Removal of Nickel and Lead from Pharmaceutical Wastewater Using Agricultural Waste

Abstract

The present study deals with the adsorption of nickel and lead from pharmaceutical wastewater by agricultural waste material. Wild jack fruit and acasia bark were treated with sulphuric acid to improve the surface properties such as pore volume and particle size. The SEM and EDX analysis were used to find the surface structure and the metal ions present on the surface of the adsorbent. From the FTIR analysis it was possible to find the various functional groups existing on the surface of adsorbent which were responsible for the adsorption process. From the equilibrium studies and the adsorption capacity obtained it showed that both the materials were effective adsorbents to remove the metal ions from the solution.

Full text

807| International Journal of Pharmaceutical Research | Apr - Jun 2020 | Vol 12 | Issue 3
Research Article
Removal of Nickel and Lead from Pharmaceutical
Wastewater Using Agricultural Waste
SHREYAS A SHENOY1, SRINATH SHANBHAG1, MADIVADA SUMANTH1, NIKIL RAO1, KLARA
BORKOVCOVA2, C.R GIRISH1*
1Chemical Engineering Department, Manipal Insitutue of Technology, MAHE, Manipal, India.
2Faculty of Chemical Technology, University of Chemistry and Technology, Prague, Czech Republic.
*Corresponding Author
Email ID: girishcr1@rediffmail.com
Received: 16.01.20, Revised: 18.02.20, Accepted: 19.03.20
ABSTRACT
The present study deals with the adsorption of nickel and lead from pharmaceutical wastewater by agricultural
waste material. Wild jack fruit and acasia bark were treated with sulphuric acid to imporve the surface
properties such as pore volume and particle size. The SEM and EDX analysis were used to find the surface
structure and the metal ions present on the surface of the adsorbent. From the FTIR analysis it was possible to
find the various functional groups existing on the surface of adsorbent which were responsible for the
adsorption process. From the equilibrium studies and the adsorption capacity obtained it showed that both the
materials were effective adsorbents to remove the metal ions from the solution.
Keywords: Pharmaceutical Wastewater, Wild Jack Fruit, Acasia Bark, Adsorption, Nickel, Lead.
INTRODUCTION
Because of rapid growth in industries and
urbanization, large quantity of industrial wastes
and toxic wastes are released into the
environment [1]. The industrial waste water are
released from different industries such as
pigments, plastics, pharmaceuticals, batteries,
electroplating and metal surface industries [2, 3].
The quality of water is getting degraded because
of these pollutants and also it has harmful effects
on the aquatic life and human health [4].
Pharmaceutical wastewater is considered as one
of the important source of pollution because it
contains highly concentrated toxic chemicals. It is
produced by various pharmaceutical products
produced in the industry [5]. It is the water mixes
with the raw materials, by products, products,
intermediates and waste products [6]. The
wastewater mainly contains high organic matter,
BOD, COD, residual nutrients, organic solvents
[3]. It also contains volatile matter, suspended
solids, dissolved oxygen, oil, grease, sulphides,
phenols and other metals such as aluminium,
copper, lead, zinc, nickel, iron and mercury [7,
8]. Thus by treating this wastewater will reduce
the cost of disposing the waste and feed water
requirement [6]. Heavy metals like lead, copper,
zinc, chromium, cobalt, iron and nickel are the
important pollutants which are to be treated since
they are present in very low concentration.
Lead is one of the major pollutant released from
the electroplating, pharmaceutical, paints, glass
operating, petrochemical, oil, metallurgical,
tannery, pigments and rubber industries and
considered to be hazardous waste [9, 10]. It
affects the food chain and causes harmful effects
on human beings [11]. It causes carcinogenic,
toxicological and neurotoxical problems such as
loss of memory in human beings [9, 12]. As per
the environmental regulations the allowable
concentration of lead in drinking water as 10µg/L
[11].
Nickel is found in the wastewater from the
industries like electroplating, battery, mining,
metal finishing, pharmaceutical and fertilizer
industries [13, 14] It cannot be biodegraded and
accumulates in the living organisms and affects
nervous, gastrointestinal systems and causes
pulmonary and skin problems [15, 16, 17]. The
environmental regulations has made the
concentration of nickel in wastewater to be less
than 0.5 mg/L [16].
Various treatment processes are available such as
adsorption, membrane separation, solvent
extraction, coagulation, electrodeposition and
reverse osmosis for treating pharmaceutical
wastewater [18]. Adsorption is one of the effective
method for the removal of the heavy metals from
wastewater using activated carbon. Because of
the expensive nature of activated carbon, an
effort has been made to treat the metals lead and
nickel from wastewater using adsorbent prepared
from wild jackfruit and acasia bark.
MATERIALS AND METHODS
A. Chemicals used
The chemicals used Nickel chloride hexahydrate
(Merck India Limited) and Lead nitrate (Finar Ltd)
ISSN 0975-2366
DOI:https://doi.org/10.31838/ijpr/2020.12.03.117

Shreyas a Shenoy et al / Removal of Nickel and Lead from Pharmaceutical Wastewater Using
Agricultural Waste
808| International Journal of Pharmaceutical Research | Apr - Jun 2020 | Vol 12 | Issue 3
were used for the preparing the solutions. The
other chemicals such as sodium hydroxide pellets
(Fischer Scientific Limited) and sulphuric acid
(Merck India Limited) were used for adjusting pH
values and other for treatment of the adsorbent.
B. Preparation of chemically treated carbon from
wild jackfruit and acasia bark and
characterization of the treated carbon
Dried buds of wild jackfruit (Artocarpus hirsutus)
and dried bark of Acasia penninervis were
collected from the vegetation present around
Karkala. The buds and bark were water washed
to remove impurities like dust, sand particles,
twigs, etc. Then they were washed with double
distilled water to remove other impurities such as
the characteristic yellowish brown colour and
other soluble impurities. The buds were later
dried at 90 – 100 °C for 2 hours in an oven. The
buds were broken into pieces of 1 -3 cm length in
order to further reduce the size. The broken
pieces were later ground to fine powder.
The powder was mixed with 0.5M H2SO4 in the
ratio 1:4 w/v. By preliminary studies, the
temperature required for treatment was found out
to be 590oC. It was heated inside a muffle
furnace for 90 minutes. The treated carbon was
washed with double distilled water to remove the
excess H2SO4. The washing was repeated two
times, to make sure that the pH above 6 is
maintained. The sample was later dried at 250oC
to remove the moisture and stored in an air tight
container.
The pore volume and surface area were
measured by BET apparatus (Smart Instruments,
India). The functional groups present on the
surface of the adsorbent were analysed using
Fourier transform infrared spectroscopy
(Shimadzu, Japan). The surface structure of the
adsorbent was studied using Scanning Electron
Microscopy (Zeiss Company, Germany) and the
existence of metal ions were determined using the
Energy dispersive X-ray (EDX) analysis.
C. Determination of equilibrium time
1000 ppm lead and nickel solution were
prepared by dissolving 1.5984 g of lead nitrate
and 2.208 g of Nickel chloride with distilled water
respectively. Then the solutions were made up to
the mark in a 1000 mL standard flask. From the
stock solutions 50 ppm concentration of both the
lead and nickel solutions were prepared.
1 g of adsorbent prepared from wild jackfruit was
mixed with 250 mL of 50 ppm lead solution and
1 g of adsorbent from acasia bark was mixed
with 250 mL of 50 ppm nickel solution and stirred
on incubator shaker. Sample was withdrawn from
each of the conical flasks at known intervals of
time and filtered. Then the concentrations of the
lead and nickel were analyzed with atomic
absorption spectrophotometer (Thermo Scientific,
Australia) at a wavelength of 217 nm and 231.1
nm respectively. The equilibrium time was found
to be 6 hrs.
RESULTS AND DISCUSSIONS
A. Adsorbent Characterization
The surface area and pore volume were
measured for both the chemically treated
adsorbents and are shown in the table 1. The
above results signified that the adsorbent is
having better adsorption capacity for removing
pollutant [19].
Table 1: The surface properties of the adsorbent
prepared from wild jackfruit and acasia bark
Wild
jackfruit
Acasia
bark
Surface area,
(𝑚2𝑔
⁄)
435.22
358.46
Pore
volume,(𝑐𝑚3𝑔
⁄)
0.2568
0.3706
B. SEM and EDX Analysis of the Adsorbent
SEM is a technique used for determining surface
structure and morphology of the material [20].
The porous nature, shape and size distribution of
the molecules can also be studied from the
analysis [21]. The surface images of the
adsorbent prepared from wild jackfruit and
acasia bark before adsorption are shown in fig 1
and 3 and the images of the adsorbent after
adsorption are given in fig 2 and 4. The pores
present on the adsorbent surface were useful for
adsorbing the pollutant from the wastewater [22].
Before the adsorption process surface was having
heterogeneous pores and after the adsorption
process pores were occupied with pollutants and
the change in the structure of the adsorbent was
observed [23, 24].
EDX analysis was used for identifying the
presence of elements on the adsorbent surface
[25, 26, 27]. The EDX analysis of the adsorbents
prepared from wild jackfruit and acasia barka
before and after the adsorption process are
shown in Fig. 5-8. The EDX analysis for both the
adsorbents before adsorption showed various
peaks for the metal ions like Ca+, Al3+, K+, Fe2+,
Si4+ . These metal ions the vital plant nutrients in
the wild jackfruit and acasia bark. The peaks
obtained after adsorption were dominant in the
Ni2+ and Pb2+ ions on the adsorbent surface.
Thus it indicates the adsorption of these metal
ions by the ion exchange process [28, 29].

Shreyas a Shenoy et al / Removal of Nickel and Lead from Pharmaceutical Wastewater Using
Agricultural Waste
809| International Journal of Pharmaceutical Research | Apr - Jun 2020 | Vol 12 | Issue 3
Fig.1: SEM image of the adsorbent prepared
from wild jackfruit before adsorption
Fig.2: SEM image of the adsorbent prepared
from wild jackfruit after adsorption
Fig. 3: SEM image of the adsorbent prepared
from acasia bark before adsorption
Fig. 4: SEM image of the adsorbent prepared
from acasia bark after adsorption
Fig.5: EDX of the adsorbent prepared from wild
jackfruit before adsorption
Fig.6: EDX of the adsorbent prepared from wild
jackfruit after adsorption

Shreyas a Shenoy et al / Removal of Nickel and Lead from Pharmaceutical Wastewater Using
Agricultural Waste
810| International Journal of Pharmaceutical Research | Apr - Jun 2020 | Vol 12 | Issue 3
Fig.7: EDX of the adsorbent prepared from
acasia bark before adsorption
Fig. 8: EDX of the adsorbent prepared from
acasia bark after adsorption
C. FTIR Analysis
The FTIR spectra of the wild jackfruit and acasia
bark treated with sulphuric acid before and after
the adsorption are represented in fig 9-12. It can
be observed from the fig 9 and 10 for wild
jackfruit that the peak obtained at 3633.88 and
3622.32 cm-1 was due to the O-H bond of
hydrogen bonded molecules [30] and at 2850.79
and 2864.29 cm-1 was because of the C-H bond
of alkanes [31]. The peaks obtained at 3047.53
and 3049.46 cm-1 was contributed by O-H of
carboxylic acid [30] and at 1583.56 and
1558.48 cm-1 was attributed by NH2 group [32].
The FTIR spectra of the acasia bark showed
various peaks from fig 11, 12. The prominent
among them were 1602.86 and 1610.56 cm-1
was due to stretching of C-C bond [33]. The
peaks at 3612.67 cm-1 are because of O-H bond
of hydrogen bonded molecules and at 1271.09
and 1278.81 cm-1 are because of C-N bond of
amines [30].
Fig.9: FTIR analysis of the adsorbent prepared from wild jackfruit before adsorption
7501500225030003750 1/cm
80
85
90
95
100
%T
3878.85
3846.06
3801.70
3734.19
3653.18
3633.89
3612.67
3047.53
2914.44
2850.79
2688.77
2596.19
2484.32
2351.23
2322.29
2218.14
1695.43
1678.07
1660.71
1583.56
1546.91
1535.34
1521.84
1502.55
1483.26
1435.04
1425.40
1338.60
1301.95
1155.36
883.40
813.96
756.10
671.23
613.36
530.42
468.70
1 A

Shreyas a Shenoy et al / Removal of Nickel and Lead from Pharmaceutical Wastewater Using
Agricultural Waste
811| International Journal of Pharmaceutical Research | Apr - Jun 2020 | Vol 12 | Issue 3
Fig. 10: FTIR analysis of the adsorbent prepared from wild jackfruit after adsorption
Fig. 11: FTIR analysis of the adsorbent prepared from acasia bark before adsorption
Fig. 12: FTIR analysis of the adsorbent prepared from acasia bark after adsorption
7501500225030003750 1/cm
80
85
90
95
100
%T
3888.49
3838.34
3819.06
3724.54
3664.75
3622.32
3049.46
2914.44
2864.29
2806.43
2708.06
2628.98
2343.51
2216.21
2144.84
1689.64
1558.48
1544.98
1527.62
1512.19
1494.83
1454.33
1429.25
1402.25
1394.53
1344.38
1172.72
885.33
815.89
769.60
673.16
609.51
534.28
464.84
1 B
7501500225030003750 1/cm
60
70
80
90
100
%T
3878.85
3828.70
3728.40
3653.18
3612.67
3061.03
2966.52
2916.37
2594.26
2349.30
2222.00
1697.36
1680.00
1602.85
1585.49
1570.06
1554.63
1535.34
1523.76
1463.97
1450.47
1425.401338.60
1271.09
1188.15
879.54
819.75
758.02
673.16
605.65
530.42
457.13
424.34
2 A
7501500225030003750 1/cm
60
75
90
%T
3878.85
3863.42
3828.70
3728.40
3624.25
3612.67
3574.10
3061.03
2970.38
2353.16
2222.00
1697.36
1680.00
1610.56
1552.70
1517.98
1506.41
1463.97
1450.47
1433.11 1352.10
1278.81
881.47
821.68
758.02
671.23
528.50
470.63
2 B

Shreyas a Shenoy et al / Removal of Nickel and Lead from Pharmaceutical Wastewater Using
Agricultural Waste
812| International Journal of Pharmaceutical Research | Apr - Jun 2020 | Vol 12 | Issue 3
D. Adsorption Capacity
After the equilibriums studies, the adsorption
capacity for both the adsorbents were evaluated.
It was calculated as 25.5 mg/g and 17.3 mg/g
for the adsorbent prepared from wild jackfruit
and acasia bark respectively. The wild jackfruit
showed the better adsorption capacity compared
to acasia bark. This may be because of the better
surface properties found in the wild jackfruit.
CONCLUSION
The current investigated proved the capability of
the wild jack fruit and acasia bark to remove
nickel and lead from pharmaceutical wastewater.
The chemical treatment with sulphuric acid was
successful in improving the properties of the
adsorbent. The improved properties pore volume
and surface area were useful in increasing the
adsorption capacity. The FTIR analysis
represented the various functional groups which
were responsible for adsorbing the metals on the
surface. The adsorption capacity was obtained as
25.5 mg/g and 17.3 mg/g for the adsorbent
prepared from wild jackfruit and acasia bark
respectively indicating that both are potential
adsorbent for removing the pollutants from
pharmaceutical wastewater.
ACKNOWLEDGMENTS
The authors gratefully acknowledge the IAESTE
India LC Manipal for the IAESTE internship
student exchange program.
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