27 5 Vol127 No15 JOURNAL OF THE CH INESE RARE EARTH SOC IETY 2009 10 Oct12009 3,,, (, 310035) : (MAR)pH, 14 h 308 K, ph 6. 50, Langmuir 379 mg g - 1 ( k = 4. 37 10-5 5. 06 10-5 s - 1 ) Freundlich, Langmuir : H = 16. 7 kj mol - 1, S = 130 J (mol K) - 1, G 298 K = - 22. 0 kj mol - 1 0. 5 mol L - 1 HCl : (MAR) ; ; ; ; ; : O614. 3: A : 1000-4343 (2009) 05-0698 - 06 ( 80% ),, (),, [ 1 5 ], - COOH, ph 1 1. 1 : (MAR ) ; La 2 O 3 () ; ph = 5. 00 7. 50 HAc2NaAc ; : UV22550 ; DSHZ2300A ; THX2C21 ; DELTA 320 ; SK5200LH ; N icolet 380 1. 2 1. 2. 1, ph = 5. 00 7. 50, 24 h,,, (Q ) (D ) : Q = c 0 - c e w V (1) D = c 0 - c e V (2) w c e Q ( mg g - 1 ) ; c 0 c e (mg m l - 1 ) (mg m l - 1 ) ; w ( g) ; V (m l) 1. 2. 2 La ( ) 25 m l, ph = 7. 20 2 10. 0 m l 0. 1% 2I 2. 0 m l, 25 m l,, 575 nm, 1 cm : 2009-02 - 25; : 2009-05 - 29 : (2008F70059) : (1959 - ),, ; : 3 ( E - mail: xiongch@163. com)
5 699,,, 1. 2. 3, ph = 6. 50 HAc2NaAc,,, ph = 6. 50 3,,, 2 2. 1pH, ph 15. 0 mg 6, T = 298 K, ph = 5. 00 7. 50, c 0 = 10 mg/30 m l, 100 r m in - 1,, HAc2NaAc La ( ), 11, ph 5. 00 7. 50, La ( ) ph = 6. 50 ph, La ( ),, H + La ( ), ph, La ( ), ph = 6. 50 [ 6 ] 2. 2 3 15. 0 mg, T = 288, 298 308 K, ph = 6. 50, c 0 = 10. 0 mg/30 m l, 100 r m in - 1,,, Q, Q t 2 2, La ( ), 14 h,,, MAR La ( ) : B rykina [ 7 ], k - ln (1 - F) = kt (3) F = Q t Q (4) Q t Q t ( mg g - 1 ), k - ln (1 - F) t, ( 3) MAR La ( ) : k 288 K = 4. 37 10-5 s - 1, k 298 K = 4. 72 10-5 s - 1, k 308 K = 5. 06 10-5 s - 1 Boyd [ 8 ] - ln ( 1 - F ) t, 1 ph Fig. 1 Influence of ph on distribution ratio
700 27 2. 3, Lang2 muir [ 9 ] Freundlich [ 10 ] Langmuir Freundlich: Langmuir : c e 1 = Q e Q K L + c e Q (5) Freundlich : lgq e = lgk F + 1 n lgc e (6) c e La ( )(mg m l - 1 ), Q e (mg g - 1 ), K L Lang2 muir, K F Freundlich, n 5 15. 0 mg, ph 6. 50, c 0 = 12. 0 mg/30. 0 m l; 13. 0 mg/30. 0 m l; 14. 0 mg/30. 0 m l; 15. 0 mg/30. 0 m l; 16. 0 mg/ 30. 0 m l,,, c e /Q c e Langmuir, 4 lgq lgc e Fre2 undlich, 5 Freundlich n 2 10, MAR [ 11 ] MAR La ( )Langmuir Freundl2 ich 1, R, MAR La ( ) Freundlich, LangmuirLangmuir,, 1,, 308 K, 379 mg g - 1 2. 4 15. 0 mg 3, c 0 = 10. 0 mg/ 30. 0 m l, ph = 6. 50, 100 r m in - 1, 288, 298 308 K La ( ) lgd 1 / T, 6, 0. 9940,,, MAR 6, lgd = H 2. 30R T + S 2. 30R (7) G = H - T S (8) 1 M AR Table 1 Isotherm con stan ts for the adsorption of La( ) on M AR a t var ious tem pera tures T /K 288 298 308 Langmuir Freundlich c e /Q vs c e R L Q e / (mg g - 1 ) n lgq vs lgc e R F y = 0. 0035x - 0. 0002 y = 0. 0031x - 0. 0002 y = 0. 0029x - 0. 0001 0. 9940 0. 9949 0. 9990 304 341 379 2. 77 3. 25 2. 85 y = 0. 3612x + 2. 7950 y = 0. 3072x + 2. 8232 y = 0. 2668x + 2. 8230 0. 9799 0. 9979 0. 9924 4 Langmuir Fig. 4 Langmuir isotherm curve 5 Freundlich Fig. 5 Freundlich isotherm curve
5 701, 2,, MAR [ 12 ] 2. 5 1. 2. 3, La ( ) MAR 30 m l0. 5 3. 0 mol L - 1 HCl, La ( ), 3, 3,, 0. 5 mol L - 1 HCl, 100% 2. 6 2. 6. 1 150 mg, ph = 6. 50 HAc2NaAc 24 h, 0. 20 mg m l - 1 La ( ), ( ) 0. 278 m l m in - 1 La ( ) MAR, ( c ad =La ( ) ( c o ) 2La ( ) ( c e ) ) La ( ) La ( ) ( c e / c o ) 2 Table 2 Therm odynam ic param eters H / (kj mol - 1 ) S / (J (K mol) - 1 ) G/ (kj mol - 1 ) T =288 K T =298 K T =308 K 16. 7 130-20. 7-22. 0-23. 3 3 Table 3 Elution test of La( ) HCl concentration / (mol L - 1 ) 3. 0 2. 0 1. 0 0. 5 Elution /% 88. 3 93. 7 96. 8 100. 0 [ 13 ] (Q; mg g - 1 ), (9) : ( c Q = V 0 - c e ) 0 dv (9) m m ( g) (9) Q 321 mg g - 1,, [ 14 ] : c e 1 = c 0 1 + exp [ K T (Q m - c 0 V ) / ] (10) K T (m l (m in mg) - 1 ), (m l m in - 1 ) : ln ( c 0 c e - 1) = K TQ m - K T c 0 V (11) K T Q, ln[ (c o / c e ) - 1 ] t, 7 K T =2. 39 10-2 ml (m in mg) - 1 Q = 324 mg g - 1, ( 8) MAR La ( ),, ( R 2 = 0. 9875), (11),, 2. 6. 2, MAR, 6 Fig. 6 Influence of temperature on distribution 7 ln[ ( c o /c e ) - 1 ] t Fig. 7 Relationship of ln[ ( c o /c e ) - 1 ] vs t ( resin 150 mg, ph = 6. 50, c o = 0. 20 mg m l - 1, flow rate = 0. 278 m l m in - 1 )
702 27 0. 5 mol L - 1 (V ) ( c e ) 9, 40 m l, 4. 5 h,, 0. 5 mol L - 1 2. 7 MAR La ( ) ( H > 0) C =O C - OH La ( ),, 1713 cm - 1 C =O, 1539 cm - 1, C - OH 1405 cm - 1 1415 cm - 1 MAR La ( ) 3 10 Fig. 10 Infrared spectra 1., HAc2NaAc, ph = 6. 50, 298 K341 mg g - 1 0. 5 mol L - 1 HCl, 100% 2. La ( ) Langmuir k 298 K = 4. 72 10-5 s - 1 H = 6. 7 kj mol - 1, S = 30 J (mol K) - 1, G 298 K = - 22. 0 kj mol - 1 3. La ( ) : [ 1 ],. [ J ]., 2002, 21: 89. [ 2 ] Xiong C H, Yao C P. Sorp tion behavior of weak acid resin (D113) for zinc [ J ]. The Chinese journal of nonferrous metals, 2008, 18 (4) : 745. [ 3 ] Xiong C H, Yao C P, W ang Y J. Sorp tion behaviour and mech2 anism of ytterbium ( ) on im ino2diacetic acid resin [ J ]. Hydro2 metallurgy, 2006, 82 (324) : 190. [ 4 ] Xiong C H, Yao C P. Study on the adsorp tion of cadm ium ( II) from aqueous solution by D152 resin [ J ]. J. Hazard. Mater., 2009, 166: 815. [ 5 ] Tan IA W, Ahmad A L, Hameed B H. Adsorp tion of basic dye using activated carbon prepared from oil palm shell: batch and fixed bed studies [ J ]. Desalination, 2008, 225: 13. [ 6 ] Gode F, Pehlivan E. A comparative study of two chelating ion2ex2
5 703 change resins for the removal of chrom ium ( ) from aqueous so2 lution [ J ]. J. Hazard. Mater., 2003, B100: 231. [ 7 ] B rykina G D, Marchak T V, Krysina L S. Sorp tion photo2 metric determination of copper by using AV217 anion exchanger modified with 12( 22thiazolyl2azo ) 222naphthol23, 62disulphonic acid [ J ]. Zhur. Anal. Khim., 1980, 2294: 35. [ 8 ] Boyd G E, Adam son A M, MyersL S. The exchange adsorp tion behavior of ions from aqueous solutions by organic zeolites ki2 netics [ J ]. J. Am. Chem. Soc., 1947, 69: 2836. [ 9 ] Langmuir I. The constitution and fundamental p roperties of sol2 ids and liquids [ J ]. J. Franklin Institute, 1917, 183: 102. [ 10 ] Freundlich H M F. Over the adsorp tion in solution [ J ]. Z. Phys. Chem., 1906, 57: 385. [ 11 ] Gode F, Pehlivan E. Removal of chrom ium ( ) from aqueous solutions using Lewatit S 100: The effect of ph, time, metal con2 centration and temperature [ J ]. J. Hazard. Mater., 2006, B136: 330. [ 12 ] Βnl N, ErsozM. Adsorp tion characteristics of heavymetal ions onto a low cost biopolymeric sorbent from aqueous solutions [ J ]. J. Hazard. Mater., 2006, B136: 272. [ 13 ] Aksu Z, Ggnen F. B iosorp tion of phenol by immobilized activa2 ted sludge in a continuous packed bed: p rediction of breakthrough curves [ J ]. Process. B iochem., 2004, 39: 599. [ 14 ] Mathialagan T, V iraraghavan T. Adsorp tion of cadm ium from a2 queous solutions by perlite [ J ]. J. Hazard. Mater., 2002, 94: 291. Adsorption of Lan thanum ( ) on M acroporous Acrylic Resin from Aqueous Solution s: Ba tch and Column Stud ies Xiong Chunhua 3, Zheng Zhanwang, Yao Caip ing, Shen Chen (D epartm ent of A pplied Chem istry, Z hejiang Gongshang U n iversity, Hangzhou 310035, Ch ina) Abstract: The adsorp tion and desorp tion behaviors of La ( ) on macroporous acrylic resin (MAR ) were investigated in order to op tim ize the adsorp tion techno2 logical condition of lanthanum. studies were carried out w ith ph, temperature. move La ( ) The batch adsorp tion contact time and The results showed that MAR could re2 ions effectively from aqueous solution. The adsorp tion equilibrium tim e was observed w ithin 14 h. In the batch system, MAR exhibited the highest La ( ) up take as 379 mg g - 1 at 308 K, at an initial ph value of 6. 50, calculated from the Langmuir iso2 therm model. The adsorp tion kinetics, tested w ith liq2 uid film diffusion model, gave good fitted ( k = 4. 37 10-5 s - 1 to 5. 06 10-5 s - 1 ). The adsorp tion data fit2 ted better w ith Langmuir isotherm isotherm. than Freundlich The adsorp tion parameters of thermodynam ic were H = 16. 7 kj mol - 1, S = 130 J (mol K) - 1, G 298 K = - 22. 0 kj mol - 1, respectively. The thomas model was app lied to experimental column data to de2 term ine the characteristic parameters of column useful for p rocess design and to p redict the breakthrough curves. The La ( ) could be eluted by using the 0. 5 mol L - 1 HCl eluant. The surface characterization of both before2 and after adsorp tion of La ( ) on MAR was undertaken using IR spectroscop ic technique. Key words: macroporous acrylic resin (MAR) ; lanthanum ( ) ; kinetics; adsorp tion; thermodynam ic; rare earths