Project LIFE10 ENV/IT/364 "Environmentally friendly natural

Transcript Project LIFE10 ENV/IT/364 "Environmentally friendly natural

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 15 th 2013

Target of the project

Replacing well performing traditional fatliquoring agents as H 3 C Cl Cl C H 2 H C H 2 C H 2 C H C H 2 C H C H C H C H C H 2 C H C 2 H 3 Cl Cl Cl Chlorinated paraffins H 3 C Cl Cl C H 2 CH C H 2 C H 2 C H C H 2 C H C H C H 2 C H C H 2 CH CH

2 3

O S O Cl Cl Cl Sulpho Chlorinated paraffins

Target of the project

with chlorinated natural substrates as : H 3 C Cl Cl O C H 2 C H C H 2 C H 2 C H C H 2 C H C H C H 2 C H C Cl Cl Cl O C H

Chlorinated fatty acid methyl esters (C 12 -C 18 ) H 3 C Cl Cl O C H 2 CH C H 2 C H 2 C H C H 2 C H C H C H 2 C H C O S O Cl Cl O C H

Cl Sulfochlorinated fatty acid methyl esters (C 12 -C 18 )

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

Aspect Colour Density at 25 °C Chlorine content Cinemat. viscosity at 25 °C Cinemat. viscosity at 40 °C Thermal stability Index

(4h a 175 °C)

Units

Hazen g/L cSt cSt % m/m % HCl

Specification

Clear liquid

Results

Clear liquid 0-150 1160-1175 44,5-46,5 150-240 60-90 < 0,15 125 1168 45,2 214 76 < 0,15

Anal. Meth.

visual ASTM D 2108-85 ASTM D 4052-91 ASTM E 256-88 ASTM D 445-82 ASTM D 445-82 IND2013

Project LIFE10 ENV/IT/364

Sulpho chlorinated paraffin selected as benchmark :

CLOPARTEN Z

(2,0 kg samples provided to partners on March 2012)

Parameters

Aspect Colour Density at 25 °C Chlorine content Sulfur content

Units

Hazen g/L % m/m % m/m

Specification

Clear liquid

Results

Clear liquid 0-200 1035-1055 29-31 2,7-3,2 40 1050 30,5 3,1

Anal. Meth.

visual ASTM D 2108-85 ASTM D 4052-91 ASTM E 256-88 IND2047

Project LIFE10 ENV/IT/364

ACTION 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 C 12 – C 18 and chlorine and sulphur content approaching the benchmark products Chloparin 44F and Chloparten Z

Project LIFE10 ENV/IT/364

The following natural based substrates were considered: A ) METHYL STEARATE B ) FATTY ACID METHYL ESTERS (SATURATED) MIXTURE C) FATTY ACID CHLORIDES MIXTURE D) PALMKERNEL OIL FATTY ACID METHYL ESTERS

Project LIFE10 ENV/IT/364

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

Project LIFE10 ENV/IT/364

SERICHIM photochlorination lab equipment

Project LIFE10 ENV/IT/364

A nitrogen flow purges the reactor to remove residual oxygen Substrate to be chlorinated is charged into the jacketed – stirred glass reactor A thermostatic temperature at 60 bath °C keeps

Project LIFE10 ENV/IT/364

Off gases are analyzed for residual content … chlorine UV lamp is switched ON to irradiate the substrate … and then adsorbed in basic solutions aqueous Gaseous chlorine is allowed to flow from tank to reactor, bubbling into the substrate through a glass septum

Project LIFE10 ENV/IT/364

When desired chlorine content (and sulfur content if it is) is reached, reactant gas flows are stopped and UV lamp switched off If sulfo chlorinated product is to be achieved, a SO 2 flow is feed to the reactor through a separated line

Project LIFE10 ENV/IT/364

A nitrogen flow purges the chlorinated product from residual gases (Cl 2 , HCl and SO 2 ) 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)

Project LIFE10 ENV/IT/364

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/364

D ) 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/364

The natural based substrate considered was a mixture of PALMKERNEL OIL FATTY ACID METHYL ESTERS which typical composition is:

Component

Capric acid (C

) Methyl ester Lauric acid (C

) Methyl ester Myristic acid (C

) Methyl ester Palmitic acid (C

) Methyl ester Oleic acid (C

:) Methyl ester

Weight % m/m 0 - 3,0 54,0 - 59,0 17,0 - 21,0 8,0 – 11,0 9,0 - 17,0

Project LIFE10 ENV/IT/364

ACTION 5 :

• Fatting at a semi-industrial level by using natural

products ROLE of SERICHIM :

• Preparation of samples of Chlorinated and

Sulphochlorinated FAME at “few kilograms scale” to make available to project partners

Project LIFE10 ENV/IT/364

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.

Project LIFE10 ENV/IT/364

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) 130116 2,0 Sent to COLORTEX Density at 25 °C (g/L) Viscosity at 25 °C (cSt) Viscosity at 40 °C (cSt) Chlorine content (%m/m) 1287 1849 355 47,5 Test report 2013/002 130422 130520 130529 2,7 7,2 7,7 INESCOP COLORTEX INESCOP 1319 1306 1302 3316 2914 2869 684 548 546 48,6 48,2 48,1 2013/012 2013/017 2013/018

Project LIFE10 ENV/IT/364

B) SULFO CHLORINATED PALMKERNEL OIL FAME :

Lot no: 130118 Quantity (kg) 2,2 Sent to COLORTEX Density at 25 °C (g/L) Chlorine content (%m/m) 1161 24,1 Sulfur content (%m/m) 8,2 Test report 2013/003 130404 130520 Cloparten 10-15 130604 130611 1,0 1,8 2,2 7,6 7,5 COLORTEX INESCOP INESCOP COLORTEX INESCOP 1317 1317 1055 1334 1334 38,0 38,0 16,5 39,0 39,2 8,6 8,6 10 8,6 8,0 2013/007 2013/007 n.a.

2013/020 2013/021

Project LIFE10 ENV/IT/364

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

Project LIFE10 ENV/IT/364

Fleshing is a typical by-product from tannery process and it is treated as a waste (they pay for disposal).

Fleshing contains 10-15 % of fat as triglycerides.

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

This fat, due to the high free fatty acid content, has poor commercial value (ca.

0,15-0,25 €/kg )

Project LIFE10 ENV/IT/364

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

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

Project LIFE10 ENV/IT/364

ACID FAT CATALYST

DeACIDO process flow sheet

METHANOL MAKE UP WASTE FAME GLYCEROL

Project LIFE10 ENV/IT/364

O R O O R

O O R O O R

1 +

H 3 C OH

 acid

R O O CH 3

H 2 O OH

First step : fatty acid esterification

Project LIFE10 ENV/IT/364

O R R

O O O O O O H O R

1 +

H 3 C OH



base R X

H O O CH 3 R O CH 3 OH

Second step : triglycerides transesterification

Project LIFE10 ENV/IT/364

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

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)

Giulio Puntin Alfonso Nardelli

Thanks for your attention !

Vera Nocent Giusi Vassallo