Defence University College of

Engineering

Chemical Engineering Department

Assessment of Electroplating Waste Water at

Gafat Armament Engineering Complex

By
Group one Sub Group three
 Content

Unit One

I. Introduction

1.1. Background
1.2. Company profile
1.3. Objective of the project
1.4. Significance of the project
1.5. Scope of the project
1.6. Method and Materials

I.6.1 Method
I.6.2 Materials

Unit Two

2. Literature Review

Unit Three

3. Result and Discussion

Unit Four

Conclusions and Recommendations

References
UNIT - ONE

I Introduction

1.1 Back ground

Electroplating is one of the varieties of several techniques of Metal Finishing. It

is a technique of deposition of a fine layer of one metal on another through
electrolytic process to impart various properties and attributes, such as corrosion
protection, enhanced surface hardness, lustre, colour, aesthetics, value addition
etc.

Electroplating is considered a major polluting industry because of the discharge

of toxic materials and heavy metals through wastewater (effluents), air emission
and solid wastes in to the recipient environment.

The chemicals used in various electroplating operations are numerous. These

chemicals can be classified generally as (i) Acids and Alkalis for cleaning
purpose,( ii)inorganic chemicals, particularly heavy metals, which take part in
reaction pertaining to plating and (iii)organic chemicals which help in achieving
certain properties or to enhance the process of plating. Throughout the process
of electroplating, there are a number of wastes discharged to the environment
which has diverse effect on human being as well as other living things.

The environmental effect are caused by several routs- (i) by directly reaching
with air water and soil, resulting in degradation of disintegration, (ii) by
accumulating as persistent chemicals - geo-accumulation (iii) by entering
environmental pathways and transcending from non-living to living beings,
causing toxicity to living organisms and (iv) entering in to food chain- finally
affecting humans and cattle. Some are carcinogenic, while others are mutagenic.
Central and most important in this matter are health effects on workers, who are
exposed routinely and persistently. Over a period of time such exposures, even
at a low level, have been known to cause diseases and various infirmities.

Liquid wastes obtained from industries generally much more polluted than
domestic or even commercial liquid wastes. It becomes necessary for the
industries to treat their liquid wastes in their industrial treatment plants before
discharging their effluents either on land or lake or river or in municipal sewers.

Industrial liquid wastes usually contain several chemical pollutants and toxic
substances in too large proportion. The characteristics of the liquid wastes will
usually vary from industry to industry and also vary from process to process.

Therefore, this is a graduation project focused on Gafat Armament Engineering

Complex, one of the industry engaged in electroplating process, in order to
 assess pollutants and degree of pollution caused by the discharges from the
company, its impact on the environment and human beings and to recommend
possible solutions to minimize its adverse effect.

1.2 Company profile

Gafat Armament Engineering Complex is built by joint collaboration of

Government of People Democratic Republic of Korea and Democratic Republic
of Ethiopia by the name of Gafat Engineering Factory. The factory was
inaugurated on May 27, 1973 in Ethiopian Calendar by the then President
Mengistu H/Mariyam. The factory is located 66 KM from Addis Ababa in the
direction of South East and 19 KM from Bishoftu town and stationed with in
18,400,000 m2

The objective of the factory is to satisfy the military need of the country with
advanced technology through designing and production of appropriate war
equipment that enhances the economic and industrial development of the
country.

The factory is highly contributing for the industrial and technological

advancement of the country in producing efficient war tools with low cost and
high quality that satisfies its customers needs.

Currently, five departments are operating in the factory such as simple tools
operation department, middle calibre production department, Rocket launcher
production department, complex tools howitzers production department and
army tools spare parts production department. And through these departments
different war tools like snipers, Shrapnel lawounchers, anti tank lawounchers
etc... has been producing in the factory. In addition, different plastic materials
are also producing.

While engaging in production of such tools, the factory has been utilizing
different chemicals in order to electroplating and alkali colouring, which on
process changed in to hazardous wastes.

1.3 Objective of the project

The general objectives of this project are

• To indicate the degree of pollution caused by the effluences

discharge
• To assess pollutants within the west water

The specific objective of the project

• To suggest liquid waste treatment mechanism with less cost

 • To identify type and characteristics of pollutants that are
discharged during electroplating process
• To propose recycling methods and mechanisms
• To evaluate the degree of pollution affecting the environment and
make them aware

1.4 Significant of the project

In Gafat Armament Engineering Industry waste treatment mechanism are

technologically supported. However, the current treatment mechanism being
used is not as required due to several reasons. Therefore, it is necessary to
identifying the problem clearly through assessing the current mechanism by
which the company been treating its waste water so that environmentally
friendly mechanisms should be recommended.

1.5 Scope of the project

 To assess the source of industrial liquid wastes

 To evaluate the effect of industrial wastes disposed to the environment
 To propose how to mange the liquid waste of the industry

1.6 Method and Materials

1.6.1 Methods

In order to undertake the project, the group will visit GAEC /Gafat Armament
Engineering Complex/ for first hand information and also review different
literatures and internet for 2nd hand information. In addition, the group will
undertake experiment in laboratory in order to come up with tangible results.

The methods used to achieve the project objectives are:-

• Observation :- observing the type of chemicals that are used for plating
purpose in Gafat Armament Engineering complex; identify the effect of
liquid west discharged to the environment
• Consultation:- consulting at all stage and activities of the project with
the advisor, Laboratory technicians, and other relevant persons ( the
factory workers)
• Secondary data collection :- collect secondary data which is relevant to
the study from various sources
• Sampling
o Primary data collection with appropriate type and quantity
o Site visit and liquid waste sample collection at different times
from the site
 o Proper and careful transportation of the collected sample to the
laboratory
• Laboratory work /experiment

Determine the degree of pollution and PH value of the liquid wastes, so as to

characterize it.

• Data analysis and interpretation of the results obtained

The data collected has to be analyzed thoroughly by adopting analytical

technique and by identifying the similarities and differences with the
secondary data

• Evaluate the data based on the analysis

1.6.2 Materials

Some of the materials required for laboratory work and sample collections are:-

• Laboratory equipments such as

o conical flask,
o Beaker -100ml
o Burette
o Hot plate
o Measuring cylinder
• Personal safety equipments
o Glove
o Mask (mouth and nose)
o Goggle
o Eye glass

• Reagents that facilitates the experiment

o Sulphuric Acid
o Phenolphthalein
o Iron sulphate
o Potassium permanganate
 UNIT-TWO

II. REVIEW OF RELATED LITERATURE

2.1 Electroplating waste

Electroplating is considered a major polluting industry because of the discharge of

toxic materials and heavy metals through wastewater (effluents), air emission and
solid wastes in to the recipient environment,( Newsweek 2008, Central Pollution
Control Board, DELHI)

In electroplating, a wide variety of chemicals and substances are used, depending up

on the surface properties of the object to be electroplated, plating and finishing
requirements as well as the technology / facility offered by platters/. Among the
metals used in platting, chrome platting is the most widely used one.

2.1.1 Chromium

Chromium is bluish- white and lustrous metal that is resistant to corrosion in most
atmospheres. Chromium plating, therefore, is extensively used as a final finishing
operation.

Chromium is naturally found in rocks, animals, plants, soil and in volcanic dust and
gases. It is one of the high priority persistent, bio-accumulative and toxic (PBT)
chemicals that do not readily break down in the environment, are not easily
metabolized, may accumulate in human or ecological food chains through
consumption or up take and may be hazardous to human health or environment. PBT
chemicals, once released to the environment, may present increasing long term toxic
effects to human health and the environment, even if the release was of a small
amount.

Chromium is present in the environment in several different forms. The most

common forms are chromium (O), trivalent (III), and hexavalent (VI). Chromium
occurs naturally in the environment and is an essential nutrient required by the
human body . Chromium enters the environment mostly in the Chromium (III) and
(VI) forms as a result of natural processes and human activities. It cycles between
the soil, the atmosphere, surface and ground waters. Electroplating is one of the
several industrial activities (like stainless steel welding, chemical manufacturing,
tanning, textile process & dyeing and coal ash from power plants), that discharge
both Cr(III) and Cr(VI) in to water and soil. Chromium (III) is considered safe and
is an essential nutrient.

Cr (Vl) is a strong oxidant and is reduced in the presence of electron donors.

Electron donors commonly found in soils include aqueous Fe (l I), ferrous iron
minerals, reduced sulfur, and soil organic matter. The reduction of Cr(Vl) by ferrous
iron can be written as HCrO~ + 31% + 7H+ + Cr3+ + 3F23+ + 4H 0 This reaction is
very fast on the time scales of interest for most environmental problems with the
reaction going to completion in less than 5 minutes even in the presence of dissolved
oxygen (Eary and Rai, 1988). Only when the pH is greater than 10 or when PO~
concentrations exceed 0.1 molar does the rate of oxidation of F&+ by dissolved
oxygen exceed the rate of oxidation by Cr(Vl) (Eary and Rai, 1988). When the pH of
the groundwater is greater than 4, Cr(lll) precipitates with the Fe(lll) in a solid
solution with the general composition CrXFel..JOH), (Sass and Rai, 1987; Amonette
and Rai, 1990). If the reduction of Cr(Vl) by Fe(n) is the only source of Fe(lll) and
Cr(lll), a solid solution with the composition CrO,z~FeO,JOH), forms via the
reaction HCrO~ + 3F62+ + 3H20 + 50H+ + 8~0 + Fe2+ where the ions in the
brackets denote ions within the crystal structure of biotite. To maintain charge
balance, K is released to solution as the iron in the crystal structure is oxidized. The
Cr(Vl) in solution is then reduced by the Fez+. The Fes+ resulting from this
reduction reaction is then adsorbed to the surface of the biotite where it is again
reduced to F&+, thus setting up a cycle that ultimately results in the reduction of
more Cr(Vl) than is stoichiometricaliy possible for the amount of iron that is in
solution.

There are some key experimental difficulties in studying groundwater/mineral

interactions such as those just described that have some bearing on the transfer of
knowledge to the field. Although the processes can in some cases be interpreted
from the data on mineral reactions, the rates themselves may be quite useless. A key
difficulty in studying mineral reactions in the laboratory is that the rate of the
reaction depends on how the solid phase was prepared. For example, if the samples
are ground and simply washed before use, microparticles can adhere to the larger
grain surfaces. These microparticles have greater specific surface area and can react
at a much faster rate than the larger size particles. Such experimental artifacts were
observed in weathering studies of pyroxenes (Schott et al., 1981). Another important
reductant in soils is organic matter. In fact, bichromate reduction has been used as a
wet combustion method for the determination of soil organic carbon (Walkley and
Black, 1934). Bichromate can react with soil organic carbon according to 2Cr20~- +
3C + 16H+ --+ 4Cr3+ + 3C0 (Eary and Rai, 1988; Sass and Rai, 1987). The
volubility of CrXFe,-X(OH)~ decreases as the mole fraction of Fe(lll) in the solid
increases. Therefore, if the pH is between 5 and 12, the concentration of Cr(lli) is
expected to be less than 10+ molar.

Numerous minerals in geologic materials contain ferrous iron that is potentially

available for the reduction of hexavalent chromium. These iron-containing minerals
may be silicates, oxides, or sulfides. Common ferrous iron-containing silicates
include olivine; pyroxenes such as augite and hedenbergite; the amphiboles
hornblende, cummingtonite, and grunerite; micas such as biotite, phlogopite, and
glauconite; chlorites, and the smectite nontronite. Iron oxides such as magnetite
(Fe2+Fe~+OJ contain iron as a major constituent, however, hematite (Fe~+03) can
contain small amounts of (FeO). In sulfide minerals such as pyrite (FeS2), both the
ferrous iron and the sulfide are active in reducing hexavalent chromium. Lancy
(1966) suggested that pyrite could be used for treating spent cooling waters that
contain Cr(Vl) as a corrosion inhibitor. He stated that the reduction of Cr(Vl) occurs
at the pyrite surface rather than in solution. Lancy (1966) found that reduction by
pyrite occurred even in slightly alkaline solutions; however, the pyrite had to be
continuously abraded to remove surface coatings. Blowes and Ptacek (1992)
conducted batch tests in continuously agitated reaction vessels containing a solution
of 18 mg/L Cr(Vl) and pyrite both in the presence and in the absence of calcite. In
the experiments that used both pyrite and calcite, 509!. Of the Cr was removed in
less than 6.5 hours. Concentrations were <0.05 mg/L after 20 hours. Experiments
conducted without the calcite attained 50% removal in 1 hour and concentrations
were c 0.05 mg/L in less than 4 hours. Cr( Vl) reduction in the presence of iron
oxides has been observed in several experiments. White and Hochella (1989) found
that magnetite and ilmenite reduced Cr(Vl) to Cr(lli). The reduction of Cr(Vl) in the
presence of hematite (Fe20J was demonstrated by Eary and Rai (1989). They
attribute the reduction to the presence of a small amount of an FeO component in the
hematite. They suggest that reduction occurs in solution after the FeO component
has been solubilized.

Reduction of Cr(Vl) by ferrous iron-containing silicates has been reported. Eary and
Rai (1989) suggest that the reduction of Cr(Vl) in the presence of biotite occurs in
solution rather than at the mineral surface. They observed an increase in the rate of
reduction when their suspensions were spiked with Fe&. They explain their results
with the mechanism proposed by White and Yee (1985) in which Fe3+ is reduced at
the mineral surface by the reaction [Fe(n), K+]~iOtit~ + Fe3+ ~

Persistent, bio accumulative and toxic (PBT) chemicals do not readily break down in
the environment, are not easily metabolized, may accumulate in human or ecological
food-chains through consumption or uptake and may be hazardous to human health
or the environment. A PBT chemical, once released to the environment, may present
increasing long-term toxic effects to human health and the environment, even if the
release was of a small amount. Chromium is a high priority PBT chemical.
Hexavalent chromium or chromium(VI) is a recognized carcinogen. Exposure to
chromium(VI) in dust is associated with increased incidence of lung cancer and is
known to cause inflammation of the skin (dermatitis). In contrast, trivalent
chromium or chromium(III) is considered relatively safe. It is an essential nutrient
that helps the human body utilize sugar, protein and fat. It is not known if exposure
to chromium will result in birth defects or other developmental effects in people.
body. Chromium(VI) and chromium(0) are generally produced by industrial
processes. The metal chromium, or chromium(0), is a steel-gray solid with a high
melting point. It is used mainly for making steel and other alloys. The naturally
occurring mineral chromite in the chromium(III) form is used as brick lining for
high-temperature industrial furnaces, for making metals, alloys and chemical
compounds. Chromium compounds, mostly in chromium(III) or chromium(VI)
forms produced by the chemical industry, are used for chrome plating, the
manufacture of dyes and pigments, leather tanning and wood preserving. Smaller
amounts are used in drilling muds, rust and corrosion inhibitors, textiles and toner
for copying machines. Chromium enters the environment mostly in the Chromium
(III) and Chromium (VI) forms as a result of natural processes and human activities.
Emissions from burning coal and oil and producing steel can increase Chromium
(III) levels in air. Birth defects have been observed in animals exposed to Chromium
(VI). Studies with mice have shown that chromium crosses the placenta and
concentrates in fetal tissue. Therefore, pregnant women who are exposed to
chromium in the workplace or by living near chromium waste sites may transfer
chromium from their blood into the baby where it may build up at levels greater than
in the mother. There is some evidence that chromium can be transferred from the
human mother to infant through breast milk.

Today, both hexavalent chromium [chrome (VI)] and trivalent chromium [chrome
(III)] electroplating processes are commercially available for decorative chrome
plating operations. Because electroplating with (V1) has historically been easier than
chrome (III), chrome (V1) was essentially the only decorative chromium process
used for almost 70 years.

Electroplating with chrome (VI), however, is more toxic than chrome(III) And
presents a real threat to both you and your-workers. What is more, Chrome (V1)
operations cost you more in waste management and disposal costs.

Chrome (V1) is dangerous to plating shop personnel. It is highly toxic material,

known to cause skin ulcers and dissolve mucous membranes upon prolonged
exposure. In decorative chrome plating, problems with chrome (V1) are further
compounded as plating times are shorter and more parts are removed from the per
hour of plating compared to functional chromium plating. In a system where parts
are manually removed, workers are exposed to the bath chemicals more often.

Rinsing concentrated chrome (V1) plating solution from the plated part can be
difficult because of its high viscosity. Inevitably, a large quantity of chrome (V1)
gets dragged out the tank along with the parts. The dragged out chrome (V1)
contaminates rinse waters, stains parts, and exposes shop personnel to additional
health hazards. a result of the chemistry of chrome(V1)’s electrolyte, large quantities
of Hydrogen and oxygen gas are generated during plating. The gases bubble to air.
This mist-can be inhaled. Good ventilation, use of mist suppressants, and good
housekeeping can minimize the transfer chrome (V1) from the tank, but does not
totally eliminate it. Air scrubbers, which are expensive to Purchase and operate, are
typically required to reduce airborne chromium leaving the plating shop to very low
levels. Protective gear may also be necessary to keep airborne chromium from
workers.

In January 1986, the California Air Resources Board(CARB) identified chrome(V1)

as a toxic air contaminant and a possible human carcinogen. chrome(V1) control
plan was approved by CARB in February 1988 along with the adoption of the first
control measure to reduce emissions from chrome plating and chromic acid
anodizing operations. For decorative plating shops, the control measure requires that
uncontrolled emissions be reduced by at least 95% or a rate of less than 0.15
mg/amp-hour.

CayOSHA standard GISO sets minimum air control velocities for local exhaust
ventilation systems for chrome plating tanks. Failure to comply with GISO 154 may
constitute failure to comply with the Safe Drinlung Water and Toxic Enforcement
Act of 1986, popularly known as Proposition 65. Proposition 65 prohibits employers
from exposing workers to certain chemicals (including chrome(V1)) above specified
levels without first warning them. Daily with carbon
In most plating applications, chrome(V1) and chrome(II1) processes are
interchangeable. However, in the conventional treatment of chrome(V1) wastewater,
chrome(V1) must be reduced to chrome(II1) before it can be precipitated.
Approximately three pounds of sodium metabisulfite are needed in the reduction
step to treat each pound of chromic acid. In the chrome(II1) system no reduction
step is needed. The quantities of chemicals used, the need for auxiliary equipment,
and the costs of labor are significantly reduced. Chemical costs for treating
chrome(II1) rinsewater are approximately one-tenth that of the costs for treating
chrome(V1) rinsewater. The amount of sludge generated from treatment is reduced
by as much as Performance differences of the two plating operations are shown in
Table The typical operating conditions for chrome(II1) and chrome(V1)
electroplating processes are compared in . There are two significant reactions in the
chrome(II1) processes. Both are very simple: Deposition Reaction: Cr'" 3e'+ Side
Reaction: Cr"' Crv'+ 3e- The side reaction takes place at the anode under some
conditions. To prevent the side reaction from occurring, either a single cell process
or a double cell process can be used. The single cell process has the anode in the
same chrome (II1) ion containing solution as the cathode or part, hence the term
"single cell". An insoluble inert graphite anode is used for this process. The bath
chemistry in combination with the anode prevents the formation of chrome(V1) ions.
The double cell process requires the isolation of a lead anode from the chrome(II1)
ion containing solution that surrounds the cathode or part. The anode is in an anode
box that physically separates from the electrolyte by an ion-selective membrane.
For this reason, the process is referred to as a "double cell" process. involves the
plating of metallic impurities on to a dummy cathode. The problem with dummying,
however, is that it takes a long time to complete, typically 8 hours for metallic
impurities at a concentration of ppm. Dummying slows down production. For the
single cell process, there are two other methods apart from dummying that can be
used. First, there is chemical precipitation wherein you can choose from a variety of
commercially available purifying chemicals that remove the metallic impurities in
about an hour. Second, a selective ion exchange unit can be installed to continuously
treat the plating solution. The installation of an ion exchange is often the preferred
method of treatment for the single cell process (see case study). Dummying is the
only way to remove metallic impurities from the double cell process; it must be done
at the beginning or end of each plating shift. Otherwise, an off line tank can be
installed to allow for the simultaneous dummying of an alternate bath of plating
solution during the plating shift.

The double cell process must also be treated to remove organic impurities which are
either dragged in from the preceding nickel plating tank or generated during 175-300
Air 4-15 Carbon 4-20 , 4-15 Lead-7% 4-12 Lead-7% tin or about 0.005-0.007
0.007-0.010 less plating by the breakdown of organic additives. Since no
breakdown products occur in the single cell process, only occasional treatment for
excess organics is necessary. Activated carbon treatment removes the organics for
both processes.

Some platers and their customers are reluctant to convert from chrome(V1) to
chrome(II1) because they remember the problems with older chrome(II1) processes.
Historically, operational problems of chrome(II1) included: poor metal distribution,
requirements for extremely high limiting current densities, and +buming,d the
formation of dark-colored deposits during plating. Today, however, all of these
problems can be managed. Both of chrome(II1) processes, single or double cell, can
use the same bath tanks, equipment and rectifiers as those used for chrome(V1)
plating. For process control, chemical analysis of the baths are typically conducted
more often with chrome(II1) than with chrome(V1) as the baths are more sensitive
and take more care. Platers generally rely upon a pH meter for pH control, a
hydrometer for chromium concentration. and an amp/ hour meter for timing bath
additions. The concentration of metallic impurities in the bath is determined by a test
paper similar to pH paper. Since chrome(II1) deposits resist buming, a higher
amperage rectifier can used to increase the process’ throwing power. Throwing
power is property of the plating bath to distribute metal uniformly over parts. The
rectifier does not have to

AC-filtered to remove ripple, as required for chrome(V1). Chrome(II1) solutions

drain and rinse from parts more easily since they are less concentrated g/L versus
150 g/L for hexavalent solutions) and less viscous than chrome(V1). A The throwing
power and covering power of chrome(II1) is very good. Parts are almost significant
reduction in drag-out volume and material costs for makeup chemicals is the result.
impossible to bum and there are no whitewashing problems as compared to
chrome(V1). As a result, there are fewer rejects. Also, parts can be placed 30 to 40%
closer together With a chrome(II1) system, it unnecessary to add sodium bisulfite or
other reducing agents to the wastewater to convert chrome(V1) to chrome(II1)
before precipitation. Lower material concentrations reduce the amount of sludge
generated by as much as 80%. on the racks. This increases production yield.
Chrome(II1) processes do not require air scrubbers or tank ventilation if shop is
adequately ventilated. Also, auxiliary anodes that are sometimes necessary with
chrome(V1) processes to obtain coverage in recesses are seldom necessary in
chrome(II1) processes. processes. Chemical additions are based upon amp-hours,
specific gravity, and pH only.

Health hazards associated with misting and odor are almost completely eliminated
with Operational control of chrome(II1) plating processes is typically easier than for
chrome(V1) chrome(II1) processes because of the low chromium concentrations and
the greatly reduced toxicity and corrosion properties of chrome(II1) as compared to
chrome(V1). There are also fewer waste handling problems. Chrome(II1) is not a
suspected human carcinogen nor classified as a toxic air contaminant as is
chrome(V1) by the California Air Resources Board. Chrome(II1) processes more
easily meet the strinpmt industrial wastewater discharge requirements set by the
Regional Water Quality Control Boards and local sewage authorities. Capital costs
for making the switch are generally limited to the costs of the new bath chemicals
and the costs of disposing of the old. The lead anode must be replaced if switching
over to a single cell process. The old process tanks must be given a thorough
cleaning to remove all lead and chrome(V1) residues to avoid poisoning the new
bath chemicals. A selective ion exchange unit may also be procured to maintain
quality control of bath metallic impurities to prevent coloring of parts.
2.2 Environmental Effects of electroplating waste and Chemicals

Agency for Toxic Substances and Disease Registry, Division of Toxicology and Environmental
Medicine, 1600 Clifton Road NE, Mailstop F-32, Atlanta, GA 30333. Phone:

1-800-232-4636, FAX: 770-488-4178. ToxFAQs Internet address via WWW is

http://www.atsdr.cdc.gov/toxfaq.html.

Skin contact with certain chromium(VI) compounds can cause skin ulcers. Some
people are extremely sensitive to chromium(VI) or chromium(III). Allergic reactions
consisting of severe redness and swelling of the skin have been noted.

How likely is chromium to cause cancer?

The Department of Health and Human Services (DHHS), the International Agency
for Reseach on Cancer (IARC), and the EPA have determined that chromium(An
increase in stomach tumors was observed in humans and animals exposed to
chromium(VI) in drinking water.

Cr (VI) compounds are known human carcinogens. In workers, inhalation of

chromium(VI) has been shown to cause lung cancer. Chromium(VI) also causes
lung cancer in animals.

How can chromium affect children?

It is likely that health effects seen in children exposed to high amounts

of chromium will be similar to the effects seen in adults.

We do not know if exposure to chromium will result in birth defects or

other developmental effects in people. Some developmental effects have
been observed in animals exposed to chromium (VI).

How can families reduce the risks of exposure to chromium?

Children should avoid playing in soils near uncontrolled hazardous

waste sites where chromium may have been discarded. Chromium is a
component of tobacco smoke. Avoid smoking in enclosed spaces like
inside the home or car in order to limit exposure to children and other
family members. ‘Although chromium (III) is an essential nutrient, you
should avoid excessive use of dietary supplements containing chromium
Is there a medical test to determine whether I’ve been
exposed to chromium?

Since chromium(III) is an essential element and naturally occurs in food,

there will always be some level of chromium in your body. Chromium
can be measured in hair, urine, and blood.

Higher than normal levels of chromium in blood or urine may indicate that a person
has been exposed to chromium. However, increases in blood and urine chromium
levels cannot be used to predict the kind of health effects that might develop from
that exposure.

government made recommendations to protect human

health?

Has the federal The EPA has determined that exposure to chromium in drinking
water at concentrations of 1 mg/L for up to 10 days is not expected to cause any
adverse effects in a child. The FDA has determined that the chromium concentration
in bottled drinking water should not exceed 1 mg/L. The Occupational Health and
Safety Administration (OSHA) has limited workers’ exposure to an average of 0.005
mg/m3 chromium(VI), 0.5 mg/m3 chromium(III), and 1.0 mg/m3 chromium(0) for
an 8-hour workda,y 40-hour workweek
 UNIT-THREE
3. Result and Discussion

3.1 Observation and identification of Chrome Wastes

In Gafat Armament Engineering Complex three basic pollutants wastes

are observed: these are:- Solid, Liquid and Gaseous.

The liquid waste discharged from the industry includes Chrome plating

• For de-oiling purpose

• O - 20-30 Kg

• - 3-5 Kg

• HCl for pickling purpose

• CaCO3 – viscose solution & cold or hot water for neutralization

The chemicals that are used for anode preparation by pb plating

• PbO 100-120kg
• Hf 100-120 kg
• H3BO3 100-110 kg
• Glue 3-5
For plating

1. Cr 140-180g/l

1.5-2.2g/l

2. Cr 30-280g/l

2.5-3g/l

In Gafat Armament Engineering Complex, it was observed that waste is flows

from de-oiling, picking, neutralization and plating baths in to the main waste water
tanks. Due to the uncontinuity of the plating work, it is difficult to determine the
amount of waste water discharged per day, weekly and monthly.

Gafat Armament Engineering Complex has use two chromic waste tanks. Each
tank has the capacity to contain 10000 lt of waste water. These tanks full in 45-60
days and discharged /disposed/ to the environment after treatment. During disposal
the PH values range from 605 to 8.0.

Pl C S Sedimentation & Dispose to

Plating Collecting & final checking point the
bath treating tank pointpopoint environment

Fig1. process of treatment plant in Gafat Armament Engineering Complex

3.1.1 PROCESS DESCRIPTION OF ELECTRO PLATING

Waste Disposal treatment

 De- Oiling Picking Neutralization Plating

1. For De-oiling

Hot –cold O wash

- Hard chrome ( )

- NaOn 20-30

- 100-150

- 12 O 20 -30

- 3-5

2. For picking

• Cold O wash
o Above 20%

3. For neutralization
o Cold- Hot O wash

 Pbo 100-125
 Hf 100-120

 100-110

 Glue 3-5
4. For plating
o Anode preparation lead plating

 230 -280 gm/l

 2-3 gm/l

IONS EXPECTED TO BE FOUND IN CHROME WASTE TANKS

 Cat ions:-

- Chrome – hexavalent ions ( )

- Chrome –trivalent ions( )

- Sodium ions ( )

- Calcium ions ( )

- Lead II ions ( )

- Hydrogen ions ( )

An ions

- Sulphate ions ( )

- Hydroxide ions ( )

- Boric ions ( )

- Carbonate ion ( )

- Phosphate ion ( )

1. Disposal of chrome waste water

To dispose chrome waste water to the environment, first the analysis must be done
carefully to calculate the amount of chrome in that disposable solution.

The process of the analysis is as follows

- Take 4ml sample from the chrome waste water bath

- Dilute this sample up to the scale line ( dilute by adding 96 ml of distilled
water)
- From the diluted solution take %ml and put in 250 ml beaker
 - Add 15 ml 28% sulphuric acid ( ) in to it.

- Shake the sample for uniform distribution ( good mixing) of and

the sample

- Titrate this first by reagent until the solution colour become green

- Next titrate this green color solution by KMn reagent until the solution
become rose in colour
- Finally, the calculation

(gm/l) = ( F Of x consumed in ml) – ( F of KMn x consumed ml) x 3.33

Sample

After calculating the amount of CR which is found in a litre solution magnifies the result

for the total bath volume.

• To neutralize the chromium waste water first add 283 gm Sulphuric acid
in to every 1000 gr of the calculated chrome.
• ……. Add 1400 gr ferrous sulphate per 1000gr of six valances????
chrome and perform the first stage reaction for about 10 min.
• After the above reaction is finished put 995 gr of Sodium Carbonate in to
every 1000gr of hexavalent chrome, finally, make sur in analysis that
concentration of hexavalent chrome among the taken sample is reached
as allowable value.
• The allowable concentration of hexavalent chrome among waste water
of chrome must be below 0.1 mg/l and allowable PH should be in range
of 7 to 8.5.

DATA 1.

• Take 4ml sample from the chrome waste water bath

• 4ml of Cr dilute by 96 ml of water distilled water)
• Take 5ml of Cr dilution solution and dilute with 100 ml of
water

• Take 15 ml of which is 28 %
 • Shake gently to mix the acid mixture with diluted water
solution

• Titrate this first by reagent until the solution colour

become green

• Next titrate this green color solution by KMn reagent

until the solution become rose in colour finally the
calculation is as follows

(gm/l) = ( F Of x consumed ) – ( F of KMn x consumed KMn ) x 3.33

Sample

(gm/l) = ( 1.01 x 2.6 ) – (1.03x 0.1) x 16.65

= 42.01 g/l

1000g Cr = 283g of

= 1400g of )

= 795g of

Therefore, if 1000g Cr waste = 283 g of

42.01g Cr = ?

= 11.89 g of or 0.1189 kg of

* 1000g Cr waste = 1400g of O

42.01g Cr ----- b
 42.10 g Cr x 1400g O = 10009Cr waste x b

10009 Cr 1000g Cr

b = 58.82 g of Og or 0.05882 Kg of O

* 1000 g Cr waste + 795 g

42.01 g Cr -----b

42.01 g Cr x 795 = 1000 g Cr x b

1000 g Cr 1000 g Cr

b = 33.39 g of or 0.03339 Kg of

= 1840 Kg /

= 0.01189Kg

? = m/v

V = m/? = = 6.462 X

1 = 1000b

6.462x =b
 b = 6.462x x 1000 l

= 6.462 x l or 0.00646 ml of

1L = 1000ml

0.00646=0.00646ml

1L x 0.00646 = 6.46x L

1000

1L = 0.00646ml

10000L = ?

= 10,000L x 0.00646ml of = 64.6L of

1L

DATA 2.

- Take 4ml sample from the chrome waste water bath

- Dilute by 96 ml of distilled water
- From the diluted solution take 5 ml and put in 250 ml beaker

- Dilute 5ml by 15 ml of 28% )

- Shake gently to mix the acid mixture with diluted waste water solution
- Titrate this first by reagent until the solution colour become green

- Next titrate this green color solution by Kmn reagent until the solution
become rose in colour
- Finally, the calculation as follows
 o Consumed = 1.2 ml

o Consumed Kmn = 0.1 ml

o Factor of = 1.01 ml

o Factor of Kmn = 1.03

Calculation

(g/l) = ( F Of x consumed ) – ( F of KMn x consumed in ml KMn ) x 3.33

/ 100

( 1.01 x 1.2 ml ) – 1.03x0.1 ) 3.33

0.2

= 1.104 x 3.33

0.2

= 18.47 g/l of Cr

☛1000g of Cr = 283g of

= 1400g of
 = 7959 g of

• 18.47g/l of Cr

1000 g Cr = 283g of

18.47 g/l of Cr = X?

1. X= 5.23g of ------ 5.2 x kg ------0.005 Kg

2. 1000g Cr + 1400

18.47g/l Cr ----- X ?

X = 25.860gm of ---------------------------0.026 Kg

3. 1000g of Cr -----------795g of

18.47 gm Cr ---------X ?

X = 14.689gm of ----------------------0.015 Kg

To know the volume of

Þ( ) = 1840 kg/

Mm( ) + 0.0052kg, then

 V (( ) =m( )

Þ )

= = 2.8 x

☛1 ----------1000L

2.8 x -------X?

X = 2.8 x 1000L = 2.8x L of is added in 1 litter of Cr wastes

☛ 1L Cr waste ----------2.8 ml

10,000 l Cr waste -----------X?

X= 10,000L Cr waste x 2.8 ml

1 L Cr waste

X = 28000ml of or 28 L of

Then add 28L of in 10,000 l of chromium waste water tank, after treatment

- Take 4ml sample from the treated solution

 - Dilute by 96 ml of water
- Take 5 ml of solution and dilute with 100 ml of water

- Take 15 ml of which is 28 %

- Shake gently to mix the acid mixture with treated waste water solution
- Titrate this first by reagent , until the solution colour become green

- Next titrate this green colour solution by Kmn reagent until the solution
become rose in colour

Finally,

o Consumed = 0.1 ml

o Consumed Kmn = 0.025ml

o Factor of = 1.01 ml

o Factor of Kmn = 1.03

Therefore :

(g/l) = ( F Of x consumed ) – ( F of KMn x consumed in ml KMn ) x 3.33

= (g/l) = ( 1.01 x 0.1ml ) – ( 1.03x0.025) x 3.33

0.2

= ( 0.101- 0.02575 ) x16.65

= 1.25g/L

Recommendation based on TMT process

As we seen the procedure, they followed can not related with that of
calculated volume to be added to treat the chrome waste.

Environmental related influence

The waste which discharged after treated can not be checked its PH –
value and other related problems

As a result, it may pollute the soil as well as well waters that communities
used and neighbouring crops etc.

Related to Cost

Since the amount of calculated value cannot related to that of added

values, it may be over or lesser than the amount of added chemicals
therefore, is the TMT method they followed is not cost wise.

Therefore, the process, which they follow were practical based, but not
theoretical lab – analysis with that of practical related values to be added
in the treatment procedure ( process)