Industrialization of Green Chemistry at Mahad

Industrialization of Green Chemistry at Mahad Seminar on Awareness of Green Chemistry & Engineering 22-23 April 14 Dr. Babasaheb Ambedkar Technological University, Lonere Nitesh H. Mehta Newreka Green-Synth Technologies Pvt. Ltd. nitesh.mehta@newreka.co.in

Flow Source of our inspiration to focus on industrialization of GC Why industrialization of Green Chemistry? E-Factor & its impact Impact on our Water Resources & on our Businesses Approaches & Strategies for industrialization of Green Chemistry Case Study: Recycle@Source TM Solution in H-Acid plant at Mahad Barriers Solution Providers perspective Conclusions

Our source of Inspiration Patented Technology Customer s Feedback : Recycling mother liquor for over 2.5 years now. Over 800 batches (at times on campaign basis) Just make-up for Water loss (saved millions of lit of water) Amine Quality 99%+ on HPLC, 10% Yield improvement

Potential Impact of a Green Chemistry Solution Impact of Recycle@Source TM Solutions that are ready with Newreka: No. Product Total Production in (TPM) E-Factor * (kgs waste/kg product) Effluent Quality Minimum No. of Recycles Effluent quantity before & after implementing NRS (litres per month) before after 1 Nevirapine 20 4 Mixture of solvents 500+ 80,000 0 2 Sildenafil Citrate 25 14 Neutral effluent 25 3,50,000 14,000 3 Omeprazole 50 8 Highly alkaline effluent 10 4,00,000 40,000 4 Albendazole 100 8 Highly alkaline effluent 25 8,00,000 32,000 5 Quietiapine 20 6 Neutral effluent 10 1,20,000 12,000 6 H-Acid 2000 26 Acidic effluent 15 5,20,00,000 35,00,000 7 OAPSA 75 13 Acidic effluent 15 9,75,000 65,000 8 FC Acid 50 10 Acidic effluent 15 5,00,000 33,000 9 4-ADAPSA 40 10 Acidic effluent 15 4,00,000 26,000 10 m-phenylene Diamine Sulphonic Acid (MPDSA) 100 5 Acidic effluent 15 5,00,000 33,000 Total Impact on environment : effluent discharge to environment & fresh water consumption of industry reduced by over 50,000 MT per month.

E-Factor in Chemical Industry E-Factor = Environmental Impact Factor = kgs waste generated / kg product Sector E - Factor Product Tonnage Oil Refining 0.1 10 6-10 8 Bulk Chemicals 1 5 10 4 10 6 Fine Chemicals 5 50+ 10 2 10 4 Pharmaceuticals 25 100+ 10-10 3 Nature of Pharma, Specialty & Fine Chemicals manufacturing: Complex molecules & multi-step synthesis Chemistry Intensive processes Stringent quality & regulatory requirements Low process yields (low conversion, low selectivity & low separation efficiency) The above leads to High E - Factor or Environmental Impact Factor. Source: R A Sheldon

Impact Impact: huge threat to water bodies & human health Quantity Practice Issue Degradation : Billions of kgs of liquid effluents from Chemical Industries include solid & gaseous effluents include all wastes from all other sectors (mining, steel, power,..) : End-of-pipe-treatment (converting one kind of effluent in to other) : Toxicity not fully known (Ecotoxicity data available for less than 1% of human pharmaceuticals Ref: journal Regulatory Toxicology Pharmacology, April 2004) : very slow, impact unknown after degradation Impact on Economics Direct Cost : loss of solvent, raw material & finished product, loss of utilities, treatment cost, higher overheads, loss of business Indirect Cost : unreliable supplies, loss of credibility in market, anxiety, etc.

Impact on our Water Resources Just 3% of all water on planet is Fresh Water Only 1% of all this Fresh Water is ready available for human use In 20 th Century, population tripled. Water consumption up 6 times 1 in 5 people don t have access to safe drinking water 1 in 3 people lack access to adequate sanitation As per UN, a child dies of water related disease every 15 seconds By 2050, another 3 billion people on planet. Water for them? India: 1 bn people need fresh water daily, limited water resources, increasing outsourcing business & expanding chemical industry

Green Chemistry: A Possible Solution Principles of Green Chemistry & Green Engineering can provide a powerful toolbox for innovations which offer Economic & Environmental Competitiveness. These solutions have the potential to offer Triple Bottomline of: People Planet Profit

Reality of our processes Step 1 Step 2 Step 3 Step 4 4-5 different chemicals 4-5 different chemicals 4-5 different chemicals 4-5 different chemicals Cocktail of 15-25 different chemicals No option except Effluent Treatment Plant or Incineration

Reality of our plants Mfg. Block for Dedicated Products Manufacturing Site Mfg. Block for Campaign Products Dedicated Product Product 1 Product 2 Product 3 Step 1 Step 2 Step 3 Step 1 Step 2 Step 1 Step 2 Step 3 Step 1 Step 2 Step 3 Step 4

Reality of our effluent streams Each effluent stream has its own: Physical properties colour, ph, temperature Chemical composition organics, inorganics Volume Characteristics COD, BOD, TDS, ammonical nitrogen, etc. Toxicity & hazard What we have is: multiple effluent streams with widely differing quantities & characteristics

Reality of our effluent streams Effluent stream from dedicated products Effluent stream from product 1 Effluent stream from product 2 Effluent stream from product 2 Cocktail of 40-50 different chemicals End-of-the-pipe Treatment (primary & secondary treatment, triple effect evaporator, incineration, solid waste disposal sites, land fill, etc.) Impossible to separate, recover or recycle Our Environment

Approaches to deal with environmental challenges Central Effluent Treatment Plant (CETP) - Capital intensive - Cost centric approach - Ineffective same treatment to wide variety of effluents End-of-the-pipe Treatment (ETP) - Capital intensive - Cost centric approach - Converts one type of effluent in to another Economics & Environmental Footprint Industrial Ecology - Low value creation - Logistics & capacity mismatch issues - Doesn t address problem at source level Green Chemistry - Address problem at source level - Profit centric approach, high value creation - Less capital intensive

Strategies for industrialization of Green Chemistry Where to start from? Basis of selection? Green Chemistry Metrices: may start with effluent stream with highest E-Factor, PMI, or any other matrices Toxicity Internal Competency Cost pressures Regulatory pressures Demand from customer Resources available Management s priority Ready availability of a particular technology in market place

Identification of project: E-Factor Calculations Reality of E-Factor & Effluents Load in current process Stage I Sulphonat ion Stage II Nitration Stage III Neutralizatio n Stage IV Reduction Stage V Caustic Fusion Stage VI Isolatio n E-Factor 1.32 1.44 5.20 8.83 7.66 24.65 (per kg H-Acid) Effluent 264 TPM 308 TPM 1040 TPM 1766 TPM 1532 TPM 4930 TPM (for 200TPM plant) E-Factor for Overall Process = 50 (i.e. 50 kgs waste per kg H-Acid manufactured) Final Isolation Stage contributes around 50% of the overall waste generated. All isomers being carried forwarded through all stages to the final isolation step.

Identification of project: Mass Balance/Yield Calculations Reality of Yield in current process 1 kg of Naphthalene 2.4 kgs of H-Acid (Theoretically) 1 kg of Naphthalene 1.28 kgs of H-Acid (Current average yield of manufacturers) 53% of Theoretical Stage I Sulphonat ion Stage II & III Nitration & Neutralization Stage IV Reducti on Stage V Caustic Fusion Stage V Isolation Overall Yield 16% 12% 2% 7% 10% 47% Loss

Strategies for industrialization of Green Chemistry Medium term e.g. Process Intensification of Unit Processes & Unit Operations (Greener catalyst, etc) Short term e.g. Immediate, workable solution (reduce COD or reduce effluent load by recycling) Long term e.g. Paradigm shift in Engineering like micro reactors Very Long term e.g. designing new route of synthesis starting from renewable feedstock, using Biomimicry

Strategies for industrialization of Green Chemistry Medium term Time: 2 to 4 years Resources : low to medium Risk: low to medium Short term Time : 1 to 2 years Resources: very low Risk: very low Long term Time: 4 to 8 years Resources: high Risk: high Very Long term Time : 8 to 16 years Resources: very high Risk: very high

Case Study: Industrialization of GC in H-Acid at Mahad H Acid (1-Amino-3-Hydroxy Naphthalene 3,6 Disulphonic Acid): One of the oldest & biggest volume Dye Intermediates (goes mainly in to Black Dyes) High volume product (India alone makes over 20,000 TPA) Known in the industry for it s high E-Factor (over 50 kgs waste / kg H-Acid) Uses mostly conventional technologies Theoretical yield 2.4 kgs H-Acid/kg naphthalene, Industry yield is 1.28 (53%) Last innovation happened 5 years back solvent based Fusion, yield increased from 1.1 to 1.28 Lot of efforts put in by private companies, government bodies, academic & research institution to change the process & reduce E-Factor

Case Study: Industrialization of GC in H-Acid at Mahad

Recycle@Source TM applied to H-Acid effluent Amine Methanol Caustic Dilute Sulphuric Acid Fusion & Evaporation Isolation Vessel CENTRIFUGE H-Acid Representative diagram of Conventional Process Acidic Mother Liquor Characteristics Colour Deep Red ph 1.5-2.0 COD 150,000 TDS 15-20% Toxicity Not Known

Recycle@Source TM applied to H-Acid effluent Amine Methanol Caustic Mother Liquor Recycle Storage Vessel Recycle Cat TM Fusion & Evaporation Isolation Vessel RCat Treatment Patented Technology More than 15 recycles E-Factor = 90% Yield = 10% CENTRIFUGE H-Acid Acidic Mother Liquor Filter Spent RCat Representative diagram to explain the concept of Recycle@Source TM solution as applied to H-Acid

Recycle@Source TM applied to H-Acid effluent Product Characterization & Impact on Yield (Basis: 500 gms batch size) Batch No. Product Colour Product Appearance Product Obtained (gm) Product Purity Fresh Offwhite Powder 66.3 99.84% Recycle 2 Offwhite Powder 67.8 99.65% Recycle 6 Offwhite Powder 68.3 99.52% Recycle 8 Offwhite Powder 68.4 99.44% Recycle 10 Offwhite Powder 70.2 99.62% Recycle 14 Offwhite Powder 69.0 97.30% Similar, Recycle Solutions developed for MPDSA, FC Acid, OAPSA, etc.

Case Study: Industrialization of GC in H-Acid at Mahad Journey of this Innovation: Journey 1 st phase of technology development 2 nd phase of technology development 3 rd phase of technology development 4 th phase of technology development No. of expts No. of Days Aim 60 50 150 350 120 (4 months) 75 (2.5 months) 250 (8 months) 600 (20 months) To selectively remove impurities from ML for recycle back in process. a. To selectively remove impurities from ML for recycle back in process and reproduce results on bigger batch size. b. 5-7% Rise in Yield per recycle, c. Passing Std. Specs, d. Complete Recycle of Mother Liquor. a. Various water factors studied and optimized to control volumes. b. Catalyst treatment optimized for better impurity bleeding from the Mother Liquor. a. Various water factors studied and optimized to control volumes. b. Catalyst treatment optimized for better impurity bleeding from the Mother Liquor and better by product recovery.

Case Study: Industrialization of GC in H-Acid at Mahad Journey of this Innovation: Journey 1 st phase of technology development 2 nd phase of technology development 3 rd phase of technology development 4 th phase of technology development Gaps Identified Technical: High R-Cat consumption, Poor Salt recovery. Impurities in Product observed. More unit processes involved. Human Did not acknowledge possibility of recycle technology. Rise in volume of Mother Liquor per recycle. Increase in impurity profile of the product per recycle. Rise in volume of Mother Liquor per recycle. Increase in impurity profile of the product per recycle. Byproduct bleeding not consistent. Rise in volume of Mother Liquor per recycle. Increase in impurity profile of the product per recycle. Byproduct bleeding not consistent. Did not encourage benefits of Green Chemistry.

Case Study: Industrialization of GC in H-Acid at Mahad Journey of this Innovation: Journey 1 st phase of technology development 2 nd phase of technology development 3 rd phase of technology development 4 th phase of technology development Accomplish ments Milestones Customized Rcat formulation, No. of formulations customized 5 1 st Lab Scale technology demonstration No of technology Validation demonstration experiments 6 Nos. (5 Recycles) No of days for demonstration 10 Delivered Complete recycle of mother liquor, 5-7% Rise in Yield per recycle product, matching Std. Specifications. Milestones high salt recovery, Optimized R-Cat consumption with low impurities. 5-7% Rise in Yield per recycle passing Std. Specifications. Complete ML Recycle. 2 nd Lab Scale technology demonstration No. of demonstration expts 6 Nos. (5 Recycles). No. of days - 15 Milestones Customized RCat formulation, optimized unit process for Rcat treatment No. of Rcat formulation customized and experimented 2 3 rd Lab Scale technology demonstration No of expts 2 Recycles No of Days - 4 Milestones Customized RCat formulation, optimized water and other raw material consumption. 4 th Lab Scale technology demonstration executed successfully. No. of expts 7 Recycles No of Days - 18

Case Study: Industrialization of GC in H-Acid at Mahad Resources invested in developing Recycle@Source Solution: Time 5 yrs Team Dedicated Team 4 Chemists 2 Technologists 2 Senior Team Members External Consultants No. of Experiments Over 1200 experiments No. of Lab Scale Demo 3 times (to customer for feedback & inputs) Financial Investment In Crores

Case Study: Industrialization of GC in H-Acid at Mahad Tangible Benefits: 3 10% improvement in Yield Lower effluent treatment cost Higher productivity, freedom from shutdown due to closure Overall lower cost of production Saving of huge capital investments required to build effluent treatment facilities Intangible Benefits: Brand & credibility in local community as well as international customers Freedom from treatment of huge quantities of effluents Freedom from pressure of regulatory bodies & closure notices Reliable production & supplies to customers Saving of time & energy which otherwise goes in dealing with regulatory bodies

Case Study: Industrialization of GC in H-Acid at Mahad Need Green Chemistry based solutions for: Sulphonation of Naphthalene Currently being done with 65% Oleum & 98% Sulphuric Acid Amount of Sulphuric used is 2.4 times that of theoretical 20% Yield loss, other undesired isomers (disulpho & tetra sulpho, etc) Handling of hazardous raw materials Nitration of Naphthalene Trisulphonic Acid Currently being done in Mix Acid (Sulphuric Nitric Acid Mixture) Approx. 20 25% of total nitrated mass in undesired nitro 15% Yield loss, other undesired isomers

Barriers Solution Provider s perspective Inertia to New Paradigm against the gravity of existing paradigm Technical Barriers: no ecosystem for knowledge-based entrepreneurship Seed capital & funding barriers IP Barriers: protecting IP Market Barriers: awareness, business model Human Barriers: Inertia to change, culture, language Scale-up Barriers: same result in lab as in plant, availability of plant, risk Barriers created by Old Nexus Regulatory Barriers: changes in DMF, FDA & Customer approvals Financial Barriers: working capital for growth

Barriers Solution Provider s perspective Human Barriers inertia to change from old paradigm to New Paradigm decades of shop-floor experience becomes barrier instead of resource Scale-up Barriers want to see same result in lab as that expected in plant availability of plant to take trials with new technology risk of scale-up who will bear? Market Barriers Lack of awareness about potential of Green Chemistry tool box Some myths like it s expensive, it will increase cost, etc IP Barriers challenge to protect IP little respect for IP in the industry no hesitation in copying idea

Conclusions We have all it takes to develop & commercialize Green Chemistry solutions. What s needed is: Connect, Collaborate, Create & Commercialize Environmental challenges are opportunities to make PROFITS. Calculate E-Factor. Start wherever you want to or can. But START. Create short term & long term strategy to implement Green Chemistry & Green Engineering in to operations. GC Solutions are affordable & viable for SMEs as well. Need to be open, adventurous, willing to take some risk, stretch Patience & Perseverance, no ready-made solutions customization Barriers : 10% Technological. 90% Human Mind Set. For a solution provider, its all worth it when customers acknowledge & we see tangible difference made to the quality of our Environment.

Thank you For resources on Green Chemistry & Green Engineering: Please visit www.industrialgreenchem.com