Wat. Res. Vol. 34, No. 2, pp.

597±601, 2000
# 1999 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S0043-1354(99)00151-7 0043-1354/99/$ - see front matter

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REMOVAL OF DYES AND INDUSTRIAL DYE WASTES BY

MAGNESIUM CHLORIDE
BOON HAI TAN, TJOON TOW TENG* and A. K. MOHD OMARM
School of Industrial Technology, University Science of Malaysia, 11800 Minden, Penang, Malaysia

(First received 1 June 1998; accepted in revised form 1 March 1999)

AbstractÐMagnesium chloride, as compared to alum and polyaluminium chloride (PAC) is a less

commonly used coagulant in the ®eld of wastewater treatment, with a cost in between alum and PAC.
It has been used in this study as a coagulant to investigate the e€ectiveness in the chemical
precipitation method for the removal of colouring matters. The colour concentration of dye solutions
was measured by visible spectrophotometry. Parameters such as the e€ect of pH, the e€ect of coagulant
and coagulant aid dosages and the e€ect of di€erent coagulants have been studied. The results show
that MgCl2 is capable of removing more than 90% of the colouring material at a pH of 11 and a dose
of 4 g MgCl2/l of dye solution. MgCl2 is shown to be more e€ective in removing reactive dye than
alum and PAC in terms of settling time and amount of alkalinity required. Optimal operating
conditions such as pH value, coagulant dose and e€ect of polyelectrolyte have been determined.
Wastewaters of a dyeing and printing mill on di€erent days have been treated by MgCl2 aqueous
solution in bench scale. The treatment of the industrial waste has shown a reduction of 88% in COD
and 95% of suspended solids. # 1999 Elsevier Science Ltd. All rights reserved

Key wordsÐchemical coagulation, colour reduction, textile waste e‚uent

INTRODUCTION industrial wastewater treatment. A number of

The rapidly growing textile industries in Malaysia
produce large amounts of colour e‚uent. The col-
our of the textile e‚uent is unacceptable under
Malaysia environmental regulation besides other
parameters such as COD, BOD, total iron, etc. The
colour e‚uent from the dyeing and printing pro-
cesses has to be decolored before being fed to the
subsequent treatment units, such as the adsorption
and the biological treatment. Decolorization treat-
ment operations include adsorption (Ahmed and
Ram, 1992; Mohammed, 1991; McKay, 1981, 1982,
1984; Rodman, 1971; William, 1979), ozonation
(Lin and Lin, 1993; Snider and Porter, 1974) and
chemical precipitation (Dziubek and Kowal, 1983;
Lu et al., 1989; Wang and Chen, 1983). Each has
its merits and limitation in application.
A study on chemical precipitation technique has
been carried out. This technique uses a coagulant
and produces ¯ocs together with dye materials. The
¯ocs are then separated from the aqueous solution
by means of physical sedimentation. In this study,
MgCl2 is used as the coagulant. The application of
MgCl2 as coagulant has been compared with the
well known coagulants such as alum and PAC.
MgCl2 is a less commonly used coagulant in the
*Author to whom all correspondence should be addressed.
Fax: +60-604-6573678; e-mail: ttteng@usm.my
597
researchers have revealed that enhanced removal of
impurities or pollutants has been observed in the
presence of magnesium. Liao and Randtke (1986)
and others (Folkman and Wachs, 1973; Black and
Christman, 1961) reported good coagulation could
be achieved if enough Mg2+ ion was present in the
system of lime treatment. Dolomite and bittern,
which are enriched in magnesium are found to be
very e€ective in the removal of turbidity and col-
ouring matters (Dziubek and Kowal, 1983; Wang
and Chen, 1983).
Alum (Al2(SO4)3  H2O) is presently the most
widely used coagulant (Edzwald, 1993). It is exten-
sively used in the drinking water and wastewater
treatment, due to its proven performance in treating
water and wastewater of di€erent characteristics
and its low cost. Recently, polyaluminium chloride
(PAC) has been increasingly used at treatment
plants throughout the world. It is a polymerised
form of aluminium. The advantage of this pre-
formed polymeric aluminium over alum may be
due to the partial elimination of polymerisation
process that occurs after the coagulant is added
to the water (Viraraghavan and Wimmer, 1988;
Benschoten and Edzwald, 1990).
Wastewater from the textile ®nishing industry
contains various undesirable chemicals and dye ma-
terials. The characteristics of this wastewater have
598 Boon Hai Tan et al.

Fig. 1. The wastewater ¯ow chart of a typical dyeing and printing mill.

been discussed by Lin and Lin (1993) and Lin and
Chen (1997). The wastewater ¯ow chart of a typical
textile dyeing and printing mill is outlined in Fig. 1.
The major colour e‚uent comes from the dyeing
and printing process. The wastewater from these
processes is separated from other non-colour waste-
water and treated by the decolorization method
before being fed to the biological treatment unit.
Separation of this wastewater can reduce the waste-
water loading to decolorization plant and thus
reduce the chemical cost.
The aim of the present work is to test the ability
of MgCl2 as a coagulant to remove the reactive
dye, Leva®x Brill Blue EBRA and the industrial
dye wastewater. The study focused on the e€ect of
pH, coagulant dosage, amount of coagulant aid
and comparing di€erent types of coagulants. The
e€ectiveness of using MgCl2 as a coagulant is com-
pared with those of alum and PAC.
was measured with a pH meter (Corning pH Meter 220).
For the sample of industrial e‚uent, the colour concen-
tration was measured by HACH DR/2000
Spectrophotometer in the unit of Point Colour (Pt/Co).
The COD and the SS analyses were performed according
to Standard Methods (APHA, 1980).
A six-beaker jar test apparatus was used in this study.
Each beaker contained 150 ml of the dye solution. A
period of 3 min was allowed for the mixing of the coagu-
lant, NaOH and the sample at 80±85 rpm, followed by a
period of 10 min of slow agitation at 30±35 rpm after add-
ing of polyelectrolyte. The solution was then allowed to
settle and the time of settlement (to reach half of the bea-
ker height) was recorded. The supernatant was taken for
analysis.

MATERIALS AND METHODS

Magnesium chloride was obtained from R&M

Marketing, Essex, UK, alum or Al2(SO4)3
16H2O was sup-
plied by Fluka and polyaluminium chloride (PAC-250AD)
was supplied by CCM Chemicals. Polyelectrolyte, Koaret
PA 3230 from Giulini Chemie was used as coagulant aid.
MgCl2 and alum were of analytical grade whereas PAC
and polyelectrolyte was of industrial grade. NaOH and
H2SO4 were of reagent grade. The reactive dye, Leva®x
Brill Blue EBRA was used to prepare the dye solution and
it was supplied by Bayer. Industrial dye wastewater was
collected from the equalisation pond of a dyeing and
printing mill at Prai, Malaysia. The dye concentrations
were measured at a wavelength corresponding to the maxi-
mum absorbance, lmax, by means of a spectrophotometer
(Shimadzu UV-160A). Dilutions were undertaken when
the absorbance exceeded 1.5. The percentage of colour
removal was calculated by comparing the absorbance
value of the supernatant to the standard curve obtained Fig. 2. Colour removal rate of reactive dye by 4.0 g/l
by a known dye concentration. The pH of the solution MgCl2 as function of pH.
 Removal of dyes and industrial dye wastes by magnesium chloride 599

RESULTS AND DISCUSSION

The results of visible spectrophotometry which is

used to measure colour concentration of the EBRA
dye solutions show light absorbance at the wave-
length of maximum absorbance, lmax=600 nm is
proportional to the concentration of the colour.
This phenomenon suggests that aqueous solution of
dyes undertaken in this study obeys Beer's law in
the range of investigation. The Beer's law can be
expressed as: A=abc, where A is the absorbance of
the dye solution, b is the cell path length, a and c
are the absorptivity and the concentration of the
dye solution respectively.
The e€ect of the pH on colour removal
The removal of EBRA dye from a 1.0 g/l dye sol-
ution by an aqueous MgCl2 solution has been stu-
died at various pH. Figure 2 is a plot of the
percentage of the removal of EBRA vs the pH of
the solution. It shows that no colour can be Fig. 3. Colour removal rate of reactive dye, EBRA by
removed until a pH of 9. As the pH value of the di€erent coagulant dosages.
solution increases from 9 to 11, the colour removal
rate increases. The rate decreases as the pH
increases beyond 11. This is probably due to the at 11.0. The results are shown in Fig. 3. The
formation of magnesium hydroxide precipitate that removal rate is shown to increase with the MgCl2
can be expected at pH values greater than 10.5, due dosage. It is evident that for the quantitative
to its solubility constant. When the alkalinity of the removal of more than 90% of a 1.0 g/l EBRA dye
solution containing MgCl2 is increased by adding solution, a minimum dosage of MgCl2 of 3.0 g/l of
NaOH, Mg(OH)2 precipitates are formed. The solu- dye solution is required. Further increase in the
bility of Mg(OH)2 is given by MgCl2 dosage does not produce better removal
  rate, as almost all the dyes have been removed at
Ksp ˆ Mg2‡ ‰OHÿ Š2
this stage. The presence of excessive MgCl2 will
where Ksp is the dissociation constant of the hy- form too much ¯ocs which may result in longer
droxide. Increase in Mg2+ ion or OHÿ ion concen- settling time.
tration beyond the Ksp value favours the formation
of the hydroxide, Mg(OH)2. When the pH value
falls in the range 10.5±11.0, good ¯occulation
occurs. This can be shown in Fig. 2, with 97% of
the colour removal rate at a pH of 11.0. At this pH
value, almost all the magnesium ions are converted
into precipitable hydroxide. It has been reported
(Leentvaar and Rebhun, 1982) that the precipitate
of Mg(OH)2 acts through an adsorptive coagulating
mechanism. Its structure provides a large adsorptive
surface area and its positive electrostatic surface
charge enables it to act as a powerful and ecient
coagulant. At the pH beyond 11.0, the results show
lower removal rate. This phenomenon is probably
due to the increase in the solubility of magnesium
precipitate. The solubility studies on the alum and
PAC also show this phenomenon at the pH beyond
their optimum values (Benschoten and Edzwald,
1990).
The e€ect of the MgCl2 dosage on colour removal
The study of the e€ect of the MgCl2 dosage on
the colour removal rate has been undertaken by
varying the amount of MgCl2 in the solution, whilst Fig. 4. E€ect of amount of Koaret PA 3230 on ¯oc
keeping other conditions constant. The pH is kept settling time.
600 Boon Hai Tan et al.
Fig. 5. Colour removal rate of reactive dye by di€erent co-
agulants as function of pH.
The e€ect of the polyelectrolyte on ¯oc settling time
Polyelectrolyte, Koaret PA is commonly used as
a coagulant aid to improve the coagulation process
and subsequently the ¯oc settling velocity. Higher
settling velocity is desired so that the size of the
settling tank can be reduced. Figure 4 shows the
e€ect of the ¯oc settling time as a function of the
amount of the coagulant aid used. The pH and the
MgCl2 dosage are kept at 11.0 and 4.0 g/l respect-
ively. The result shows that the addition of 1 ppm
of Koaret PA reduces the settling time from 1230 s
to about 90 s. This has an implication of reduction
in the retention time in the settling tanks with cor-
Fig. 6. In¯uence of NaOH on the pH of solution treated
with di€erent coagulants.
Fig. 7. Flocs settling time of di€erent coagulants.
responding savings in capital investment and produ-
cing cleaner water for the subsequent processes.
The comparison of the application of di€erent coagu-
lants
Figure 5 shows the plot of the rate of removal of
EBRA versus the pH values for di€erent coagu-
lants. The e€ective range of the pH for alum, PAC
and MgCl2 are 4.0±6.0, 6.0±9.0 and 10.5±11.0 re-
spectively. If the coagulant such as alum, PAC or
MgCl2 is added to water during coagulation, the
pH of the water is depressed due to the presence of
excess hydrogen ions. Therefore, alkali is always
added to resist the pH depression that occurs
during coagulation. In this case, the alkali used is
NaOH. Figure 5 shows that MgCl2 is more e€ective
in a higher pH range. However the amount of alka-
linity required is less as compared to alum and
PAC. This can be seen in Fig. 6 in which the pH
value after adding of the coagulant is plotted
against the amount of NaOH, less amount of
NaOH is needed to increase the pH of solutions
containing MgCl2 than to the solutions containing
alum or PAC. Fig. 7 shows the settling time of the
¯ocs as a function of the coagulant dosage of di€er-
ent coagulants, with the same amount of Koaret
PA, 1 ppm used. The settling times of the ¯ocs trea-
ted with PAC and alum are about the same, in the
range of 13±24 min whereas for the system treated
by MgCl2, the settling time is less than 3 min.
Higher dosage of MgCl2 shows a higher settling
time. This could be due to the excessive Mg(OH)2
in the solution.
The treatment on an industrial dye waste
A similar test has been carried out on e‚uents
from a dyeing and printing mill. The colour e‚uent
 Removal of dyes and industrial dye wastes by magnesium chloride 601

Table 1. The percentage removal of colouring matters from a dye e‚uent by MgCl2

Test Samplea Raw Treated % Removal Average (%)

Colour Pt/Co (point colour) 1 7200 100 98.6

2 6600 130 98.0 97.9
3 7700 190 97.5
4 8100 220 97.3
COD (ppm) 1 2040 250 87.7
2 2450 220 91.0 88.4
3 2330 230 90.1
4 3190 270 84.6
SS (ppm) 1 530 35 93.4
2 620 26 95.8 95.5
3 590 19 96.8
4 620 25 96.0

a
E‚uent from a dyeing and printing mill, Prai, Malaysia.

was collected from the equalisation pond of the
mill. A preliminary test shows that 1.5 g MgCl2/l of
the wastewater at a pH of 11.0 is the optimum con-
dition for this process. Therefore the samples were
collected on di€erent days and treated with 1.5 g
MgCl2/l of waste at a pH of 11.0. The results are
summarised in Table 1. An average reduction rate
of 97.9% for colouring matters, 88.4% COD and
95.5% suspended solid are registered.
CONCLUSION
The removal rate of the reactive dye by chemical
precipitation technique depends signi®cantly on the
pH value of the dye solution. The e€ective range of
pH for the MgCl2 treatment is between 10.5 and
11.0, and beyond the range, the percentage of col-
our removal decreases tremendously. Flocs formed
by the MgCl2 treatment are found to give shorter
settling time than the alum and PAC treatment.
The MgCl2 treatment has been used on the indus-
trial dye waste, the removal rates of 97.9% for col-
ouring matter, 88.4% in COD, and 95.5%
suspended solid can be achieved.
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