Aquacultural Engineering 6 (1987) 51-68

Aquaculture Water Treatment by Ion-Exchange: II. Selectivity Studies with Clinoptilolite at 0.01 N
H. T. D r y d e n t and L. R. Weatherley
Department of Chemical and Process Engineering, Heriot-Watt University, Chambers Street, Edinburgh EH1 1HX, UK

ABSTRACT The selectivity behaviour of clinoptilolite in the presence of the ionic species Na , K +, Ca 2 and Mg 2 was determined for each ion relative to the ammonium ion N i l + ~at a total solution concentration of O'O1 u. With the exception of the N H 4 / K exchange each of the binary exchange systems exhibited a degree of irreversibility and partial exchange. The selectivity sequence K > N H + ~ > Na > Ca 2 > Mg 2 was determined and is consistent with the low change density structure of clinoptilolite. Comparison with other data for clinoptilolite suggests significant variations in the selectivity behaviour of the zeolite which may depend upon the source of the mineral. The isotherm data for the system NH+~/Na + confirm the potential of clinoptilolite as an ammonia removal technique for fish farm water treatment.

1. INTRODUCTION The relative characteristics of biological filtration and ion-exchange as water treatment tools in the context of aquaculture were discussed in an earlier paper (Dryden and Weatherley, 1987). Removal of ammonia as ammonium ions is the primary role of an ion-exchange system in this context and thus selective removal of NH ] compared with other cations present is required. In closed cycle intensive aquaculture systems where the water inventory is essentially fixed, the use of ion-exchange could seriously affect the balance of ion concentrations present, thus adversely influenc+Present address: Dryden Aquaculture Ltd, Abbeymount Techbase, 2 Easter Road, Edinburgh EH7 5AN. UK. 51 Aquacultural Engineering 0144-8609/87/S03.50- Elsevier Applied Science Publishers Ltd. England. 1987. Printed in Great Britain

52

Ho T. Dryden, L. R. Weatherley .

ing culture conditions. The zeolite clinoptilolite has again been selected for study as a cheap and readily available ion-exchanger for application in this context. The objective of the experimental work presented was to investigate the selectivity of clinoptilolite for potassium, sodium, magnesium, calcium and ammonium ions at a total solution concentration of 0.01 N. Previous published work with clinoptilolite has shown that the selectivity characteristics can be successfully determined by batch equilibrium experiments. Ames (1967) determined binary selectivity data using ammoniumbased clinoptilolite at 23C and a total solution concentration of 0.01 N. The selectivity sequence determined was found to be: K + > NH ~ > Na + > C a
2+ >

Mg 2+

The reversibility of the exchangers was not investigated. Skudder (1976) also investigated binary exchange equilibrium in clinoptilolite at a total solution concentration of 0.1N. The reported results showed a slightly different selectivity sequence from that of Ames (1967), namely: K + > NH ~ > Ca 2 > Na + > Mg 2~ Skudder presented clear evidence of irreversibility in the ammonium-sodium exchange system showing typically that ammonium uptake by sodium-based zeolite was approximately 86% that of sodium uptake by ammonium-based zeolite at 0.1 N. Further work by Cridland (1979) on the ammonium-sodium system exchange at 0.01 N demonstrated that irreversibility is also exhibited at the lower concentration. Similar behaviour was reported in the ammonium-calcium exchange on clinoptilolite at 0-01 N. The results of Skudder and Cridland suggest that the apparently irreversible exchange behaviour of clinoptilolite may be explained by hysteresis and slow exchange. Howery and Thomas (1965)suggested that partial exchange may be a more probable explanation in the context of multi-ion-exchange. In common with other zeolites, clinoptilolite does not exhibit the much more predictable behaviour of conventional synthetic ion-exchangers, even in single 1:1 exchanges, and this unique behaviour is attributed both to the novel structural and chemical nature of the zeolite. It is believed that a number of parameters associated with the structure of clinoptilolite influence selectivity. These include framework topology, number and position of the fixed anionic site groupings, degree of hydration and temperature.

Aquaculture water treatment by ion-exchange -- H

53

2. EXPERIMENTAL The objective of the experiments was to determine the binary ionexchange equilibrium for the following ion pairs: NH4/Na , N H ] / K ~ , NH ] / C a 2+, NH ]/Mg 2+, Na +/K +, Na +/Ca 2 at a total concentration of 0.01 N and in the presence of chloride ion. A batch equilibrium technique was used to determine equilibrium isotherms starting, for each pair of ions, with homo-ionic samples of zeolite at each end of the composition range. Equilibria were established at discrete compositions by bringing a sample of clinoptilolite of known weight and composition to equilibrium with a specific volume of aqueous solution of known normality and ionic composition. Experimental details are summarised in Table 1.
TABLE 1

Experimental Detailsof BinaryIon-Exchange Weightof clinoptilolite Particle size Total solutionnormality Temperature Equilibrium period Equilibrium solution volume 0"500 g 0"60-0"85 mm 0"01 18-21C 7 days 150 ml

Two types of clinoptilolite from the Hector deposit were selected for study. These are designated A and B, being distinguished by different colorations, white and green respectively. The initial samples of clinoptilolite were obtained as detailed earlier (Dryden, 1984), by column elution into pure sodium, potassium, calcium, magnesium and ammonium forms. Traces of conditioning solution were removed by vigorous washing with deionised water. The mixtures of clinoptilolite and solution were allowed to equilibrate at 20C for a period of seven days, after which nd discernible change in solution composition was measured. The compositions of each phase were determined by analysis of the aqueous phase for each cationic species present. Ammonium ion analysis was conducted by addition of Nessler reagent followed by spectrophotometric determination. Potassium and sodium were determined by flame photometry and calcium and magnesium by a titrometric technique given by Mackereth et al. (1978).

54

H. T. Dryden, L. R. Weatherley

All solutions were prepared from analytical-grade reagents of the appropriate chloride salt. The total solution normalities were checked by chloride ion analysis. The zeolite phase compositions were then calculated by mass balance. Particular care was taken during the experiments to ensure that the bottles in which equilibration was conducted were clean and sterile, to avoid the effects of possible bacterial oxidation of ammonium ions. The binary exchanges involving ammonium, potassium and sodium ions were conducted across the whole composition range starting with homo-ionic samples of clinoptilolite in the appropriate form. In the systems involving calcium and magnesium ions homo-ionic forms of zeolite were unachievable; see the earlier measurements of capacity (Dryden, 1984). The conditioning procedure adopted here meant that at maximum calcium or magnesium ion loading a significant amount of ammonium ion was present on the zeolite. As a consequence of this the isotherm data were calculated on the basis that ammonium, potassium and sodium ions had access to all exchange sites and that calcium and magnesium had access to a proportion of the sites in accordance with the values of total capacity for these ions.

3. EXPERIMENTAL RESULTS The solution concentrations before and after equilibration were used in the usual way to calculate the net transfer of ions from solution to zeolite

1.0
x X Z Z

(]0

o5 IO LIQUID R-IASE FRACTION(NI-~]

Fig. 1.

Batch isotherm (NH ~/K +) of clinoptilolite '~.

Aquaculture

water treatment by ion-exchange - - 11

55

or vice versa. The final zeolite phase ion fraction of, say, ammonium ion was calculated from the initial zeolite composition and weight and the net transfer of ammonium ions calculated from the change in solution phase composition. The total initial ionic composition of the zeolite was calculated on the basis of the total capacity measured for each particular ion. Thus the ion fractions of ammonium ion (or other ion) in zeolite and solution phases at equilibrium were calculated. The results are plotted in Figs 1-10 as ion fraction in zeolite phase versus ion fraction in solution phase. It was immediately evident from all but the ammonium-potassium exchange that only partial exchange was achieved when homo-ionic

1.0

Ca)
I.--

C:I 0

O.QQO

Q5 I0 LIQUID PHASE FRACTION(NH,*I

+,
Z

(b)

-r n e'~

QO

0.0

05 1.0 LIQUID PHASE FRACTION (NH~)

Fig. 2.

Batch isotherm (a) and normalised isotherm (b)(f.=0"89)(NH~/Na +) of clinoptilolite ~'.

56

H. T. Dryden, L. R. Weatherley

-- 10 I
.

(a)

O0 oo

tO
Z 0

oS 1.o LIQUID PHASE FRACTION (N~)

= Cb) u. (IS

QO

OO

LIQUID PHASE FRACTION (NH~)

c l i n o p t i l o l i t e 'A'.

O5

1.0

Fig. 3.

Batch isotherm (a) and normalised isotherm (b)(f. = 0.445)(NH~/Ca2I of

samples of zeolite were equilibrated with solutions containing a second counter-ion. For example, the case of the ammonium-sodium exchange in clinoptilolite '?/, shown in Fig. 2, shows that starting with homo-ionic ammonium-form clinoptilolite successive equilibrations along the composition curve to the pure sodium form cannot be achieved. A number of authors are agreed that a convenient way to deal with such systems is to express the equilibrium isotherms in terms of the true reversible exchange capacity for the pair of ions present. Sherry (1966, 1968) and Barrer et al. ( 1966, 1973) develop a normalisation procedure which involves defining a fractional exchange capacity factor, fn, where:
fn ~

Reversible exchange capacity Maximum homo-ionic exchange capacity

Aquaculture water treatment by ion-exchange -- H

57

Z Z

e: 05
0..

(a)

O0

O0

O5 I0 LIIIUID PHASE FRACTION (NH?',)

1.0

_e
QS

(b)

O0 O0

0.5
w

1(}

LIQUID PHASE FRACTION(NH~,)

Fig. 4.

Batch isotherm (a) and normalised isotherm ( b ) ( L = 0 - 2 0 ) ( N H : / M G 2+) of clinoptilolite ~'.

1.o
x

e~

05
e~

ao Fig. 5.

oo LIQUID

Q5 1.o PHASE FRACTION (NH~)

" I

Batch isotherm (NH ] / K + ) of clinoptilolite "B'.

58 1.0

H.T. Dryden, L. R. Weatherley

im

(a)

uJ Qc
t~

O }
on
1.0

' '

05 'tO LIQUID PHASE FRACTION (Na)

s~ 0.5
(b)

O0 O0

0.5 10 LIQUID PHASE FRACTION (Na*)

Fig. 6.

Batch isotherm (a) and normalised isotherm ( b ) ( f , = 0 - 6 5 ) ( N a + / C a 2+) of clinoptilolite 'B'.

Thus the fractional exchange capacity factor will vary from system to system. The values of fractional exchange capacity were determined in two ways. Firstly, with reference to Figs 1-10, the equilibrium isotherms were extrapolated. The isotherms starting at (I, 1) were extrapolated to cut the y-axis at x -- 0, and the isotherms starting from (0, 0) extrapolated to cut the y-axis at x -- 1. The values of cut-off on each y-axis indicate the limit of exchange achievable in that direction for the zeolite in contact with solution containing a single species of counter-ion at 0-01 N. A more convenient and useful approach was to calculate an effective reversible exchange capacity, unique for each binary system. This was achieved on a trial-and-error basis by finding the value of exchange capacity which would result in the calculated isotherm points being

Aquaculture water treatment by ion-exchange -- H

59

1.0

Q5

(a)

oo[
O 0
1.0

O5 1.o LIS.UID PHASE FRACTION(N~)

"* Q5

(b)

t~

0.0

0.5

1.0

LIQUID PHASE FRACTION(NHZ)

Fig. 7.

Batch isotherm (a) and normalised isotherm ( b ) ( f . = 0 " 8 5 ) ( N H ~ / N a +) of clinoptilolite 'B'.

coincident on a single line across the x - y diagram. Exchange capacity calculated in this way is referred to as the normalised exchange capacity. Isotherms calculated from the experimental data on this basis are also shown. The resulting x - y data were fitted to a polynomial equation indicated on each Figure. A comparison of the forward and reverse exchange capacities obtained by extrapolation of the unnormalised isotherm data with the normalised exchange capacities is shown in Table 2. In order to make a qualitative appraisal of the selectivity order of the ions relative to ammonium, values of separation factor a, defined in eqn (1), were calculated at a solution ion fraction of 0"5. These data, together with a

60
I,G,

H. T. Dryden, L. R. Weatherley

z
Z

. o'" 0~ 0 o o .o~"

QS

'X

(a)

O0 1.0
Z Z

(15 'to LIQUID PHASE FRACTION (NF~)

O 0

05

(b)

o0 oD

o.5 1D LIQUID PHASE FRACTION ( NHI~)

Fig. 8.

Batch isotherm (a) and normalised isotherm clinoptilolite 'B'.

(b)(f.=0.43)(NH~/Ca :+)

of

s u m m a r y of those presented b y A m e s ( 1 9 6 7 ) and Skudder (1976) at 0-01 r~, are shown in Table 3. a = B.Aaq.

A. Baq.

(1)

4. DISCUSSION OF RESULTS The only previously recorded isotherm data for clinoptilolite in contact with solutions at 0.01 N are those of Cridland (1979) for the binary * systems NHa/Ca 2+ and N H4/Na in the presence of chloride. Comparison of Cridland's data with those determined here are shown in Figs 11 and 12.

Aquaculture water treatment by ion-exchange

1.0 %.,
Z

61

03.

(a)

QOI QO
1.0

05 1.0 LIQUID PHASE FRACTION{NH Z}

Z Z

05
o,,

b)

O0 O0

05

1.0

LIQUID PHASE FRACTION(NH~)

Fig. 9.

Batch isotherm (a) and normalised isotherm (b)(f.= 0.176)(NH~/Mg 2) of clinoptilolite 'B'.
tO
M

Z Z

Q5
-re~

O0

05 1C LIQUID PHASE FRACTION (Nd')

Fig. 10.

Batch isotherm (Na /K ) of clinoptilolite 'B'.

62

H. T. Dryden, L. R. Weatherley

Figure 11, for the system NH4/Ca 2, shows a higher degree of reversibility in Cridland's data compared with those measured here. It is
significant perhaps that the clinoptilolite used in Cridland's experiment was pretreated by drying at 70C prior to use and it is very possible that exposure to this level of temperature may affect subsequent behaviour. Nevertheless, partial exchange is noted in both cases. Figure 12 shows comparison with Cridland's data for the system + + NH 4/Na ; in this case the current data show a lower degree of reversibility than Cridland's. The differences between these two sets of data may indicate very significant batch-to-batch variations in the properties of clinoptilolite. Whilst a degree of inhomogeneity is quite likely to exist, a more likely explanation is that true thermodynamic equilibrium has not been achieved in any of these cases and that the position of any point on the diagrams may be time-dependent. Skudder (1976) suggested that ammonium exchange on to sodium-based clinoptilolite could be a twostage process with the bulk of the exchange occurring in a fairly rapid first stage followed by a very slow approach to completion. Partial exchange is observed in all the systems studied with the exception of the NH4/K exchange and the Na+/K exchange. In these two cases it appears that total and reversible exchange is achievable (see Figs 1, 5 and 10). This is consistent with other work by Lai and Rees (1976),

TABLE 2
Normalised Exchange Capacities and Isotherm Cut-Off Points

Binary system

Fractional capacity (meq g- ~) Forward exchange Reverse exchange

Normalised capacity (meq g- i)

Clinoptilolite 'A? (max. capacity 2.066 meq g - ~) NH ~/K + Completely reversible NH4/Na 1.67 NH 4/Ca 2+ 0.96 0.99 NH 4/Mg 2 0.22 0.46 Clinoptilolite 'B' (max. capacity 2.159 meq g- ~) NH ~/K + Completely reversible NH~/Na + 1-77 1.079 NH ~/Ca 2+ 0"99 1"04 NH j/Mg'- 0.10 0.43 Na /K + Completely reversible Na /Ca 2+ 0.64 " "Exchange cut-off points could not be determined from the isotherms.

2"066 1"84 0"92 0.415 2.159 1"84 0"93 0"38 2.159

1.40

Aquaculture water treatment by ion-exchange -- H

+

63

+,..~

E <

Z
+

.~_
+

.~~

+,.~.

,-

"6

.~-

~
e.

,..J
z t~

"5~+

r"

<~,~.~_z

64
Solid

H. T. Dryden, L. R. Weatherley
phase f r a c g i o n ( N n 4 ~ )

~X X

0.5 X

Zl
A

0.5

I
I

.0

liquid phase fraction(Nil4)

Fig. 11. Present work: x , N H ~ / C a 2+ exchange; zx, Ca2+/NH~ exchange. Cridland's data ( 1979):

who report 100% exchange in both directions for the NH~/K + exchange. + + The other four systems studied, NH4/Na , N H ] / C a 2+, Na+/Ca 2 and N H ] / M g 2+, all exhibit a degree of partial exchange and irreversibility. In the case of NH4 uptake on to sodium-based zeolite, 80% (clinoptilolite ') and 82% (clinoptilolite 'B') of the maximum possible uptake was achieved. These figures compare with 86% of total capacity for the same system recorded by Skudder (1976) at 0-1 N. In the case of the reverse exchange a cut-off point at 50% total capacity was recorded (clinoptilolite 'B').

Aquaculture water treatment by ion-exchange

solid 1.0

65

phase

fractxon(NH 4

--

/
Fig. 12.

.J.
liquid + phase +

[
0.5

I
1.0

f r a c t i o n (H4*) + +

Present work: / x NH 4/Na exchange; x, Na /NH ~ exchange. Cridland's data (1979):

Similar cut-off points are also noted in the case of NH4/Ca 2+ exchange in both directions; see Figs 3 and 8 for clinoptilolite 'A' and 'B' respectively. Experimental points for the system Na+/Ca 2 on clinoptilolite 'B' at 0.01 N are shown in Fig. 6 and the normalised data indicate that about 65% of available exchange sites can participate in this exchange reversibly. The sigmoid shape of the normalised isotherm indicated that two or more different types of exchange sites may be involved in the

66

1t. T. Dryden, L. R. Weatherley

exchange, resulting in the observed selectivity reversal. Referring to the unnormalised isotherm in Fig. 6, calcium loading onto sodium-based zeolite proceeds selectively until reversal occurs at a zeolite composition of approximately 0"51 sodium ion fraction. The exchange proceeds until 65% of the total capacity is replaced by calcium ion. The normalised isotherm shown in Fig. 6 illustrates much more clearly the selectivity reversal in those sites participating in the exchange. The data for the system NH4/Mg 2 are shown in Figs 4 and 9 for clinoptilolite 'A~ and 'B' respectively. These data show that only about 20% of the available sites participate reversibly in the exchange. The participating fraction of exchange capacity amounts to 0"43 meq g- ~and appears to show preference for the magnesium ion. Other work by Dryden (1984) shows that magnesium ion-exchange with ammonium is greater at 0"05 rq compared with that at 0.01 N. It was further reported that sites loaded with magnesium ion at 0-05 n could not be entirely exchanged subsequently at 0.01 N. A possible explanation for this concentration dependence of capacity could be the formation of stable co-ordinated magnesium/lattice bonds by incorporating hydrated magnesium ion at the higher concentration. The selectivity data presented in Table 3 calculated at an aqueous phase counter-ion fraction of 0'5 show the selectivity sequence to be as follows: K + >NH~- > N a + > C a 2+ > M g 2+ This sequence is entirely consistent with the low charge density structure of clinoptilolite and the consequent preference for ions having a large ionic radius and low hydration energy. The same sequence was determined for clinoptilolite by Ames (1967) at 0.1 N. The order of the above sequence is also significant in that it represents an indicator of the level to which partial exchange occurs in the presence of each ion. The N H ] / K exchange showed complete reversibility. The other NH]/cation systems showed, progressively less exchange in the cation order shown above. Thus it may be concluded that increasing cation hydration energy not only reduces selectivity for clinoptilolite but also reduces the maximum level of exchange which may be achieved. Calculation of the selectivity sequence from the normalised isotherm data yields a rather different pattern. The sequence is as follows: Mg 2+ > K > NH ~ > Ca 2 > Na ~ Thus although only a small proportion of the total sites are available for magnesium uptake it appears that those which are show a high selectivity for the ion.

Aquaculture watertreatment by ion-exchange -- H

67

This observation is significant when uptake of ions from a multicomponent mixture containing magnesium is considered, in that a certain proportion of sites will be very quickly occupied by the magnesium ion. Continuous column experiments have been conducted which demonstrate this behaviour.

ACKNOWLEDGEMENT The authors wish to acknowledge the Science and Engineering.Research Council for financial support for H. T. Dryden during the course of this work.

REFERENCES Ames, L. L. (1967). Zeolite removal of ammonium ions from agricultural and other wastewaters. Proc. 13th PaCific Northwest Indust. Wastewater Conf., Washington State University, Pullman, WA, USA. Barrer, R. M., Rees, L. V. C. & Shamsuzzoha, M. (1966). Thermochemistry and thermodynamics of ion exchange in a near faujasite. J. Inorg. NucL Chem., 28, 629-43. Barrer, R. M., Klimowski, J. & Sherry, H. S. (1973). Zeolite exchangers, thermodynamic treatment when not all ions are exchangeable. J. Chem. Soc., Faraday Trans. 11, 69, 1669-76. Cridland, M. (1979). Ammonia removal from wastewaters. Ph.D. Thesis, Cambridge University. Dryden, H. T. (1984). Ammonium ion removal from dilute solutions and fish culture water by ion-exchange. Ph.D. Thesis, Heriot-Watt University, Edinburgh. Dryden, H. T. & Weatherley, L. R. (1987). Aquaculture water treatment by ionexchange: I. Capacity of Hector clinoptilolite at 0.01-0-05 ~. Aquacultural Engineering, 6, 39-50. Howery, D. E. & Thomas, H, C. (1965). Ion exchange on the mineral clinoptilolite. J. Phys. Chem., 69(2), 531-7. Koon, J. & Kaufman, W. J. ( 1971 ). Optimisation of Ammonium Removal by IonExchange Using Clinoptilolite. University of California, Berkeley, SERL Report No. 17080 DAK. Lai, P. P. & Rees, L. V. C. (1976). Szilard-Chalmers cation recoil studies in zeolites X and Y. Part 2. Recoils from open to locked sites. J. Chem. Soc., Faraday Trans. 1, 72, 1818-26. Mackereth, F. J. H., Heron, J. & Talling, J. E (1978). WaterAnalysis. Freshwater Biological Association, Scientific Publication No. 36. Sherry, H. S. (1966). The ion-exchange properties of zeolites. I. Univalent ionexchange in synthetic faujasite. J. Phys. Chem., 70, 1158-68.

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H. T. Dryden, L. R. Weatherley

Sherry, H. S. (1968). The ion-exchange properties of zeolites. III. Rare earth ionexchange in synthetic faujasite. J. Coll. Interface Sci., 28,288-92. Skudder, A. J. (1976). Ammonium ion-exchange on zeolites. Ph.D. Thesis, Cambridge University.