Research proposal

Removal of heavy metals from wastewater using low cost absorbent

By
Zahra Batool
2018-ag-5468

Submitted to
Ma’am Asma Alam

Master of Science
In
Chemistry
DEPARTMENT OF CHEMISTRY
SUB-CAMPUS BUREWALA-VEHARI
UNIVERSITY OF AGRICULTURE,
FAISALABAD, PAKISTAN
2020
1. Introduction
Water is the basis of fluid of living organisms. In many part of the world such as in Rural
communities or in an urban area the major source of drinking water is the groundwater.
However, in recent years, due to day by day increase in industrial and agricultural
activities produced a large amount of tonic pollutants such as inorganic anion heavy
metals, synthetic organic chemical those increased public concern about the quality of
groundwater. Heavy metals have been released into environment due to increase
industrial activity and have created major global concern cadmium, zinc, lead, Copper,
nickel, mercury and chromium are present in industrial waste water, which generate from
metal plating, mining activities, smelting, battery manufacturer, printing and
photographic industries etc, (Wan Ngah and Hananfiah 2007).Discharge of uncontrolled
textile waste water is dangerous not only to water bodies but also to the aquatic system,
animals, plants and environment. Although textile product play an important rule but it
also contain high number of contaminant such as oxygen demand (COD) and biological
oxygen demand (BOD) concentration, it is rich in colour, reactive dyes higher chromium
and many other substance.(Olaoye et. al, 2018)Moreover, the more usage of water in
industry, agriculture and households has resulted in the daily accumulation of billions of
gallons of wastewater to be freshwater reserves. According to UN approximation, the
total amount of the produced wastewater is about 1500km3, which is the six time more
water than exist in all the rivers of the world.(Amin et, al, 2015). Municipal wastewater
release openly that causes the water pollution mostly of surface.Municipal waste includes
industrial wastewater, domestic, infiltration, stromwate. Before it drained to surface water
it should be cleaned. Pollutants such as heavy metals, turbidity, taste and odor causing
compound are removed. Mostly for the removal of the heavy metals such as zinc, lead,
arsenic, chromium etc. Different researcher used the adsorption methods. (Girgis, et, al,
2002.).Among various heavy metals, one of the most common and highly toxic pollutant
is lead that pollute the natural water from different industrial activities such as metal
plating, Oil refining and manufacturing of storage batteries, television tube, photographic
materials, gasoline additives and matches brought lead bearing wastewater. This toxic
level of lead causes many dangerous health problems. (Bachale et, al, 2016).If the
concentrations of heavy metals increase from allowable limit they can cause health
hazards to man and aquatic lives. In heavy metals arsenic is one of the most toxic metal
that pose serious health problems many countries of the world, which could increase the
risk of the skin, lung and kidney cancer. Different methods are urgently required to
remove the large amount of arsenic from water and wastewater. Arsenic exist in both
organic and inorganic from in nature. In natural water system mostly inorganic arsenic
are present. Generally inorganic arsenic is more toxic than organic arsenic and ass(ii) is
approximately ten time more toxic than As(v). (Chiban et, al, 2011).On the daily basis
thousands of chemical discharge directly and indirectly in aquatic system. No doubt, the
small amount of heavy metals is very hazardous and harmful, they store in the tissue
 living organisms. Inorganic coagulant use for the wastewater treatment extensively.
Aluminum sulphate and activated carbon are used as inorganic coagulant. Mostly in
developing countries aluminum sulphate is used as coagulant. However aluminum
sulphate reported to some neurological diseases for example senile dementia or
Alzheimers disease. (sabreen alfra et, at 2014).

2. Objective
Keeping in view above facts the main objective of removal of heavy metals from
wastewater is:
 To reduce hazardous effects that pose to human health.
 To reduce the water pollution.
 To save the aquatic life.

3. Literature Review
The exclusion of heavy metals from aqueous clarification is one of the most significant
environmental matters facing every country today. According to recent surveys, the most
common impurities reported in groundwater are heavy metals (Cigdem et al, 2000). Heavy
metals are also among the common pollutants of many industrial wastewaters. Therefore,
cheap materials for removing and tricking heavy metal wastes from contaminated water
are required. Different methods or techniques are used for the treatment wastewater.

4. Methods
i. Distillation
Distillation is probably the oldest method of water cleansing (Joao et, aI, 2005).
Water is first heated to boiling. The water vapor rises to a condenser where
cooling water lowers the temperature so the vapor is condensed, collected and
stored. Most pollutants remain behind in the liquid phase vessel. However,
organics with boiling points lower than 1 00°C cannot be removed efficiently and
can actually become focused in the product water. Another disadvantage is the
high cost of parting due to the large amounts of energy wanted in the distillation
process.
ii. Reverse Osmosis
Reverse osmosis (RO) is one of the shared action methods used in heavy metals
removal. Natural osmosis occurs when solutions with two different concentrations
are separated by a semi-permeable membrane. Osmotic pressure drives water
through the membrane' the water thins the more focused solution; and the end
result is equilibrium. In water cleansing systems, hydraulic pressure is applied to
the concerted solution to counteract the osmotic pressure. Pure water is driven
from the concentrated solution and collected downstream of the membrane.
 Different feed waters may require different types of RO membranes. Membranes
are manufactured from cellulose acetate or thin-film composites of polyamide on
a polysulfide substrate. Because RO membranes are very restrictive, they yield
very slow flow rates. Storage cisterns are required to produce an adequate volume
in a sensible quantity of time. In addition to this, this method is considered
luxurious compared to the adsorption process (Tonni et al., 2005).
iii. Electrodialysis
In this process, the ionic components, e.g., heavy metals are separated through the
use of semi-permeable ion-selective membranes. Application of an electrical
possible between the two electrodes causes a relocation of cations and anions
towards respective electrodes. Because of the alternate spacing of cation and
anion holey membranes, cells of focused and dilute salts are formed. The
disadvantage is the formation of metal hydroxides which block the membrane
(Marhol et aI, 1 982).
iv. Chemical Precipitation
Rain of metals is achieved by the adding of coagulants such as alum, ime, iron
salts and other organic polymers. The large amount of sludge containing toxic
compounds produced during the process is the main disadvantage of this method
(Reedard et ai., 1 993; Pisken, 1 996; Denizli et ai, 1 998; Marhol et aI, 1 982).
v. Ion Exchange
In this process, metal ions from di lute solutions are exchanged with ions held by
electrostatic forces on the exchange resin. Chelating exchangers that are more
selective to heavy metals are commercially available for example, the use of
chelex 1 00, which has imminodiacetic functional group, has been widely
reported (Pisken et ai, 1 996).

vi. Ultra-Filtration
The deletion methods using UF membranes are pressure driven membrane
operations that use absorbent membranes for the deletion of heavy metals. The
main disadvantage of this procedure is the generation of sludge that needs further
treatment (Tonni et al , 2005).
vii. Adsorption
Adsorption includes parting of a substance from one phase escorted by its
accumulation or concentration at the surface of another. The adsorbing phase is
the adsorbent, and the material concentrated or adsorbed at the surface of that
phase is the adsorbate. Adsorption on solid matrices has been shown to be one of
the most efficient treatment methods for heavy metals eliminations. General
Sorbents, such as triggered carbon, metal oxides, and ion-exchange resins have
been used. Specific sorbents consisting of a metal chelating ligand which interacts
 with the heavy metal ions particularly, and a carrier matrix which may be an
inorganic material (e.g., activated carbon, alumina, silica or glass) or polymer
microspheres (e.g., polystyrene or polymethymethacrylate) have also been stated
(Reedard et aI ., 1 993 ; Pisken, 1 996).

Numerous agrarian by-products, such as husks, fruit stones, bagasse, and

agricultural residual from sugar cane, rice, and peanut hulls, sawdust date pits and
barks from some easy growing wood species, among others lignocellulose
materials, have been investigated in the last years as possible precursors for ACs
manufacture using different start processes (Remacle et ai, 1 984; Muraleedharan
et ai, 1 990; Aslam et at., 2004). The prepared ACs has been found to be worthy
heavy metals adsorbents. The polar acidic oxygen functional groups on the
surface of the se carbons have been documented as playing a key part on metal
adsorption.

 Bark and other tannin-rich materials

Bark is available as a by-product of the wooden industry. Bark is real because of
its high tannin content. The polyhydroxy polyphenol collections of tannin are
thought the active species in the adsorption process. Ion exchange takes place as
metal cations move head-to-head phenolic hydroxyl groups, forming a chelate
(Randall et al., 1974a; VaÂzquez et al., 1994). One problem with tannin-
containing materials is staining of the water from soluble phenols. Chemical
pretreatment of bark has been shown to overcome the problem. Certain
pretreatments, such as acidified formaldehyde (VaÂzquez et al., 1994) and acid,
base, or formaldehyde (Alves et al., 1993) have been shown to remove the
hemorrhage of colored compounds without noticeably affecting capacity. While
pretreatment will increase cost, some pretreatment may be necessary for
controlling color.
Some other tannin-rich agricultural by-products have been examined for their use
as metal sorbents. Randall et al. (1974a, b) compared bark adsorption to that of
peanut skins, walnut expeller meal and coconut shells and showed their capacities
to be comparable. Randall et al. (1978) also did a study with peanut skins,
polymerized with formaldehyde to prevent leaching of color and disintegration
upon prolonged contact with water. The subsequent material was stable in water
and was effective for binding Cd, copper (Cu), Hg, and Pb. Orhan and
BuÈyuÈkguÈngoÈr (1993) associated nut and walnut shell, leftover tea, and
coffee to activated carbon and observed the capacities of the tannin-containing
products to be only slightly less than that of stimulated carbon.

 Dead biomass and rice hulls

Matis and Zouboulis (1994) established sorption of heavy metal ions such as Cd2+ by
deceased biomass. Deceased cells accrue heavy metals to an equal or greater extent than
living cells. The bacterial cell surfaces are anionic due to the presence of ionized groups
in the cell wall polymers, causing the cell to attract metal cations. Large quantities of
waste microbial biomass are shaped in many industries such as citric cutting biosynthesis
and penicillin manufacture. Berkeley (1979) estimated that fermentation industries
produce some 790,000 tonnes of microbial waste each year, with 41,000 tonnes resulting
from citric acid production by Aspergillus niger. The use of dead rather than live biomass
eliminates the problems of waste toxicity and nutrient requirements.
Seaweed is an abundant source of metal-sorbing biomass. Some seaweeds have been
identified for the ion exchange properties associated with their polysaccharide content.
These properties are chiefly marked in brown algae. Trials by Volesky and Prasetyo
(1994) used the brown marine algae, Ascophyllum nodosum, in sorption columns to
remove Cd. The all-out adsorption capacity for the seaweed was shown to be
approximately 67 mg Cd/g seaweed. In an experiment by Wilson and Edyvean (1994) the
brown seaweeds, Fucus serratus and Laminaria digitata, outperformed other biological
materials such as fungi, green seaweed and unicellular green alga for Cd and Hg
elimination. The green seaweed, Ulva lactuca, was just somewhat less effective than the
two brown seaweeds.

 Clay
Like zeolite, the adsorption competences of clay consequence from a net negative charge
on the structure of fine-grain silicate minerals. This bad charge is neutralized by the
adsorption of positively charged species, giving clay the ability to attract and hold cations
such as heavy metals. The large surface area of clays (up to 800 m2 /g) also contributes to
the high adsorption capacity (Cadena et al., 1990). There are three basic classes of clays:
kaolinite, micas (such as illite), and smectites (for example montmorillonite). Of the three
species, montmorillonite clays have the smallest crystals, the largest surface area and the
highest cation exchange capacity. Thus montmorillonite clays would be predictable to
have the highest sorptive capacity. A study by Grin et al. (1977) found the removal of
Hg by montmorillonite to be five times greater than that by kaolinite. Viraraghavan and
Kapoor (1994) noted that the profusion and low cost of bentonite make it a sturdy
applicant as an adsorbent for the removal of heavy metals from wastewaters. The
composition of bentonite varies, though it consists mostly of montmorillonite.

 Fly ash
Grover and Narayanaswamy (1982) practical that fly ash, a waste product from thermal
power plants, has some adsorption capabilities for Cr (VI). Fly ash consists of carbon and
oxides of silica, alumina and iron. An adsorption capacity of 4.250 mg Cr (VI)/g was
experiential at pH 2.0. Kapoor and Viraraghavan (1996) noted that the possessions of fly
ash are extremely mutable and the adsorption capacity varies with the lime content.
Banerjee et al. (1997) presents information on the adsorption kinetics of organic
compounds and reports increasing capacity with increasing carbon content. The insincere
area of fly ash is reported as 1± 6 m2 /g. A potential advantage of fly ash is that it could
easily be solidified after the metals are adsorbed because it encompasses pozzolanic
particles that react with lime in the presence of water, forming cementitious calcium-
silicate hydrates. It is important to note that fly ash may contain heavy metals and
suggestion amounts of radioactive rudiments. The option of competitive movement or
leaching should also be careful and evaluated.

 Other sorbents
Other materials have been studied less extensively as low-cost sorbents. Masri and
Friedman (1974) investigated the potential of wool for removing metal ions from aqueous
media. In their education, raw wool was modified by the addition of numerous functional
groups such as sulfhydryl to increase adsorption capacity. It is optional that the sulfhydryl
groups bind with metal ions to form metal mercaptides. Between the different
modifications, the maximum adsorption capacities achieved are some of the highest
volumes stated for these metals. While changes can recover the volume of the wool, the
native (raw) wool alone is still quite efficient. Freeland et al. (1974) also studied wool
modified with polethylenimine (PEI) for Hg adsorption. A capacity of 330.97 mg Hg/g
was attained for the PEI-wool. Roberts and Rowland (1973) studied the removal of Hg
using modified cotton. Cotton fibers are 90% cellulose, which is ineffective without
modification. In this study, cotton was chemically modified with four amine units, whose
effectiveness appears to be proportional to the amine content. Cross-linked
polyethylenimine (CPEI) cotton exhibited the best results when cottons were compared
on a weight-toweight basis. Although cotton in chopped form attained better, cotton
fabric could be more suitable for continuous, automated procedures. Masri et al. (1974)
presented Hg adsorption capacities for several natural materials, while no other
information is given on the sorption machines of these materials or their chemical
constituents. The adsorption capacities of some of these materials are given in Table 9.
Shukla and Sakhardande (1992) also reported adsorption capacities for several cellulosic
materials dyed with C.I. Reagent Orange, a reactive dye of the monochlorotriazine type.
However, they provide no insight on how the color improves metal sorption. Other
interesting sorbents include rice and bambara nut husks (Said et al., 1992), leaf mould
(Sharma and Forster, 1994), bone gelatin beads (Petersen et al., 1991), iron oxide coated
sand (Bailey et al., 1992), and both untreated (Low and Lee, 1991) and dye-coated moss
(Low et al., 1993).

5. Conclusions
 Inexpensive, real, readily available materials can be used in residence of inspired carbon
or ion discussion resins for the removal of heavy metals from solution. A wide range of
low-cost sorbents has been studied. Comparisons of the sorbents are difficult because of
inconsistencies in data staging. However, from the literature reviewed, a few sorbents
that stand out for high porosity are chitosan, zeolite, lignin, and seaweed. Table 10
presents a summary of some of the highest adsorption capacities reported. Due to the
scarcity of consistent cost material, cost assessments are problematic to make. Although
much has been talented in the area of low-cost sorbents, plentiful effort is essential to
better comprehend low-cost adsorption procedures and to prove the technology.

6. REFERENCES
1) Abdulkarim, M. Abu I-Rub F. A., Adsorption of lead ions from aqueous solutions on activated
carbon and chemical ly modified activated carbon prepared from date pit . Ads. ci . TechnoL, 22
(2004) 1 1 9-134.
2) Abu AI-Rub, F., El-Naas, M. Benyahia F., Ashour, I., Biosorption of nickel on blank alginate beads,
free and immobilized algal cells. Process Biochemistry, 39 (2004) 1 767- 1 773
3) Abu AI-Rub, F., Sorption of Lead Ions from Simulated Industrial Wastewater onto Jordanian Low-
grade Phosphate, Adsorption Science Technology, 22 (2004) 1 65-1 79
4) l-Omerie., Remo al of heavy metals via adsorption on activated carbon synthesized from solid
wastes. International conference on chemistry and industry chern. Dept. Col leg of science King
Saud University proceeding. 26 (2004).
5) Al-Asheh. Duvnj ak, Z., Adsorption of metal ions by moss, Adv. Environm. Res., ( 1 997) 1 94-2 1
2.
6) Al len S , Murray, M., Brown, P., Flynn, 0., Peat as an adsorbent for dyestuffs and metals in
wastewater, Resources, Conservation and Recycling 1 1(1994) 25-39.
7) Aslam, M., Hassan, I., Murtaza, M., Sand as adsorbent for removal of zinc from industrial
effluent. Electronic Journal of Environmental, Agricultural and Food Chemistry, 3 (2004).
8) Aygun, A., Yenisoy-Karaka, S., Duman, I., Production of granular activated carbon from fruit
stones and nutshells and evaluation of their physical, chemical and adsorption properties,
Microporous and Mesoporous Materials, 66 (2003) 1 89- 1 95
9) Baes, C., Messmer, R., The hydrolysis of cations. Krieger publishing Co. Florida, ( 1 976). 8
Alves M. M., GonzaÂlez Bec°a C. G., Guedes de Carvalho R., Castanheira J. M., Sol Pereira M. C.
and Vasconcelos L. A. T. (1993) Chromium removal in tannery wastewaters ``polishing'' by Pinus
sylverstris bark. Water Res. 27(8), 1333-1338.
10) Baba Y. and Hirakawa H. (1992) Selective adsorption of palladium (II), platinum (IV), and mercury
(II) on a new chitosan derivative possessing pyridyl group. Chem. Lett. 10, 1905-1908.
Banerjee K., Cheromisino€ P. N. and Cheng S. L. (1997) Adsorption kinetics of o-xylene by flyash.
Water Res. 31(2), 249-261.
11) Bailey R. P., Bennett T. and Benjamin M. M. (1992) Sorption onto and recovery of Cr (VI) using
iron-oxidecoated sand. Water Sci. Technol. 26(5-6), 1239-1244.
 Berkeley R. C. W. (1979) Chitin, Chitosan and Their Degradative Enzymes. In Microbial
Polysaccharides, eds. R. C. W. Berkeley, C. W. Gooday and D. C. Elwood, pp. 205-236. Academic
Press. New York.
12) Bricka R. M. and Hill D. O. (1989) Metal immobilization by solidi®cation of hydroxide and
xanthate sludges. In Environmental Aspects of Stabilization and Solidi®cation of Hazardous and
Radioactive Wastes, ASTM STP 1033, eds. P. L. Coà te and T. M. Gilliam, pp. 257-272. American
Society for Testing and Materials, Philadelphia.
13) Bryant P. S., Petersen J. N., Lee J. M. and Brouns T. M. (1992) Sorption of heavy metals by
untreated red ®r sawdust. Appl. Biochem. Biotechnol. 34-35, 777-788.
14) Cadena F., Rizvi R. and Peters R. W. (1990) Feasibility studies for the removal of heavy metals
from solution using tailored bentonite. In Hazardous and Industrial Wastes, Proceedings of the
Twenty-Second Mid-Atlantic Industrial Waste Conference, Drexel University, pp. 77- 94.
15) Chen X.-H., Gosset T. and TheÂvenot D. R. (1990) Batch copper ion binding and exchange
properties of peat. Water Res. 24(12), 1463-1471.