展前景预测.中国矿业,1994,3(3):16-21,30.
[34] M. S. Hassan, I. A. Ibrahim, I.S. Ismael. Diatomaceous Deposits of Fayium, Egypt;Characterization and Evaluation for Industrial Application. Chinese journal of geochemistry, 1999, 18(3):233-241.
[35] 晓非.硅藻土开发利用技术专利信息.矿产保护与利用,1997,(1):38-46.
[36] 王泽民,马晓凡,王义,岳贵春,孙文田.硅藻土提纯研究(Ⅲ).非金属矿,1997,(6):20-23.
[37] 马崇勇,黄发政.硅藻土处理造纸等有机废水.CN86106871,1988,04,27.
[38] 生化工业株式会社,岩井重久,内田千寻,户田茂等.一种改善水域底层质量和水质的方法及用于该方法的一组加入剂.中国专利CN1085877,1994,04.
[39] 朱济成.新兴的工业资源硅藻土.百科知识,1995,(4):41-42.
[40] 朱志华,梁基照,杨卫国.硅藻土对聚合物的填充改性.上海塑料,2005,6(2):38-40.
[41] 陈荣三,杨宇翔,侯祺泰.国产硅藻土研究进展及其新应用.化工时刊,1997,11(5):54-56.
[42] William A., Pierre B., et al. Absorption of Streptococcus faecalis on diatomite carriers for use in biotransformations. J. Chem. Tech. Biotechnol., 1990, 47(2):93-100.
[43] Brennan, John F. Macroporous alumina/diatomaceous earth bio-supports. U. S. Pat. No. 4980334, Sep 13, 1989.
[44] Robertson, John S., LiPuma, Mildred M., Gross, Stephen E. Preparation of catalyst supports and materials produced thereby. U. S. Pat. No. 4581338, May 31, 1985.
[45] Jacques, Roland, Dupin, et al. Preparation of spheroidal alumina particulates. U. S. Pat. No. 4514511, May 19, 1983.
[46] 谢祖芳,黄锁义.国产硅藻土研究的进展及新应用.贵州化工,2002,27(1):5-7,16.
[47] 张若愚.用硅藻土制取四氯化硅.云南化工,1994,(4):44-46.
[48] Biswajit Ghosh, Dinesh C. Agrawal, Subhash Bhatia. Synthesis of zeolite A from calcined diatomaceous clay:optimization. Industrial & engineering chemistry research, 1994, 33(9):2107-2110.
[49] Vilma Sanhueza, Ursula Kelml, Ruby Cid. Synthesis of mordenite from diatomite: a case of zeolite synthesis from natural material. Journal of Chemical Technology and Biotechnology, 2003, 78(5): 485-488.
[50] A. Chaisena, K. Rangsriwatananon. Synthesis of sodium zeolites from natural and modified diatomite. Materials Letters, 2005, 59(12): 1474-1479.
[51] 中华人民共和国轻工行业标准—洗涤剂用4A沸石,QB/T1768-93.
[52] 国家标准GB 6287-86.
[53] 徐如人,庞文琴,屠昆刚等.沸石分子筛的结构与合成.长春:吉林大学出版社,1987.
[54] 赵善雷.新型P沸石的性能及应用前景.日用化学工业,2003,33(5):321-323.
[55] 董家禄,刘杨,姜斌臣,张骏.半合成法制备洗衣粉助剂4A沸石.江苏化工,1998,26(1):25-29.
[56] C. Poole et al. Synthesis of zeolite adsorbents by hydrothermal treatment of PFA waste: a comparative study. Minerals Engineering, 2000, 13(8-9):831-842.
[57] 申少华,张术根,王大伟.天然红辉沸石合成P型沸石工艺优化研究.非金属矿,2001,24(3):40-42.
[58] 王仰东,刘杨,董家禄,须沁华.小晶粒A型分子筛的合成及其晶貌.催化学报,1998,19(6):610-612.
[59] Leszek Gora, Robert W. Thompson. Controlled addition of aged mother liquor to zeolite NaA synthesis solutions. Zeolites, 1997, 18(2):132-141.
[60] Mathavee Sathupunya, Erdogan Gulari, Sujitra Wongkasemjit. Na-A(LTA) zeolite synthesis directly from alumatrane and silatrane by sol-gel microwave techniques. Journal of the European Ceramic Society, 2003, 23(8): 1293-1303.
[61] 申少华,张术根,王大伟.酸处理红辉石-碱-铝酸钠-水的水热反应体系A型沸石的晶化合成.硅酸学报,2001,29(5):451-454.
[62] 罗玉长,罗鹤鹏,魏召刚.4A沸石分子筛晶体生长过程.粉体技术,1995,1(3):21-25.
[63] S. Chandrasekhar, P. Raghavan, G. Sebastian, A. D. Damodaran. Brightness improvement studies on "kaolin based" zeolite 4A. Applied clay science, 1997, 12(3):221-231.
[64] K. Rajagopalan, A. W. Peters, G. C. Edwards. Influence of zeolite particle size on selectivity during fluid catalytic cracking. Appl. Catal., 1986, 23: 69-80.
[65] Navarro. Uriel, Trujillo. Carlos A., Oviedo. Alfredo, Lobo. Raul. Impact of deactivation conditions on the acidity of Y zeolites used in the formulation of FCC Catalysts, studied by FTIR of adsorbed CO. Journal of Catalysis, 2002, 211(1): 64-74.
[66] B. De Witte, J. Patarin, D. Le Nouen, et al. Cyclic polyols: a new class of structure-directing agents? Study of inositol in the synthesis of FAU-and LTA-type zeolites. Microporous and mesoporous materials, 1998, 23(1-2): 11-22.
[67] H. Gies, B. Marler. The structure-controlling role of organic templates for the synthesis of porosils in the system SiO_2/template/H_2O. Zeolites, 1992, 12: 42-49.
[68] F. Delprato, L. Delmotte, J. L. Guth, L. Huve. Synthesis of new silica-rich cubic and hexagonal faujasites using crown-ether-based supramolecules as templates. Zeolites, 1990, 10(6): 546-552.
[69] Sathy Chandrasekhar, P. N. Pramada. Kaolin-based zeolite Y, a precursor for cordierite ceramics. Applied Clay Science, 2004, 27(3-4): 187-198.
[70] Norihiro Murayama, Hideki Yamamoto, Junji Shibata. Mechanism of zeolite synthesis from coal fly ash by alkali hydrothermal reaction. International Journal of Mineral Processing, 2002, 64: 1-17.
[71] Ruiz R., Blanco C., Pesquera C., Gonzalez F., et al. Zeolitization of a bentonite and its application to the removal of ammonium ion from waste water. Applied Clay Science, 1997, 12(1-2): 73-83.
[72] B. R. Albert, A. K. Cheetham, J. A. Stuart, C. J. Adams. Investigations on P zeolites: synthesis, characterisation, andstructure of highly crystalline low-silica NaP. Microporous and mesoporous materials, 1998, 21(1-3): 133-142.
[73] H. Julide Koroglu, Alper Saroglan, et al. Effects of low-temperature gel ageing on the synthesis of zeolite Y at different alkalinities. Journal of Crystal Growth, 2002, 241(4): 481-488.
[74] 刘欣梅,阎子峰,王槐平.由煤系高岭土原位合成NaY分子筛.石油大学学报(自然科学版),2002,26(5):94-99.
[75] 马跃龙,陈诵英,彭少逸.小颗粒NaY分子筛透明液相导向剂的制备及其性能.催化学报,1995,16(5):410-414.
[76] 董家禄,鲍书林,须沁华.新型液相晶化导向剂.南京大学学报,1986,22(1):83-87.
[77] Wang Bo, Ma Hongzhu. Factors affecting the synthesis of microsized NaY zeolite, Microprous and mesoporous materials, 1998, (25):131-136.