~~:er Res. Vol. 19. No. 7. pp. 869-873.

1985 Pnn'ed in Great Britain All rights reserved

0043-1354 85 53.00+0.00 Copyright c~ 1985 Pergamon Press Ltd

COPPER(II) REMOVAL FROM AQUEOUS SOLUTIONS BY FLY ASH

K. K. PANDAY, GUR PRASAD and V. N. SINGH Applied Chemistry, Institute of Technology, Banaras Hindu University. Varanasi-221005, India (Received June 1984) A~tract--The removal of Cu(II) by adsorption on fly ash has been found to be concentration, pH and temperature dependent. The kinetics of adsorption indicates the process to be diffusion controlled. The Langmuir constants have been calculated at different temperatures, and the adsorption has been found to be endothermic (AH = 15.652 kcal mol-~). The maximum removal is observed at pH 8.0, and variation in adsorption with pH has been explained on the basis of surface ionisation and complexation. Key words--fly ash, Cu(II), adsorption dynamics, mass transfer coefficient, pore diffusion, Langmuir isotherm, surface ionisation, complexation

NOMENCLATURE t= q= q, = Co = C, = K= K' = m= k= /3~ = S~ = W= V= dp = pp = ~p= C, = Q: =

b b'm

AH= AG= AS= T=

time (min) amount of Cu(II) adsorbed at time, t (mgg -~) amount of Cu(II) adsorbed at equilibrium (mg g- ~) initial concentration of Cu(II) (rag 1-i) concentration of Cu(II) at time, t (rag 1-~) rate constant of adsorption (rain-t) rate constant of pore diffusion (rain -~-') mass of fly ash particle per unit volume of particlefree slurry (g I -t) Langmuir constant (Q~b) (1 g-i) mass transfer coefficient (cm s-i) outer surface of silica particles per unit volume of particle-free slurry (cm -1) weight of adsorbent (g) volume of particle-free solution (1.) particle diameter (cm) density of fly ash particles (g I -I) porosity of fly ash particles (era era-~) equilibrium concentration of Cu(II) (mg I-~) Langmuir constant related to the adsorption capacity (rag g-t) Langmuir constant related to the energy of adsorption (I rag-t) adsorption energy constant (1 rag-t) enthalpy change for adsorption of Cu(II) on fly ash (kcal tool-i) free energy change for adsorption of Cu(II) on fly ash (kcal tool -~) entropy change for adsorption of Cu(II) on fly ash (cal mot- t) solution temperature (K) metal ion of charge, Z.
INTRODUCTION

enough in natural waters (Camp, 1964). McKee and W o l f (1963) reported the permissible limit of copper to be 1.0 mg I -~. The methods for Cu(II) removal from wastewaters include precipitation, ion exchange, electrolysis, adsorption on activated carbon etc. (Dean et al., 1972). Adsorption at solid-solution interface is an important means for controlling the extent of pollution due to metallic species of industrial effluents (Elliot and Huang, 1981; Krauskopf, 1956; Panday et al., 1983). The use of activated carbon is not suitable for developing countries due to its high cost. The huge deposit of fly ash around thermal power plants poses problems in its disposal. Besides its utilisation in preparing bricks, Portland cement, puzzolona etc., it has also been recently used in water pollution control (Chu et al., 1978; Panday et al., 1984; Jain et al., 1979, 1980). The aim of the present work is to study the removal of Cu(II) by fly ash at different concentrations, temperatures and pH of the solution, and to investigate the mechanism of Cu(II) adsorption at fly ash-solution interface.
EXPERIMENTAL

The potential sources of copper in industrial waste streams include metal cleaning and plating baths, pulp, paper and paperboard mills, wood pulp production, fertilizer industry etc. (Dean et al., 1972). Excessive intake of copper results in its accumulation in the liver. The chronic copper poisoning is related to hemochromatosis and produces gastrointestinal catarrh when present in large amounts (Camp, 1964). It is also toxic to fish life when its content is small

Fly ash was obtained from Obera Thermal Power Plant, Mirzapur (U.P.). The adsorbent was sieved through 53 # sieve and used as such without any pretreatment. The average particle size was measured by HIAC-320, Model 8002917 (ROYCO Institute Division, U.S.A.) and the surface charge was characterised by electrophoretic measurements (Fig. 6) using Lazer Zee Meter, Model 500 (Penkem, Inc., New York, U.S.A.). The surface area was determined by a "three-point" N., gas adsorption method using a Model QS-7 Quantasorb Surface Area Analyzer (Quantachrome Corp., U.S.A.) and the porosity was determined by Mercury Porosimeter. The constituents of fly ash were analysed following standard methods. Batch adsorption experiments were carried out by shaking 1.0 g fly ash with 50mi aqueous solutions of copper sulphate of desired concentrations in different polythene bottles. Initial pH of the solution was adjusted with 0.05 and 0.I M HCIO4 and NaOH respectively using a pH meter. The samples were

869

870 Table 1. Characterisationof fly ash Constituent o by ,,,eight

SiO, AI.,O3 CaO Fe,O~ MgO Loss on ignition Mean particle diameter Surface area Porosity Density pHz~ 56.04 25.90 2.22 1.26 0.94 13.64 48 x 10-~cm 5.77 m" g-~ 0.38 3.42 gcm -J 2.40

K.K. PA.~DAYet al.

J9 :J 3 6 [ I

-o.8

-~.z i

~'~ -I=

,21
0

2o!
I 10 I 20
Time

I 30
[rain)

40

E 50

,3.6

shaken at 125rpm in a temperature-controlled shaking machine. The progress of adsorption during the experiment was determined by withdrawing a certain volume of adsorbate solution, centrifuging at 15,000rpm and analysing the supernatant spectrophotometrically (APHA, 1980). Blanks without fly ash were also prepared to correct for any adsorption in polythene bottles.
RESULTS A N D DISCUSSION

Fig. 2. Kinetics of Cu(I[) adsorption. (a) Lagergren plot (O) and McKay et al. plot (A). (b) Weber et al. plot. Conditions: 1.0 x 10-* M CuSO4, 0.5 M NaCIO~, 6.5 pH. 30:C. For rate constant of pore diffusion

C,

K,tOs.

(2)

Co
For mass transfer coefficient

It is clear from Table 1 that fly ash mainly contains alumina and silica and other oxides are present in trace amounts. It is thus expected that Cu(ll) will be mostly adsorbed either by alumina, silica or by a combined influence of these oxides.

l -F mk

=In l+m~

fltS~t.

(3)

The values of m and S, were calculated from equations given below: W m = -V S, = 6m (4) (5)

Effect of concentration
The removal of Cu(II) by fly ash decreases from 100 to 89.69% (Fig. 1) by increasing the Cu(II) concentration from 1.0x 10 -4 to 2.0 x 10-4M at pH 6.5 and 30C. This shows that the removal of Cu(II) is highly concentration dependent. It may be noted from the figure that the equilibrium is established in 60 min and the period of equilibration is concentration independent.

dppp( l -- ep)"

Adsorption dynamics
The rate constants of adsorption, pore diffusion and mass transfer coefficient of Cu(II) were determined at 30"C using equations of Lagergren (1898), Weber and Morris (1962) and McKay et al. (1981) respectively which are as follows: For rate constant of adsorption K log(q~ - q) = log q, - ~ t.
g-- Q 8

(1)

E O.6

o.-

0.4
G o-

E O.2 E '~
I I I
I

A straight line plot of log ( q , - q ) v s t [Fig. 2(a)] suggests the applicability of Lagergren equation, however, the plot of Ct/Co vs t -5 [Fig. 2(b)], although linear for a wide range of contact period, do not pass through the origin, indicating that the pore diffusion is not the only rate controlling step (Poots et al., 1978). The rate constant of adsorption and pore diffusion were calculated from the slopes of the respective plots and found to be 6.931 10-2 min -~ and 0.200 rain-t!'- respectively. These rate parameters have different units, therefore, the rate values cannot be compared. The plot of ln{(C,/Co)-[1/(1 + mk)]} against t also gives a straight line [Fig. 2(a)] up to the limit C/Co >> 1/(I + mk). The mass transfer coefficient was calculated from the slope and intercept of the plot and found to be 3.89 x 10--'cms -t. This suggests that the velocity of mass transfer of Cu(II) on fly ash is rapid enough to use the adsorbent for the treatment of wastewater enriched in copper. The product fl~S, has the unit of rate (time -t ) and is equal to 7.69 x 10--'rain -~, indicating that the rate of adsorption is diffusion controlled (fl~S~ ~ K).

20

aO

60

80

100

12o

140

Langmuir model
The data for the uptake of Cu(II) by fly ash has been analysed in the light of Langmuir mode of adsorption. The rearranged Langmuir equation may

Time (rain)

Fig. 1. Effect of concentration on removal of Cu(ll) by fly ash: ([~) 1.0 x I0 -~ M; (~) 1.5 x 10-~ M; (O) 2.0 x 10-4 M. Conditions: 0.05 M NaCIO4, 6.5 pH. 30C.

Copper(II) removal by fly ash

IOO

871

32 00 ~ 24 o

6o

Z ~6
u 8

N 40 20

10

15

20

25

50

I 35

C (rag 1-1)

0 3

6 pH

10

Fig. 3. Lan~'nuir pJot for the adsorption of Cu(Jl) on fly

ash, (C)) 20:C, (/k) 30C, ([~) 40C. Conditions: 0.05 M NaCIO~, 6.5 pH. be described as C 1
- +

Fig. 4. Speciation of Cu(II) as a function of pH. In(l/b) = A G / R T aS

-

(9)

C
(6)

The plot of C/q, against C gives straight line (Fig. 3) at each temperature showing the applicability of Langmuir isotherm. The values of Q ' and b at 20, 30 and 40:C are given in Table 2. The validity of Langmuir isotherm was further confirmed by regression analysis of the data at 30~C (Panday et al., 1984). The regression equation relating C/q, and C at 30C is found as C/q, = 0.7187643C + 1.9596628. (7)

By comparing equations (6) and (7), the values of Q and b were found to be 1.3913mgg -~ and 0.36681mg -~ respectively which are in good agreement with the graphical values at 30C. Effect of temperature The adsorption capacity, Q, of fly ash for the uptake of Cu(II) increases from 1.2547 to 1.5341 mg g-~ by increasing temperature from 20 to 4 0 C indicating the process to be endothermic (Bye et al., 1982; Dutta, 1954; Tewari et al., 1952). The increase in uptake of Cu 2+ ions with temperature may be due to the desolvation of the adsorbing species, changes in the size of the pores, and enhanced rate of intraparticle diffusion of adsorbate (Knocke and Hemphill, 1981). The change in apparent enthalpy, free energy and entropy of adsorption were calculated using following relations: In b = In b' - & H / R T (8)

AH -- AG (t0) T The enthalpy change of adsorption, as determined from the slope of lnb vs I/T is equal to 15.652kcalmol -~ which suggests the possibility of strong bonding between adsorbate and adsorbent. Tewari et al. (1952) have reported AH equals to 14.9 kcal tool -~ for the adsorption of Co(II) on alumina. The values of AG are negative and small (Table 2) which suggests the process to be spontaneous with a high preference of Cu(lI) for fly ash. Further, the free energy change decreases with the rise in temperature showing increase in feasibility of adsorption at higher temperatures (Singh et al., 1982). The positive value of entropy change (Table 2) suggests some structural changes in adsorbate and adsorbent. Effect o f p H The removal of pollutants from wastewaters by adsorption is highly dependent on pH of the solution which affects the surface charge of the adsorbent, and the degree of ionisation and speciation of adsorbate (Fig. 4) as suggested by Elliott and Huang (1981). With increase in pH of the solution from 3.0 to 8.0 the extent of removal increases from 13.93 to 100~ (Fig. 5) at 30C and concentration 2.0 10 -~ M. It is often suggested that the adsorption of metal ions at the solid-solution interface is not governed by the "free" metal concentration, but by the much stronger adsorbed hydroxo, sulfato, carbonato and other metal species (Stumm and Bilinski, 1972): M~ + n H 2 0 ~ - M ( O H ) ~ , z - " ) + n H +. z+ (I1) The pHm,~ where maximum adsorption of the metal takes place seems to be related to the pK of the first

Table 2. Langmuir constants and thermodynamic parameters at different temperatures Thermodynamic Langmuir cgnstant parameters
Temperature (:C) 20 30 40 Q~ ( m g g -I ) 1.2547 1.3854 1.5341 b (ling -t ) 0.1538 0.3692 0.8150 - AG (kcal tool -~ ) 5.3568 6.0677 6.3292 AS (cat mol -L ) 71.70 71.68 70.23

8.'2
--08 i = 0.6

K.K. PAND~.Yeta/.

2F
!

"~ ~ o

0.4

o
d

E 0.2 E <
o

I 3

I 4.

I 5 pH

I 6

I 7

=L I
-3 I 3 1 5 I 7 pH l 9 r 11

Fig. 5. Removal of Cu(lI) by fly ash as a function of pH. Conditions: 2.0 10-~M CuSOa, 0.05 M NaCIO4, 30:C. hydrolysis product of the metal (e.g. CuOH + = pK 8.0). The exact nature and distribution of hydroxo complexes depend on the concentration of the ligands, i.e. solution pH (Fig. 4) and on the soluble metal concentration. The presence of hydroxide ion seems to be the key reason for the enhanced removal. Menzel and Jackson (1950) proposed that the presence of one hydroxyl ion would alter one absorbed cupric ion to be more readily accommodated in the surface lattice which follows further adsorption. An alternative interpretation for the coincidence of adsorption and hydrolysis involves surface complex formation between "'free" metal ions and deprotonated surface functional groups as ---~SiOH + M z~ ~ (--,SiO)M~Z-~+ H + 2(--*SiOH) + M z+ ~ - (--~SiO):M~z-'~ + 2H +. (12) (13)

Fig. 7. Effect ofpH on solubility of(C)) alumina, (A) silica. Conditions: 0.5 g t -~ solid. 0.05 M NaCIO4, 30:C. scheme may be written as Cu(OH)_, + 2 ~ SiO- ~ (---*SiO)2Cu(OH)~-. (14)

The other reactions taking place prior to pHm~, may be written as Cu(OH) + + 2 ~ SiO- ~ ( S i O ) : C u O H pH range 4-5.5, Cu-'+ + 2 ~ SiO- ~ ( ~ SiO):Cu (16) (15)

It is interesting, however, to note that the above two views are simply the two faces of the same coin. Similar results have been reported by James et al. (1973) for the adsorption of Cu(II) on silica surface considering the hydroxo species in one case and the deprotonated surface in the other. The electrophoretic mobility results (Fig. 6) indicate PHzpc for fly ash to be 2.4 while for pure alumina and silica the PHzt,c are 2.2 and 8.3 respectively. The variation of solubility of alumina with pH (Fig. 7) shows a maximum near the neutral pH region suggesting a relatively small number of aluminum sites available for adsorption of Cu(II) whereas in case of silica the change is not pronounced. It appears that for the maximum adsorption of Cu(II) the major
30 A

pH range 3-3.9. Taking into account the dominating metal species (Fig. 4) in the pH range of interest, SiOH groups are probably unimportant towards Cu(II) adsorption within the pH range of interest, although Schindler et al. (1976) have considered them in their work. As the surface of alumina is positively charged in the pH range studied for Cu(II) adsorption, the adsorption cannot be described by electrostatic attraction. It appears that at pH < 8 the oxide surface is protonated and the major adsorption scheme may be written as Cu 2+ + A I O H ~ A I O C u + + H +. (17)

CONCLUSIONS

'E t~
i > i O

E
fl_ t~

-30

The use of fly ash as an adsorbent for the removal of Cu(II) from aqueous solutions was studied and 100% removal was noted when the solution concentration was initially of the strength of 1.0 x 10-4M, temperature 30C and I = 0.05 M. The rate constant of adsorption and diffusion were nearly equal indicating the rate of uptake of Cu(II) to be diffusion controlled. The positive change in enthalpy suggests the formation of strong bonds between adsorbate and adsorbent. The hydrolysed species of Cu(ll) are involved in complexation with surface active sites of fly ash. The data thus obtained will be helpful in designing and performance of fixed-bed adsorber.
Acknowledgements--The authors are thankful to Professor C. P. Huang, Environmental Engineering Division, University of Delaware, U.S.A., for helpful discussion and laboratory facilities, and to the Council of Scientificand Industrial Research, New Delhi for financial help.

-6,0

4 pH

Fig. 6. Electrokinetic behavior of fly ash. Conditions: 1g 1-1 fly ash. 0.05 M NaCIO4, 30:C.

Copper(lI) removal by fly ash

REFERENCES

873

APHA (1980) Standard Methods for the Examination o f Water and Wastewater, 15 Edition. American Public Health Association, Washington. DC. B)e G. C., McEvoy M. and Malati .%1.A. (1982) Adsorption of copper(If) from aqueous solutions on five silica samples. J. chem. Tech. Biotechnol. 32, 781. Camp R. T. (1964) Water and its Impurities, 2nd Edition. Reinhold, New York. Chu T. J., Steiner G. R. and McEntyre C. L. (1978) Removal of complex copper-ammonia ions from aqueous solutions with fly ash. J. Wat. Pollut. Control Fed. 50, 2157. Dean J. C., Bosqui F. L. and Lanovette K. H. (1972) Removing heavy metals from wastewater. Ent'ir. Sci. Technol. 6, 518. Dutta R. (1954) Effect of temperature and ageing on the adsorption of Cu(II), oxalate(ll) and dichromate(II) by different samples of berylium oxide. J. Indian chem. Soc. 31, 211. Elliott H. A. and Huang C. P. (1981) Adsorption characteristics of some Cu(ll) complexes on alumino silicates. Water Res. 15, 849. Jain K. K., Singh V. N. and Prasad G. (1979) Application of fly ash instead of activated carbon for oxalic acid removal. J. chem. Tech. Biotechnol. 29, 36. Jain K. K., Singh V. N. and Prasad G. (1980) Application of Langmuir isotherm for oxalic acid adsorption by fly ash and activated carbon. Indian J. Chem. 19A, 154. James R. O., Steglich P. J. and Healy J. W. (1973) Analysis of models of adsorption of metal ions at oxide-water interface. Trans. Faraday Soc. 59, 142. Knocke W. R. and Hemphill L. H. (1981) Mercury sorption by waste rubber. Water Res. 15, 275. Krauskopf K. B. (1956) Factors controlling the concen-

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