Pickling

Following the bating operation is the pickling stages where the skins are treated with
common salts (sodium chloride) and subsequently with sulfuric acids in the event a mineral
tanning process is to be competed. The purposes of pickling process is to prepare pelt for
tanning by stopping enzymatic bating and adjust acidity and pH or its water content for
subsequent process. A homogeneous distribution of tanning materials is obtained and
penetration of mineral tanning agent into the substance is facilitated by pickling the raw
hides. Different pickling parameters are used depending on the subsequent tanning step.

During pickling, the raw hides 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 for
approximately 2 hours until satisfactory penetration is achieved. Pickling will produce a pH
of 1-2, and there is enough salt present to induce some reduction in the thickness of the
skins, which are now white, soft, and flaccid. Acid swelling is prevented by adding 3% salt
to the entire volume of water present.

For tannage by pickling, the limed or bated skins must be adjusted to a proper
acidity. Pickling the pelt involves acidifying it in a way that prevents it from swelling at the
same time as the acid. This is commonly accomplished by adding salt. The presence of acid
in the media prevents carboxylic groups in collagen chains from dissociating. Because the
acid and salt solution outside the pelt is hypertonic in comparison to the water inside the
pelt, it has a larger osmotic tension. The electrolytes in the pelt become more dissociated
and diffuse into the interfibrillary gaps in collagen as the solution in the pelt surrounding
becomes less concentrated. This process comes to a halt when the concentrations of ions in
the pelt and in solution are equalized, and an interaction between salt cations and collagen
carboxyl, as well as between salt anions and basic groups of collagen side chains occurs.
The pickled pelt is hydrophilic and mellow because the ions that remain in the pelt preserve
their solvation water.

Pickling slows down the chrome tanning process, does not allow the tanning agents
to be bound to the external pelt layers, as this would stop their deeper penetration. Acid,
contained in the pickle, reacts with the basic functional groups of collagen side chains and
imparts to it a pH of about 1.5. The purpose of the salt addition is to reduce the swelling of
collagen in acidic medium.

When pickling for preservation purposes, a fresh pickle liquor should contain
between 1.5-2.0% (w/v) concentrated sulfuric acid and 12-15% sodium chloride. At the end
of pickling, it should contain around 0.7% acid and 9-10% sodium chloride (Leather
International, 2002). Further, 0.03-2% of fungicides and bactericides are usually added to
the pickling bath for long term storage or storage at elevated temperatures (Leather
International, 2002). For example, wet salted hides, also as “Salted Bovine Leather” are
pickled pelts temporarily saturated in a brine solution of salt water. This concentrated salt
solution ensures protein destroying organisms cannot function. This process takes about 12-
18 hours to “cure” (salt) the hides.

Wastewater from a preservation pickling bath has a high sodium chloride content
and high concentrations of acids that cause a pH of around 1-1.5pH, leading to serious
water pollution. Therefore, to reduce the waste flows being generated, minimisation
alternatives such as reducing the water consumption, amount of products used and the
pollutant load of the waste need to be carried out. The recommended improved alternative
is to recycle the picking bath because up to 70% of the solution can be recycled (Morera et
al., 2011). By doing so, the consumption of water, sodium chloride and sulphuric acid is
minimized as well as able to prevent disposal of high concentration of salts and acids
wastewater.

Degreasing

Degreasing is a process in which the excess natural fats from fatty skins and hides
were removed by using lipases, detergents, or solvents. Natural grease in raw skin and
hides could contribute to defects of leather and complications on finishing processes. For
instance, fatty spues will form when there are fluctuations in temperature and humidity,
uneven dyeing and finishing, waxy patches in alum tanned leather and pink stain on moist
chrome-tanned leather. Fats are eliminated from the interfibrillar 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. Degreasing of raw hides and skins is especially crucial
before chrome tannage as the chromium salts can react with the greases and form insoluble
chromium soaps, a compound that is hard to remove.

There are three common methods used for degreasing, and the first method is
degreasing in an aqueous medium with an organic solvent and a non-ionic surfactant. The
second and third method are degreasing in an aqueous medium with a non-ionic surfactant
and degreasing in a solvent medium. During degreasing, efficient surfactant products should
be used to ensure less than 1% of natural fat in limed pelts (Ricardo Tournier, 2015).

In enzymatic degreasing technology, lipase catalyses the breakdown of natural fats

and correspondingly produces fatty acids. The hydrolysates of fats are removed from skins
in a timely manner to speed up the processing rate of leather making. However, fatty acids
are hydrophobic and pH responsive, and their aqueous solubility is uncertain under different
pH conditions, because the exact pKa values of free fatty acids is mostly unknown (Alina et
al., 2018).

Lipases allow tensides on the bovine hides to be removed completely. Moreover,

solvents used in degreasing tend to dry out the skin and making it become paler. Lipases
and surfactants can replace the solvents that are used to degrease the sheepskins, which
contain up to 40% fat. Surfactant used in degreasing process is also contributed to pollution
and causes many environmental impacts due to the large amount of degreasing agents used
in conventional degreasing process. There are many new technologies been developed for
the treatment of the sewage by avoiding the use of surfactant in the beamhouse processing
of leather making. When using lipases to degrease the hides, the initial surfactant dosage
can be decreased by at least 50%. In addition, nonyl phenol ethoxylate which is a strong
surfactant that is commonly used in degreasing sheepskins can be substituted with more
biodegradable surfactants. To conclude, lipases allow for a more uniform colour, cleaner
appearance, improve production of waterproof leather, and do not cause dryness in the
leather besides being much safer and less toxic to workers and the environment.
Alina A. Pashkovskaya, Mario Vazdar, Lars Zimmermann, Olga Jovanovic, Peter Pohl, Elena
E. Pohl, 2018 . Mechanism of Long-Chain Free Fatty Acid Protonation at the
Membrane-Water Interface,Biophysical Journal, Volume 114, Issue 9, 2018, Pages
2142-2151,

Kanagaraj, J., Babu, N. K. C., Sadulla, S., Rajkumar, G. S., Visalakshi, V., & Chandrakumar,
N. (2000). New approach to less-salt preservation of raw skin/hide.  Journal of the
American Leather Chemists Association,  95(10), 368-374.

Leather International. (2002). Burns and swelling.

https://www.leathermag.com/features/featureburns-and-swelling/

Morera, J.M., Bartoli, E., Chico, R., Sole, C., Cabeza, L.F., 2011. Minimization of the
environmental impact of chrome tanning: a new process reusing the tanning floats.
J.
Cleaner Prod., 19, 2128-2132.

Ricardo Tournier. (2015, August 1). Diagnosis, prevention and treatment of fatty spew in
the tannery. ResearchGate.
https://www.researchgate.net/publication/286125382_Diagnosis_prevention_and_tre
atment_of_fatty_spew_in_the_tannery