Aquacultural Engineering 6 ( 1987) 39-50

Aquaculture Water Treatment by Ion-Exchange: I. Capacity of Hector Clinoptilolite at 0-01-0.05 N

H. T. Drydent and L. R. Weatherley
Department of Chemical and Process Engineering, Heriot-Watt University, Chambers Street, Edinburgh EH 1 1HX, UK

A B S T R A CT The capacity of the naturally occurring zeolite clinoptilolite has been determined for the ions NH~, K *, Ca "-+ and Mg 2+ in the range of total concentrations 0.01 u-0.05 U. The results show that the effective capacity of the zeolite varies according to the ionic species involved in the exchange. Maximum ion uptake was achieved for the exchanges Na /NH + 4and Na* /K and the measured capacities for N i l + 4and K + were significantly greater than those measured for Ca 2* and Mg 2+. The data provide a useful pointer to the use of clinoptilolite as a water treatment medium in recirculating aquaculture systems.

1. I N T R O D U C T I O N

The steadily increasing growth of fish farming and aquaculture in the UK and over parts of Western Europe since 1970 has been accompanied by a corresponding increase in the application of new and existing technology to the design and operation of fish rearing systems. One of the significant developments, is a growing desire for a comprehensive water treatment strategy which gives the fish farm operator a high degree of control over the environmental conditions in which his stock grows. This is reflected in the recent development of intensive closed recirculating systems which allow almost total reuse of water inventory by the employment of efficient and rapidly responding water treatment systems which maintain water quality at an optimum level. The initial water quality criteria in this context are metabolite levels, including ammonia, temperature, oxygen concentration, undissolved
+Present address: Dryden Aquaculture Ltd, Abbeymount Techbase, 2 Easter Road, Edinburgh EH7 5AN. UK. 39 Aquacuhural Engineering 0 1 4 4 - 8 6 0 9 / 8 7 / S 0 3 . 5 0 - Elsevier Applied Science Publishers Ltd, England, 1987. Printed in Great Britain

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14. T. Dryden, L. R. Weatherley

solids content and pH. It is the removal of ammonia as ammonium ions by ion-exchange to which the present work was directed and it is appropriate briefly to put the use of ion-exchange into context. Traditionally, biological filtration is the process used for the removal of ammonia from fish farm waste water; the process is economic to install and the operating and maintenance costs are minimal. The capacity of the filter to remove ammonia at the desired rate is achieved by conditioning of the filter over a period of several weeks. During this period colonies of suitable biomass are cultivated on the filter support until the required level of activity is achieved. The long build-up to design capacity means that biological filters exhibit a relatively slow response to changes in ammonia concentration and overall loading. Thus biofiltration lends itself to steady-state environments. By contrast, ion-exchange offers a rather more flexible system, albeit confined to freshwater systems, which can respond rapidly to changes in feed water concentration, flowrate and overall loading. It offers a turn-key process which may be brought on-line at very short notice and offers a significantly greater turndown flexibility compared with biofiltration. Water treatment performance can be maintained over a wider range of temperatures and concentrations and ion-exchange is likely to show the most useful application to aquaculture systems for water treatment during fish transportation and as a back-up system to biological filtration in large systems. The ion-exchanger selected for study here was the naturally occurring zeolite clinoptilolite. This material is highly selective for ammonium ions and has been used with considerable success in secondary sewage effluent treatment (Polta and de Fore, 1978) and other large-scale water treatment systems (Sherman, 1978). The ammonia concentrations considered to be a maximum for fish culture waters are very much lower than those encountered in sewage waters and thus the ion-exchange capacity of clinoptilolite at concentrations of the order of 0.01 N were studied. This value represents an upper limit of cation concentrations normally encountered in fish farm waters. Typical fish farm water also contains significant concentrations of sodium, potassium, calcium and magnesium ions. The sodium ion presence can be appreciably enhanced due to the use of sodium ion solutions for the regeneration of ion exchangers. Thus five cations were -t"~+ "~+ chosen for capacity studies, i.e. NH4, Na+, K +, Ca- , Mg- . 2. CAPACITY In the design of cyclic ion-exchange systems optimal sizing of the columns requires an accurate knowledge of the specific capacity of the

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exchanger for particular ions. This is in addition to the selectivity for those ions present. In the case of clinoptilolite there is clear evidence that capacity is variable; see Jorgensen et al. (1979), Ames (1967), Cridland (1979) and Klieve and Semmens (1980). Qualitative interpretation of oberved data indicates that total single ion capacity can be influenced by ionic strength of the contact solution, zeolite history, regeneration mode and pretreatment conditions. A comparison of total exchange capacities for Hector clinoptilolite measured by a number of investigators is shown in Table 1. Measured compositions of clinoptilolite are less variable than indicated by the variations in homo-ionic capacity and the mode of pretreatment prior to capacity determination may be a major factor affecting the observed variability. For example, pretreatment with mineral acid, sometimes practised to remove carbonate and clay impurities, may result in dealumination (see Muminov et al., 1977; Barrer and Makki, 1964), with a consequent reduction in capacity. In the case of alkali pretreatment, increases in capacity have been observed (Yokota, 1975; Yoshida et al., 1976; Klieve and Semmens, 1980; Jorgensen etal., 1979). Heat treatment and the concentration of conditioning solutions are also likely to influence operating capacity of clinoptilolite (see Salek et al.. 1979; Galabova, 1979; Chelishchev and Volodin, 1976).

TABLE 1 Ion-Exchange Capacities of Hector Clinoptilolite

In vestigator Cation Capacity (meq. cation g- 9
1"7 1"81 2.14 1.83 1.9-2.1 (2-04) h 1-9 2"046 + 0"0177 2"039+0"011 1.97 1-9-2.1 (2.04) b 1.84

Ames(1963) Ames(1967) Barrer and Townsend (1976) Barrer et al. (1967) Skudder i 1976) Koon and Kaufman (1975) Howery and Thomas ( 1965)"

Cridland ~1979) Laporte (personal communication. 1982

L'

Cs + NH ~ NH] NH; NH] Na + Na* Cs NH ~ NH ~ NH]

Geological source of mineral was not specified. "Mean .,riven in parentheses.

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H. T. Dryden, L. R. Weatherley

3. EXPERIMENTAL
3.1. Capacity at 0.05 N

Two types of clinoptilolite from the Hector deposit were Selected for study. These are designated A and B, being distinguished by different colourations. The clinoptilolite was dry-sieved to a particle size range between 0.60 and 0"85 mm, and washed in distilled water to remove the fines. Since the ion-exchange filtration is a cyclic process, the conditioning procedure prior to capacity determination was based on a similar pretreatment strategy. The clinoptilolite was converted to the ammonium form by repeated contact with 0.05 r~-Na+C1 -, at pH 11.5 to 12.0 (pH regulation with Na+OH - ) followed by 0.05 N-NHaCI solution at a temperature between 18 and 21C. The clinoptilolite (30g) was supported by a perforated plastic plate in a glass column 250 mm in length, and 26 mm internal diameter. During each cycle of the conditioning procedure, 24 litres of contact solution were passed up-flow through the zeolite bed at a constant flowrate of 500 ml h-1, maintained by a peristaltic pump (Watson Marlow type MHRE 200). The cycle was repeated four times, but for the last treatment 60 litres of ammonium chloride solution were passed through the zeolite bed. Finally, the zeolite was thoroughly washed with de-ionised water at a flowrate of 1000 ml h-1 until the effluent gave a negative chloride ion reaction with silver nitrate solution, and a zero reading with Nessler's reagent for ammonia. The zeolite generally required approximately 60 litres of de-ionised water to give an ion-flee effluent. The conditioned clinoptilolite was removed from the columns and left to dry on a tray at room temperature for a period of one month, after which time it was stored in a constant-humidity bottle above 1.0 yammonium chloride for an additional period of one month. This lengthy procedure was required to avoid heat treatment, to elute all sorbed solute ions, and to ensure a constant water content prior to weighing. The capacity of clinoptilolite for the ammonium ion was determined by a small column elution technique similar to the method described by Howery and Thomas (1965). A small glass column measuring 80 mm in length and 5.0 mm internal diameter was filled with 0.500 g of ammonium-based hydrated clinoptilolite. The zeolite was contacted with 1 litre of 1.0 N-sodium chloride solution at a flowrate of 50 ml h-i. The eluant was collected and analysed for ammonia; thus the ammonium ion capacity was determined and the sodium ion capacity by inference, since the exchange reaction is stoichiometric. Solid-phase ammonium ion

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analysis gave a zero reading, indicating that all of the ammonium ions had exchanged off the clinoptilolite. This analysis involved waterwashing a crushed sample of the zeolite followed by addition of Nessler's reagent. A negative reaction confirmed the sample to be ammonia-free. A similar procedure using potassium chloride in place of sodium chloride enabled the potassium ion capacity of the zeolite to be determined. Calcium and magnesium ion capacities were measured by a modification of the described procedure. Six litres of 0.05 N calcium and magnesium chloride solutions were passed through small columns containing 0.500 g of clinoptilolite, followed by a wash with 1 litre of de-ionised water (flowrate 50 ml h-~). One litre of 1.0 N-sodium chloride solution was next passed through each column and the eluant was analysed for ammonia. The calcium and magnesium ion capacities were calculated by subtracting the milliequivalents of ammonium eluted by sodium from the total ammonium ion capacity of the zeolite. This procedure was adopted because of the difficulty in analysing for ammonia in the presence of 1.0 N-calcium or magnesium chloride, due to the precipitation of these ions at the high pH required for ammonia analysis. The small-column elution technique and liquid-phase analysis was chosen in preference to direct solid-phase analysis by Kjeldahl distillation (Bremner, 1960; Skudder, 1976; Cridland, 1979; Fletcher, 1979) because of the simplicity and accuracy of the method. Reagent-grade chemicals were used throughout the conditioning and capacity determinations.
3.2. Capacity at 0"01 N

It was shown in the previous section that homo-ionic ammonium-form clinoptilolite which was conditioned with 0.05 N solutions could be totally .depleted of the resident counter-ion by elution with 1"0 N solutions of sodium or potassium chlorides. It was decided to repeat the elution procedure using solutions at a total concentration of 0"01 N in order to establish the available effective exchange capacity at this lower concentration. The exchange systems shown in Table 2 were studied and the column conditions are summarised in Table 3. The various cationic forms of clinoptilolite B were produced as previously described and were exchanged with solutions containing only the exchanging counter-ion and chloride co-ion at 0"01 N. Samples of eluant were taken at hourly intervals for the first 24 h and at two-hourly intervals for the second 24 h interval.

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H. T. Dryden, L. R. Weatherlev
TABLE 2

Small-Column Binary Cation Exchange System

Run no.
1

Solid-phase ion
Na +

Liquid-phase ion
Mg: +

2 .3 4 5 6 7 8 9

Na + Na NH~ NH~ NH ~ Na + Ca 2+ Mgz+

Ca:* K* Na" Ca 2+ Mg2+ NH~ NH NH~

TABLE 3

Experimental Conditions of the Binary Ion-Exchange Column Runs

Variable Value

Total normality of feed solution (chloride-ion salt) Particle size of clinoptilolite Weight of hydrated zeolite in ammonium form per column Flowrate (bed volume per hour) Bed volume Direction of flow Temperature Internal diameter of the glass column Duration of run

0"01 N 0'60-0"85 mm 30 g 10 BV h -I 34"5 ml Downflow 19-2 IC 26 mm 48 h

A t t a i n m e n t of steady state was c o n f i r m e d b y cessation of cation elution. T h e total exchange achieved at steady state was calculated f r o m the elution curve data b y curve fitting and integration.

4. E X P E R I M E N T A L

RESULTS

T h e m e a s u r e d capacities of b o t h clinoptilolite 'A? and 'B' for the cations N H +, K +, C a 2+ and M g 2+ at 0.05 N are given in Tables 4 and 5. T h e results are p r e s e n t e d as milliequivalents (cation) g-~, weighed as 1 g of a m m o n i u m - b a s e d clinoptilolite. T h e r e f o r e , in o r d e r to arrive at the

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TABLE 4 Capacity of Clinoptilolite ~A'for Cations

Capacity (meq. cation g - ~)
N

H + 4

K +

Ca 2+

M g 2+

Number of replicates Mean capacity (meq. gStandard deviation Confidence limits (59%) Low High

6 2"066 0"010 2'046 2"086

5 2-067 0"031 2'006 2"130

3 1"905 0"008 1'890 1"920

3 0"839 0"020 0'799 0"878

TABLE 5 Capacity of Clinoptilolite 'B" for Cations

Capacity (meq. cation g - ; ) NH + ~ K + Ca 2+ Mg 2+

Number of replicates Mean capacity t meq. g-~) Standard deviation Confidence limits (95%) Low High

6 2-159 0"026 2.106 2-211

5 2"114 0"010 2.095 2.133

3 2.004 0"003 1.999 2.009

3 0.682 0"020 0.642 0.722

TABLE 6 Water Content of Clinoptilolite 'B'

Form of clinoptilolite Mean water content (% wt)

Na + 14.7

K* 13.7

Ca-"+ 15.8

Mg 2+ 14.5

precise capacity for each respective ion, the different atomic weights of each cation and the percentage water content of each cationic form of the zeolite required consideration. The water content of clinoptilolite ~B" based on Na , K +, Ca 2- and Mg 2- was determined by heating 1 g samples of the zeolite to 850C for a period of 24 h, after which the zeolite was weighed at 200C to determine weight loss. Most of the weight loss will be attributed to water, but loss of aluminium and carbonates as carbon dioxide may occur. The results are presented in Table 6.

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H. T. Dryden, L. R. Weatherley
x
I

0 Fig. 1.

I0

20

30

~0

50

60

TIME(HOURS)
Binary cation column exhaustion profiles: e, run 1, Na~_/Mg2+; w, run 2, Na+/ Ca-'+; x, run 3, Na+/K +.

The elution data obtained at 0.01 N for each of the exchanges listed in Table 2 are plotted in Figures 1, 2 and 3. The capacity data inferred from the curves are shown in Table 7 for each individual case.

5. DISCUSSION OF RESULTS The results obtained in this investigation show that the cationic exchange capacity of clinoptilolite 'X and 'B' at 0.05 N are very similar for ammonium, sodium, potassium and calcium but differ greatly for magnesium. The results also indicate that full exchange, except for that of calcium and magnesium, has been achieved in a period of less than 20 h at room temperature. This result is rather surprising in view of the reported findings of Skudder (1976), Cridland (1979) and Noda (1980) in which full exchange was only achieved after several weeks at room temperature. The mean capacity of clinoptilolite 'A? and 'B' obtained by the exchange of sodium with solid-phase ammonium was 2.066 and 2.159 meq g- t respectively. These results are amongst the highest recorded for Hector clinoptilolite (see Table 1), and taking into account that the

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10.0]
80

TIME (HOURS)

Fig. 2.

Binary cation column exhaustion profiles: o, run 4, NH~/Na +, "; run 5, N H ] / Ca 2+; x , run 6, NH ]/Mg 2+.

10.0.

l//
0
Fig. 3.
10 20 30 ~ TIME (HOURS) 50
+ +

60

Binary cation column exhaustion profiles: o, run 7, Na /NH ~; I, run 8, Ca-'+/ NH .~: x , run 9, Mg 2+/NH ~.

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H. T. Dryden, L. R. Weaiherley
TABLE 7 Total Ion U p t a k e by Clinoptilolite 'B' After 48 h

Run no.
1 2 3 4 5 6 7 8 9

Solid-phase cation
Na + Na + Na NH] NH: NH~ "Na Ca -' Mg 2+

Liquid-phase cation
Mg 2+ Ca 2 K Na + Ca -'+ Mg 2+ NH4 NH~ NH:

Ion uptake Oneq. g- i)

0.112 0.979 2.216 1.018 1.178 0"119 2"117 1'508 0.342

samples were fully hydrated, the capacities measured probably represent, or are close to, maximum exchange. The capacity values measured with the calcium and magnesium ions are lower than the maximum capacity. This result implies either that exchange is very slow and insufficient time (about five days) was given to permit full exchange, or that cation exchange terminates at a point less than the maximum capacity, especially in the case of magnesium. Koyama and Takeuchi (1977) reported that the magnesium ion was only found at the M(4) exchange site and that its occupancy at this site was very low. This observation may explain the low capacity value determined in this investigation. Howery and Thomas ( 1965) commented on the capacity of clinoptilolite in the binary system sodium/caesium. Total exchange capacity in the mixed ion solution was always less than the sum of the homo-ionic capacities for each ion. No explanation could be given for the result except that it was not due to hysteresis. There is very little information in the literature regarding partial ion-sieving with clinoptilolite, and it is not known if exchange actually terminates or proceeds only slowly to full exchange. The uptake data for exchange of potassium ions at 0.01 N on to sodium-based zeolite and for ammonium ions on to sodium-based zeolite (see Figs 1 and 3) show that exchange is essentially complete after 48 h. This is reflected in the capacity values for these exchanges (see Table 6) when compared with the capacities determined at 0'05 ~. In the case of individual uptake of sodium, calcium and magnesium ions at 0.01 N on to ammonium-based zeolite (Fig. 2), the elution of the

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49

resident ion appears to be still in progress even after 48 h and thus no true final capacity figure was obtained. The effective uptake capacities calculated in these cases and presented in Table 6 confirm this when comparison with the capacity values obtained at 0-05 N is made. In the cases of uptake of ammonium ions at 0"01 N on to homo-ionic calcium, sodium and magnesium forms of clinoptilolite a much more favourable uptake was observed (see Fig. 3), and this is reflected in uptake values shown in Table 6. The uptake capacity values shown in Table 6 are not strictly true capacities in all cases as it is clear from the elution data that exchange can proceed at a finite but very slow rate towards the final stages of uptake. However, the data are consistent with the idea of partial exchange with certain species of ions and in specific directions of exchange. Later work on selectivity of clinoptilolite has confirmed this observation (see part II).

ACKNOWLEDGEMENT The authors wish to acknowledge the support of the SERC for a studentship for H. T. Dryden. REFERENCES Ames, L. L. (1963). Mass action relationships of some zeolites in the region of high competing cation concentrations. Am. Mineralogist, 48,868-82. Ames, L. L. (1967). Zeolite removal of ammonium ions from agricultural and other wastewaters. Proc. 13th Pacific Northwest lndust. Wastewater Conf., Washington State University, Pullman, WA, USA. Barrer. R. M. & Makki, M. B. (1964). Molecular sieve sorbents from clinoptilolite. Can. J. Chem., 42, 1481-7. Barrer. R. M. & Townsend, R. P. (1976). Transition metal ion-exchange in zeolites. Part 2 - Amines of Co 3, Cu 2+ and Zn 2 in clinoptilolite, mordenite and phillipsite. J. Chem. Soc., Faraday Trans. I., 72, 2650-60. Barter. R. M.. Papadopoulos, R. & Rees, L. V. C. (1967). Exchange of sodium in clinoptilolite by organic cations. J. lnorgan. Nucl. Chem., 28,629-43. Bremner. J. M. (1960). Determination of nitrogen in soil by the Kjeldahl method. J. Agric. Sci., 55, 11-33. Chelishchev. N. F. & Volodin, V. F. (1976). Ion-exchange kinetics of alkalis and alkaline earths in natural clinoptilolite. Geochem. Internat., 13(6), 127-36. Cridland. M. (1979). Ammonia removal from wastewaters. Ph.D. Thesis, Cambridge University. Fletcher, P. (1979). Transition metal ion-exchange in zeolites. Ph.D. Thesis, City University. London.

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H.. 1".Dryden, L. R. Weatherley

Galabova, I. M. (1979). Relationships between new structural data on clinoptilolite and its behaviour in ion-exchange in heating. Z. Naturforsch., 34(9). 248-50. Howery, D. E. & Thomas, H. C. (1965). Ion-exchange on the mineral clinoptilolite. J. Phys. Chem., 69(2), 531-7. Jorgensen, S., Libor, O., Barkaes, K. & Kuna, L. (1979). Equilibrium and capacity data of clinoptilolite. Water Res., 13, 159-65. Klieve, J. R. & Semmens, M. J. (1980). An evaluation of pretreated natural zeolites for ammonium removal. Water Res., 14(2), 161-8. Koon, J. & Kaufman, W. J. (1975). Ammonia removal from municipal waste~ waters by ion-exchange. J. WaterPollution Control Fed., 47(3), 448-65. Koyama, K. & Takeuchi, Y. (1977). Clinoptilolite: the distribution of potassium atoms and its role in thermal stability. Zeit. Kristallographie, 145, 216-39. Muminov, S. Z., Mirsalimov, A. M. & Aropiv, E. A. (1977). A comparative study of the modification of clinoptilolite with acid. Zh. Fiz. Khim., 51(1), 168. Noda, S. (1980). A simple method for determining the cation exchange capacity of natural zeolites. Nendo Kagaku, 20(3), 78-82. Polta, R. C. & de Fore, R. W. (1978). A demonstration of ammonia removal by ion-exchange. Proc. Industrial Waste Conf., 9-11 May. Purdue Univ., Lafayette, Indiana, USA, 33,604-13. Salek, H., Vincent, H. & Patton, M. (1979). X-ray diffraction studies of stabilities of zeolites to temperature changes and solution treatment. Advan. X-ray Anal., 22, 193-9. Sherman, J. D. (1978). Ion-exchange separations with molecular sieve zeolites. A.I.Ch.E. Symposium Series, 74(179), 98-116. Skudder, A. J. (1976). Ammonium ion-exchange on zeolites. Ph.D. Thesis, Cambridge University. Yokota, E (1975). Zeolites for advanced wastewater treatment. Chem. Abstr., 82, 115687. Yoshida, H., Kurata, Y. & Sange, K. (1976). Removal of heavy metal ions from polluted water with zeolites. Miza Shori Gifutsa, 17(3), 219-26.