TANNERIES

Description of the tanning-process

Figure 1 presents a flow diagram of the tanning-process. Hides are a by-product of slaughter activities
and can be processed into a wide range of end products. For each end product, the tanning process is
different and the kind and amount of waste produced may vary enormously.

The chemicals traditionally used for tanning have been derived from plants, whereas the most
common process nowadays is a combination of chrome salts (chrome tanning) and readily usable
vegetable extracts (vegetable tanning). While chrome tanned shoe leather is the most widely produced
leather, this kind of leather will receive most attention in the following.
In most cases raw hides produced at slaughterhouses are preserved by pickling and drying for
transport to tanneries and further treatment. In the very few cases that hides are instantly tanned there
is no need for preservation. During the tanning process at least 300 kg chemicals (lime, salt etc.) is
added per ton of hides.

Pretanning
Soaking:
The preserved raw hides regain their normal water contents. Dirt, manure, blood,
preservatives (sodiumchloride, bactericides) etc. are removed.
Fleshing and trimming:
Extraneous tissue is removed. Unhairing is done by chemical dissolution of the hair
and epidermis with an alkaline medium of sulphide and lime. When after skinning at
the slaughterhouse, the hide appears to contain excessive meat, fleshing usually
precedes unhairing and liming.
Bating:
The unhaired, fleshed and alkaline hides are neutralised (deliming) with acid
ammonium salts and treated with enzymes, similar to those found in the digestive
system, to remove hair remnants and to degrade proteins. During this process hair
roots and pigments are removed. The hides become somewhat softer by this enzyme
treatment.
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 hide from swelling. For preservation
purposes, 0.03 - 2 weight percent of fungicides and bactericides are applied.
Tanning
There are two possible processes:
1: Chrome tanning:
After pickling, when the pH is low, chromium salts (Cr3+) are added.
To fixate the chromium, the pH is slowly increased through addition
of a base. The process of chromium tanning is based on the crosslinkage of chromium ions with free carboxyl groups in the collagen.
It makes the hide resistant to bacteria and high temperature. The
chromium-tanned hide contains about 2-3 dry weight percent of Cr3+.
Wetblue, i.e. the raw hide after the chrome-tanning process, has
about 40 percent of dry matter.
2: Vegetable tanning:
Vegetable tanning is usually accomplished in a series of vats (first
the rocker-section vats in which the liquor is agitated and second the
lay-away vats without agitation) with increasing concentrations of
tanning liquor. Vegetable tannins are polyphenolic compounds of
two types: hydrolysable tannins (i.e. chestnut and myrobalan) which
are derivatives of pyrogallols and condensed tannins (i.e. hemlock
and wattle) which are derivatives from catechol. Vegetable tanning
probably results from hydrogen bonding of the tanning phenolic
groups to the peptide bonds of the protein chains. In some cases as
much as 50% by weight of tannin is incorporated into the hide.
Finishing
Wetblue:
Chromium tanned hides are often retanned - during which process the desirable
properties of more than one tanning agent are combined - and treated with dye and fat
to obtain the proper filling, smoothness and colour. Before actual drying is allowed to
take place, the surplus water is removed to make the hides suitable for splitting and

shaving. Splitting and shaving is done to obtain the desired thickness of the hide. The
most common way of drying is vacuum drying. Cooling water used in this process is
usually circulated and is not contaminated.
Crust:
The crust that results after retanning and drying, is subjected to a number of finishing
operations. The purpose of these operations is to make the hide softer and to mask
small mistakes. The hide is treated with an organic solvent or water based dye and
varnish. The finished end product has between 66 and 85 weight percent of dry
matter.
Emissions
The discharge of solid waste and wastewater containing chromium is the main environmental
problem. Chromium is a highly toxic compound and the dumping of chromium containing material is
in most countries restricted to a few special dumping grounds. Reduction of chromium discharge is
therefore essential. Emissions into the air are primarily related to energy use, but also the use of
organic solvents and dyes causes emissions into the air.
Solid waste
The production of fresh hides has been estimated at about 8-9 million tonnes per year. During the
processing of these hides a total of 1.4 million tonnes of solid waste is produced. This means that in
all likelihood ca 16% of the processed hides is leather waste. Trimmings and splittings (i.e. leather
waste) at a total of 225 kg/ton hide (i.e. ca 23%). This is almost the same amount of waste produced
as meat from fleshing activities (7 - 23%). For every ton of raw hide processed, the amounts of solid
waste and by-products may be produced as given in Table 1. These figures show that the solid waste
produced per ton of raw hide is about 450-600 kg. About half of this contains 3% chrome on a dry
matter basis.
Pretanning Tanning Finishing
Trimmings
Fleshings

120*

110

70-230

Wet blue split

115

Buffing dust
Total

32

2
190-350

225

34

GRAND TOTAL Approx. 450-600

*: hides not trimmed in the abattoir itself
Wastewater
As for the production of wastewater, over 80 per cent of the organic pollution load in BOD terms
emanates from the beamhouse (pretanning); much of this comes from degraded hide/skin and hair
matter. The beamhouse is also the source of all non-limed and limed solid waste such as fleshing,
trimming and waste split. As already mentioned, during the tanning process at least ca 300 kg of
chemicals (lime, salt etc.) are added per ton of hides. Excess of non-used salts will appear in the
wastewater. Because of the changing pH, these compounds can precipitate and contribute to the
amount of solid waste or suspended solids.

Every tanning process step, with exception of the crust finishing operations, produces wastewater. An
average of 35 m3 is produced per ton of raw hide. This wastewater contains:
- salts (Cl), fat, protein, preservatives (soaking);
- lime and ammonium salts, ammonia, protein (hair), and sulphides (fleshing,
trimming, bating);
- chromium(salts) and polyphenolic compounds (tanning); and
- dye and solvent chemicals (wet-finishing).
Solid waste produced consists of fleshings containing lime, chromium containing wet-blue shavings
and of trimmings (leather).
Water will not only have a diluting effect, it also increases the number of kg of BOD per ton of hides.
BOD range of 1000 - 3000 mg/l depending upon the volume of water used and on other impurities.
TNO gives BOD and COD values both for precipitated and mixed wastewater. BOD- and CODvalues for precipitated wastewater show a reduction of BOD and COD of ca 50%. This implies that it
is worth precipitating dissolved organic compounds and treating this as solid waste. It is known that
treatment of solid waste can in general be undertaken without too many efforts and that the costs and
energy required are lower than those for the treatment of wastewater.
Tanneries that perform the complete tanning procedure, produce mixed wastewater. The composition
of this wastewater is not solely the result of separate waste streams that merge together. The different
pHs and the different compounds influence each others solubility. In composite wastewater,
compounds precipitate while they stay dissolved in the wastewater from the separate processes. Most
reports give reliable values for composite wastewater. Some reports only give data for the separate
wastewater streams. These values should be used with great care and should not be merely added in
order to arrive at a compound value.
In Table 2 high and low values for BOD, COD, SS and Cr3+ are given. This variation might be caused
by a high amount (45 m3 per ton of hide) or low amount (25 m3 per ton of hide) of water used during
the tanning process.,50 m3 per ton of hide for traditional manufacturing processes of Wet-blue and 20
m3 per ton of hide when water saving actions are applied.
(1)

(2)

(3)

BOD 110 40-100 80

COD 265 120-280
SS

216 70-200

Cr

8.8

In Table 3, the quantity and composition of wastewater for every step of the tanning process in a
Dutch situation. Per ton of hide a total of 35 m3 wastewater is produced. The Dutch figures of the
COD produced during the pretanning process, chromium-concentrations were 3-7 times higher than
the estimated figures. Moreover, in the Netherlands about 50% of the hides processed in tanneries
have already been pretanned or tanned.

Process step

Amount of water

pH

COD

NKj

Cr

(m3/ton)

Soaking

4-6

6-9

30-40

1-1.5

Unhairing, liming

5-9

12-13

40-60

3-5

Fleshing

1-3

Deliming, bating

5-7

8.5-9

5-8

3.5-4

0.5-1

3.8-4

2-3

0.3-0.6

0.5-5

0.4-0.6

3.6-4.5

1.2-1.8

0.11-0.22

0.5-5

Neutralisation

1-1.5

4.5-4.7

2.5-3

0.5-0.8

0-1.0

Painting, fatting

3-4.5

3.8-4.5

5-6

0.2-0.3

0-5.0

kg COD/m3 kg N/m3 kg Cr/m3

Pretanning:

Tanning:
Chrome tanning
Pressing

Finishing:
Drying

3-6

Finishing

1-2

Cleaning

Air pollution
Table 4 gives the emissions into the air during the tanning process. Few figures are available about
the amount of air pollution.
An important part of the air pollution by leather tanneries is caused by the need for energy. Dutch
tanneries at: 439 kWh (electricity) per ton of raw hides and 108 m3 of gas per ton of raw hides. Gas is
used for heating. Table 4 gives the emissions into the air as a result of gas-combustion. No figures are
available about the emissions into the air as resulting from the use of electricity.
Process-step

Air pollutants

Unhairing/liming H2S
Deliming/Bating NH3

kg/ton raw hide

Finishing

solvents, formaldehyde 25*

heating with gas CO

0.033*

CO2

190*

NO2

0.17*

H2S may be emitted into the air when the pH of the processwater is less then 7. During the finishingprocess volatile organic compounds are used.
Prevention of waste production
Considerations for the reduction of the amount of polluting value of the produced wastewater are:
- a reduction of the total water use by re-use of produced wastewater and by the
development of technologies that minimize the quantity of water needed during the
tanning process; and
- a reduction of the used chemicals such as lime, salt, sulphide etc and a reduction of
chromium.
Water conservation
A reduction of water use can lead to a reduction of the total waste load. Re-use of wastewater with a
minimal harmful or even a moderately beneficial effect on earlier processes may be considered as an
option.
Curing hides and skins
A reduction of the use of salt for preservation can be considered as an option. Fifteen percent of salt
on weight basis may preserve the hides for even 6 weeks, and 5 per cent of salt plus biocide lead to a
preservation for two months. Chilling without salt can preserve hides for a few days. Another
alternative preservation method is radiation by electron beam or gamma rays. Where possible,
biodegradable preservatives (insecticides etc.) should be used instead of derivatives of chlorinated
aromatic hydrocarbons. The latter persist in the waste and are highly toxic to the environment.
Beamhouse processes
Hair saving methods are recommended to prevent degraded keratin from entering the waste streams.
Unhairing/liming fluids can be recycled after recharging. It is also recommended that the unhairing
and liming stages should be seperated. Both liquids can be recharged and hair can be screened out.
The intermediate wash can be re-used as a soak liquid.
Tanning
Low chrome systems, possibly requiring an aluminium salt for pretannage will produce a wet-white
leather. Splitting and shaving wastes will contain less chromium. Alternative mineral salts such as
aluminium, zirconium, titanium and iron are might be used as substitutes for chromium salts.
However, under certain conditions aluminium is known to be more poisonous to aquatic life than
trivalent and even hexavelant chromium. Re-use of chromium is a more realistic alternative. The
unused tanning fluids which contain chromium can be collected separately. From these fluids and
from the solids that contain chromium, chromium can be recovered. The remainder may be used as
source material for glue and animal feedstuff. In countries where discharge of chromium is strictly
prohibited, great efforts are made to recover and re-use chrome.
Alternative vegetable tanning methods can replace chrome tanning to a high degree. An example is
the Liritan process, developed in South Africa. A high chemical uptake, low pollution load, uniform
penetration of the tan and a shortened process time with consequent financial efficiency are claimed
to be the main advantages of this process, but little is known on the practical implications.

Finishing
A reduction of volatile organic compounds (VOC) can be accomplished by using aqueous finishes for
base and middle finishing coatings.