Scope of Biotechnology in Paint Industry

Prof. D.K. Bhattacharyya

Adjunct ProfessorSchool of Community Science & TechnologyBengal Engineering and Science University

Shibpur

Definition of Biotechnology

Biotechnology is defined as the kind of technology that utilizes the living systems as well as their constituents to produce materials for service.

Biotechnology Methodologies

Genetic Engineering (Recombinant

DNA technology)

Microbial Enzyme Technology or

Biocatalyst Technology

Microbial Fermentation Technology

Production of Vegetable Oils with desirable Fatty Acid Composition by Gene Cloning Technology (Biomodified Oils)

Gene Trait of the Biomodified Oils

1. Stearoryl-ACP 1. High stearate oil or High oleate oil

desaturase 2. Δ15 desaturase 2. Low or High polyunsaturated oil

3. ACP 3. High laurate oil thioesterase

Microbial Production of Oils with desired fatty acid composition (Single Cell Oils)

Oleic acid (18:1) rich oil Linoleic acid (18:2) rich oil Linolenic acid (18:3) rich oil

SOME LIPASE CATALYSED REACTIONS:

Oxidation. Isomerization. Hydrolysis. Esterification. Interesterification Alcoholysis Ester-Ester Interfication

Acidolysis

Major Biocatalysts/Enzymes and Sources

Enzymes Sources Lipase Fungus Phospholipase Mold Protease Yeast Amylase Bacteria Pectinase Living Cells are

also used Cellulase as catalysts Phytase Tannase Lipoxygenase

Some Commercial Biocatalysts (Lipases & Phospholipases)

Mucor miehei Rhizopus arrhizus Geotrichum candidum Candida cylindracae Candida rugosa Candida tropicalis Pseudomonas sp. (Flourescence) Candida antarctica Phospholipase A1 & A2 Phospholipase C & D

BIOISOMERISATION OF VEGETABLE OILS

Vegetable oils Treated with Anaerobic

bacteria(Haying Conjugase &

Isomerase Enzymes), 37˚C,

Atmospheric Pressure

Bioisomersed oils

BIOEPOXIDATION OF OILS

Unsaturated (Linoleic acid-rich) oil

Oxygen Enzyme Lipoxygenase Hydroperoxy-Conjugated Octadecadienoic Acids

Epoxy Fatty Acids

Production of Dibasic Acids by Biooxidation Process from Fatty Acids and Hydrocarbons

Yeast such as Candida tropicalis M2030 is capable of producing ‘Dibasic’ acids from the ‘Monobasic’ acids derived from vegetable oils and Hydrocarbons by the Biooxidation process in a fermentor. The yield is almost quantitative.

Some Dibasic Acids from Fatty Acids and

Hydrocarbons:Fatty Acids/Hydrocarbons Dicarboxylic AcidsOleic Acid 18:1 Palmitic Acid 16:0 Linoleic Acid 18:2n-Hexane Adipic acid (6:0) n-Octane Sebacic acid (8:0) Tri-decane 13:0 Tetra-decane 14:0

ENZYMATIC ESTERIFICATION FOR SYNTHESIS OF MONOGLYCERIDE

Fatty acids + Glycerol Hexane + Lipase from

Penicllium Species, Room temperature (24˚C)

Monoglycerides (85˚C Mol % Incorporation

Of fatty acids)

MONOGLYCERIDE BY GLYCEROLYSIS OF ALKYL (C1-C4) ESTERS OF FATTY

ACIDS USING ENZYME (BIOCATALYST)

Glycerol + Alkyl(C1-C4)esters of fatty acids

Lipase/60˚C/Vacuum

Monoglyceride (s)

Production of Monoglyceride by Lipase Catalyzed Glycerolysis

Process

Fat/Oil Lipase Optimum Temp. MG Yield(Max.)%

Palm Pseudomonas fluorescens 40°C 67

Coconut Pseudomonas fluorescens 30°C 77

Palm Mucor miehei 40°C 57

Palm SP 398 40°C 43

Rapeseed Pseudomonas fluorescens 5°C 77

Production of Bioalkyds (Alkyds made from Biorenewable Oils/Fats are called Bioalkyds)

Involves Two Steps:Step 1: Bioalcoholysis (Bioglycerolysis) of oils

with Pseudomonas fluorescens, Mucor meihei and Glycerol

Step 2: i]Bioesterification of the Monoglycerides (MGs) with long chain dibasic acids with 1,3-specific lipase at 60°C for a long period (72hrs.) under vacuum

ii] Biointeresterification of the MGs with Alkyl Esters (C1 or C4 Alcohols) of Phthalic Acid with 1,3-specific Lipase

BIOALKYDS CONTAINING CONJUGATED FATTY ACIDS

Conjugated C18:3-acid rich oils Bitter Gourd (Momordica charantia) Having ~ 50%

Conjugated C18:3-acid (Elaeostearic with 66% Trans & 33% Cis acid)

Snake Gourd Having ~ 50% Conjugated C18:3-acid

with 66% Trans & 33% Cis acid)

ENZYMATIC SYNTHESIS OF POLYOL ESTERS OF FATTY ACIDS

FOR COATING USE

A. Esterification process: Polyol + Fatty acid (Sorbitol, Mannitol) Hexane + Lipase ; 60˚C Product Mix Hexane removed Desolventised Product Mix Further reaction 60˚C under vacuum Polyol Ester products (Suitable as Paint ingredient varnish oils depending on the fatty acid composition)

B. Alcoholysis Process: Polyol + Alkyl Esters (C1-C4) of fatty acid (s)

Lipase/ 60˚C/Vacuum to remove the alcohol part Polyol Esters

Production of Specific Fatty Acids from Appropriate Vegetable Oils by Biohydrolysis Process

Eg. For making Dimer Acid by Microbial Enzymatic Hydrolysis Process and Clay-Catalyzed Dimerisation

Biohydrolysis in a batch stirred reactorOil/Fat:Water Lipase Temp. /Time Fatty Acid Yield (w/v) Non-Specific (%w/w)Castor oil: Water Mucor miehei 37±2°C/30hr. 89.7(1:2) Sp 398

Coconut acid oil Candida cylindracea 40±2°C/24hr. 82.7 (As Lauric)

Rice bran acid oil Candida cylindracea 25±2°C/72hr. 93.8 (As

Oleic)

Enzymatic Polymerisation of Natural Anacardic Acid

Anacardic Acid(Cashew Nut Shell Liquid) Soy bean peroxidases+2 Propanol+ hydrozen peroxide+ Phenothiazine+ Phenothiazine-10- Propionic acid

Poly anacardic Acid Polymer (Mol, wt.=3,900) 61% yield With Methanol, Polymer ( Mol. Wt.=5000) in 45% yield

The polymer shows antibiofouling effect against Gram Negative and Gram Positive

bacteria.

Preparation of Soyphospholipids with hydroxy and epoxy fatty acids by

enzyme catalysed interesterification

Major Fatty Acids Composition (%w/w) and Interficial Tension (IT) IT 16:0 18:1 18:2 18:3 18:1(OH) 18:1

(Epoxy) Soyphospholipids 13.2±0.08 27.3 14.7 52.5 3.8 - -

Soyphospholipids 23.6±0.08 6.4 7.1 17.4 1.2 65.1 - with hydroxy oleic acid

Soyphospholipid with 21.5±0.08 8.2 7.3 35.5 2.5 - 43.1

epoxyoleic acid

Soyphospholipid with 19.0±0.08 7.0 6.7 23.0 3.2 57.6 - hydroxystearic acid (18:0-OH)

Biodiesel Feed StockMajor Oils: Minor Oils:1. Soyabean 1. Tree-borne seed oil like

Karanja Mowrah, Undi, Nahor2. Rapeseed 2. Plant seed oil Jatropha

(Ratanjyot)3. Mustard 3. Rice bran4. Sunflower 4. Watermelon5. Palm and its 5. Tobacco seed Fractions 6. Niger seed6. Coconut7. Palm Kernel8. Cottonseed9. Tallow

One Step Biocatalyst Process for Biodiesel Production

Simultaneous Esterification and Transesterification (Acidolysis) of Triglyceride Oils

R.COOH + MeOH RCOOMe + H2O

TRANSESTERIFICATION: CH2OCOR CH2OH Lipase CHOCOR + 3MeOH 3 R.COOMe + CHOH CH2OCOR CH2OH

Lipase: Candida Cylindraceae, Candida Rugosa, Candida Antartica &Lipase 3A (1,3-specific lipase)

Biobutanol Butanol is an important fuel. Its characteristics make it a better fuel

than ethanol in the formulation of gasohol for the following reasons. Much lower Reid vapour pressure. Higher flash point. Higher octane rating. More miscible with gasoline.

Production TechnologyLow value inexpensive renewable feed stock

Glucose Anaerobic fermentation using Clostridium

acetobutyicum

Butanol

Biotechnology Applications in Paint Industry

Production of Specific Fatty Acids rich Vegetable Oils

Production of Specific Fatty Acids from Vegetable Oils

Production of Short and Long Chain Dibasic Acids

Production of Bioalkyds

Production of Surfactants

Conclusion Biotechnology has enormous potential in Paint industry.

Biotechnology offers the advantages like• Low Energy• Low Ecology• Low Capital Investment• High Specificity & Selectivity• High Quality of Products

Industries should explore the Biotechnology- based process developments at commercial level.

THANKYOU