11

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

5

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

8

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