Alice Dall ’ Ara – ENEA Sergio Sangiorgi - ENEA

1. ECOFATTING Use of Environmentally friendly natural products instead of chloroparaffines in the fatting phase of the tanning cycle ENEA activities months 18-24 Alice Dall’Ara – ENEA Sergio Sangiorgi - ENEA Italian National Agency for New Technologies, Energy and Sustainable Economic Development UTTMATF Research Laboratories Faenza (Ra, Italy) LIFE10 ENV/IT/364 Ecofatting 24 Month Meeting Pisa, December 11th, 2013

2. ENEA Project Progress July-November 2013

3. Action10 Demonstration of technical-economic viability 1. Market Analysis of the tannery sector 2. Law indications and constrains 3. Technical viability 4. Environmental viability 5. Economical viability Expected results - Proof of quality and economic viability

4. Action10 Demonstration of technical-economic viability • Market Analysis: Analysis of the leather Industry, with special focus on the Italian and Spanish market The World and European leather trade Market of the Italian Tannery Industry Market of the Spanish Tannery Industry Characterization of the products used in the fatting phase of the leather tanning cycle Most common Fat Liquoring agents Oils and virgin fats Sulfated products Sulphited products Phosphated products Chloroparaffins

5. Action10 Demonstration of technical-economic viability 2. Law indications and costrains: Chlorinatedparaffins and Sulfochlorinatedparaffins Regulation 1907/06/CE (REACH) Chlorinatedparaffins (C10-13 SCCP included in Annex XIV (LIST OF SUBSTANCES SUBJECT TO AUTHORISATION) SCCP (Short Chain Chlorinated PARAFFIN) are very persistent and bioaccumulable p. 42 Annex XVII RESTRICTIONS ON THE MANUFACTURE, PLACING ON THE MARKET AND USE OF CERTAIN DANGEROUS SUBSTANCES, PREPARATIONS AND ARTICLES Alkanes, C10-C13, chloro (short-chain chlorinated paraffins): Shall not be placed on the market for use as substances or as constituents of other substances or preparations in concentrations higher than 1 %: - for fat liquoring of leather F.A.M.E. (Fatty Acid methyl Esther) sono esteri metilici di origine lipidica. Ai sensi del Reg. 1907/2006 non costituiscono una miscela. Come tutte le sostanze chimiche devono essere registrate all’ECHA.

6. Action10 Demonstration of technical-economic viability 3.Technical viability: quality proof Chloroparaffins and sulfur- chloroparaffins CLOPARIN 44F and CLOPARTEN Z as bench mark (why Action 2) The following natural based substrates were considered in PARAFFIN backbone substitution: A ) METHYL STEARATE B ) FATTY ACID METHYL ESTERS (SATURATED) MIXTURE C) FATTY ACID CHLORIDES MIXTURE D) PALMKERNEL OIL FATTY ACID METHYL ESTERS

7. Action10 Demonstration of technical-economic viability 3. Technical viability: starting points : - No variation in operation conditions and use - No variation in output quality Consequences: Changes on product production Changes in waste/discharge reduction of cost is i.e due only to formulate cost and or initial cost (NB no difference in use)

8. Action10 Demonstration of technical-economic viability Technical viability: quality proof Case A (B) Final Compound for fattening Reference for technical viability and then economic viability

9. Action10 Demonstration of technical-economic viability Technical viability: quality proof Case C Final Compound for fattening Reference for technical viability and then economic viability

10. Action10 Demonstration of technical-economic viability 3. Technical viability – quality proof FACL Gli ingrassi pronti all’uso formulati Con oli clururati al 44% Cl - Good shelf life (IMPROVED) - Buone proprietà di dispersione - Buona stabilità nell’applicazione - Si ottengono bene, gli articoli Desiderati FATTENING • FASCL Comportamento degli ingrassi • formulati usando oli solfoclorurati • - Emulsioni stabili • Buona capacità di ottenere l’articolo desiderato FATTENING

11. Action10 Demonstration of technical-economic viability Technical viabilityConclusion Più simili sono le caratteristiche chimiche dei nuovi prodotti (in termini di lunghezza di catena e di contenuto in Zolfo e Cloro), più simili sono le caratteristiche degli articoli con essi prodotti. I nuovi composti sia clorurati che solfoclorurati possono essere facilmente impiegati per produrre ingrassi di uso comune. I nuovi prodotti clorurati e solfoclorurati non richiedono particolari processi applicativi e possono sostituire in pieno le corrispondenti paraffine.

12. Action10 5. Economical viability Cost evaluation for natural fatting agents: Price* for CLOPARIN 44F: 1,05 €/kg Price* for CLOPARTEN Z: 1,35 €/kg * (data from COLORTEX) Price for C14 C17 paraffin: 1,31 €/kg Price for natural raw material #: 1,42 €/kg #(data from GAMMA CHIMICA for Palmere M1218 PK) Estimated final price for new tanning agents from natural source: CHLORIN. PALM KERNEL FAME: 1,12 €/kg SULFO CHLORIN. PALM KERNEL FAME: 1,23 €/kg * (data from SERICHIM)

13. Action10 Demonstration of technical-economic viability Economical viability All data are referred to % ton leather Case C All data are referred to 1 ton leather Final Compound for fattening Reference for technical viability and then economic viability

14. Project LIFE10 ENV/IT/364 New costs evaluation : FAME mixtures obtained from DeACIDO technology have an industrial price of 0,90-1,00 €/kg. Using this alternative raw material, estimated final price for new tanning agents from natural source are: CHLORIN. FAME from ACID FATS: 0,91 €/kg SULFO CHLORIN. FAME from ACID FATS : 1,02 €/kg Price* for CLOPARIN 44F: 1,05 €/kg Price* for CLOPARTEN Z: 1,35 €/kg * (data from COLORTEX)

15. Action 2 Demonstration of technical-economic viability Market Analysis Sampling About 0.5 liter of bating floats were collected at bating phase before discharge, Samples of chromium tanned leather (CL) treated with PM and standard formulation respectivetely Measurement methods On bating float samples volatile compounds were monitored with 2 different methods of enrichment/extraction before CGMS analysis: purge & trapp for preliminary bating tests and head space for second generation poultry manure tests (DPM, technical product suitable for bating). Head space CGMS analysis was also performed on CL samples treated with PM and standard formulation in the maceration step. A few grams of wet CL samples were placed in a 10 mL vial (60°C for 1800 s). 15

16. Thank you for your attention alice.dallara@enea.it www.pi.iccom.cnr.it/ecofatting/it Torviscosa, January 24th, 2013

17. ENEA Action involved SAMPLES: TANNED LEATHER “FAME IND”: bovine leather, Chrome tanned, treated with chloromethylstearate (leather, FAME-IND) as fatliquoring agent “CP44”: bovine leather, Chrome tanned, treated with chlorinated paraffins (CP44 ) as fatliquoring agent “FAME NAT”: bovine leather, Chrome tanned, treated with chloromethyl-stearate (FAME-NAT) as fatliquoring product “CP44”: bovine leather, Chrome tanned, treated with chlorinated paraffins (CP44 – R2) as fatliquoring product Torviscosa, January 24th, 2013

18. Preliminary SEM-EDS characterization(Scanning Electron Microscopy – X-rays Energy Dispersive Spectroscopy) Backscattered images aquiredatdifferentmagnifications: 50X, 100X, 200X, 500X, 1000X. Morphologicalanalysis As-received samples were characterized in partial vacuum condition (VP-SEM). Examinations on samples surface X-Raysmicroanalysis: • qualitative: EDS spectra • semi-quantitative: elementalcomposition Compositionalanalysis Torviscosa, January 24th, 2013

19. Leather Morphological analysis • NAT. SAMPLES: comparison between treatment with • FAME NAT. and CP44 - As samples IND., surfaces of NAT samples are similar at low magnification, but more fibers are present on the CP44 surface. Surface of FAME IND. is very similar to FAME NAT. any morphologic difference were observed.

20. Leather Morphological analysis • IND. SAMPLES: comparison between treatment with • FAME IND. and CP44 100 X 1000 X At low magnification, pores are present on both surfaces. At high magnification, more fibers are visible on CP44 surface.