CLEANER TECHNOLOGIES IN THE TANNING INDUSTRY

Dr Ken Alexander (Assistant Director - Technical);

Veronica Donohue (Assistant Information Officer - Computer Applications)
British Leather Confederation, Northampton, England

The British Leather Confederation, which provides the Secretariat for the
International Union of Leather Technologists and Chemists Environment and Waste
Commission, is gathering information on clean technologies of leather manufacture,
in co-operation with other leather industry associations. First results of this work will
be presented as an example of the role that industrial associations can play in
networking and promoting cleaner production.
Key aspects of the work are:

.
.

Development of a practical database of clean technologies for the

leather industry
Development of networks of experts on clean technology for the
leather industry

19

ENVIRONMENTAL IMPACT OF LEATHER PRODUCTION

Leather manufactureis one of the oldest established industries and has a current
annual turnover of approximately US$25 lion, providing employment for around
half a million workers on a worldwide b a s i 8 . It is essentially a by-product industry,
utilising hides and skins from animals raised primarily for their meat. Statistical
informationfrom the United Nations Food and Agriculture Organisation shows that
in 1987 global leather productio as nearly 14 billion square feet, produced from
over 5 million tonnes of rawstocfi2? In this sense the tanning industry considerably
reduces the environmentalimpact of the meat industry, which would otherwise have
a major waste disposal problem.
However, only approximately one-fifth of the rawstock can in practice be
converted into saleable leather, the remainder forming wastes or by products. For
example, some of the raw material, such as hair, soluble proteins and fat has to be
removed during processing to prepare the collagen fibre structure of the hide for
tanning and some parts of the leather also have to be trimmed or shaved during the
production process. Residual chemicals from the leather manufacturing process
contributefurther to the tannery wastes. An indicationof the amountsof liquideffluent
and solid wastes or by-productsresulting from the processing of 1 tonne of rawhide
to leather is given in Figure 1.
A more detailed analysis of leather processing showing the stages at which
chemical inputs are made and liquid effluent and solid wastes produced is given in
Figure 2, and discussed below. The reader is also referredto a number of excellent
reviews published in recent years that provide comprehensive information on the
environmental impact of leather processing and pollution abatement, eg, The
Technical Guide to R ucing the Environmental Impact of Tannery Operations
(F Balkau; UNEP/IEO) , Pollution Abatement and Control in the Leather Industry
(R L Sykes, D R C ning, British Leather Confederation; UNEP Industry and
Environment Journal)%; Environmental Impact Guidelin for New Source Leather
Tanning and Finishing Industries (Wapora; U EPA
Wastes from Tanning,
Leather, Dressing and Fellmongering (UK DOE) .

BY.

8)

LEATHER PRODUCTIONAND WASTE MANAGEMENT

It can be seen in Figure 2 that after soaking hides to remove curing salt and

soluble, non-collagenousproteins (eg, albumins), the hair and epidermal layer of the
hide are degraded by chemical digestion of the hair/epidermal keratin with alkaline
sodium sulphide. This unhairing step accounts for much of the BOD, COD, and
suspended solids produced in the tannery effluent. The alkaline treatment also
removes additional interfibrillaryprotein to open up the collagen fibre structure of the
hide, which is essential for the production of soft leather. Although alkaline sodium
sulphide itself poses few problems, toxic hydrogen sulphide gas would be evolved if
the pH droppedinthe effluent and most tanneries, at least inthe developingcountries,
therefor use a manganese catalysed aeration treatment originally developed by
BLMRA to comply with the low sulphide levels required by control authorities for
discharges. Physico-chemical treatments are frequently employed to reduce the
organic load and COD in the effluent (by around 50%) and to reduce the suspended
matter by 8040%. A typical tannery effluent treatment system is illustratedin Figure3.

0)

20

GIVES

50 m3 LIQUID EFFLUENT
CONTAINING
COD
BOD
Susp solids
Chromium
Sulphide

235-250 kg
c 100 kg
c 150 kg
5-6 kg
c 10 kg
I

SOLID WASTES AND

BY-PRODUCTS
Untanned
Raw trimmings
Fleshings

120 kg
70-230 kg

Tanned
Blue sheetings
Trimmings
shavings

115 kg

Dyed/finished
Buffing dust
Trimmings

G
LEATHE

Figure 1 Environmental inpadof leather processing (source a)

21

100 kg
2 kg
32 kg

CHEMICAL INPUTS
salt

PROCESS STAGE

LIQUID EFFLUENT

SOLID WASTES

RAWHIDE

-)-----salt

trim---

)trimmings

h)

sulphlde/lime
5'

ammonium salts b
en mes
a c z salt

I : - ,

remove flesh- - - - delime - - - - -7"

- ac picklebate- --

(cl

-#-

retanniyagents
dyes, bu er salts, etc.
lubricants

salts
)."onium
Hrease
)acid brine

wet'blue

POST TANNING
WET WORK
-- retannage
dyeinfl
- - - lubricat on

-- -

liquors containing
process chemicals in
low concentration

hdry
m -- - - -

bleather trimmings

stress softening

v)

LI

water and solvent-basedw

-polymers; pigments

)fatty fleshings

sheetings (very thin splits)

hrome shavings

ving---

wei blue
Q
3.
7

sulphide, lime

sludges
mainly lime, protein

chromium 111

basic chromium sulphate

auxiliary chemicals, buffer
salts, acid, etc.

salt solutions

BEAYHOUSE
$oak---b -_-- unM&--

FINISHING
buffing -surface coating
trimmingsorting

- ---

)(solvent vapour)

)buffing dust
Weather trimmings

POST TANNINQ

L
RINSES

._

TANNINQ

COARSE

SCREEN

DISCHARQE
TREATMENT

TO SEWER

SLUDQE

DEWATER
G
D1SPOSAL

Figure 3 Physico-chemical treatment of tannery effluent (source (3))

Physico-chemical treatment requires

initial balancing (homogenisation) of
collected liquors followed by controlled
addition of flocculants and sedimentation
(or flotation) to remove sludge, which is,
in most cases, then dewatered. Biological
oxidation can provide a more effective
treatment system for tannery effluent,
although considerable land space is
required. The oxidation ditch shown in
Figure 4 reduces BOD levels in tannery
effluent from 500-1OOO mg/l down to levels
as low as 1-2 mg/l residual BOD, with
almost
complete
elimination
of
suspended solids and of ammonia, some
of which is derived from the use of
ammonium salts used for lowering the pH
to prepare the skins for enzyme treatment
(bating). The fatty fleshings that have to
be removed from hides can be used as a
source of tallow, although profitable
disposal. of chrome shavings produced Figure 4 Oxidationditch for biological oxidation
after chrome tanning is difficult and often
treatment of tannery effluent
(courtesy
of W E & J Pebody Ltd, England)
has to be disposed to landfill. Excess
chromium (111) in the effluent is strictly controlled.
Clean Technology and Pollution Control

Despite the fact that pollution abatement is a considerable, non-productive cost

burden on leather manufacturers, the industry itself has taken the initiative in
introducingcleaner technologies and improving pollution control. At the last meeting
of the International Union of Leather Technologists and Chemists Societies in
Philadelphia, USA in 1989 over 60% of the scientific papers presentedw e concerned
In a recent
with the development of cleaner technologies for leather manuf
survey of research directors of leather research organisationsbylEan technology
was highlighted as the most important priority for future research, after cost
reductions.

81.

23

The key targets identified in that 1987 survey were:

.
.
.
..
.
.
.
.

Replacement of chromium
More effective use of chromium
More efficient use of chemicals
Sulphide free unhairing, possibly with hair recovery
Utilisationof wastes
Re-use of water
Odour control
Solvent free finishing
N-free deliming

In fact many of these targets are now already being achieved and Figure 5
illustrates just a small selection of new clean technologies that are currently being
introduced by the leather industry, or are already in place. These include:

.
.
.
.
.

.
.

Hide chilling to avoid salt in the effluent

Hair recovery processesto reduce BOD/COD of the effluent
Enzyme-assistedunhairing to reduce sulphide
C02 deliming to reduce ammonia in the effluent
Better uptake/exhaustion of chrome or chrome recovery/recyclingto
reduce chrome in the effluent
Alternative mineral tanning agents to avoid chrome in the effluent or
solid wastes
Water-based and solvent-free top coats to avoid VOC emissions

More detailed informationon the processes are reported in the References cited
in Figure 5.

Development of a Clean Technology Database for the Leather Industry

A lack of clear, objective and practically useful information is a major difficulty
facing the busy tanner who wishes to introduce cleaner technologies of leather
manufacture.

This need for an easily accessible source of information on clean technologies

was the driving force behind the decision to set up a suitable database. The British
Leather Confederation, which provides the Secretariat for the International Union of
Leather Technologists and Chemists Environment and Waste Commission is
therefore currently gathering information on clean technologies of leather
manufacture, in co-operation with other leather industry associates. The work is
dependent upon the developmentof a network of co-operationand support, involving

24

PROCESS

PROCESS STAGE

cLEANTEmNouKiY

REDUCTION OF

p0UuTK)N

SALT IN SOA
uawwl

NOSALTIN
EFFLUENT

REDUCED

+ BODOF

AMMONIA
EFFLUE

CHROMIUM 111 I
EFFLUENTAN

EFFLUENT

REDUCEDUSE
OF SULPHIDE

NO AMMONIA
IN EFFLUENT

REDUCED
*CHROMIUM
IN
EFFLUENT

CHROMIUM
RECOVERWRECYCUNQ

REDUCED
IN

OR
NO CHROMIUM
-+IN EFFLUENT,

S W D WASTES

Fgure 5 Clean technology for leather production

tanners, industrial research associations, industry suppliers, Government and other

agencies (e.9. the European Commission under the SPRINT programme, the United
Nations Environment Programmeetc) and independent leather experts, as illustrated
in Figure 6.

,-

and
o l h u ~ ~ l u

(.o, UNEP. EC,

DOE,PA)

Figure 6 Network - Clean technology

information database

The main objective is to set up a practically useful system to enable the tanner
to easily shortlist appropriate technologies for his requirements from the database.
As part of this procedureit is also essentialfor the tanner to be able to identifyexisting
users of the technology and independent leather experts, as well as the
manufacturers or inventors, whom the tanner can then separately consutt. It is
considered most important that the database should not just be a bibliographic
source of informationbut should be of immediate practical use, quantifyingwherever
possible the reductions in pollution achievable by the clean technology, listing any
disadvantages and above all, giving an indication of its present level of development
and extent of use, since systems inevitably range from those just at the researchand
development stage to well-established technologies in widespread use. An outline
of the factors that have been selected for inclusion in the database is given in the
Questionnaire reproduced in Figure 7, which in this particular example/case history
has been completed for a new tanning product, Synektan TAL, manufacturedby IC1
as a replacementfor chromium.
The leather industry has made considerable investments in time and money in
reducing the pollution from tanneries and has achieved significant progress in
introducing cleaner technologies, in collaboration with the suppliers. Nevertheless,
because of the imposition of increasingly restrictive and sometimes unreasonable
environmental legislation, many tanners have been forced out of business in recent
years and the jobs of their workers lost because of the non-productive costs of
improving environmental standards. In the recent survey of research directors Of
leather research organisations, o e of the problems highlighted was the need to
eliminate environmental hysteria&. It is to be hoped that in the years to come the
legislative authorities will recognise the efforts of the tanning industry by setting
realistic and scientifically based controls and avoiding, wherever possible,
politically-motivatedor emotional responses to the environmental problems facing
all of us.

26

Figure 7 Clean Technology questionnaire

Q U E S T I O N N A I R E
1.

R r i e f S M R Y of clean technoloRy procens/nyntem i n a s feu words as p o s s i b l e :

(cs. U n h a i r i n g u s i n g enzymes. c h i i l i n g u s i n g ice)
Aluminium

2.

t i t a n i u m complex m i n e r a l t a n n i n g a g e n t (non-chrome)

Is t h e r e a SPECIFIC p r o c e s s / t r a d e name? (eg. Blair h n i r . Chromesaver A-31)

S y n e k t a n TAL
3.

I n which PROCESS STAGE is t h e c l e a n t e c h n o l o g y t o be a p p l i e d ?

0 Ravstock

0F i n i s h i n g

0 Beamhouse

OWaste T r e a t m e n t
0Energy Usage

d T a n n i n g and p r e t a n n i n g f o r wet w h i t e
d D y e i n g and F a t l i q u o r i n g and r e t a n n i n g
OOther:
4.

(Please t i c k )

(Please explain)

DESCRIPTION of t h e key f e a t u r e s of t h e c l e a n t e c h n o l o g y p r o c e s s / s y s t e m i n n o t more

t h a n 200-300 words:
(Use No. 11 f o r COMMENTS on t h e p r o c e s s )
Non-chrome t a n n i n g a g e n t , p o t e n t i a l l y u s e f u l in t h r e e a r e a s :
(1)
p r e t a n n i n g f o r w e t w h i t e , t o r e d u c e p r o d u c t i o n of chrome t a n n e d s o l i d w a s t e
a n d r e d u c e chrome consumption i n t h e t a n n e r y
(ii)
t o t a l or p a r t i a l r e p l a c e m e n t o f chrome i n main t a n n a g e , t o r e d u c e chrome
o f f e r s by a i d i n g chrome u p t a k e and by s u b s t i t u t i n g a t l e a s t p a r t of t h e
normal chrome o f f e r
( i l l ) t o t a l or p a r t i a l r e p l a c e m e n t of chrome i n c o m b i n a t i o n t a n n a g e s or r e t a n n i n g

5.

Where t h e r e is a r e d u c t i o n in e f f l u e n t l o a d i n g , QUANTIFY t h e c h a n g e s made by t h e

p r o c e s s or the a c h i e v a b l e levels
T o t a l r e p l a c e m e n t of chrome by S y n e k t a n TAL would s a t i s f y any r e q u i r e m e n t r e g a r d t n g
I f a p r a c t i c a l chrome o f f e r . e g , 1% C r z O 3 ,
s o l i d or l i q u i d chrome-bearing waste.
is r e t a i n e d ( t o m a i n t a i n chrome l e a t h e r c h a r a c t e r ) . c h r o m e d i s c h a r g e s i n t h e
e f f l u e n t might b e a p p r o x i m a t e l y 10 ppm i n t h e mixed w a s t e s t r e a m . By o p t i m i s i n g
c o n d i t i o n s , t h a t l e v e l can be s i g n i f i c a n t l y reduced.

6.

What ENVIRONMENTAL claim are made?

(Please t i c k relevant iteds)

I z:iL: 1

C l e a n e r or
Less
Recycled Better L i q u i d
I u p t a k e l waste
less t o x i c I r e q u i r e d l
benefits benefits
alternative

Ammonia
Chromium
Chloride
Nitrogen
Sulphide
Solvents
Pesticides
Biocides
Reductions:
BiochemicallChemLcal O n_ a_ e n Demand
Suspended s o l i d s
Total solids
Crease

0 Odour

reduction

0 Energy s a v i n g

B e t t e r working c o n d i t i o n s

dother:

(Please explain)

Chrome-free s o l i d by-product by p r e t a n n i n g f o r wet w h i t e

27

7.

~~~

Q u a n t i f y ADVANTAGES i t e m i s e d above:

(eg.

10% l e a s s a l t in e f f l u e n t )

P r c i c t t c a l l y . chrome i n s p e n t t a n l i q u o r might bc rccluccd try 95%

8.

What DISADVANTAGES are t h e r e ? (eg. aluminium i n e f f l u e n t ) P l e a s e e x p l a i n

(Please t i c k relevant item/a)
c d U n d c s i r o b l o e f f e c t s on t h e e n v i r o n m n t

N w i r n t prcseiit;

I I I H ~opply

High c o s t s

Technical p r o b l e m

1c~:lslutioti
Consciit L i m i t s

d Other:
P o s t - t a n n i n g s t e p s have t o b e m o d i f i e d t o t a k e a c c o u n t of A 1
9.

H w PRACTICAL is t h e c l e a n t e c h n o l o g y ?

+ Ti

i n the leather

Please explain

Very p r a c t i c a l , no c a p i t a l c o s t r e q u i r e d or c h a n g e s t o e x i s t i n g p r o c e s s i n g methods
10.

Give a n estimate of t h e 'CLEANNESS' of t h e p r o c e s s

( P l e a s e t i c k r e l e v a n t item/s)

- Best p o s s i b l e
available to date
Reasonable - Better t h a n o t h e r p r o c e s s e s
Not so good - No better t h a n o t h e r a v a i l a b l e p r o c e s s e s
Very good

Cd Good - Beat

0
0
11.

Give an OPINION or make COMMENTS on t h e 'CLEANNESS' of t h e p r o c e s s :

Synektan TAL c a n make r e a l r e d u c t i o n s i n l e v e l s of d i s c h a r g e d chrome w i t h n o
c u r r e n t a d d i t i o n a l k n v i r o n m e n t a l problems. D i s c h a r g e s of aluminium (and p o s s i b l y
t i t a n i u m ) may b e s u b j e c t t o e n v i r o n m e n t a l p r e s s u r e i n t h e f u t u r e

12.

Name of ORCANISATION/WUFACURER r e s p o n s i b l e f o r c l e a n technology:

C o n t a c t name:
Company name:
Address:
Tel:

13.

Ian Tate
I C 1 C o l o u r s and F i n e Chemicals
PO Box 42. Hexagon House, B l a c k l e y . Manchester M9 30A

0 6 1 7 2 1 2562

Telex:

667841

A t what STAGE OF DEVELOPMENT is t h e p r o c e s s now?

Fax:

061 795 6005

( P l e a s e t i c k r e l e v a n t item/s)

L i m i t e d commercial u s e
d w i d e s p r e a d use

R e s e a r c h 6 Development

0 Trial/Prototype
0 Other: ( P l e a s e e x p l a i n )

I O U W Y YEARS h a s t h e p r o c e s s / s y s t e m been in commercial u s e ? 2 y e a r s

WllAT YEAR was t h e p r o c e s s / s y s t e m f i r s t d e v e l o p e d ?
1987
P r o d u c t l a u n c h e d i n 1988

14.

TANNERY COSTS AND PAY-BACK PERIOD

PAY-BACK PERIOD:

WLEUENTATION COSTS:

fl

5000

0 f5001

10.000

@f
flO.OO1 -

5-10 y e a r s

50.000

0 f50.001
100.000
0 More t h a n flOO.OO1
15.

AVAILABILITY

(Please t i c k relevant item/a)

6 N e w Zealand

N America
S America

Africa
16.

E s t i m a t e d NUMBER OF TANNERIES u s i n g t h e t e c h n o l o g y WORLDWlUE i n y e a r 2000:

0
0

1-10

51-100

11-50

28

17.

ESTIMATED square feet of leather produced to date using this technology:

Less than I million square feet

d 1 - 5 million square feet

0 More than 5 million square feet

18.

Give details of TANNERIES using this process who uould be willing to be contacted:
Coiitnct nor:
Organisation name:
Type of business:
Address:
Tel:

051 647 6252

Dr H P Walker
The British Leather Co Ltd
Bovine tanners
Tranmere Tannery, Nev Chester Road, Birkenhead, L41 9BS
Telex:

629570

Fax:

051 647 3573

19.

If IT IS NOT POSSIBLE to give above contacts, please give details of an

INTERMEDIARY who could pass on any requeats for information to a relevant tannery:
See (12)

20.

Give full details of REFERENCES in the literature to the process:

(Continue on a separate sheet if necessary)
A D Covington

I Tate

Tannages based on aluminium (111) and titanium (111) complexes

J Amer Leather Chem Aasoc. 1987. 82. (I). 1
The use of aluminium, titanium and magnesium complexes in the
pretanning. tanning and retanning operations
Proceedings, IULTCS Congress, Philadelphia, 1989

21.

Give details of any PRODUCT DATASHEET Reference Numbers:

Product code 36003

22.

Give details of other sources of INFORMATION:

Company information pack

23.

Which individuals are considered to be THE EXPERTS in this area?

Name
Organisation
Address
Tel:

061 721 2562

Name
Organisation
Address
Tel:
21.

667841

Fax:

061 795 6005

Telex:

629570

Fax:

051 647 3573

Where information is obtained directly from the manufacturer, give details:

Tcl: 061 721 2562

I P Tate
IC1 Colours and Fine Chemicals
PO Box 42, Hexagon House, Blackley. Manchester I49 30A
Telex:

667841

Fax:

061 795 6005

EditorRersoo completing this form:

Name:
Organisation:
Address:
Tel: 0604 494131

26.

Telex:

Dr M P Walker
The British Leather Co Ltd
Tranmere Tannery, New Chester Road, Rirkenhead, L41 9BS

051 647 6252

Name:
Organisation:
Address:

25.

I P Tate/R H Webster
IC1 Colours and Fine Chemicals
PO Box 42. Hexagon House. Blackley. Manchester H9 30A

Dr A D Covington
British Leather Confederation
Leather Trade House, Moulton Park, Northampton
Telex:

317124

Fax:

NN3 1JD

0604 648220

Any COl44ENTS not covered above:

EC Supported Demonstration Project (ACE/88/UK/OOZ/AZl) currently being conducted a t
The British Leather Co Ltd. in collaboration with the Brit'iah Leather Confederation

29

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2,

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6.

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( K r ause )
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Alexander, K.T.W.
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a h l g h - e x h a u s t chrome tannage w i t h Baychromc 2403.

30

Journal 23.
Journal 24.
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J o u r n a l 26,
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Journal 28,

Journal 29.

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3 1 ( 1 ) 1-8
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and r e u s e o f chromium f r o m c h r o m e - l a d e n t a n n e r y w a s t e and a
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Andres, H.
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36 ( 2 ) 1 7 - 2 1
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I N : The w e t - w h i t e o p t i o n .
(Rohm 8 Haas)
Howie, I.
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1989
2 ( 4 ) 110-115
L e e , N . F . & J a c k i i n , C.N.
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Chr i 5 t n e r , J.
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L e a t h e r Manuf
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C o v i n g t o n , A.D.
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( R o d a c r y l 143 L Roda p u r 3 0 9 ) (Rohm GmbH)
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aaueous o o l v u r e t h a n e s .
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p r o b l e m s and s o i u t l o n s u n d e r t h e a s p e c t s o f c h e m i s t r y ,
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3 (1) 2
Wor I d L e a t h e r

Journal 30.
Journal 31.
Journal 32.
Book

33.

Journal 34.

Journal 35.
Book

36.

Journal 37.
Journal 38.
J o u r n a l 39.
Journal 40.
Book

41.

.Journal 42.

31

WASTE MINIMIZATION

APPROACHES and

1 Activities
Chicago, Illin

1 present a s
minimization

conducting a wa

the

receiving

s of suggested steps for

ssment, discuss means of
improving operations. These
process modification will be

fa
S ON POTW1s

costs and storage r

anything that doesnl
the form of a soli

ms that are generated from their

smokestacks, sewers and refuse
in an effort to reduce operating
improve public image and operating
potential risks and liabilities
aste streams can be thought of as
or as product. Waste can be in
or a combination thereof and
considered a
evaluate the

urce and no longer a waste.

act of waste minimization on
and will therefore focus

and contamina

that may be subjected to

SLUDGE PR
reducing the amount
of sludge will usually result in less sludge requiring treatment
and disposal. Care should be taken in instances where industrial
wastewater flows are substantial not to adversely affect sludge
operations at the POW.
32