·750· 工程科学学报，第37卷，第6期 降至l.08mmol·g.这同样由H部分置换孔穴中阳 treatment on Al removal,framework composition and acidity of 离子导致四，而随着盐酸浓度的增加，这种置换作用 BEA zeolite investigated by XRD,FTIR and NMR.Microporous Mesoporous Mater,2012,163:122 更为充分.可见，盐酸改性沸石会大幅降低其离子交 [12]Kley I,Traa Y.Influence of acid sites on the propene selectivity 换性能. during propane dehydrogenation on zeolite Pt/Zn,Na-MCM22 Microporous Mesoporous Mater,2012,164:145 3结论 03] Ponomareva O A,Timoshin S E,Knyazeva EE.Physicochemi- (1)天然斜发沸石具有较强的耐酸性，盐酸浓度 cal and catalytic properties of micro-mesoporous zeolite materials. Russ J Phys Chem,2011,85(12):2103 为3molL时依然能保持良好的晶体结构. [14]Vilaca N,Amorim R,Martinho 0.Encapsulation of a-cyano-4- (2）)沸石比表面积及总孔体积随盐酸浓度的增加 hydroxycinnamic acid into a NaY zeolite.J Mater Sci,2011,46 呈先上升后下降规律，其中盐酸浓度为1molL时比 (23):7511 表面积及总孔体积分别由原沸石的35.97m2·g和 05] MotsiT,Rowson N A,Simmons MJ H.Kinetic studies of the 0.0761m3·g增加至64.46m2·g和0.1156m3·g1; removal of heavy metals from acid mine drainage by natural zeolite.Int J Miner Process,2011,101(1-4):42 盐酸改性对沸石孔径分布影响明显，随着盐酸浓度的 [16]Luo X P,Li J C,Yan Q,et al.Screening of optimum adsorbents 增加，沸石微孔与介孔体积先增加后降低，大孔孔体积 for treating wastewater containing low concentration ammonia- 呈现先降低后增加：盐酸改性不会改变沸石狭缝型的 nitrogen.CIESC J,2010,61(1):216 孔道类型. (罗仙平，李健昌，严群，等处理低浓度氨氮废水吸附材料 的筛选.化工学报，2010,61(1)：216) (3)盐酸改性会导致沸石脱铝而使沸石硅铝原子 07] Yuan J S,Wang J K.Research on Na'-K'ion exchange char- 数比升高：氢离子对沸石孔道中阳离子的置换作用会 acteristic on Na-elinoptilolite (I):thermodynamics characteris- 导致沸石表面电位降低，阳离子交换容量大幅下降，使 tic of the process.Ion Exch Adsorpt,2004,26(6):541 其离子交换性能降低 (袁俊生，王静康.纳型斜发沸石Na·-K◆离子交换特性研 究(I)一离子交换过程热力学特性.离子交换与吸附， 参考文献 2004,26(6):541) Tang Q,Chen N C.Research on natural zeolite modified meth- [18]Wang J,Terigele,Li M Z,et al.Oxidative dehydrogenation of ods.Mater Rer,2009 (Suppl 1):439 propane to propylene over acid-modified natural clinoptilolite.J (汤泉，陈南春.天然沸石改性方法的研究进展.材料导报， Inner Mongolia Norm Unin Nat Sci Ed,2012,41(1):74 2009(增刊1)：439) (王奖，特日格乐，李明智，等.酸改造天然斜发沸石上丙烷 Lei LC,Li X J.Zhang X W.Ammonium removal from aqueous 氧化脱氢制丙烯的研究.内蒙古师范大学学报：自然科学汉 solutions using microwavereated natural Chinese zeolite.Sep 文版，2012,41(1)：74) Purif Technol,2008,58(3)359 [19]Elaiopoulos K,Perraki T,Grigoropoulou E.Monitoring the effect 3]JiZY,Yuan JS,Li X G.Removal of ammonium from wastewater of hydrothermal treatments on the structure of a natural zeolite using calcium form clinoptilolite.J Hazard Mater,2007,141 through a combined XRD,FTIR,XRF,SEM and N2-porosime- (3):483 try analysis.Microporous Mesoporous Mater,2010,134(1-3): 4]Wang Y F,Lin F,Pang W Q.Ammonium exchange in aqueous solution using Chinese natural clinoptilolite and modified zeolite. 220]Oztiirk N,Ucun F,Muhtar A D,et al.Infrared and SEM analy- Hazard Mater,2007,142(1-2):160 ses of polyethyleneglycol-400 adsorbed on zeolites NaA,CaA, 5]Huang H M,Xiao X M,Yan,et al.Ammonium removal from NaX and NaY.J Mol Struct,2009,922(1-3)35 aqueous solutions by using natural Chinese (Chende)zeolite as 21] Kyotani T,Mizuno T,Katakura Y,et al.Characterization of adsorbent.J Hazard Mater,2010,175(1-3)247 tubular zeolite NaA membranes prepared from clear solutions by 6]Widiastuti N,Wu H,Ang H M,et al.Removal of ammonium FTIR-ATR,GIXRD and FIB-TEM-SEM.J Membr Sci,2007, from grey water using natural zcolite.Desalination,2011, 296(1-2):162 277(1-3):15 22] Cho K,Ryoo R,Asahina S,et al.Mesopore generation by or- Erbil A C,Soyer E,Baykal B B.Ammonium ion removal with a ganosilane surfactant during LTA zeolite crystallization,investiga- natural zeolite in monodispersed and segregated fluidized beds. ted by high-tesolution SEM and Monte Carlo simulation.Solid Ind Eng Chem Res,2011,50(10):6391 State Sci,2011,13(4):750 8] Malekian R.Abedi-Koupai J,Eslamian SS,et al.lon-exchange 23]Tong X W.Zhu Y N.Experimental study on the modification of process for ammonium removal and release using natural Iranian natural stellerite and its removal of ammonia nitrogen from water. zeolite.Appl Clay Sci,2011,51 (3):323 Chin J Enriron Eng,2009 (4)635 ] Wang S B,Peng Y L.Natural zeolites as effective adsorbents in (佟小薇，朱义年沸石改性及其去除水中氨氮的实验研究 water and wastewater treatment.Chem Eng J,2010,156(1):11 环境工程学报，2009(4)：635) [10]Bai G Y,Li T Y,Yan Y H,et al.Microwave-assisted Friedel- 24]Xu RR,Pang WQ,Yu J H,et al.Chemistry Zeolites and Por- Crafts acylation of indole with acetic anhydride over tungstophos- ous Materials.Beijing:Science Press,2004:145 phoric acid modified HB zeolite.Catal Commun,2012,29:114 (徐如人，庞文琴，于吉红，等.分子箭与多孔材料化学.北 [11]Rafal B,Yannick M,Thomas O.Influence of the nitric acid 京：科学出版社，2004：145)工程科学学报，第 37 卷，第 6 期 降至 1. 08 mmol·g － 1 ． 这同样由 H + 部分置换孔穴中阳 离子导致［23］，而随着盐酸浓度的增加，这种置换作用 更为充分． 可见，盐酸改性沸石会大幅降低其离子交 换性能． 3 结论 (1) 天然斜发沸石具有较强的耐酸性，盐酸浓度 为 3 mol·L － 1 时依然能保持良好的晶体结构． (2) 沸石比表面积及总孔体积随盐酸浓度的增加 呈先上升后下降规律，其中盐酸浓度为 1 mol·L － 1 时比 表面积及总孔体积分别由原沸石的 35. 97 m2 ·g － 1 和 0. 0761 m3 ·g － 1 增加至 64. 46 m2 ·g － 1 和 0. 1156 m3 ·g － 1 ; 盐酸改性对沸石孔径分布影响明显，随着盐酸浓度的 增加，沸石微孔与介孔体积先增加后降低，大孔孔体积 呈现先降低后增加;盐酸改性不会改变沸石狭缝型的 孔道类型． (3) 盐酸改性会导致沸石脱铝而使沸石硅铝原子 数比升高;氢离子对沸石孔道中阳离子的置换作用会 导致沸石表面电位降低，阳离子交换容量大幅下降，使 其离子交换性能降低． 参 考 文 献 ［1］ Tang Q，Chen N C． Research on natural zeolite modified meth￾ods． Mater Rev，2009(Suppl 1): 439 (汤泉，陈南春． 天然沸石改性方法的研究进展． 材料导报， 2009(增刊 1): 439) ［2］ Lei L C，Li X J，Zhang X W． Ammonium removal from aqueous solutions using microwave-treated natural Chinese zeolite． Sep Purif Technol，2008，58(3): 359 ［3］ Ji Z Y，Yuan J S，Li X G． Removal of ammonium from wastewater using calcium form clinoptilolite． J Hazard Mater，2007，141 (3): 483 ［4］ Wang Y F，Lin F，Pang W Q． Ammonium exchange in aqueous solution using Chinese natural clinoptilolite and modified zeolite． J Hazard Mater，2007，142(1--2): 160 ［5］ Huang H M，Xiao X M，Yan，et al． Ammonium removal from aqueous solutions by using natural Chinese ( Chende) zeolite as adsorbent． J Hazard Mater，2010，175(1 － 3): 247 ［6］ Widiastuti N，Wu H，Ang H M，et al． Removal of ammonium from grey water using natural zeolite． Desalination， 2011， 277(1--3): 15 ［7］ Erbil A C，Soyer E，Baykal B B． Ammonium ion removal with a natural zeolite in monodispersed and segregated fluidized beds． Ind Eng Chem Res，2011，50(10): 6391 ［8］ Malekian R，Abedi-Koupai J，Eslamian S S，et al． Ion-exchange process for ammonium removal and release using natural Iranian zeolite． Appl Clay Sci，2011，51(3): 323 ［9］ Wang S B，Peng Y L． Natural zeolites as effective adsorbents in water and wastewater treatment． Chem Eng J，2010，156(1): 11 ［10］ Bai G Y，Li T Y，Yan Y H，et al． Microwave-assisted Friedel￾Crafts acylation of indole with acetic anhydride over tungstophos￾phoric acid modified Hβ zeolite． Catal Commun，2012，29: 114 ［11］ Rafal B，Yannick M，Thomas O． Influence of the nitric acid treatment on Al removal，framework composition and acidity of BEA zeolite investigated by XRD，FTIR and NMR． Microporous Mesoporous Mater，2012，163: 122 ［12］ Kley I，Traa Y． Influence of acid sites on the propene selectivity during propane dehydrogenation on zeolite Pt /Zn，Na-MCM-22． Microporous Mesoporous Mater，2012，164: 145 ［13］ Ponomareva O A，Timoshin S E，Knyazeva E E． Physicochemi￾cal and catalytic properties of micro-mesoporous zeolite materials． Russ J Phys Chem，2011，85(12): 2103 ［14］ Vilaa N，Amorim R，Martinho O． Encapsulation of α-cyano-4- hydroxycinnamic acid into a NaY zeolite． J Mater Sci，2011，46 (23): 7511 ［15］ Motsi T，Rowson N A，Simmons M J H． Kinetic studies of the removal of heavy metals from acid mine drainage by natural zeolite． Int J Miner Process，2011，101(1--4): 42 ［16］ Luo X P，Li J C，Yan Q，et al． Screening of optimum adsorbents for treating wastewater containing low concentration ammonia￾nitrogen． CIESC J，2010，61(1): 216 (罗仙平，李健昌，严群，等． 处理低浓度氨氮废水吸附材料 的筛选． 化工学报，2010，61(1): 216) ［17］ Yuan J S，Wang J K． Research on Na + --K + ion exchange char￾acteristic on Na-clinoptilolite (Ⅰ): thermodynamics characteris￾tic of the process． Ion Exch Adsorpt，2004，26(6): 541 (袁俊生，王静康． 钠型斜发沸石 Na + --K + 离子交换特性研 究( Ⅰ)—离子交换过程热力学特性． 离 子 交 换 与 吸 附， 2004，26(6): 541) ［18］ Wang J，Terigele，Li M Z，et al． Oxidative dehydrogenation of propane to propylene over acid-modified natural clinoptilolite． J Inner Mongolia Norm Univ Nat Sci Ed，2012，41(1): 74 (王奖，特日格乐，李明智，等． 酸改造天然斜发沸石上丙烷 氧化脱氢制丙烯的研究． 内蒙古师范大学学报: 自然科学汉 文版，2012，41(1): 74) ［19］ Elaiopoulos K，Perraki T，Grigoropoulou E． Monitoring the effect of hydrothermal treatments on the structure of a natural zeolite through a combined XRD，FTIR，XRF，SEM and N2 -porosime￾try analysis． Microporous Mesoporous Mater，2010，134(1--3): 29 ［20］ ztürk N，Ucun F，Muhtar A D，et al． Infrared and SEM analy￾ses of polyethyleneglycol-400 adsorbed on zeolites NaA，CaA， NaX and NaY． J Mol Struct，2009，922(1--3): 35 ［21］ Kyotani T，Mizuno T，Katakura Y，et al． Characterization of tubular zeolite NaA membranes prepared from clear solutions by FTIR-ATR，GIXRD and FIB-TEM-SEM． J Membr Sci，2007， 296(1 － 2): 162 ［22］ Cho K，Ryoo R，Asahina S，et al． Mesopore generation by or￾ganosilane surfactant during LTA zeolite crystallization，investiga￾ted by high-resolution SEM and Monte Carlo simulation． Solid State Sci，2011，13(4): 750 ［23］ Tong X W，Zhu Y N． Experimental study on the modification of natural stellerite and its removal of ammonia nitrogen from water． Chin J Environ Eng，2009(4): 635 (佟小薇，朱义年． 沸石改性及其去除水中氨氮的实验研究． 环境工程学报，2009(4): 635) ［24］ Xu R R，Pang W Q，Yu J H，et al． Chemistry Zeolites and Por￾ous Materials． Beijing: Science Press，2004: 145 (徐如人，庞文琴，于吉红，等． 分子筛与多孔材料化学． 北 京: 科学出版社，2004: 145) ·750·