BIONAD Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycle Start 01 01 2014 End 30062016 13062014 6 month meeting ID: 537649
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Slide1
LIFE12 ENV/IT/000352
BIONAD“Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycle”
Start: 01/01/2014End: 30/06/2016
13/06/2014
6-
month
meeting
Biokimica
premisesSlide2
LIFE12 ENV/IT/000352 “BIONAD“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycleThe University
of
Florence
Department
of Chemistry “Ugo Schiff”
Organic ChemistrySlide3
LIFE12 ENV/IT/000352 “BIONAD“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycleThe University
of
Florence
Laboratory
No 8
Prof
. Roberto
BianchiniRoom 161Slide4
B1
: traditional chemical acid dyes in leather dyeing (M1-M6)B2 : quality features of dyed leather with acid dyes (M1-M6)B3
: naturalised dyes as stable chemical substances (M1-M3)B4 : naturalised dyes in leather dyeing at laboratory level (M3-M9)C1 : environmental impact of acid dyes within leather manufacture (M1-M9)
C2
: depuration of dyeing effluents using bacteria at laboratory level (M3-M9)
ACTIONS
OF
THE FIRST SIX MONTHS
LIFE12
ENV/IT/000352
“
BIONAD
“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycleSlide5
Commercial
Dye
≡
Chemical
Formulation
chromophore
surfactans
dispersants
paraffins
salts
dyeing effluents
high impact
15 - 50
% of the commercial product
Unknown chemical species from the production process of the
chromophore
LIFE12
ENV/IT/000352
«BIONAD»
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycleSlide6
Naturalyzed
dyes
are a
striking
evolution
, to revolutionize the way of production and use of
dyes
Standard
dyes
Naturalyzed
dyes
40%
60%
Intermediates
Surfactants
Dispersants
Inorganic
salts
Paraffins
Chromophore
Chromophore
Sugar
"unknown" chemical formulationsingle
species LIFE12 ENV/IT/000352 “BIONAD“ Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycle50%50%?Slide7
1
st
Patent: EP1462484B1, 20042nd Patent: FI2013A000093,
2013
Innovative
research
carried out byProf. Bianchini and his team
LIFE12 ENV/IT/000352
“
BIONAD“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycle
Lactose
Chromophore
Chemical
BridgeSlide8
Laboratory scale ; period: 0 - 3 months
Nature of naturalized dyes
Elaboration of lactose to the naturalizing unit
The naturalization process
Synthetic procedures for different
chromophores
UNIFI
Synthetic strategy complying to
REACH
Action B.3
LIFE12 ENV/IT/352
“
BIONAD
“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycle
Restrictions:
Annex VIII and IX of REACH
Annex I of Directive 67/548/EEC
Analytical data to demonstrate the chemical stability of
naturalised
dyes
Spectrophotometric
, mass spectrometric and spectroscopic analysisSlide9
Analytical instrumentation
Action B.3
LIFE12 ENV/IT/000352 “BIONAD
“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycle
Nuclear Magnetic Resonance
Varian
Mercury 400 MHz
Mass Spectrometry
ThermoScientific
LCQ-Fleet
UV-Visible Spectroscopy
Varian
Cary-4000
Chemical species identification
Molecular weight
Light absorption
(color observation)Slide10
Elaboration of lactose
Action B.3
LIFE12 ENV/IT/000352 “
BIONAD
“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycle
72%
1) BnNH
2
,
MeCN
20 h , 80
C
p
-
TsOH
· H
2
O
4 h, 60
o
C
DMP
naturalizing
units
TEA, DCM
ovn, 0 – 20 Cp-TsCl93%>95%piperazineMeCN
4 -6 h, 80 oC92%2) H2, Pd/C, MeOH ovn, 20 CSlide11
LIFE12 ENV/IT/000352 “BIONAD“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycleSome examples of
chromophore
elaboration
Action B.3
THF, TEA, DMAP
ovn
, 20
o
C
DO30
92%
DY42
97%
1) ClCH
2
CO
2
Et, K
2
CO
3
KI, acetone, 4 h , 58
C
2) KOH,
MeOH
, H2O ovn, 20 CDR160% 1) BrCH2CO2
Et, NaH THF, 8 h, 0 C2) KOH, MeOH, H2O ovn, 20 C86% 1) i) SOCl2, TEA, DCM, 4 h, 0 C ii
) diethyl glutamate.HCl, TEA2) KOH, MeOH, H2O ovn, 20 Csuccinic anhydrideSlide12
LIFE12 ENV/IT/000352 “BIONAD“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycleCoupling
and
deprotection
Action B.3
THF,
ovn, 20
oC
>95%
DMTMM
HCl
, acetone
ovn
, 20
o
C
90%
DO30
Some examples of
nat
-dye purification
DB27
DB72
DO30
DR202Slide13
LIFE12 ENV/IT/000352 “BIONAD“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycleNaturalised
dyes
Action B.3
Sample dyes for action B.3Slide14
LIFE12 ENV/IT/000352 “BIONAD“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycleStability of
naturalised
dyes
Action B.3
Stability in open air
Stability in acid water
mimicking dyeing conditions
mimicking storing conditionsSlide15
LIFE12 ENV/IT/000352 “BIONAD“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycleSynthetic strategy complying to
REACH
Action B.3
Azodyes
which, […], may release one or more of the aromatic amines […] above 30
ppm in the finished articles or in the dyed parts thereof, […],
Azodyes, which are contained in Appendix 9, ‘List of azodyes’, shall not be […] used for coloring textile and leather articles […]
Appendix VIII
Appendix IX
Annex XVII
Restrictions on the manufacture, placing on the market and use of certain dangerous substances, […]Slide16
metal content (atomic absorption
spectrophotometry)
Quantification of contamination parameters from the use of acid dyes
biodegradability
COD and BOD
Preparation of dyed leathers on laboratory scale
LIFE12
ENV/IT/000352
“
BIONAD
“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycle
Laboratory scale ; period: 0 - 12 months
Environmental impact of acid dyes within leather manufacture
ICCOM-CNR, UNIFI, BIOKIMICA, INESCOP
Action C.1
mass of dye: ca. 3% (w/w) of leather sample
mass of leather sample: ca. 15 g
Biokimica
Inescop
Iccom
Unifi
Awaiting dyeing effluents from
BiokimicaSlide17
Determination of COD and BOD before and after treatment (as for action C.1)
Potential recycling of bacterial biomass
Action of bacterium strain E. coli
on dye effluents
Considerations on the mechanism of action of E.
coli
Assessment of dye reduction (visible analysis)
Potential reuse of dyeing effluent after depuration
LIFE12
ENV/IT/000352
“
BIONAD
“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycle
Laboratory scale ; period: 3 - 9 months
Depuration of dyeing effluents using bacteria
UNIFI
Action C.2Slide18
LIFE12 ENV/IT/000352 “BIONAD“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycleAction of bacterium strain E.
coli
on dye effluents
Action C.2
Tilting shaker
Escherichia
coli: DH5
Centrifuge
Regeneration on a Petri dish
Shaking at 37
C
Separation of the biomass Slide19
LIFE12 ENV/IT/000352 “BIONAD“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycleAction C.2
Preliminary tests of
decoloration
on simulated effluents
12-UNIFI-DO30-NAT
04-UNIFI-DR202-NAT
before
before
56 %
90 %
after
after
>95 %
>95 %Slide20
Assessment of dye reduction by visible
spectrophotometry
LIFE12 ENV/IT/000352 “BIONAD“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycle
Action C.2
12-UNIFI-DO30-NAT
04-UNIFI-DR202-NAT
ovn
ovn
before
before
-56%
-90%Slide21
Assessment of dye reduction by visible
spectrophotometry
LIFE12 ENV/IT/000352 “BIONAD“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycle
Action C.2
12-UNIFI-DO30-NAT
04-UNIFI-DR202-NAT
ovn
ovn
-40%
-5%
>95 %
1 week
>95 %
1 weekSlide22
Determination of COD and BOD before and after treatment (as for action C.1)
Considerations on the mechanism of action of E.
coli LIFE12
ENV/IT/000352
“
BIONAD
“
Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycleAction of bacterium strain E.
coli on dye effluents
Action C.2
Analyses to be carried out at a later stage
Decoloration
of
DR202 and DO30
indicated
that
E.
coli
may
both
metabolise the dye and adsorb it on the cell walls Metabolism is indicated by the visible analisys of the supernatant: novel
peaks may arise in the absorption pattern Evidence of adsorption is shown by the color of the pellet biomass after centrifugation of the E. coli culture for decoloration Decoloration is carried out in
aerobic conditions at 37 CSlide23
Potential recycling of bacterial biomass
LIFE12 ENV/IT/000352 “BIONAD“ Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycle
Action C.2
First test of
decoloration
of DO30 simulated effluent: 0.5 L
14%
66%
44%
Oxygenation
of the culture
may
be
an issue for the
treatment
of "large volumes" in the
laboratory
The
nutrient
Luria
-
Bertani
extract is added to aid bacteria growth/replication in each cycleA fraction of the bacteria biomass is used in further cycles of decoloration
The reuse of dyeing effluent after depuration will be assessed at a later stage-14%-30%-22%start
>90%> -24%