2nd Mercosur Congress on Chemical Engineering

4th Mercosur Congress on Process Systems Engineering

INFLUENCE OF FATS DURING LEATHERMAKING

L. M. Santos*, M. Gutterres, P. M. Aquim, G. Priebe
Departamento de Engenharia Química - Universidade Federal do Rio Grande do Sul

Abstract. Leather processing is characterized by several steps. Beamhouse operations, which are the first
steps, have as aim cleaning and preparing the structure of the hide to improve tanning. In these operations,
the natural fats are removed, in order to prevent undesired reactions, as well as increase the reaction sites for
tanning. This removal of natural fats has disadvantages: the fibers stick together, what makes the leather to
become stiff. To avoid this consequence, after tanning the leather is submitted to a fatliquoring step.
Fatliquoring makes the leather softer by adding an oil layer to the fibrils. The objective is to analyze
quantitatively the fats removed from skins and to study the fatliquoring, concerning characterization of the
chemical products added during the process. The fat content of the skin was determined by solvent extraction.
The oil component used in fatliquoring is transported into the leather as an oil-in-water emulsion, stabilized
by the presence of a hydrophilic fraction, generally sulfated or sulfited oil. The emulsion is broken within the
fiber structure, lubricating it. This study of fats is important for achieving maximum efficiency of fatliquoring
process and also for attempting to use natural fats in fatliquoring, transforming a waste stream (fat removed in
the beamhouse) in a valuable one. The process integration can reduce environmental impact, which is a
concern of the leather industry.

Keywords: Leather, Fat and Fatliquoring

1. Introduction

The transformation of hides into leather requires several chemical and mechanical steps. Pre-tanning
operations (beamhouse), such as soaking, fleshing, unhairing/liming, division, deliming, bating and pickling are
made to clean the structure and remove non-protein matter. The fleshing operation is made to remove the flesh
and natural fats of skins, since the presence of fats could accelerate skin degradation and the fats do not form the
leather structure. Besides, the fat layer makes the penetration of chemicals through the structure more difficult. In
addition, the fat removal improves tanning efficiency, through cleaning and preventing formation of undesirable
products, such soaps. The undesired consequence of removing natural fats, in fleshing or in aqueous processes, is
that the leather can become stiff after drying, due to sticking, glueing or adhesion of fibers.
In order to produce soft leather, after tanning it is made a fatliquoring step, which has as objective to involve
the fibrils with fat layers, lubricating them, what makes the leather soft and with a pleasant feel. The fatliquoring
also influences physical characteristics of leather, such as tensile strength, extensibility, wetting properties,
waterproofness and permeability to water vapour and air.
The fatliquors are applied in aqueous emulsions. The oils are made self-emulsifying, by partial sulfonation or
sulfation. According to Kronick (1996), soft leather contains 10-15% of oil on basis of dry weight.
The objective of this work is to evaluate the fat content of skins, concerning natural fats and incorporated oils.
It was also proposed a way of using natural fats as a raw material for fatliquoring, turning a waste material in a
valuable product for the process, reducing the environmental impact.

*
To whom all correspondence should be addressed.
Address: Dep. de Engenharia Química, UFRGS – Av. Luiz Englert, s/n, 90040-040 Porto Alegre - RS – Brazil
E-mail: lety@enq.ufrgs.br
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1.1. Hide and leather composition

Aquim (2004) has made an identification of components contained in processing hides, in pilot scale. For
salted hides, the composition is approximately 43% water, 13% ashes, 4% fat and 40% hide substances. The wet-
blue composition is approximately 73% water, 3% ashes, 0.3% fat and 24% hide substance.
According to Gutterres (2003), the hide composition varies with type, race, age, sex and living conditions of
the animal. The water content is usually between 60 and 70%. This capacity of absorbing water is associated to
the thermal regulating action of the animal body.
The leather composition, for box calf and sole leather, is shown in table 1.

Table 1: Composition for two types of leather, in %

Substances Box calf Sole leather

Water 14 14
Fat and oil 5 1
Chrome salt 8 -
Tannin - 30
Water soluble 1 8
Hide substance 69 47
Finishing products, other materials 3 -

2. Natural fat and fatliquoring

2.1. The pre-fleshing operation

Natural greases exist in three main areas of the skin:
- in the sebaceous glands near the hair follicles;
- in the region of the junction of the grain and the corium;
- in the subcutaneous adipose tissue adhering to the flesh.
The latter is obtained as a solid residue from pre-fleshing and fleshing operations. Pre-fleshing operation is
made before unhairing/liming, and fleshing is made after these operations. The residue from pre-fleshing is the
best available for reuse, since there are not sulfide or calcium in its composition. Therefore, the introduction of
an additional step (pre-fleshing) is important to reduce the waste load and to enhance the possibility of reusing
this byproduct.
According to Claas and Maia (1994), the pre-fleshing residue content, on dry basis, is 80% water, 50%
proteins, 35% fats and 15% minerals. The fat has a variable composition, presenting around 40% oleic acid, 27%
palmitic acid, 10% palmitoleic acid and 7% stearic acid. Aquim (2004) quantified the solid residue amount
generated in mechanical operations. The pre-fleshing operation generates 6 kg of flesh per 26 kg of hide.
The fats can be extracted from flesh in a closed system without agitation, using steam, with pressure of 4,5
kgf/cm2 and extraction time of 2,5 h.
Figure 1 shows the pre-fleshing residue.

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Fig 1. Pre-fleshing residue

2.2. Reuse of fat from pre-fleshing

The material from pre-fleshing operation is treated and fractionated, so it can be reused in fatliquoring, for
example. Since the material is obtained before liming, it is free from lime, what results in a better quality product.
This byproduct is submitted to a separation process in order to obtain an oleic product that can be used to
produce fatliquoring emulsions, added to the leather in wet end processing.
Fat digestion. The solid residue is mixed with water, in order to facilitate pumping, and then it is submitted
to digestion. The flesh is treated with steam (100ºC) to separate the grease from other residues (proteins and
minerals).
Then the grease material goes to the storage tank.
Separation of oleic material from stearic. The material from the storage tank remains into a cooling
chamber at 12ºC. Due to this cooling, the oil solidifies and separates into two phases: oleic and stearic.
The solid oil is sent to a filter press. The oleic fraction is extracted, while the stearic remains inside the press.
The stearic fraction is commercialized to the soap industry.
The extracted oleic is stored. Acid number analysis (defined as the number of milligrams of potassium
hydroxide required to saponify the free fatty acids in 1 gram of the fat or to neutralize 1 gram of fatty acids) is
made and according to the result, it is added sodium hydroxide or ammonium hydroxide to neutralize. The
product is washed and dried. Then it is ready for the production of fatliquoring emulsions.
The analyses of the product obtained from this process are shown in table 2.

Table 2: Analyses of the product from pre-fleshing fats

Oleic acid (%) 74.89
Stearic acid (%) 7.23
Palmitic acid (%) 16.22
Acid number (%) 0.38
Iodine value 61.4
Saponification value 223.0
Moisture (%) 1.33

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Production of fatliquoring emulsions. Fatliquoring oils are offered to the leather as an oil-in-water emulsion.
To become soluble in water, they are treated with sulfuric acid, so a hydrophilic portion is added to the
hydrophobic chain.
The oil reacts with approximately 20% in weight of sulfuric acid, which is added slowly to the oil, because
the reaction is exothermic. It is washed with water, to remove unreacted acid, and neutralized to pH 6.2 – 6.8
using NH4OH. This mixture is left decanting until complete separation of phases. The reaction is controlled by
the SO3 content determination.

2.3. Fatliquoring

Chemistry of fatliquoring. To allow a small amount of oil to be spread uniformly over the large surface area of
the leather, it is necessary first to dilute the oil. In an emulsion with water, the oil is dispersed in microscopically
small droplets. It is important that the drops of oil in the water remain as an emulsion until they penetrate the
leather, and not separate out as large drops or as a layer of oil, which could not penetrate the leather fiber and
result in merely a greasy surface layer.
The self-emulsifying oils exist in two main categories: sulfated and sulfited. The sulfated are chemically
treated with sulfuric acid, what increases the affinity with the tanned fibers. The sulfited oils have smaller
particles and higher capacity of bonding. There are also chemicals elaborated with emulsifiers. Crude oils can
also be added to the fatliquoring bath. They are water insoluble, but they are emulsified by the sulfated and
sulfited parts.
Both sulfated and sulfited oils are anionic and they bond to the amino groups of collagen.
According to Covington and Alexander (1993), the effect of a fatliquor may depend on several interacting
factors: solution pH and substrate charge, the nature of the neutral oil and its reactive counterpart which combine
to determine the emulsion properties and the flow characteristics of the oil.
Graffunder (2003) presented the evolution of fatliquoring products. The first substances used to emulsify oils
were the soaps. However, soaps were not completely satisfactory. The sulfated oils were developed near 1950
and they are largely used, due to their capacity of improving the pleasant feel and softness. In 1980 new synthetic
products have emerged. The sulfosuccinic compounds provide high softness with no risk of migrating substances,
in addition of giving the leather hydrophobic character.
Besides correct choice of added chemicals, it should be considered: keeping bath temperature constant, for
example at 50ºC and making a previous mix of components, adding them slowly to the hot water, to build the
emulsion, and just then add this mixture to the drum.
Fatliquoring plays an important role on hydrophobisation of leather. Peres (2003) made a correlation between
hydrophobisation and production parameters. According to the author, the fatliquoring is the main step for the
production of hydrophobic leather. The deeper the fatliquoring, the better will be the results for
hydrophobisation. For production of hydrophobic leather, the oils used must be non-polar (crude). The
emulsifying oil has surfactant structure, what does not allow the leather to become hydrophobic.
Basic fatliquoring substances are shown in table 3.

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Table 3: Basic fatliquoring substances

Biological fatty substances
Non-biological fatty substances
Vegetable oils Linseed oil, castor oil, nut oil, wood oil, sunflower
oil, soya beam oil
Vegetable fats Coconut fat, palm oil fat, palm kernel fat
Animal oils Seal oil, whale oil, sardine oil, shark liver oil,
neatsfoot oil, lard oil
Animal fats Butter fat, bone fat, horse grease
Waxes Carnauba wax, beeswax, wool grease
Parafin waxes, mineral oils, olefins, processed hydrocarbons, synthetic
fatty acid esters and waxes, fatty alcohols, alkyl benzenes.

3. Determination of fat content

3.1. Experimental method

The objective of the analytical method is to determine the total fraction of substances soluble in
dichloromethane and hexane, for hides and leathers. The fat substances are non-polar and/or little polar, from
fatliquoring in finished leather or the natural fat produced during the animal life in processing hides.
The method used was based in the standard MB – 2969, from ABNT (Brazilian Association for Technical
Standards). The standard mentions discontinuous equipment. However, the equipment used was continuous.
Therefore, it was made some modifications including determination of extraction time.

Fig 2. Equipment used for fat determination

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The first experiment was made to determine the minimum extraction time. It was used a fatliquored
upholstery leather. The percentage of extracted fat according to the time of extraction can be visualized in figure
3.

14

13
Extrated fat (%)

12

11

10

8
0 50 100 150 200 250
Time (min)

Fig 3. Percentage of extracted fats versus time

Based on this experiment, it was defined that the solvent would extract the fats for 4 hours, since after this
period the curve reaches a constant value, which means that all fat has already been extracted.
After determination of extraction time, two methods (ASTM D 3495-83 and NBR 11030) were tested to
verify if one solvent has extracted all fat. The experiments were made using as solvent dichloromethane and then
dichlorometane and hexane. The results are in table 4.

Table 4: Mass % of fat (on dry weight)

% Extracted by
% extracted by Standard Standard
Hide Mean dichloromethane + Mean
dichloromethane Deviation Deviation
hexane
Salted 13,64 12,61 2,34 14,7 13,69 2,47
11,54 13,75
15,3 16,04
9,96 10,26
Soaked 0,17 0,24 0,09 0,36 0,37 0,22
0,31 0,37
Bated 0,1 0,34 0,35 0,32 0,64 0,60
0,75 1,33
0,18 0,26

These tests showed that the first solvent (dichloromethane) removes part of the fats and the rest are removed
by the second solvent (hexane). Best results were achieved by using two solvents, so it was decided to use this
way to determine the fat content.

3.2. Samples
The experiments from soaking to tanning were made in a pilot scale. The wet end samples were obtained at a
tannery, directly from the industrial process.

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3.3. Results for natural fat content

Determinations of fat content were made for hides after each beamhouse operation, in order to evaluate the
removal of fats during these operations. The results are shown in figure 4.

8
7
6
Fat content (%)

5
4
3
2
1
0
Salted Pre- Pre- Soaked Limed Delimed Bated Pickled Wet-
soaked fleshed blue

Fig 4. Fat content after each beamhouse operation (dry weight)

As observed in figure 4, there is a great decrease in fat content between pre-soaked and pre-fleshed hides. It
shows that a significant amount of fat is removed by pre-fleshing.

3.4. Results for fat content after fatliquoring

After fatliquoring, it was made the determination of fat content in leather, to evaluate the amount of fat
absorbed. The results of fat content in leather, on dry basis, are shown in figure 5.

20
Fat content (%)

15

10

0
Wet-blue After After re- After After After re- Final
w ashing chroming neutralizing fatliquoring tanning

Fig 5. Fat content in leather (dry weight)

There is an increase of fat content after re-chroming, due to a pre-fatliquoring that is made at this step. The
decrease after retanning is due to addition of tannins, which is incorporated to the leather.

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4. Conclusions
The study of fat presence during leather processing allows us to establish the following conclusions:
- The method for determination of fat content was determined and adapted for the equipment available.
- Great amounts of natural fats are removed by pre-fleshing operation. These fats have better quality for
reusing, since there are no lime or sulfide in its composition.
- It is possible to use the natural fat contained in hides as a raw material to produce a valuable product for
the leather process. The fat is submitted to a proper treatment and then it can be used as a fatliquor.
- Good stability emulsions are used for fatliquoring in a well-controlled process, improving leather
characteristics. The oils used in fatliquoring add mass to the leather.

References
Aquim, P.M. (2004). Balanço de Massa: uma Ferramenta para a Implementação de Melhorias nos Processos de Ribeira e
Curtimento. MSc Thesis. Universidade Federal do Rio Grande do Sul. Porto Alegre.
Claas, I. C., Maia, R. A. M. (1994). Manual Básico de Resíduos Industriais de Curtume. SENAI/RS. Porto Alegre.
Covington, A. D. and Alexander, K. T. W. (1993) The Production of Soft Leather Part 1. The Mechanism of Chemical
Softening by Lubrication. Journal of the American Leather Chemists Association. Vol. 88 (7).
Graffunder, V. (2003). Óleos Engraxantes, Evolução e Ecologia. In Proceedings of XVI Congresso Nacional da Abqtic, Foz
do Iguaçu.
Gutterres M. (2003). Desenvolvimento Sustentável em Curtumes. In Proceedings of XVI Congresso Nacional da Abqtic, Foz
do Iguaçu.
Heidemann, E. (1993). Fundamentals of Leather Manufacturing. Eduard Roether KG. Darmstadt.
Kronick, P.L. (1996) Leather Processing. In "Bailey's Industrial Oil and Fat Products, Fifth Edition, Volume 5, Industrial and
Consumer Non-Edible Products from Oils and Fats". John Wiley & Sons. New York.
Peres, R.M. (2003). Couros Hidrofugados – Parâmetros de Produção e sua Correlação com o Efeito Hidrofugante. In
Proceedings of XVI Congresso Nacional da Abqtic, Foz do Iguaçu.

Acknowledgments

The authors want to acknowledge CAPES and FAPERGS for financial support, BMZ Couros Ltda., for
leather samples, and Curtume Bender S.A., for technical information.