3.

TANNERIES

3.1. Description of the tanning-process

3.2. Emissions
3.3. Prevention of waste production

3.1. Description of the tanning-process

Figure 3 presents a flow diagram of a 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) (Buljan 1994). 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 (Beamhouse operations)

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 cross-linkage 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 (Ockermann and Hansen, 1988).

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.

A more detailed description of the tanning process is found in the publication “Animal by-
product processing” by Ockerman and Hansen, 1988.

3.2. Emissions

3.2.1. Solid waste

3.2.2. Wastewater
3.2.3. Air pollution

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.

3.2.1. Solid waste

The production of fresh hides has been estimated at about 8-9 million tonnes per year
(FAO, 1990a). During the processing of these hides a total of 1.4 million tonnes of solid
waste is produced (El Boushy and Van der Poel, 1994). This means that in all likelihood ca
16% of the processed hides is leather waste. Buljan (1994) puts the figures for 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 14 (Buljan, 1994). 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 120* 110 32
Fleshings 70-230
Wet blue split 115
Buffing dust 2
Total 190-350 225 34
GRAND TOTAL Approx. 450-600
 *: hides not trimmed in the abattoir itself

Buljan (1994) states:

“Collection and safe disposal of solid waste, especially chrome containing solid
waste and sludge is normally monitored by environmental authorities and
associated with costs. Conversion of solid waste into by-products not only
reduce pollution load, it can also be commercially beneficial. This represents
great potential for producing increased returns to tannery processing through
deriving value from wastes. In any event, reduction of waste is essential in
order to meet demands for reduced pollution load from tanneries.”

3.2.2. 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 (Department of the Environment, 1978).

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. Rajamani (1987) gives a 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 COD-values for precipitated wastewater
show a reduction of BOD and COD of ca 50% (Pelckmans, undated). 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 pH’s and the different compounds influence each others’
solubility. In composite wastewater, compounds precipitate while they stay dissolved in the
wastewater from the separate processes (Pelckmans, undated). 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 15 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. Mulder and Buijssen (1994) give values of 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 5

Values are estimated from data from:

(1): Rajamani (1987); values from Kanpur, Pakistan.

(2): Clonfero (1990); refering to a UNIDO-study (1975).
(3): Taiganides (1987); an average and quit general value.

In Table 16, RIVM (1992) presents 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 are
higher than the figures mentioned in Table 15. RIVM noted that measured 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) - kg COD/m3 kg N/m3 kg Cr/m3
Pretanning:
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 -
Tanning:
Chrome tanning 0.5-1 3.8-4 2-3 0.3-0.6 0.5-5
Pressing 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
Finishing:
Drying 3-6
Finishing 1-2
Cleaning 5

Clonfero (1990) gives in annex 1 the characteristics of the wastewater of each step of the
tanning process for an Italian tannery. This tannery had produced a huge amount of water
(about 310 m3 wastewater per ton of raw hides), and high amounts of SS and a COD of
2500 kg per ton of raw hides. No explanation is given for the differences between the
figures of UNIDO (table 15) and the figures of the Italian tannery (annex 1).

3.2.3. Air pollution

Table 17 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.
RIVM (1992) estimated the need for the 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 17 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 kg/ton raw hide

Unhairing/liming H2S
Deliming/Bating NH3
Finishing solvents, formaldehyde 25*
heating with gas CO 0.033*
CO2 190*
NO2 0.17*

*: Netherlands situation, based on figures of RIVM (1992)

H2S may be emitted into the air when the pH of the processwater is less then 7. During the
finishing-process volatile organic compounds are used.

3.3. 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.

The following gives a more detailed discussion (from Higham, 1991).

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 (see par. 5.2.2). 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
(Higham, 1991), 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.