1 1 3rd technical & progress meeting inescop project progress and planned activities elda...
TRANSCRIPT
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3rd Technical & Progress Meeting
INESCOP PROJECT PROGRESS
AND PLANNED ACTIVITIES
Elda (Alicante)INESCOP13rd June 2013
Mercedes RoigJoaquín FerrerINESCOP
LIFE 10 ENV/IT/364
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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
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Action 2. Environmental impact of fatliquoring agents
Objective: To assess the environmental impact of fatliquoring agentsTasks:
– 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
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1. Selecting the fatliquoring products
Fatliquoring agents
Fat in leatherChromium VIPhysical tests
Fatliquoring products
ArsenicCadmiumLead
Fatliquored leather
Residual baths
pHConductivityCOD - BOD
BiodegradabilityChromium IIIOils & Fats
2. Parameters to be assessed
Semi-industrial Pre-industrialLaboratory
3. Leather fatliquoring tests
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Working procedure 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 leatherAir dry
4. Process performed for leather fatliquoring:
* Compensated for each commercial fat in order to ensure the same amount of fat added
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Fatliquored leather: organoleptic properties
Feel: good degree of softeningFeel: good degree of softening
Colour: different shades but acceptableColour: different shades but acceptable
Firmness: adequate firmness of the leatherFirmness: adequate firmness of the leather
There are no relevant differences in the appearance of the leathers depending on the type of fatliquoring agent used
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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
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Wastewater: reference values Laboratory test
pHConductivity
(µs/cm)COD
(mg/l)BOD
(mg/l) BiodegradabilityTotal 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
Semi-industrial test
pHConductivity
(µs/cm)COD
(mg/l)BOD
(mg/l) BiodegradabilityTotal 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
Pre-industrial test
pHConductivity
(µs/cm)COD
(mg/l)BOD
(mg/l) BiodegradabilityTotal 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
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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
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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
Semi-industrial test
Tear strength (N)
Tensile strength (N/mm2)
Elongation at break (%)
Matter soluble in Cl2CH2 (%
m.s.)
Chromium (VI)
(mg/kg)
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
Pre-industrial-test
Tear strength (N)
Tensile strength (N/mm2)
Elongation at break (%)
Matter soluble in Cl2CH2 (%
m.s.)
Chromium (VI)
(mg/kg)
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
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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
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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
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Characterization of fatliquoring residual baths
Reference pHConductivity
(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
CLPChlorinated paraffin (44 % Cl)
3.3 6,500 12,600 5,540 0.44
FAMEChlorinated vegetable fattyacid methyl ester(48.6 % Cl)
3.2 5,100 12,800 7,170 0.56
CLP_SSulpho-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
Calf hides
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Characterization of fatliquoring residual baths
Reference pHConductivity
(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
CLPChlorinated paraffin (44 % Cl)
3.7 8,350 1,800 968 0.54
FAMEChlorinated vegetable fattyacid methyl ester(48.6 % Cl)
3.6 7,670 1,681 723 0.43
CLP_SSulpho-chlorinated paraffin (44 % Cl)
3.4 10,300 1,345 403 0.30
FAME_S
Sulpho-chlorinated vegetablefatty acid methyl este(38 % Cl- 8.6 % S)
3.4 9,700 940 435 0.46
Sheep Skins
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Organoleptic test
ReferenceCalf hides
Touch (1-5)Sheep skinsTouch (1-5)
1-10 Fatliquoring product families’ average 4 4
CLPChlorinated paraffin (44 % Cl)
5 5
FAMEChlorinated vegetable fatty acid methyl
ester(48.6 % Cl)
5 5
CLP_SSulpho-chlorinated paraffin (44 % Cl)
5 5
FAME_SSulpho-chlorinated vegetable fatty acidmethyl ester (38 % Cl- 8.6 % S)
5 5
Touch and softness
Adequate levels of firmness
No significant differences in
colour
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Physical resistance tests
Reference
Tear strengt
h(N)
Tensile strengt
h(N/mm2)
Elongation at
break(%)
1-10 Fatliquoring product families’ average 156 17 72
CLPChlorinated paraffin (44 % Cl)
85 10.7 49.3
FAMEChlorinated vegetable fatty acid ethyl ester (48.6 % Cl)
119 20.3 66
CLP_SSulpho-chlorinated paraffin (44 % Cl)
331 25.4 85.3
FAME_S
Sulpho-chlorinated vegetable fatty
acid methyl ester (38 % Cl- 8.6 % S)
214 21.4 78.9
Recommended values >150 >15 >40Calf hides
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Physical resistance tests
ReferenceTear
strength(N)
Tensile strength(N/mm2)
Elongation at break
(%)
1-10 Fatliquoring product families’ average 156 17 72
CLPChlorinated paraffin (44 % Cl)
63 10.7 58.1
FAMEChlorinated vegetable fatty acid ethyl ester (48.6 % Cl)
89 20.3 77.6
CLP_SSulpho-chlorinated paraffin (44 % Cl)
123 16.2 69.2
FAME_S
Sulpho-chlorinated vegetable fatty acid methyl ester (38 % Cl- 8.6 % S)
119 17.6 65.6
Recommended values >50 >15 >40Sheep skins
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Reference
Matter soluble
in Cl2CH2
(% m.s.)
Chromium(VI)
(mg/kg)
4.4 14.3
CLPChlorinated paraffin (44 % Cl)
8.6 2.6
FAMEChlorinated vegetable fatty acid methyl
ester(48.6 % Cl)
7.7 2
CLP_SSulpho-chlorinated paraffin (44 % Cl)
10.1 2.3
FAME_SSulpho-chlorinated vegetable fatty acid
methylester (38 % Cl- 8.6 % S)
10.1 1.8
Recommended values <3 < 3
Chemical resistance tests
Calf hides
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Reference
Matter soluble in Cl2CH2
(% m.s.)
Chromium(VI)
(mg/kg)
4.4 14.3
CLPChlorinated paraffin (44 % Cl)
6.3 <3
FAMEChlorinated vegetable fatty acid methyl ester(48.6 % Cl)
7.5 <3
CLP_SSulpho-chlorinated paraffin (44 % Cl)
4.1 <3
FAME_SSulpho-chlorinated vegetable fatty acid methylester (38 % Cl- 8.6 % S)
3.7 <3
Recommended values <3 < 3
Chemical resistance tests
Sheep skins
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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).
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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.
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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
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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 CongressMay 2013
Lorca - Murcia - Spain
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International conferences and fairs
XXIX Edition Futurmoda FairApril de 2013
Alicante (Spain)
• 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)
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Updating the project website
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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
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Thanks for your attention