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
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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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ECOFATTING Use of Environmentally friendly natural products instead of chloroparaffines in the fatting phase of the tanning cycle
Alice Dall’Ara – ENEASergio Sangiorgi - ENEA
Italian National Agency for New Technologies, Energy and Sustainable Economic DevelopmentUTTMATF Research Laboratories Faenza (Ra, Italy) LIFE10 ENV/IT/364 Ecofatting24 Month MeetingPisa, December 11th, 2013
ENEA activities months 18-24
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ACTIONS
A 6. Environmental demonstration of natural products fatting at a pre-industrial levelA 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 ProgressJuly-November 2013
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1. Market Analysis of the tannery sector2. Law indications and constrains3. Technical viability4. Environmental viability5. Economical viability
Expected results- Proof of quality and economic viability
Action 10
Demonstration of technical-economic viability
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1. Market Analysis:
Analysis of the leather Industry, with special focus on the Italian and Spanish marketThe World and European leather tradeMarket of the Italian Tannery IndustryMarket of the Spanish Tannery IndustryCharacterization of the products used in the fatting phase of the leather tanning cycleMost common Fat Liquoring agentsOils and virgin fatsSulfated productsSulphited productsPhosphated productsChloroparaffins
Action 10Demonstration of technical-economic viability
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2. Law indications and costrains:
Chlorinatedparaffins and SulfochlorinatedparaffinsRegulation 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 bioaccumulablep. 42 Annex XVII RESTRICTIONS ON THE MANUFACTURE, PLACING ON THE MARKET AND USE OF CERTAIN DANGEROUS SUBSTANCES, PREPARATIONS AND ARTICLESAlkanes, 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 10Demonstration of technical-economic viability
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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 MIXTURED) PALMKERNEL OIL FATTY ACID METHYL ESTERS
Action 10Demonstration of technical-economic viability
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3. Technical viability: starting points : - No variation in operation conditions and use
- No variation in output quality
Consequences: Changes on product productionChanges in waste/dischargereduction of cost is i.e due only to formulate cost and or initial cost (NB no difference in use)
Action 10Demonstration of technical-economic viability
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Action 10Demonstration of technical-economic viability
Technical viability: quality proof
Final Compound for fatteningReference for technical viability and then economic viability
Case A (B)
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Action 10Demonstration of technical-economic viability
Technical viability: quality proof
Final Compound for fatteningReference for technical viability and then economic viability
Case C
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3. Technical viability – quality proof
Action 10
Demonstration of technical-economic viability
FACL Gli ingrassi pronti all’uso formulatiCon oli clururati al 44% Cl- Good shelf life (IMPROVED)- Buone proprietà di dispersione- Buona stabilità nell’applicazione- Si ottengono bene, gli articoli DesideratiFATTENING
FASCL Comportamento degli ingrassiformulati usando oli solfoclorurati- Emulsioni stabili-Buona capacità di ottenere l’articolo desideratoFATTENING
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Technical viability ConclusionPiù simili sono le caratteristiche chimiche deinuovi prodotti (in termini di lunghezza di catenae di contenuto in Zolfo e Cloro), più simili sonole caratteristiche degli articoli con essiprodotti. I nuovi composti sia clorurati che solfocloruratipossono essere facilmente impiegati perprodurre ingrassi di uso comune. I nuovi prodotti clorurati e solfoclorurati nonrichiedono particolari processi applicativi epossono sostituire in pieno le corrispondentiparaffine.
Demonstration of technical-economic viability
Action 10
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Cost evaluation for natural fatting agents:Cost evaluation for natural fatting agents: Price* for CLOPARIN 44F: Price* for CLOPARIN 44F: 1,05 €/kg1,05 €/kgPrice* for CLOPARTEN Z: Price* for CLOPARTEN Z: 1,35 €/kg1,35 €/kg
* (data from COLORTEX)* (data from COLORTEX)
Price for C14 C17 paraffin: Price for C14 C17 paraffin: 1,31 €/kg1,31 €/kgPrice for natural raw material Price for natural raw material ##: : 1,42 €/kg1,42 €/kg
##(data from GAMMA CHIMICA for Palmere M1218 PK)(data from GAMMA CHIMICA for Palmere M1218 PK)
Estimated final price for new tanning agents from natural source:Estimated final price for new tanning agents from natural source:CHLORIN. PALM KERNEL FAME: CHLORIN. PALM KERNEL FAME: 1,12 €/kg1,12 €/kgSULFO CHLORIN. PALM KERNEL FAME: SULFO CHLORIN. PALM KERNEL FAME: 1,23 €/kg1,23 €/kg
Action 10
5. Economical viability5. Economical viability
* (data from SERICHIM)* (data from SERICHIM)
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Action 10
Demonstration of technical-economic viability
Economical viability
Final Compound for fatteningReference for technical viability and then economic viability
FAME mixtures obtained from DeACIDO technology have an FAME mixtures obtained from DeACIDO technology have an industrial price of industrial price of 0,90-1,00 €/kg0,90-1,00 €/kg..
Using this alternative raw material, estimated final price for new Using this alternative raw material, estimated final price for new tanning agents from natural source are:tanning agents from natural source are:CHLORIN. FAME from ACID FATS: CHLORIN. FAME from ACID FATS: 0,91 €/kg0,91 €/kgSULFO CHLORIN. FAME from ACID FATS : SULFO CHLORIN. FAME from ACID FATS : 1,02 €/kg1,02 €/kg
Price* for CLOPARIN 44F: Price* for CLOPARIN 44F: 1,05 €/kg1,05 €/kgPrice* for CLOPARTEN Z: Price* for CLOPARTEN Z: 1,35 €/kg1,35 €/kg
* (data from COLORTEX)* (data from COLORTEX)
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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).