Process report on

Preparation of Modified Basic chromium sulphate

Submitted to
Institute of Chemical Engineering & Technology
University of Punjab, Lahore
In Partial Fulfillment of the Requirement
for the Degree
Of
Bachelor of Science (Chemical Engineering)
Session 2010-14

Submitted by:
Touqeer Nawaz

CE-E10-16

Jahanzeb Khalil

CE-E10-17

Muhammad Umair

CE-E10-14

Syed Ali Hassan

CE-E10-18

Supervised by:

Professor Dr. Mehmood Saleem

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Dedication
We dedicate our work and utmost efforts to ALLAH almighty the creator of this
universe and most merciful and bounteous, You have always been by my side
guiding me all the way to this destiny & Holy Prophet (PBUH) the cause of the
creation of this universe. Our parents who taught us how to be persevere and be
patient in midst of trials. Our most respected Teachers who built our knowledge
foundations, Our Friends who encouraged and strengthened us and our siblings
who are our supporters and well-wishers.

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Acknowledgment
By the Grace of Almighty Allah, the most Merciful, the most Beneficial, I'm
today submitting my report. I have the pearls of my eyes to admire the
blessings of the compassionate, omnipotent, the Merciful and the
beneficent Allah who is the entire source of knowledge and wisdom. Due to
his bounteous blessings, I become able to contribute this comprehensive
assignment toward the deep ocean of knowledge. Heart is warm with love and
thoughts have turned to the city of knowledge The Holy Prophet
(P.B.U.H) His saying Learn from to Cradle to Grave inspired the strong
desire in me to undertake this course of valuable studies. It would obviously
be injustice not to mention the name of the person involved to make this
assignment possible and helped their utmost to make us understand the
overall nature of the report as of their best knowledge. Despite of the most
hectic schedule,

Pro. Dr. Mehmood Saleem

helped us so much. I'm really grateful to them for clarifying my concepts and
making me learn from their experience. Whatever I learnt from them will
definitely help me in my upcoming study and the professional life ahead.

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Abstract
Steam economy is very important in every industrial unit as it decreases the
capital and running plant cost and ultimately boosts up the profit index of the
industry.
Tanning bath employed in leather processing units for the tanning of leather
usually constitute of Basic chromium sulphate and normally efficient at elevated
temperatures and consumes a considerable amount of steam. The steam
economy of this process can be improved by enhancing solubility of chromium
sulphate at temperature less than that, at which is being operated for the sake of
better steam economy of leather tanneries.
This report is being classified in five sections, In first part we have described the
Introduction and background of leather tanning. Second section comprises of
Chemistry of chrome tanning, third section consists of all the raw materials
required for preparing modified chrome salt. Fourth section includes methods
available to synthesize basic chromium sulphate. Whereas the final section
ponders lights upon the experimental setup, results, conclusions and
discussions.

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Table of Contents
1. Introduction ........................................................................................................ 8
1.1 Background: .................................................................................................... 8
1.2 Vegetable Tanned Leather: ............................................................................. 9
1.3 Aldehyde Tanned Leather: ............................................................................ 10
1.4 Formaldehyde Tanned Leather: .................................................................... 10
1.5 Rose Tanned Leather:................................................................................... 10
1.6 Syntans: ........................................................................................................ 10
1.7 Alum Tanned Leather: ................................................................................... 11
1.8 Chrome Tanned Leather: .............................................................................. 11
1.9 Position in Pakistan: ...................................................................................... 12
1.10 Literature Review ........................................................................................ 13
2. Chemistry of Tanning ...................................................................................... 14
2.1 Chrome tanning: ............................................................................................ 14
2.2. Mechanism of Chrome Tanning: .................................................................. 15
2.3. Chemistry of Chromium salts: ...................................................................... 17
2.4. Uses and Health hazards: ............................................................................ 17
2.5 Health safety and Environment. .................................................................... 17
3. Raw materials .................................................................................................. 18
3.1 Sodium Dichromate: ...................................................................................... 18
3.2 Sulphuric Acid: .............................................................................................. 19
3.3 Glucose: ........................................................................................................ 20
3.4 Ethylene Glycol: ............................................................................................ 21
4. Preparation methods for modified basic chromium sulphate .......................... 23
4.1. Sugar Reduction Method:............................................................................. 23
4.2. Sulfur Dioxide Reduction Method: ................................................................ 24
4.3. Selection of the Process:.............................................................................. 25
4.4.Modification in product of basic chromium sulphate: .................................... 25
5. Experimental Setup ......................................................................................... 26
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5.1 Raw materials. ....................................................................................................................... 26

5.2 Apparatus ............................................................................................................................... 26
5.1.3 Procedure ........................................................................................................................... 27
5.2 Addition of Glycols:........................................................................................ 27
6. Experimental tests ........................................................................................... 28
6.1.1 Description ......................................................................................................................... 28
6.1.2 Composition ....................................................................................................................... 28
6.2 Method of Test for Basic Chromium Sulphate (For Tanning)........................ 29
6.2.1 Determination of moisture ............................................................................................. 29
Apparatus .................................................................................................................................. 29
Procedure .................................................................................................................................. 29
Calculations ............................................................................................................................... 29
6.2.2 Determination of basicity ................................................................................................ 29
6.2.3 Determination of matter insoluble in water................................................................ 30
Apparatus .................................................................................................................................. 30
Procedure .................................................................................................................................. 30
Calculation ................................................................................................................................ 30
6.2.4 Determination of pH ........................................................................................................ 31
Apparatus .................................................................................................................................. 31
Procedure .................................................................................................................................. 31
6.2.5 Test for unreduced chromium ....................................................................................... 31
Reagent ...................................................................................................................................... 31
Procedure .................................................................................................................................. 31
6.3 Conclusions ................................................................................................... 33
Refrences ............................................................................................................ 34

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Chapter 1

1. Introduction
1.1 Background:
Leather is a durable and flexible material created by the tanning of
animal rawhide and skin, often cattle hide. It can be produced through
manufacturing processes ranging from cottage industry to heavy industry.
Leather is one of the oldest materials used by mankind. Tanning is generally
said to be the first manufacturing process of man on the earth. Leather has
remained and is still the most essential commodity of man. A lot of changes
have occurred in this industry. Due to lack of scientific knowledge and
equipment the earlier tanner had to face a lot of problems. However today,
due to the development of many leather substitutes, the present tanner is
facing even a greater test. Animal Skins and Furs have been prepared prior to
civilization and with primitive methods (for example clothing) and so made
useful. (Coulson)
Preparing animal skins to leather with the addition of tanning agents pre-dates
the Stone Age man (ca.8000 BC). It is evident that the form of fat tanning
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(Chamois Method) was done in the Neolithic period (ca.6000 BC). Also smoke
tanning over fire and the mineral tanning with alum (White Tanning) are surely
ancient tanning methods. Tanning with botanic agents (Vegetable Tanning) is
known since the Bronze Age (ca.2000 BC), where mainly the bark of the oak
and beech as tanning agents were used. Bark Tanning was traditionally used
during the medieval period. Out of these basics and through increasing
civilization and knowledge a craft and industry has emerged.
Leather is a product obtained by stabilizing proteins of animals skin through
tanning. Animal skin used for tanning is a byproduct of meat industry. Animals
are not killed in the world just for the sake of skin. The flayed skin must be
preserved so that all its leather potential is retained or protected against the
action of microorganisms, autolytic enzymes and chemical hydrolysis. The
skin is protected by reducing the moisture in the hide to 5%. Before the
development of chrome tanning all the leather was treated by vegetable
tanning. After the introduction of chrome tanning all the tanners started to tan
leather by this method

1.2 Vegetable Tanned Leather:

Vegetable-tanned leather is tanned using tannins and other ingredients found
in different vegetable matter, such as tree bark prepared in bark
mills, wood, leaves, fruits and roots and other similar sources. It is supple and
brown in color, with the exact shade depending on the mix of chemicals and
the color of the skin. It is the only form of leather suitable for use in leather
carving or stamping. Vegetable-tanned leather is not stable in water; it tends
to discolor, so if left to soak and on drying it will shrink and become less
supple, and harder. In hot water, it will shrink drastically and partly gelatinize,
becoming rigid and eventually brittle. Boiled leather is an example of this,
where the leather has been hardened by being immersed in hot water, or in
boiled wax or similar substances. Historically, it was occasionally used
as armor after hardening, and it has also been used for book binding.
Vegetable tanned leathers present unique, recognizable and natural
characteristics while respecting the environment.

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1.3 Aldehyde Tanned Leather:

Aldehyde-tanned leather is tanned using glutaraldehyde or oxazolidine compound.
This is the leather that most tanners refer to as wet-white leather due to its pale

cream or white color. It is the main type of "chrome-free" leather, often seen in
automobiles and shoes for infants.

1.4 Formaldehyde Tanned Leather:

Formaldehyde tanning (being phased out due to its danger to workers and the
sensitivity of many people to formaldehyde is another method of aldehyde
tanning. Brain-tanned leathers fall into this category and are exceptionally
water absorbent.
Brain tanned leathers are made by a labor-intensive process which uses
emulsified oils, often those of animal brains. They are known for their
exceptional softness and their ability to be washed.
Chamois leather also falls into the category of aldehyde tanning and, like
brain tanning, produces highly water-absorbent leather. Chamois leather is
made by using oils (traditionally cod oil) that oxidize easily to produce the
aldehydes that tan the leather to make the fabric the color it is.

1.5 Rose Tanned Leather:

Rose tanned leather is a variation of vegetable oil tanning and brain tanning,
where pure rose otto replaces the vegetable oil and emulsified oils. It has
been called the most valuable leather on earth, but this is mostly due to the
high cost of rose otto and its labor-intensive tanning process.

1.6 Syntans:
Synthetic-tanned leather is tanned using aromatic polymers such as
the Novolac or Neradol types (syntans, contraction for synthetic tannins). This
leather is white in color and was invented when vegetable tannins were in
short supply during the Second World War. Melamine and other aminofunctional resins fall into this category as well. Urea-formaldehyde resins were
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also used in this tanning method until dissatisfaction about the formation of
free formaldehyde was realized.

1.7 Alum Tanned Leather:

Alum-tanned leather is transformed using aluminum salts mixed with a variety
of binders and protein sources, such as flour and egg yolk. Alum-tanned
leather is technically not tanned, as tannic acid is not used, and the resulting
material will revert to rawhide if soaked in water long enough to remove the
alum salts. Very light shades of leather are possible using this process.

1.8 Chrome Tanned Leather:

Chrome-tanned leather, invented in 1858, is tanned using chromium
sulfate and other salts of chromium. It is more supple and pliable than
vegetable-tanned leather and does not discolor or lose shape as drastically in
water as vegetable-tanned. It is also known as wet-blue for its color derived
from the chromium.
After 1900 Chrome Tanning with Chrome Salts was the most important
tanning method, due to the shorter time requirement as compared to the Bark
Tanning method which can last up to 15 months.
The first concept of chrome tanned leather is attributed to Knap who
discovered in 1858 that the basic chromium compound can convert animal
hide into leather. But he failed to realize the commercial possibilities of his
discovery. In 1884 augustus Schultz, a dye man planted a two bath method of
chrome tanning process in which sodium dichromate is reduced in the skin to
form chrome tanning compound. This proved to be the revolutionary change
in the leather industry. The two bath method was replaced by one bath
method in 1893. Maton dannis used this process which was original process
used by Knap. In indo Pak this process was first used in Madras in 1913.
Chrome tanning developed rapidly in first half of the century as its greatly
speeds up the tanning operation and increases strength.

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1.9 Position in Pakistan:

Tanning industry of the undivided indo Pak gain encouragement in the
Second World War when the export of raw hide became practically
impossible. At that time fifty tanneries were organized. Majority of these were
in Kanpur, Calcutta and Madras. On division if India and Pakistan, Pakistan
was left without any recognized tannery, though it had a very rich production
of raw hide and skin. At that time Pakistan was primarily a raw hide and skin
exporting country. A very few mechanical tanneries were operating at that
time. Leather is prepared by both vegetable and chrome tanning methods.
Pakistan Tanners Association (PTA) was established in late 50s. PTA is now
functioning as a renowned trade body duly licensed by the Ministry of
Commerce under Trade Organizations Ordinance/Rules 2007, registered with
the Security & Exchange Commission of Pakistan and a bonafide member of
the Federation of Pakistan Chambers of Commerce & Industry. It is the 2nd
largest export earning sector representing highly dynamic and value added
industry in leather and leather products besides being job oriented sector. The
industry employs about 500,000 people directly, producing fine quality
finished leather for export as well as for home consumption. It contributes 5%
of GDP and 5.4% to the overall export earnings of the country and is
considered to be the most significant sector which plays viable role in
revamping
economic
spectrum
of
the
country.
There are about 800 tanneries in the country, 213 Members currently
registered with Pakistan Tanners Association from all over the country are
actively engaged in manufacturing and fully geared-up towards promoting
export of quality finished leather and leather products on modern pattern as
per international demand and are playing their positive role in earning much
needed foreign exchange by invigorating countrys export volume. They are
courageously prepared to meet the challenges of WTO regime and other
global pressures with quality consciousness and full sense of responsibilities
to uphold the impeccable image of leather industry within the ambit of national
policies, rules & regulations and international conditionality.
The superb quality of Pakistani Leather & Leather Products is exported all
over the world fetching sizeable foreign exchange. PTA has been organizing a
number of International Fairs every year for participation of its interested
member exporters to display their eye catching leather & leather products.
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The export of Leather & Leather Products is progressing gradually in terms of

Value, Quantity and Unit Price of the leather articles. The main buyers of
Pakistani Leather & Leather Products are Hong Kong, Italy, China Korea,
Vietnam, Germany, Turkey, India, South Africa, Spain, Japan, France &
Indonesia.

1.10 Literature Review

This report examines the effect of change in solubility of basic chromium sulphate at
room temperature. A detailed study on this topic was required as basic chromium
sulphate is used in leather industry for tanning purposes as a high quality tanning agent.
The process which is being employed at industry requires the temperature of tanning
bath to be at 70 degree Celsius.
Herbert B. Guynn studied from United States worked on this topic and found certain
chemicals which can enhance the solubility of basic chromium sulphate at room
temperature. The objective was achieved by in the process if manufacture of basic
chromium sulphate which is soluble in cold water by evaporating aqueous solution and
adding at least one glycol. The addition of glycols may take place before the chromium
salt solutions are adjusted to the desired basicity or just before the solution is
dehydrated. Glycols used in this process are mono or poly glycols provided they are
soluble in water. Preferred mono glycols are those which have 2 to 4 carbon atoms.
Preferred compounds are ethylene glycol, 1-2 propylene glycol, 1-2 Butylene glycol.
Particular examples of poly glycols are ethylene di glycol, ethylene tri glycol, And tri
propylene glycol. No change in the tanning efficiency of the chrome tanning was
observed as compare to the un modified basic chromium sulphate. The chrome tanning
agent prepared by this method can be used in conjunction with vegetable and synthetic
tanning agent just same as the un modified agent. The technical advance is the that
much better liquid exhaustion is achieved even in cold water due to improved solubility
of agent and the waste liquor obtained from the process contains much less chromium

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Chapter 2

2. Chemistry of Tanning
Tanning may be defined as the treatment of hides and skin to preserve and
convert them into useful articles of commerce. It is the process of treating skins
of animals to produce leather, which is more durable and less susceptible to
decomposition. Tanning leather involves a process which permanently alters the
protein structure of skin. Before tanning, the skins are unhaired, degreased,
desalted and soaked in water over a period of 6 hours to 2 days. To prevent
damage of the skin by bacterial growth during the soaking period, Biocides,
typically dithiocarbamates are used. Vegetable, chrome and most other tanning
methods yield useable leathers from tanning process alone. (Heidemann, 1982)

2.1 Chrome tanning:

In chrome tanning the reaction with the chromium salts give a very stable hide
fiber which is very resistant to bacterial attack and to high temperatures. Without
further processing, however, chrome tanned leather doesnt have many of the
qualities desired for useful articles.
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Chrome tanning must be used in conjunction with the additional processes

dyeing, fat liquoring and perhaps vegetable re-tanning to produce useable
leather articles.
The major advantages of chrome tanning are high speed, low cost light colour
and excellent preservation of hide protein. Chrome tanning took its place in
commercial world shortly after its discovery and became the most common way
of tanning light leathers and shoe upper leathers.
The original patent of Schultz was based on a two bath tannage. In the two bath
system, the skins are treated with an acid dichromate solution and later in the
process the dichromate is reduced to green trivalent state. The two bath chrome
tanning method has continued to be popular for some types of skins, though it
has been considerable modified for the modern production. (Gustavson, 1956)

2.2. Mechanism of Chrome Tanning:

Commercial chrome tanning is always done by one bath process. This is based
on the reaction between hide and trivalent chromium salts usually a basic
chromium sulphate. Chromium sulphate has long been regarded as the most
efficient and effective tanning agent. Chromium(III) compounds of the sort used
in tanning are significantly less toxic than hexavalent chromium. Chromium(III)
sulfate dissolves to give the hexaaquachromium(III) cation, [Cr(H2O)6]3+, which at
higher

pH

undergoes

processes

called olation to

give

polychromium(III)

compounds that are active in tanning, being the cross-linking of the collagen
subunits. The chemistry of [Cr(H2O)6]3+ is more complex in the tanning bath
rather than in water due to the presence of a variety of ligands. Some ligands
include the sulfate anion, the collagen's carboxyl groups, amine groups from the
side chains of the amino acids as well as "masking agents." Masking agents
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are carboxylic acids, such as acetic acid, used to suppress formation of

polychromium (III) chains. Masking agents allow the tanner to further increase
the pH to increase collagen's reactivity without inhibiting the penetration of the
chromium (III) complexes.
Collagen

is

characterized

by

high

content

of glycine, proline,

and hydroxyproline, usually in the repeat -gly-pro-hypro-gly-. These residues give

rise to collagen's helical structure. Collagen's high content of hydroxyproline
allows for significant cross-linking by hydrogen bonding within the helical
structure. Ionized carboxyl groups (RCO2-) are formed by hydrolysis of the
collagen by the action of hydroxide. This conversion occurs during the liming
process, before introduction of the tanning agent (chromium salts). The ionized
carboxyl groups coordinate as ligands to the chromium(III) centers of the oxohydroxide clusters.
In the typical one bath process the hides or skins are in a pickled state at a pH of
3 or when the chrome tanning materials are introduced.
At these low pH values, the affinity of chrome tanning salts for the protein is
moderate allowing penetration of the chrome tanning salt or agent into the hide.
After proper penetration and initial absorption of some of the chrome salts have
been achieved, the pH is raised. This brings about in both the chromium salts
and the protein and causes reaction between them. When the reaction is
completed, the leather is said to be full chrome tanned.
The chemistry of chrome tanning process is complicated and involves several
simultaneous competing reactions. (Heidemann, Ullmann's Encyclopedia of
Industrial Chemistry, 2005)

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2.3. Chemistry of Chromium salts:

Chromium tanning salts have a valency of +3. They are soluble in strong acids
but will usually precipitate as chromium hydroxide or hydrated chromium oxide,
pH value slightly above 4. They react with a number of organic materials to form
coloured soluble salts at higher pH values, and they will precipitate soluble
protein. (Greenwood, 1997)

2.4. Uses and Health hazards:

Chromium was first used to make chromium chemicals in about 1800 to 1860
and was first employed as a refractory in France in about 1879. Intensified use of
chromium metal in steel started about 1908 to 1912. These three applications;
chemical, refractory and metallurgical constitute the main usage of chromium
today.

2.5 Health safety and Environment.

Acute effects of chromates are mainly on the skin and mucous menrane, and
have been observed in workers for 150 years. The breathing of dusts or mists
containing chromium VI compounds leads to ulceration and eventual perforation
of the cartilaginous portion of the nasal septum.
In additional to these effects, chromates may produce ulcers when a cut or
abrasion in the skin is contaminated. If sufficient chromate is brought into contact
with skin lesions, fatalities may result. Dermatitis and allergic reactions may
result from prolonged exposure of skin to chromate. In the majority of workers
dermatitis results only from prolonged exposure

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Chapter 3

3. Raw materials
The essential raw materials required for the production of Basic Chromium
Sulphate includes:

Sodium Dichromate
Sulphuric Acid
Glucose
Ethylene Glycol

3.1 Sodium Dichromate:

Molecular formula of sodium dichromate is Na2Cr2O7.2H20 which have
molecular weight of 298.05, forms deliquescent, orange reddish monoclinic
crystals. The dehydrate loses water when it is heated to high temperature,
transforming into anhydrous salt.

Colour

Bright red

Solubility in water

73g/100 mL at 25 degree C

Density

2.52 g/cm3

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Melting point

356.7 degree C

Odor

Odourless
Table 3. 1 Characteristics of sodium dichromate

Sodium Dichromate is manufactured in hydrated form by fluxing chrome iron ore

with lime and sodium carbonate, the resultant sodium chromate is reacted with
Sulphuric acid which converts it into sodium dichromate which is crystallized from
water as reddish orange monoclinic crystals.
Industrially Sodium dichromate find its applications in the manufacturing of
CHROMOSOLE, pigments, chromic acid and Basic Chromium sulphate. Sodium
dichromate find its enormous applications in Leather tanneries, the present
production of this product is . Which is very limited and most of the
demand is fulfilled through imports.

3.2 Sulphuric Acid:

The increase and expansion in the industrial production in Pakistan has
necessitated rising quantum of sulphuric acid consumption. Industrial sub sector
uses relatively significant amounts of sulphuric acid in the country which includes
Fertilizers, Aluminum sulphate, Leather tanning, and Storage batteries etc.
Leather industry employs excess amount of sulphuric acid for the
preparation of sodium dichromate and basic chromium sulphate.

Molar mass

98.079 g/mole

Density

1.84 g/cm3

Melting point

10 degree C

Solubility in water

Miscible

Acidity

1.99

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Viscosity

26.7 cP
Table 3. 2 Characteristics of Sulphuric acid

There are more than 12 manufacturing units of sulphuric acid across the country
producing acid. Production capacity of the units stood at .. approximately.
At present the industry is completely dependent on imported sulphur.
However, recovery of sulphur from gaseous phase has shown some
improvement.
The important Sulphuric Acid suppliers in Pakistan are:
1.
2.
3.
4.
5.
6.
7.

Atta Chemicals PVT,LTD

A.I.K International exports
Akber Ali and sons
Acid Chemical industries PVT,LTD
Amber Chemicals industries PVT,LTD
Crescent Chemicals LTD
Exide Pakistan LTD (alibaba.com international, 1999-2014)

3.3 Glucose:
Glucose is used as a reducing agent for the reduction of sodium dichromate to
basic chromium sulphate. Sugar can also be used as reducing agent, however
glucose is more preferred over sugar if it is from impurities so that it yields finer
product.
When glucose acts as a reducing agent, it has an aldehyde group or is capable
of forming one in solution through isomerism. Glucose exists in several different
molecular
structures,
Reducing
monosaccharides
include
glucose,
Glyceraldehyde and galactose. Many disaccharides have also reducing form ,
however sucrose and trehalose are non reducing disaccharides
In Glucose, polymers such as starch and starch derivatives like glucose syrup,
maltodextrin and dextrin the macromolecule begins with reducing sugar, a free
aldehyde. More hydrolysed starch contains more reducing sugars present in
these starch derivatives is called dextrose equivalent.

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At present there are two major producers of glucose, M/S glaxo

laboratories and Rafhan maize products Ltd.

3.4 Ethylene Glycol:

Ethylene glycol is an odourless, colourless, syrupy, sweet-tasting liquid. Ethylene
glycol is only weakly toxic, but cases of poisonings are not uncommon. The
major application of ethylene glycol is as a medium for convective heat transfer in
automobiles and liquid cooled computers. Pure ethylene glycol has a specific
heat capacity about one half of the water.
In 2009, almost 85% of the mono-ethylene glycol (MEG) consumed worldwide
went into the production of polyethylene terephthalate (PET), which in turn was
converted into fibers and bottles. Another 10% was consumed in antifreeze and
5.5% in other uses. In 2009, 69% of the MEG consumed worldwide was in Asia,
followed by 13% in North America and 8% in western Europe.
About 6.7billion kilograms are produced annually.

Density

1.1132 g/cm3

Melting point

260K

Boiling point

470K

Solubility in water

Miscible

Viscosity

1.61 X 10^-2 Ns/m2

Main hazards

It is extremely harmful to pets and

children, if ingested get medical help
immediately
111 degree C

Flash point

Table 3. 3 Characteristics of ethylene glycol

The main Ethylene glycol suppliers in Pakistan are:

1. International Petrochemicals PVT,LTD
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2. Venus Corporation
3. Azwaah Associates
4. Pak Euroasia Chemicals (online shopping, 1999-2014)

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Chapter 4

4. Preparation methods for modified

basic chromium sulphate
There are normally two methods which are used for the production of basic
chromium sulphate.
Sugar Reduction Method
Sulfur Dioxide Reduction Method

4.1. Sugar Reduction Method:

Both chromium sulphate and Basic chromium sulphate have been produced in
Japan since about 1950, by reduction of Sodium dichromate with glucose. (IARC,
1980a). Sodium dichromate is reduced with molasses or glucose in the presence
of sulfuric acid. This is known as organic reduction. (COPSON, 1956)
Sodium dichromate solution is added in agitated resistant tank. Sugar and
stoichiometric amount of sulfuric acid are required for reduction. The reduction of
Cr (VI) to Cr (III) is an exothermic reaction. The rate of reduction of Cr(VI) by
organic reductants like glucose/molasses would depend on many factors,
including the concentration of reagents.
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The faster the rate of addition of glucose, on one hand influence the temperature
of reaction medium, and on the other, give rise to reductant/oxidant ratio. This
can be expected to lead to formation of increased organic acid intermediates
rather than the conversion of glucose into CO2.
The general reaction that takes place during the reduction of dichromate by
glucose is
4Na2Cr2O7+12H2SO4+C6H1206

8Cr(0H)SO4+4Na2SO4+14H2O+6CO2 (4.1)

However, in case of sugar/glucose reduction organic intermediates such as

formic acid, oxalic acid, glyoxalic acids, carbon dioxide and other precursors of
humic acids have been reported. These organic intermediates are capable of
forming complexes with the metal ion by substitution of aquo or sulphato group.
However, this method is costly but in most tanning systems sugar is used for the
reduction of dichromate.
In this method the dichromate is dissolved in water, sulfuric acid is added and
solution of glucose or glucose added slowly. An excess of glucose is necessary
since the oxidation is not complete and some oxidation products remain in the
solution. (B. chandrasekaran, January 1999)

4.2. Sulfur Dioxide Reduction Method:

The production of basic chromium sulphate is based on a chemical reaction in
which hexavalent chromium (+6 oxidation state) in the form of sodium dichromate
is reduced to trivalent state (+3) by sulfur dioxide.
Anhydrous sodium dichromate powder is reduced by burner gas. Burner gas
contains 9% sulfur dioxide. The sodium dichromate is dissolved in water to make
a strong solution which is pumped continuously over reaction towers filled with
ceramic packings where it reacts with sulfur dioxide bearing gas. Although the
reaction is exothermic, steam injection is required to maintain the temperature
and hence the reaction rate. The product is 100% reduced to +3 oxidation state
and has a basicity of 33%. The chemical reaction involved is:
Na2Cr2O7+3SO2+H2O

Cr2(OH)SO4+Na2SO4

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This compound is still freely water soluble. The sodium sulphate shown on the
right hand side of the equation is part of the product and is normally not
separated, and merely remains an inert diluent. (simpson, 1996)
An excess of sulfur dioxide is required to ensure the chromium is fully reduced to
the +3 oxidation state. A second reaction tower is used to remove the residual
sulfur dioxide. The above reaction is carried out in a steam heated vessel.

4.3. Selection of the Process:

Sulfur dioxide reduction method is costly method as compared to sugar reduction
method but it gives better quality of the product.
In sugar reduction method it was not sure that the reduction is complete or not. In
case of S02 reduction method the product may be dried using spray tower and
the spray drier has not necessarily anti corrosive lining.
In sulfur dioxide absorption method the sodium dichromate solution should be
between the range of 10-15% concentration but in sugar reduction case the
restriction of concentration is not taken into consideration. (Udy, 1956)

4.4.Modification in product of basic

chromium sulphate:
When basic chromium sulphate that is water soluble at high temperature which is
produced by sugar or sulfur dioxide reduction method is prepared then we add
specific glycol into our basic chromium sulphate product. By the addition of glycol
into product the basic chromium sulphate becomes soluble in water at room
temperature. This is the modified form of basic chromium sulphate.
The modified form of basic chromium sulphate can be dried into spray drier and
can be stored as solid dry product. (Hans- Joachin Nebel, July 5th, 1974)

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Chapter 5

5. Experimental Setup
5.1 Raw materials.
Basic Chromium sulphate was prepared in the laboratory by sugar reduction
method. The raw materials are given below.

Glucose
Sulphuric acid
Sodium dichromate
Water (utility)

Figure 1 Raw materials

5.2 Apparatus
For making chromium sulphate from sugar reduction
method we need following apparatus
4 beakers (500 ml)
2 beakers (100 ml)
Stirrer
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2 petri dishes
Thermometer
Pipette
Burette

5.1.3 Procedure
Basic Chromium sulphate was produced in laboratory by dissolving 100g of
green powdered Sodium Dichromate in 150 cm3 water in beaker followed by
constant stirring.
When it was completely mixed in water to
produce homogenous solution, 25g Glucose as
reducing agent was added. 50ml of 98% Sulphuric
acid was taken in measuring cylinder and was
introduced drop by drop in chromium sulphate
solution. This reaction was highly exothermic,
Beaker was placed in ice bath in order to control
the temperature to 40C. From the reaction flask,
solution was taken in sample bottle and analysis
was carried out to determine basicity.

5.2 Addition of Glycols:

Figure 2 Exothermic reaction b/w

Sulphuric acid and sodium
dichromate

The purpose of the whole process was to enhance the solubility of basic
chromium sulphate in water at room temperature. In beginning different
chemicals were tested and the solubility was initially checked by physical
methods. It was found that the basic chromium sulphate was fairly soluble in
water when we used glycols preferably poly glycols

Added Glycol

Solubility

Ethylene glycol

Sparingly soluble

Di ethylene glycol
Tri ethylene glycol

Fairly soluble
Fairly soluble

Table5. 1 solubility of glycols

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Chapter 6

6. Experimental tests
In order to check the quality and the to meet the requirement of the tanning
process we performed certain tests on modified basic chromium sulphate. The
requirement for performing these tests is listed below.

6.1.1 Description
Basic chromium sulphate shall be in the form of flakes or powder. 5 percent
aqueous solution of basic chromium sulphate shall be transparent and optically
clear. A solution is to be considered as optically clear if a bright object is clearly
visible through 5-cm thick layer and if a 1-cm layer in a beaker placed on black
glass or a paper appears black and not opalescent when viewed from above in a
good light.

6.1.2 Composition
The material shall comply with the requirements of the process and should be of
the of the required quality and characteristics

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6.2 Method of Test for Basic Chromium

Sulphate (For Tanning)
Unless specified otherwise, pure chemicals and distilled water shall be used in
tests.
NOTE- Pure chemicals shall mean chemicals that do not contain impurities
which affect the results of analysis.

6.2.1 Determination of moisture

Apparatus
Air Oven with thermostatic control capable of maintaining 105 2C.

Procedure
Transfer about 1 g of basic chromium sulphate into a tared wide mouth weighing
bottle and weigh accurately. Dry at about 105 +2C in an air oven for three to
four hours. Cool in a desiccator for about 20 minutes and weigh again accurately.
Repeat the process of drying and weighing until two weightings at an interval of
1h do not differ by more than 2 mg. NOTE - If the weight of the dried material is
found to increase on longer drying, then the lowest weight found shall be taken.

Calculations
Moisture, percent by mass = [(W1- W2)x 100]/W1
where
W1= mass in g of the material taken for the test, and
W2= mass in g of the material after drying.

6.2.2 Determination of basicity

Basicity of chrome salt is defined as the percentage of total chrome which is
combined with the hydroxyl groups, that is,
percentage basicity = (Cr combined with OH x 100)/Total chromium
It may be calculated as follows:
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If V ml of 0.1 N titrant is required in the chromium titration and V2 ml of 0.1 N

sodium hydroxide solution for a similar volume in the acid titration, then percent
Basicity = {(V1V2) x 100}/V1
Therefore, in this method firstly the amount of chromium in the basic
chrome sulphate is determined and then the amount of sulphate combined
with chromium is determined. From this the percentage basicity is calculated

6.2.3 Determination of matter insoluble in water

Apparatus
Steam-Bath
Vacuum Oven with thermostatic control capable of maintaining 100C.

Procedure
Dissolve 10 g of the basic chrome sulphate in 1 000 ml of water at 27 2C
within a period of 30 minutes. Filter through a dry filter paper, Whatman No. 42 or
equivalent, into a dry beaker. Discarding the first 20-25 ml of filtrate, measure out
250 ml of the filtratein another beaker or better, in a dish and evaporate on a
steambath. Dry the residue at 100 2C in a vacuum oven, cool in a desiccator
for about 20 minutes and weigh accurately. Repeat the process of drying and
weighing until two weighings at an interval of one hour do not differ by more than
2 mg.

Calculation
Calculate matter insoluble in water, percent by mass as given below:
Matter insoluble in water, percent by mass 100 (40 W + M)
Where
W = mass in g of the residue left after evaporating 250 ml of the solution, and
M= moisture percent by mass.

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6.2.4 Determination of pH
Apparatus
pH Meter- with glass electrode.

Procedure
Dissolve about 15 g of basic chrome sulphate in 250 ml water at 27 2C to give
a concentration ofabout 1 percent chromium. Measure the pH of the solution
immediately by using a suitable pH meter.
NOTE - The pH of chrome liquors depend not only on the concentration but on
ageing, temperature of preparation or dilution. For results to have any
comparative value, the strength of the solution should be the same and should
be prepared in an identicaltemperature and the pH should be measured
immediately after the preparation of the solution.

6.2.5 Test for unreduced chromium

Reagent
Ammonium Hydroxide Solution
Dilute Hydrochloric Acid - 0.1 N.
Potassium Iodide Solution - 10 percent (w/v),
Starch Solution -see A-4.2.8.

Procedure
Transfer a measured volume of basic chromium sulphate solution containing
about 1 g of chromium per litre to a 250-ml conical flask. Add sufficient amount of
ammonium hydroxide solutionto precipitate all chromium as hydroxide. Filter and
add to the filtrate hydrochloric acidto acidify the solution. Add 10 ml of potassium
iodide solution. Allow the flask to stand for about 10 minutes in the dark. Add
starch solution. To pass the test there shall be no change in colour of the solution
on addition of starch solution.

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Sr no

Characteristics

Moisture, % by mass

Free sulphate ( as Na2S04),

% by mass

Basicity (%)

Chromium (as Cr2O3), % by

mass

Matter insoluble in water, %

by mass

pH of aqueous solution

Results

Table 6. 1 Results of difference tests

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6.3 Conclusions

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Refrences

1. Thomas C. Thorstensen: Practical leather technology 1969, Van

Nostrand Reinhold company
2. J.M Coulson & J.F. Richardson: Chemical Engineering volume
11, 3rd edition,1983, Pergamon Press.
3. William L. Jolly: Synthetic Inorganic Chemistry, 1960, Prentice Hall
Inc.
4. Mc Cabe & Smith: Unit operation of Chemical Engineering , 3rd ed,
1976, Mc graw hill book company
5. David M. Himmelblau: Basic principles and Calculations in
Chemical Engineering ,5th ed, 1992, Prentice hall Inc.
6. Norris Sherve: Chemical process industries , Mc Graw hill book
company N.Y.
7. Marvin J. Udy: Chemistry of chromium and its compound vol 1,
1956, Reinhold publishing cooperation N.Y
8. Chromium Sulphate tanning powder: CW Harland and Jenny
Simpson , 1996

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