ECOFATTING Final meeting - ICCOM

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
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ENEA Project Progress
July-November 2013
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
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Action 10
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
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Action 10
Demonstration of technical-economic viability
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
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Action 10
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.
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Action 10
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
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Action 10
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)
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Action 10
Demonstration of technical-economic viability
Technical viability: quality proof
Case A (B)
Final Compound for fattening
Reference for technical viability
and then economic viability
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Action 10
Demonstration of technical-economic viability
Technical viability: quality proof
Case C
Final Compound for fattening
Reference for technical viability
and then economic viability
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Action 10
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
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Action 10
Demonstration of technical-economic viability
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.
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Action 10
5. Economical viability
Cost evaluation for natural fatting agents:
Price* for CLOPARIN 44F:
Price* for CLOPARTEN Z:
1,05 €/kg
1,35 €/kg
* (data from COLORTEX)
Price for C14 C17 paraffin:
Price for natural raw material #:
#(data
1,31 €/kg
1,42 €/kg
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)
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Action 10
Demonstration of technical-economic viability
Economical viability
Product
Case A -toFattening
FACL2
All data are referred
% ton leather
Case C
Amount
(kg)
Cost ∆ (€)
12
+ 0.84
Case B
FASCL
12
-1.44
Case C
FACL +
6+
-1.02
FASCL
12
All data are referred to 1 ton leather
Final Compound for fattening
Reference for technical viability and then economic viability
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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:
Price* for CLOPARTEN Z:
1,05 €/kg
1,35 €/kg
* (data from COLORTEX)
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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).
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Thank you for your attention
[email protected]
www.pi.iccom.cnr.it/ecofatting/it
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Torviscosa, January 24th, 2013
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
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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
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Torviscosa, January 24th, 2013
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.
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Surface of FAME IND. is very similar to FAME NAT. any morphologic difference were observed.
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.
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