ENZYME/ A GREEN TECHNOLOGY- WAY TO REDUCE ENVIRONMENTAL POLUTION IN TEXTILE WET
PROCESSING INDUSTRIES
Kh. M. Gaffar Hossain, PhD (E.U)
Department of Textile EngineeringDhaka University of Engineering & Technology (DUET),
Gazipur-1700, Bangladesh
V-Trion GmbH Textile Research Head of the Institute
Schwefelbadstr. 2, A-6845, Hohenems, AustriaTel.:0043 676 843771600
E-Mail: [email protected]
27.07.2011
The total quantity of chemicals used in textiles mills varies from 10% to over 100% of the weight of fabric
Hendrickx et. al., Virginia, 1995
This can be categorized in following four steps.i.Fabric preparation
ii.Dyeing
iii.Printing
iv.Finishing
A process in which the textile materials (fibre/yarn/fabric) are treated in a liquid medium (Water, foam etc.)
TEXTILE WET PROCESSING
Cotton processing in textile industries Process wise classification of textile chemicals
L.W
L.W
L.W
L.W
L.W
L.W
L.W
Categorization of Textile Wastei.Hard to treat waste (Colour, metals, phenols,toxic organic compounds, etc.)
ii.Hazardous or toxic wastes (Chlorinated solvents, non-biodegradable or volatile organic)
iii.Dispersible waste (Print paste, coating operation, solvent, waste stream, finishing etc)
iv.High volume waste (knitting oils, warp sizes, alkaline wastes)
Textile wet processing activity contributes about 70% of pollution in textile industry
Dyes and auxiliary chemicals used in textile mills are developed to be resistant to environmental influences. As a result, they are hard to remove from wastewater generated during the dyeing processes.
10% of dyes are lost during the textile coloration process [Easton, 1995]
Wagle, N.P., 2001
PROBLEM(ENVIRONMENTAL IMPACT)
Untreated industrial sewage
Arsenic poisoning of polluted water lead to skin cancer and excessive
growth of keratin on the feet
N Williams et al, Env. Sci. & Tec., 2006
PlantFish
Dolphin
How long can we continue to harm environment? Will our business exist if biosphere is polluted? Will textile industry survive and be able to compete?
Pollution in the river:- hundreds of acres agricultural land, - estroyed the river water's ecosystem. - the Buriganga river (gone across the Dhaka city) now has virtually no aquatic life.
PROBLEM(ENVIRONMENTAL IMPACT)
TEXTILE AREAS TARGETED BY BIOTECHNOLOGY
Alternatively, the applications of this technology to replace existing high energy, chemicals and water consuming processes would considerably reduce the environmental burden
BIOTECHNOLOGY IN TEXTILE INDUSTRY
The major areas of application of biotechnology in textile industry are given below:
Improvement of plant varieties used in the production of textile fibres and in fibre propertiesImprovement of fibres derived from animals and health care of the animalsNovel fibres from biopolymers and genetically modified microorganismsReplacement of high energy and harsh chemical treatments by enzymes in textile processingEnvironment friendly routes to textile auxiliaries such as dyestuffsNovel uses for enzymes in textile finishingDevelopment of low energy enzyme based detergentsWaste management
The objective of this presentation is to introduce bio-based enzymatic process to replace harsh chemicals in textile wet processing industries
OBJECTIVE
Enzymes (extracted from any living organism e.g. fungi yeast, bacteria, animals, plants etc.) are biological catalysts that accelerate the rate of virtually all biochemical reactions without undergoing any change (e.g. enzymes typically enhance the reaction rates by 106 to 1013 times).
ES ES Pk1
k-1
k2
A B
S P
S + E ES (Enzyme-substrate complex)
ES P + E
Catalyst
Enzyme
Substrate Product
Reactant Product
Binding step Catalytic step
BASIC ENZYME REACTION
ENZYME SUBSTRATE INTERACTION
1. Lock and key model Emil Fischer (1890)
2. Induced fit model Daniel Koshland (1958)
The active site:•The Substrate Binding Site•The Catalytic Site
HOW DO ENZYMES WORK?
1. Temperature (20-60 ºC)
2. pH (5-8.5)
3. Enzyme concentration [E]
4. Substrate concentration [S]
Factors affect rate of enzyme reactionsProduct
Complex
Without enzyme
Progress of reaction
With enzyme
Enzyme lowers activation
energy by this amount
Enzyme
Substrate
En
erg
y
1- Optimum Temperature
Little activity at low temperature (low number of collisions)Rate increases with temperature (more successful collisions)
– rate doubles for every 10°C increase in temperatureMost active at optimum temperatures (usually 37 C in humans) Enzymes isolated from thermophilic organisms display maxima around 100°C Enzymes isolated from psychrophilic organisms display maxima around 10°C.Activity lost with denaturation at high temperatures
2- Optimum pH
Effect of pH on ionization of active site.Effect of pH on enzyme denaturation.Each enzyme has an optimal pH (~ 6 - 8 )
– Exceptions : digestive enzymes in the stomach( pH 2) digestive enzymes intestine (pH 8)
3/4- Substrate concentration
Increasing [S] increases the rate of reaction (enzyme concentration is constant) BUT
Maximum activity reaches when all E combines with S (all the enzyme is in the ES, ,form).
21 3 4 5 6 7 80
0 2 4 6 8
Substrate (mmole) [S]
Pro
duct (v
)
80
60
40
20
0
S+E
(in a fixed period of time)
Constant
[E]
P
Juang RH (2004) BCbasics
Enzyme Velocity Curve
ENZYMES IN TEXTILES PROCESSING
Textile processing with enzymes aims to develop environmentally friendly alternatives to chemical processes at almost all steps
amylases PectinasesProteases
XylanasesProteasesGlucose oxidasesLaccasesHaloperoxidasesCatalases…
LaccasesTyrosinasesPeroxidasesAzo reductases…
LaccasesProteasesLipasesCutinasesNitrilasesHexokinasesPDITransglutaminases…
preparation
dyeing finishingdesizing scouring bleaching
“MY CONTRIBUTION” TO THE STATE OF THE ART IN THIS FIELD
Bio-preparation of textilesEnzymes for textile finishingEnzymatic functional modification of textilesElectrochemistry of redox enzymatic systems Enzymatic dyeing/polymerizationEnzymes immobilization for application in the textile industry
ORAL PRESENTATIONS IN CONFERENCES 1.Kh. M. Gaffar Hossain, María Díaz González, Ascension Riva Juan and Tzanko Tzanov. A single step enzymatic modification of wool textile to
improve its various properties. AATCC's International Conference (IC), May 18-20, 2010, Atlanta, Georgia, USA2. Kh. M. Gaffar Hossain, María Díaz González, Guillem Rocasalbas Lozano, and Tzanko Tzanov. Multifunctional wool produced in an enzymatic
process from aqueous-organic medium. 3rd World Congress of Industrial Biotechnology (ibio-2010), July 25-27, 2010 Dalian, China.3.Kh. M. Gaffar Hossain. A green technology- enzyme application in wet processing textile industries. 2nd International Alumni-Workshop (DAAD-
Germany) February 15-19th, 2010, Dhaka, Bangladesh4.Kh. M. Gaffar Hossain, María Díaz González, Guillem Rocasalbas Lozano, and Tzanko Tzanov. Enzymatic process for multifunctional protein fibres.
237th ACS National Meeting, March 22-26, 2009. Salt Lake City, Utah, USA5.Kh.Md. Gaffar Hossain, Ascensión Riva, Josep Ma. Canal,Tzanko Tzanov. Enzymatic process for machine washable wool. 21st IFATCC Congreso,
May 6-9, 2008, Barcelona, Spain6.K.M.G. Hossain, G. R. Lozano, and T. Tzanov. Antimicrobial biopolymer coating of wool. International Conference on Chemical Engineering,
(ICChE2008), Dec. 31st, 08-Jan. 1st, 09, 2008, Dhaka, Bangladesh
SCIENTIFIC PAPERS & PUBLICATIONS1.Kh. M. Gaffar Hossain, María Díaz González, José María Dagá Monmany and Tzanko Tzanov. Effects of alkyl chain lengths of gallates upon
enzymatic wool functionalisation. J. Molecular and Biocatalysts B: Enzymatic, 67, 231-235, 20102.Kh. M. Gaffar Hossain, María Díaz González, Ascension Riva Juan and Tzanko Tzanov, Enzyme-mediated coupling of a bi-functional phenolic
compound onto wool to enhance its physical, mechanical and functional properties. Enzyme and Microbial Technology. 46, 326-330, 20103.Kh. M. Gaffar Hossain, María Díaz González, Guillem Rocasalbas Lozano and Tzanko Tzanov. Multifunctional modification of wool using an
enzymatic process in aqueous-organic media, Journal of Biotechnology,141, 58-63, 20094.Kh.Md. Gaffar Hossain, Ascensión Riva, Josep Ma. Canal,Tzanko Tzanov. Enzymatic process for machine washable wool. 21st IFATCC Conference
Paper, B44, 20085.Kh. M. Gaffar Hossain, Ascension Riva Juan, Tzanko Tzanov. Simultaneous protease and transglutaminase treatment for shrink resistance of wool.
Biocatalysis and Biotransform, 26 (5), 405-411, 2008.6.K.M.G. Hossain, G. R. Lozano, and T. Tzanov. Antimicrobial biopolymer coating of wool. ICChE2008, Conference Paper, 70-74, 20087.Kh. M. Gaffar Hossain. Enzymatic bioprocess for shrink resistance of protein fibre. ITET Journal, 9, 34-36, 20088.Kh. M. Gaffar Hossain, José M. Daga, Ascension Riva, Josep M. Canal, Tzanko Tzanov, Un proceso enzímatico para lana resistente al
encogimiento, Quimica Textil, 190, 29-35, 2008
BIO-PREPARATION OF TEXTILES
Bleaching - brightening effect, impact on subsequent wet processing operationsAcidic to alkaline conditions, wide temperature rangeH2O2 - most widely used bleaching agent
H2O2 can be generated enzymatically from glucose/GOX
Gluconic acid produced in the reaction acts as H2O2 stabilizer
Enzymatic peroxide production
0
0,05
0,1
0,15
0,2
0,25
0,3
0,35
0,4
0,45
60 120 180 240 300 360 420 480 540 600
time, min
H2O
2, g
/l 15,14 U/ml GOX+20 g/l Glu
22,68 U/ml GOX+20 g/l Glu
20 g/l glucose, 3.78 U/ml GOX
20 g/l glucose, 3.78 U/ml GOX
0
0.05
0.1
0.15
0.2
0.25
0.3
30 60 90 120 150 180 210 240 270 300
H2O
2, g
/l
time, min
Enzymatic peroxide production
oxygen
shaking
Single step scouring/bleaching with GOX-generated peroxide, reusing starch containing desizing baths
desizingscouring/bleaching
amylases GOX/glucose
Scoured
fabric
Standard
H2O2
(0.17 g l-1)
bleaching
Bleaching with H2O2 (0.30 g l-1) generated from:
Free
enzyme
Immobilized enzyme
pH 11,
95 C
pH 11,
95 C
Persulfate,
pH 11, 25 C
Peroxidase,
pH 5, 55 C
CIE
whiteness
37.9 74.5 73.6 74.1 55.4 47.3
BIO-PREPARATION OF TEXTILES
Bleaching with laccasesLaccases (EC 1.10.3.2) are multi-copper enzymes, which catalyse the oxidation of many aromatic substances using O2 as an electron acceptor.
-2
-1
0
1
2
3
4
5
6
0,06 0,11 0,17 0,22 0,28 0,34 0,39
laccase concentration, mg/ml
W
* ² W*laccase² W* lac./perox.
Pre-treatment with laccase 10 min, 60˚C, pH 5
0
0,2
0,4
0,6
0,8
1
1,2
0 10 20 30 40 50 60
Time (min)
Con
s. O
2 (m
g/l)
0,1g cotton in buf.
0,1g cotton +laccase
0,2g cotton+laccase
laccase in buf.
Oxygen consumption in laccase reaction
Dyes and wavelengths Sample K/S dyed K/S laccase K/S bleach. K/S decreaseBlank 9.17 8.75 3.01 67 %R.Yellow 160, 430 nmSample 9.34 11.45 2.22 76 %Blank 17.40 17.13 9.69 44 %R. Green 19, 640 nmSample 17.34 17.21 4.83 72 %Blank 4.95 4.46 0.94 81 %R. Orange 16, 530 nmSample 5.08 4.79 0.51 90 %
BIO-PREPARATION OF TEXTILES
ENZYMATIC DYEING
Laccases are also known to polymerize phenolic compounds resulting in colour generation.
Small colourless aromatic compounds - dye precursors (diamines, aminophenols, aminonaphtols, phenols) are oxidized by laccase to aryloxy-radicals, which may undergo further non-enzymatic reactions resulting in coloured dimeric, oligomeric and polymeric molecules.
The dye precursors can be used alone or in combination with suitable modifier – another phenolic compound, which will enlarge the colour pallet
LACCASES DYEING OF PROTEIN FIBRES
Expected mechanism of the reaction between dye precursor and modifier
Cross section of laccase-dyed wool fibres
Tzanov, Tz., Silva, C., Zille, A., Oliveira, J., Cavaco-Paulo, A. Appl. Biochem. Biotechnol. Part A: Enz. Eng. Biotechnol. Vol.111, 2003
OH
OH
NH
SO3H
NH2
O
O
OH
OHNH2
SO3H
NH2
Laccase
ENZYMATIC DYEING
CATIONIC DYE ADSORPTION OF ENZYMATICALLY MODIFIED WOOL
0
20
40
60
80
100
120
0 20 40 60
Dye
exh
autio
n (%
)
Time (min)
C Lac Lac+CA Sample Fixation (%) (±) Error
C 74.1 1.4
Lac 61.16 2.94
Lac+CA 90.62 0.74
(a)
(b)
Dye exhaustion (a) and fixation (b) of caffeic acid modified fibres using laccase can be possible to increase from 86 % to 96 % and 74 % to 90 % respectively
5 min
2ºC/min
Room temperature
30 º C
55 min
Dyed fabric was takenout, rinsed and washedwith cold and hot water
Cool down to room temperatureModified/
Unmodified wool
CV dye solution
Dyeing procedure of protein fibres with the C. I. Basic Violet 3
Exhaustion Fixation
DYING WITH CATIONIC DYE (CV) ON MODIFIED WOOL
Modification treatment condition:0.1 M Na/acetate Buffer pH: 4.5; 40 ºC; 180 min, 40
rpm, 0. 125 mg prot/ml laccase, 50 mM CA C: Wool previously treated with only bufferLac: Wool previously treated with laccase
Lac+CA: Wool previously treated with Laccase + Hydrocaffeic
Dying recipeCrystal violet (CV): 0.001%, 30 ºC, 60 min, 85 rpm,
M:R: 1:60 After treatment
Hot wash at 80 º C, 60 min, then cold wash
Lac +CAC Lac
C Tyr Tyr+CA
Modification treatment condition:0.1 M Phosphate buffer pH: 6.5, 25 º C, 180 min, 60 rpm, 50 U/ml
Tyrosinase, 20 mM CA C: Wool previously treated with only buffer
Tyr: Wool previously treated with TyrosinaseTyr+CA: Wool previously treated with Tyrosinase + Hydrocaffeic acid
DYEING WITH PDI
Protein disulfide isomerase PDI (EC 5.3.4.1) catalyzes thiol-disulfide exchange between various small molecules and proteins by nucleophilic substitution at divalent sulfur.
ENZYMATIC DYEING
Woo/lHair
Wool/Hair
Dye
Tzanov, Tz.., Cavaco-Paulo, A. Portuguese Patent 102779 (2002).
Dye-SH + keratinous fibres Dye-S-S-keratinous fibresPDI
N N
C NH
Me2N
O
CH
COO Me
CH2 SH
Transglutaminase-assisted dyeing
Dye C
O
NH2 keratin NH2 Dye C
O
NH keratin NH3
Dye NH2 keratin C
O
NH2Dye C
O
NH keratin NH3
++TG
+TG
+
ENZYMATIC DYEING
ENZYMES FOR TEXTILE FINISHING
Conventional durable-press finishes - ether bond crosslinking
- Products with high formaldehyde release, i.e. dimethyloldihydroxyethylenurea (DMDHEU)
- Products with lower formaldehyde content, i.e. -hydroxyalkylamides, polymers from urea and glutaraldehyde, and diamidodihydroxyethane products
ENZYMES FOR TEXTILE FINISHING
New formaldehyde-free products - ester bond cross-linkingPolycarboxylic acids:1,2,3,4-cyclopentanetetracarboxylic, 1,2,3,4-butanetetracarboxylic (BTCA), combination of citric acid and polymers of maleic acid
Drawback of any durable-press finish - decreased fabric strength
Enzymes- controlled degradation of the cross-links in order to restore partially the strength loss, without deteriorating the crease-resistance effect
A multifunctional wool material combining water repellency (contact angle increased from 115º to 146º), reduction of bacteria growth by 50 % and antioxidant activity expressed in 60 % inhibition of DPPH compared with the unmodified fabric have been produced in a one-step process using laccase and Gallates ester
Antibacterial & Anti oxidant activityWater repellent finish
C ( 100 sec)Lac+DG
(600 Sec)
1. Kh. M. Gaffar Hossain, María Díaz González, Guillem Rocasalbas Lozano, and Tzanko Tzanov. Enzymatic process for multifunctional protein fibres. 237th ACS National Meeting, March 22-26, 2009. Salt Lake City, Utah, USA
2. Kh. M. Gaffar Hossain, María Díaz González, Guillem Rocasalbas Lozano, and Tzanko Tzanov. Multifunctional wool produced in an enzymatic process from aqueous-organic medium. 3rd World Congress of Industrial Biotechnology (ibio-2010), July 25-27, 2010 Dalian, China.
3. Kh. M. Gaffar Hossain, María Díaz González, Guillem Rocasalbas Lozano and Tzanko Tzanov. Multifunctional modification of wool using an enzymatic process in aqueous-organic media, Journal of Biotechnology,141, 58-63, 2009
ENZYMES FOR TEXTILE FINISHING
4. Kh. M. Gaffar Hossain, María Díaz González, Ascension Riva Juan and Tzanko Tzanov. A single step enzymatic modification of wool textile to improve its various properties. AATCC's International Conference (IC), May 18-20, 2010, Atlanta, (GA), USA
5. Kh. M. Gaffar Hossain, María Díaz González, Ascension Riva Juan and Tzanko Tzanov. Enzyme-mediated coupling of a bi-functional phenolic compound onto wool to enhance its physical, mechanical and functional properties. Enzyme and Microbial Technology 46 (2010) 326–330
This one step enzymatic coating process improved the physical and mechanical properties of wool fabrics such as shrink resistance, crease recovery angle and tensile strength by respectively 14, 5 and 24 %.
Antioxidant activity expressed in 85 % inhibition of DPPH and protection against UV-radiation.
ControlControlEnzymatic dyeing
Enzymatic dyeing
UV-protection
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
290 300 310 320 330 340 350 360 370 380 390 400
Tra
nsm
itta
nce
Wavelength (nm)
C Lac NDGA Lac+NDGA
ENZYMES FOR TEXTILE FINISHING
ENZYMATIC PROCESS FOR MACHINE WASHABLE WOOL
0
5
10
15
20
25
30
C TG P P+TG
%
Tensile strength loss (%) Shrinkage (%) Weight loss (%)
•Weight and tensile strength loss of 2 % in the simultaneous process appear rather insignificant compared to the 25 % strength deterioration and 7 % loss of protein material in the protease treatment
•Besides of the simplicity of the simultaneous method, the relatively short treatment time (60 min) to obtain the desired shrink-resistance properties is another advantage.
•SEM images of the fabrics confirmed the insignificant fibre damage in the simultaneous process
6. Kh.Md. Gaffar Hossain, Ascensión Riva, Josep Ma. Canal,Tzanko Tzanov. Enzymatic process for machine washable wool. 21st IFATCC Congreso, 6-9 May 2008, Barcelona, Spain
7. Kh. M. Gaffar Hossain, Ascension Riva Juan, Tzanko Tzanov. Simultaneous protease and transglutaminase treatment for shrink resistance of wool. Biocatal Biotransform, 2008, 25 (5), 405-411
P P+TG
Activation of the textile material for FR finishing Fibre types Enzymes Mechanism for activation /modification Cellulosic Cotton
Flax Cellulases Hydrolysis of glucosidic linkages in cellulose and formation of
hydroxyl groups able to graft through addition to electrophilic o-and p-quinones and imines from the FR
Hexokinase Phosphorylation of polysaccharides Haloperoxidases Halogenation of organic compounds forming stable C-Cl bonds
Proteic Wool Silk
Protease Amide hydrolysis to improve hydrophilicity/accessibility and to create new -COOH and -NH2 groups able to crosslinks with the activated FR
Laccase Tyrosinase Peroxidase
Formation of reactive electrophilic quinones and imines to further react with nucleophilic groups from the FR (e.g. -OH, -SH, -CONH2, -NH2)
Synthetic PES Lipases, cutinase
Ester hydrolysis to yield more -OH and -COOH groups
PA Protease Hydrolysis of amide groups to -COOH and -NH2 PAN Nitrilase Nitrile groups hydrolysis to amide/carboxyl able to esterify with -
COOH groups from the FR PE Laccase Alkenes oxidation to epoxides able to react with nucleophilic
groups (e.g. -NH2) from the FR Durable FR application Fibre types Enzymes Mechanism of coat/coated material bonding Proteic Cellulosic Synthetic
PDI TG Oxidoreductases Hydrolases
Thiol-disulfide exchange and formation of disulfide bonds Acyl transfer and formation of amide linkages Radical polymerization (crosslinking) Polycondensation, esterification/transesterification
ENVIRONMENTAL ASSESSMENT TOOL
Raw material extraction
Production
Use
Disposal
Conventional process Enzyme based process
Different environmental impact !
Same output..
PROBLEMS
The still relatively high price of the biocatalysts
The natural enzymes’ substrates in most cases are low molecular species, instead of polymers, and the catalysis occurs normally in homogeneous systems
The textile processes are characterized with high turbulence of the baths, high temperature and extreme pHs.
IMAGINE THE BIOBASED SOCIETY ….. where everything can be made from renewable sources ……
Renewable Raw materialsEnd Product
Enzymatic hydrolysis
CONCLUSION
Enzyme is eco-friendly, completely biodegradable and they will not leave any chemical residues on the processed materials, and the colour change on the dyed goods is minimum.
Bio-processing also offers the potential for new industrial processes that require less energy, less water and less effluent problems with effective results Applications of biotechnology to textile wet processing are an example of more environmentally compatible processes
Engineers with knowledge and basic understanding in both textile technology and enzymology will help to introduce these environmentally-friendly processes more extensively to the wet processing industries in Bangladesh
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