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Production of Industrial Coagulant (Poly Aluminium Chloride) From Used

Beverage Cans

Article in Journal of Scientific & Industrial Research · July 2019

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Journal of Scientific & Industrial Research
Vol. 78, July 2019, pp. 448-453

Production of Industrial Coagulant (Poly Aluminium Chloride)

From Used Beverage Cans
H Deena1, P Khadeeja 1, PK Fahmi Leena 1, JS Lekshmi 1 and N Sreekumar2*
1
Department of Biotechnology, Sree Chitra Thirunal College of Engineering, Trivandrum, Kerala, India
*2
School of Bio and Chemical Engineering, Kalasalingam Academy of Research and Education (KARE), Anand Nagar,
Krishnankoil-626126, Tamil Nadu, India

Received 10 August 2018; revised 25 March 2019; accepted 03 June 2019

Because of the positive contribution of aluminium products to modern living, their demands are growing steadily. The
second most widely used metal is aluminium and the most recycled consumer product in the world is aluminium can.
Aluminium (Al) manufacture and expenditure are considered to be two sides of a coin and both are increasing. In this work,
a novel method for the reuse of aluminium scrap is proposed. The used aluminium cans are crushed into fine powders and
converted to aluminium chloride (AlCl3). The prepared AlCl3 was used to produce poly aluminium chloride (PAC), a
coagulant. This study also includes an investigation of the effect of different varying parameters such as coagulant dosage,
pH of the solution, temperature and mixing speed. Using the predetermined optimal conditions coagulation-flocculation of
industrial effluent was carried out, and the COD removal efficiency was calculated; and compared with that of commercially
available flocculants. The cost analysis for the production of 1L of synthesised PAC and commercially available PAC is also
included in this work.

Keywords: Aluminium, poly aluminium chloride, coagulation, COD, flocculant dosage, recycle

Introduction the sample wastewater. Used beverage cans were

The industrial and technological development over collected from APM Restaurant, Pappanamcode
the last few decades has been phenomenal but has (8°28'13.8"N 76°58'50.2"E) and crushed in a Metal
caused depletion of natural resources at an workshop in Industrial Estate, Pappanamcode.
unprecedented rate1, 2. Development of sustainable Potassium antimonyl tartrate, Ammonium molybdate,
wastewater treatment and reuse technology is essential Ascorbic acid, Sodium salicylate, Aluminium chloride,
in our generations’ battle to conserve natural Aluminium sulphate and all other required chemicals
resources 3, 4. Globally, the aluminium industry were purchased from SRL Chemicals, Chennai.
produces 100.5 billion cans, or 1.5 million tonnes.
About 60% of used beverage containers are processed Methods
back again into aluminium cans by aluminium recycling Extraction of aluminium chloride from used beverage cans
5
. However, they can also be used in the synthesis of Initially, 20 used beverage cans were taken. The lid
aluminium based coagulants like alum, poly aluminium portion was cut off, and the paint on the cans was
chloride etc. 6, 7. The process newly proposed is helpful removed manually by scrubbing. Then, they were
to recycle wasted resources and protect the environment, crushed into fine powder using can crusher. The powder
and also can reduce production cost by lowering the cost was collected and then subjected to sieve analysis to
of purchasing raw materials. It will help to reduce the determine the average particle size. Aluminium solution
toxicity and hazardous nature of industrial effluents to a was prepared by dissolving 30g of can powder (to be
greater extent 8, 9. added in portions to preheated (65–70℃) HCl solution
with constant stirring) in 105 ml of commercial HCl
Materials and methods (38%). The following reaction takes place:
Materials
The industrial effluent from HLL Lifecare limited, 2Al + 6HCl → 2AlCl3+ 3H2
Peroorkkada (8°31'40.7"N 76°58'03.9"E) was used as
Preparation of poly aluminium chloride (PAC)
––––––––
*Author for Correspondence 100ml of 0.25M aluminium chloride (3.33g)
E-mail: [email protected] (from can aluminium + pure hydrochloric acid
 SREEKUMAR et al.: PRODUCTION OF INDUSTRIAL COAGULANT FROM BEVERAGE CANS 449

38 - 35%) solution were placed in 500ml glass beaker. phosphate solutions were pipetted into a 100ml
Then, the solution was heated to 85℃ in a water bath. volumetric flask, equivalent to 1-6ppm.
After 20 minutes, 240ml of 0.25M Sodium hydroxide
solution (2.4g) was added slowly under continuous Preparation of Combined Reagent
stirring and accurate temperature control 70℃ to yield 0.27g of potassium antimonyl tartrate was diluted
the required flocculant, i.e., poly aluminium chloride. with 100ml distilled water to prepare potassium
antimonyl tartrate solution. Ammonium molybdate
Characterization of industrial effluent solution was prepared by dissolving 4g of ammonium
The physical and chemical characteristics of molybdate in 100 ml water. 1.76 g of ascorbic acid
industrial effluent like pH, TSS, amount of was dissolved in 100ml to get ascorbic acid solution.
phosphates, sulphates, ammonia, nitrates etc. are Combined reagent was prepared by mixing 50ml of
calculated. All the methods were performed according 5N sulphuric acid, 5ml potassium antimonyl tartrate
to Standard Method for The Examination of Water solution, 15ml ammonium molybdate solution, and
and Wastewater (20th Ed)10. 30ml of the ascorbic acid solution.
Determination of total suspended solids Phosphate Analysis
The total suspended solids (TSS) are the retained 10ml of each of the standards, blank and samples
materials on a filter after filtration of a well-mixed were measured into a test tube. 2ml of combined
sample. The well-mixed sample was filtered through a reagent was added to the standards, blanks and
weighed Whatman filter paper and the residue samples. One drop of phenolphthalein indicator was
retained on the filter was dried at 100℃. The increase added to the solutions. A pink colour was developed.
in weight of the filter represents the total suspended In order to dissolve the colour, sulphuric acid (5N)
solids 10. was added. After ten minutes, the absorbance of each
Determination of total dissolved solids solution was measured at 620nm using colorimeter.
A well-mixed sample was filtered through a filter
Estimation of ammonia
paper, and the filtrate was evaporated to dryness in a Initially, the burette was filled with 0.1N NaOH
weighed dish at 100℃. The increase in dish weight solution. Then, 10 ml of the sample was pipetted into a
represents the total dissolved solids10. beaker. Two drops of phenolphthalein indicator were
Determination of chemical oxygen demand added to the content of the beaker. The sample in the
20ml of industrial effluent was taken in a conical beaker was titrated against the standard alkali in the
flask. 10ml of 0.25N Potassium dichromate and 30ml burette until it is just pink. Take the reading of the
of dilute sulphuric acid (50% v/v) were also added to burette (R1). To the contents of the beaker, 2 ml of
it. The solution was refluxed for 1.5 hours in the 40% formaldehyde was added. The pink colour
presence of a trace amount of silver sulphate and disappeared. It was again titrated with the standard
allowed to cool down to room temperature. The alkali until the pink colour just reappears. Take the
unreacted potassium dichromate is then titrated burette reading (R2). The difference between the
against 0.025N Mohr’s salt solution by adding Ferroin second and first reading (R2-R1) is the volume of
indicator. Ferroin gives a colour change from blue- standard alkali (R) equivalent to the ammonia content
green to red-brown at the endpoint 11. The same of 10ml of the sample 12.
procedure was followed to determine the chemical Amount of ammonia in the sample (in mg/ml) =
oxygen demand of untreated industrial effluent and (R2-R1) * 0.17
also that of the industrial effluent treated with
commercial PAC 10. Estimation of nitrates
The effluent sample was treated with sodium
Estimation of phosphates salicylate in an acid medium (pH around 5), the
Preparation of Phosphate Standards mixture was made alkaline (pH 8) and the yellow
1000ppm of standard phosphate solution was colour obtained was measured using a colorimeter at
prepared by weighing 1.43g of potassium dihydrogen 420 nm. A blank (without sample) with all the
orthophosphate and diluting to1000ml in a standard reagents and distilled water was also conducted. A
volumetric flask using distilled water. 0.1ml, 0.2ml, calibration curve is determined with standard nitrate
0.3ml, 0.4ml, 0.5ml and 0.6ml of the standard solution 13.
450 J SCI IND RES VOL 78 JULY 2019

Nitrate nitrogen (as N) mg/L = w/v 6 at 35℃. 14. Flocculation of latex effluent was carried
Where, w = weight in mg of nitrogen (as N) as read out using each coagulant separately at their optimum
from the curve, and v = volume in mL of the sample conditions.
taken for the test.
Results and Discussion
Study of the effect of various parameters on flocculation Preparation of poly aluminium chloride (PAC)
Effect of flocculant dosage From 20 cans, 190 g of aluminium powder was
1, 2, 3, 4 and 5ml of poly aluminium chloride was obtained after grinding. On sieving, this 190g of
added respectively to 5ml of the sample. One tube aluminium powder using a sieve shaker apparatus,
was taken as zero flocculant control. Water was added particles of different sizes were retained in sieves of
to give a total liquid volume of 10ml in each tube. different mesh sizes. By studying the particle size
Samples were mixed thoroughly by inverting the distribution, it was found that the maximum amount
tubes 20 times and centrifuged at 1000rpm, to remove of particles retained was on the sieve of mesh size
suspended solids, if any. Optical density was recorded 90µm, and the amount of aluminium obtained was
at 600nm for the top 2ml of the supernatant, including 112g. Using 30g of aluminium and 105ml of
control. The flocculant volume corresponding to Hydrochloric acid, 90ml of aluminium chloride was
which optical density was identified, and optimum obtained. This 90ml is then made up to 100ml
flocculant dosage was determined. aluminium chloride using 0.25M sodium hydroxide.
Then 340ml of poly aluminium chloride was prepared
Effect of pH by treating 240ml of sodium hydroxide with 100ml of
The adjustment of pH was conducted from 2 to 10 aluminium chloride.
with 0.1M HCl and 0.1M NaOH solution. For optimal
pH selection, constant dose of poly aluminium Characterization of latex effluent
chloride (30 mg/ml) was added to the sample and Wastewater collected from the latex industry
flocculation was carried out at various pH. The best was characterised for their pollution characteristics
output corresponding to maximum removal was (Table 1). The parameters analysed were pH, COD,
selected as optimum pH. total suspended solids (TSS), Dissolved solids (DS),
ammonia, nitrates and phosphate contents. Results of
Effect of temperature the analysis show that the COD, TSS and DS were
The influence of temperature variation on 3216mg/ml, 2420mg/ml and 995mg/ml respectively.
coagulation-flocculation was analysed at temperatures These values show that the wastewater has pollution
ranging from 20℃ to 60℃ with intervals of 10℃. For potentials and so need to be treated before discharge
the determination of optimal temperature, constant into the environment. The values for ammonia, nitrate
dose of poly aluminium chloride was added to the and phosphate were 2.49mg/ml, 1.36mg/ml and
sample and flocculation was carried out at a fixed pH 1.32mg/ml respectively.
of 6.
Study of the effect of various parameters on coagulation-
Effect of mixing speed flocculation
Experiments were performed at constant pH of 6 Effect of temperature
and temperature of 35℃ with optimum flocculant Results showed that as the temperature rises from
dosage. In each experiment, speed was varied from 40 20℃ to 60℃, efficiency for COD reduction lowers
to 200rpm with an increment of 40rpm while mixing from 31.8% to 27.98% Figure 1. This means that high
time of 3 minutes was used. Table 1 — Characterization of latex effluent
Comparison of PAC with other coagulants Parameter Value
Three commercial coagulants, namely, aluminium pH 10
chloride, aluminium sulphate (alum) and ferric COD (mg/ml) 3216
chloride, were selected for comparing with PAC. The Total suspended solids (mg/ml) 2420
optimum pH, temperature and mixing speed was Dissolved solids (mg/ml) 995
obtained from the literature. Reports show that Ferric Ammonia (mg/ml) 2.49
chloride, alum and aluminium chloride has optimum Nitrate (mg/ml) 1.36
mixing speed of 120, 140 and 140rpm at pH 4, 4 and Phosphate (mg/ml) 1.32
 SREEKUMAR et al.: PRODUCTION OF INDUSTRIAL COAGULANT FROM BEVERAGE CANS 451

Fig. 1 — Effect of various parameters

temperatures have adverse effects on settling the most important parameters considered. The
condition. It can be due to the reduction in viscosity insufficient dosage or overdosing would result in the
and consequently, bio-flocculation reduction and poor performance in flocculation. It was a crucial task
settling. The maximum COD removal was obtained at to determine the optimum dosage of PAC in
20℃. treatment. The effect of dosage was measured at pH 7,
room temperature and 120 rpm of mixing speed. The
Effect of pH
The pH not only affects the surface charge of PAC optimum flocculant dosage was obtained as 30%
but also affects the stabilisation of suspension. As the (v/v). The results are represented in Figure 2.
pH was varied from 2 to 10, first there was an Comparison of PAC with other coagulants
increase, and then a decrease in coagulation The objective of this step was to compare PAC
efficiency. The reduction in COD was observed to be with other commercially available coagulants, namely
good at pH 6 to 8, with a maximum of 31.592%. The Aluminium chloride, Aluminium sulphate (alum) and
results are presented in Figure 1, which shows the ferric chloride that can be used to coagulate the
effect of pH on COD level reduction. suspension particles in the latex wastewater. It was
Effect of mixing speed understood from the literature survey that the
Mixing speed is one of the important factors in behaviour of coagulant according to many factors
achieving higher flocculation efficiency during the including pH, temperature, mixing speed and the
coagulation-flocculation process15. Figure 1 shows characteristics of wastewater. So, the coagulation was
that, at a lower mixing speed of 40rpm, the COD of carried out at their optimal conditions and a constant
the effluent was 2490mg/ml, showing a removal coagulant dosage.
efficiency of 22.57%. Also, at a higher mixing speed Out of the four coagulants, Ferric chloride was
of 200rpm, the value of COD was 2660 mg/ml, thus found to have maximum COD removal efficiency,
suggesting a decrease in the efficiency of the i.e., 43.65%. Poly aluminium chloride synthesised
coagulant to 17.28%.The best result of the mixing also had a comparable efficiency of 36.97% Figure 3.
speed was at 120rpm, with 35.38% removal The least efficiency was observed for alum and
efficiency. Hence, it was observed that, at lower aluminium chloride. Ferric chloride is highly acidic
mixing speeds (below 80rpm), the collisions between and hence is corrosive such that it needs to be stored,
the flocculant and suspended particles are low and pumped and conveyed in synthetic corrosion-resistant
lead to the lower flocculation rate while at higher materials. However, PAC works exceptionally well at
mixing speed (above 160rpm), the flocculate chains low raw water temperatures and is non-corrosive.
tend to break and limiting the size of the flocs formed.
Process economics
The small size flocs are not dense to settle down in
wastewater and thus, indirectly cause the sample to be Comparison of the performance and efficiency of
PAC with other commercially available coagulants
turbid again.
was studied and was found that ferric chloride has a
Effect of flocculant dosage removal efficiency of 43.65%. Also, PAC synthesised
To determine the optimum condition of PAC in has a comparable removal efficiency of 36.97%.
coagulation and flocculation, dosage was one of In this context, it is important to note that this study
452 J SCI IND RES VOL 78 JULY 2019

Table 2 — Cost analysis for the production of 1L PAC

Material / equipment Specification Cost (in rs.)
Heating Mantle 1000ml, 350W 0.437
Sieve Shaker 3kg, 180W 0.3
Can Crusher 200-300kw/hr., 7.5 kw 0.003
HCl 38% 6.684
NaOH Solid form 3.57
Total cost 11

such that the cost of raw material for synthesising

PAC is negligible and that this method is beneficial in
Fig. 2 — Absorbance v/s Flocculant dosage graph
lowering environmental pollution. So, the proposed
method for the synthesis of PAC is not only economic
but also a step towards a clean environment.
Conclusion
Removal of turbidity from water is an essential step
in the treatment of industrial effluent. This is achieved
by coagulation-flocculation using some chemicals like
alum salts and polymers. One of the important
inorganic polymers used is the poly aluminium
chloride (PAC) which found to be very effective in
removing the turbidity from water. In this work, PAC
was produced by using the waste aluminium beverage
Fig. 3 — Comparison of PAC with other coagulants cans. The recycling of aluminium cans for production
was aimed to compare the operating costs of the PAC of PAC will lower the cost of PAC production and
synthesised and the commercially available PAC. helps in cleaning and protecting the environment. The
Thus, a preliminary economic evaluation has been removal of turbidity using PAC solutions was initially
carried out. The operating costs involve the costs attempted and gave good results. The optimisation
related to the price of the coagulant reagents and the experiments for coagulation using PAC was carried
energy consumption required for the production of out, and the optimum conditions for the coagulant
PAC in coagulation and flocculation processes. To dosage of 30 mg/ml was pH 8, 30℃ temperature,
estimate the energy costs, one must take into account 120 rpm mixing speed. It was observed that
that the prices of electricity are highly dependent on flocculation efficiency decreased when the pH was
the particular country (in our case Kerala, India). The changed from the optimum range. On the other hand,
present unitary electricity cost for industrial use in the temperature had a very negligible effect on
India is Rs.5.50 per kWh (Table 2). The process flocculation, even though high temperature slightly
economics was analysed, and the total cost required reduced the stability of flocs formed. At lower mixing
for the production of 1 litre of PAC from waste speeds, the collisions between the flocculant and
aluminium cans was found out. suspended particles are low and lead to the lower
The cost of synthesised and commercial PAC for 1 flocculation rate while at higher mixing speed, the
litre is obtained as follows: flocculate chains tend to break and limiting the size of
Cost of production of synthesised PAC= Rs.11 per the flocs formed. The synthesised coagulant was also
litre compared with ferric chloride, alum and aluminium
Cost of commercial PAC= Rs.42 per litre chloride, in which, ferric chloride was found to be
From the comparison study made between the cost more efficient, followed by PAC, alum and
of production of synthesised PAC and commercially aluminium chloride. However, from the comparison
available PAC, it can be concluded that the cost of study made between the cost of production of
production of synthesised PAC is less than that of the synthesised PAC and commercially available PAC, it
commercially available PAC. Moreover, the PAC was can be concluded that the cost of production of
synthesised from waste aluminium beverage cans synthesised PAC is less than that of the commercially
 SREEKUMAR et al.: PRODUCTION OF INDUSTRIAL COAGULANT FROM BEVERAGE CANS 453

available PAC. This technique of treating wastewater 6 Khatri, J, P Nidheesh, T A Singh, & M S Kumar, Advanced
is beneficial in lowering environmental pollution and oxidation processes based on zero-valent aluminium for
treating textile wastewater, Chem Eng J, 348 (2018) 67-73.
thus can be studied upon further to be considered as 7 Dubey, S, M Agarwal, A B Gupta, & Y Solanki,
an effective method of wastewater treatment. Performance of Alum & Polyaluminum Chloride as Efficient
Coagulants for Fluoride Removal in Batch and Continuous
Acknowledgement Reactors, J Energy Environ Sustain, 5 (2018) 25-29.
8 Kasprzak, P, T Gonsiorczyk, H-P Grossart, M Hupfer,
The authors thank the Department of R Koschel, T Petzoldt, & G Wauer, Restoration of a eutrophic
Biotechnology and biochemical engineering, SCT hard-water lake by applying an optimised dosage of poly-
College of Engineering for the continuous support aluminium chloride (PAC), Limnologica, 70 (2018) 33-48.
provided throughout the work. The authors declare 9 Atari, L, S Esmaeili, A Zahedi, M J Mohammadi, A Zahedi,
that no external funding was used in the work. There & A A Babaei, Removal of heavy metals by conventional
water treatment plants using poly aluminum chloride,
is no conflict of interest whatsoever. Toxin Rev, (2018) 1-8.
10 Apha, A, WEF,“Standard Method for Examination of Water
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