Treatment of Tannery Effluent and Extraction of Chromium From Chrome Tannery Solid Waste

Alexandria University Faculty of
Engineering
ChemicalEngineeringDepartment
Extraction of chromium from Chrome Tannery Solid Waste
Presented By:
Ragab Mahmoud Ragab (53)
Khaled Mohamed Abouelwafa (49)
Ali Ashraf Ali (79)
Supervised by:
Prof.Dr./Dina El-gayar
(July 2022)
I
I. Acknowledgement
A great thank to Prof.Dr.Dina El╴gayar for supervising ourproject,giving

us suggestions during planning and development of this project .Her
valuable supervision and giving her time arevery appreciated .
II
II. Abstract
Modern tanning activities generate considerable liquid and solid wastes into the
environment. The management of tannery solid waste has been a challenge to the
tanning industry for years and a focal point for researches carried out in the
tanning industry. This Project reports the study and development of a more efficient de-
chroming process for tannery solid wastes in which the recovered collagen tissues
are intact.
A chrome shaving is a process by which the pelt thickness is adjusted according to its
utilization purposes. This chrome shavings which constitute 2.5−5.0 % chromium are mainly
disposed at the outside the premises of the tannery and left to dry, posing a
hazardous environment.
When the chrome shavings are dried, they exposed to air and UVlight rays and
will transform chromium III to chromium VI. Chromium VI is 500 times toxic than
chromium III and most harmful pollutants in tannery waste. Chromium VI also affects soil
quality, more dangerous and carcinogenic. Therefore recovery of chromium VI is
very essential.
In our study we use acid and alkali leaching to extract chromium from chrome shaving
dust. Chromium concentration was measured using Titration process with ferrous ammonium
sulfates and then shows the effect of different parameters (PH ,Solid to liquid
ratio ,Time ,Temperature ,speed of stirrer) on rate of extraction chromium (VI)
The results show that the alkaline hydrolysis method gave a better de-chroming
process Than acid hydrolysis method , The rate of dechroming process increases with
increasing pH , time , temperature ,solid to liquid ratio and speed of motor stirrer
does not effect on rate of dechroming process.
III
Table Of Contents
1. Introduction .............................................................................................................................. 1
1.1 Leather Industry ..................................................................................................................... 1
1.2 History .................................................................................................................................. 2
2. THEORITICAL PART .................................................................................................................. 4
2.1 Preparation [1] ...................................................................................................................... 4
2.2 Tanning [2] ........................................................................................................................... 5
2.3 Beam-house Operations [3] ..................................................................................................... 7
2.3.1 Soaking ......................................................................................................................... 7
2.3.2 Liming and unhairing .................................................................................................... 7
2.3.3 Fleshing and deliming ...................................................................................................7
2.3.4 Bating ............................................................................................................................ 8
2.3.5 Degreasing ....................................................................................................................8
2.3.6 Pickling ..........................................................................................................................8
2.3.7 Tanning Processes ....................................................................................................... 8
2.4 Chrome tanning ...................................................................................................................10
2.5 Benefits of chrome tanning ...................................................................................................11
2.6 Vegetable tanning ............................................................................................................... 12
2.7 Alternative tanning ..............................................................................................................12
2.8 Shavings .............................................................................................................................13
2.9 Solid wastes [4] ..................................................................................................................... 13
2.10 Characteristics of Tannery Solid Wastes .................................................................................... 14
2.11 Environmental Impacts of Tannery Solid Wastes ......................................................................14
2.12 Effect of chromium in human health ....................................................................................... 16
.......................................................................................................................................................16
2.13 Solid Waste Management [5] .................................................................................................17
2.14 Leaching [6] .......................................................................................................................... 18
2.15 Types of Leaching .................................................................................................................19
2.15.1 Cyanide Leaching ..........................................................................................................19
2.15.2 Ammonia Leaching ..................................................................................................... 19
2.15.3 Alkali Leaching .............................................................................................................19
2.15.4 Acid Leaching ...............................................................................................................19
2.16 Factors influencing the rate of extraction: [7] .................................................................... 20
2.17 Types of equipment .............................................................................................................. 20
2.18 Leaching of coarse solids [8] ................................................................................................. 21
2.19 Leaching of fine solids .......................................................................................................... 23
IV
2.20 AIM OF WORK ..................................................................................................................... 24
3. LITERATURE SURVEY .............................................................................................................. 25
3.1 De-Chroming of Chrome Tanned Leather Solid Waste using Alkaline Hydrolysis Process[14]
26
3.2 Extraction of Chromium Six from Chrome Shavings ..................................................................26
3.3 Effect of Alkali Concentration in Extraction of Chromium III from Tannery Solid Waste ......27
3.5 Extraction of Chromium Six from Chrome Shavings by acid leaching .................................. 29
3.6 A review on management of chrome-tanned leather shavings: a holistic paradigm to combat
the environmental issues ............................................................................................................... 29
4. EXPERIMENTAL PART ..........................................................................................................30
4.1 Acid Leaching ...................................................................................................................... 30
4.1.1 Materials ......................................................................................................................... 30
4.1.2 Equipment .......................................................................................................................30
4.1.3 Experimental procedures .................................................................................................. 32
4.2 Alkaline leaching .................................................................................................................. 33
4.2.1 Materials ......................................................................................................................... 33
4.2.2 Equipment .......................................................................................................................33
4.2.3 Experimental procedures .................................................................................................. 33
5. Results and discussion ...........................................................................................................35
.......................................................................................................................................................39
6. Conclusion .............................................................................................................................. 43
7. References ...............................................................................................................................48
8.Appendix………………………………………………………………………..………………………51
V
LIST OF FIGURES
Figure 1 Earlier steps of leather chrome tanning process, Further steps (drying, buffling,
finishing) ............................................................................................................................. 6
Figure 2 Collagen fibers with different binding sites ................................................................ 9
Figure 3 The binding of chrome and carboxyl group ................................................................ 9
Figure 4 Chrome tanning in the tanning drum ........................................................................11
Figure 5 Chromium (III) oxide in powder form ......................................................................11
Figure 6 Effect of heavy metal as chromium in human health ..................................................16
Figure 7continuou leaching tank ........................................................................................ 22
Figure 8 chrome shavings dust .............................................................................................30
Figure 9 leaching process ................................................................................................. 31
Figure 10 Effect of pH on the rate of extraction of cr(VI) ........................................................ 36
Figure 11 Effect of solid to liquid ratio on the rate of extraction of cr(VI) ..........................................37
Figure 12 The effect of temperature on the rate of extraction of cr(VI) ...................................................38
Figure 13 The effect of speed of motor stirrer on the rate of extraction of Cr(VI) ...................................... 39
Figure 14 The effect of Time on the rate of extraction of cr(VI) ...........................................................40
VI
1. Introduction
1.1 Leather Industry

Leather industry, which is one of the oldest industries in the human history, plays a significant role
in today‘s global economy, leather process transform animal hides/skins into a physically
and chemically stable material. By subjecting hides/skins to chemical and mechanical
sequentialprocesses, therefore production product to meet various needs havepeople.
The major process of the tanning industry is chrome tanning in which theraw hides and skins
are transferred into leather characterized by tophandling quality, high hydro-thermal
stability and excellent properties Currently more than 90% of global leather
production is producedthrough chrome tannage, the majority of the shoe uppers are tanned
withchromium compound. Leather manufacture is steadily increasing the use ofchromium
compounds in the manufactures of various types of leathers suchas garment, clothing, gloving,
bags, textile and furniture Leather industryhas been categorized as one of the high polluting
industries and concernsthat leather making activity can have adverse impact on the
environmentto the industry considering the harmful nature of some of the chemicalsused in
leather processing. The leather industry is responsible for a largegeneration of chrome waste
during tanning processes. Solid wastesgenerated from tanning industries contain different
chemicals which areused during leather manufacturing process. These tannery solid wastes
have different characteristics as different chemicals
And mechanical processes are applied to the raw hides/skins. If these solid waste generated
during various tanning operations are not properly utilized or disposed they are likely to
cause a number of problems on the environment.
Tanneries produce a great variety of waste, in particular, the solid waste coming from the
leather tanning with trivalent chromium salts as trims andshavings. These need special treatment
due to environmental regulationsand the controlling laws requirements for those wastes.
The data obtained from FAO reveals that approximately 8.5 million tonsof solid waste is
generated during the production of 11 million tons of rawhide processed in the world which
is in agreement with the fact statedthat 60% of solid waste is generated During chrome tanning
process 75- 80% of chromium sulphate absorbs into pelts. Up to 33% of chromium is used for
tanning by typical tannery is lost in the solid waste in shavings and trimmings.
The waste containing chromium are classified as class one hazardous waste , and chromium six
1
is found to be the third most common pollutant hazardous waste , therefore they need
treatment before disposalContamination of soil and groundwater due to chromium six is one
of the significant environmental problems to date.
1.2 History
The English word for tanning is from Medieval Latin tannāre, derivative oftannum, from French
tan (tanbark), from old-Cornish tann (red oak). These terms are related to the hypothetical
Proto-Indo-European *dʰonumeaning 'fir tree'. (The same word is source for Old High German
tanna meaning 'fir', related to modern Tannenbaum). Despite the linguistic confusion between
quite different conifers and oaks, the word tan referring to dyes and types of hide
preservation is from the Gaulic usereferencing the bark of oaks (the original source of
tannin), and not firtrees. Ancient civilizations used leather for water skins, bags, harnesses and
tack, boats, armour, quivers, scabbards, boots, and sandals. Tanning wasbeing carried out by
the inhabitants of Mehrgarh in Pakistan between 7000 and 3300 BCE.Around 2500 BCE,
the Sumerians began using leather, affixed by copper studs, on chariot wheels.
simply allowing the skin to putrefy for several months then dipping it in a salt solution.
After the hair was loosened, the tanners scraped it off with a knife. Once the hair was
removed, the tanners would "bate" (soften) the material by pounding dung into the
skin, or soaking the skin in a solution of animal brains. Bating was a fermentative
process that relied on enzymes produced by bacteria found in the dung. Among the
kinds of dung commonly used were those of dogs or pigeons. Historically the actual
tanning process used vegetable tanning. In some variations of the process, cedar oil, alum, or
tannin was applied to theskin as a tanning agent. As the skin was stretched.
2
Formerly, tanning was considered a noxious or "odoriferous trade" and relegated to the
outskirts of town, among the poor. Indeed, tanning by ancient methods is so foul-smelling
that tanneries are still isolated from those towns today where the old methods are used.
Skins typically arrived at the tannery dried stiff and dirty with soil and gore. First, the
ancient tanners would soak the skins in water to clean and soften them. Then they would pound
and scour the skin to remove any remaining fleshand fat. Hair was removed by soaking the
skin in urine, painting it withan alkaline lime mixture, or simply allowing the skin to putrefy
for several months then dipping it in a salt solution. After the hair was loosened, the
tanners scraped it off with a knife. Once the hair was removed, the tanners would "bate"
(soften) the material by pounding dung into the skin, or soaking the skin in a solution of
animal brains. Bating was a fermentative process that relied on enzymes produced by
bacteria found in the dung. Among the kinds of dung commonly used were those of dogs or
pigeons.
Historically the actual tanning process used vegetable tanning. In some variations of the
process, cedar oil, alum, or tannin was applied to theskin as a tanning agent. As the skin
was stretched, it would lose moisture and absorb the agent. Following the adoption in
medicine of soaking gut sutures in a chromium (III) solution after 1840, it was discovered
that this method could also beused with leather and thus was adopted by tanners.
3
2. Theoretical Part
This chapter shows all the theoretical information about the tanning process including
preparation, its types, Beam-house Operations, Characteristics of Tannery Solid Wastes,
Environmental Impacts of Tannery Solid Wastes, and treatment of tannery effluent.
2.1 Preparation [1]

The tanning process begins with obtaining an animal skin. When an animal skin is to
be tanned, the animal is killed and skinned before the body heat leaves the tissues.
This can be done by the tanner, or by obtaining a skin at a slaughterhouse, farm, or
local fur trader.
Preparing hides begins by curing them with salt to prevent putrefaction of the
collagen from bacterial growth during the time lag from procuring the hide to when
it is processed. Curing removes water from the hides and skins using a difference in
osmotic pressure. The moisture content of hides and skins is greatly reduced, and
osmotic pressure increased, to the point that bacteria are unable to grow. In wet-
salting, the hides are heavily salted, then pressed into packs for about 30 days. In
brine- curing, the hides are agitated in a saltwater bath for about 16 hours. Curing
can also be accomplished by preserving the hides and skins at very low
temperatures.
4
2.2 Tanning [2]
Raw hides and skins are transformed into stable finished products by series of
chemical and mechanical processes, among these processes tanning is very important.
Tanning means the conversion of raw skin into finished leather through technical
processes. The collagen proteins will deform when heated, and in water they will turn
into gelatin. Thus tanning is an essential process of the conversion of the collagen in a
natural skins and hides into stable form, giving the material individual durability by
allowing penetration of various tanning agent with different characteristic the
structure through mechanical action in floats, and by reaction with reactive groups of
collagens. Thus tanning is the main process that protects leather against some
environmental effects such as microbial degradation, heat, sweat or moisture.
Tanning involves a complex combination of mechanical and chemical Processes. The
heart of the process is the tanning operation itself in which organic or inorganic
materials become chemically bound to the protein structure of the hide and preserve
it from deterioration. The substances generally used to accomplish the tanning process
are chromium or extracts from bark of trees, such as chestnut. These tanning agents
give rise to the two predominant types of tanning operations - chrome and vegetable
tanning.
There is a vast array of tanning methods and materials and the choice depends
chiefly on the properties required in the finished leather, the cost of alternative
materials, the plant available, and the type of raw material
Hides and skins have the ability to absorb tanning acid and other chemical substances
that prevent them from decaying, make them resistant to wetting and keep them
supple and durable.
The conversion from raw hides into leather comprises many steps. The major processes
are curing, soaking, fleshing, hair removal, scudding, deliming, tanning, dyeing, and
5
finishing .
Figure 1 Earlier steps of leather chrome tanning process, Further steps (drying, buffling,
finishing)
6
2.3 Beam-house Operations [3]
2.3.1 Soaking
Tanneries often receive salted rawhides and skins, which must be cleaned
And rehydrated through soaking, or by placing the skins or hides in water, usually in
paddles or drums. Dirt, blood and dung are also removed in the process. Chemicals
used in soaking are 0.2 – 2.0 grams per liter sodium hydroxide, up to 1 gram per
liter sodium hypochlorite and/or 0.5 – 2.0 per cent wetting agents, emulsifiers,
surfactants etc. The soak bath is often changed every 8 hours to prevent bacterial
growth.
2.3.2 Liming and unhairing

The hide is treated with a solution of lime and sodium sulphide or sodium hydrogen
sulphide to remove hair and loosenthe hide structure. Unhairing is normally
carried out by dissolving in a chemical solution. Chemicals generally used are 2-10
per cent calcium hydroxide (lime), 1- 4 per cent sodium sulphide or sodium hydrogen
sulphide. Some caustic soda may also be used. Enzymatic preparations have been
increasingly used in the last years.
2.3.3 Fleshing and deliming

Fleshing is the mechanical scraping of adhering connective tissue, fat etc. from the
flesh side. On the other hand, deliming solubilizes the absorbed calcium hydroxide
and brings the skin to the desired pH, mainly to avoid interference with the
subsequent tanning stage. The process is carried out By washing and by using water
combined with neutralizing chemicals.
Chemicals used are ammonium chloride or sulphate, 0.5– 2.0 per cent acids (lactic,
formic, boric and mixtures), acidic salts, sodium bisulphite, hydrogen peroxide. The
7
use of gaseous CO2 instead of ammonium salts has been increasing.
2.3.4 Bating
Bating treats the hides with proteolytic enzymes to purify the material prior to tanning.
It loosens the hide structure and removes unwanted proteins, and is often carried out
in the deliming liquor. The chemical used is often a 0.5 per cent bating material, which
consists of 50 per cent wood flour (or another carrier), 30 per cent deliming agent
(ammonium chloride) and 1-5 per cent pancreatic enzyme.
2.3.5 Degreasing
Degreasing is the process of removing fats from the skin. This is especially
important in sheepskin tanneries as the fat content of their raw material is large. The
process uses solvent degreasing. Solvents, which are increasingly substituted or
combined with surfactants and/or enzymes, include perchloroethylene,
monochlorobenzene and kerosene.
2.3.6 Pickling
Pickling increases the acidity of the hide to a pH value of 3 by addition
of acid liquor and salts, enabling chromium tannins to enter the hide. Salts are added
to prevent the hide from swelling. For preservation purposes, 0.03- 2% by weight of
fungicides and bactericides are usually applied.
2.3.7 Tanning Processes

The production of leather depends on the generation of complexes
between the tanning agent and the skin collagen. The stability of the leather can be
ascribed to the strong chemical bonding between the collagen fibers of the skin ridge
and the tanning agent. Collagen fibers consist of proteins and have different binding
sites available.
The binding sites used differ depending on the respective tanning agent (Mineral,
vegetable and synthetic tanning agent). The different binding sites are shown in
figure(2)
8
Figure 2 Collagen fibers with different binding sites
The carboxyl groups are the important binding sites for the mineral tanning agents
(like chrome) [13]. These binding sites have to be prepared for the tanning step and
the collagen has to be activated. This is achieved by a pickle-solution right before the
tanning takes place.
During the pickle process hair and epidermis are removed from the hide at a pH-
value of2.5.
Proteins are hydrolyzed and washed out. Collagen fibers gain more space and
therefore the leather is gaining softness. Due to the low pH- value the collagen starts
to swell. The swelling is limited and kind of controlled via buffering salts.
The basis for the tanning solution is the pickle-solution. For a good tanning the pH-
value has to be raised to 4. At a pH of 2.5 only some carboxyl groups of the skin
collagen are ionized. By raising the pH-value to 4 a maximum binding of chrome and
collagen can be reached. Under these conditions 3.8 wt.-% chrome in skin can be
reached. Experimentally it was found, that at least 3 wt.-% of chrome have to bind
into the skin for producing leather of good quality. The binding of chrome and
carboxyl groups generates chrome complexes under formation of water and sulphuric
acid. The mechanism is shown in figure(3)
Figure 3 The binding of chrome and carboxyl group
The tanning is carried out in rotating tanning drums. Conventional tanning takes
9
approximately 24 to 35 hours. The products of chrome tanning are Called ―wet
blue‖ because of their blue color. Tanning is a major step but Until finally ―leather‖
is generated, some more finishing and fattening steps are required.
2.4 Chrome tanning
Chrome-tanned leather tends to be softer and more pliable than vegetable tanned
leather, has higher thermal stability, is very stable in water, and takes less time to
produce than vegetable-tanned leather. Almost all leather made from lighter-weight
cattle hides and from the skin of sheep, lambs, goats, and pigs is chrome tanned .
Chrome is the most used type of tanning materials and widely used over the world.
Chrome tanned leathers are characterized by top handling quality, high hydro-
thermal stability and excellent properties, light weight and high tensile strength.
Chrome tan cross-links with polypeptide chains by principle valences Through
coordination bonds with the acidic amino acid side chains of the Collagen. The cross-
links induce physical and mechanical properties that Give the chrome tanned leathers
its high quality. Although, there are some Disadvantages of chrome tanned leather
such as lack of fullness and course nap especially in suede leather. Chrome tannage is
still the most widely used method in the tanning industry.
Now a day the use of chromium has accelerated in the leather industry as it is
enables faster and cheaper production of highly resistance and durable leathers.
Today more than 80% of finished goods are tanned using basic chromium sulphate.
However high pH value, temperature, UV lights, unsuitable storage conditions and the
effect of using lubricants with double bonds in the molecule during production possibly
run up the oxidation of the trivalent chromium into the hexavalent form.
After pickling, when the pH value is low, chromium (III) salts are added. To fixate the
chromium, the pH is slowly increased through addition of a Base. The process of
chromium tanning is based on the cross- linkage of The process of chromium tanning is
based on the cross- linkage of chromium ions with free carboxyl groups in the
10
collagen. It makes the hide resistant to bacteria and high temperature.
Figure 4 Chrome tanning in the tanning drum
2.5 Benefits of chrome tanning

The use of chromium (III) salts is currently the commonest method of tanning. In the
following decades, chrome tanning became the most common and dominant form of
tanning. One of the main reasons why it was adopted so rapidly is that the process
was much faster than vegetable tanning. The invention of chrome tanning coincided
with The discovery of the fat liquoring (regressing) process and also the development
of synthetic dyes. Together these changes to the chemistry of leather production led to
chrome tanning becoming the preferred method. Chromium salts belong to the group
of mineral tannins. Immediately after tanning, the leather is still wet and is tinged with
blue; hence it is also referred to as wet blue.
Figure 5 Chromium (III) oxide in powder form
11
2.6 Vegetable tanning
Vegetable tanning agent is considered the "green tanning agent" because of its
biodegradation, vegetable tanned leather has excellent fullness, moldering
properties, wear resistance, air permeability and solidness; hence, it is of great
significance to reduce chrome pollution in leather making process. Vegetable tanned
leather is used in making heavy leather such as furniture leather, garment leather and
shoe upper leather.
Worldwide, researchers are paying particular attention to the use of Vegetable
tanning agents to replace chrome tanning agent and progress has already been
achieved. Some plants are preferred for tanning over others due to the level of their
tannin content. Tannin is found in various plants‘ parts such as tree barks, wood, fruits,
pods, leaves, roots, tubers and many other plant parts, indicating that different plant
parts are used in tanning.
2.7 Alternative tanning

Tanning with organic tanning agents, using polymers or condensed plant Polyphenols
with aldehydic cross- linkers can produce mineral free leather with high hydrothermal
stability similar to chrome- tanned leather. However, organic- tanned leather usually
is more full and hydrophilic than chrome- free leather, with equally high hydrothermal
stability. This tanning process is carried out with a combination of metal salts,
preferable but not exclusively aluminum (III), and a plant polyphenol containing
pyrogallol groups, often in the form of hydrolysable tannins.
12
2.8 Shavings
Shaving process is to adjust the thickness to make the wet blue pelts ready for
retannage and the following processes. Shaving is carried out by a shaving machine
taking off about 20% of the wet- blue pelt weight from the flesh side.
The quality of finished leather depends to a great extent on the degree of uniformity
in shavings. Shaving is undertaken to achieve an even thickness throughout tanned or
crusted leather. Shaving is carried out when splitting is not possible or when minor
adjustments to the thickness are required. If the thickness of the leather is not uniform
throughout the area, the mechanical effects like glazing, staking, ironing, pressing etc.,
will be ununiformed on the leather surface and the total absorption of season by
different portions of the leather surface will be different.
2.9 Solid wastes [4]

Tanneries produce a great variety of waste, in particular, the solid waste Coming
from the leather tanning with trivalent chromium salts as trims and Shavings. These
need special treatment due to environmental regulations And the controlling laws
requirements for those wastes. Large
Quantities of solid wastes are also generated during leather processing and
subsequently during effluent treatment. Although some of the wastes find limited
applications, the safe disposal of the bulk of the solid wastes has posed serious
problems. Out of which some portion of chromium Containing hazardous wastes are
also generated. These chrome containing wastes are categorized as hazardous
wastes. The main sources of solid wastes are from trimming, fleshing, splitting and
shaving processes. The tanned waste contains up to 4.5% of chromium, it can oxidized
to chromium VI which is toxic and carcinogenic. About 3o tons of chromium tannery
waste is generated worldwide per year.
13
2.10 Characteristics of Tannery Solid Wastes
The chemical composition of solid wastes generated from beam-house Operations

(fleshing, trimmings, and splits) depends mainly on a kind and Quality of the raw
material, treatment type and process conditions. The Main components are proteins
and fat, up to 10.5% (w/w) for both groups.
Water content is high, moisture amounts up to 60%. These wastes contain Small
amounts of mineral substances, 2-6% (w/w). Chromium compounds Are not present in
the material.
The tanned leather wastes are mainly useless splits, shavings and trimmings. These
waste groups differ mostly in size and shape, the chemical composition is comparable
for each.
They contain 3-6% (w/w) of fat and about 15% (w/w) of mineral Components,
including 3.5- 4.5% (w/w) of chromium as Cr2O3. Sludge From wastewater
treatment plants contains mostly water (up to 65% (w/w)), organic substances (30%
(w/w)) and chromium (III) compounds (about 2.5% (w/w).
The tanned leather wastes are mainly useless splits, shavings and trimmings. These
waste groups differ mostly in size and shape, the chemical composition is
comparablen for each.
They contain 3-6% (w/w) of fat and about 15% (w/w) of mineral components,
including 3.5- 4.5% (w/w) of chromium as Cr2O3. Sludge From wastewater
treatment plants contains mostly water (up to 65% (w/w)), organic substances (30%
(w/w)) and chromium (III) compounds (about2.5% (w/w).
2.11 Environmental Impacts of Tannery Solid Wastes
Solid wastes generated from tanning industries contain different chemicals which are
used during leather manufacturing process. These
tannery solid wastes have different characteristics as different chemical and
mechanical processes are applied to the raw hides/skins. If these solid waste
generated during various tanning operations are not properly utilized or disposed
they are likely to cause a number of problems on the environment. Salt dust or de-
dusted salt if stored in heaps outside the tanneries or dumped in open dumping area
is likely to be washed away during rains and cause groundwater pollution. Hair
14
waste and lime sludge if discharged along with the effluents are likely to choke the
drains. Raw and green fleshing, limed fleshing, splits (splitting waste) and trimmings
putrefy easily and give rise to noxious smells. In many tanneries, it is the foul odor
which emanates some of these putrescible solid wastes which accounts for much of the
smell traditionally associated with tannery wastes. Some of the biodegradable
tannery solid wastes are sources of pathogenic bacteria and volatile organic
compounds emission. Vegetable and chrome tanned shavings and splits do not easily
decompose. If they are not utilized, problems of disposal are encountered. Primary
and secondary sludge obtained during the treatment of tannery wastes are also
putrescible Excess heavy metal accumulation in soil is toxic to humans and other
animals. Exposure to heavy metals is normally chronic (exposure over a longer period
of time), due to food chain transfer. Acute (immediate) poisoning from heavy metals is
rare through ingestion or dermal contact, but is possible. Some of tannery solid waste
contains chromium metal which is the most widely used in tanning industries as
chromium salt and it causes carcinogenic effect when it enters human body through
food chain.
The standard safe limit for chromium metal in the soil is 150ppm.
In general where tanning industries have long been established there has Been
usually a simultaneous growth in industries which can use tannery solid wastes to
produce some valuable products. This pattern is especially Helpful to the tanning
industry in the case of obnoxious rag and limed Fleshings, trimmings and splits which
are lifted by glue and gelatin units. When solid waste is disposed off on land in open
dumps or in improperly Designed landfills (e.g. in low lying areas), it causes the
following impact On the environment
a) Ground Water Contamination by the Leachate Generated by the Waste Dump.

b) Surface Water Contamination by the Run-off from the Waste Dump.
c) Bad odor, Pests, Rodents and Wind-Blown Litter in and Around the Waste
Dump.
d) Generation of Inflammable Gas (e.g. Methane) Within the Waste Dump.
e) Bird Menace above the Waste Dump Which Affects Flight of Aircraft.
f) Fires within the Waste Dump.
g) Erosion and Stability Problems Relating to Slopes of the Waste Dump.
h) Epidemics through Stray Animals.
15
i) Acidity to Surrounding Soil And.
j) Release of Green House Gas.
2.12 Effect of chromium in human health
When chromium enters the water system in large quantities it can cause
respiratory problems, infertility and birth defects. The use of chromium also puts
workers at risk during the tanning process. If the dust, which is produced when chrome
tanned leather is buffed or ground up, is inhaled, it can cause respiratory problems
and increase the risk of lung cancer.
When chromium comes in contact with the skin it causes dryness and cracking and
sores, known as ‗chrome holes‘. An important health risk factor for the tannery
workers is occupational exposure to Chromium, which is used as a basic tanning
pigment. The workers on exposure to leather dust, which contains chromium in the
protein-bound form, exhibited a higher mean concentration of urinary and blood
chromium than the reference values.
Figure 6 Effect of heavy metal as

chromium in human health
The higher biological values of chromium among the tanners could be explained by
atmospheric pollution caused by the liberated leather dust at the work place. The
increased pulmonary morbidity is also associated with certain characteristic symptoms
such as dry cough (5.6%), throat irritation (3.6%) and lung congestion in 3.0% of the
workers. The hexavalent chromium is rapidly absorbed by the lungs into the blood
16
and easily penetrates the cellular membranes and binds to the hemoglobin in the red
blood cells thereby affecting the oxygen carrying capacity and impairing the lung
function status. Even chrome tanned leather in its finished form poses an environmental
threat: if the leather seats from scrapped cars are burnt then toxic chromium IV may
be released into the atmosphere. This can even occur as a result of car upholstery
being exposed to prolonged strong sunlight. New, ‗green technologies‘ do hold out
the prospect of converting toxic waste into useful products and purifying and
recycling contaminated waste water, however it is unlikely that in poorer countries,
where the bulk of chrome tanning takes place, there will be an investment in costly
alternative ‗green technology.
2.13 Solid Waste Management [5]
Solid waste management is the collection, transportation, storage, recycling or

disposal of solid waste, or the subsequent use of a disposal site that is no longer
operational. It is a complex process because it involves many technologies and
disciplines. These include technologies associated with the generation (including source
reduction), on-site handling and storage, collection, transfer and transportation,
processing, and disposal of solid wastes. All of these processes have to be carried out
within existing legal, social, And environmental guidelines that protect the public
health and the Environment and are aesthetically and economically acceptable. The
Objective of solid waste management is to reduce the quantity of solid Waste
disposed off on land by recovery of materials and energy from solid waste.
Preliminary treatment
Typically, in the case of common effluent treatment plants (CETPs) servicing tannery clusters
often found in developing countries, it is essential to have pre-treatment units installed in
individual tanneries.Their role is to remove large particles, sand/grit and grease, but also to
significantly reduce the content of chrome and sulphides before the effluent is discharged
into the collection network.
Physical-chemical treatment (primary)
The objective here is the removal of settle able organic and inorganic solids by
sedimentation, and the removal of materials that will float (scum) by skimming.
Approximately 25-50% of the incoming biochemical Oxygen demand (BOD5), 50-
70% of total suspended solids (SS), and 65% of the oil and grease are removed
during primary treatment. The effluent and sludge from primary sedimentation are
referred to as primary effluent and sludge.
17
Biological treatment (secondary)
In most cases, secondary treatment follows primary treatment, its goal being the
removal of biodegradable dissolved and colloidal organic matter using aerobic
biological treatment processes. Aerobic biological Treatment is carried out in the
presence of oxygen by aerobic micro- organisms (principally bacteria) that
metabolize the organic matter in the wastewater, thereby producing more micro
organisms and inorganic .End products (principally CO2, NH3, and H2O). Several
aerobic biological processes are used for secondary treatment and the differences
among them have to do primarily with the manner in which oxygen is supplied to the
micro-organisms and with the rate at which organisms metabolize the organic matter.
Advanced (tertiary) treatment
Tertiary or advanced wastewater treatment is employed to reduce residual COD

load and/or when specific wastewater constituents are not removed by previous
treatment stages.
Sludge handling and disposal

Effluent treatment plants produce treated, ―cleaned‖ effluent and sludge because
inherently the primary aim of wastewater treatment is the removal of solids and some
potentially hazardous substances from the Wastewater. Furthermore, biologically
degradable organic substances are converted into bacterial cells, and the latter are
removed from the wastewater.
2.14 Leaching [6]
The extraction of a soluble constituent from a solid by means of a solvent is generally

referred to as leaching. The process may be employed either the production of a
concentrated solution of a valuable solid material, or in order to free an insoluble
solid from a soluble material with which it is contaminated. The method used for the
extraction will be determined by the proportion of soluble constituent present, its
distribution throughout the solid, the nature of the solid.
Generally the processes which is responsible for limiting the extraction rate can be
18
considered one of three parts, first the change of phase of the solute as it dissolves in
the solvent, secondly its diffusion through the solvent in the pores of the solid to the
outside of the particle, and thirdly the transfer of the solute from the solution in
contact with the particles to the main bulk of the solution.
The selection of the equipment for an extraction process will be influenced by the
factors which are responsible for limiting the extraction rate.
2.15 Types of Leaching

The mechanism by which components of a solid material are released into a touching
water phase is leaching. Although some species may be of greater environmental
significance than others, the leaching mechanism is indiscriminate in such a manner that
all components (e.g., major or minor components of the matrix as well as inorganic,
organic and radionuclide contaminants) are emitted under a general collection of
chemical phenomena that may include mineral dissolution, desorption and
complication, and mass transport processes.
2.15.1 Cyanide Leaching
A cyanide solution, or lixiviate, is percolated into ore deposited in vats, columns or

heaps during the cyanide leaching process. The cyanide dissolves gold, which is then
extracted from the heap or columns. It is then removed by adsorption of carbon or
resins from the pregnant leaching solution.
2.15.2 Ammonia Leaching
In hydrometallurgical processes, ammonia and ammonium salts have been recognized
as efficient leaching agents due to low toxicity and expense, fast recovery and
elevated selective metal recovery. New research studies on the major benefits of
leaching by these agents and the removal of acid leaching-related issues have
resulted in a new worldwide approach to this process.
2.15.3 Alkali Leaching

Generally, alkaline leaching works more selectively. In addition, it is considered cost-effective,
quick and fast to operate and handle the extraction of zinc from oxidized zinc ores or waste, it can
hardly be leached out in alkaline media for impurities such as Fe, Cu, Cd, Co, Ni, etc. and its lower
energy usage in the electro winning process compared to acidic electro winning process
2.15.4 Acid Leaching

19
As the first stage of extraction of base metals, acid leaching is often used, especially
in the case of copper, for which mineral acids such as HCl, H2SO4 or HNO3 are used
in conjunction with H2O2, a powerful oxidant that enhances the acid‘s leaching
efficiency. For the recovery of copper from PCB, the mixture of H2SO4 as a leaching
agent and H2O2 as an oxidizing agent is widely used.
2.16 Factors influencing the rate of extraction: [7]

1- The particle size:
The smaller size of particle has a greater interfacial area between the solid and
liquid and therefore the rate of transfer of material is high. Further the smaller is the
distance the solute must diffuse within the solid as already indicated. It is generally
desirable that the range of particle size should be small so that each particle requires
approximately the same time for extraction, and in particular the production of a
large amount of fine material should be avoided as it may wedge in the interstices of
the larger particles and impede the flow of the solvent.
2- The Solvent:
The liquid chosen should be good selective solvent and its viscosity should Be
sufficiently low to circulate freely.
3- The temperature:
In most cases, the solubility of the material which is being extracted will
Increase with temperature to give a higher rate of extraction. Further the Diffusion
coefficient will be expected to increase with raise in temperature and this will also
improve the rate.
4- The agitation of the fluid:

Agitation of the solvent is important, it increase the eddy diffusion and Therefore
increases the transfer of material from the surface of the particles to the bulk of the
solution.
2.17 Types of equipment

Three distinct processes are involved in the normal leaching operation.
They are:
20
a) Dissolving the soluble constituent.
b) Separating the solution, so formed, from the insoluble solid residue.
c) Washing the solid residue in order to free it of unwanted soluble matter or to
obtain, as product, as much of the soluble materials as possible.
The type of equipment employed will depend on the nature of the solid, whether it
granular or cellular and whether it is coarse or fine. The normal distinction between
coarse and fine solids is that the former have sufficiently large settling velocities for
them to be readily separable from the liquid whereas the latter can be maintained I
suspension with the aid of only a small amount of agitation. Generally the solvent can
be allowed to percolate through beds of the coarse materials whereas the fine solids
offer too high a resistance.
The rate of extraction will in general be a function of the relative velocity Between
the liquid and the solid. In some plants the solid is stationary and the liquid flows
through the bed of particles, in some continuous plants the solid and liquid move
counter-currently.
2.18 Leaching of coarse solids [8]

The simple batch plant is used for coarse solids consists of a cylindrical Vessel in which
the solids rest on a perforated support. The solvent is Sprayed over the solids and,
after extraction is complete the residue is Allowed to drain. If the solids contains such
a high proportion of solute that is disintegrate, it's treated with solvent in tank and the
solution is decanted.
In the simple counter-current system, the solid is contained in a number of Tanks and
the solvent flows through each in turn. The first vessel contains Solid which is almost
extracted and the last contains fresh solid. After a Time, the first tank is disconnected
and a fresh charge is introduced at the Far end of the battery. The solvent may flow
by gravity or be fed by Positive pressure, and is generally heated before it enters
each tank.
A continuous unit in which counter-current flow is obtained is the tray Classifier (fig 7).
Solid is introduced near the bottom of a sloping tank and is gradually moved up by
means of a rake. The solvent enters at the top and flows in the opposite direction to
the solid and passes under a baffle before finally being discharged over a weir , the
classifier operates satisfactorily provided the solid does not disintegrated , and it can
be arranged so that the solids are given simple time to drain before they are
discharged . A number of these units can be connected in series to give counter-
current flow.
The leaching plant consists of an open tank 10 ft. in diameter, into the outer portion of
which the solid is continuously introduced from an annular Hopper. Inside the tank a 6
ft. diameter vertical pipe rotates very slowly at the rate of about one revolution
every 40 min. it carries three ploughs Stretching to the circumference of the tank, and
these gradually the solid Through holes into the inside of the pipe. A hollow shaft,
21
about 3 ft. in Diameter rotates in the center of the tank at about one revolution in 3
min and carries a screw conveyor which lifts the solid and finally
discharges it through an opening. So that it falls down shaft and is deflected into a
waste pipe passing through the bottom of the tank. Leaching takes place in the outer
proportion of the tank where the reheated mother liquor rises through the descending
solid. The make-up water is introduced under the flouts of the screw elevator, flows
down over the solid and then joins the reheated mother liquor. The counter- current
extraction takes place in the outer part of the tank and counter- current washing in
the central portion. The plant described operates efficiently and gives between 85
and 90% extraction, as compared with only 50% in the batch plant.
Figure 7continuou leaching tank
22
2.19 Leaching of fine solids
Whereas coarse solids can be reached by causing the solvent to pass Through a bed
of the material, fine solids offer too high a resistance to flow.
Particles less than 200 meshes may be maintained in suspension with only a small
amount of agitation, and as the total surface area is large an adequate extraction
can be effected in a reasonable time. Because of the low settling velocity of the
particles and their large surface, the subsequent separation and washing operations
are more difficult for fine materials than for coarse solids. Agitation can be achieved
either by the use of a mechanical stirrer or by means of compressed air. If a paddle
stirrer is used, precautions must be taken to prevent the whole of the liquid being
swirled, with very little relative motion occurring between solids and liquid. The stirrer
is often placed inside a central tube (fig2.5) and the shape of the blades so
arranged that the liquid is lifted upwards through the tube, the liquid then discharges
at the top and flows downwards outside the tube, thus giving contiguous circulations.
The Dorr agitator uses a compressed air for stirring; consist of a cylindrical flat-
bottomed tank fitted with a central air lift inside a hollow shaft which slowly rotates.
To the bottom of the shaft are fitted rakes which drag the solid material to the center
as it settles, so that it is picked up by the air lift.
At the upper end of the shaft the air lift discharges into a perforated launder which
distributes the suspension evenly over the surface of the liquid in the vessel. When the
shaft is not rotating the rakes automatically fold up so as to prevent the plant from
seizing up if it is shut down full of slurry. This type of agitator can be used for batch
or contiguous operation. In the latter case the entry and delivery points are situated
at opposite side of the tank.
The discharge pipe is often in the form of a flexible connection which can arranged to
take off the product from any desired depth. Many of these agitators are heated by
steam coils.
23
2.20 AIM OF WORK
Modern tanning activities generate considerable liquid and solid wastes into the
environment. The management of tannery solid waste has been a challenge to the
tanning industry for years and a focal point for researches carried out in the tanning
industry. This Project reports the study and development of a more efficient de-
chroming process for tannery solid wastes in which the recovered collagen tissues are
intact.
The objectives of our study:
o Using acid and alkali leaching to extract chromium VI fromchrome

shavings dust
o Reduction of hexavalent chromium to basic chromium sulphate from chrome
shavings This is achieved by hydrolyzing the Heptaoxodichromate (�2 ��2 �7 )
solution with concentrated Tetraoxosuphate (IV) acid to give chromium
sulphate and Water.
�2 ��2 �7 + 6 �2 ��4 → 2��2 ��4 3 + 7 �2 �
o Application of basic chromium sulphate obtained for tannage ofpickled pelts.
o Protection of the environment from toxic and carcinogenicchromium VI.
24
3. LITERATURE SURVEY
Solid waste management is the collection, transportation, storage, recycling or
disposal of solid waste, or the subsequent use of a disposal site that is no longer
operational. It is a complex process especially chromium Recovery because it involves
many technologies and disciplines. These include technologies associated with the
generation (including source reduction), on-site handling and storage, collection,
transfer and transportation, processing, and disposal of solid wastes.
All of these processes have to be carried out within existing legal, social, And
environmental guidelines that protect the public health and the Environment and are
aesthetically and economically acceptable. The Objective of solid waste management
is to reduce the quantity of solid Waste disposed off on land by recovery of
materials and energy from solid waste.
Recovery of chromium made by acid or alkaline leaching at different parameters by
converting chromium III into chromium IV and then dilution it to regulate waste flow
dilution so after that can dispose of it safely.
25
3.1 De-Chroming of Chrome Tanned Leather Solid Waste
using Alkaline Hydrolysis Process[14]
Gurashi.A.Gasmeleed and etal investigate dechroming process by Leaching of

chromium III in form of dichromate and oxidation it by hydrogen peroxide to convert
into chromium (VI) .
A hydrolytic process was carried out using twenty grammes (20g) each of pulverized
chrome tanned leather shavings at two millimeter (2mm) particulate size for both
established alkaline hydrolysis. A triplicate result shows that the alkaline hydrolysis
method gave a better de-chroming process with minimal chromium concentration when
compared with the acid hydrolysis method. Also, when the alkaline hydrolysis process
is used with different washing solutions, results obtained showed that washing with the
established method gave an improved washing with minimal chromium concentration
when compared with other washing solutions.
3.2 Extraction of Chromium Six from Chrome Shavings[15]

Salma A.A Sharaf and etal investigate dechroming process by Leaching of
chromium III in form of dichromate at different levels of solid/liquid ratios,
temperatures, degree of mixing and time.
A hydrolytic process was carried out using twenty grammes (20g) each of
pulverized chrome tanned leather shavings at two millimeter (2mm) particulate size
for both established alkaline hydrolysis, and then add NaOH and sodium
carbonate then Hydrogen peroxide The results shows that The rate of
dechroming process increases with increasing pH ,time ,
temperature ,solid to liquid ratio and speed of motor stirrer doesnt
effect on rate of dechroming process.
26
3.3 Effect of Alkali Concentration in Extraction of
Chromium III from Tannery Solid Waste [16]
Putshaka J. D., Yakubu A., Aliyu Jauro, and etal investigate dechroming process by
Leaching of chromium III in form of dichromate and oxidation it by hydrogen
peroxide to convert into chromium (VI) .
It was discovered from this study that although more chromium was found in leather
shaving waste than leather buffing waste, the percentage recovery of the metal from
leather buffing waste was higher considering the parameters used in this study.
Optimum recovery of chromium from both samples was however achieved when they
were treated with 25% solution of sodium carbonate, carbonized at 60°C, acidified
with 1.0M sulphuric acid, contacted with steam at temperature of 100°C in the
reactor for a maximum period of 40minutes. With these results, further study can be
carried out to recycle and ascertain the efficiency of chromium extracted in leather
tanning process.
3.4 Chrome Tanned Leather Waste Dechroming Optimization for

Potential Poultry Feed Additive Source: A Waste to Resources
Approach of Feed for Future [17]
Abebaw G, and etal investigate dechroming optimization for potential poultry feed
additive source were investigated. Recovery of chrome waste would have
environmental and economic benefits and, in this study, the possible application of
tannery solid waste as poultry feedstuff additive for poultry growers is investigated.
A structured questionnaire was used to collect chrome shaving and got good
information about the waste. The elemental analysis of chromium in chrome shaving is
around 5.6 mg/kg which satisfies the requirement of poultry feed.Chrome shaving
survey and collection: Surveying of chrome shaving about ten tanneries were selected
27
for giving us a feedback through the prepared questioner, and from these only four
factories were volunteer others were not reactive to give us a feedback due to their
own reasons. Chrome containing leather shavings were collected from the tannery of
the Habesha Tanning Factory, Bahir Dar Leather Factory plc, Bahir Dar. Ten kilograms
of chrome shaving collected.
Dechroming step: To increase the surface area grinding of the material was applied
without affecting the molecular structure of collagen fibers in order to achieve
maximum elimination of chromium from the sample. For optimizing the Dechroming
process four samples of Chrome shavings (CS) each of (CS-20 g/100ml) were taken
and placed in sodium sulphate (10% w/w), (20%w/w), (30%w/w) and (40%w/w),
respectively. To increase the washing effect sodium carbonate (8%w/w) (16%w/w),
(24%w/w) and (32%w/w) solution were added and soaked for 30 minutes. And then
solutions of (6%w/w), (12%w/w), (18%w/w) and (24%w/w) weight of calcium
hydroxide were added for each samples sequentially and stirred for 1 hour. Sodium
hydroxide solution (0.1% v/v), (0.2% v/v), (0.3% v/v) and (0.4% v/v) was then
added to increase the hydrolysis effect.
28
3.5 Extraction of Chromium Six from Chrome Shavings
by acid leaching[18]
Putshaka J. D., Yakubu A., and etal study the Effect of Alkali and Acid Concentration
in Extraction of Chromium III from Tannery Solid Waste.
A hydrolytic process was carried out using twenty grammes (20g) each of pulverized
chrome tanned leather shavings at two millimeter (2mm) particulate size for both
established Acid hydrolysis.
20gram of chrome shaving ash/dust was taken in a beaker with 100ml of nitric acid
and stirred in stirrer tank for 1 hour at room temperature then contents of the beaker
were filtered wit Whitman filter paper and analyzed by Atomic Absorption
spectrometer .
The results shows that acid leaching is not effective way for extraction of chromium
from chrome shaving dust.
3.6 A review on management of chrome-tanned leather

shavings: a holistic paradigm to combat the environmental
issues [19]
Rubina Chaudhary and etal study investigate how much chrome in the shaving waste
that could be recovered and used again for tanning leather and thus reducing the
environmental pollution. Three kilograms of chrome shaving waste was hydrolyzed
with NaOH in 10 liters of water, at a temperature of 100oC for 1 hour. NaOH
concentration was varied from 1 to 3% and study the effect of of speed of motor
stirrer .
The result shows that speed of motor stirrer doen’t any effect on rate of extraction
chromiunm VI .
29
4. EXPERIMENTAL PART
This chapter shows the experiments done on chrome shavings dust to

extract chrome and shows the effect of different parameters (PH, Solid to
liquid ratio, Time, Temperature, speed of stirrer).
4.1 Acid Leaching
4.1.1 Materials
1. Chrome shaving dust
2. Nitric acid
3. Hydrogen peroxide
5. Sodium sulphate solution
6. Ammonium iron (II) sulfate (0.1N)
7. Di phenyl amine (indicator)
4.1.2 Equipment
1. Burette
2. Digital PH meter
3. Motor Stirrer
Figure 8 chrome shavings dust

30
Electric Motor stirrer
Impeller
Figure 9 leaching process
31
4.1.3 Experimental procedures
Step 1: Chrome shavings (sample) weighing 20g per 100ml is placed in Nitric acid
solution (5% w/v) solution for 30 minutes.
Step 2: Hydrogen peroxide (15% v/v) is added to the solution at PH 1. The reacting
medium is kept air tight and the reaction is left to take place for 30minutes.
2Cr(OH)_3 + 3 H_2 O_2 →H_2 Cr_2 O_7 + 5H_2 O
Step 3: Water is removed by filtration.
Step 4: The hydrolyzed leather shavings is washed three times with sodium sulphate
solution (10% w/v) and filtered.
Step 5: Making Titration with ferrous Ammonium sulfates.
32
4.2 Alkaline leaching
4.2.1 Materials
1. Chrome shaving dust

2. Sodium carbonate
3. Sodium hydroxide solution
4. Hydrogen peroxide
5. Sodium sulphate solution
6. Ammonium iron (II) sulfate (0.1N)
4.2.2 Equipment
1. Heater
2. Burette
3. Digital PH meter
4. Motor Stirrer
4.2.3 Experimental procedures
Step 1: Chrome shavings (sample) weighing 20g per 100ml is placed in sodium
carbonate (5% w/v) solution for 30 minutes.
Step 2: Sodium hydroxide solution (2% w/v) is then added.
Cr(OH)SO_4+NaOH → Cr(OH)_3 + Na_2 SO_4
Step 3: Hydrogen peroxide (15% v/v) is added to the solution. The reacting medium
is kept air tight and the reaction is left to take place for 30minutes.
33
2Cr(OH)_3 + 3 H_2 O_2→H_2 Cr_2 O_7 + 5H_2 O
Step 4: Water is removed by filtration.

Step 5: The hydrolyzed leather shavings is washed three times with sodium sulphate
solution (10% w/v) and filtered.
Step 6: take 5ml from the filtrate and then Making Titration with ferrous Ammonium
sulfates
Step 7: change the PH in alkali range to determine the best PH which can give the
best extraction concentration of chromium VI
Step 8: change solid to liquid ratio at constant PH gave the best extraction
concentration of chromium VI
Step 9: change the speed of motor stirrer at constant PH and solid to liquid ratio
which gives the best extraction concentration of chromium VI. Step 10: change time at
constant PH and solid to liquid ratio and the speed of motor stirrer which gives the
best extraction concentration of chromium VI.
34
5. Results and discussion
Acid Leaching
No extraction for chromium from chrome shavings dusts. Therefore, acid leaching is
not effective Way for extraction of chrome.we don’t use temperature up to 60 to
don’t change the structure of chrome leather shaving dust as we use after that in
application .
35
Alkaline Leaching
Effect of pH on the rate of extraction of cr(VI)
Change on PH done by changing the concentration of NaoH in step 2
Figure 10 Effect of pH on the rate of extraction of cr(VI)
The effect of pH on the concentration of Cr+6 extracted from chrome

shaving leather was studied by changing the amount of sodium hydroxide.
The figure (10) shows the highest chrome ions concentration at pH 12.
Increasing pH by increasing the amount of sodium hydroxide break the
coordinate bond between chrome ion and collagen, so the extraction of
chrome ions is more effective at pH 12.
36
Effect of solid to liquid ratio on the rate of extraction of cr(VI)
Figure 11 Effect of solid to liquid ratio on the rate of extraction of cr(VI)
The effect of liquid-solid ratio on chromium leach was shown on figure(). As presented,
the leaching amount slightly increasing as the liquid-solid ratio increasing.
37
The effect of temperature on the rate of extraction of cr(VI)
Figure 12 The effect of temperature on the rate of extraction of cr(VI)
Temperature has a great influence on the extractive chrome content as shown in

figure (). As the Temperature increase the extractive chrome concentration increase.
However, we can’t increase Temperature above to 60 (Co) to protect collagen in
chrome shaving solid waste which can be used in further application.
38
The effect of speed of motor stirrer on the rate of extraction of Cr(VI)
Figure 13 The effect of speed of motor stirrer on the rate of extraction of Cr(VI)
The speed of motor stirrer has weak effect on chromium ion extracted as shown in
figure() .That's mean that the reaction is chemically control not diffusion controlled So,
we operate at 200 rpm to reduce the power consumption.
39
The effect of Time on the rate of extraction of cr(VI)
Figure 14 The effect of Time on the rate of extraction of cr(VI)
The extractive content of chromium ion increased steadily as the contact

time increased as shown in figure (). By increasing the contact time, the rate
of reaction increases until reaches equilibrium.
40
6. Conclusion
From the result obtained from the analysis carried out on the products from the two
de-chroming processes (i.e. Acid hydrolysis and alkaline hydrolysis), shows that the
alkaline hydrolysis method gave a better de-chroming process Than acid hydrolysis
method at Temperature range (25-55). The acid hydrolysis method effective at
Temperature 500 and higher that will affect collagen fibers and it can't be used for
applications.
As acid leaching is not effective way to extract chrome VI.
The alkaline leaching gives the best concentration of extraction chrome VI at PH 12.
The extraction process efficiency (leaching efficiency ) increases by increasing the
solid to liquid ratio and increases by increasing temperature as the heat help to
break the coordinate bond between the chrome tanning agent and the collagen
fibers .
The extraction process efficiency (leaching efficiency) increases by increasing the
time and doesn‘t effect by the speed of motor stirrer.
The concentration of extracted chrome VI at PH 12 is 0.056 mg/l and at PH 12 and
solid to liquid ratio 40:100 is 0.116 mg/l and at PH 12 and solid to liquid ratio
40:100 and temperature 55°C is 0.24 mg/l
And at PH 12 and solid to liquid ratio 40:100 and temperature 55°C after 2.5
hour is 0.54 mg/l (the best concentration of extracted chrome VI at the best
condition).
41
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43
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volume 2, 5th ed. Bath Press. Path. Britain. Chapter 10. PP 502-540.
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chemist.
Appendix
46
Table 1 Effect of pH on Concentration of chromium(vI)Extracted frome chrome leather
shaving dust at pH=9
Before First Second Third
washing washing washing washing
Volume of
Ammonium iron(II) 1.9 1.4 0.5 ----
sulfate
(ml)
Concentration of No chrome
chromium(vI) 0.038 0.028 0.01 extracted
Extracted (mg/l)

Before First washing Second Third

washing washing washing
Volume of
Ammonium 1.7 1 0.3 -----
iron(II) sulfate
(ml)
Concentration 0.034 0.02 0.006 No chrome
of chromium(vI) extracted
Extracted
(mg/l)
47

Volume of
Ammonium 2 1.4 ----- -----
iron(II) sulfate
(ml)
Concentration 0.04 0.028 No chrome No chrome
of extracted extracted
chromium(vI)
Extracted
(mg/l)


Volume of
Ammonium 3.1 1.4 ----- -----
iron(II) sulfate
(ml)
chromium(vI)
Extracted
(mg/l)
48

Volume of
Ammonium 2.8 1.6 0.7 -----
iron(II) sulfate
(ml)
of extracted
chromium(vI)
Extracted
(mg/l)
Table 6 Concentration of extracted Chromium(VI) at pH 12 and solid to liquid ratio 1:5

Volume of
Ammonium 3.1 0.7 0.5 -----
iron(II) sulfate
(ml)
of extracted
chromium(vI)
Extracted
(mg/l)
49

Volume of
Ammonium 3.5 0.7 0.45 -----
iron(II) sulfate
(ml)
of extracted
chromium(vI)
Extracted
(mg/l)

Volume of
Ammonium 4 0.45 ----- -----
iron(II) sulfate
(ml)
chromium(vI)
Extracted
(mg/l)
50

Volume of
Ammonium 4.7 0.7 ----- -----
iron(II) sulfate
(ml)
chromium(vI)
Extracted
(mg/l)

Volume of
Ammonium 5.8 0.7 ----- -----
iron(II) sulfate
(ml)
chromium(vI)
Extracted
(mg/l)
51
Table 11 Concentration of extracted Chromium(VI) at pH 12 and solid to liquid ratio
2:5 and Temp.25°C

Volume of
Ammonium 5.8 0.45 ----- -----
iron(II) sulfate
(ml)
chromium(vI)
Extracted
(mg/l)

2:5 and Temp.35°C

Volume of
Ammonium 8 0.45 ----- -----
iron(II) sulfate
(ml)
chromium(vI)
Extracted
(mg/l)
52
2:5 and Temp.45°C

Volume of
Ammonium 9.5 0.7 ----- -----
iron(II) sulfate
(ml)
chromium(vI)
Extracted
(mg/l)

2:5 and Temp.50°C

Volume of
Ammonium 10.6 0.45 ----- -----
iron(II) sulfate
(ml)
Concentration 0.212 0.0009m No chrome No chrome
chromium(vI)
Extracted
53
(mg/l)
Table Concentration of extracted Chromium(VI) at pH 12 and solid to liquid ratio 2:5

and Temp.50°C

Volume of
Ammonium 12 0.6 ----- -----
iron(II) sulfate
(ml)
chromium(vI)
Extracted
(mg/l)

40:100 and Temp.55°C and speed of motor stirrer 200 rpm

Volume of
Ammonium 12 0.6 ----- -----
iron(II) sulfate
(ml)
54
chromium(vI)
Extracted
(mg/l)


Volume of
Ammonium 12.3 0.6 ----- -----
iron(II) sulfate
(ml)
chromium(vI)
Extracted
(mg/l)
55
Table 17 Concentration
of extracted Chromium(VI) at pH 12 and solid to liquid ratio

Volume of
Ammonium 12.4 0.6 ----- -----
iron(II) sulfate
(ml)
chromium(vI)
Extracted
(mg/l)

Volume of
Ammonium 12.5 0.6 ----- -----
iron(II) sulfate
(ml)
chromium(vI)
Extracted
(mg/l)
56

Volume of
Ammonium 12.5 0.6 ----- -----
iron(II) sulfate
(ml)
Concentration 0.244l 0.012 No chrome No chrome
chromium(vI)
Extracted
(mg/l)
40:100 and Temp.55°C and speed of motor stirrer 300 rpm and 0.5 hr

Volume of
Ammonium 12 0.5 ----- -----
iron(II) sulfate
(ml)
chromium(vI)
Extracted
(mg/l)
57
40:100 and Temp.55°C and speed of motor stirrer 300 rpm and 1 hr

Volume of
Ammonium 13.5 0.5 ----- -----
iron(II) sulfate
(ml)
chromium(vI)
Extracted
(mg/l)


Volume of
Ammonium 17.2 0.6 ----- -----
iron(II) sulfate
(ml)
chromium(vI)
Extracted
(mg/l)
58
40:100 and Temp.55°C and speed of motor stirrer 300 rpm and 2 hr

Volume of
Ammonium 23.2 0.5 ----- -----
iron(II) sulfate
(ml)
Concentration 0.464l 0.01 No chrome No chrome
chromium(vI)
Extracted
(mg/l)


Volume of
Ammonium 27 0.45 ----- -----
iron(II) sulfate
(ml)
chromium(vI)
Extracted
(mg/l)
59

Treatment of Tannery Effluent and Extraction of Chromium From Chrome Tannery Solid Waste

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Treatment of Tannery Effluent and Extraction of Chromium From Chrome Tannery Solid Waste

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Alexandria University Faculty of

Extraction of chromium from Chrome Tannery Solid Waste

A great thank to Prof.Dr.Dina El╴gayar for supervising ourproject,giving

1.1 Leather Industry

2.1 Preparation [1]

2.3.2 Liming and unhairing

2.3.3 Fleshing and deliming

2.3.7 Tanning Processes

Figure 3 The binding of chrome and carboxyl group

2.4 Chrome tanning

Figure 4 Chrome tanning in the tanning drum

2.5 Benefits of chrome tanning

Figure 5 Chromium (III) oxide in powder form

2.7 Alternative tanning

2.9 Solid wastes [4]

The chemical composition of solid wastes generated from beam-house Operations

2.11 Environmental Impacts of Tannery Solid Wastes

a) Ground Water Contamination by the Leachate Generated by the Waste Dump.

2.12 Effect of chromium in human health

Figure 6 Effect of heavy metal as

2.13 Solid Waste Management [5]

Solid waste management is the collection, transportation, storage, recycling or

Physical-chemical treatment (primary)

Advanced (tertiary) treatment

Tertiary or advanced wastewater treatment is employed to reduce residual COD

Sludge handling and disposal

2.14 Leaching [6]

The extraction of a soluble constituent from a solid by means of a solvent is generally

2.15 Types of Leaching

2.15.1 Cyanide Leaching

A cyanide solution, or lixiviate, is percolated into ore deposited in vats, columns or

2.15.3 Alkali Leaching

2.15.4 Acid Leaching

2.16 Factors influencing the rate of extraction: [7]

4- The agitation of the fluid:

2.17 Types of equipment

2.18 Leaching of coarse solids [8]

Figure 7continuou leaching tank

o Using acid and alkali leaching to extract chromium VI fromchrome

Gurashi.A.Gasmeleed and etal investigate dechroming process by Leaching of

3.2 Extraction of Chromium Six from Chrome Shavings[15]

3.4 Chrome Tanned Leather Waste Dechroming Optimization for

3.6 A review on management of chrome-tanned leather

This chapter shows the experiments done on chrome shavings dust to

Figure 8 chrome shavings dust

Figure 9 leaching process

2Cr(OH)_3 + 3 H_2 O_2 →H_2 Cr_2 O_7 + 5H_2 O

Step 3: Water is removed by filtration.

Step 5: Making Titration with ferrous Ammonium sulfates.

1. Chrome shaving dust

Step 2: Sodium hydroxide solution (2% w/v) is then added.

Cr(OH)SO_4+NaOH → Cr(OH)_3 + Na_2 SO_4

Step 4: Water is removed by filtration.

Effect of pH on the rate of extraction of cr(VI)

Change on PH done by changing the concentration of NaoH in step 2

Figure 10 Effect of pH on the rate of extraction of cr(VI)

The effect of pH on the concentration of Cr+6 extracted from chrome

Figure 11 Effect of solid to liquid ratio on the rate of extraction of cr(VI)

Figure 12 The effect of temperature on the rate of extraction of cr(VI)

Temperature has a great influence on the extractive chrome content as shown in

Figure 14 The effect of Time on the rate of extraction of cr(VI)

The extractive content of chromium ion increased steadily as the contact