Transcript Slide 1

BAT THEORY AND PRACTICAL REALITY
IN ROMANIAN TANNERIES
LUMINITA ALBU1, MIRCIU VASILE2, VICTORIA BRATULESCU1
– LEATHER AND FOOTWEAR RESEARCH INSTITUTE
93, Ion Minulescu str., 031215, sector 3, Bucharest, ROMANIA
2 Ministry of Economy and Commerce
152, Calea Victoriei, 010072, Bucharest, ROMANIA
1INCDTP
GENERAL VIEW ON ROMANIAN LEATHER INDUSTRY
Leather industry it’s one of tradition and very old known in Romania.
As final product for tanneries, the leather represents a “raw” material for
other industries as: footwear (about 62%), clothes (about 15%), leather goods
(about 12%), upholstery and automotive leathers (about 11%). Leather
processing is generating, in the same time, by-products applicable for other
fields of activity: protein sources for food, chemical or cosmetically
purposes, medical products, artificial leathers or soles etc.
The most intensive development has taken place in the period 1965 –
1980, for Romanian leather sector. It had an important economical value in
the areas of counties Timis, Sibiu, Cluj, Bihor and in Bucharest. In that
period, most of equipments, chemicals and technologies had to be Romanian
and production was directed for internal consumption and for export into
the socialist states.
After 1989, Romanian leather and shoe industry has to compete, in an
open concurrential market, with high performant industries/products all
over the world. At the beginning of this period, the differences between
technical and technological level of our leather industry were about
15 – 20 years, compared with those from developed countries.
In ’90s the internal demands for leather products has decreased
continuously, socialist market has disappeared and the quality and
competitively of Romanian products were inferior.
Simultaneously exports and imports of raw and finished products have
became free and the prices of energy resources have raised drastically,
producing a decapitalizing process, a lot of viable companies being closed as
the nonprofitables ones.
As a consequence of all internal and external factors, in leather and
shoe sector has developed an industrial restructuring process:
Nonperforming techniques and equipments have been changed into
new ones, modern and more flexible, there where financial possibilities
have existed;
Reorganisation of technological flow charts and efficient management
of working area;
Modernisation of tanneries, especially in finishing sector;
Significant changes in raw hides /skins processed by diminishing of
internal resources and raising imports of finished leathers for uppers
and leather goods; after 1994, about 80% of shoe production is made in
lohn system and the demands of domestic finished leathers have
drastically decreased.
Although, all problems and deficiencies the leather/shoe industry
remains an important industrial sector in Romania; a sector which try to
increase its products competitiveness on the single market.
So, in 2003, leather/shoe industry has realised [1]:





0.9%
5.2%
8.9%
4.5%
1.6%
from Romanian GDP;
personnel from industry is working in this field;
from Romanian exports;
from Romanian imports;
from Romanian industrial production;
On international market Romanian leather/shoe industry has an
important place, on EU, CSI, CEFTA and USA markets. From CEECs,
Romania is on 1st place regarding shoe exports to EU market and on 9th
place worldwide.
The internal situation of leather/shoe industry, nowadays, is
synthetically presented in Table 1 and in Figure 1.
19 – LEATHER
COUNTY
TURNOVER
[EURO]
PERSONNEL
[NUMBER]
BIHOR
77,750,125
20,426
BUCURESTI+ILFOV
71,337,500
17,547
TIMIS
42,537,250
14,166
SIBIU
19,473,750
5,806
ARAD
14,187,200
6,235
MURES
11,377,025
3,153
BACAU
10,463,775
2,536
ALBA
10,420,750
5,258
CLUJ
10,162,075
4,014
SUCEAVA
9,793,725
3,701
SATU MARE
9,201,750
2,984
VALCEA
7,296,325
2,446
HUNEDOARA
6,012,075
2,524
IASI
5,675,000
2,443
DOLJ
4,299,600
1,336
Table 1 - Most important leather/shoe
area in Romania
Figure 1. - Geographical distribution
of tanneries/ shoe factories in Romania
The companies’ structure in leather/shoes field is presented in table 2.
From these companies about 120 are reported as leather companies. This
doesn’t means that there are 120 tanneries; most of them have as activity
object “leather processing” but they are processing hides in an existing
tannery [2].
Table 2. Leather/shoes companies’ structure
Total light industry
Leather/shoe
industry
8942
1731
364
91
Medium size
1352
282
Small size
1897
419
Micro size
5329
939
TOTAL:
Large size
ECOLOGICAL ASPECTS OF ROMANIAN LEATHER INDUSTRY
In our days, the industrial development is achieved in correlation with
environmental factors, these representing an essential component of the industrial
competitiveness.
The compliance with the balance between the efficient capitalisation of the
material and human resources and the preservation of the environmental quality,
especially in the perspective of Romania’s integration in the European Union, is to
be found in all sector strategies for the industrial development.
The Romanian Industry is progressively adapting to the new models of the
consumption and production by:
 The use of technologies with low energetic and material consumption;
 The promotion of the renewable resources;
 The diminishing of the economic factors’ pressure upon the environment.
The environment management is an important instrument for the improvement of
the environment performance of the industrial activities, the implementation of
such a system supporting the global approach of the environment problems, the
economic relief of the impact upon the environment and the effectiveness of the
human and material effort in the process of complying with the regulations in the
environment protection field.
In 2002 was adopted by the Romanian Government the Order No. 34 regarding
IPPC and Best Available Techniques where the tanning industry is nominated too.
These regulations are not very well known by the factories technical personnel,
but they are the subject for some research projects which intend to disseminate
the documents and to apply best available techniques at least for some segments
of tanning process.
Regarding principal chapters in BAT the situation in Romanian tanneries is the
following:
Management and good housekeeping
 Good management in technologies choice, good maintenance and operation
control are applied;
 Trained personnel is available and have good skills on process control and
safety use and handling chemicals;
 Chemicals storage is conform with BAT recommendations;
 Measures to prevent accidental environment pollution are respected;
 Personnel protection measures against potentially harmful agents and
accidents are implemented;
 In this moment there are no possibilities for segregation of waste streams in
order to allow recycling.
Substitution of chemicals
 Romanian tanneries are using chemicals supplied by European companies
which have representatives and storehouses in Romania (only 5-10% of
chemicals are indigene);
 Parameters of environmental releases are monitorized by companies
themselves and by local authorities;
 Most of harmful chemicals are substituted by less dangerous ones, as BAT
recommend; especially in finishing are used polymeric aqueous emulsions with
low monomer content and solvent free products;
 Are not still substituted sulphide in unhairing/liming process and ammonium
deliming agents. (Only for research purposes have been made trials.)
Process-integrated BAT measures
In table 3 are presented BAT measures and Romanian situation for the principal process units
in a tannery [3].
BAT is:
ROMANIAN situation:
PROCESS
UNIT
B
E
A
M
H
O
U
S
E
Curing
and
soaking
●To process fresh hides as far as they are available
Exceptions:
- When long transport time is necessary (max 8 - 12 hours for fresh,
unchilled hides; 5 - 8 days if a cooling chain of 2°C is maintained)
- For certain types of end-products
- Sheepskins, calf skins
●To reduce the amount of salt used as far as possible.
●In Romania are processed only cured hides
/skins (especially salted);
●There are not available chilling systems for
transport or for storing raw hides and skins.
Unhairing
&
liming
●To use hair-save technology, but economics can be an issue for
existing plants when re-use of the saved hair is not possible
●To reduce sulphide consumption by the use of enzyme
preparations; not for sheepskins
●To recycle spent liquors only when processing sheepskins, which
are dewoolled by painting
●No hair-save technology is used in industrial
production;
●Sulphide is the most used for unhairing;
●Limited use of enzymes or other products
which allow a reduction of sulphide (max. 50%);
●No recycle of spent liquors.
Splitting
●To use lime splitting
Exceptions:
- When the starting material is wet blue
- When a firmer leather has to be produced (e.g. shoe-leather)
- When a more uniform and accurate thickness is needed in the final
product
●To maximise the use of split
●Very few equipments for lime splitting, so most
tanneries don’t use lime splitting;
●Bovine leather and splits are mostly processed
for shoe uppers (about 80%).
Table 3. BAT measures and Romanian situation for the principal process units in a tannery
BAT is:
ROMANIAN situation:
PROCESS UNIT
T
A
N
Y
A
R
D
O
P
E
R
A
TI
O
N
S
Deliming
and bating
●To make a partial substitution of ammonium salts with CO2 and/or
weak organic acids
●Partial substitution of ammonium salts was
experimented for research purposes, only
Sheepskin
degreasing
●To optimise wet degreasing using surfactants, with or without
organic solvents
●Closed machines with abatement for air and waste water releases
when organic solvents are used to degrease skins in dry state
●Yes
●Yes
Pickling
To use partial recycling or re-use of pickle liquors
●To use a volume of floats in the range of 50 – 60 % (based on
fleshed weight) for ovine skins and bovine hides in order to reduce
salt consumption
●Low volume of float is used, but no
recycle or re-use of pickling bath are applied.
Tanning
●To increase the efficiency of the chrome tanning process through
careful control of pH, float, temperature, time and drum speed, all in
combination with chrome recovery through precipitation for waste
water streams containing Crtotal > 1 g/l
●To use high-exhaustion tanning methods where chrome recovery is
not possible
●To maximise exhaustion of the vegetable tanning liquor with
counter-current (pit system) or recycling (drum tanning)
●Tanning process control (pH, float, time,
temperature, drum speed) is applied but no
chrome recovery (tanning spent floats are not
collected and treated separately);
●High-exhaustion tanning methods are
applied for research purposes;
●Vegetable tanning rarely applied, most
used chrome-vegetable process.
P
O
S
T
T
A
N
N
I
N
G
O
P
E
R
A
T
I
O
N
S
PROCESS
UNIT
BAT is:
Retanning,
chrome
fixation and
neutralisation
●To enhance exhaustion of post-tanning treatment agents and
fixation of tanning agents in the leather
●To reduce the salt content of spent liquors
Dyeing
To enhance exhaustion of dyestuffs
ROMANIAN situation:
●Yes
●In all post-tanning operations,
processes are carefully
controlled to enhance exhaustion
of chemicals used.
●Yes
Fatliquoring
●To enhance exhaustion of fatliquor
●Yes
Drying
●To optimise mechanical dewatering prior to drying where possible
●Mechanical dewatering
applied.
Applying a
surface
coat
●To use roller coating
●To use curtain coating
●To use HVLP spray guns
●To use airless spray guns
●Exception for all four above-mentioned techniques:
●When very thin finishes are applied, e.g. on aniline and aniline-type
leather
●Yes
●Not so often
●Yes
●Yes
●All finishing processes are using
water
based products. Antiex equipments for
solvent based finishing are not anymore
available.
WATER MANAGEMENT AND TREATMENT
 Water consumption in Romanian tanneries is higher (75 -100m3/1 t of
hides processed) because no recycling or re-use of liquors are applied.
 For Romanian tanneries one of the biggest problem is represented by
the waste waters; the treatment plants are old, with low efficiency and
the costs are high (a large percent being represented by taxes and
penalties).
 Another problem is the treatment which usually is made in two steps
(physical – mechanical and chemical) on total effluent; no biological
treatment is applied.
 For research purposes, have been used modern system for monitoring
water consumption and water’s characteristics (before and after
treatment); the treatment was applied separately on chrome containing
effluent.
 The treatment efficiency, obtained when have been applied polyelectrolyte on
the chrome tanning effluent was over 95%. (Figure 1 and Figure 2)
Figure 2
Figure 1
BOD BEFORE AND AFTER TREATMENT
CHROME (III) CONTENT IN WASTE WATERS
BEFORE AND AFTER TREATMENT
5
1.Tannery 1 before treatment
2.Tannery 1 after treatment
3.Tannery 2 before treatment
4.Tannery 2 after treatment
5.Value admitted by the Norm for discharge
4
3
2
1
1000
mg/dm3
6
mg/dm3
1200
LEGEND:
800
600
400
200
0
0
1
1
2
3
4
2
3
4
5
5
This treatment system was experimented (pilot level) by the Research
Institute and two tanneries successfully and one tannery is working to apply
it at industrial level. The investment effort it is significant and it’s very
difficult to be supported by only one company.
WASTE MANAGEMENT AND TREATMENT
“Landfill is not BAT, although, in some cases it is the only option
available”, is said in chapter 5.5 of BREF documents.
Now, in Romania it seems to be the only option available for tanning
and shoes companies too.
Although, before 1989 there were about 7 chemical stations for leather
wastes, now is functioning only the pilot station from Research Institute.
Leather companies are working together with Research Institute to turn to
life some of these stations or to make some new ones, because is also
expensive to landfill leather solid wastes.
The Leather and Footwear Research Institute, has a department
specialized in collagen - based products for cosmetic and human or
veterinary medicine use. The production is directed in this moment to
collagen hydrolysate for cosmetic and some medical sponges for burns
treatment.
In our research work there are also some projects as the followings:

Innovative technologies for useful protein components recovery and
reuse in industry and agriculture;

Recycling technology for leather industry’s protein wastes with
industrial applications;

Innovative process for obtaining composite materials from wastes of
leather industry;

Plant and technology for lime fleshings and trimmings valorisation in
a bovine tannery;

Modern techniques and BAT application in order to respect IPPC and
for effluent pollutant limitation, in a tannery;
ICPI is also associate partner in a Business Support PHARE project
“PERFECTLINK” which subject is the dissemination on the Acquis and all
other legislative and regulatory issues that have an impact on the
performance of companies from candidate countries; BREF documents,
have been also discussed and disseminated to Romanian leather companies.
CONCLUSIONS
 BAT principles and IPPC Directive need a higher dissemination
in Romanian SMEs, as to be known in each tannery, by each
leather technician;
 Continuation of the periodical organisation of actions for
information dissemination – the information of the economic
agents upon the new regulations;
 Solving ecological problems in tanning industry, needs technical
support and substantial investments, especially in modern plants
for waste waters treatment and solid wastes valorisation;
 It is a really demand for an European collective effort in:
 collecting information from each country or to update the
existing information and exchange experience between
different actors in this field of activity;
 R&D work to identify those BAT solutions which are not so
expensive and could be easily applied, even in a candidate
country as Romania.
REFERENCES:
1. *** Development Strategy for Leather and Shoe Industry, on
Medium and Long Term, 2003
2. Mirciu Vasile - Romanian Light Industry (Textile, Clothes and
Leather – Shoes Industry) – Present and Perspectives; Industrial
Policies, paper presented in PERFECTLINK Romanian National
Event
3. European Commission – Integrated Pollution Prevention and
Control (IPPC); Reference Document on Best Available Techniques
for the Tanning of Hides and Skins, 2003