Biotechnology in Textiles

Rossari Biotech, Mumbai

BIOTECHNOLOGY - The Application of Nature's

Toolset
Examples of Biotechnology
Bio-based polymers

Market penetration
Effluent Decolourisation

Enzymes for the textile industry

Today

Time

ENVIRONMENT: Decreasing the Footprint

Impact of BIOTECHNOLOGY

Reduction of:
Increased energy and process efficiency

Greenhouse gas emissions Emissions to water Emissions to air

Renewable feedstock

Resource usage

Bio-Based POLYMERS

Impact
NatureWorks Bio-degradable polymer made from corn Environmental
Average reduction of fossil inputs - 17% to - 55%

Sorona Polymer based on dextrose from corn

Economic Currently competitive in niche applications Future competitiveness highly dependent on feedstock costs

Bio-Polymer Production (Cargill-Dow, USA)

Production of Polylactic acid (PLA) polymer from corn sugar replaces petroleum feedstock. PLA can replace PET, polyesters and polystyrene. PLA is compostable. PLA is carbon neutral CO2 is recycled. In the future, PLA will be made from ligno-cellulosic biomass.

Effluent Decolourisation

Why WATER a Problem?

Why a water concern when the planet has 71% water ? Problems Scarcity of fresh water; Needs of water for life preservation; Needs of water in agro-industrial activities; Development of a consumer society; Cost of wastewater treatment, etc.

Wastewater Purification Mechanism by Activated Sludge

Equalizing tank
(equalization, pH adjustment) Organic Substances

Activated sludge
(aeration)

Settling tank
(separation)

Microbes Sludge (anabolism, H2O, CO2, catabolism) residual o.s. In general about 90-95 % of the BOD load is removed; The supernatant is discharged as treated water; The activated sludge is re-circulated.

BIOCLAR Process
The wastewater treatment consists in:
- Aeration in contact with recycled activated sludge; - Oxygenation; - Sedimentation.

Characteristics:
- High concentration of sludge; - Re-aeration of sludge in the second step.

Performance:
- Removal of more than 94% BOD, COD.

ENZYMATIC Treatment
Special microorganism or enzymes:
Ligninolytic fungi Laccases Cocktail of oxidoreductases

Combined procedures:
Biological anoxic decolorization, aerobic combined with O3 oxidation (azo dyes) Activated sludge combined with membrane plant Absorption and coagulation combined technology Fungal Laccase together with redox mediators

ENZYMES

A New BIOCATALYST
.An Essential Tools for Sustanable 21st Century Textile Industry

What are Enzymes?

Proteinaceous polymers
Made up of 200-250 amino acids Catalyze chemical reactions - i.e. hydrolysis, oxidation, reduction, etc.

Produced by living organisms - i.e. fungi or bacteria Act as Organic Bio-Catalysts

Accelerate reactions by reducing activation energy

Enzymes are not alive

Are complex organic polymers

Enzymes are Specific i.e. amylases act on

starch, cellulase on cellulose

Enzymes are Biodegradable

Enzymes - A Biological Catalyst

Manufacture Through FERMENTATION

How Enzymes work?

Types of ENZYMES
ENZYME CLASS Hydrolases Lyases Transferases TYPES OF REACTIONS CATALYSED Hydrolysis of molecules and degradation in some cases. Nonhydrolytic cleavage of degradation of molecule. Transfer of a group from one molecule to another. ENZYMES Cellulase, Protease, Amylase, Lipase Laccases Transaminase Fumarase Glucosephoshate, Isomerase Glutamine, Synthetase

Oxireductases Oxidation or reduction of molecules. Isomerases Ligases Conversion of one isomer to another. Joining of two molecules with ATP.

Enzymes - Textile Applications

Fading Backstain Cleanup Biopolishing Biosoftening - wool Print washing Silk degumming Bio-scouring Bio-bleaching Washing off Reactives H2O2 removal Effluent colour removal Fibre retting and carbonising Detergent Cellulases: Denim fashion and colour. Special Proteases Cellulases increase depth. Colour yield & shrinkage. Brightens colour. Higher depth. Opens newer possibility. Denim different effects. Reactive soaping. Aids level dyeing, consistency. Environment friendly. Processing flax, ramie, wool etc. Blend of amylase, protease, lipase etc.

Factors Influencing Enzyme Activity

1. pH 2. Temperature 3. Time 4. Dosage 5. Mechanical action 6. Auxiliaries used 7. Heavy metal impurities 8. Dyefixing treatment 9. Microbiocides 10. Various dyestuffs

Factors affecting Enzyme Activity

Enzymes can be denatured by temperature and pH

Active (functional) protein

Denatured Protein

AMYLASES
DESIZING OF STARCH

Size Composition
Natural Sizing agents  Starch and its derivatives,
 Cellulose derivatives,  Carboxy methyl cellulose,  Methyl cellulose,  Oxy ethyl cellulose,  Protein sizes,  Glue, gelatin

Synthetic Sizing agents

 PVA (Polyvinyl alcohol),  Polyvinyl acetate,  Acrylic acid,  Polyester,  Copolymers of styrene and maleic

acid Blends like starch and PVA etc. Wax, Lubricants & other ingredients

What is Starch?
CH2OH O OH O OH O OH OH O OH CH2OH O OH O CH2OH O

Amyl s (MW = 0000-50000) CH2OH O OH CH2O OH OH O OH Amyl p ctin (MW = 50000- 00000) O O OH OH O CH2OH O

Enzymatic Desizing
 Alpha-amylase is commonly used to remove starch size  Hydrolyses the 1,4 glycosidyl bond of starch  Two major types of alpha-amylases  Conventional low temperature alpha-amylase  Thermostable alpha-amylase

Enzymatic Desizing - Mechanism

 Wetting, pH buffering, anti catalytic action  Swelling, penetration, cracking and de-stabilization of size layers  Gelatinization  Enzyme attack - The enzyme takes the role of molecular scissors.  Wash off, dispersion of the degradation products

Starch Hydrolysis

glucoamylase

Famylase

E-amylase

E -D-glucosidase

pullulanase

exo (1 4)- E -Dglucanase

cyclomaltodextrin D-glucotransferase

isoamylase

Reducing D-glucosyl residue or D-glucose Non-reducing D-glucosyl residue

PECTINASE
BIO-PREPARATION & BIOSCOURING

Bio-Scouring of Cotton
Cotton Structure
Lumen

Whole Fibre Primary Layer Cellulose Protein Pectins Wax Ash Others 94% 1.3% 0.9% 0.6% 1.2% 54% 14% 9% 8% 3% 4%

Secondary Wall

Winding Primary Wall

Cuticle

Concept of Scouring of Cellulosics using synergistic mixture of Enzymes & Surfactant

Bio-Scouring - Comparison
Bio-Scouring Dosage
(g/kg cotton) pH Energy (kcal/kg cotton) Environmental Impact ater m3/t cotton

Conventional 3 Alkaline

.3 Neutral

1 , No .

23, Yes 4.2

Conventional Scouring - Pros & Cons

ADVANTAGES
Efficient in continuous pad process Superior whiteness Mote removal

DISADVANTAGES
Hazardous Rinsing Cost (labour/water/corrosion) Effluent treatment Alters morphology of cotton fibre Higher weight loss

CELLULASES
GARMENT FADING BIO-POLISHING

Cellulose Cellulose fibres

Cellulose is a polymer of Beta 1,4 glucose Cotton Flax Jute Ramie Regenerated Rayon Tencel or Lyocell

Cotton Primary Wall

Netlike association of chains Lowest contribution to tensile strength Target of both wear and enzyme treatment

Secondary Wall
Ordered crystalline micro-fibrils Highest contribution to tensile strength

Cellulase Enzyme Endoglucanases Cellobiohydrolases

   
A A D AN

Cellulase Enzy e
N G ycosylation

Converts cellulose to smaller, more soluble sugar units Its a multi-unit enzyme that contains: -a catalytic core -cellulose-binding domain -flexible and heavily glycosylated linker

    

Beta Glucosidases

O-Glycosylation

E U SE ND NG AN D

Cellulase- Mode of Action

Endo cellulases (Endoglucanases) Cut in the middle of the chain Exo cellulases (Cellobiohydrolyses) Cut cellobiose (DP2) from either the reducing or non-reducing ends of the cellulose chain

Beta glucosidases Cut cellobiose into two molecules of glucose

Acid Cellulases/ Whole Cellulases

- Synergistic blend of enzymes designed to convert cellulose to

glucose
From many fungal and bacterial organisms - i.e. Trichoderma, Humicola, etc. Contains different enzymes. 6.5
Aggressive Short Process Time Wide Range of Abrasion High Back-staining Bluish cast
5.0 pH 5.5 6.0

4.5

40

45

50 55 60 Temperature oC

65

68

Modified Cellulases - Whole cellulase with proprietory process and formulation

technology
Medium Contrast Short Process Time Broad operating temperature Medium Back-staining Medium Grey Cast Good Salt & Pepper Effect
4.5 40 45 50 55 60 Temperature oC 65 68 5.0 pH 5.5 6.0 6.5

Engineered Cellulases
Genetically modified organisms with reduced CBDs
Maximum Processing Flexibility Premium high Contrast
8 9

Broad operating range of pH & temperature Wide range of abrasion No Back-staining

pH 7

Grey Cast
5 40 45 50 55 Temperature oC 60

Action of Cellulase

Cotton treated without Cellulase

Cotton treated with Cellulase

BIO-POLISHING

Genetic Modification of Cellulases

High throughput Robotic screening (HTRS) to identify proteins from Eukaryotic organism followed by making enough functional protein and finally commercialization Genetically modified Organisms Cellulase with Increased filter paper activity Bio-polishing Acid Cellulases designed for low backstain Genetically modified cellulase enzymes for a particular Endo glucanase activity producing higher yields Cold acting cellulases

Factors Influencing Biopolishing Efficiency

Desired Benefits
Improvement in Fabric Hand
Smooth fabric surface Enhanced Drapeability and softness

Improvement in Fabric Aesthetics and Characteristics

Removal of surface fuzz and pills, pilling prevention Elimination of neps and motes Increased lustre, brighter colour Improved surface appearance

. and these benefits are permanent!

Fabric Type and Construction Process Time Equipment Economics

Substrate Type
Fiber type Cotton Desired benefits  Surface fiber removal; Pill prevention and removal; Softening; Smooth fabric surface; Elimination of neps and motes; Wash down  Removal of fibrillation; Improved hand (softness, drapeability); Peach skin touch  Softness; Surface fiber removal; Smooth fabric surface; Wash down  Softness; Smooth fabric surface; Wash down

Lyocell Rayon Linen

Rate of enzymatic hydrolysis.

LYOCELL < POLYNOSIC RAYON < VISCOSE RAYON < COTTON << LINEN
LOW HIGH

Considerations in Biopolishing
Fabric Strength Loss from Cellulose Treatment
Cellulase susceptibility on substrates (Linen>Cotton>Rayon>Lyocell) Fabric weight and construction Equipment, mechanical action Treatment conditions and type of cellulase used

Shade /Colour Loss

Specific to certain dyes and colours

Fabric Bulk
Adversely affected when treatment is not optimised

Accumulation of Lint in Tubular Knits

Problem worst when knits are over treated

Economics
Easy payback with cost of high quality fabrics vs. enzymatic treatment

GARMENT FADING

Denim Look

Cellulase Action

Performance Testing
Abrasion Biofinishing Strength loss Back staining Softening Weight loss Fabric damage Cast

Effect of Cellulase on Denim

Desired effects
Abrasion
Faded look highlighting seams, hems, pockets etc.

Undesired effects
Crease marks
Uneven abrasion with whiter lines

Softness Contrast
Difference in color of blue yarns and white yarns

Backstaining
Redeposition of indigo dye on white yarns

Strength loss

Characteristics of final look

Backstaining
Redeposition of indigo dye on denim during cellulase wash; masks abrasion and results in undesirable flat look

Abrasion contrast
Difference between the colour of the blue warp yarns and the white fill yarns in indigo dyed denim; highest constrast desired

Abrasion cast
Typically gray shade/cast is preferred

Cellulase - Comparison Acid

Aggressive More wash down Patchy contours High Backstaining Bluish cast

Engineered
1.Moderate surface fn 2.Good wash down 3.Medium Backstain 4.Nice salt pepper 5.Med Grey cast 6.Cold application possible

Neutral
Mild Darker wash Even, homogenous wash No back staining Grey cast

Back staining

Engineered

Acid

Acid

Neutral

CATALASE
PEROXIDE NEUTRALISATION

Peroxide Neutralisation
Completely eliminates residual hydrogen peroxide By-products are completely inert to dystuffs and fabrics No need to inactivate Fastest Known catalyst

Why Catalase
Ensures dye shade quality when using reactive dyestuffs and peroxide bleaching
Small levels of residual peroxide can visibly impact dye shade

Reduces the complexity, cost and time of using reducing chemicals to neutralise residual peroxide
Residual reducing chemicals will also effect dye shade quality; catalase is inert towards dyestuffs

Conserves water when peroxide is used

Since catalase effectively eliminates peroxide and is inert to dyestuffs, less rinsing water and time is necessary to neutralise peroxide

LACCASE
BIO-BLEACHING OF DENIMS EFFLUENT TREATMENT

What is Laccase?

Laccase is an ..Oxidoreductase
Catalyse the transfer of electrons from a donor to an accep

How oxidoreductase work?

Chemistry of Laccase Bleaching

H2O

Enzyme (ox)

Mediator

Isatin

O2

Enzyme

Mediator Radical

Indigo

Mediator By-Products

Chemistry of Laccase Bleaching

O NH NH O NH

Indigo
O

O NH2 OH O O NH2 OH

Isatin

Isatic acid

Decolorization

Anthranilic acid

Specificity of Laccase

It does not attack the cotton fibre

It does not effect sulfur-black dye or sulfurincrease whiteness of fill yarns

BIO-BLEACHING OF DENIMS

Bio-Bleaching of denims

An Enzyme Alternatives in Denim Processing...

Alkali + heat Pumice stones Hypochlorite

Desizing
Amylase + Lipase

Abrasion
Cellulase

Bleaching
Laccase

Clean Finishes

Abrasion Enhancement

Backstaining Clean-up

Destruct Finishes

Cellulase / Laccase Bleach

ENZYMATIC WOOL PROCESSING

Raw Wool - Composition

Wool is Kerateneous Fibre

15-72% 12-47% 3-24% 2-24% Wool fibres Fat & Suint Vegetable matter Moisture

Carbonisation of Wool

Cellulases, Lignases and Pectinases modifies wool without damage Reduce amount of Sulphuric acid for carbonizing Reduces effluent load Softens wool Improves colour yield

Biosoftening & Shrink Proofing of Wool

Neutral / Alkaline Proteases softens wool Enzymes combined with Chlorine or polymers or Oxidative agents produces
Enhanced shrink resist wool Cashmere like feel and Far less toxic AOX ,

SILK DEGUMMING

Silk Degumming
Effective gum removal by combination of Serine protease enzyme & surfactant Pepsin and trypsin Protolytic enzymes hydrolyses peptide links producing
additional whiteness, lustre and Increased dye up take

Enzymatic Modification of Polyester

Polyesterase
Eco-friendly eliminates Caustic Improves properties like
- De-pilling
- Hydrophillicity - Size removal - Decreases luster - Improves stain removal

Enzymatic Modification of Acrylic

The different groups of enzymes are involved in hydrolysis of nitriles Nitrilases: Hydrolyse nitriles to the corresponding carboxylic acids forming ammonia Nitrile Hydratases: nitriles are converted to amides,which can be subsequently hydrolysed using amidases Hydrolysis of nitriles and amides is catalysed via thiol acyl enzymes intermediate

Advantages
Better dye uptake Imparts hydrophilicity

Detergent Enzymes

 Renders complete removal of various stains , greasy and soily streaks  Exhibit complete bio souring action on kitchen , hospital and industrial garments.  Eco friendly , easier and milder in action.  Works at neutral and slight alkaline pH ( 7.5 - 10 )  Helps removing other proteinacious stains on clothes

Summary
Investigations so far reveal that enzymes seem unlikely to be toxic or eco-toxic New technology might have increased enzyme stability hence bio-degradability must be checked. Genetic Engineering is either modifying the protein or using recombinant microorganisms, both of which have to be carefully regulated. Biotechnology holds great promise for the future as we are almost as ignorant about microorganisms as we were 2000 years ago.

Thank You! For Your Attention.