Green Solvents- A sustainable option

Sangeeta Srivastava Godavari Biorefineries Limited Mumbai www.somaiya.com Solvents!!!!

• Playa major rolein manyareas of technology

• Provide many opportunities for improvement of environmental aspects.

• Represent a very large proportion of the volatile organic compounds (VOCs) released into theatmosphere.

• Used in coating, cleaning, extraction, reaction, energy control, mixing etc. What are Green Solvents?

• Chemicals arising from fermentation and renewable resources

• Minimizetheuseand generation of hazardous substances

• Theymeet thegoal to minimizeenvironmental impact

• Therefore Theyare–A sustainableOption. Market of Green & Biosolvent

• The market size, in terms of value--about USD 5.58 Billion in 2015 and is projected to reach USD 8.17 Billion by 2020, at a CAGR of 7.94% between 2015 and 2020. • The green and bio-solvents market, along with its applications, witnessed a moderate-to-high growth in the past few years and is likely to continue so in the in the coming years. • Bio-solvents have made rapid incursions into a variety of end-use segments such as printing inks, coatings, edible oil adhesives, food processing, and cleaning products, among others. • Regulatory mandates for the printing ink industry have set stringent guidelines for the use of solvents, thereby driving the increased use of bio-solvents in the printing ink industry. Principles of Green Chemistry

Prevention

Inherently safer chemistry for Atom Economy accident prevention

Real-time analysis for pollution prevention Less Hazardous chemical synthesis

Designing safer Design of Green chemicals Degradation Chemistry

Catalysts Safer Solvents & Auxiliaries

Reduce Design of Energy Derivatives efficiency

Use of Renewable RM Use of Renewable RM-Green Solvent

• A natural resource that can replenish itself over time • Feed stock should be renewable rather than non-renewable • Reduce the consumption of fossil fuel

• Renewable Raw-materials – Agricultural – Forestry – Animal or microbial products

• Examples of renewable agricultural raw materials which are used industrially – Cellulose – Starch – Sugar – Oils and Fats Commonly used solvents

Preferred Usable Undesirable Water Cyclohexane Pentane Acetone Methylcyclohexane Hexane(s) Ethanol Toluene Di-isopropyl ether 2-propanol Heptane Diethyl ether 1-propanol Methyl t-butyl ether Dicholoromethane Ethyl acetate/Ethyl Isooctane Dicholoroethane lactate Iso-propyl acetate Acetonitrile Chloroform Methanol 2-methyltetrahydrofuran Dimethyl formamide Methyl ethyl ketone Tetrahydrofuran N-methylpyrrolidinone 1-butanol Xylenes Pyridine t-butanol Dimethyl sulfoxide Dimethyl acetamide Red Category Solvents

Red Category Flash Reason Solvents Point (OC) Pentane -49 Very low flash point, good alternative available

Hexane(s) -23 More toxic than the alternative heptane

Di-isopropyl ether -12 Very low flash point, good alternative ethers available Diethyl ether -40 Very low flash point Dicholoroethane 15 Carcinogen Chloroform N/A Carcinogen Dimethyl formamide 57 Toxic N-methylpyrrolidinone 86 Toxic carcinogen, toxicity, very low threshold limit value TLV Pyridine 20 for worker exposures Dimethyl acetamide 70 Toxic Benzene -11 Carcinogen, toxic to humans and environment Solvents when manufactured!

Green Solvent Petroleum Solvent

Rate of reaction Slow Rapid

Quality of Produces product with other Much purer product Product impurities, which can be purified

Reaction High temperature & Gentle temperature & pressure conditions pressure

Uses renewable resources based Uses finite resources Use of resources on plant material. based on crude oil. About Somaiya Group

Somaiya group established in 1939 is one of the oldest and well established industrial houses in India and has diversified interest in:

 Sugar  Renewable energy

 Ethanol  Education

 Bulk Organic Chemicals  Healthcare

 Specialty Chemicals  Printing and Publishing

 Agriculture & Agricultural  Food Processing Research GBL’S MILESTONES

- No.1 Processor for Sugar at a Single Location. - Processing 2 – 2.5 Million Tons of Sugarcane per year. - Sugar Production & Sugar Refinery Capacity - 550 Thousand MTPA

- Power plant capacity 50 MW.

- Ethanol Production Capacity - 85 Mn liters p.a. - Leading manufacturer of Beverage Grade Ethanol & Anhydrous Ethanol used in blending with gasoline.

- Produces various chemicals using Ethanol as feedstock. - Among top 10 producers in the world of Ethyl Acetate with production capacity of 80,000 MT p.a & 1,00,000 MT p.a including other Somaiya Group Companies. - GBL’s Chemical Unit is an Export Oriented Unit (EOU).

Private & Confidential About Godavari Biorefineries Ltd (GBL) …

 GBL through its journey of 70 years has created a well integrated sugarcane processing complex & has become a leading manufacturer of Sugar, Ethanol, Organic Chemicals, Power & Bio -Fertilizers.

 GBL is actively pursuing the goal of creating a unique Biorefinery using green & renewable sugarcane as a feedstock.

 GBL is involved in production of various agricultural products & sugar manufacturing since 1939, started producing ethanol from 1961, has launched a cogeneration unit in 2002, and is selling carbon credits since 2007. GBL’s Value Chain

Ethyl Lactate

Crotonaldehyde

1,3-BG Green Solvents GBL

 Ethanol

 Ethyl Acetate

 Paraldehyde

 1,3-Butanediol

 Acetaldehyde diethyl acetal

 3-Ethoxy Butanol

 Acetic Acid

 Ethyl Lactate  Levulinic acid and esters Ethyl Acetate

• One of the most popular Solvent

• Molasses Ethanol Ethyl Acetate

• Esterification reaction

CH3CH2OH + CH3COOH CH3COOCH2CH3 + H2O

• Properties & Applications • Low cost, low toxicity, and agreeable odour. • Present in confectionery, perfumes, and fruits. • In perfumes, it evaporates quickly, leaving only the scent of the perfume on the skin. • In paints act as an activator or hardener • As a solvent it is pretty harmless to the environment and to people too. • Non-carcinogenic EA as alternative

Parameters Ethyl Acetate Dicholoromethane Molecular weight (g/mol) 88.10 84.93 Density (20 OC){g/cm3} 0.897 1.33 Boling Point (OC) 77.1 39.6 Melting Point (OC) -83.6 -96.7 Flash Point (OC) 13 N/A Viscosity (25 OC){cP} 0.426 0.44 n (refractive index) (20 OC) 1.3720 1.424 Dielectric constant (25 OC) 6.02 8.93 Azeotropic point with water (20 OC) 70.4 38.1 Solubility in water (20 OC){g/100g} 7.8 1.3 Explosion range (vol%) 2.2 to 11 14 to 22 Ethyl Lactate

• A renewable Solvent

• Sugarcane/Molasses Lactic Acid Ethyl Lactate

• It’s an important organic ester

• Biodegradable solvent with excellent properties and low toxicity being produced by lactic acid aqueous solution and ethanol, via an esterification process

CH3CH(OH)CO2H + C2H5OH CH3CH(OH )CO2C2H5 + H2O

• Variety of lactate esters possible

• Renewable source (non-petrochemical) Ethyl Lactate

• Attractive Solvent Properties – Biodegradable, – Easy to recycle, – Non-corrosive, – Non-carcinogenic – Non-ozone depleting – Good solvent for variety of processes – Low volatility & Non-toxic – Low-Cost and Environmentally Friendly

• Commonly used in the paint and coatings industry – Potentially has many other applications. EL as alternative

Parameters Ethyl Lactate Methyl Ethyl Ketone Molecular weight (g/mol) 118.13 72.11 Density (20 OC){g/cm3} 1.03 0.805 Boling Point (OC) 151 – 155 79.64 Melting Point (OC) -26 -86 Flash Point (OC) 46 -9 Viscosity (25 OC){cP} 2.8 0.43 n (refractive index) (20 OC) 1.4118 1.3788 Dielectric constant (25 OC) 18.5 8.93 Azeotropic point with water (20 OC) No azeotrope 73.4 Solubility in water (20 OC){g/100g} Totally Soluble 27.5 Ethyl Lactate as an alternative

TOXIC RELEASE EVAPORATION EFFECTIVENESS SOLVENTS INVENTORY (TRI) RATE XYLENE = 1

Xylene Yes 0.86 1

Toluene Yes 2.4 1.025

Acetone Yes 7.7 1.375 N-methyl,1,2 pyrolidone (NMP) Yes 0.03 3.5 Methyl Ethyl Ketone (MEK) Yes 6 1.275

Ethyl Lactate No 0.22 10 Biomass based Solvents Levulinic acid as a platform chemicals Ethyl Levulinate

• A renewable Solvent

• Sugarcane/Molasses Levulinic acid Acid Ethyl Levulinate

• It’s an important organic ester

• Biodegradable solvent with excellent properties and low toxicity being produced by levulinic acid aqueous solution and ethanol, via an esterification process

• Variety of esters possible

• Renewable source (non-petrochemical) 1,3-Butylene Glycol

• Solvent for food flavouring agents

• Molasses Ethanol Aldehyde Aldol 1,3-BG

CH3CH(OH)CH2CHO + H2 CH3CH(OH)CH2CH2(OH)

• Properties & Applications • Practically odourless, viscous, • Hygroscopic liquid of low toxicity. • Better efficacy of preservatives • Has anti-microbial effect itself • Contributes to the preservation of cosmetics against spoilage by micro-organisms. • Intermediate in the manufacture of polymeric plasticizers • Outstanding humectant • Non-irritating Different Solvents

Ethyl Lactate Ethyl Acetate 1,3-Butylene Glycol Source Molasses Ethanol Acetaldehyde Paint and coatings Paints and printing ink Application Cosmetic industry industry, industry, Flash Point, OC CC - Closed Cup 46 CC –4 CC 109 CC OC - Open Cup 130 OC 13 OC 115 OC Solubility Totally soluble 78 g/l @ 20 C Totally soluble Azetropic point with water, OC 70.4 No azeotrope No azeotrope & composition 91.5/8.5 Conclusion

• Green Solvents is a Sustainable option . • Many Solvents are available with better performance.

How many of you would be willing to pay 2-3 times more for Solvents because they are“environmentally friendly” and Green? “But this will change as it is important for creating a better world.” Thanks