1 1 3rd Technical & Progress Meeting INESCOP PROJECT PROGRESS AND PLANNED ACTIVITIES Elda (Alicante) INESCOP 13rd June 2013 Mercedes Roig Joaquín Ferrer INESCOP LIFE 10 ENV/IT/364

2 2 INESCOP Project Progress (Jun-Dec’12) ACTIONSTATUS 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 productionIn progress Action 13. Training course for Spanish tanneriesIn progress Action 19. Dissemination in fairs and other eventsContinuous Action 21. Contribution to the updating of the project websiteContinuous Action 23. Project managementContinuous

3 3 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

Selecting the fatliquoring products Fatliquoring agents Fat in leather Chromium VI Physical tests Fatliquoring products Arsenic Cadmium Lead Fatliquored leather Residual baths pH Conductivity COD - BOD Biodegradability Chromium III Oils & Fats 2. Parameters to be assessed Semi-industrial Pre-industrial Laboratory 3. Leather fatliquoring tests

5 Working procedure for leather fatliquoring PRODUCT/PROCESS% by wet-blue weight Water (45-50 ºC)500 % Fatliquoring product8 % (*) 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 4. Process performed for leather fatliquoring: * Compensated for each commercial fat in order to ensure the same amount of fat added

6 6 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

7 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 pH Conductivity (µs/cm) COD (mg/l) BOD (mg/l)Biodegradability Total Cr (mg/l) Oils & Fats (mg/l) Minimum3, ,170,765 Maximum3, ,595,42380 Average3, ,413,0991,5 Semi-industrial test pH Conductivity (µs/cm) COD (mg/l) BOD (mg/l)Biodegradability Total Cr (mg/l) Oils & Fats (mg/l) Minimum3, ,110,427 Maximum3, ,484,0980 Average3, ,312,2348,4 Pre-industrial test pH Conductivity (µs/cm) COD (mg/l) BOD (mg/l)Biodegradability Total Cr (mg/l) Oils & Fats (mg/l) Minimum3, ,100,931 Maximum3, ,483,5684 Average3, ,272,0230

9 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

10 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) Minimum13215,259,91,67,8 Maximum ,6822 Average155,616,9572,324,4214,3 Semi-industrial test Tear strength (N) Tensile strength (N/mm2) Elongation at break (%) Matter soluble in Cl2CH2 (% m.s.) Chromium (VI) (mg/kg) Minimum5515,267,80,96,7 Maximum31418,9103,1420,4 Average211,817,3985,922,6712,97 Pre-industrial-test Tear strength (N) Tensile strength (N/mm2) Elongation at break (%) Matter soluble in Cl2CH2 (% m.s.) Chromium (VI) (mg/kg) Minimum6715,4670,84,1 Maximum34320,4933,517,8 Average229,918,0882,52,3710,7

11 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

12 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

13 Characterization of fatliquoring residual baths ReferencepH Conductivity (µs/cm) COD (mg O 2 /l) BOD 5 (mg O 2 /l) Biodegradability (BOD 5 / COD) 1-10 Fatliquoring product families’ average3.82,75015,3606, CLP Chlorinated paraffin (44 % Cl) 3.36,50012,6005, FAME Chlorinated vegetable fatty acid methyl ester (48.6 % Cl) 3.25,10012,8007, CLP_S Sulpho-chlorinated paraffin (44 % Cl) 2.412,10010,3004, FAME_S Sulpho-chlorinated vegetable fatty acid methyl este (38 % Cl- 8.6 % S) 2.410,2005,4402, Calf hides

14 Characterization of fatliquoring residual baths ReferencepH Conductivity (µs/cm) COD (mg O 2 /l) BOD 5 (mg O 2 /l) Biodegradability (BOD 5 / COD) 1-10 Fatliquoring product families’ average3.82,75015,3606, CLP Chlorinated paraffin (44 % Cl) 3.78,3501, FAME Chlorinated vegetable fatty acid methyl ester (48.6 % Cl) 3.67,6701, CLP_S Sulpho-chlorinated paraffin (44 % Cl) 3.410,3001, FAME_S Sulpho-chlorinated vegetable fatty acid methyl este (38 % Cl- 8.6 % S) 3.49, Sheep Skins

15 Organoleptic test Reference Calf hides Touch (1-5) Sheep skins Touch (1-5) 1-10 Fatliquoring product families’ average44 CLP Chlorinated paraffin (44 % Cl) 55 FAME Chlorinated vegetable fatty acid methyl ester (48.6 % Cl) 55 CLP_S Sulpho-chlorinated paraffin (44 % Cl) 55 FAME_S Sulpho-chlorinated vegetable fatty acid methyl ester (38 % Cl- 8.6 % S) 55 Touch and softness Adequate levels of firmness No significant differences in colour

16 Physical resistance tests Reference Tear strength (N) Tensile strength (N/mm 2 ) Elongation at break (%) 1-10 Fatliquoring product families’ average CLP Chlorinated paraffin (44 % Cl) FAME Chlorinated vegetable fatty acid ethyl ester (48.6 % Cl) CLP_S Sulpho-chlorinated paraffin (44 % Cl) FAME_S Sulpho-chlorinated vegetable fatty acid methyl ester (38 % Cl- 8.6 % S) Recommended values>150>15>40 Calf hides

17 Physical resistance tests Reference Tear strength (N) Tensile strength (N/mm 2 ) Elongation at break (%) 1-10 Fatliquoring product families’ average CLP Chlorinated paraffin (44 % Cl) FAME Chlorinated vegetable fatty acid ethyl ester (48.6 % Cl) CLP_S Sulpho-chlorinated paraffin (44 % Cl) FAME_S Sulpho-chlorinated vegetable fatty acid methyl ester (38 % Cl- 8.6 % S) Recommended values>50>15>40 Sheep skins

18 Reference Matter soluble in Cl 2 CH 2 (% m.s.) Chromium(VI) (mg/kg) CLP Chlorinated paraffin (44 % Cl) FAME Chlorinated vegetable fatty acid methyl ester (48.6 % Cl) 7.72 CLP_S Sulpho-chlorinated paraffin (44 % Cl) FAME_S Sulpho-chlorinated vegetable fatty acid methyl ester (38 % Cl- 8.6 % S) Recommended values<3 Chemical resistance tests Calf hides

19 Reference Matter soluble in Cl 2 CH 2 (% m.s.) Chromium(VI) (mg/kg) CLP 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 FAME_S Sulpho-chlorinated vegetable fatty acid methyl ester (38 % Cl- 8.6 % S) 3.7<3 Recommended values<3 Chemical resistance tests Sheep skins

20 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 % with respect to the average value of the assessed fatliquoring products (1-10 product families).

21 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.

22 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

23 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

24 International conferences and fairs XXIX Edition Futurmoda Fair April 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)

25 Updating the project website

26 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

27 Thanks for your attention