Green Solvents- A sustainable option Sangeeta Srivastava Godavari Biorefineries Limited Mumbai www.somaiya.com
Solvents!!!! Playamajor 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 the atmosphere. Used in coating, cleaning, extraction, reaction, energy control, mixing etc.
What are Green Solvents? Chemicals arising from fermentation and renewable resources Minimize the use and generation of hazardous substances They meet the goal to minimize environmental impact Therefore They are A sustainable Option.
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 accident prevention Atom Economy Real-time analysis for pollution prevention Less Hazardous chemical synthesis Design of Degradation Green Chemistry Designing safer chemicals Catalysts Safer Solvents & Auxiliaries Reduce Derivatives Design of Energy 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 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 ( O C) 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 20 Dimethyl acetamide 70 Toxic carcinogen, toxicity, very low threshold limit value TLV for worker exposures Benzene -11 Carcinogen, toxic to humans and environment
Solvents when manufactured! Green Solvent Petroleum Solvent Rate of reaction Slow Rapid Quality of Product Reaction conditions Use of resources Produces product with other impurities, which can be purified Gentle temperature & pressure Uses renewable resources based on plant material. Much purer product High temperature & pressure Uses finite resources 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 Ethanol Bulk Organic Chemicals Specialty Chemicals Agriculture & Agricultural Research Renewable energy Education Healthcare Printing and Publishing Food Processing
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 CH 3 CH 2 OH + CH 3 COOH CH 3 COOCH 2 CH 3 + H 2 O 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 O C){g/cm3} 0.897 1.33 Boling Point ( O C) 77.1 39.6 Melting Point ( O C) -83.6-96.7 Flash Point ( O C) 13 N/A Viscosity (25 O C){cP} 0.426 0.44 n (refractive index) (20 O C) 1.3720 1.424 Dielectric constant (25 O C) 6.02 8.93 Azeotropic point with water (20 O C) 70.4 38.1 Solubility in water (20 O C){g/100g} 7.8 1.3 Explosion range (vol%) 2.2 to 11 14 to 22
A renewable Solvent Ethyl Lactate 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 CH 3 CH(OH)CO 2 H + C 2 H 5 OH CH 3 CH(OH )CO 2 C 2 H 5 + H 2 O 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 O C){g/cm3} 1.03 0.805 Boling Point ( O C) 151 155 79.64 Melting Point ( O C) -26-86 Flash Point ( O C) 46-9 Viscosity (25 O C){cP} 2.8 0.43 n (refractive index) (20 O C) 1.4118 1.3788 Dielectric constant (25 O C) 18.5 8.93 Azeotropic point with water (20 O C) No azeotrope 73.4 Solubility in water (20 O C){g/100g} Totally Soluble 27.5
Ethyl Lactate as an alternative SOLVENTS TOXIC RELEASE INVENTORY (TRI) EVAPORATION RATE EFFECTIVENESS 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
A renewable Solvent Ethyl Levulinate 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 CH 3 CH(OH)CH 2 CHO + H 2 CH 3 CH(OH)CH 2 CH 2 (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 Application Paint and coatings industry, Paints and printing ink industry, Cosmetic industry Flash Point, O C 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, O C & composition No azeotrope 70.4 91.5/8.5 No 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