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1 ECOFATTING Use of Environmentally friendly natural products instead of chloroparaffines in the fatting phase of the tanning cycle Alice Dall’Ara – ENEA.

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Presentation on theme: "1 ECOFATTING Use of Environmentally friendly natural products instead of chloroparaffines in the fatting phase of the tanning cycle Alice Dall’Ara – ENEA."— Presentation transcript:

1 1 ECOFATTING Use of Environmentally friendly natural products instead of chloroparaffines in the fatting phase of the tanning cycle 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 ENEA activities months 18-24

2 2 ACTIONS A 6. Environmental demonstration of natural products fatting at a pre-industrial level A 8. Study of the demonstration about the environmental benefits from the natural products fatting process A 10. Demonstration of technical-economic viability A 11. Natural products fatting manual Dissemination Actions ENEA Project Progress July-November 2013

3 3 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 Action 10 Demonstration of technical-economic viability

4 4 1.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 Action 10 Demonstration of technical-economic viability

5 5 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. Action 10 Demonstration of technical-economic viability

6 6 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 Action 10 Demonstration of technical-economic viability

7 7 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) Action 10 Demonstration of technical-economic viability

8 8 Action 10 Demonstration of technical-economic viability Technical viability: quality proof Final Compound for fattening Reference for technical viability and then economic viability Case A (B)

9 9 Action 10 Demonstration of technical-economic viability Technical viability: quality proof Final Compound for fattening Reference for technical viability and then economic viability Case C

10 10 3. Technical viability – quality proof Action 10 Demonstration of technical-economic viability 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 11 Technical viability Conclusion 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. Demonstration of technical-economic viability Action 10

12 12 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 Action Economical viability * (data from SERICHIM)

13 13 Action 10 Demonstration of technical-economic viability Economical viability Final Compound for fattening Reference for technical viability and then economic viability All data are referred to % ton leather All data are referred to 1 ton leather ProductAmount (kg) Cost ∆ (€) Case A - FatteningFACL Case BFASCL Case CFACL + FASCL Case C

14 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 15 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). Action 2 Demonstration of technical-economic viability

16 16 Thank you for your attention Torviscosa, January 24th, 2013

17 17 “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 SAMPLES: TANNED LEATHER Torviscosa, January 24th, 2013 ENEA Action involved

18 18 Preliminary SEM-EDS characterization (Scanning Electron Microscopy – X-rays Energy Dispersive Spectroscopy) As-received samples were characterized in partial vacuum condition (VP-SEM). Examinations on samples surface Morphological analysis Compositional analysis Backscattered images aquired at different magnifications: 50X, 100X, 200X, 500X, 1000X. X-Rays microanalysis: -qualitative: EDS spectra -semi-quantitative: elemental composition Torviscosa, January 24th, 2013

19 19 - 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. Leather Morphological analysis -NAT. SAMPLES: comparison between treatment with -FAME NAT. and CP44

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


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