3rd Technical & Progress Meeting
INESCOP
PROJECT PROGRESS
AND PLANNED
ACTIVITIES
LIFE 10 ENV/IT/364
Elda (Alicante)
INESCOP
13rd June 2013
Mercedes Roig
Joaquín Ferrer
INESCOP
1
INESCOP Project Progress (Jun-Dec’12)
ACTION
STATUS
Action 2. Study on the fatliquoring agents environmental impact
Completed
Action 4. Environmental demonstration of natural products at
laboratory level
Completed
Action 5. Fatliquoring at a semi-industrial level with natural products
In progress
Action 6. Environmental demonstration at pre-industrial level
In progress
Action 9. Quality assessment of leather products production
In progress
Action 13. Training course for Spanish tanneries
In progress
Action 19. Dissemination in fairs and other events
Continuous
Action 21. Contribution to the updating of the project website
Continuous
Action 23. Project management
Continuous
2
Action 2. Environmental impact of fatliquoring agents
Objective:
To assess the environmental impact of fatliquoring agents
Tasks:
– Selection of leather fatliquoring product families
– Definition of parameters to be analysed
– Preparation of leathers
– Laboratory, semi-industrial and industrial scale tests
– Analysis of fatliquoring products
– Characterization of fatliquoring residual baths
– Leather analysis: physical-chemical tests / organoleptic properties
3
Fatliquoring agents
1. Selecting the fatliquoring products
2. Parameters to be assessed
Fatliquoring
products
Arsenic
Cadmium
Lead
Residual
baths
pH
Conductivity
COD - BOD
Biodegradability
Chromium III
Oils & Fats
Fatliquored
leather
Fat in leather
Chromium VI
Physical tests
3. Leather fatliquoring tests
Laboratory
Semi-industrial
Pre-industrial
4
Working procedure for leather fatliquoring
4. Process performed for leather fatliquoring:
PRODUCT/PROCESS
% by wet-blue weight
Water (45-50 ºC)
500 %
Fatliquoring product
8 % (*)
Rotate for 90 min
Formic acid (1:10 dilution)
3%
Rotate for 20 min
Wash, drain drum, take bath sample and remove leather
Air dry
* Compensated for each commercial fat in order to ensure the same amount of fat added
5
Fatliquored leather: organoleptic properties
Feel: good degree of softening
Colour: different shades but acceptable
Firmness: adequate firmness of the leather
There are no relevant differences in the appearance of the leathers
depending on the type of fatliquoring agent used
6
Wastewater: conclusions
•
The polluting load of all baths was quite similar
•
Results at pre-industrial scale tests are always better probably due
to a better fixation of the products thanks to the greater
mechanical effect in the bigger tanning drums
•
None of the families assessed stand out for their lower
environmental impact on wastewater in all the parameters
7
Wastewater: reference values
Laboratory test
pH
Conductivity
(µs/cm)
COD
(mg/l)
BOD
(mg/l)
Total Cr
(mg/l)
Oils & Fats
(mg/l)
Minimum
3,54
1.900
12.700
2.570
0,17
0,7
65
Maximum
3,98
5.000
18.300
8.850
0,59
5,4
2380
Average
3,81
2.750
15.360
6.291
0,41
3,0
991,5
pH
Conductivity
(µs/cm)
COD
(mg/l)
BOD
(mg/l)
Total Cr
(mg/l)
Oils & Fats
(mg/l)
Minimum
3,42
1.100
8.200
1.310
0,11
0,4
27
Maximum
3,76
3.900
17.100
5.130
0,48
4,0
980
Average
3,66
2.130
12.000
3.611
0,31
2,2
348,4
pH
Conductivity
(µs/cm)
COD
(mg/l)
BOD
(mg/l)
Total Cr
(mg/l)
Oils & Fats
(mg/l)
Minimum
3,37
800
7.500
1.130
0,10
0,9
31
Maximum
3,71
3.700
16.700
4.192
0,48
3,5
684
Average
3,56
1.982
11.500
2.844
0,27
2,0
230
Biodegradability
Semi-industrial test
Biodegradability
Pre-industrial test
Biodegradability
8
Fatliquored leathers conclusions
•
There are some differences in the laboratory, semi-industrial and
pre-industrial tests results due to better mechanical effect, but
not so significant as those mentioned for wastewater parameters
•
Oxidised lecithin, Phosphoric ester, Sulphited fish oil, Sulphited
olein and Sulphated olein are the fatliquoring agents showing a
higher Cr(VI) formation after aging
•
All physical properties tested are above recommended thresholds
for their use in shoe uppers, leather goods, upholstery and
garments
•
None of the families assessed stand out for their better quality in
all the parameters
9
Fatliquored leather: reference values
Laboratory test
Tear strength
(N)
Tensile strength
(N/mm2)
Elongation at
break (%)
Matter soluble in
Cl2CH2 (% m.s.)
Chromium (VI)
(mg/kg)
Minimum
132
15,2
59,9
1,6
7,8
Maximum
211
19
84,6
8
22
Average
155,6
16,95
72,32
4,42
14,3
Tear strength
(N)
Tensile strength
(N/mm2)
Elongation at
break (%)
Minimum
55
15,2
67,8
0,9
6,7
Maximum
314
18,9
103,1
4
20,4
Average
211,8
17,39
85,92
2,67
12,97
Tear strength
(N)
Tensile strength
(N/mm2)
Elongation at
break (%)
Minimum
67
15,4
67
0,8
4,1
Maximum
343
20,4
93
3,5
17,8
Average
229,9
18,08
82,5
2,37
10,7
Semi-industrial test
Matter soluble in
Cl2CH2 (% m.s.)
Chromium (VI)
(mg/kg)
Pre-industrial-test
Matter soluble in
Cl2CH2 (% m.s.)
Chromium (VI)
(mg/kg)
10
Action 4-6. Environmental demonstration of natural products
Objective:
To assess the environmental impact of natural fatliquoring products
and compare with the results obtained with commercial products (action 2)
Tasks:
– Laboratory, semi-industrial and pre-industrial scale fatliquoring tests
– Characterization of natural fatliquoring products
– Characterization of fatliquoring residual baths
– Analysis on leather
11
Characterization of natural fatliquoring products
Determining the levels of arsenic, cadmium, and lead contained in the
products, in order to prevent these substances from being present in
leather in accordance with the criteria of the European Eco-label for
footwear (Decision 2009/563/EC).
Arsenic: < 60 ppm *
Cadmium: < 6 ppm *
Lead: < 8 ppm*
* Limit of detection of the analysis technique employed
12
Characterization of fatliquoring residual baths
pH
Conductivity
(µs/cm)
COD
(mg O2/l)
BOD5
(mg O2/l)
Biodegradability
(BOD5 / COD)
1-10 Fatliquoring product families’ average
3.8
2,750
15,360
6,290
0.41
CLP
Chlorinated paraffin
(44 % Cl)
3.3
6,500
12,600
5,540
0.44
FAME
Chlorinated vegetable fatty
acid methyl ester
(48.6 % Cl)
3.2
5,100
12,800
7,170
0.56
CLP_S
Sulpho-chlorinated paraffin
(44 % Cl)
2.4
12,100
10,300
4,225
0.41
FAME_S
Sulpho-chlorinated vegetable
fatty acid methyl este
(38 % Cl- 8.6 % S)
2.4
10,200
5,440
2,990
0.55
Reference
Calf hides
13
Characterization of fatliquoring residual baths
pH
Conductivity
(µs/cm)
COD
(mg O2/l)
BOD5
(mg O2/l)
Biodegradability
(BOD5 / COD)
1-10 Fatliquoring product families’ average
3.8
2,750
15,360
6,290
0.41
CLP
Chlorinated paraffin
(44 % Cl)
3.7
8,350
1,800
968
0.54
FAME
Chlorinated vegetable fatty
acid methyl ester
(48.6 % Cl)
3.6
7,670
1,681
723
0.43
CLP_S
Sulpho-chlorinated paraffin
(44 % Cl)
3.4
10,300
1,345
403
0.30
FAME_S
Sulpho-chlorinated vegetable
fatty acid methyl este
(38 % Cl- 8.6 % S)
3.4
9,700
940
435
0.46
Reference
Sheep Skins
14
Organoleptic test
Touch and softness
Reference
1-10 Fatliquoring product families’ average
Calf hides
Touch (1-5)
Sheep skins
Touch (1-5)
4
4
CLP
Chlorinated paraffin
(44 % Cl)
5
5
FAME
Chlorinated vegetable fatty acid methyl ester
(48.6 % Cl)
5
5
CLP_S
Sulpho-chlorinated paraffin
(44 % Cl)
5
5
FAME_S
Sulpho-chlorinated vegetable fatty acid
methyl ester (38 % Cl- 8.6 % S)
5
5
Adequate levels of firmness
No significant differences in colour
15
Physical resistance tests
Tear
strength
(N)
Reference
1-10 Fatliquoring product families’ average
Tensile
strength
(N/mm2)
Elongation
at break
(%)
156
17
72
Chlorinated paraffin
(44 % Cl)
85
10.7
49.3
FAME
Chlorinated vegetable fatty acid
ethyl ester (48.6 % Cl)
119
20.3
66
CLP_S
Sulpho-chlorinated paraffin
(44 % Cl)
331
25.4
85.3
Sulpho-chlorinated vegetable fatty
acid methyl ester (38 % Cl- 8.6 % S)
214
21.4
78.9
>150
>15
>40
CLP
FAME_S
Recommended values
Calf hides
16
Physical resistance tests
Tear
strength
(N)
Tensile
strength
(N/mm2)
Elongation
at break
(%)
156
17
72
Chlorinated paraffin
(44 % Cl)
63
10.7
58.1
FAME
Chlorinated vegetable fatty acid
ethyl ester (48.6 % Cl)
89
20.3
77.6
CLP_S
Sulpho-chlorinated paraffin
(44 % Cl)
123
16.2
69.2
Sulpho-chlorinated vegetable fatty
acid methyl ester (38 % Cl- 8.6 % S)
119
17.6
65.6
>50
>15
>40
Reference
1-10 Fatliquoring product families’ average
CLP
FAME_S
Recommended values
Sheep skins
17
Chemical resistance tests
Matter soluble
in Cl2CH2
(% m.s.)
Chromium(VI)
(mg/kg)
4.4
14.3
Chlorinated paraffin
(44 % Cl)
8.6
2.6
FAME
Chlorinated vegetable fatty acid methyl ester
(48.6 % Cl)
7.7
2
CLP_S
Sulpho-chlorinated paraffin
(44 % Cl)
10.1
2.3
Sulpho-chlorinated vegetable fatty acid methyl
ester (38 % Cl- 8.6 % S)
10.1
1.8
<3
<3
Reference
CLP
FAME_S
Recommended values
Calf hides
18
Chemical resistance tests
Matter soluble
in Cl2CH2
(% m.s.)
Chromium(VI)
(mg/kg)
4.4
14.3
Chlorinated paraffin
(44 % Cl)
6.3
<3
FAME
Chlorinated vegetable fatty acid methyl ester
(48.6 % Cl)
7.5
<3
CLP_S
Sulpho-chlorinated paraffin
(44 % Cl)
4.1
<3
Sulpho-chlorinated vegetable fatty acid methyl
ester (38 % Cl- 8.6 % S)
3.7
<3
<3
<3
Reference
CLP
FAME_S
Recommended values
Sheep skins
19
Conclusions
• Leathers have an acceptable appearance, full and firm, with a soft
and pleasant feel and no significant differences were observed in the
addition of the different natural fatliquoring tested.
• Natural fatliquoring products showed were less than the Arsenic,
Cadmium and Lead limits
• The biodegradability of the FAME fatliquoring bath samples (based
of fatty acid methyl esters) improves by 5 - 36% with respect to the
average value of the assessed fatliquoring products (1-10 product
families).
20
Conclusions
• Regarding the touch of the leathers tested, this was graded on the
level of softness obtained
• In reference to the firmness of the leather, all of the natural
fatliquors that were tested, none produced leather with loose grain
characteristics
• Regarding colour, differences in final leather colour tone were
observed upon the use of the various natural fatliquors, but no
significant differences were present.
• Finally, the determinations of physical and chemical parameters of
the leathers have shown to be compliant with the limits required for
footwear manufacture.
21
INESCOP’s Newsletters
• INESCOP Environment Newsletter Jan’12
• INESCOP Environment Newsletter Feb’12
• INESCOP Environment Newsletter April’12
• INESCOP Environment Newsletter Jun’12
• INESCOP Environment Newsletter Jul’12
• INESCOP News Jun’12
• INESCOP Environment Newsletter Dec’12
22
INESCOP’s dissemination at Congresses
• Conference in Green Week 2012, Brussels (Belgium)
• 1st Water, Waste and Energy Management Congress, Salamanca
(Spain)
• Industrial Technologies Congress 2012, Aarhus (Denmark)
• 18th Congress of the Latin American Federation of Leather
Technologists and Chemists (FLAQTIC 2012), Montevideo (Uruguay)
• 62nd Congress of the Spanish Leather Chemists Association
(AQEIC 2013), Lorca – Murcia (Spain)
• LIFE+ Networking Event, Valencia (Spain)
62nd AQEIC Congress
May 2013
Lorca - Murcia - Spain
23
International conferences and fairs
• 21st Edition of ECOFIRA 2012, International Fair of Environmental
Solutions. Valencia (Spain)
• 12th Edition of Green Week, Brussels (Belgium)
• 28th Edition of the International Footwear Fair, FUTURMODA,
Alicante, (Spain)
• 29th Edition of the International Footwear Fair, FUTURMODA,
Alicante (Spain)
XXIX Edition Futurmoda Fair
April de 2013
Alicante (Spain)
24
Updating the project website
25
INESCOP´s next steps
ACTION
Action 4. Environmental demonstration of natural products at lab level
Action 5. Fatliquoring at a semi-industrial level with natural products.
Action 6. Environmental demonstration at pre-industrial level
Action 7. Environmental demonstration of hides fatted with natural products
Action 8. Study of the demonstration about the environmental benefits from the natural
products fatting products
Action 9. Quality assessment of leather products
Action 16. Training course for Spanish tanneries
Action 20. Digital supports for international diffusion (video)
Dissemination (fairs, press releases, conferences, etc.)
Contribution to updating of the project website
26
Thanks for your attention
27