ASSIGNMENT TOPIC: PICKLING AND DEGREASING OF LEATHER

NAME KAIF AKRAM ROLL NO 06

MS CHEMISTRY COURSE: INDUSTRIAL PROCESS CHEMISTRY

COURSE CODE: CHEM-534 INSTRUCTOR: DR.OMER JAVED

PICKLING:
The use of liquors containing acid and salt is referred as pickling. The treatment of delimed or
bated hide with acids and salts is termed as pickling.

SALTS AND ACIDS:

Salts that are used in pickling process of leather are sodium chloride (NaCl), sodium sulphate
(NaSO4), sodium formate (HCOONa), sodium acetate (CH3COONa).

Acids that are being used in pickling process are sulphuric acid (H2SO4) and formic acid
(HCOOH).

PURPOSE OF PICKLING:
 Pickling increases the acidity of the hide to a pH of 3, enabling chromium tannins to enter
the hide.
 Salts are added to prevent the fibers from swelling. For preservation purposes, fungicides
and bactericides are used.
 Produce softer, thinner white pelt.
 Oxidize hair root and remove if hair remains after liming.
 Preserve hide for further use.
The pickle and degree of pickling is of great importance in determining the quality of leather
produced and the speed of tannage.

PROCESS OF PICKLING:
The skins are paddled in the salt and water until all salt has dissolved and diffused evenly.
Sulphuric acid (diluted at least 10 times) is added and run (about 2 hrs.) until good penetration.
Pickling will give pH 1-2 and there is ample salt present not only to prevent acid swelling, but to
cause some decrease in thickness of the skins, which are now white, soft and flaccid. 3 % salt on
the total volume of water present will prevent acid swelling.
The limed or bated skins must be adjusted to a suitable acidity for tannage by pickling. To pickle
the pelt means to acidify it in such a way as to prevent it from simultaneous swelling under the
action of acid. This is usually done by salt addition. The presence of acid in the medium
suppresses dissociation of carboxylic groups of collagen hide chains. Solution of acid and salt
outside the pelt is hypertonic relative to the water contained in the pelt, so it has a higher osmotic
tension. This is a reason for the coming over of water molecules from pelt to the solution.
Solution in the pelt surrounding becomes less concentrated, and owing to this the electrolytes in
it become more dissociated, and diffuse into the inter fibrillary spaces in collagen. This process
stops when concentration of ions in pelt and in solution become equilibrated, and at the same
time an interaction occurs between salt cations and collagen carboxyl’s, and between anions of
salts and basic groups of collagen side chains. Ions remaining in the pelt keep their solvation
water, thus the pickled pelt is hydrophilic and mellow.

Introduction of formaldehyde to the pickling bath, still containing organic acids, causes
only slight tannage due to a low pH. Other tanning agents for pretanning pelts may be as well
introduced to the pickling. Introduction of organic acids into the pelt may be considered as a
method of chrome salt masking. This method is based on introduction of a tanning agent as a
non-active agent.

PICKLING OF LEATHER PICKLED LEATHER

DEGREASING:
In the process of degreasing, fats and grease are removed with the use of lipases, detergents or
solvents. Fats are removed from the interfibrillary space to allow for the even penetration of
various tanning materials and dyes. Degreasing helps make leather soft and pliable when used
for other purposes. Enzymatic degreasing is a better way of carrying out degreasing than the use
of solvents and detergents. Lipases are much safer and less toxic to workers and the
environment. Furthermore, lipases allow for a more uniform color, cleaner appearance, improve
production of waterproof leather, and do not cause dryness in the leather.

METHODS OF DEGREASING:

The three different methods commonly used for degreasing are:

1. Degreasing in an aqueous medium with an organic solvent and a non-ionic surfactant

2. Degreasing in an aqueous medium with a non-ionic surfactant

3. Degreasing in a solvent medium.

ENZYMATIC DEGREASING:
The increase in the amount of enzyme in a soaking solution affects faster rehydration, higher
content of removed non-collagen proteins but, unfortunately, has an effect on the collagen of
hide not only during the soaking but also during subsequent liming as well, which can be the
reason for defects in the finished leather. The next step in employing enzymes is the degreasing
of hides/skins. The degreasing is generally applied to raw materials with a high fat content in
skin tissues: pig, sheep skins, among others. For an enzymatic preparation to be an effective
degreasant, it needs to perform a triple action of proteolysis, lipolysis and emulsification. The
enzymatic degreasing can be carried out as, for example, during skin soaking or simultaneously
with other processes: soaking, liming, bating and de-pickling, after which optimum degreasing
treatment is realized.

PURPOSE OF DEGREASING:
Degreasing is most relevant in processing sheepskins, where the natural fat content is about 10 –
20 % of dry weight. Degreasing as a separate process step is not usual for bovine hides. The
nature of this fat makes it difficult to remove because of the presence of glycerides and a high
melting temperature. Excessive amounts of grease in the skin may interfere with uniform
penetration of tan or dye, causing difficulties in the finishing processes and creating dark and
greasy patches on the finished leather. Degreasing of greasy skins is particularly important
before chrome tannage as the chromium salts can react with the greases and form insoluble
chromium soaps, which are very difficult to remove subsequently.

PROCESS OF DEGREASING:
Degreasing is carried out in a closed-loop process using solvent recovery. The extraction agent
used is dimethyl ether (DME). The working pressure is approximately 686 kPa and the process
temperature is between 15 and 30 °C. Fat and water are removed from the collagen matrix. Fat
and water are separated from the DME by distillation at low temperatures, since the boiling point
of DME is -25 0C. Fat and water can be collected separately. The process allows hides and skins
to be dried resulting in a stabilized, low weight, easy-to handle material. The dried hides or skins
can be stored or transported. Use of salt/acid pickling is avoided. Pretanning is unnecessary.
Grease is recovered in a re-usable form. It is of high quality and has a high value in comparison
with fat obtained from the traditional aqueous or organic solvent based degreasing processes.
The fat will also not contain any traces of surfactants or other chemicals. Moreover, as the
degreasing is conducted as relatively low temperatures, the thermal degradation and hydrolysis
of the fat is minimal resulting in a low peroxides index. This technique replaces one or several
polluting steps in the treatment of hides and skins requiring fat removal. These are especially
polluting when additional solvent degreasing is required, as in most wool-on production.
BENEFITS OF DEGREASING TECHNIQUE:
The key-drivers to implement the technology are given below.

 No water is used in processing.

 No contaminated waste water is produced.
 Working conditions are improved for production people.

This technique has low energy requirements; little mechanical energy is used, and it operates at
low temperatures. This compares favorably with the relatively high energy used in the treatment
of water from the aqueous degreasing process in order to break the emulsion and separate
fat/surfactant mixtures. The energy requirements for the distillation of the extraction solvent
DME, are low compared with the distillation of, e.g. PER (b.p. 120 ºC as against -25 ºC for
DME). A low temperature energy source, e.g. steam condensates returning to a boiler, is
sufficient to distil the DME from the water/fat mixture extracted from the skins. Hence the
carbon foot-print as compared to that of the traditional leather manufacturing process is
significantly improved.

This technique decreases the number of steps in the treatment of skins and hides, decreasing the
total process time considerably compared to a traditional process. Furthermore, no water is
consumed, no chemicals are added to the hides/skins prior to degrease, and other solvents, e.g.
PER (an R40 substance), are not required to reach high levels of fat removal and removal
efficiency
DEGREASING OF HIDE PROCESS OF DEGREASING

REFRENCES
i. Joint Research Centre, Best Available Techniques (BAT) Reference Document for the
Tanning of Hides and Skins, 2013
ii. Bienkiewiecz, K. (1983). Physical Chemistry of Leather Making. Robert E. Krieger. p.
298. ISBN 0-89874-304-4.
iii. https://leatherenzymes.weebly.com/degreasing.html
iv. Murali Sathish, Balaraman Madhan, Kalarical Janardhnan Sreeram, Jonnalagadda
Raghava Rao, Balachandran Unni Nair,Alternative carrier medium for sustainable leather
manufacturing – a review and perspective,Journal of Cleaner Production,Volume 112,
Part 1,2016,Pages 49-58,ISSN 0959-6526