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SHORT-TERM PRESERVATION OF HIDE/SKIN AS AN APPROACH TO GREENER

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 SHORT-TERM PRESERVATION OF HIDE/SKIN AS AN APPROACH
TO GREENER PROCESS
1
VIRGILIJUS VALEIKA, 2KESTUTIS BELESKA, 3SKAISTE MIKULYTE, 4VIOLETA VALEIKIENE
1,3
Department of Physical and Inorganic Chemistry, 2,4 Department of Chemistry ant Technology of Polymers, Kaunas
University of Technology, Lithuania
Email: 1virgilijus.valeika@ktu.lt, 2kestutis.beleska@ktu.lt, 3skaiste.mikulyte@ktu.edu, 4violeta.valeikiene@ktu.lt

Abstract: The wet salting method, which is mostly used for hide or skin preservation requires approximately 40-50% of
sodium chloride on raw hide/skin weight. All this salt falls into wastewater during soaking process and significantly
increases pollution of the environment. Ttreatment of hide by sprinkling of dry mixture containing 5% of sodium chloride
and 1% of sodium hexafluorosilicate(percentage are based on raw hide/skin mass)allows storage of the hide without
putrefaction symptoms during 14 days when the storage temperature is 22±2oC. Leather produced from short-term preserved
hide is not lower in quality comparing with leather produced from conventionally preserved by salting hide.

Keywords: Hide, Skin, Preservation, Sodium Hexafluorosilicate, Tanning, Leather.

I. INTRODUCTION [2]; cooling in vacuum [1]; irradiation [8] or electron

Despite incomes, the leather industry is a high
pollutant (polluting) industry. The reason for this is
that leather is not a “friend” of the environment, as it
plays a role in the environmental destruction caused
by the meat industry as well as the pollution caused
by the materials used in leather preservation and
processing. For this reason, raw hide preservation has
always been a challenge for leather manufacturers
[1]. Deterioration of the skin starts within 5–6 h after
flaying; hence, there is a requirement for an effective
preservative. Thus, it is essential to preserve the
protein matrix and to arrest temporarily microbial
attacks as well [2]. Preservation is accomplished
either by destroying active bacteria, by preventing
bacterial activity or by preventing bacterial
contamination [3].
Wet salting, the conventional method of curing is
followed by most of the tanners because of its
practical advantages; employs approximately 40-50%
sodium chloride on raw material and is subsequently
removed during the soaking operation [4]. The use of
salt enhances the pollution load of tannery effluent,
however, which becomes highly contaminated with
increased total dissolved solids (TDS) and chlorides
(Cl–) [5]. We should not to forget that all chlorides,
which fall into wastewater of tanneries are not
eliminated from it and pass into environment. So, it is
very serious reason to pursue new and more
environmentally friendly preservation methods
because sometimes is last 1-2 weeks to gather for
processing enough skins or hides. Therefore, such
methods are titled as “short-term preservation
methods” and allow preservation of hides or skins
relatively short time comparing with storage duration
after salting [6]. There are developed methods of
short-term preservation, which can be divided into
physical and chemical ones. As physical methods can
be mentioned cooling [7], cooling wit addition of ice
beam processing [9].Despite the fact that the physical
methods of short-term preservation are very
convenient because any chemical materialsare not
required for the treatment, they are too complicated
for little slaughterhouses. Therefore, chemical
methods of short-term preservation are more
welcome due to simplicity of use and needless of
special equipment. Such materials as neem oil [10],
potassium chloride [11], polyethylene glycol [4]
silica gel [12], sodium sulphite with acetic acid [13],
and acetic acid with benzoic acid [14] are
investigated as possible preservatives for short-term
preservation of skins/hides. The main problem of the
use of suggested methods is that preservation
materials act on collagen, they cause undesirable
changes in derma structure and these factors require
changes in leather processing technology seeking to
produce high quality leather [6]. On the other hand,
the methods of preservation using reduced amounts
of sodium chloride as well-known material single or
with low amount of other additives remain as mostly
attractive due to the simplicity of their execution. For
sample, the use of 15% of sodium chloride allows
preservation of both hare and wild pigskin for 28
days. The bacteriostatic or bactericidal additives to
sodium chloride are preferable but not essential if
storage time is no longer than 28 days [15]. New
preservation system by using sodium meta-
bisulphite(5% NaCl with 0.5% sodium meta-
bisulphite) was developed by Kanagaraj et al [16].
It was found that system containing 2% boric acid +
5% sodium chloride, exhibited comparable
preservative effect to the conventional 40% SC
preservation system [17].
There is one interest material, which commonly is
used as additive for long-term preservation of hide
when about 50% of sodium chloride is used for
preservation: sodium fluorosilicate. This material is
used for water fluorination as well. The current

Proceedings of ISER International Conference, Buenos Aires, Argentina, 3rd-4th September 2017
10
 Short-term Preservation of Hide/Skin as an Approach to Greener Process
research is devoted for the investigation of one more
simple method of short-term preservation of hides
using dry mixture (% are based on raw hide/skin
mass) which contains 5% of sodium chloride and
0.25-1% of sodium hexafluorosilicate.
II. DETAILS EXPERIMENTAL
2.1. Materials
Fresh hides of cattle (taken not later than 2 hours after
flaying) were used. The hides were cut into pieces 10-
10 cm and formed into experimental series contained
8 pieces.After the treatment (preservation) each
experimental series was stowed in polyethylene boxes
to prevent evaporation of moisture at stored at
22±2oC. All chemicals used in experiments were of
analytical grade. The commercial chemical materials
conventionally used for leather processing were
employed as well.
2.2. Determination of preservation quality
The quality of preservation was assessed
organoleptically observing any hair slip, appearance
of bad odour and appearance of mucous surface on
the hide. Determination of content of nitrogen
extracted from hide was carried out as follows [1]: a
weighed piece of hide (about 5 g) was cut into small
pieces (3x3 mm). These pieces were placed into a
glass flask and covered with 25 ml of distilled water.
Each flask was embedded into a shaker and stirred for
30 minutes. The acquired liquid was then filtered and
10 ml of the filtrate was used for nitrogen
determination according to the Kjeldahl procedure.
Amount of nitrogen was expressed as g from 1 kg of
absolutely dry hide mass.
2.3. Determination of hide and leather properties
Shrinkage temperature of hide samples was
determined as standard [18].Determination of
chromed leather samples was carried out using
special equipment and method described in the
literature [18] when the distilled water is replaced by
glycerol. Content of moisture in the samples was
determined according to standard [19]. The amount of
chromium compounds in chromed leather, soluble
matter in dichloromethane and strength properties
were detected according to standards [20, 21, 22].
2.4 Statistical Analysis
All data were expressed as the averagevalue of
triplicate measurements. Confidence limits were set
at P˂0.05. Standard deviations did not exceed 5% for
the values obtained.
III. RESULTS AND DISCUSSION
The samples of flayed hide were evenly sprinkled
with dry mixture constituted (percentage are based on
raw hide/skin mass) from 5% of sodium chloride and
0.25; 0.5 or 1% of sodium hexafluorosilicate. The
Proceedings of ISER International Conference, Buenos Aires, Argentina, 3rd-4th September 2017
11
sprinkled samples were stored as described in
Experimental, and the quality of preservation was
tested during storage time organoleptically. Another
index which indicates a condition of preserved hide is
the amount of ammonia released, which is formed
when the hydrolysis of proteins begins due to the
action of microorganisms.The kinetic of released
nitrogen during storage of the samples is presented in
Fig. 1.
1.6
1.4
Released nitrogen, g/kg of hide
1.2
1
0.8
0.6
0.4
0.2
0
0 4 8 12 16
Storage duration, days
Fig.1. Kinetic of nitrogen release when hide is treated by
mixture containing 5% of sodium chloride and 0.25 (curve 1);
0.5 (curve 2) or 1% (curve 3) of sodium hexafluorosilicate
(percentage are based on raw hide/skin mass).
Evidently, the increase of sodium hexafluorosilicate
amount in the mixture for the hide treatment leads to
the slowdown of nitrogen release from the hide
samples. By the way, the organoleptical symptoms of
hide deterioration (hair slip, bad odour and mucous
surface)appear when amount of released nitrogen
reaches about 1 g/kg of hide. Accordingly, this
quantity can be used as a limit for the assessment of
preservation quality. The use of 0.5% (Fig. 1, curve
3) of sodium hexafluorosilicate in the preservation
mixture allows storage of the treated hide without
hide tissue putrefaction up to 10 days when the
storage temperature is 22±2oC. It should be noted that
increasing of amount of sodium hexafluorosilicate in
the preservation mixture up to 1% leads to
prolongation of storage duration up to 14 days, but
not to two times longer comparing with the case
when 0.5% hexafluorosilicate is used.
The next index, which allows estimation the changes,
which occur after preservation in the treated hide
derma, is shrinkage temperature. Shrinkage
temperature of hide depends on the action of
materials on collagen proteins when bonds in
collagen are formed or broken. A decrease of amount
of hydrogen bonds, crosslinks or, especially, peptide
bonds leads to lower shrinkage temperature of
hide/skin. The results of shrinkage temperature
 Short-term Preservation of Hide/Skin as an Approach to Greener Process

evaluation during preserved hide storing are Of course, one or another preservation method can be
presented in Fig. 2. validated by checking the quality of the leather
64.5
processed from hide preserved by this method [1].
The suitability of the preservation method was
examined producing leather from the preserved hide
Shrinkage temperature, oC

64 and assessing properties of the leather produced from

such hide.

63.5 68

63 66

Moisture content, %
64
62.5

62
62
0 5 10 15 20 25
Storage duration, days 60
Fig.2. Shrinkage temperature of hide treated by mixture
containing 5% of sodium chloride and 1% of sodium
hexafluorosilicate (percentage are based on raw hide/skin 58
mass) change depending on storing duration. 0 1 2 3
Note: the shrinkage temperature of raw hide was65.2oC. Soaking duration, hours

Trend of shrinkage temperature change during the Fig.3. Moisture content change in hide treated by
treated hide storage has interest character. First eight mixture containing 5% of sodium chloride and 1% of
days goes on decrease of the shrinkage sodium hexafluorosilicate (percentage are based on raw
hide/skin mass) during soaking process
temperature,probably, due to slow hydrolysis of
sodium hexafluorosilicatewith formation ofhydrogen
Ten ox hides (experimental) supplied by Siauliai
fluoride eventually, which,in turn, acts on collagen
broking hydrogen bonds. After that, these broken meat enterprise (Lithuania) were preserved
immediately after flaying by sprinkling of mixture
bonds begin to form back and shrinkage temperature
containing 5% of sodium chloride and 1% of sodium
increases. When begins the bacteriological process,
hexafluorosilicate. Other ten hides (control) were
which leads to autolysis of proteins and to break of
salted using 50% of sodium chloride. After
bonds in derma structure as well, the shrinkage
temperature of derma starts to decrease irreversibly. preservation, all hides were stored one week.
Afterward, shoe upper leather was produced from
The determination of moisture content in the hide
treated by mixture containing 5% of sodium chloride these hides in JSC “Elnias” (Lithuania). Qualitative
indexes of the produced leather are presented in
and 1% of sodium hexafluorosilicatehas shown that
Table. The industrials trials have shown that leather
amount of moisture decreases from 64.2% (in raw
produced from short-term preserved hide has not
hide) down to 57.6% during two days of storing after
lower quality comparing with conventionally
the treatment, and practically does not change more.
For comparison, the moisture content in preserved by preserved and produced one. Herewith, it joined more
wet salting (50% of sodium chloride based on raw chromium compounds and matter soluble in
hide/skin mass) decreases even down to 45%. dichloromethane. Organoleptic test of experimental
and control leather has not revealed any differences in
their properties as well.
The first process of leather processing is soaking
which has aim to remove preserving materials and to
rehydrate hide reaching the initial moisture content in Index Leather
it (duration of the soaking process for the salted hides Experimental Control
commonly is not shorter than 8 hours. The Moisture content in 16.0 15.6
experiment was carried out to establish the hydration leather, %
behavior of short-term preserved hide. The results are Cr2O3 content in 4.3 3.9
presented in Fig. 3. leather, %
Shrinkage 108.2 108.0
When soaking the short-term preserved hide the temperature, oC
rehydration of it is on very intense: the value Matter soluble in 7.3 6.4
moisture content in rawhide (64.2%) was reached dichloromethane, %
during 2 hours of process. Tensile strength, 22.5 22.6

Proceedings of ISER International Conference, Buenos Aires, Argentina, 3rd-4th September 2017
12
 Short-term Preservation of Hide/Skin as an Approach to Greener Process
2 [8]
N/mm
Strain when grain 17.6 17.6
breaks, N/mm2
Relative elongation at 32.2 30.8 [9]
break, %
Table. Qualitative indexes of leather produced from variously
preserved hide
[10]
CONCLUSIONS
The treatment of hide by sprinkling of dry mixture
[11]
containing 5% of sodium chloride and 1% of sodium
hexafluorosilicate(percentage are based on raw
hide/skin mass)allows storage of the hide without
putrefaction during 14 days when the storage [12]
temperature is 22±2oC. During the storage go on
negligible changes of dermal structure related with
breaking and, afterward, forming of bonds in
collagen. The short-term preservation leads to [13]
decrease of moisture content of the hide by 6%.
Soaking during 2 hours is enough for the rehydration
of the short-term preserved hide. Leather produced
from short-term preserved hide hasnot lower quality [14]
comparing with leather produced from conventionally
preserved by salting hide.
[15]
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percentage extension.

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