Project LIFE10 ENV/IT/364 “Environmentally friendly natural products instead of chloroparaffines in the fatting phase of the tanning cycle” SERICHIM Project

Project LIFE10 ENV/IT/364“Environmentally friendly natural products

instead of chloroparaffines in the fatting phase of the tanning cycle”

SERICHIM Project progress Desk Officer Visit – Santa Croce sull’Arno (PI), October 15th 2013

Target of the project

Replacing well performing traditional fatliquoring agents as

Chlorinated paraffins

Sulpho Chlorinated paraffins

CH3

CH2CHCH2CH2

CHCH2

CHCH

CH2CHCH2CH2

CH3

Cl

Cl Cl

Cl Cl

CH3

CH2CHCH2CH2

CHCH2

CHCH

CH2CHCH2

Cl Cl

Cl ClS OO

Cl

CH2

CH3

Target of the project

with chlorinated natural substrates as :

Chlorinated fatty acid methyl esters (C12-C18)

Sulfochlorinated fatty acid methyl esters (C12-C18)

CH3

CH2CHCH2CH2

CHCH2

CHCH

CH2CHC

Cl

Cl Cl

Cl Cl

O

OCH3

CH3

CH2CHCH2CH2

CHCH2

CHCH

CH2CHC

Cl Cl

Cl Cl

O

OCH3

S OO

Cl

Project LIFE10 ENV/IT/364

• Chlorinated paraffins are used as greasing agents in the finishing working step in leather manufacturing, in order to provide an oily and soft “touch “ to the leather.

• Sulpho Chlorinated paraffins are sometimes used as direct tanning agents, but in the majority of cases are subjected to a further saponification reaction, in order to be used as emulsifiable greasing agent.

Project LIFE10 ENV/IT/364 Chlorinated paraffin selected as benchmark : CLOPARIN 44F (2,0 kg samples provided to partners on March 2012)

Parameters Units Specification Results Anal. Meth.

Aspect Clear liquid Clear liquid visual

Colour Hazen 0-150 125 ASTM D 2108-85

Density at 25 °C g/L 1160-1175 1168 ASTM D 4052-91

Chlorine content % m/m 44,5-46,5 45,2 ASTM E 256-88

Cinemat. viscosity at 25 °C cSt 150-240 214 ASTM D 445-82

Cinemat. viscosity at 40 °C cSt 60-90 76 ASTM D 445-82

Thermal stability Index (4h a 175 °C) % HCl < 0,15 < 0,15 IND2013

Project LIFE10 ENV/IT/364Sulpho chlorinated paraffin selected as benchmark : CLOPARTEN Z (2,0 kg samples provided to partners on March 2012)

Parameters Units Specification Results Anal. Meth.

Aspect Clear liquid Clear liquid visual

Colour Hazen 0-200 40 ASTM D 2108-85

Density at 25 °C g/L 1035-1055 1050 ASTM D 4052-91

Chlorine content % m/m 29-31 30,5 ASTM E 256-88

Sulfur content % m/m 2,7-3,2 3,1 IND2047

Project LIFE10 ENV/IT/364ACTION 3 – 4

• Selection, preparation and evaluation of natural based Chlorinated and Sulpho chlorinated products

• A set of derivatives from natural products were selected as best candidates. Selection criteria was based on a carbon chain lenght C12 – C18 and chlorine and sulphur content approaching the benchmark products Chloparin 44F and Chloparten Z


The following natural based substrates were considered:

A ) METHYL STEARATE B ) FATTY ACID METHYL ESTERS (SATURATED) MIXTURE C) FATTY ACID CHLORIDES MIXTURED) PALMKERNEL OIL FATTY ACID METHYL ESTERS


In order to proceed with the preparation of samples for application tests up to kilograms scale, a specifically designed equipment for photo-chlorination was set up in SERICHIM labs.


SERICHIM photochlorination lab equipment

Project LIFE10 ENV/IT/364Substrate to be chlorinated is charged into the jacketed – stirred glass reactor

A thermostatic bath keeps temperature at 60 °C

A nitrogen flow purges the reactor to remove residual oxygen


UV lamp is switched ON to irradiate the substrate

Gaseous chlorine is allowed to flow from tank to reactor, bubbling into the substrate through a glass septum

Off gases are analyzed for residual chlorine content …

… and then adsorbed in basic aqueous solutions


If sulfo chlorinated product is to be achieved, a SO2 flow is feed to the reactor through a separated line

When desired chlorine content (and sulfur content if it is) is reached, reactant gas flows are stopped and UV lamp switched off

Project LIFE10 ENV/IT/364A nitrogen flow purges the chlorinated product from residual gases (Cl2, HCl and SO2)

Chlorinated product is admixed with stabilizer, cooled and packed

Project LIFE10 ENV/IT/364 Since July to December 2012 the following samples were prepared and delivered to project partners:A ) CHLORINATED METHYL STEARATE :

Four chlorinated methyl stearate samples at different chlorination degree were produced: Lot 120710B (21,3 % m/m Chlorine content - 0,20 kg) Lot 120710D (37,9 % m/m Chlorine content - 0,20 kg) Lot 120712 (34,4 % m/m Chlorine content - 0,20 kg; viscosity and density as for Cloparin 44F) Lot 120907 (45,2 % m/m Chlorine content - 0,60 kg; . chlorine content as for Cloparin 44F)


B ) SULFO CHLORINATED METHYL STEARATE :

Lot 120925 (8,6% m/m sulfur content - 1,50 kg)

C) CHLORINATED FAME (SATURATED) MIXTURE :

A synthetic mixture of methyl esters of fatty acids (lauric, myristic, palmitic and stearic) was prepared, simulating the acid composition of Palmkernel oil. Stearic was present as satured substitude of oleic acid.

Lot 120903 (40,5 % m/m Chlorine content - 2,80 kg)

Project LIFE10 ENV/IT/364D ) CHLORINATED PALMKERNEL OIL FAME:

Lot 130116 (47,5 % m/m Chlorine content - 2,00 kg)

E) SULFO CHLORINATED PALMKERNEL OIL FAME :

Lot 130118 (8,2% m/m sulfur content - 2,20 kg)

These last two preparations have allowed to test the influence of chlorinated unsaturated FAME present into natural raw material on fatting agent properties.

Project LIFE10 ENV/IT/364The natural based substrate considered was a mixture of

PALMKERNEL OIL FATTY ACID METHYL ESTERS

Component Weight % m/ m

Capric acid (C10) Methyl ester 0 - 3,0 Lauric acid (C12) Methyl ester 54,0 - 59,0 Myristic acid (C14) Methyl ester 17,0 - 21,0 Palmitic acid (C16) Methyl ester 8,0 – 11,0 Oleic acid (C18:) Methyl ester 9,0 - 17,0

which typical composition is:


ACTION 5 :

• Fatting at a semi-industrial level by using natural products

• Preparation of samples of Chlorinated and Sulphochlorinated FAME at “few kilograms scale” to make available to project partners

ROLE of SERICHIM :


In order to proceed with the preparation of samples for semi-industrial application tests up to “few kilograms scale”, the previous photochlorination kilolab plant was replaced with a larger one.


Kilolab photochlorination plant Pilot photochlorination plant

Project LIFE10 ENV/IT/364 Since January to June 2013 the following samples were prepared and delivered to project partners:

A ) CHLORINATED PALMKERNEL OIL FAME:

Lot no: Quantity

(kg)Sent to

Density at 25 °C

(g/ L)

Viscosity at 25 °C

(cSt)

Viscosity at 40 °C

(cSt)

Chlorine content

(% m/ m)

Test report

130116 2,0 COLORTEX 1287 1849 355 47,5 2013/ 002

130422 2,7 INESCOP 1319 3316 684 48,6 2013/ 012

130520 7,2 COLORTEX 1306 2914 548 48,2 2013/ 017

130529 7,7 INESCOP 1302 2869 546 48,1 2013/ 018

Project LIFE10 ENV/IT/364B) SULFO CHLORINATED PALMKERNEL OIL FAME :

Lot no: Quantity

(kg)Sent to

Density at 25 °C

(g/ L)

Chlorine content

(% m/ m)

Sulfur content

(% m/ m)

Test report

130118 2,2 COLORTEX 1161 24,1 8,2 2013/ 003

130404 1,0 COLORTEX 1317 38,0 8,6 2013/ 007

130520 1,8 INESCOP 1317 38,0 8,6 2013/ 007

Cloparten 10-15

2,2 INESCOP 1055 16,5 10 n.a.

130604 7,6 COLORTEX 1334 39,0 8,6 2013/ 020

130611 7,5 INESCOP 1334 39,2 8,0 2013/ 021

Project LIFE10 ENV/IT/364Cost evaluation for natural fatting agents:Cost evaluation for natural fatting agents:

Price* for CLOPARIN 44F: Price* for CLOPARIN 44F: 1,05 1,05 €/kg€/kg

Price* for CLOPARTEN Z: Price* for CLOPARTEN Z: 1,35 1,35 €/kg€/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


Project LIFE10 ENV/IT/364Alternative raw material to palm kernel oil :Alternative raw material to palm kernel oil : FleshingFleshing is a typical by-product from tannery process is a typical by-product from tannery process and it is treated as a waste (they pay for disposal). and it is treated as a waste (they pay for disposal).

FleshingFleshing contains 10-15 % of fat as triglycerides. contains 10-15 % of fat as triglycerides. Industrial processes use fleshing for protein hydrolizate Industrial processes use fleshing for protein hydrolizate recovering, obtaining as by-product a sterile fat, recovering, obtaining as by-product a sterile fat, containing up 10-20% of free fatty acid.containing up 10-20% of free fatty acid.

This fat, due to the high free fatty acid content, has This fat, due to the high free fatty acid content, has poor commercial value (ca. poor commercial value (ca. 0,15-0,25 €/kg0,15-0,25 €/kg))

Alternative raw material to palm kernel oil :Alternative raw material to palm kernel oil : Alternative raw material to palm kernel oil :Alternative raw material to palm kernel oil :


SERICHIM is owner of SERICHIM is owner of DeACIDO technologyDeACIDO technology, a process , a process developed in 2008 for using high acidity animal fats developed in 2008 for using high acidity animal fats and vegetable oils as raw materials for biodiesel, and vegetable oils as raw materials for biodiesel, making them an ethical alternative to food sources for making them an ethical alternative to food sources for this production.this production.

The The DeACIDO technology DeACIDO technology applies to the esterification of applies to the esterification of free fatty acids (FFA) present in fats and oils: it free fatty acids (FFA) present in fats and oils: it represents a first section of the triglycerides represents a first section of the triglycerides transesterification process with methanol to produce transesterification process with methanol to produce Fatty Acid Methyl Esters (FAME) and glycerol. Fatty Acid Methyl Esters (FAME) and glycerol.

Alternative raw material to palm kernel oil :Alternative raw material to palm kernel oil :


DeACIDO process DeACIDO process flow sheetflow sheet

ACID FAT

METHANOL MAKE UP

FAME GLYCEROL

CATALYST

WASTE


RO

OH

+ CH3 OH RO

O CH3

+ OH2

a c id

OO

O

R

R1R2

O

O

O

First step : fatty acid esterificationFirst step : fatty acid esterification


+ CH3 OH RO

O CH3

+

OO

O

R

R1R2

O

O

O

base

RO

O CH3

OH

OH

OH

XR

O

O CH3

Second step : triglycerides transesterificationSecond step : triglycerides transesterification


The DeAcido process core consists of two phases The DeAcido process core consists of two phases esterification reaction, at the end of which the acid esterification reaction, at the end of which the acid catalyst is removed by means of an easy decanting catalyst is removed by means of an easy decanting operation. At this stage other polar components operation. At this stage other polar components present in the oil (phospholipids, glycolipids, etc) are present in the oil (phospholipids, glycolipids, etc) are removed with the polar phase, obtaining removed with the polar phase, obtaining deacidification and degumming in a single stage, deacidification and degumming in a single stage, allowing use of fats and oils of very poor quality as allowing use of fats and oils of very poor quality as raw materials for FAME preparation.raw materials for FAME preparation.

Alternative raw material to palm kernel oil :Alternative raw material to palm kernel oil :


New costs evaluation :New costs evaluation :

FAME mixtures obtained from DeACIDO technology FAME mixtures obtained from DeACIDO technology have an industrial price of have an industrial price of 0,90-1,00 €/kg0,90-1,00 €/kg..

Using this alternative raw material, estimated final price for Using this alternative raw material, estimated final price for new tanning agents from natural source are:new tanning agents from natural source are:CHLORIN. FAME from ACID FATS: CHLORIN. FAME from ACID FATS: 0,91 0,91 €/kg€/kgSULFO CHLORIN. FAME from ACID FATS : SULFO CHLORIN. FAME from ACID FATS : 1,02 1,02 €/kg€/kgPrice* for CLOPARIN 44F: Price* for CLOPARIN 44F: 1,05 1,05

€/kg€/kgPrice* for CLOPARTEN Z: Price* for CLOPARTEN Z: 1,35 €/kg1,35 €/kg

* (data from COLORTEX)* (data from COLORTEX)

Giulio Puntin

Alfonso Nardelli

Thanks for your

attention !

Giusi Vassallo

Vera Nocent

Documents

Project LIFE10 ENV/IT/364 “Environmentally friendly natural products instead of chloroparaffines in the fatting phase of the tanning cycle” SERICHIM Project