CHAPTER ONE

1. INTRODUCTION

1.1Background
Production of leather from raw hides and skins, by-products of meat industry, has been one of
the most important industrial processes since ancient times [1]. The Ethiopian leather
industry is a relatively older industry with more than 80 years of involvement in processing
leather [2]. Leather industry in Ethiopia plays significant role for economic growth of the
country as a main source of foreign currency. Because it generates the second largest export
revenue next to coffee [3]. Ethiopia is one of the leading countries that have the largest livestock
populations in the world providing a strong raw material base for the leather industry. Its
livestock population is estimated at 50 million cattle, 25 million sheep and 23 million goats.
About 80% of all hides and skins entering the formal market come from rural areas where they
are collected by private traders. The remaining 20% are derived from slaughtering facilities
found in major town and cities. About 15.5 million pieces of sheep and goat skins and 1.2million
pieces of cattle hides are supplied to the tanneries per annum [4].There are presently 27 tanneries
operating in the country, employing over 5,000 people and having soaking capacity of 1.3
million pieces of hide and 32 million pieces of skins annually. The existing daily soaking
capacity of tanning industries is 145, 524 pieces of skins and 7,800 pieces of hides. About one-
third of these tanneries are found in Addis Ababa and its surrounding [5].Leather industry has
been categorized as one of highly polluting industries and it has adverse impact on environment
because of the generation of liquid, solid and gaseous wastes. However, most of the tanneries in
Ethiopia dispose their liquid and solid waste to the environment without any treatment
mechanisms. The situation with solid waste by product management is even worse than the
liquid effluent. Because there is no designated site for disposal of huge solid wastes the tanneries
generate every day. Hence tanneries are using the nearby water ways for dumping their solid
waste [3]. In leather industry, tanning is the main process that protects leather against some
environmental effects such as microbial degradation, heat, sweat or moisture. About 90% of
tanneries in the world use chromium salts as tanning materials because of the excellent properties
of the chromium compounds in the tanning process [6]. During the tanning process, chromium
forms cross links between the collagen fibers and the resulting hides have a good mechanical

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resistance, an extraordinary dyeing suitability and a better hydrothermal resistance in comparison
with hides treated with vegetable materials [7]. However, up to two-thirds of the chromium used
to tan hides by a typical tannery never gets into the finished product. Because about 10 to 40
percent of the chromium finds its way into the liquid waste, depending upon the degree of
chromium recycling and the use of various exhaust additives in each tannery. Another third of
the chromium used becomes lost in the solid waste in the form of shavings and trimmings [8].
Among the numerous solid wastes, the chromium containing tannery solid wastes such as wet
blue shavings, chrome tanned leather trimmings, buffing dust and wastewater treatment sludge
are of major concern, due to their high chromium content and their toxicity. Sanitary landfills are
reluctant to accept chromium containing tannery solid wastes because of the possibility of
trivalent chromium (III) being oxidized to hexavalent chromium (VI) [9].which consequently
contaminates surface and ground waters. Chromium (VI) is more toxic and more mobile in the
environment than chromium (III) and, as hazardous landfills are expensive, there is an urgent
need to find an economically attractive and efficient method of disposal for chromium containing
tannery solid waste [10]. The environmental impact of chromium (Cr) discharged from tanneries
has been the subject of extensive scientific and technical dispute. This because chromium (III) is
less toxic even it is an essential nutrient for human body [11]. But Chromium (VI) compounds
are responsible for the majority of the health problems associated with all chromium compounds
[12]. Normally during the tanning process only chromium (III) salts are used. Nevertheless,
under certain conditions specially in the presence of oxidizing agent like manganese oxide the
chromium (III) can be transformed into chromium (VI) [9]. A number of researches and
experiments have been made to remove or recycle chromium from tannery wastewater and
different methods like precipitation and adsorption have been developed for the removal of
chromium from tannery waste water. However, for the removal of chromium from tannery solid
waste there is no alternative and feasible methods developed. Of course there are some methods
to extract chromium from tannery solid wastes like enzymatic hydrolysis and microbial
fermentation of chromium containing tannery solid waste [10]. But these methods are
complicated and expensive which make them difficult to apply in large scale especially in
developing countries. The simplest method for chromium containing tannery solid waste is to
dump it in open air land fill instead of trying to remove chromium from the solid waste. But
these methods have a problem of leaching the chromium (III) from the solid waste which can be

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oxidized to chromium (VI) which is one of the carcinogenic substances that can contaminate soil
and ground water [13].

In recent years the intensities of pollution have increased because of the problems brought about
by the high rate of industrialization and the applicability of the methods of removal. Presently
reuse of the hazardous industrial waste is advocated worldwide. Solidification has been
considered as an option of the disposal of chrome containing total solid waste (CCTSW) from
Debre brhan tannery factory. Chromium containing tannery solid wastes generated from Debre
brhan Tannery factory per year were found to be wet blue shaving (189800 kg/year) and buffing
dust (53000 kg/year) .chrome containing total solid wastes are mixed with various binding
materials to obtain a new product, with improved physical and chemical properties of wastes.
Concrete block based stabilization of the industrial solid waste has been practiced in Debre brhan
tannery factory as an effective solution in reducing of heavy metal containing solid waste. This
approach may also serve as economically viable and environmental friendly option for Debre
brhan tannery factory. However, detailed study appears necessary for determining the proper mix
design and methodology concerning the stabilization of the solid waste with concrete blocket
without significantly sacrificing the strength.

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1.2 Statement of the problem
Tanneries generate huge amount of CCTSW, such as wet blue shaving waste and buffing dust.
Most of these wastes are highly acidic and contain trivalent chromium. And in acidic medium
trivalent chromium is highly soluble and leachable. Hence when these solid wastes dispose to the
receiving environment or utilized for different purpose without any treatment, trivalent
chromium has the tendency to leach and oxidized in to hexavalent chromium which is highly
toxic even in a very small amount to all living organisms. Beside to this the acidity of most of
CCTSW which is around pH 3-4 will lower the pH of the receiving environment which will
disturb the fauna and flora found there Sanitary landfills in countries that have strict
environmental regulation are reluctant to accept CCTSW because of the possibility of trivalent
chromium being leached from CCTSW and converted to hexavalent chromium in gentle
condition in wide range of pH (both in acidic and alkali media). But most of the tanneries in
Ethiopia dispose their CCTSW in the nearby rivers and water ways .And some tanneries like
Debre brhan tannery factory dispose their CCTSW without any treatment to landfill which is not
secured for such hazardous waste disposal. This subsequently causes both surface and ground
water pollution and soil contamination with the toxic chromium metal. And there are a lot of city
farms near this land fill site which might create a possibility for chromium to enter in to the food
chain. Chromium is not biodegradable and tends to bio accumulate in living organisms causing
serious disease and disorders. Therefore, these waste are utilized in the field of construction by
partial replacement of fine aggregate with tannery shaving waste and buffing dust then there
could be some reduction in the amount of waste which coming out of the industries

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1.3. Objective

1.3.1 General objective

The overall objective of this study is Utilization tannery waste (chrome shaving waste and
buffing dust as fine aggregate in concrete blocket from Debre brhan tannery factory.

1.3.2 Specific objective

 To evaluate the characteristics of the chrome containing solid waste collected from
Debre brhan tannery factory.
 To estimate the compressive strength of the concrete blocket mixed with different ratios
of tannery waste.
 To assess the effect of chrome containing solid waste addition on the water absorption
and density of concrete blocket.

1.4 Motivation idea of study

To do one research same one have their own initiative things /idea that he/ she they see clearly
when he/she they opens their eyes to the environment .There for we have So many things that
initiate us to do this study in same area are the following.

 Environmental pollution
 Fine aggregate naturally degradable

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1.5. Significance of the study
In this study huge amount of chromium containing tannery solid wastes generated per hide / skin
processed in Debre brhan Tannery. This enables to know the total amount of chromium
containing solid wastes generated from Debre brhan Tannery and also helps to reducing the total
amount of chromium containing solid wastes generated from other tanneries in Ethiopia based on
their process capacity. This is important information for tannery solid waste utilization program.
Beside to this the study provides baseline information about the environmental impact of
chromium containing tannery solid wastes specially about the conversion of chromium(III) that
is mainly found in CCTSW in to chromium(VI) which is a more toxic form of chromium in the
receiving environment. This study also proposes for the manufacturing of concrete blocket from
chrome containing total solid wastes. This sequentially reduces the environmental impact of
CCTSW.

1.6 The scope of study

In this study the collected tannery solid waste sample was mixed with the binding material (i.e.
Cement) and aggregates to obtain the new product (i.e. concrete blocket). The properties
evaluated for the solidified concrete blocket were compressive strength, water absorption and
density. The quality of the mixtures differs according to the proportions of the additives. For
better understanding, a large number of samples need to be analyzed from Debre brhane tannery
factory. In this study solid waste sample from Debre brhane tannery has been used. The solid
waste sample was collected in untreated and partially degraded condition, which was later dried
and sieved before mixing into the concrete blocket. The heavy metals of concern for this study
were Chromium (Cr). The primary purpose of the study is the compressive strength and other
physical and chemical properties of the solid waste mixed concrete blocket were evaluated to
validate the stability of the concrete blocket.

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 CHAPTER TWO
2. LITERATURE REVIEW
2.1 History
The story of leather is long and colorful. Many years before recorded history people wrapped
themselves in dried animal pelts. The fact that the skins turned stiff and rotted was a problem,
but ways of softening and preserving the hides were discovered. This was the beginning of
leather processing. At first the hides or skins were probably dried in air and sunlight. Later they
may have been soaked in water and dried over a fire. Still later it was discovered that certain
twigs, barks and leaves soaked with the hides in water helped to preserve them. Through
archeologist’s findings, we know that primitive man used the skins of hunted animals for food as
well as clothing. Nomadic tribes made shelters from the hides of larger animals, such as bison.
As civilization advanced, preserving hides and tanning them into leather became an important
industry. In the 18th century tanning was an old and respectable trade and a tedious one. Nearly a
year was spent manipulating a hide before it was delivered as leather to the saddle maker,
harness maker or other craftsmen. Now days the process is automated and modern techniques.
Tannery industries generate waste containing various types of organic particles and
toxic chemicals, which are discharged in open drains and ultimately find its way on to
land surface and in natural waters near the tannery. The huge amount of pollution from tannery
waste has already highly impact in the public health and the environment. This chapter contains a
review of the relevant literature.

2.2 Characteristics of tannery solid waste and effluent

2.2.1 Unhairing and fleshing effluent

The effluent from unhairing operation is more or less continuous and contains mostly
hairs and sulphides. Fleshing operation gives rise to an effluent which is also more or
less continuous and contains fatty and fleshy matters in suspension.

2.2.2 Vegetable tanning effluent

The spent vegetable tan liquor is probably the strongest fraction in a composite tannery
effluent. Although its discharge is batch wise or intermittent and constitutes about 10% of

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total volume of effluent, it is acidic in nature and has a persistent color, which is difficult
to remove by known chemical or biological method, and characteristic offensive odor.

2.2.3 Chrome tanning effluent

The major process of the tanning industry is chrome tanning which produces leathers
characterized by top handling quality, high hydro-thermal stability and excellent properties .The
majority of the shoe uppers are tanned with chromium compound. Tanneries produce a great
variety of waste, in particular, the solid waste coming from the leather tanning with trivalent
chromium salts as trims, buffing dust and shavings. The spent chrome tan liquor is greenish in
color and highly acidic. The waste contains a high concentration of trivalent chromium ranges
from 100 to 200 mg/l. These need special utilization due to environmental effect and the
controlling requirements for those wastes. Basic chromium sulfate containing trivalent chromium
has been recognized as a less toxic compared with the hexavalent form which is more toxic and
carcinogenic .Many noxious residues are routinely utilized for manufacture of concrete blocket.
2.2.4 Dyeing and fat liquoring wastes

The effluent from the dyeing and fat liquoring process is generally small in volume and
discharged intermittently. The principle components are the residual of various dyes
used in tannery and oily emulsion.

2.3 Description of leather processes

Leather technology consists of different process steps and unit operations to convert raw hide
and skin into different finished leather. Although the technologies used by all tanneries are not
the same there are common operations in leather making activities. These main operations in
leather making process are beam house, tan-yard, post tanning and finishing operations each
comprising a number of sub operations as described below.

2.3.1 Beam house processes

The beam house process is the first process where the raw hide or skin is soaked, washed, limed, un
haired, fleshed, delimed and bated prior to tanning. The raw hide must be kept well preserved before
coming to the tannery in order to retard its putrefaction. The most common methods of preserving raw
hides are; wet-salting, dry-salting and sun-drying. The aim in all the three methods being the reduction
of moisture there by making condition unfavorable for bacterial growth.

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Soaking ; Soaking is carried out to allow hides and skins to re-absorb any water which may have
been lost after flaying, to clean the hides and skins (removal of dung, blood, dirt etc), and to
remove inter fibrillary material. The soaking methods depend on the state of the hides. The
process is mostly carried out in two steps: presoak to remove the salt and dirt and a main soak to
re hydrate the raw hide or skin and to adjust the pH to 8-10. The process is carried out in
processing vessels, such as mixers, drums, paddles, pits, or raceways. The duration of soaking
may range from several hours to a few days. Depending on the type of raw materials used,
soaking additives can be used such as surfactants, enzyme preparations and bactericides [6].
Un haring and liming of bovine hides; the function of liming and un - haring is to remove hair,
inter fibrillary components and epidermis and to open up the fiber structure. Hair removal is
performed by chemical and mechanical means. The keratinous material (hair, roots, and
epidermis) and fat are eliminated from the pelts mainly with sulphides (NaHS or Na2S) and
hydrated lime [Ca (OH 2]. Alternatives to inorganic sulphides include organic compounds such
as mercaptans or sodium thioglycolate in combination with strong alkali and amino compounds.
Enzymatic preparations are sometimes added to improve the performance of the process. The
process of liming and unhearing can be carried out in process vessels such as drums, paddles,
mixers, or pits [14].
Painting & liming of sheep skins; the aim of painting is to bring about the breakdown of the
wool root within the skin so that as much undamaged wool fiber as possible can be pulled
easily from the pelt. Paint, generally consisting of a mixture of sodium sulphide and lime, is
applied to the flesh side of the skin and left for several hours. Application of the paint can be
through a spraying machine or manually. After several hours the wool can be ‘pulled’ from
the skin, either manually or mechanically. After pulling the wool, the skins are limed in
process vessels, with the same purpose as the liming of bovine hides. Wool- on skins is not
painted, unhaired or limed.
Fleshing; Fleshing is a mechanical scraping off of the excessive organic material from the
hide (connective tissue, fat, etc.). The pelts are carried through rollers and across rotating
spiral blades by the fleshing machine. Fleshing can be carried out prior to soaking, after
soaking, after liming or after pickling .The process of fleshing is called green fleshing if the
removal is done prior to liming and unhairing. If fleshing is performed after the liming and
unhearing it is called lime fleshing. Sheep skins maybe fleshed in the pickle stage.

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Splitting; by mechanical splitting the thickness of hides and skins is regulated and they are
split horizontally into a grain layer and a flesh layer. Splitting is carried out on splitting
machines, fitted with a band knife. Splitting can be done in limed condition or in the tanned
condition. The inner part which is called pelt split or wet blue split considered as byproduct
and may be used for glue production or split leather production. The upper part (the grain part)
will be proceeding to the next leather making processes.

Raw hide/Skin

Soaking

Lemming &
Unhairing

Feshing &
splitting

Deliming &
Bating

Pelt

Figure 2.1 Flow Diagram of the Beam House Operation

2.3.2 Tan-yard processes

Deliming; the aim of deliming is to remove residual lime from the pelts and to take the pelts to
the optimum condition for bating. This involves a gradual lowering of the pH up to 8.2 - 8.8 (by
means of washing and addition of deliming chemicals), an increase in temperature and the
removal of residual chemicals and degraded skin component. Generally, deliming is performed
in a processing vessel such as drum, mixer or paddle.

Bating; Bating is a partial degradation of non-collagenic protein achieved by enzymes to

improve grain of hide and the subsequent run and stretch of leather. In this process the rest of the

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unwanted hair roots and scud can be removed. Bating is processed in the same deliming float by
using pancreatic enzyme.

Degreasing; Excess grease must be eliminated from fatty skins (sheep, pig) to prevent the
formation of insoluble chrome-soaps or prevent the formation of fat spues at a later stage.
Degreasing is most relevant in processing sheepskins, where the natural fat content is about
10 % - 20 % on dry weight. The nature of this fat makes it difficult to remove because of the
presence of cerides and a high melting temperature [6]. The three different methods
commonly used for degreasing are degreasing in aqueous medium with organic solvent and
non-ionic surfactant, degreasing in aqueous medium with non-ionic surfactant and degreasing
in solvent medium.

Pickling; Pickling is carried out to reduce the pH of the pelt prior to mineral tanning and
some organic tannages (e.g. chrome tanning, zirconium tanning gluterdialdehyde tanning, and
vegetable tanning). The choice of the exact pickling parameters depends on the subsequent
tanning step. Very often tanning is carried out in the pickle liquor; however, pickled pelts, e.g.
sheepskins, can be traded. Pickled pelt sheepskins must contain fungicides to protect them
from mould growth during storage.

Tanning; In the tanning process the collagen fiber is stabilized by the tanning agents such
that the hide or skin is no longer susceptible to putrefaction or rotting. In this process the
collagen fibers are stabilized by the cross-linking action of the tanning agents. Furthermore,
their dimension stability, resistance to mechanical action and heat increase after tanning
process [6]. The various tanning agents can be categorized in three main groups: Mineral
tannages like chromium tannage, Vegetable tannages and alternative tanning agents, which
includes syntans, aldehydes and oil tannage.

Sammying and setting; After tanning, the leathers are drained, rinsed and either horsed up to
age, or unloaded in boxes and subsequently sammed to reduce the moisture content prior to
further mechanical action, such as splitting and shaving. The setting out operation can be
carried out to stretch out the leather. Machines exist which combine the sammying and setting
action. After sammying and setting, hides and skins can be sorted into different grades after
which they are processed further or sold on the market.

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Shaving; The shaving process is carried out to achieve an even thickness throughout the
skin/hide, and it can be carried out on tanned or crusted stage of the leather. Shaving is carried
out where splitting is not possible or where minor adjustments to the thickness are required.

Trimming; Trimming is the process of removing the un wanted part (rags or flags) from the skin
or hide to reduce the damage by different machines in the next leather making operations and to
maintain the shape of the leather.

Pelt

Pickling

Tanning

Sammying

shaving

Trimming

shaved wet blue

Figure 2 .2 Flow diagram of tan-yard operation

2.3.3 Post-tanning operations

Post-tanning involves neutralization and washing, followed by retanning, dyeing, fat liquoring
and fixation mostly done in a single processing vessel. At this stage of the process, specialist
operations may also be carried out to add certain properties to the leather such as water
repellence or resistance, gas permeability, flame retarding, abrasion, anti-electrostatics etc. This
done by using some chemicals in this process that can bring the above mentioned characteristics.

Neutralization; Neutralization is the process by which the tanned hides are brought to a pH
suitable for the process of retanning, dyeing and fat liquoring. During neutralization the pH

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should be raised up to 4.8-6.5 based on the type of the product. There are neutralization agents
like sodium formate, sodium carbonate and neutralization syntans.

Bleaching; Vegetable tanned skins and leathers with wool or hair may need to be bleached in
order to remove stains, or to reduce the coloring in the hair, wool, or leather prior to retanning
and dyeing. In leather making process bleaching agent like sodium bi sulphite is commonly used.
There are also some syntans that have bleaching power in leather making processes.

Retanning; The retanning process can be carried out to improve the feel and handle of the
leathers and to fill the looser and softer parts of the leather in order to produce leathers of
more uniform. A wide variety of chemicals can be used for the retannage of leather such as
vegetable tanning extracts, syntans, aldehydes, mineral tanning agents like chromium meatals
and resins.

Dyeing; The dyeing process is carried out to produce level colors over the whole surface of
each hide and skin and exact matching between hides in a commercial pack. Typical dyestuffs
are water based acid dyes. Basic and reactive dyes are less commonly used. Sometimes
ammonia solution will be added during dyeing process to open up the fiber of the leather and
help the dyestuffs to penetrate through the leather. This is mostly done during dyeing process
of thick leathers like cow and buffalo leather.

Fat liquoring; Leathers must be lubricated to achieve product specific characteristics and to
reestablish the fat content lost in the previous procedures. The oils used may be of animal or
vegetable origin, or might be synthetics based on mineral oils. Stuffing is an old technique
used mainly for heavier vegetable tanned leather (commonly known as sole leather). The
sammed leather is treated in a drum with a mixture of molten fat. The retanned, dyed, and fat
liquored leather is usually fixed with formic acid to avoide bleeding of the dyes and fat
liquors and washed before being piled on a 'horse' to age (let the fat migrate from the surface
to the inside of the leather).

Drying; The objective of drying is to dry the leather whilst optimizing the quality and area
yield. There is a wide range of drying techniques and some may be used in combination. Each
technique has a specific influence on the characteristics of the leather. Drying techniques
include samming, setting, centrifuging, hang drying, vacuum drying, toggle drying and paste
drying. Generally samming and setting are used to reduce the moisture content mechanically

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before another drying technique is used to dry the leather further. After drying, the leather may
be referred to as crust which is a tradable intermediate product.

Neutralizing

Retanning

Dyeing

Fat liquoring

Setting out

Drying

Crust leather

Figure 2 .3 Flow diagram of post tanning processes

2.3.4 Finishing

The overall objective of finishing is to enhance the appearance of the leather and to provide the
performance characteristics expected of the finished leather with respect to: color, gloss,
handle, flex, adhesion, rub fastness, as well as other properties including extensibility, break,
light and perspiration fastness, water vapor permeability and water resistance as required for
the end use. Generally, finishing operations can be divided into mechanical finishing processes
and surface coat finishing process.

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  Mechanical finishing processes; A wide range of mechanical finishing operations
may be carried out to improve the appearance and the feel of the leather. The
following operations are commonly used mechanical finishing operations. However,
the list is not exhaustive and many other operations exist for special leathers such as
sole leathers and special effects leathers: Staking (softening and stretching of leather),
Buffing and dedusting (abrading of the leather surface and removing the resulting dust
from the leather surface), Dry milling (mechanical softening), Polishing and Plating or
embossing (flattening or printing a pattern into the leather).
 Surface coat finishing; There are a wide range of surface coat application methods
each of which has its advantages and disadvantages. A combination of methods can
be used to achieve the desired effect on the finished product. Commonly used surface
coating systems are roller coating, spraying and paddling. The purposes of applying a
surface coat are:
 To provide protection from contaminants (water, oil, soiling)
 To provide color (to even the color) or to disguise defects.
 To provide modifications to handle and gloss performance
 To provide attractive fashion or fancy effects

There are commonly two types of finished leathers; aniline finished leather which is slightly
sprayed with some finishing chemicals like wax & oils and pigment finished leathers that have
open defects and to cover these defects some finishing chemicals like pigments, filers and
binders will be coated by spray machines or roller machines .

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 Crust leather

Buffing

Impregnation

Base coat

Middle coat

Top coat

Finished leather

Figure 2.4 Flow diagram of finishing processes

Tannery industries generate solid waste containing various types of organic particles and
toxic chemicals, which are discharged in open drains and ultimately find its way on to
land surface and in natural waters near the tannery. The magnitude of pollution from
tannery solid waste has already highly impact in the public health and the environment. This
chapter contains a review of the relevant literature.

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2.2 Wastes generated from a tannery

The environmental impacts of tanneries originate from liquid, solid and gaseous waste streams
and from the consumption of raw materials such as raw hides, energy, chemicals and water. Only
20 % of the weight of the raw hide is processed to finished leather. The rest of the weight plus
the chemicals input ends up as either waste or by-products. The main releases to wastewater
originate from wet processing in the beam house, the tan yard, and the post tanning operations.
The main releases to air are due to the dry finishing processes, although gaseous emissions may
also arise in all other parts of the tannery. The main sources of solid wastes originate from
fleshing, splitting and shaving. A further potential source of solid waste is the sludge from the
effluent treatment plant, but this is not an onsite activity in all tanneries [6].

Solid wastes; Quantities of solid waste produced by tanneries depend on the type of leather
processed, the source of hides and skins and the techniques applied (Technologies used by
individual tanneries). The major solid wastes consist of dusted curing salt, wet trimmings, dry
trimmings, wet shaving, buffing dust and wastewater treatment sludge [15]. During handling of
raw skins, adhered dusted salt, which is contaminated with blood, hair, dirt and certain type of
bacteria is removed and dumped. Trimmings are cuttings of edges of raw skins. Fleshing is the
flesh material of the limed skins generated during fleshing operation. Chrome wet shavings and
trimmings are produced when skins / hides are shaved for proper thickness (uniform thickness)
after chrome tanning [6].Approximately 8.5 million tons of solid waste is generated during the
production of 11 million tons of raw hide processed in the world [16]. Currently, solid waste
disposal is increasingly becoming a huge challenge to tanners due to paucity of landfill sites and
strict environmental legislations worldwide. Hence, finding a holistic solution to the tannery
solid waste disposal problem is a challenge for researchers [17]. Tannery solid wastes that
contain chromium are more difficult to dispose and to utilize because of the possibility of
chromium (III) in the solid wastes converted to highly toxic chromium (VI). Hence chromium
containing tannery solid wastes need special treatment before disposal to mitigate leachabilty of
chromium (III) from the solid wastes and formation chromium (VI) [13]. The main types of
solid wastes generated from leather making industries (tanneries) and their rate of generation is
described in the next table (Table 2.1).

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Table 2.1 Types of solid wastes and their rate of generation from tanneries

Type of solid Rate of Characteristics of the solid waste

No waste generation

1 Dusted Salt 0.1 kg /skin Contains120 gm/kg of moisture, 120 gm/kg of

volatile matter, and 450 gm/kg of salt.
2 Raw trimmings 0.024 kg/skin Proteins

3 Fleshing 0.25 kg / skin Contains around 240 gm/kg of proteins,

200 gm/kg of fats, and 3gm/kg of sulphide.
4 Wet trimmings 0.14 kg / skin Contains around 240 gm/kg of proteins, 30
and wet shaving gm/kg of fats, and 15 gm/kg of Chromium
oxide.
5 Dry trimmings 0.06 kg / skin Contains around 300 gm/kg of proteins, 130
and dry shaving gm/kg of fats, 30 gm/kg of chromium oxide

6 Assorted No consistent Primarily cartons, bags, drums, etc.

refuse quantity.

Source; [18]

2.3.2 Role of chromium in tanning process

The discovery of leather tanning with plant and organic materials may have been accidental and
started in ancient time. With increasing demand for aesthetic appeal and softer types of leathers
as well as the need for reduction in process time, alternative tanning methods and post tanning
operations have been developed. The discovery of chromium tanning in 1858 is a landmark in
leather processing. Although many alternative mineral tanning materials have been explored,
chromium based tanning methods in the manufacture of light and softer types of leathers have
stood the test of time [19]. Chromium (III) salts, especially chrome alum and chromium (III)
sulfate, are used in the tanning of leather. Chromium (III) stabilizes leather by cross linking the
collagen fibers. Reaction sites for chrome tanning are the ionized carboxyl groups on side chains
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of the collagen found in the skin or hide [20]. Most commercial chrome tanning products are
used in powder form; they contain about 25 % Cr2O3 of 33 % basicity. Basic chrome sulphate
(BCS) liquors are also used for leather tanning process [19]. These liquors are prepared by
reducing the sodium or potassium dichromates in the presence of sulphuric acid. Under standard
conditions, 60 - 80 % float on pelt weight is used for tanning process. The corresponding chrome
offer in tanning is usually 6-8 % Cr2O3 on pelt weight. However, only -60 % of the total
chromium reacts with the hides. The rest of the chromium (40%) remains in the tanning effluent
and are subsequently sent to a tannery waste water management plant where the chromium salts
end up in the sludge [7]. Chromium tanned leather can contain between 4 and 5% of chromium,
which is tightly bound to the proteins. Although the form of chromium used for tanning is not the
toxic hexavalent variety, there remains interest in management of chromium in the tanning
industry such as recovery and reuse, direct/indirect recycling, use of less chromium or "chrome-
less" tanning are practiced to better manage chromium in tanning and to reduce its
environmental impact [6]. Chrome tanning is the most common type of tanning in the world,
more than 90 percent of tanning processes in the world use chromium as the main tanning agent
[19]. Chrome tanned leathers are characterized by top handling quality, high hydro-thermal
stability, user-specific properties and versatile applicability. Most alternative tanning agents like
vegetable tanning agents lack to bring such important characteristics of leathers that are the main
reason for tanneries to use chromium as a main tanning agent [6]. However, waste chrome from
leather manufacturing, poses a significant disposal problem because of the toxicity of chromium
specially hexavalent chromium [21].

2.3.3 Toxicity of chromium

The utilization of chromium in tanning procedures accelerates the mobility and transport rates of
chromium, which by far exceed the rates of natural cycle processes, resulting in serious problems
in countries involved with the tanning industry [10].Chromium is not biodegradable and tends to
accumulate in living organisms, causing serious diseases and disorders[7] . Chromium (III) is
toxic only at high concentrations, whereas Chromium (VI) is toxic to mammals even at low
concentrations, with a potential carcinogenic effect [12].Chromium used for tanning process is
in trivalent state and it is normally nontoxic in the trivalent state, but a recent study indicates
oxidation of the trivalent chromium to the hexavalent state occurs under alkaline conditions and
in the presence of manganese oxide [8]. Beside to this the study by the chromium(III) in tannery
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solid waste can spontaneously oxidized in to chromium (VI) both in acidic and alkaline
conditions. The overall toxicity of trivalent chromium is relatively low. Indeed, chromium (III) is
an essential element in human metabolism [11]. Hexavalent chromium on the other hand is of
significant toxicity. It is classified by both the International Agency for Research on Cancer
(IARC) and US Environmental Protection Agency (USEPA) as a known human carcinogen and
hexavalent chromium compounds are also known to have mutagenic potential [22]. Toxicity
arising from chromium (VI) may occur via inhalation, ingestion or dermal exposure. It has an
irritating and corrosive effect on skin and mucous membranes resulting in ulceration and
dermatitis.

Figure 2.5 Human health ill effect of Chromium (VI) like skin allergies [26].

2.4 Chromium containing tannery solid wastes

The main sources of Tannery solid wastes originate from fleshing, splitting, shaving, buffing and
trimmings. A further potential source of tannery solid waste is the sludge from the effluent
treatment plant [6]. However, all tannery solid wastes are not chromium containing. Solid wastes
generated after tanning process such as wet blue splits, wet blue shavings, buffing dusts and
trimmings contain chromium. This is because 6 - 8% of the basic chromium sulphate salt is used
for conventional tanning process [14]. After tanning process chromium binds with the

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collagenous protein of raw hide or skin and will be part of finished leather and solid wastes
generated from different process steps [27].

2.4.1 Type of chromium containing tannery solid wastes

The main chromium containing solid wastes generated from tanneries are wet blue shavings,
wet blue trimmings, crust trimmings, buffing dust, finished leather trimmings and waste water
treatment sludge. The rate of generation for each solid waste differs from tanneries to tanneries
depending on the technologies and resources used and the type of product produced in each
tannery [6]. These solid wastes contain 15-30 gm/kg chromium [21].
a) Wet blue shaving waste;

Wet blue shaving waste is generated during the shaving process (thickness adjustment) of wet
blue leather. It is sometimes called shaving dust or shaving chips because it mainly contains
small scraps that are removed from the reverse part of wet blue leather [10]. Like other
chromium containing tannery solid waste it contains high amount of chromium. The
chromium present in chrome shavings is in trivalent state [17]. In many countries specially in
developing counties wet blue shavings are disposed as a land fill. But in some countries wet
blue shaving waste is being used for leather board manufacturing [15]. From processing one
tone (1000 kg) of wet salted hide 99 kg of wet blue shavings will be produced [21].

b) Wet blue trimming waste;

Wet blue trimmings are chromium containing tannery solid waste that are generated from the
trimming process of wet blue leather (chrome tanned leather) mainly on shaving and splitting
processes [6]. This solid waste consists wet blue leather cuttings that originate from un-usable
parts of wet blue leather and rags created during shaving operation [14]. From processing one
tone (1,000 kg) of wet salted raw hide, 20 kg wet blue trimmings will be produced from
trimming of wet blue leather during shaving and splitting processes[21]. These trimmings
(estimated at 5.5%–6% of wet weight of hides) are collected from the tannery and utilized in
the manufacture of leather boards and bricks production [28].

c) Crust leather trimming waste;

Generally, crust leathers (leathers obtained after re tanning, dyeing, and fat liquoring
operations) are trimmed after staking, toggling, and mailing processes to remove the torn and

21 | P a g e
ragged edges from the crust leather to maintain the shape of the leather and also to process the
leather in the subsequent machine without any damage. From processing one tone (1,000 kg)
of wet salted raw hide about 15kg of crust leather trimmings will be generated [6]. The crust
leather trimmings are collected and used for making leather boards, insoles and production of
bricks [17].
d) Finished leather trimmings;

After finishing, the leathers are trimmed at the edges uniformly. The purpose of trimming is
to maintain the shape of finished leather, aesthetic value and for easy measurement of the
leather. The finished leather trimmings are collected and used for making leather boards and
production of bricks [17]. From processing one tone (1,000 kg) of wet salted raw hide about
15kg of finished leather trimmings will be generated [6].

e) Buffing dusts;

The crust leathers are buffed on the flesh side and sometimes on the grain side. The buffing
which is done on flesh side and snuffing operation which is done on the grain side to produce
specialty leathers such as nubuck generates fine lightweight leather fluffy mass [14]. Buffing
dust is chromium containing tannery solid waste that is generated from buffing of skins or
hides at crust stage. From processing one tone (1000 kg) of wet salted raw hide about 2 kg of
buffing dust will be produced [6].

f) Waste water treatment sludge;

Waste water treatment sludge is produced directly in the tannery from first treatment steps or
from a full waste water treatment on-site or at the waste water treatment plant to which they
are released. Both sources have to be taken into account when figures for the amounts of
sludge produced are discussed. The amount of sludges generated is influenced directly by the
requirements set for wastewater effluents [6].Wastewater treatment effluent contains high
amount of chromium. This is because the chromium used during tanning and retanning
processes will not be fixed on the leather fully. More than 40% of the chromium used in
leather making process will join the waste water treatment plant and finally end up with waste
water treatment sludge [8]. From processing one tone (1000 kg) of wet salted raw hide 420 kg
waste water treatment sludge with 30% dissolved solids will be generated [21]. Wastewater

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treatment sludge can be used for bricks making and for the production of biogas energy [28].
Table 2.2 indicates the amount of chromium containing tannery solid wastes generated during
processing one ton of raw hide and their chromium oxide (Cr2O3) content.

Table 2.2 CCTSW generated from processing one ton of wet salted hide.

S.No Type of solid wastes Chrome oxide content Rate of generation

(gm/kg) (kg/ton)
1 Wet blue splitting 15 167

2 Wet blue shavings 15 99

3 Wet blue trimmings 15 20
4 Crust trimmings 30 15
5 Finished leather trimmings 30 15
6 Waste water treatment sludge 150 – 400 420

Sources; [21, 6 and 29].

2.4.2 Environmental impact of chromium containing tannery solid wastes

The 25% of raw hide or skin processed in tanneries end as chromium containing leather wastes
(CCLW). Statutory limits have been set for chrome discharge and disposal, and relevant
guidelines have been drawn up throughout the world. Due to high correlation between chrome
tanning and its environmental impact, checking of the efficiency of processing operations and
treatment plant is very important [30].Wastewater and solid waste from tanning operations often
find their way into surface water, where toxins are carried downstream and contaminate water
used for bathing, cooking, swimming, and irrigation. Chromium waste can also seep into the soil
and contaminate groundwater systems that provide drinking water for nearby communities. In
addition, contamination in water can build up in aquatic animals, which are a common source of
food. Soil that is contaminated by chromium waste also poses a health hazard, since toxic dust
can be inhaled by both people and livestock [31].

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Worldwide chromium contamination of soils has arisen predominantly from the common
practice of land-based disposal of tannery wastes under the assumption that the dominant species
in the tannery waste would be the thermodynamically stable chromium (III) species. However,
recent detection of significant levels of toxic chromium (VI) in surface water and groundwater in
different part of the world raise critical questions relating to current disposal of chromium-
containing wastes [30]. Despite the thermodynamic stability of chromium (III), the presence of
certain naturally occurring minerals, especially MnO2 oxides (Manganese oxide) can enhance
oxidation of chromium (III) to chromium (VI) in the soil environment.

Figure 2.7 Global assessments of chromium pollution and number of population at risk in
selected polluted sites [31].

Chromium (VI) is known as the most mobile Chromium form in soil and water and tends to
dominate in these systems, whereas Chromium (III) is generally not transported over great
distances because of its low solubility and tendency to be adsorbed in the pH range typical of
natural soils and water. But redox conversion of Chromium (III) to Chromium (VI) can increase

24 | P a g e
Chromium dislocation from the soil into the water systems [27]. Tanneries not only discharge
contaminated wastewater into rivers, but also dump a large amount of chromium-mixed solid
wastes such as skin and hide scraps, waste water treatment sludge and fats onto the banks of
rivers and on fields near residential areas and villages. This leads to the contamination of water
sources and soil with cadmium, iron, magnesium, chromium, calcium, nickel, lead, and zinc in
addition to tanning agents. Therefore, the populations near a tannery are often exposed to
pollutants through contaminated water. People use the water from contaminated rivers and
streams for several purposes, including irrigation, swimming (mostly children), bathing, and
washing dishes and clothing. There is also a high risk of this hazardous waste water mixing with
the ground water, which is extracted for drinking water.

Figure 2.6 Kids Playing in tannery scraps containing chromium world worst pollution problem
report [32].
Poultry feed manufacturers collect CCTSW and use it due to the protein content of the solid
wastes. But these wastes contain significant amount of chromium. A recent survey under
Pakistan Tanneries Association showed that poultry feed made using solid wastes contain
hexavalent form of chromium, beside to trivalent chromium. It seems that during feed
preparation, partial transition of trivalent chromium to hexavalent chromium takes place. This

25 | P a g e
poses a serious threat to human health [18].The huge quantity of chromium salts discharged with
tannery waste has raised several ecological concerns. The sludge generated by chromium based
industries is usually damped on the ground which pollutes surface and sub soil water in the
vicinity of industrial units. The main environmental impact of chromium containing tannery
waste is concerning the possibility of oxidation of chromium (III) into chromium (VI) in gentle
conditions by air in the wide range of PH. Principally, oxidation of chromium (III) in to
chromium (VI) can be realized after the following equations;

2Cr2 O3 + 8OH- + 3O2 4Cr O4 + 4H2O (in alkali medium)………….Equation 2.1

2Cr2O3 + 3O2 + 2H2O 2Cr2 O7 + 4H+ (in acid medium) ………..Equation 2.2

2.4.4 Utilization of chromium containing tannery solid wastes

Recently, solid waste has become a new source for creating wealth and the amount of industrial
solid waste is growing in many countries; therefore, waste management and waste treatment
methods are of utmost importance [17]. The leather industry itself uses a waste (by product) of
meat industry, and, as such, significantly reduces the environmental impact. It is therefore,
evident that the term waste is relative. It can be argued that if the "waste" generated in one
industry sector can successfully be utilized as a raw material in another industry sector for the
manufacture of goods, we need to rethink our philosophy on the use of resources. Some
chromium containing tannery solid wastes (CCTSW) are partly used for the production of some
valuable products, but most are deposited in land-fill. Wet blue shavings and trimmings are used
in the manufacture of leather board; they also undergo chemical and / or enzymatic hydrolysis,
pyrolysis, and incineration treatments to utilize these chrome tanned solid wastes for different
purposes [21]. The process can help the leather industry in solving the difficulty of CCLW
disposal problem and obtain economic benefits. There are various technologies to utilize
chromium containing tannery solid wastes. Currently, these technologies are implanted mostly in
developed countries. Generally, utilization of chromium containing tannery solid waste can be
categorized as follows:

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Concrete blocket; Mixing of limited amounts of chrome shaving into clay for block making is
carried out in South America. Block making from some other CCTSW like buffing dust and
wastewater treatment sludge is common practice in some other countries [34]. The mix ratio of
CCTSW and cement or clay is important to get good quality bricks or concert block.

Table 2.3 shows the type of chromium containing tannery solid wastes, the common practices to
management these solid wastes and the advanced technologies currently available in the world to
utilize them for different purposes.

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Table 2.3 Summery of different technologies to utilize CCTSW

S.N Type of Common practice Advanced Technologies

CCTSW

1 Wet blue Leather board Separation of protein for application

shaving waste production as fillers and bio fertilizers.
Land fill For gelatin and glue production
Separation of chromium for reuse in
tanning process.
2 Wet blue Leather board Separation of protein for application
trimmings production as fillers and bio - fertilizers
Land fill For gelatin and glue production
Separation of chromium for reuse in
tanning and re tanning process.
3 Crust shaving Leather board Generation of Bio‐gas energy
production Bricks making
Land fill For gelatin and glue making
Incineration Bricks making
4 Crust Land fill Production of fancy leather goods
trimmings Incineration Generation of Bio‐gas energy

5 Buffing dust Landfill Generation of Bio‐gas energy

Incineration. Bricks making or concrete block

7 Waste water Land fill High compressive bricks making

treatment Incineration concrete bloc
sludge Fertilizer
Generation of Bio‐gas energy
Source; [35]

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In some countries there is a common practice to use some of the CCTSW as animal feed like
chicken feeding [15]. But this is not advisable because of the danger of chromium (VI) and other
toxic pollutants found within the chromium containing tannery solid waste may enter in the food
chain.
2.4.5 Cement based stabilization process of tannery solid waste
The process of tanning produces both liquid and solid wastes. The solid wastes are
Pre-dominantly from the initial and final stages of processing while the effluents are
produced mostly during tanning and dying. Most of the wastes and effluents are subjected to
natural decomposition in the environment, causing serials of pollution problems affecting oil,
water, air and human life. Currently, about 90% of the finished trimming wastes are used by
local shoemakers. About half the tanneries apply some kind of solid waste reuse.
Solidification/stabilization (S/S) is an economical process for the disposal of many types
of hazardous wastes. The method involves mixing solid wastes with binders to produce a solid
which is structurally sound and relatively impermeable. Binders often consist of Type I Portland
cement (Ordinary Portland Cement, OPC) or OPC. Sometimes polymers, by themselves or in
various combinations, are used. The mechanisms of S/S are very incompletely understood. The
process usually involves addition of a heavy metal waste to a cementations binder, with or
without pretreatment with lime. The hydroxides are subsequently immobilized in the dense
matrix of binder, where ionic transport is decreased as the porosity and permeability are reduced.
Very few detailed micro structural and micro chemical studies of OPC with complex wastes
exist, and the waste itself has been investigated even less. Solidification is one of the most
effective methods of dealing with heavy metal contaminated sites. By this method mobility of
hazardous substances and contaminates is significantly reduced in the environment through both
physical and chemical means. In general, solidification is typically a process that involves
mixing the waste with a binder to reduce the contamination leach ability by physical and
chemical means, which convert the waste into an environmentally acceptable waste form for safe
disposal or construction. Therefore, the main objective of solidification/stabilization is to achieve
and maintain the desired physical properties and to chemically stabilize or permanently bind
contaminants. Moreover, the stabilized wastes may attain adequate stress-strain properties to
enable their utilization in construction applications. For the purpose of solidification, many
organic and inorganic binders have been used, most of which have stabilizing characteristics.

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Ordinary Portland Cement (OPC) is the most widely used binder due to its cost effectiveness,
availability and compatibility with a variety of wastes .Cement based solidification has been
widely used in the world for about 50 years .The high strength, low permeability and relatively
high durability of hydraulic cement make it a good binder for this waste management technique
.The overall process of cement hydration includes a combination of solution process, interfacial
phenomena and soil-state reaction. It is extremely complex; especially in the presence of heavy
metals [36] .The influence of cement chemistry on the properties of solidified wastes forms was
studied [37]. In this study Portland cements with a little bore composition ranging from 25 to
65%, and ferrite and aluminates fixed at 10% were used. The waste used was a commercially
blended and neutralized hazardous waste, which was solidified at three loading rates. The cement
composition mainly the amount of calcium silicate hydrate (CSH) was seen to influence the
strength development and the differences in phase development were more apparent at the
highest waste additions. The morphology of the inner gel products appeared to be different based
on the Ca/Si ratio. The metallic waste species had the optimum lowest leaching level [38].

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 CHAPTER THREE

3. MATERIAL AND METHOD

3.1 Introduction

Based on the review of literature the methodology is formulated. To achieve the objectives,
different proportions of chrome shaving waste and buffing dust are added and tested for various
performance indices. In this study chrome shaving waste and buffing dust was blended with
cement, coarse aggregate, fine aggregate and water to have a modified binder and tested for the
high strength concrete block. The encapsulation of buffing dust and chrome shaving waste with
modified binder gives a technique to dispose it without polluting the environment, without
impact of healthy and give a safe secured solution to tannery industry.

3.2 Materials/facilities needed

The main raw materials needed to manufacture concrete block from chrome containing total
solid waste like buffing dust, chrome shaving etc. are the followings.

Ingredients of concrete blocket:-

 Ordinary Portland Cement (OPC)

 Water
 Aggregates (Fine aggregate and Coarse aggregate)
 Sand
 Buffing dust and chrome shaving waste
Chemicals equipment’s:-
 Oven dry
 PH meter
 Beaker
 Furnace
 Bunsen burner flame
 Volumetric flask
 Filter paper
 Atomic absorption spectrophotometer

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 Chemicals:-

 Distilled water
 Selenium powder
 Sodium sulphate
 Sulphric acid
 Sodium hydroxide
 Boric acid
 Hydrochloric acid
 Silver nitrate solution

Manufacturing equipment

 Mixer
 Molding Equipment
 Weighing balance
 sieve
 Shovel
 Trowel
 Vibrator(compactor)

3.3 Materials and its properties

3.3.1 Cement

The type of cement used in this study is OPC. The specific gravity of the cement is 3.14.

3.3.2 Fine aggregate

Fine aggregate is river sand and having the specific gravity of 2.63.The density of the fine
aggregate is found to be 511.4 kg/m3.Fine aggregates should be pass through a sieve of nominal
aperture of 9.5 mm in addition to this the size of aggregate should not exceed two–third of the
thickness of the thinnest part of the shell or mesh unit [39].The zone of fine aggregate is
determined by sieve analysis. As per Ethiopian standards is obtain this data

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Table:-1 Grading requirements for fine aggregate [ES]

Sieve Percentage passing

9.5 mm 100
4.75 mm 95-100
2.36 mm 80-100
1.18 mm 50-85
600 µm 25-60
300 µm 10-30
150 µm 2-10

3.3.3 Coarse aggregate

Coarse aggregate having a size of 20mm were used. Its specific gravity is 2.65. The crashed
aggregates are a combination of 00 and 01 size.

3.3.4 Tannery chrome shaving waste

The chrome shaving waste of the processed tannery is brought from Debre brhan Tannery
industry. The tannery is replaced for sand, the waste that is obtained should be sieved and used
for the work. The tannery waste obtained from the industry is sieved with 2.36mm sieve and the
passed materials are taken for the replacement.

Figure 1:- Tannery chrome shaving waste

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3.3.5 Buffing dust

Buffing dust is in the form of fine particles generated as leather industry waste. It is a portentous
solid with chromium, synthetic fat, oil, tanning agents, and dye chemicals.

Fig 2: Tannery Buffing dust

3.4 Effective utilization tannery shredded waste and buffing dust

The effect of concrete blocket with partial replacement of fine aggregate with tannery shredded
waste (buffing dust) and chrome shaving waste. The present study covers the use of the tannery
shredded waste as a partial replacement for fine aggregate and to determine the mechanical
properties of the concrete blocket after replacing. Fine aggregate is an integral part in concrete
blocket. Due to increase in the construction activities the requirement of fine aggregate is more.
In other hand tannery waste is abundant in nature; a proper replacement of tannery waste over
the fine aggregate will not only reduce the tannery waste but also reduce demand for fine
aggregate. The concrete blocket produced due to this replacement will have reduced weight and
also possess higher strength than the conventional concrete blocket.

3.5 Hollow concrete blocks production process

Hollow concrete blocks are passed through different steps of production. These are batching,
mixing, molding (vibration), curing and drying. Each and every production process requires
control to maintain quality of production. In case of batching of ingredients used for production
of hollow concrete blocks, all respondents use volume batching. It is done without any
adjustments, but it is supported by observation. Adding and reducing amount of water by

34 | P a g e
observation is not sufficient because excess water in the mix causes of difficulty in molding, due
to this wastage may be increase. During observation all the respondents used hand mixing, and it
is done on the ground directly as shown in the figure 3.3.

Fig 3:-mixing of ingredients in Debre brhan Aman and Asrar site

Very dry cohesive concrete is used in masonry production, in conjunction with power full mould
vibration in order to compact the concrete sufficiently to achieve the required strength; it is done
for about 60 seconds before extruded as hollow concrete block [40]. But as seen during
observation, the respondents did not care for the time of vibration; they compact the concrete by
guessing. This practice may affect hollow concrete blocks due to over or under vibration. On the
curing of finished concrete blocks of the respondents cured for 7 days for block produced with
OPC cement and 14 days for block produced with PPC cements. Curing must be done under the
shade to prevent evaporation, In addition to this, hollow blocks shall be stocked with voids
(honey comb fashion) horizontal to facilitate through passage of air. Based on observation the

35 | P a g e
curing is not sufficient especially for OPC because it is done for 7 days but blocks on the site
shall be cured in water tank or a curing yard by being kept thoroughly moist with water for a
period of at least 14 days. Insufficient curing leads reduction in compressive strength.

Figure 4 :- Curing of hollow concrete block in Debre brhan Aman and Asrar site

The finished hollow concrete blocks, on observation, after three days of production stored outside the
shade for minimum of 4 weeks up to 10 courses, the time of stocking on the shade is not sufficient.

 Generally the process of manufacture of hollow concrete blocks (HCB) involves the
following 5 stages
(1)Proportioning
(2) Mixing
(3) Compacting
(4) Curing
(5) Drying

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3.6 Method
The study may be broadly classified into four categories:

1. Collection of tannery buffing dust and chrome shaving waste

2. Preliminary analysis of the buffing dust and chrome shaving waste

3. Concrete mixing with buffing dust and chrome shaving waste

4. Analysis of the properties of the buffing dust and chrome shaving waste mixed concrete to
assess the usability.

The concentration of the heavy metal in the buffing dust and chrome shaving waste sample will
be determined in the laboratory. The methodologies are elaborately discussed in subsequent
sections in this chapter. The flowchart showing the logical sequence of the will be adopted
methodologies is provided in the following sequence.

37 | P a g e
 3.7 Process flow diagram of methodology employ for the study

Collection of tannery chrome

shaving waste and buffing
dust

Storage of the sample

Preliminary analysis of the sample(for pre-selected

physical and chemical analysis

Preparation of concrete blocket

Analysis of property of chrome containing buffing dust and shaving

waste mixed concrete block

Selection of the acceptable % of buffing dust and shaving waste

Trial mix with selected % of buffing dust and shaving waste contents and analysis
of property

Water Compressive Density test

absorption strength
test

Acceptable buffing and shaving content must be recorded

Fig 5:- The flow diagram of methodology employ for the study

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3.7.1 Collection of tannery buffing dust and chrome having waste

Buffing dust and chrome shaving waste sample from leather industry was considered in this
study. The DB Tannery factory was selected to collect buffing dust and chrome having waste
sample. With assistance of the tannery, authority, the buffing dust and chrome shaving waste
sample was collected directly from the DB tannery factory. The buffing dust and chrome shaving
waste sample was not degraded some content mixed with concrete.

3.7.2 Analysis of the chrome containing shaving waste and buffing dust properties

The characteristics of the chrome shaving waste and buffing dust sample were analyzed for
preselected parameters to record the chemical properties and physical properties of the (CCTSW)
in the open environment. These may influence the workability, compressive strength and and
tensile strength setting time of the resultant (CCTSW) mixed concrete. The properties are
physical analyzed in size reduction for only chrome containing shaving waste and also chemical
analyzed includes pH, alkalinity, and chloride, sulfide, sulfate, silica, nitrate, etc.

3.7.3 Chemical Analysis of the chrome containing shaving waste and buffing dust
Constituents

The methodology applied for analyzing (CCTSW) was the standard methodologies
applicable for sediments. Analysis of the anions were done on the standard extract from
(CCTSW).In order to determine selected physicochemical parameters (pH, moisture content,
volatile organic compound, ash content, carbon content, nitrogen content, calorific value, ), all
others were performed with Spectrophotometer. The concentrations of the constituents were
expressed in mg/ kg of chrome containing shaving waste and buffing dust. The methods are
described briefly below:

3.7.3.1 Determination of PH

The pH of the sample solid wastes were determined by shaking five gram of sample of solid
wastes in 100ml of distilled water for 16 – 24 hours followed by direct measurement of the
pH according to Standard Methods for Leather Chemical Analysis [41].The level of pH in the
waste depends upon the decomposition rate and characteristics of feed material.

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3.7.3.2 Determination of moisture content

Moisture content of solid waste is usually expressed as the mass of moisture per unit mass of
wet or dry materials. In order to determine the moisture content of the chrome containing total
solid wastes, samples of the solid waste was first weighed and put in an oven at 105℃ for 24
hours. It was kept in desiccators for about 30 minutes and then weighed and recorded. The wet-
mass moisture content is expressed as follows [42].

Moisture content (%) = ((w-d) /w) x 100 …………………………………………………3.1

Where w = initial mass of sample as delivered and

d = mass of sample after drying.

3.7.3.3 Determination of volatile organic compound and ash content

The volatile organic compound and ash content were determined after burning the dry solids
in a furnace at 600 to 6500C for 2 hours [43]. The samples were again sent to a desiccator for
about 30 minutes and weighed.

Ash Content (%) = ( W1/W2 ) * 100 ……………………………………………………….3.2

Volatile organic compound (%) = (W2 – W1/W2) * 100 ………………………………….3.3

Where: W1 is the weight of the sample solid waste left after burning

W2 is the weight of the sample solid waste before burning

3.7.3.4 Determination of carbon content

The determination of the C/N ratio, which is so important in regard to nitrogen conservation
and for estimating the quantity of the finished compost, is more of a problem, because the
quantitative analysis of carbon is difficult, time consuming, and expensive. For composting
work, the percentage of carbon can be estimated satisfactorily from the percentage of ash a
much simpler test by the equation

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C = (100 - %Ash) ……………………………………………………………..3.4
(1.8)
The University of California group on checking this simpler method, found the results to be
within 2%-10% of the more accurate carbon determination [43].
3.7.3.5 Determination of Total Nitrogen

To determine the total nitrogen content of the sample solid waste a standard method of SMLCA
[41] which is kjeldhal method was used. It involves two steps, digestion, distillation and
titration.

i Digestion

Ten grams of milled organic was weighed into a 500ml flask moistened with distil
water. Selenium powder and sodium sulphate was added as a catalyst and 30ml of
concentrated sulphuric acid was also added and then digested for 2 hours using the Bunsen
burner flame. The solution was then cooled and decanted into a 100ml volumetric flask and
made up to the mark.

ii Distillation and Titration

An aliquot of 10ml of the digested sample was taken into a distillation unit and 20ml of 40%
NaOH was taken and 10ml of 4% boric acid was added to it resulting in a pink color. The
distillate was then collected over NaOH solution and boric acid for about 5 minutes. The
presence of nitrogen gave a blue color. The solution was titrated with 0.1MHCL until the
blue color changed to pink signifying the end point. Using the recorded titrate value and the
relation below the % of nitrogen was then calculated.

%Total Nitrogen = 14*(A–B)*N*100 ………………………………………..3.5

1000*1

Where: A is the volume of standard HCl used in the sample titration.

B is the volume of the standard solution used in the blank titration.

N is the normality of standard HCl

41 | P a g e
3.7.3.6 Determination of Carbon to Nitrogen (C: N) ratio

The carbon to nitrogen ration of the sample solid wastes was determined by dividing the
percentage of carbon content to the percentage of nitrogen content of the samples. Carbon
and nitrogen are essential to microorganisms that break down organic material. In the process
of breaking down the organic material, microorganisms utilize the carbon as a source of
energy and the nitrogen as the building block for protein synthesis. Carbon can be considered
as "food" and nitrogen as the digestive enzymes. A nutritional requirement for
microorganisms is that the C: N ratio of organic matter must be at a level for optimum
decomposition efficiency. The limiting C: N ratio for most microbial organisms ranges from
25:1 to 30:1 (i.e., 25–30 parts carbon to 1 part nitrogen). When the C: N ratio of the compost
exceeds 30:1, the organisms become deficient in nitrogen and the process of decomposition is
slowed [42].

3.7.3.7 Determination of Chloride:

chrome containing shaving waste, buffing dust and water were mixed at 1: 5 (W:V) ratio. The
mixture was stirred for 30 minutes. The slurry was then allowed to settle for an hour and the
supernatant liquid was filtered through filter paper. The extract was then titrated with standard
silver nitrate solution.

3.7.3.8 Sulfate:

Chrome containing shaving waste, buffing dust and water were mixed at 1: 5 (W:V) ratio and
stirred vigorously for 30minutes. The slurry was then allowed to settle for an hour and the
supernatant liquid was filtered through filter paper. The extract was then analyzed with atomic
absorption Spectrophotometer (AAS).

3.7.3.9 Silica:

Chrome containing shaving waste, buffing dust and water were mixed at 1: 10 (W:V) ratio and
stirred vigorously for 30minutes. The slurry was then allowed to settle for an hour and the
supernatant liquid was filtered through filter paper. The extract was then analyzed with
Spectrophotometer through Methylene Blue Method (Range: 0.005-0.80 mg/L).

42 | P a g e
3.7.3.10 Nitrate:

Chrome containing shaving waste, buffing dust and water were mixed at 1: 10 (W: V) ratio and
stirred vigorously for 30minutes. The slurry was then allowed to settle for an hour and the
supernatant liquid was filtered through filter paper. The extract was then analyzed with atomic
absorption spectrophotometer (AAS)

3.7.3.11 Extraction method for heavy metal

The digestion technique will be adopted for extraction of total heavy metal by using aqua regia
method[44]. The digested sample will be analyzed with Atomic Absorption Spectrophotometer.

3.7.4 Mix proportion

The mixing proportion of concrete blocket adopted for this study was 1:2:2:1 which is a
conventional volume basis-mixing ratio of cement, aggregate (00, 01) and sand with
respectively. Control mixture for B grade concrete blocket was designed .The concrete blocket
mix is prepared with replacement of tannery waste from 0%, 10%, 15%, 20%,30 and 100% with
sand by volume batching method. In this study totally six concrete blocket mixes namely CT0,
CT10, CT15, CT20, CT30 and CT100 were used and cured with normal water for 28 days. For
each mix 3 numbers of concrete blocket was taken and then check the compressive strength,
density and water absorption.

Table concrete blocket mix with different proportion.

Mix Cement Fine Coarse sand Tannery waste

aggregate aggregate
Volume(m3)
CT0 0.02 2*0.04 2*0.04 0.04 0
CT10 0.02 2*0.04 2*0.04 0.036 0.004
CT15 0.02 2*0.04 2*0.04 0.0346 0.0054
CT20 0.02 2*0.04 2*0.04 0.032 0.008
CT30 0.02 2*0.04 2*0.04 0.028 0.012
CT100 0.02 2*0.04 2*0.04 0 0.04

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3.8 Testing of concrete blocket

 Compressive Strength test:

 Water absorption
 Density of Concrete blocket taste

3.8.1 Compressive strength test:

One of the basic parameters for the concrete blocket is compressive strength. It is known that
concrete blocket is good in compression and weak in tension. For a good concrete blocket the
compressive strength must be relatively higher. The table shows the compressive strength of
concrete blocket with various replacement of tannery waste with sand.

Table 28th day compressive strength of concrete blocket

Mix Average load (kN) Compressive strength

(N/mm2)
CT0 174 7.73
CT10 177 7.87
CT15 194 8.62
CT20 173.5 7.71
CT30 120 5.33
CT100 11.74 0.52

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 Series 1
5
4.5
4
3.5
3
2.5
Series 1
2
1.5
1
0.5
0
0 10 15 20 30

Figure : 28th day compressive strength of concrete blocket

3.8.2 Density of concrete:

Density of Tannery waste concrete blocket is found to be less than normal concrete blocket. This
shows that the addition of tannery waste reduces the weight and results in light weight concrete
blocket.

Table : 28th day density of concrete blocket.

Mix Density(kg/m3) Average weight(kg)

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CT0 1383.33 16.6
CT10 1291.7 15.5
CT15 1226.7 14.7
CT20 1125.00 13.5
CT30 1058.33 12.7
CT100 1003.33 12.04

Figure : Density of Concrete

3.8.3 Water absorption concrete blocket test

First dry weight of CCTSW concrete blocket is found (W1). The Concrete blocket is immersed
in water for 24 hours. After 24 hours the concrete blocket is taken out from water and weigh
(W2). Water absorption of the concrete blocket is found out by the following formula.

Water absorption(WA) of concrete blocket = (W2 – W1)/W1 X100

Water absorption standard = less than 5%

Table : 28th day water absorption of concrete blocket.

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Mix W1(kg) W2(kg) 𝑊2−𝑊1
%WA= ∗ 100
𝑊1

CT0 16.6 17.264 4

CT10 15.5 16.04 3.5
CT15 14.2 14.65 3.2
CT20 13.5 13.92 3.1
CT30 13 13.39 3.07
CT100 12.00 12.336 2.8

CHAPTER FOUR

4 RESULT AND DISCUSSION

The analysis of this study started with the analysis of buffing dust and chrome shaving waste
sample for preselected buffing dust and chrome shaving waste constituents and their possible
influence on the buffing dust and chrome shaving waste mixed concrete blocket. This study was
carried out to analyze the variation in the basic properties of the solidified concrete mixed with
buffing dust and chrome shaving waste. This section highlights the analysis of the experimental
results and findings. Based on the test results a suitable buffing dust and chrome shaving waste
ratio was selected. The buffing dust and chrome shaving waste sample was analyzed for
determining the characteristics of the buffing dust and chrome shaving waste in terms of their
physical and chemical properties (Table 4.1). The parameters analyzed included pH, alkalinity,
percent organic, sulfate, sulfide, nitrate, chloride and silica.

Table 4.1: Results of preliminary analysis of the buffing dust and chrome shaving waste sample

parameters Tannery buffing dust and chrome shaving

waste.

PH 5

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Moisture content (%) 27.23
VOC (%) 83
carbon content 46.11
Ash content (%) 17

 There is gradual increase in the Mechanical properties of the concrete blocket by

increasing the tannery waste (shaving waste buffing dust) up to 15% and on further
addition of the tannery waste decreases the strength parameters.
 Compressive strength of the concrete blocket is increased by 11.5% of the normal
concrete blocket mix for 15% replacement of tannery waste.
 The partial replacement of 15% of tannery waste (shaving waste buffing dust) over fine
aggregate will eventually increase the strength of the concrete blocket and found to be
optimum replacement.
 The partial replacement of tannery waste (shaving waste buffing dust) increase with fine
aggregate the density of concrete blocket decrease.
 The partial replacement of tannery waste (shaving waste and buffing dust) increase with
fine aggregate the water absorption decrease.

48 | P a g e
 CHAPTER FIVE

5 CONCLUSION AND RECOMMENDATION

5.1 Conclusion

Tannery waste (shaving waste and buffing dust) from the Debre brhan tannery area has been
categorized as solid hazardous waste particularly due to the presence of heavy metals i.e.
Chromium. Disposal of this shaving waste and buffing dust into land and the concentrated
growth of this contaminant have shown how it can cause irreversible damage to the environment
in the area. However, the lack of coordination between the environmental authorities and the
industries regarding the management has resulted the companies to set up their own chrome
containing total solid waste. Therefore, the environment is under increasing pressure from this
originating shaving waste, buffing dust and other wastes of tannery industry. The main objective
of this study was to utilize tannery waste and reduce environmental pollution. The secondary
objective of the study was to assess the performance of the shaving waste and buffing dust added
concrete blocket to recommend a suitable concrete blocket mix for the major construction work
using the partial replacement of fine aggregate. Laboratory tests and analysis were done to
determine the chemical properties of the shaving waste, buffing dust sample, like PH analysis,
moisture content, ash contents, carbon content and volatile organic compound. The shaving
waste, buffing dust was used as a replacement of the fine aggregate by weight of certain concrete

49 | P a g e
blocket. Six trial mixes was conducted with different ratio tannery waste to evaluate concrete
blocket properties. The brief summary of the findings are stated below:

 Tannery waste can be used effectively in the construction field.

 The disposal of tannery waste can be done safely without causing any pollution to the
environment.
 There is reduction in the cost of construction and provides a new replacing material for
the concrete blocket.
 Increase in Tannery waste in concrete blocket from 0% to 20% decreases the density of
the concrete from 1383.33 kg/m3 to 1226.7 kg/m3
 Tannery waste concrete blocket can reduce the use of river sand in concrete blocket and
results in light weight concrete.

5.2 Recommendation

This study has considered the heavy metal (chromium) concentration of the shaving waste,
buffing dust sample collected from Debre brhan tannery factory. Chrome containing total solid
waste from different tannery industry with extensive analysis of both physical and chemical
properties such as C:N ratio, content of chloride and extraction of heavy metal include for future
study to accumulate a better understanding of its impact and effect on concrete blocket
properties.

This study had covered a conventional mixing ratio to produce structural concrete blocket
without any chemical admixture. However, the water content has a huge impact on the
compressive strength of the concrete blocket and volumetric mix design can be considered
for production concrete blocket.

This study did not include the test of durability, soundness and permeability and firing test of the
concrete blocket. The above mentioned tests of the concrete blocket are important to evaluate the
performance of the shaving waste, buffing dust mixed concrete blocket in the long run which
might be included in the scope of the future study.

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REFERANCE

1. FAO World Statistical Compendium For Raw Hides and Skins, Leather And Leather
Footwear19192009:http://www.fao.rog/fileadmin/templates/est/COMM_MARKETS_M
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2. Proceeding of National Workshop On Enhancing The Ethiopian Leather Industry And Its
Market Competitiveness , Organized By Leather Industry Development Institute (LIdI) In
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3 Isayas Tadesse (2003). Tannery effluent treatment in advanced integrated waste water Pond
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4 Ethiopian Leather Journal, By Ethiopian Leather Industries Association, March 2012, 6th
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5 http://ethiopianleather.org/sector.asp

6 IPPC (2003).Integrated Pollution Prevention and Control; Reference Document on Best

Available Techniques for the Tanning of Hide and Skin.

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8 Jones.B (1979). Chromium recovery through incineration of liquid and solid tannery wastes.
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9 Kolomaznik, K., Vasek, V.and Janacova,D.( 2009). Control Recycling Technology of Tannery
Chromium Wastes. Department of Automatic Control Faculty of Applied Informatics Tomas
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10 Katsifas, E., Giannoutsou, E., Lambraki, M. Barla, M and Karagouni, (2004).Chromium

recycling of tannery waste through microbial fermentation, J Ind Microbial Biotechnology 31:
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13 Mandal ,B.K., Vankayald,R. and Kumar,L.U (2011). Speciation of Chromium in Soil and
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park road Moulton park, North ampton NN3 1JD.

15 Kanagaraj, J., Velappan, K., Babu,N . and Sadulla, S. (2006). Solid waste generation in the
leather industry and its utilization for cleaner environment. Journal of Scientific
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16 Ozgunay, H., Colak, S., Mutlu, M. and Akyuz, F (2007). Characterization of Leather
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17 Fathima, N., Rao,R. and Nair,B.U.(2012). Tannery solid waste to treat toxic liquid wastes: A
new holistic paradigm. Environmental engineering science volume 29,
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18 Chattaha, J.A. and Shaukat, M.M. (2000). An assessment of environmental concerns in the
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19 Sreeram, K.J.and Ramasami, T. (2003). Sustaining tanning process through conservation,

recovery and better utilization of chromium. Resources, conservation and recycling 38
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20 Sharphouse J.H (1983). Leather Technician hand book. Leather producers association, Kings
park road Moulton park, North ampton NN3 1JD.

21 UNIDO (2000). United Nation Industrial Development Organization, seminar report on

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22 Assem, L. and Zhu, H.(2007). Chromium Toxicological Over view. Institute of Environment
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24 Santos, C.and Rodriguez, E. (2012). Review on some emerging endpoints of chromium (VI)
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25 OSHA (2009). Occupational Safety and Health Administration, Hexavalent chromium; U.S.
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26 www.Wiakato, District health board 2010

27 Mwinyihija, M (2010). Ecotoxicological diagnosis in the tanning industry. Springer

Science and Business Media, LLC 2010.

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28 IUE (2008). International Union of Environmental Commission; Recommendation for
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29 ETPI (1998). Environmental Report of the Leather Sector, Draft Final Report, Environmental
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30 Alebel Abebe (2010). Impacts of chromium from tannery effluent and evaluation of
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31 Harris and Cartor, A. (2011). Top ten toxic pollution problems. Blacksmith institute’s world
worst pollution problems report 2011. Produced in collaboration with Green Cros Switzerland.
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32 Cartor, A.M. and Becker, D. (2010).Top six pollutants that jeopardize the health of tens of
millions of people lead, mercury, chromium, arsenic, pesticides and radio nuclides. Blacksmith
institute’s world´s worst pollution problems report 2010. Produced in collaboration with green
cross Switzerland. (www.worstpolluted.org).

33 Kolomaznik, K., Vasek, V.and Janacova,D.( 2009). Control Recycling Technology of

Tannery Chromium Wastes. Department of Automatic Control Faculty of Applied Informatics
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34 IUE (2008). International Union of Environmental Commission; Recommendation for

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35 Ramalingam, B. (2011).Value addition in leather industry; Value addition in leather by

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36 Hossain, A. M. (2004), Stabilization of Heavy Metals in Industrial Sludge with Concrete

Mix, M.Sc. Thesis, Department of Civil Engineering, Bangladesh University of
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38 Al-Tabbaa, A., and Perera, A. (2006), “State of Practice Report UK
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39 Ethiopian standard (ES 596:2001); specification for concrete masonry units

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 Appendix A

A.1 Aqua-regia method: extraction method for heavy metals

 5 gm of sample will be taken in a conical flask

 5 ml distilled water will be added to obtain slurry
 7.5 ml HCL (1:3) and 2.5 ml HNO3 (1:3) will be added to make a 300 ml of sample
 The sample will be covered and kept overnight
 Covered sample and then heated for about 2.5 hours at 100º c under reflux
condition to reduce the volume to 25 ml.
 The sample will be allowed to cool and then mixed with distilled water to obtain 500
ml of sample.
 Filtration will be done and the sample will be collected.

A.2 Volumetric amount of the materials to produce of concrete blocket (Converted from
1:2:2:1 volumetric basis ratio

The mixing proportion of concrete blocket adopted for this study was 1:2:2:1 which is a
conventional volume basis-mixing ratio of cement, aggregate(00,01) and sand with respectively.
Control mixture for B grade concrete blocket was designed .The concrete blocket mix is
prepared with replacement of tannery waste from 0%, 10%, 15%, 20%,30 and 100% with sand
by volume batching method.

Volume =L*W*H

Volume=(50*40*20)cm=0.04m3

Density=mass/volume

Density of cement(OPC)=3150kg/m3

Mass of cement=50kg

Volume=0.02m3

56 | P a g e
Mix Cement Fine Coarse sand Tannery waste
aggregate aggregate
Volume(m3)
CT0 0.02 2*0.04 2*0.04 0.04 0
CT10 0.02 2*0.04 2*0.04 0.036 0.004
CT15 0.02 2*0.04 2*0.04 0.0346 0.0054
CT20 0.02 2*0.04 2*0.04 0.032 0.008
CT30 0.02 2*0.04 2*0.04 0.028 0.012
CT100 0.02 2*0.04 2*0.04 0 0.04

A.3 Leather Processing

Leather tanning is essentially the conversion of raw animal hides (cows, sheep, goats,
and buffalo) into leather by a series of chemical reactions that alters the protein structure
to preserve the hide. It involves three main stages: the first to produce “wet blue” leather,
the second to produce “crust leather,” and the third to produce finished leather.

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