XXXVI Seminarium Fizykochemiczne Problemy Mineralurgii, 1999, 117-123 Physicochemical Problems of Mineral Processing, XXXVI Symposium, 1999, 117-123

DUSICA VUCINIC', RUDOLF TOMANEC'

REMOVAL OF TOXIC METALS FROM WASTE WATERS USING CLINOPTILOLITE

The ion-exchange properties of natural clinoptilolite (Zlatokop deposit, Yugoslavia) and its modified form, potassium-clinoptilolite and calcium-clinopttilolite were examined. The obtained results showed that clinoptilolite can be used to effectively remove such from wastewaters ( for example: mineral processing wastewater or acidic mine waters).

Key word: toxic metals, waste waters, clinoptilolite

INTRODUCTION

Although there arc more than thirty known natural zeolites only serven-mordenite, c1inoptilolite, ferrierrite, chabazite, erionite, phillipsite and analcime occur in sufficient quantity and purity to be individually considered as variable mineral resources (Vaughan 1978). Because of their specific crystal structures and physicochemical properties they have many applications in industry and ecology. An important property of zeolites is their ability to undergo ion exchange.

Clinoptilolite is natural zeolite with ideal unit cell M6[AI6Si30072]-24H20. The tetrahedral anionic framework is crossed by the channels (channels A,B and C), (Koyama, Takeuchi 1977), of various diameters (Markle, Slaughter 1968), in which four types of cation site with different strength of electrostatic field and number of water molecules have been identified (Koyama, Tekeuchi 1977). The alkali and alkaline earth cations usually compensate the aluminium charge in the zeolite framework and participate in the ion-exchange reactions. Due to different diameters of channel openings, c1inoptilolite has the molecular sieve properties Mercer, Amlan 1978, Semmens 1980, Townsend, Loizidou 1984, Andrews et al. 1995, Carland, Aplan 1995, Vaca-Mier at al. 1997, Vucinic, Tomanec 1998).

The cation-exchange properties and the selectivity of this ion-exchanger for alkali (especially for Cs+), ammonium and alkaline earth cations have been investigated mostly on natural Na-clinoptilolite. Also, it can be seen from the literature data that

• Faculty of Mining and Geology, University of Belgrade, nooo Belgrade, Djusina 7, Yugoslavia

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DUSICA VUCINIC, RUDOLF TOMANEC

clinoptilolite from different localities shows different ion-exchange properties depending on the type of dominat catioms in zeolite channels.

In this work the ion-exchange properties of c1inoptilolite from the Zlatokop deposit,(Yugoslavia) were examined. Considered for protection of the environment and purification of waste waters, especially mine waters and mineral processing wastewaters, for some haevy metal ions (Cu, Zn, Cd, Pb, Ni and Mn). Also, the natural clinoptilolite was transformed into the postassium-clinoptilolte and their cation-exchange affinities for examined cations were detected.

EXPERIMENTAL

The fraction of -0.1 + 0.063 mm of natural zeolite was separated upon grinding in ceramic mill, as zeolite crystallizes in crystallites amaller than 0.1 mm (Gottardi, Obradovic 1978). The residual dust was removed by sedimentation in distilled water. The further removal on non-zeolite impurities with densities higher than 2.2 g em", such as quarz, feldspars, calcite was performed using CHBr3-CCI4 mixture of 2.2g em" density. Upon rinsing destilled water, drying and complete hydration over saturated NH4CI solution, a sample of natural clinoptilolite, denoted as CL, was obtained.

The CL sample was treated with aqueous chloride solution ofK+ (0.1 mol dm") or Ca2+ (0.05 mol dm") at 298K five times for five hours always with a fresh solutions in order to attain the maximum exchange under the given condition. The liquid to solid ratio was 10, and ionic strength 1=0.1 of the solution. Thus prepared samples, after rinsing with distilled water, drying and complete hydration over saturated N~CI solution were marked as CL-K (potassium-clinoptilolite) and CL-Ca (calciumClinoptilolite). The treatment with nitrate solutions of Cu(II), Zn(II), Cd(II), PB(II) Ni(II) or Mn(H) was performed by 0.05 mol dm" solution concentration, at pH=4.5 in order to prevent hydrolysis of denoted cations. The phase ratio of solution and zeolite was also 10, and the exchange was repeated five times for five hours always with fresh desired solution, at 298K. Upon rinsing, drying and hydration, the obtained samples, as was as CL, CL-Ca and CL-K, were chemically analysed.

RESULTS AND DISCUSSION

The quantative composition of natural clinoptilolite< CL and its modified forms, potassium-clinoptilolite (CL-K) and calcium-clinoptilolite (CL-Ca) is given in Table 1. The concentrations of non-zeolite impurities (quartz, feldspars, calcite) were determined using the procedure described by Ceranic (Ceranic et al. 1987) The CL sample contains about 93 % w/w clinoptilolite. The unit cell (U.C.) composition of

Removal of toxic metals from waste waters using clinoptilolite

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zeolite in CI was: Nao4Ko.sCaL9Mgo5[AI6Sho072]-21.2H20. Thus the natural clinoptilolite has most Ca2+ ions in the cation-exchange sites in zeolite channels. According to the structural model of Koyama and Takeuchi (Koyama, Takeuchi, 1977) the four cation sites exist in the channels of cIinoptilolite, with different strengths of electrostatic field and numbers of water molecules in it. The dimensions of the channels and cations site locations in clinoptilote, and the probability of location of different cations are presented i table 2.

Tab. I. Chemical composition of natural clinoptilolite, CL, and the modified, CL-K and CL-Ca Tab. I. Sklad chemiczny naturalnego klinoptilolitu, CL. i zmodyfikowanych form CL-K i CL-Ca

Component CL CL-K CL-Ca
%w/w %w/w %w/w
Si02 65.68 65.82 65.66
Al203 12.69 12.64 12.54
Na20 0.83 0.38 0.48
K20 1.35 9.26 0.90
CaO 4.00 0.26 4.49
MgO 0.90 0.60 0.64
Fe203 1.19 1.11 1.04
H2O 13.32 10.10 14.01
Totals 99.96 100.17 100.14 The calculation unit cell compositions of modified form, potassium- and calcium-

clinoptilolite, were:

CI-K K5.6Mgo2[AI6ShoOn]-H20

CL-Ca Nao2Ko6Ca23Mgo3[AI6Si30072]-22.4 H20

It is evident that under the applied experimental conditions monoionic forms of clinoptilolite were not obtained. The CEC values of natural clinoptilolite, CL for K+ and Ca2+ and 0.166 eq/l OOg zeolite and 0.018 eqllOOg zeolite, respectively.

K+ ions from the solution replaced all Ca2+ and Na+ ions from CL, located in channels A and B, thus CL was "cationic sieve" for potassium ions, without steric hindrances (Table 2 and 3). The small exchange degree with Mg2+ from CL is because magnesium ion is strongly hydrated in position M.(4), without electrostatic oxygenion coordination. The CEC of CL for Ca2+ ions from the solution is much lower than for K+ ions. It may be explained by the high Ca2+ content in CL. The free energy of hydrotion of Ca2+ in the solution, LlGo h is higher than the free energies of hydration of the concurrent cations in CL: K+ and Na+ (Table 3), so that Ca2+ is thermodynamically more stable in the solution. Also, the low hydrated M.(3) site in CL are not convenient for calcium ion.

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Tab. 2 Dimensions of the channels (Merkle, Slaughter 1968) and ion site locations in clinoptilolite (Kayama, Tekeuchi 1977)

Tab. 2. Wymiary kanalik6w i miejsc lokalizacji ion6w w klinoptilolitu (Koyama, Takeuchi 1977)

Channel Dimensions Ion coordinated by Site Probability of
(nm) Framework Water cation location
oxygen atoms molecules
(IO-membered 0.705xO.425 2 5 M.(l) Na+, Ca2+
rings)
(8-membered 0.460xO.395 3 5 M.(2) Ca2+, Na+
rings)
(8-membered 0.540xO.390 6 3 M.(3) K+
rings)
Inversion 0.705xO.425 - 6 M.(4) Mi+
channel of
chanel A Tab. 3. The crystalline radius, re, hydrated radius, rh, and the free energies of hydration, ~Goh some cations (Markus, Kertes ,1969)

Tab. 3. Promienie i energia hyratacji ~GOh kation6w r, promien jonu w strukturze krysztalu, rh promien jonu shydratyzowanego (Markus, Kertes, 1969)

Cation r, (nrn) rh (nm) ~GOh (kJ/mol)
K+ 0.133 0.331 -735.26
Na+ 0.098 0.358 -872.35
Ca2+ 0.099 0.412 -2452.41
Mi+ 0.065 0.428 -2798.93
Cd2+ 0.103 0.426 -1799.49
Pb2+ 0.132 MOl -1495.60
Zn2+ 0.083 0.430 -2025.63
Ne+ 0.083 - -2159.88
Mn2+ 0.091 - -2002.22
Cu2+ 0.082 0.419 -2084.57 Removal of toxic metals from waste waters using clinoptilolite

121

Tab. 4. CEC values (eq/lOOg zeolite) and capasities (g metalllOOg zeolite) of different forms of ciinoptilolite for examined heavy metal ions

Tab. 4. Wartosci CEC (eq/lOOg zeolitu) i pojemnosc (g metaluJlOOg zeolitu) roznych form klinoptilolitu

Form of clinoptilolite CL CL-Ca CL-K
Pb2+ 0.122 0.126 0.198
Zn2+ 0.093 0.103 0.145
CEC Cu2+ 0.087 0.102 0.137
eq/100g Cd2+ 0,109 0.114 0.159
zeolite Mn2+
0.098 0.109 0.149
Ni2+ 0.062 0.080 0.098
Pb2+ 12.64 13.35 20.51
Zn2+ 3.04 3.37 4.74
Capasity Cu2+ 2.76 3.24 4.35
g metalll OOg Cd2+ 6.13 6.40 8.94
zeolite Mn2+
2.69 2.99 4.09
Ni2+ 1.82 2.35 2.98 The examination of ions-exchange properties of c1inoptilolite for some heavy metal ions was very interesting. The obtained CEC values of CL, CL-Ca and CL-K for Ca2\ Zn2+, Pb2+, Cd2+, Ne+ and Mn2+ are shown in Table 4. If the hydrated ionic radii of the examined channels (Table 2 and 3), it would show that only partially dehydrated ions Cu2+, Zn2+, Pb2+, Cd2+, Ni2+ and Mn2+ could pass through the channels. Hence, the selectivity of clinoptilolite was determined by steric hindrances and by the free energies of hydration of examined heavy metals ions, as well as ions in zeolite (Tablela 2 and 3). Namely, the greater ~G\ indicates that water molecules are held more strongly to the central cations. This would make it more difficult for the ion to enter andlor traverse the zeolite pores, and a high .'lGoh would also make exchange at an active exchange site (Table 4) is probably due to the Pb2+ lower free energy of hydration than that of other examined ions and an easier loss of the hydrated shell. Also, the lowest CEC value was obtained for nickel ions, as this is the highest hydrated among examined heavy metal ions. According to the obtained CEC results the observed selectivity of c1inoptilolite forms is: Pb2+ >Cd2+>Mn2+>Zn2+>Cu2+»Ni2+

The CL-K has the highest exchange capacity for Pb2+(O.198 eq Pb(II)1l00g zeolite or 20.5g Pb(II)/l OOg CL-K).

CONCLUSIONS

Natural zeolite, c1inoptilolite from the Zlatokop deposit (Yugoslavia) and its modified form, potassium-c1inoptilolite and calcium-clinoptilolite, were found to have

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DUSICA VUClNIC, RUDOLF TOMANEC

the ability to separate some toxic heavy metal ions from water. The cation exchange capacity (CEC) of clinoptilolite showa the order of selectivity to be Pb2+>Cd2+>Mn2+>Zn2+>Cu2+»Ne+. Based on the obtained results it can be concluded that examined zeolite (its different cation forms) can be used in purification of mine or mineral processing wastewaters, which contain examined heavy metal ions, wit the highest affinity for lead ions and the lowest affinity for nickel ions. Zeolite systems for treating such waters have been developed which may allow recovery of valuable metals simultaneously protecting the environment.

REFERENCES

ANDREWS R.D., LAFFON L., HULZENGA H., PRICE ME., 1995, Abstracts of Sofia Zeolite Mecting'95, Inter. Conf and Exhibition on Natural Zeolites, Sofia, 49.

CARLAND RM., APLAN F.F., 1995, Preceedings of the xix Inter. Miner. Process.

Congress, Colorado, 95-100.

CERANIC T., TOMAZOVIC B., SIJERIC G., LUKIC T., 1987, JSerb.Chem.Soc.,

52, 111.

GOTTARDI B., OBRADOVIC J., 1978, Fortschr. miner., 56,547. KOYAMA K., TAKEUCHI Y., 1977, ZiKrisuallogr., 145,216.

MARCUS Y., KERTES A.S., 1969, Ion Exchange and Solvent Extraction of Metal Complexes, Int. Publ. Co., London.

MARCER B.W., AMES L.L., 1978, in Natureal Zeolites, Occurrence, Properties, Use, L.B.Sand, F .A.Mumpton (eds.), Pergammon Press, New York, 451-462.

MARKLE A.B., SLAUGHTER M., 1968, amer. mineral., 53, 1120.

SEMMENS MJ., 1980, Proc. 5th Int. Con! of Zeolities, L.V.Rees (ed.) Heyden and Son Ltd., London, 795.

TOWNSEND R.P., LOIZIDOU M., 1984,Zeoliles, 4, 191.

VACA-MIER M., GIRAL P.B., JIMENEZ-CISNEROS B., 1997, Zeolite '97, Abstracts of s" Inter. Conf. on the Occurrence, Properties and Utilization of Natural Zeolites, Naples, 314-316.

VAUGHAN D.E.W., 1978, in Natureal Zeolites, Occurence, Properties, Use, L.B.

Sand F.a., Mumpton (eds.) Pergammon Press, New York. 353-370.

VICINIC D., TOMANEC R., 1998, in Natural Zeolites, G.Kirow, L.Filizopova, O.Petrov (eds.) PENSOFT, Sofia, 199-206.

D. Vucinic, R. Tomanec, Usuwanie jon6w toksycznych metali ze sciekow przy pomocy klinoptilolitu, XXXVI Seminarium Fizykochemiczne Problemy Mineralurgii, 1999, 117-123 (w jez, angielskim)

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Jonowymienne wlasciwosci naturalnego klinoptilolitu (z pokladow Zlotokop, Jugoslawia) oraz jego zmodyfikowane formy potasowa i wapniowa poddano badaniom laboratoryjnym. Uzyskane wyniki wskazuja, ze klinoptilolit moze efektywnie usuwac ze sciekow toksyczne jony metali ciezkich takie jak: miedz, cynk, kadm, olow, nikiel i mangan. Procesowi usuwania jonow metali moga bye poddawane wody kopalniane oraz scieki z zakladow wzbogacania surowc6w mineralnych.