凹凸棒石复合颗粒的制备及净水性能的研究
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摘要
本文针对日益严重的饮用水污染,利用凹凸棒石比表面积大、化学稳定性好、吸附能力强等特点,研究具有去除水中重金属离子和有机污染物、抗菌等多重功能的凹凸棒石复合颗粒的制备技术及其性能。
研究了凹凸棒石复合颗粒的制备技术。通过正交试验研究了主要影响因素增孔剂添加量、热活化温度、盐酸浓度和粘结剂添加量对凹凸棒石复合颗粒吸附Cr~(6+)和甲基橙性能的影响。确定优化制备的工艺条件是:首先对凹凸棒石用2 mol/L盐酸活化2 h,添加抗菌剂和其他添加剂后对粉体球磨30 min,4wt%粘结剂和2wt%增孔剂溶解后与粉体一起制粒,烘干后,500℃焙烧1.5h。
在优化条件下制备的凹凸棒石复合颗粒对六价铬离子和甲基橙有较好的吸附性能。当铬离子浓度为500μg/L,吸附颗粒添加量为2g/100ml时,吸附率为94%。当pH值为7,颗粒添加量为3g/100ml,甲基橙浓度为100 mg/L时,吸附容量为1.25 mg/g。不同pH值的水溶液经凹凸棒石复合颗粒处理后有趋向于中性的趋势。
对比表面积的研究显示,增孔剂、热活化和酸活化的作用,使凹凸棒石复合颗粒的比表面积和孔径分布发生了较大变化,增加了2 nm、2.5 nm和20 nm孔的分布。扫描电镜的研究显示,改性改善了复合颗粒的微观结构,形成多数凹凸棒石单根晶体交织堆叠的疏松多孔的复合颗粒。X射线研究表明,凹凸棒石复合颗粒的晶体结构在经过改性处理后发生了改变,增加了12.9501 nm的新峰位。采用表面张力仪对接触角和表面能的研究表明,改性增加了凹凸棒石复合颗粒的表面能,原因可能是改性方法增加了吸附中心,吸附作用增强。红外光谱研究显示对甲基橙的吸附主要是物理吸附,有少部分是化学吸附。
抗菌结果显示,当二氧化硅载银抗菌剂的添加量为2wt%时,凹凸棒复合颗粒的抗菌性能较好,6h抗菌的杀菌率达到98.7%。原因可能是,铝盐作为粘结剂和抗菌剂的比例达到了优化。而抗菌剂添加量再增加时,会引起银离子的团聚,从而降低复合颗粒的抗菌性能。
This work aim at the serious drinking water pollution, using the attapulgite which have great surface area, chemic stability, good absorbent ability, study the preparing method for compound grains which can absorb the heavy metal, organic pollutions and have anti-bacteria function.The attapulgite compound grains preparation method was studied. Studied the effect of concentration of HC1, the appending quantity of binder and pore former, the temperature of heat treatment to performance of absorbing Cr~(6+) and methyl-orange. The optimized preparing method is: firstly, acid activate the attapulgite with 2mol/L HC1, then add the anti-bacterial and other appending agents into the powder, ball the mixture of the powder for 30 min, prepare solution with 4% binder and 2% pore former, prepare grains with the powder and the solution. Drying this grains and bake them at 500℃ for 1.5 h.The compound grains have good absorbent performance on Cr~(6+) and methyl-orange. When the concentration of the Cr~(6+) is 500Mg/L and the appending quantity is 2g/100ml, the adsorbent percentage is 94%. When the appending quantity is 3g/100ml and the concentration is 100mg/L, the adsorption capacity is 1.2mg/g at pH7. The pH has the trend to pH7 after the water be treated by the attapulgite compound grains.The study to surface area and SEM of compound grains showed that the heat treatment temperature, pore former and acid activating obviously changed the surface area and the pore distribution. The pore volume at 2 nm, 2.5 nm and 20 nm increased. The microstructure of the compound grains was improved. Majority of single fibres pile into a loose and porous grain. The study of X-ray showed that the crystal structure changed after adding pore-former and heat treatment. The grains formed a new peak at d=12.9501 nm. The study of surface free energy
shows that above modification increased the surface free energy of the compound grains. The reason that the surface free energy increased is likely the modification increased the absorbent center, then increased the adsorbent performance. The infrared spectra showed that the adsorption on methyl-orange is mainly physical adsorption, and a few chemic adsorption.The anti-bacterial result shows that when the appending percentage of anti-bacterial agent is 2%, the anti-bacterial performance is good, the bacteria killing rate to Escherichia coli reaches 98.7% when the anti-bacterial time is 6 h. The reason that the anti-bacterial performance of this percentage of anti-bacterial agent is good is likely this percentage is the optimum ratio of binder and anti-bacterial agent. But when the percentage of anti-bacteria agent increase continuously, the silver ion will reunite, decrease the anti-bacterial performance.
研究了凹凸棒石复合颗粒的制备技术。通过正交试验研究了主要影响因素增孔剂添加量、热活化温度、盐酸浓度和粘结剂添加量对凹凸棒石复合颗粒吸附Cr~(6+)和甲基橙性能的影响。确定优化制备的工艺条件是:首先对凹凸棒石用2 mol/L盐酸活化2 h,添加抗菌剂和其他添加剂后对粉体球磨30 min,4wt%粘结剂和2wt%增孔剂溶解后与粉体一起制粒,烘干后,500℃焙烧1.5h。
在优化条件下制备的凹凸棒石复合颗粒对六价铬离子和甲基橙有较好的吸附性能。当铬离子浓度为500μg/L,吸附颗粒添加量为2g/100ml时,吸附率为94%。当pH值为7,颗粒添加量为3g/100ml,甲基橙浓度为100 mg/L时,吸附容量为1.25 mg/g。不同pH值的水溶液经凹凸棒石复合颗粒处理后有趋向于中性的趋势。
对比表面积的研究显示,增孔剂、热活化和酸活化的作用,使凹凸棒石复合颗粒的比表面积和孔径分布发生了较大变化,增加了2 nm、2.5 nm和20 nm孔的分布。扫描电镜的研究显示,改性改善了复合颗粒的微观结构,形成多数凹凸棒石单根晶体交织堆叠的疏松多孔的复合颗粒。X射线研究表明,凹凸棒石复合颗粒的晶体结构在经过改性处理后发生了改变,增加了12.9501 nm的新峰位。采用表面张力仪对接触角和表面能的研究表明,改性增加了凹凸棒石复合颗粒的表面能,原因可能是改性方法增加了吸附中心,吸附作用增强。红外光谱研究显示对甲基橙的吸附主要是物理吸附,有少部分是化学吸附。
抗菌结果显示,当二氧化硅载银抗菌剂的添加量为2wt%时,凹凸棒复合颗粒的抗菌性能较好,6h抗菌的杀菌率达到98.7%。原因可能是,铝盐作为粘结剂和抗菌剂的比例达到了优化。而抗菌剂添加量再增加时,会引起银离子的团聚,从而降低复合颗粒的抗菌性能。
This work aim at the serious drinking water pollution, using the attapulgite which have great surface area, chemic stability, good absorbent ability, study the preparing method for compound grains which can absorb the heavy metal, organic pollutions and have anti-bacteria function.The attapulgite compound grains preparation method was studied. Studied the effect of concentration of HC1, the appending quantity of binder and pore former, the temperature of heat treatment to performance of absorbing Cr~(6+) and methyl-orange. The optimized preparing method is: firstly, acid activate the attapulgite with 2mol/L HC1, then add the anti-bacterial and other appending agents into the powder, ball the mixture of the powder for 30 min, prepare solution with 4% binder and 2% pore former, prepare grains with the powder and the solution. Drying this grains and bake them at 500℃ for 1.5 h.The compound grains have good absorbent performance on Cr~(6+) and methyl-orange. When the concentration of the Cr~(6+) is 500Mg/L and the appending quantity is 2g/100ml, the adsorbent percentage is 94%. When the appending quantity is 3g/100ml and the concentration is 100mg/L, the adsorption capacity is 1.2mg/g at pH7. The pH has the trend to pH7 after the water be treated by the attapulgite compound grains.The study to surface area and SEM of compound grains showed that the heat treatment temperature, pore former and acid activating obviously changed the surface area and the pore distribution. The pore volume at 2 nm, 2.5 nm and 20 nm increased. The microstructure of the compound grains was improved. Majority of single fibres pile into a loose and porous grain. The study of X-ray showed that the crystal structure changed after adding pore-former and heat treatment. The grains formed a new peak at d=12.9501 nm. The study of surface free energy
shows that above modification increased the surface free energy of the compound grains. The reason that the surface free energy increased is likely the modification increased the absorbent center, then increased the adsorbent performance. The infrared spectra showed that the adsorption on methyl-orange is mainly physical adsorption, and a few chemic adsorption.The anti-bacterial result shows that when the appending percentage of anti-bacterial agent is 2%, the anti-bacterial performance is good, the bacteria killing rate to Escherichia coli reaches 98.7% when the anti-bacterial time is 6 h. The reason that the anti-bacterial performance of this percentage of anti-bacterial agent is good is likely this percentage is the optimum ratio of binder and anti-bacterial agent. But when the percentage of anti-bacteria agent increase continuously, the silver ion will reunite, decrease the anti-bacterial performance.
引文
[1] 肖羽堂,张晶晶,吴鸣,等.我国水资源污染与饮用水安全性研究[J].长江流域资源与环境,2001,10(1).
[2] 赵璇,吴天宝,叶裕才.我国饮用水源的重金属污染及治理技术深化问题[J].给水排水,1998,24(10):22～25.
[3] 饶俊,张锦瑞,李玉凤.饮用水源地水体有机物污染研究现状[J].河北理工学院学报,2005,27(2):137—138.
[4] 王宴山,颜酉斌,张洪林.我国饮用水中存在的主要问题及解决方法[J].2005,31(4):17—19.
[5] 邹启光,等.二氧化氯取代液氯消毒剂的可行性研究[J].水处理技术,2002,28(5):249—252.
[6] 樊瑛,田宏迩.生活饮用水水质卫生质量状况分析[J].现代预防医学,2001,28(2):247—249.
[7] 王丽花,张晓健,吴红伟,等.国内饮用水生物稳定性的调查研究[J].净水技术,2005,24(3):45—47.
[8] 周宪堂,刘晓辉,孙晓晖.生活饮用水微生物污染调查[J].中国卫生工程学,2005,4(3):197.
[9] 白慧兰,贺兰喜,王宝贞.常规饮用水净化技术面临的挑战及对策[J].水科学进展,2002,13(1):122～127
[10] F X R Van Leeuwen. Safe Drinking Water: the Toxicologist's Approach[J]. Food and Chemical Toxicology, 2000, 38(S1): 51—58.
[11] 白晓慧,张玲,原喆,等.饮用水水质安全性及其保障策略[J].中国公共卫生,2004,20(9):1147—1148.
[12] 辜娟娟,胡九成.饮用水处理技术的现状与进展[J].化学工程师,1999,3:37—51.
[13] 孙忠,侯晓勇.改性沸石在饮用水净化中的应用研究[J].非金属矿,2002,25(2):49—51.
[14] 马勇,邵红,王恩德,等.铝钛柱撑系列改性膨润土处理含铬废水的应用研究[J].环境科学研究,2004,17(4):48～50.
[15] 王代芝,姬艳萍.酸改性膨润土处理含铅废水的研究[J].中国非金属矿工业导刊,2005,2:44～46.
[16] 王雪琴,李珍,杨有生.海泡石的改性及应用研究现状[J].中国非金属矿工业导刊,2003,3:11—14
[17] 杨胜科,王文科.改性海泡石除氟影响因素分析及机理探讨[J].化工矿物与加工,2000,4:1—3.
[18] 杨胜科,王文科,李翔.改性海泡石处理含砷饮用水研究[J].化工矿物与加工,2000,10:13—16.
[19] Lee J F, Lee C K, Juang L C. Size effects of exchange cation on the pore structure and surface fractality of montmorillonite[J]. J. Coll. Inter. Sci. 1999, 217: 172～176.
[20] Toia. Process for disposing of human wastes, a disposable container for collecting human wastes and a container- grinding machine[P]. USP: 6351858, March 5, 2002.
[21] Jun Sawai. Inorganic Antibacterial Agents[J]. Inorganic Materials, Japan, 1997, 4(3): 156-162.
[22] Toshikau Tomioka. Anti-Microbial Material[M]. New Ceramics, 1998, 11(12): 31.
[23] 陆春华,倪亚茹,许仲梓,等.无机抗菌材料及其抗菌机理[J].南京工业大学学报,2003,25(1):107—110.
[24] 冯乃谦,严建华.银型无机抗菌剂的发展及其应用[J].材料导报,1998,12(2):1—3.
[25] 汪山,程继健,陈奇.载银型无机缓释抗菌材料的研究与应用[J].中国陶瓷,2000,36(2):7—9.
[26] 黄国平,陈晓莹,胡晓.无机抗菌剂的开发与应用[J].建筑人造板,2000,(3):34—36.
[27] 张文钲.载银抗菌抗霉涂料的应用[J].化工新型材料,1997,(9):29—30.
[28] 袁鹏,何宏平.银系无机抗菌剂的研究进展[J].化工矿物与加工,2002,(10):5—10.
[29] 肖清华,李博文,王宁.载银无机抗菌剂的研究现状和发展趋势[J].中国非金属矿工业导刊,1999,(6):5—7.
[30] 田煦.中国坡缕石矿石特征及物化性能研究[J].矿产综合利用,1996,(6):1—4.
[31] 陈天虎.凹凸棒石吸附性能应用的制约因素[J].安徽地质,1999,9(3):199—203.
[32] 张国宇,王鹏.凹凸棒石粘土及在水处理中的应用[J].工业水处理,2003,23(4):1—5.
[33] 王红艳,张莉莉,张艳,等.酸处理对凹凸棒石粘土表面及其吸附Hg(Ⅱ)的影响[J].应用化工,2005,34(2):94—96.
[34] 王红艳.硝酸改性凹凸棒石粘土及吸附Cu~(2+)的工艺研究[J].工业用水与废水,2005,36(4):59—61.
[35] 胡振琪,杨秀红,高爱林.粘土矿物对重金属镉的吸附研究[J].金属矿山,2004,(6):53—55.
[36] E. Alvarez-Ayuso, A. Garcia-Sonchez. Palygorskite as a feasible amendment to stabilize heavy metal polluted soils[J]. Environmental Pollution, 2003, (125): 337—344.
[37] 邓爱军.凹凸棒石粘士吸附水中Cr(Ⅵ)的研究[J].安徽化工,1999,(3):15—16.
[38] 彭书传,黄川徽,陈天虎,等.坡缕石对Zn~(2+)的吸附性能及吸附工艺条件优化研究[J].岩石矿物学 杂志,2004,23(3):282—286.
[39] R. A. Alvarez-Puebla, C. Aisa, J. Blasco, etal. Copper heterogeneous nucleation on a palygorskitic clay: an XRD, EXAFS and molecular modeling study[J]. Applied Clay Science, 2004, (25): 103—110.
[40] 申华,杨卫东,石中亮.凹凸棒石粘土吸附剂处理含镍(Ⅱ)废水的研究[J].辽宁化工,2005,34(5):187—189.
[41] Guangren Qian, Darren Delai Sun, Joo Hwa Tay. New aluminium-rich alkali slag matrix with clay minerals for immobilizing simulated radioactive Sr and Cs waste[J]. Journal of nuclear materials, 2001, (299): 199—204.
[42] 宋金如,龚治湘,罗明标.凹凸棒石粘土吸附铀的性能研究及应用[J].华东地质学院学报,1998,21(3):265—272.
[43] 易发成,李玉香,钱光人.凹凸棒石粘土对中低放核素Sr、Cs的吸附研究[J].矿产综合利用,2002,(1):16—20.
[44] 陈天虎.凹凸棒石粘土吸附废水中污染物机理探讨[J].高校地质学报,2000,6(2):265—270.
[45] K. Khider, D. E. Akretche, A. Larbot. Purification of water effluent from a milk factory by ultrafiltration using Algerian clay support[J]. Desalination, 2004, 167: 147-151.
[46] 陈天虎.改性凹凸棒石粘土吸附性能对比实验研究[J].工业水处理,2001,20(4):27—29.
[47] 裘祖楠,姚振淮,漆德瑶.用凹凸棒石净化污染河水的研究[J].上海环境科学,1993,12(10):14—16.
[48] 许坤,姜兆春,贾智萍.粉末凹凸棒石对水溶性阳离子染料废水的脱色研究[J].环境化学,1998,17(3):276—278.
[49] 裘祖楠,翁行尚,李勇.活化凹凸棒石对阳离子染料的脱色作用及其应用研究[J].中国环境科学,1997,17(4):373—376.
[50] 胡发社,罗淑湘,杨飞华,等.新型无机抗菌剂载体——天然纳米坡缕石显微表观结构研究[J].中国非金属矿工业导刊,200l,(5):12—15.
[51] 陈天虎,李宏伟,汪家权,等.凹凸棒石—银纳米复合颗粒抗菌材料制备方法和表征[J].硅酸盐通报,2005,(2):123—126.
[52] 赵娣芳,周杰,楼必君,等.凹凸棒石及其改性产物的抗菌性能研究[J].中国非金属矿工业导刊,2005,(2):23—25.
[53] 朱海青,周杰,赵娣芳,等.凹凸棒石载铜抗菌剂的研制及其抗菌性能[J].中国非金属矿工业导刊,2005.(4):31—33
[54] 胡发社,程海丽,杨飞华,等.坡缕石型载银抗菌剂的研制[J].现代化工,2001,21(6):35—37.
[55] Bradley W F. The structure scheme of attapulgite[J]. Am. Mineral, 1940, 25(6): 40—410.
[56] M. Suarez Barrios, L. V. Flores Gonzalez, M. A. Vicente Rodriguez, J. M. Martin Pozas. Acid activation of a palygorskite with HCl: Development of physico-chemical, textural and surface properties[J]. Applied Clay Science, 1995, (10): 247—258.
[57] 陈天虎,徐惠芳,彭书传,等.凹凸棒石与酸反应纳米尺度研究——反应机理和表面积变化[J].高校地质学报,2004,10(3):98—103.
[58] 郑自立,罗淑湘,李虎杰,等.坡缕石的耐酸碱性研究[J].矿产综合利用,1996,(6):33—37.
[59] 郑茂松,朱振海.中性高效凹土吸附剂生产工艺技术研究[J].非金属矿,2002,25(2):11—13.
[60] Wenxing Kuang, Glenn A. Facey, Christian Detellier. Dehydration and rehydration of palygorskite and the influence of water on the nanopores[J]. Clays and Clay Minerals, 2004, 52 (5): 635—642.
[61] R. L. Frost, Z. Ding. Controlled rate thermal analysis and differential scanning calorimetry of sepiolites and palygorskites[J]. Thermochimica Acta, 2003, (397): 119—128.
[62] 王彦华,雷家珩,袁启华.烷基铵盐改性坡缕石的结构与表面性质[J].非金属矿,1999,22(2):8—10.
[63] 彭书传,魏凤玉,周元祥,等.有机凸棒粘土吸附水中苯酚的试验[J].城市环境与城市生态,1999,2(2):14—16.
[64] 宋金如,范桂英,将小良.AMA吸附剂吸附铬(Ⅵ)的性能研究及应用[J].东华理工学院学报,2004,27(3):271—276.
[65] 赵娣芳,周杰,刘宁.凹凸棒石改性机理研究进展[J].硅酸盐通报,2005,(3):67—69.
[66] 尹琳,陆现彩,胡欢,等.多孔结构矿物(岩石)及其环境修复材料的实用性[J].岩石矿物学杂志,2003,22(4):403～406.
[67] 秦非,许欧永,蒋挺大.AT—SS复合颗粒吸附剂的制备和除铅性能研究[J].环境科学,1996,17(4):47—50.
[68] 孙秀云,王连军,周学铁.凹土棒土-粉煤灰颗粒吸附剂的制备及改性[J].江苏环境科技,2003,16(2):1—3.
[69] 刘晓东,孙秀云,周学铁,等.凹凸棒土颗粒吸附剂的制备[J].污染防治技术,1999,12(3):168—170.
[70] 孙治荣,范延臻,王宝贞.国内外饮用水净水器的发展现状评述[J].哈尔滨建筑大学学报,1999,32(4):61—64.
[71] 张荣,田向红,刘保华.我国饮用水现状及卫生标准发展[J].中国卫生工程学,2004,3(3):185—187.
[72] 孙亦彬,陆现彩,尹琳,等.初级加工对凹凸棒石矿产品表面性质及孔结构的影响[J].中国非金属矿工业导刊,2004,4:29—31.
[73] 郑自立,鞠党臣,罗淑湘,等.坡缕石中微孔特征及其吸附机理讨论[J].矿产综合利用,1996,(6):9—12.
[74] Hoffman M R, Martin S T, Choi W et al. Environmental Applications of Semiconductor Photocatalysis[J]. Chem Rev, 1995, 95 (1): 69—96.
[75] 杨辉,王可,丁新更,等.无机抗菌粉体中银价态与抗菌性能研究[J].硅酸盐学报,2002,30(5):585—589.
[76] Li Z, Flytzanic stephanopoulos M. Selective Catalytic Reduction of Nitric Oxide by Methane voer Cerium and Silver Ion-exchanged ZSM-5 Zeolites[J]. Applied Catalysis A: General, 1997, 165: 15—34.
[2] 赵璇,吴天宝,叶裕才.我国饮用水源的重金属污染及治理技术深化问题[J].给水排水,1998,24(10):22～25.
[3] 饶俊,张锦瑞,李玉凤.饮用水源地水体有机物污染研究现状[J].河北理工学院学报,2005,27(2):137—138.
[4] 王宴山,颜酉斌,张洪林.我国饮用水中存在的主要问题及解决方法[J].2005,31(4):17—19.
[5] 邹启光,等.二氧化氯取代液氯消毒剂的可行性研究[J].水处理技术,2002,28(5):249—252.
[6] 樊瑛,田宏迩.生活饮用水水质卫生质量状况分析[J].现代预防医学,2001,28(2):247—249.
[7] 王丽花,张晓健,吴红伟,等.国内饮用水生物稳定性的调查研究[J].净水技术,2005,24(3):45—47.
[8] 周宪堂,刘晓辉,孙晓晖.生活饮用水微生物污染调查[J].中国卫生工程学,2005,4(3):197.
[9] 白慧兰,贺兰喜,王宝贞.常规饮用水净化技术面临的挑战及对策[J].水科学进展,2002,13(1):122～127
[10] F X R Van Leeuwen. Safe Drinking Water: the Toxicologist's Approach[J]. Food and Chemical Toxicology, 2000, 38(S1): 51—58.
[11] 白晓慧,张玲,原喆,等.饮用水水质安全性及其保障策略[J].中国公共卫生,2004,20(9):1147—1148.
[12] 辜娟娟,胡九成.饮用水处理技术的现状与进展[J].化学工程师,1999,3:37—51.
[13] 孙忠,侯晓勇.改性沸石在饮用水净化中的应用研究[J].非金属矿,2002,25(2):49—51.
[14] 马勇,邵红,王恩德,等.铝钛柱撑系列改性膨润土处理含铬废水的应用研究[J].环境科学研究,2004,17(4):48～50.
[15] 王代芝,姬艳萍.酸改性膨润土处理含铅废水的研究[J].中国非金属矿工业导刊,2005,2:44～46.
[16] 王雪琴,李珍,杨有生.海泡石的改性及应用研究现状[J].中国非金属矿工业导刊,2003,3:11—14
[17] 杨胜科,王文科.改性海泡石除氟影响因素分析及机理探讨[J].化工矿物与加工,2000,4:1—3.
[18] 杨胜科,王文科,李翔.改性海泡石处理含砷饮用水研究[J].化工矿物与加工,2000,10:13—16.
[19] Lee J F, Lee C K, Juang L C. Size effects of exchange cation on the pore structure and surface fractality of montmorillonite[J]. J. Coll. Inter. Sci. 1999, 217: 172～176.
[20] Toia. Process for disposing of human wastes, a disposable container for collecting human wastes and a container- grinding machine[P]. USP: 6351858, March 5, 2002.
[21] Jun Sawai. Inorganic Antibacterial Agents[J]. Inorganic Materials, Japan, 1997, 4(3): 156-162.
[22] Toshikau Tomioka. Anti-Microbial Material[M]. New Ceramics, 1998, 11(12): 31.
[23] 陆春华,倪亚茹,许仲梓,等.无机抗菌材料及其抗菌机理[J].南京工业大学学报,2003,25(1):107—110.
[24] 冯乃谦,严建华.银型无机抗菌剂的发展及其应用[J].材料导报,1998,12(2):1—3.
[25] 汪山,程继健,陈奇.载银型无机缓释抗菌材料的研究与应用[J].中国陶瓷,2000,36(2):7—9.
[26] 黄国平,陈晓莹,胡晓.无机抗菌剂的开发与应用[J].建筑人造板,2000,(3):34—36.
[27] 张文钲.载银抗菌抗霉涂料的应用[J].化工新型材料,1997,(9):29—30.
[28] 袁鹏,何宏平.银系无机抗菌剂的研究进展[J].化工矿物与加工,2002,(10):5—10.
[29] 肖清华,李博文,王宁.载银无机抗菌剂的研究现状和发展趋势[J].中国非金属矿工业导刊,1999,(6):5—7.
[30] 田煦.中国坡缕石矿石特征及物化性能研究[J].矿产综合利用,1996,(6):1—4.
[31] 陈天虎.凹凸棒石吸附性能应用的制约因素[J].安徽地质,1999,9(3):199—203.
[32] 张国宇,王鹏.凹凸棒石粘土及在水处理中的应用[J].工业水处理,2003,23(4):1—5.
[33] 王红艳,张莉莉,张艳,等.酸处理对凹凸棒石粘土表面及其吸附Hg(Ⅱ)的影响[J].应用化工,2005,34(2):94—96.
[34] 王红艳.硝酸改性凹凸棒石粘土及吸附Cu~(2+)的工艺研究[J].工业用水与废水,2005,36(4):59—61.
[35] 胡振琪,杨秀红,高爱林.粘土矿物对重金属镉的吸附研究[J].金属矿山,2004,(6):53—55.
[36] E. Alvarez-Ayuso, A. Garcia-Sonchez. Palygorskite as a feasible amendment to stabilize heavy metal polluted soils[J]. Environmental Pollution, 2003, (125): 337—344.
[37] 邓爱军.凹凸棒石粘士吸附水中Cr(Ⅵ)的研究[J].安徽化工,1999,(3):15—16.
[38] 彭书传,黄川徽,陈天虎,等.坡缕石对Zn~(2+)的吸附性能及吸附工艺条件优化研究[J].岩石矿物学 杂志,2004,23(3):282—286.
[39] R. A. Alvarez-Puebla, C. Aisa, J. Blasco, etal. Copper heterogeneous nucleation on a palygorskitic clay: an XRD, EXAFS and molecular modeling study[J]. Applied Clay Science, 2004, (25): 103—110.
[40] 申华,杨卫东,石中亮.凹凸棒石粘土吸附剂处理含镍(Ⅱ)废水的研究[J].辽宁化工,2005,34(5):187—189.
[41] Guangren Qian, Darren Delai Sun, Joo Hwa Tay. New aluminium-rich alkali slag matrix with clay minerals for immobilizing simulated radioactive Sr and Cs waste[J]. Journal of nuclear materials, 2001, (299): 199—204.
[42] 宋金如,龚治湘,罗明标.凹凸棒石粘土吸附铀的性能研究及应用[J].华东地质学院学报,1998,21(3):265—272.
[43] 易发成,李玉香,钱光人.凹凸棒石粘土对中低放核素Sr、Cs的吸附研究[J].矿产综合利用,2002,(1):16—20.
[44] 陈天虎.凹凸棒石粘土吸附废水中污染物机理探讨[J].高校地质学报,2000,6(2):265—270.
[45] K. Khider, D. E. Akretche, A. Larbot. Purification of water effluent from a milk factory by ultrafiltration using Algerian clay support[J]. Desalination, 2004, 167: 147-151.
[46] 陈天虎.改性凹凸棒石粘土吸附性能对比实验研究[J].工业水处理,2001,20(4):27—29.
[47] 裘祖楠,姚振淮,漆德瑶.用凹凸棒石净化污染河水的研究[J].上海环境科学,1993,12(10):14—16.
[48] 许坤,姜兆春,贾智萍.粉末凹凸棒石对水溶性阳离子染料废水的脱色研究[J].环境化学,1998,17(3):276—278.
[49] 裘祖楠,翁行尚,李勇.活化凹凸棒石对阳离子染料的脱色作用及其应用研究[J].中国环境科学,1997,17(4):373—376.
[50] 胡发社,罗淑湘,杨飞华,等.新型无机抗菌剂载体——天然纳米坡缕石显微表观结构研究[J].中国非金属矿工业导刊,200l,(5):12—15.
[51] 陈天虎,李宏伟,汪家权,等.凹凸棒石—银纳米复合颗粒抗菌材料制备方法和表征[J].硅酸盐通报,2005,(2):123—126.
[52] 赵娣芳,周杰,楼必君,等.凹凸棒石及其改性产物的抗菌性能研究[J].中国非金属矿工业导刊,2005,(2):23—25.
[53] 朱海青,周杰,赵娣芳,等.凹凸棒石载铜抗菌剂的研制及其抗菌性能[J].中国非金属矿工业导刊,2005.(4):31—33
[54] 胡发社,程海丽,杨飞华,等.坡缕石型载银抗菌剂的研制[J].现代化工,2001,21(6):35—37.
[55] Bradley W F. The structure scheme of attapulgite[J]. Am. Mineral, 1940, 25(6): 40—410.
[56] M. Suarez Barrios, L. V. Flores Gonzalez, M. A. Vicente Rodriguez, J. M. Martin Pozas. Acid activation of a palygorskite with HCl: Development of physico-chemical, textural and surface properties[J]. Applied Clay Science, 1995, (10): 247—258.
[57] 陈天虎,徐惠芳,彭书传,等.凹凸棒石与酸反应纳米尺度研究——反应机理和表面积变化[J].高校地质学报,2004,10(3):98—103.
[58] 郑自立,罗淑湘,李虎杰,等.坡缕石的耐酸碱性研究[J].矿产综合利用,1996,(6):33—37.
[59] 郑茂松,朱振海.中性高效凹土吸附剂生产工艺技术研究[J].非金属矿,2002,25(2):11—13.
[60] Wenxing Kuang, Glenn A. Facey, Christian Detellier. Dehydration and rehydration of palygorskite and the influence of water on the nanopores[J]. Clays and Clay Minerals, 2004, 52 (5): 635—642.
[61] R. L. Frost, Z. Ding. Controlled rate thermal analysis and differential scanning calorimetry of sepiolites and palygorskites[J]. Thermochimica Acta, 2003, (397): 119—128.
[62] 王彦华,雷家珩,袁启华.烷基铵盐改性坡缕石的结构与表面性质[J].非金属矿,1999,22(2):8—10.
[63] 彭书传,魏凤玉,周元祥,等.有机凸棒粘土吸附水中苯酚的试验[J].城市环境与城市生态,1999,2(2):14—16.
[64] 宋金如,范桂英,将小良.AMA吸附剂吸附铬(Ⅵ)的性能研究及应用[J].东华理工学院学报,2004,27(3):271—276.
[65] 赵娣芳,周杰,刘宁.凹凸棒石改性机理研究进展[J].硅酸盐通报,2005,(3):67—69.
[66] 尹琳,陆现彩,胡欢,等.多孔结构矿物(岩石)及其环境修复材料的实用性[J].岩石矿物学杂志,2003,22(4):403～406.
[67] 秦非,许欧永,蒋挺大.AT—SS复合颗粒吸附剂的制备和除铅性能研究[J].环境科学,1996,17(4):47—50.
[68] 孙秀云,王连军,周学铁.凹土棒土-粉煤灰颗粒吸附剂的制备及改性[J].江苏环境科技,2003,16(2):1—3.
[69] 刘晓东,孙秀云,周学铁,等.凹凸棒土颗粒吸附剂的制备[J].污染防治技术,1999,12(3):168—170.
[70] 孙治荣,范延臻,王宝贞.国内外饮用水净水器的发展现状评述[J].哈尔滨建筑大学学报,1999,32(4):61—64.
[71] 张荣,田向红,刘保华.我国饮用水现状及卫生标准发展[J].中国卫生工程学,2004,3(3):185—187.
[72] 孙亦彬,陆现彩,尹琳,等.初级加工对凹凸棒石矿产品表面性质及孔结构的影响[J].中国非金属矿工业导刊,2004,4:29—31.
[73] 郑自立,鞠党臣,罗淑湘,等.坡缕石中微孔特征及其吸附机理讨论[J].矿产综合利用,1996,(6):9—12.
[74] Hoffman M R, Martin S T, Choi W et al. Environmental Applications of Semiconductor Photocatalysis[J]. Chem Rev, 1995, 95 (1): 69—96.
[75] 杨辉,王可,丁新更,等.无机抗菌粉体中银价态与抗菌性能研究[J].硅酸盐学报,2002,30(5):585—589.
[76] Li Z, Flytzanic stephanopoulos M. Selective Catalytic Reduction of Nitric Oxide by Methane voer Cerium and Silver Ion-exchanged ZSM-5 Zeolites[J]. Applied Catalysis A: General, 1997, 165: 15—34.