Green Solvents- A sustainable option

Sangeeta Srivastava

Godavari Biorefineries Limited

Mumbai

www.somaiya.com

Solvents!!!!

• Playamajor role inmanyareas 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,mixingetc.

What are Green Solvents?

• Chemicals arising from fermentation and renewable

resources

• Minimizetheuseandgenerationof hazardous substances

• Theymeet thegoal tominimizeenvironmental impact

• ThereforeTheyare–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

Green

Chemistry

Prevention

Atom Economy

Less Hazardous chemical synthesis

Designing safer chemicals

Safer Solvents & Auxiliaries

Design of Energy efficiency

Use of Renewable RM

Inherently safer chemistry for accident prevention

Real-time analysis for pollution prevention

Design of Degradation

Catalysts

Reduce Derivatives

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 lactate

Isooctane Dicholoroethane

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 Solvents

Flash Point (OC)

Reason

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

Pyridine 20carcinogen, toxicity, very low threshold limit value TLV 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 Product

Produces product with other impurities, which can be purified

Much purer product

Reaction conditions

Gentle temperature & pressureHigh temperature & pressure

Use of resourcesUses renewable resources based on plant material.

Uses finite resources based on crude oil.

Sugar

Ethanol

Bulk Organic Chemicals

Specialty Chemicals

Agriculture & AgriculturalResearch

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

Renewable energy

Education

Healthcare

Printing and Publishing

Food Processing

About Somaiya Group

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

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

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

GBL is involved in production of various agricultural products & sugarmanufacturing since 1939, started producing ethanol from 1961, haslaunched a cogeneration unit in 2002, and is selling carbon credits since2007.

About Godavari Biorefineries Ltd (GBL) …

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 toxicitybeing produced by lactic acid aqueous solution and ethanol, via anesterification 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

SOLVENTSTOXIC RELEASEINVENTORY (TRI)

EVAPORATIONRATE

EFFECTIVENESSXYLENE = 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 toxicitybeing produced by levulinic acid aqueous solution and ethanol, viaan esterification process

• Variety of esters possible

• Renewable source (non-petrochemical)

• 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

1,3-Butylene Glycol

Different Solvents

Ethyl Lactate Ethyl Acetate 1,3-Butylene Glycol

Source Molasses Ethanol Acetaldehyde

ApplicationPaint and coatings

industry, Paints and printing ink

industry, Cosmetic industry

Flash Point, OC

CC - Closed Cup

OC - Open Cup

46 CC

130 OC

–4 CC

13 OC

109 CC

115 OC

Solubility Totally soluble 78 g/l @ 20 C Totally soluble

Azetropic point with water, OC

& compositionNo azeotrope

70.4

91.5/8.5No azeotrope

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