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

1

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

2

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

3

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

4

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

5

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.


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 MIXTURED) PALMKERNEL OIL FATTY ACID METHYL ESTERS


7

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)


8


Technical viability: quality proof

Final Compound for fatteningReference for technical viability and then economic viability

Case A (B)

9


Technical viability: quality proof


Case C

10

3. Technical viability – quality proof

Action 10


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

11

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.


Action 10

12

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)

13

Action 10


Economical viability


All data are referred to % ton leather

All data are referred to 1 ton leather

Product Amount (kg)

Cost ∆ (€)

Case A - Fattening FACL2 12 + 0.84

Case B FASCL 12 -1.44

Case C FACL +

FASCL

6 +

12

-1.02Case C

14

Project LIFE10 ENV/IT/364New costs evaluation :New costs evaluation :

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)

1515

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


16

Thank you for your attention

www.pi.iccom.cnr.it/ecofatting/it

[email protected]

Torviscosa, January 24th, 2013

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


ENEA Action involved

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


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

-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

Documents

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