ECODEFATTINGEnvironmentally friendly natural products instead of chemicalproducts in the degreasing phase of the tanning cycle

LIFE13 ENV/IT/000470

Emilia Bramanti ICCOM-CNR

12 MONTH MEETING, October 22 2015 –Newport, Santa Croce, Pisa

Gantt chart

ACTION A.1, A.2Study of the interaction between leather and the defatting  agents (commercial and natural products, Action A2) by Fourier Transform Infrared Spectrometry (FTIR) and Thermogravimetric Analysis (TGA)

ACTION C.1, C2, C3, C4Analytical method to determine the metal  content in the defatting wastewaters and also the fat content: ICP-MS, ICP-OES, atomic spectrometry (DMA80) and FTIR

ACTION C.2, C3 (in progress)Metal content in the wastewaters obtained  from the treatment with natural derived compounds (before and after microbial degradation).

ECODEFATTING ACTIONS at ICCOM-PI in the first 12 months

Methods (A, B and C Actions)

Infrared spectroscopy (ATR-FTIR) for the study of defatting agents/leather protein interactions and the residual fat content in leather

Thermogravimetric Analysis (TGA) for the study of defatting agents/leather proteins

ICP-MS, ICP-OES, DMA80 for the determination of metals

A flow injection Dynamic Surface Tesion Detector for the determination of surfaceActive agents (?)

Agilent 7700 Series ICP-MS with a 3rd generation Octopole Reaction System with improved ion focusing and increased collision efficiency and a kinetic energy discriminationsystem (KED) Determination

of the metal content in the defatting wastewaters from the treatment with commercial and natural products

ATR-FTIR analysis

Sample in contactwith penetrating radiation (evanescent wave) (d=0.5-5 m)

Infraredbeam from source

To detectorrefractive index of the crystalmust be significantly greaterthan that of the sample (2.38 and 4.01 at 2000 cm-1) (diamond or ZnSe or KRS-5 ie thallium iodide)

Reflected bean is attenuated at characteristic wavelength (absorption bands)

Diameter = 2 mm

Solids liquids

The frequency deconvolution procedure implemented in LabView

FTIR and TGA analysis of leather samples:-B1-B4-COM1-COM4-EDF1-EDF25-Leather before the soaking process EDF20- Leather before the soaking process SG50- Pre-tanned leather EDF20- Pre-tanned leather SG50- Crust EDF20- Wet-Blue EDF20

- FTIR of residual bath EDF19-EDF25 and B3- Metal analysis by DMA80 (Hg) and ICP-OES and ICP-MS of

residual baths of:- COM 1-4- Rokanol - Etocas 15 - Tripropionin - Trietyl Citrate- Castor oil - Exilene Glycol- EDF20

-Leather before the soaking process EDF20- Leather before the soaking process

SG50- Pre-tanned leather EDF20- Pre-tanned leather SG50

Summary of samples analysed

Pictures of leather samples B1-B4-COM1-COM4-EDF1-EDF25

R10_081015c

R3_081015c

R5_081015c

R6_081015c

R7_081015c

R8_081015c

Nome

pelle EDF20 32 scan ATR

pelle B3 32 scan ATR

pelle Com1 32 scan ATR

pelle Com2 32 scan ATR

pelle Com3 32 scan ATR

pelle com4 32 scan ATR

Descrizione

4000 6003500 3000 2500 2000 1500 1000

1,0

-0,0-0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0

cm-1

A

1633,01cm-1

1547,37cm-1

2921,66cm-13299,74cm-1

2851,78cm-1

1741,8

Area 1StretchingCH2/CH3

Area 2StretchingC=O

Amide I

Amide II

ACTION A1, A2, B1 and B2Study of the interaction between leather and the defatting  agents (commercial and natural products) by Fourier Transform Infrared Spectrometry (FTIR)

0

5

10

15

20

25

ACTION A.1-A2 and B1-B2Study of the fat content in leather samples treated or not (blanks) with defatting  agents (commercial and natural products) by Fourier Transform Infrared Spectrometry (FTIR)

CH2/CH3 stretching area (Area 1)

0 5 10 15 20 250

0.2

0.4

0.6

0.8

1

1.2

1.4

f(x) = 0.056710035715814 x − 0.261717278337105R² = 0.800691575864182

Area 1

Are

a 2

ACTION A, B and CLab demostration tests of defatting  agents (commercial and natural products)COM 1: Anionic slightly Oxyethylenated

COM 2: Synthetic oxo-alcohol ethoxylateCOM 3: Polyglycol fatty chain linearCOM 4: Non-ionic / anionic surfactant

(*) extracted in dichloromethane

Best ECODEFATTING product

0 2 4 6 8 10 120

5

10

15

20

25

f(x) = 1.8224126613913 x + 4.69547609350224R² = 0.566199999778216

Fat content in leather after defattingP

eak a

rea C

H2

/CH

3 s

tretc

hin

g

0 1 2 3 4 5 6 7 80

10

20

30

40

50

60

70

f(x) = 8.81321042005424 xR² = 0.904020015074178

Fat extracted by defatting agent (“before”-“after”

defatting)

Peak a

rea C

H2

/CH

3

str

etc

hin

gR10_021015c

R3_021015c

R4_021015c

R5_021015c

R6_021015c

R7_021015c

R8_021015c

R9_021015c

Nome

Bagno residuale EDF 25 16 scan BaF2

Blanco B3 16 scan BaF2

Bagno residuale EDF 19 16 scan BaF2

Bagno residuale EDF 20 16 scan BaF2

Bagno residuale EDF 21 16 scan BaF2

Bagno residuale EDF 22 16 scan BaF2

Bagno residuale EDF 23 16 scan BaF2

Bagno residuale EDF 24 16 scan BaF2

Descrizione

4000 6003500 3000 2500 2000 1500 1000

1,0

-0,0-0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0

cm-1

A

1102,11cm-12918,80cm-1

2851,33cm-1

3357,41cm-1

1737,38cm-1

ACTION C.1, C2, C3, C4FTIR to determine the fat  content in the wastewaters (baths) (dried films)

EDF1

0

COM4

EDF1

2

COM1

COM2

EDF1

9

EDF2

0

COM3

EDF1

4

EDF1

7

Ref2_

0615

c

EDF1

6ED

F6

EDF1

1ED

F8

EDF2

2

EDF1

5

EDF2

1 B2

Ref1_

0615

c

EDF2

3 B3

EDF1

3ED

F3ED

F5

EDF1

8ED

F2ED

F7

Ref_P

elle

_cED

F9ED

F1

EDF2

4ED

F4

EDF2

5 B1 B40.73

0.75

0.77

0.79

0.81

0.83

0.85

0.87

0.89

0.91

AII/AI

Amide I

Amide II

ACTION A1, A2, B1 and B2Study of the interaction between leather and the defatting  agents (commercial and natural products, Action A2) by Fourier Transform Infrared Spectrometry (FTIR)

AII/AI ratios from FTIR SPECTRA of leather samples treated withcommercial and ECODEFATTING products

ACTION A.1-A2 and B1-B3Study of the interaction between leather and the defatting  agents (commercial and natural products) by Fourier Transform Infrared Spectrometry (FTIR)

FTIR spectra of leather samples EDF 20 Crust and EDF 20 Wet Blue

R1_021015c R2_021015c R1_191015c

Nome EDF20 Crust 128 scan ATR EDF20 Wet-Blue 128 scan ATR pelle B3 128 scan ATR

Descrizione 4000 600 3500 3000 2500 2000 1500 1000

1,8

-0,1 -0,0

0,2

0,4

0,6

0,8

1,0

1,2

1,4

1,6

cm-1

A

1549,96cm-1 1652,80cm-1

2922,71cm-1 3313,44cm-1

2852,99cm-1 1741,6

1632 Area 1StretchingCH2/CH3

Area 2StretchingC=O

ACTION A.1-A2 and B1-B3Study of the interaction between leather and the defatting  agents (commercial and natural products) by FTIR- peak fitting analysis

Area 1 3000-2760Area 2 1770-1700 Area1 Area 2 Area1 Area 2 Area1 Area 2 Area1 Area 2

1 123.79 24.56 26.85 0.36 5.47 0 5.32 02 74.49 11.68 49.49 1.62 18.4 0 16.94 03 274.38 57.09 208.61 33.85 5.37 0.1 19.29 04 32.18 0.73 34.49 0.55 5.14 0 7.71 05 116.96 17.5 60.42 1.6 8.48 0.18 6.87 0

Media 124.36 22.31 75.97 7.60 8.57 0.06 11.23 0.00Dev. St 91.58 21.31 75.28 14.69 5.66 0.08 6.40 0.00CV% 73.64 95.51 99.09 193.36 66.06 145.95 57.02 0.00

Spettri normalizzati

rispetto all'ammide I

(1640)

Pelle da rinverdire EDF20 Pelle da rinverdire Polause SG50 Pelle preconciata EDF20 Pelle preconciata Polause SG50Repliche

RinverdimentoCalcinaioSpaccatura/scarnatura???1° lavaggio purga2°lavaggio purgaPikelpreconcia

EDF20 or PolauseSG50 0,2% w/w

EDF20 or PolauseSG50 0,1% w/w

EDF20 or PolauseSG50 0,2% w/w

ACTION A.1, A.2. Study of the interaction between leather and the defatting  agents (commercial and natural products) by Thermogravimetric Analysis (TGA)

COM 1

COM 2

COM 3

COM 4

Leather Sample Peak 1 (°C) Peak 2 (°C) Peak 3 (°C) Peak 4 (°C) Peak 5 (°C) Peak 6 (°C) Peak 7 (°C) Residuo finale %B3 66 315 394 523 863 7.1

EDF20 63 314 389 502 859 6.1Pelle da rinverdire EDF20 67 214 321 577 811-850 4.1Pelle da rinverdire SG50 70 329 606 799 3.9Pelle preconciata EDF20 57 307 560 767-856 7.1Pelle preconciata SG50 72 306 448 570 800 11.5

Pelle Crust EDF20 61 319 380 7.3Pelle Wet-Blue EDF20 63 318 388 487-512 807 6.3

COM1 63 306 403 482 3.3COM2 66 309 417 485 3.8COM3 68 311 413 482 4COM4 58 316 395 434 487 5.3

TGA 30-900 °C 10°C/min Aria

B3 EDF 20

Leather Crust EDF 20 Leather Wet Blue EDF 20

Leather before the soaking process EDF 20 Pretanning leather EDF 20

Leather before the soaking process SG 50 Pretanning leather SG 50

ACTION A.1, A.2. Study of the interaction between leather and the defatting  agents (commercial and natural products) by Thermogravimetric Analysis (TGA)

Leather Sample

Peak 1 (°C) Peak 3 (°C)

Peak 4 (°C)

Peak 5 (°C)

Peak 6 (°C) Peak 7 (°C)

Residuo finale %

B1 63 315 392   519 887 7,3B2 63 315 395   538 814 5,3B3 66 315 394   523 863 7,1B4 64 312 389   498 777 5,2

COM1 63 306 403   482   3,3COM2 66 309 417   485   3,8COM3 68 311 413   482   4COM4 58 316 395 434 487   5,3Ref1_9 72 310 411       6,6Ref2 67 313 396   534 870 5,7EDF1 68 317 383   476   5,7EDF2 71 309 402       5EDF3 70 308 392 433     5,2EDF4 74 312 413   477   6,1EDF5 72 313     479   4,9EDF6 68 302 385   494 794 7,6EDF7 69 315 388   499 883 8,3EDF8 63 327 391   487 867 7,8EDF9 65 316 381   469 850 7,7

EDF10 71 312 386   503   11,2EDF11 62 318 391   511   16,4EDF12 59 320 385   501 789 13,7EDF13 61 315 391   518 791 14,7EDF14 64 314 390   514 787 11,3EDF15 65 313 397   537 796 6,7EDF16 71 310 394   531 890 6,7EDF17 67 312 393   521 793 9,7EDF18 70 314 392   521 894 11,4EDF19 61 319 389 424 497 813 7,4EDF20 63 314 389   502 859 6,1EDF21 61 317 393 427 505 818 6,4EDF22 64 306 403   525 882 4,9EDF23 64 312 394   508 774 6,7EDF24 64 310 393   524 878 6EDF25 55 321 389 424 501 847 5,9

ACTION A.1, A.2. Study of the interaction between leather and the defatting  agents (commercial and natural products) by Thermogravimetric Analysis (TGA)

TGA Peak 306-329 °C TGA Peak 380-417 °C

TGA Peak 482-606 °C

Residual (%)

ACTION A.1, A.2. Study of the interaction between leather and the defatting  agents (commercial and natural products) by Thermogravimetric Analysis (TGA)

ACTION C.2, C3Metal content in the wastewaters obtained  from the treatment with natural and commercial defatting agents

ACTION C.2, C3Metal content in the wastewaters obtained  from the treatment with natural and commercial defatting agents (mg/Kg, ppm)

ACTION C.2, C3Metal content in the wastewaters obtained  from the treatment with natural and commercial defatting agents (mg/Kg, ppm)

ACTIONS A1-A2PEAK FITTING of Fourier Transform Infrared Spectrometry (FTIR)Thermogravimetric Analysis (TGA)Correlation with several leather chemical physical parameters (ICCOM/INESCOP)

ACTIONS C1-C2- C3Analytical method to determine the metal  content in the defatting wastewaters and in the wastewaters obtained  from the lab and semi-industrial treatment with natural derived compounds (before and after microbial degradation).

ECODEFATTING ACTIONS of the next 6 months

ECODEFATTING PEOPLE @ ICCOM-PI

Emilia BramantiAlessandro D’Ulivo

Massimo Onor

Manuela Cempini

Emanuela Pitzalis

Marco Carlo Mascherpa

SimonaBiagi

Valentina Della Porta