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 Chlorinated paraffins Sulpho Chlorinated paraffins

Target of the project with chlorinated natural substrates as : Chlorinated fatty acid methyl esters (C 12 -C 18 ) 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)

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

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, a specifically designed equipment for photo- chlorination was set up in SERICHIM labs.

Project LIFE10 ENV/IT/364 SERICHIM photochlorination lab equipment

Project LIFE10 ENV/IT/364 Substrate 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

Project LIFE10 ENV/IT/364 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

Project LIFE10 ENV/IT/364 If sulfo chlorinated product is to be achieved, a SO 2 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/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 B (21,3 % m/m Chlorine content - 0,20 kg) Lot D (37,9 % m/m Chlorine content - 0,20 kg) Lot (34,4 % m/m Chlorine content - 0,20 kg; viscosity and density as for Cloparin 44F) Lot (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 (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 (40,5 % m/m Chlorine content - 2,80 kg)

Project LIFE10 ENV/IT/364 D ) CHLORINATED PALMKERNEL OIL FAME : Lot (47,5 % m/m Chlorine content - 2,00 kg) E) SULFO CHLORINATED PALMKERNEL OIL FAME : Lot (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:

Project LIFE10 ENV/IT/364 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 :

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 plantPilot 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 :

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

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

Alternative raw material to palm kernel oil : Fleshing is a typical by-product from tannery process and it is treated as a waste (they pay for disposal). Fleshing contains % 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) Alternative raw material to palm kernel oil :

Project LIFE10 ENV/IT/364 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. Alternative raw material to palm kernel oil :

Project LIFE10 ENV/IT/364 DeACIDO process flow sheet

Project LIFE10 ENV/IT/364 First step : fatty acid esterification

Project LIFE10 ENV/IT/364 Second step : triglycerides transesterification

Project LIFE10 ENV/IT/364 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. Alternative raw material to palm kernel oil :

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 ! Giusi Vassallo Vera Nocent