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ENZYME/ A GREEN TECHNOLOGY- WAY TO REDUCE ENVIRONMENTAL POLUTION IN TEXTILE WET PROCESSING INDUSTRIES Kh. M. Gaffar Hossain, PhD (E.U) Department of Textile Engineering Dhaka University of Engineering & Technology (DUET), Gazipur-1700, Bangladesh V-Trion GmbH Textile Research Head of the Institute Schwefelbadstr. 2, A-6845, Hohenems, Austria Tel.:0043 676 843771600 E-Mail: [email protected] 27.07.2011

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ENZYME/ A GREEN TECHNOLOGY- WAY TO REDUCE ENVIRONMENTAL POLUTION IN TEXTILE WET PROCESSING INDUSTRIESKh. M. Gaffar Hossain, PhD (E.U)V-Trion GmbH Textile Research Head of the Institute Schwefelbadstr. 2, A-6845, Hohenems, Austria Tel.:0043 676 843771600 E-Mail: [email protected]

27.07.2011

Department of Textile Engineering Dhaka University of Engineering & Technology (DUET), Gazipur-1700, Bangladesh

TEXTILE WET PROCESSING

A process in which the textile materials (fibre/yarn/fabric) are treated in a liquid medium (Water, foam etc.)

This can be categorized in following four steps. i. Fabric preparation ii. Dyeing iii. Printing iv. FinishingThe total quantity of chemicals used in textiles mills varies from 10% to over 100% of the weight of fabricHendrickx et. al., Virginia, 1995

L.W

L.W L.W

L.W

L.W

L.W

L.W

Cotton processing in textile industries

Process wise classification of textile chemicals

PROBLEM (ENVIRONMENTAL IMPACT)Categorization of Textile Waste i. 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)

Wagle, N.P., 2001

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]

Untreated industrial sewage

PROBLEM (ENVIRONMENTAL IMPACT)Dolphin

Fish Plant Arsenic poisoning of polluted water lead to skin cancer and excessive growth of keratin on the feetN Williams et al, Env. Sci. & Tec., 2006

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.

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?

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 properties Improvement of fibres derived from animals and health care of the animals Novel fibres from biopolymers and genetically modified microorganisms Replacement of high energy and harsh chemical treatments by enzymes in textile processing Environment friendly routes to textile auxiliaries such as dyestuffs Novel uses for enzymes in textile finishing Development of low energy enzyme based detergents Waste management

OBJECTIVE

The objective of this presentation is to introduce bio-based enzymatic process to replace harsh chemicals in textile wet processing industries

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).

BASIC ENZYME REACTION

AS S+E

Catalyst

Reactant

Product

BP

Enzyme

Substrate

Product

ES (Enzyme-substrate complex) ES P+Ek1 k-1

S

E

S

E

k2

P

Binding step

Catalytic step

ENZYME SUBSTRATE INTERACTION1. Lock and key model Emil Fischer (1890)The active site: The Substrate Binding Site The Catalytic Site

2. Induced fit model Daniel Koshland (1958)

HOW DO ENZYMES WORK?Without enzymeEnzyme lowers activation energy by this amount

Energy

With enzyme

Enzyme Substrate Complex

Product

Factors affect rate of enzyme reactions

1. 2. 3. 4.

Temperature (20-60 C) pH (5-8.5) Enzyme concentration [E] Substrate concentration [S]

1- Optimum TemperatureLittle activity at low temperature (low number of collisions) Rate increases with temperature (more successful collisions) rate doubles for every 10C increase in temperature Most active at optimum temperatures (usually 37 C in humans) Enzymes isolated from thermophilic organisms display maxima around 100C Enzymes isolated from psychrophilic organisms display maxima around 10C. Activity lost with denaturation at high temperatures

2- Optimum pHEffect 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 concentrationIncreasing [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).

Enzyme Velocity Curve0 1 2 3 4 5 6 7 8 S + E

80 60 40 P Product (v)

200

(in a fixed period of time)

0

2

4

6

8Juang RH (2004) BCbasics

Substrate (mmole) [S]

ENZYMES IN TEXTILES PROCESSINGTextile processing with enzymes aims to develop environmentally friendly alternatives to chemical processes at almost all steps Laccases Proteases Lipases Cutinases Nitrilases Hexokinases PDI Transglutaminases

amylases

Pectinases Proteases

Xylanases Proteases Glucose oxidases Laccases Haloperoxidases Catalases

desizing

scouring

bleaching

dyeing

finishing

preparation

Laccases Tyrosinases Peroxidases Azo reductases

MY CONTRIBUTION TO THE STATE OF THE ART IN THIS FIELDBio-preparation of textiles Enzymes for textile finishing Enzymatic functional modification of textiles Electrochemistry of redox enzymatic systems Enzymatic dyeing/polymerization Enzymes immobilization for application in the textile industrySCIENTIFIC PAPERS & PUBLICATIONS 1. Kh. M. Gaffar Hossain, Mara Daz Gonzlez, Jos Mara Dag Monmany and Tzanko Tzanov. Effects of alkyl chain lengths of gallates upon enzymatic wool functionalisation. J. Molecular and Biocatalysts B: Enzymatic, 67, 231-235, 2010 2. Kh. M. Gaffar Hossain, Mara Daz Gonzlez, 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, 2010 3. Kh. M. Gaffar Hossain, Mara Daz Gonzlez, 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 4. Kh.Md. Gaffar Hossain, Ascensin Riva, Josep Ma. Canal,Tzanko Tzanov. Enzymatic process for machine washable wool. 21st IFATCC Conference Paper, B44, 2008 5. 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, 2008 7. Kh. M. Gaffar Hossain. Enzymatic bioprocess for shrink resistance of protein fibre. ITET Journal, 9, 34-36, 2008 8. Kh. M. Gaffar Hossain, Jos M. Daga, Ascension Riva, Josep M. Canal, Tzanko Tzanov, Un proceso enzmatico para lana resistente al encogimiento, Quimica Textil, 190, 29-35, 2008 ORAL PRESENTATIONS IN CONFERENCES 1. Kh. M. Gaffar Hossain, Mara Daz Gonzlez, 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, USA 2. Kh. M. Gaffar Hossain, Mara Daz Gonzlez, 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 (DAADGermany) February 15-19th, 2010, Dhaka, Bangladesh 4. Kh. M. Gaffar Hossain, Mara Daz Gonzlez, 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 5. Kh.Md. Gaffar Hossain, Ascensin Riva, Josep Ma. Canal,Tzanko Tzanov. Enzymatic process for machine washable wool. 21st IFATCC Congreso, May 6-9, 2008, Barcelona, Spain 6. 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

BIO-PREPARATION OF TEXTILESBleaching - brightening effect, impact on subsequent wet processing operations Acidic to alkaline conditions, wide temperature range H2O2 - most widely used bleaching agent H2O2 can be generated enzymatically from glucose/GOX Gluconic acid produced in the reaction acts as H2O2 stabilizerEnzymatic peroxide production0.3 0.25

Enzymatic peroxide production0,45 0,4 0,35 0,3 0,25 0,2 0,15 0,1 0,05 0

H2 O2 , g/l

0.2

H2O2, g/l

oxygen0.15 0.1 0.05 0 30 60 90 120 150 180 210 240 270 300

15,14 U/ml GOX+20 g/l Glu 22,68 U/ml GOX+20 g/l Glu

shaking

60 120 180 240 300 360 420 480 540 600

time, min 20 g/l glucose, 3.78 U/ml GOX

time, min

20 g/l glucose, 3.78 U/ml GOX

BIO-PREPARATION OF TEXTILESSingle step scouring/bleaching with GOX-generated peroxide, reusing starch containing desizing baths

amylases

GOX/glucose

desizing

scouring/ bleachingScoured fabric Standard H2O2 (0.17 g l-1) bleaching Bleaching with H2O2 (0.30 g l-1) generated from: Free enzyme pH 11, 95 C CIE whiteness 37.9 74.5 73.6 pH 11, Persulfate, Peroxidase, pH 5, 55 C 47.3 Immobilized enzyme

95 C pH 11, 25 C 74.1 55.4

BIO-PREPARATION OF TEXTILESBleaching with laccases Laccases (EC 1.10.3.2) are multi-copper enzymes, which catalyse the oxidation of many aromatic substances using O2 as an electron acceptor.Pre-treatment with laccase 10 min, 60C, pH 5 Oxygen consumption in laccase reaction1,26 5 4 3 W*

1Cons. O2 (mg/l)

0,8 0,6 0,4 0,20,1g cotton in buf. 0,1g cotton +laccase 0,2g cotton+laccase laccase in buf.

2 1 0 0 ,0 6 -1 -2 laccase concentration, mg/ml 0 ,1 1 0 ,1 7 0 ,2 2 0 ,2 8 0 ,3 4 0 ,3 9

W*laccase W* lac./perox.

0 0 10 20 30 T ime (min) 40 50 60

D yes a n d w ele n g av ths Sample R. Ye w 1 6 0 , 4 3 0 Blank llo m n Sample R. Gee n 1 9 , 6 4 0 n Blank r m Sample R. Oan g e 1 6 , 5 3 0 n r m Blank Sample

K/S d y e d 9.17 9.34 17.40 17.34 4.95 5.08

K/S laccase 8.75 11.45 17.13 17.21 4.46 4.79

K/S b leach. 3.01 2.22 9.69 4.83 0.94 0.51

K/S d e c ase re 67 % 76 % 44 % 72 % 81 % 90 %

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

ENZYMATIC DYEINGLACCASES DYEING OF PROTEIN FIBRESExpected mechanism of the reaction between dye precursor and modifierOHS O3H

OHNH2

OH OH Laccase

O OH 2N

NH

SO3H NH2

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

CATIONIC DYE ADSORPTION OF ENZYMATICALLY MODIFIED WOOL30 C 2C/min 55 min Cool down to room temperature

Modified/ CV dye Unmodified solution wool Room temperature

5 min

Dyed fabric was taken out, rinsed and washed with cold and hot water

Dyeing procedure of protein fibres with the C. I. Basic Violet 3C Lac Lac+CASample Fixation (%) () Error

120Dye exhaution (%)

100

8060 40 20 0 0 20 Time (min)(a)

C

74.1

1.4

LacLac+CA

61.1690.62

2.940.74

40

60(b)

Exhaustion

Fixation

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

DYING WITH CATIONIC DYE (CV) ON MODIFIED WOOLDying recipe Crystal violet (CV): 0.001%, 30 C, 60 min, 85 rpm, M:R: 1:60 After treatment Hot wash at 80 C, 60 min, then cold wash

C

Lac

Lac +CA

Modification treatment condition: 0.1 M Na/acetate Buffer pH: 4.5; 40 C; 180 min, 40 rpm, 0. 125 mg prot/ml laccase, 50 mM CA C: Wool previously treated with only buffer Lac: Wool previously treated with laccase Lac+CA: Wool previously treated with Laccase + Hydrocaffeic

C

Tyr

Tyr+CA

Modification treatment condition: 0.1 M Phosphate buffer pH: 6.5, 25 C, 180 min, 60 rpm, 50 U/ml Tyrosinase, 20 mM CA C: Wool previously treated with only buffer Tyr: Wool previously treated with Tyrosinase Tyr+CA: Wool previously treated with Tyrosinase + Hydrocaffeic acid

ENZYMATIC DYEINGDYEING 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.Dye-SH + keratinous fibresO

PDI

Dye-S-S-keratinous fibres

O C O Me C NH CH H2C SH Me2N N NWool/Hair

Dye

Woo/lHairTzanov, Tz.., Cavaco-Paulo, A. Portuguese Patent 102779 (2002).

ENZYMATIC DYEINGTransglutaminase-assisted dyeing

Dye

C NH2 + ke ratin O

TG NH2 Dye

C NH keratin + NH3 O

Dye

NH2

+

TG keratin C NH2 O Dye

C NH keratin + NH3 O

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 FINISHINGNew formaldehyde-free products - ester bond cross-linking Polycarboxylic 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

ENZYMES FOR TEXTILE FINISHINGC ( 100 sec) Lac+DG (600 Sec)

6050 Antioxidant activity (%) Bacterial growth reduction (%)

Percentage

40 30 20 10 0

GA

EG

PG

OG

DG

Water repellent finish

Antibacterial & Anti oxidant activity

A multifunctional wool material combining water repellency (contact angle increased from 115 to 146), 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 ester1. Kh. M. Gaffar Hossain, Mara Daz Gonzlez, 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, Mara Daz Gonzlez, 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, Mara Daz Gonzlez, 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 FINISHING4.5 4 3.5 3 2.5 2 1.5 1 0.5 0

C

Lac

NDGA

Lac+NDGA

Transmittance

290 300 310 320 330 340 350 360 370 380 390 400 Wavelength (nm)

UV-protection

Enzymatic dyeing

Control

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.4. Kh. M. Gaffar Hossain, Mara Daz Gonzlez, 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, Mara Daz Gonzlez, 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) 326330

ENZYMATIC PROCESS FOR MACHINE WASHABLE WOOLTensile strength loss (%) 30 25 20%

Shrinkage (%)

Weight loss (%)

P

P+TG

15 10 5 0 C TG P P+TG

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, Ascensin 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

Activation of the textile material for FR finishingFibre types Enzymes Cellulosic Cotton Cellulases Flax Mechanism for activation /modification Hydrolysis of glucosidic linkages in cellulose and formation of hydroxyl groups able to graft through addition to electrophilic oand p-quinones and imines from the FR Hexokinase Phosphorylation of polysaccharides Haloperoxidases Halogenation of organic compounds forming stable C-Cl bonds Protease Amide hydrolysis to improve hydrophilicity/accessibility and to create new -COOH and -NH2 groups able to crosslinks with the activated FR Laccase Formation of reactive electrophilic quinones and imines to further Tyrosinase react with nucleophilic groups from the FR (e.g. -OH, -SH, Peroxidase CONH2, -NH2) Lipases, cutinase Protease Nitrilase Laccase Ester hydrolysis to yield more -OH and -COOH groups Hydrolysis of amide groups to -COOH and -NH2 Nitrile groups hydrolysis to amide/carboxyl able to esterify with COOH groups from the FR Alkenes oxidation to epoxides able to react with nucleophilic groups (e.g. -NH2) from the FR Mechanism of coat/coated material bonding Thiol-disulfide exchange and formation of disulfide bonds Acyl transfer and formation of amide linkages Radical polymerization (crosslinking) Polycondensation, esterification/transesterification

Proteic

Wool Silk

Synthetic PES PA PAN PE

Durable FR application Fibre types Enzymes Proteic PDI Cellulosic TG Synthetic Oxidoreductases Hydrolases

ENVIRONMENTAL ASSESSMENT TOOLRaw material extraction Conventional process Enzyme based process

Production Use Disposal Same output..

Different environmental impact !

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 systemsThe textile processes are characterized with high turbulence of the baths, high temperature and extreme pHs.

.. where everything can be made from renewable sources End Product Renewable Raw materials

IMAGINE THE BIOBASED SOCIETY

Enzymatic hydrolysis

CONCLUSIONEnzyme 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