IMPACT™ Technology A Greener Polyether Process Jack Reese Ken McDaniel Robert Lenahan Robert Gastinger Mark Morrison Polyurethanes Presentation Overview Introduction to Polyether Polyol Market and Applications Polyether Polyols Chemistry IMPACT™ Technology – Catalyst and Process A Greener Polyether Process Technology Summary Polyurethanes Introduction to Polyether Polyols Main Application Area for IMPACT™ Technology is Polyether Polyols for Polyurethanes. Lower Molecular Weight (<10,000 Daltons) Polymers with Terminal Hydroxyl Groups. Starters for Polyols are Typically Propylene Glycol, Glycerin, Sorbitol, etc. Formed by the Catalytic Reaction of a Starting Polyol with an Epoxide Containing Monomer. Other Application Areas for Alkoxylation Technology include Surfactants and various Functional Fluids. Polyurethanes Polyether Polyol Use in Polyurethanes CH3 NCO NCO O n Long Chain n > 8; Short Chain n < 8; O TDI n O OH Functionality = 2-6 n Functionality = 2-8 Blowing Agent MDI NCO O O OCN O Catalyst HO Additives Polyether Polyols Isocyanates HO Polyether Polyols: Polyurethanes R H N O O Polyurethanes R' ~ 40% of Polyurethane ~ 350 Different Varieties Determine Unique Properties Polyurethanes World Consumption 1970 - 2010 (in mT) Polyether Consumption ~ 4.6 mT or 10.2 billion lbs/yr 16 Steady growth at 4% (average) per year 14 2008: 11.6 mT 12 Forecast 10 8 6 4 2 0 1970 1975 Polyurethanes 1980 1985 1990 1995 2000 2005 2010 Polyurethanes World Consumption by Application 2008 Others 18,5% (e.g. TPU, Shoes, RIM, Fibers) Rigid Foam 25,5% (Construction, Insulation Elastomers 5,5% Adhesives and Sealants 5,5% Coatings 2,5% Molded Foam 11,0% (Automotive,Furniture) Total: 11.6 Mio T Polyurethanes Source: Marketing-Dienste Dreger: div. professional articel, Plastics 10-2008 BMS expansion and estimate Traditional Polyether Process Chemistry Polyether Polyols are made by ring opening polymerization of an epoxide group onto a starter alcohol. Main catalyst for the last 50 years is KOH. R OH HO OH Starter Glycerin as example Polyurethanes + H2C CH O R = CH2 for Propylene Oxide (PO) R = H for Ethylene Oxide (EO) KOH Traditional Polyether Process Chemistry Polyether Polyols are made by ring opening polymerization of an epoxide group onto a starter alcohol. Main catalyst for the last 50 years is KOH. R OH HO O- K+ + H2C CH O CH3 OH HO O O- K+ Polymerizate or Crude Polyol Polyurethanes Traditional Polyether Process Chemistry CH3 OH O HO O- K+ PO / EO PO PO / EO ... PO OH O PO O HO PO ... PO O ... Polymerizate or Crude Polyol Contains between 0.2 to 0.4% KOH Polyurethanes PO O -K+ Traditional Polyether Process Chemistry PO ... PO OH O HO PO ... PO O O PO PO O- K+ ... Crude Polyol with 0.2 to 0.4% KOH Work-up for K+ Removal Neutralization Distillation Solvent Recovery Purification Polyurethanes + H2SO4 + H2O PO ... PO OH O ... PO O O PO ... PO OH -K2SO4 HO PO -H2O Final Refined Polyether Polyol Containing less than 10 ppm K+ KOH Technology Advantages – Inexpensive catalyst. – Wide range of products / Industry standard. – Narrow molecular weight distribution. Disadvantages – Long reaction times. – Need to remove catalyst (multi-step, energy intensive). – Side reaction that reduces functionality at higher MW. H2C PO O H C CH3 K+ Isomerization OH Allyl Alcohol Polyurethanes OH Allyl Alcohol K+ OH + n PO / EO n Monol or unsaturation Double Metal Cyanide (DMC) Catalysts Zinc Hexacyanocobaltate, originally with glyme as ligand. Invented in 1964 by General Tire. ZnCl2 + K3 [Co(CN)6 ] Zn3 [Co(CN)6 ]2 .8 H2 O. Crystalline solid Ligand = Glyme Zn3 [Co(CN)6] 2. ZnX. Glyme Amorphous/Crystalline Catalysts Advantages of glyme DMC catalyst over KOH: – Lower by-product formation (50 – 70% reduction). – Faster (shorter cycle times). Disadvantages of glyme DMC catalyst over KOH: – Cost (Much more expensive than KOH). – Difficult DMC catalyst removal step. Polyurethanes IMPACT™ Catalyst Developed in mid-1990s by ARCO Chemical (now part of Bayer). Order of magnitude improvement in activity over glyme catalyst. – Low catalyst levels possible – no catalyst removal required. Faster Reactivity, Increased Selectivity, Simpler Process: The Key to a Greener Technology Reactivity ~ 1000x more Reactive than KOH More selective – little to no by-product KOH Polyurethanes IMPACT™ IMPACT™ Catalyst Key invention was the novel combination of two ligands. Amorphous catalyst structure. ZnCl2 + K3[Co(CN)6] XRD of IMPACT™ Ligand 1 Ligand 2 3500 Zinc Hexacyanocobaltate 3000 IMPACT™ IMPACT 3 H R 1O 2500 Lin (Counts) 2000 Zn 3 1500 1000 O R2 Zn Cl CN CN Co CN NC NC CN M a trix 3- 2 Amorphous/Crystalline Catalyst 500 0 5 50 2-Theta - Scale Zn3[Co(CN)6]2• ZnClY(OH)Z•L1•L2 • H2O Polyurethanes IMPACT™ Characteristics Zn3[Co(CN)6]2• ZnClY(OH)Z•L1•L2•wH2O PO Low Molecular Weight Starter PG, Glycerin Catalyst Inhibited Reversible -H2O Inactive Catalyst undergoes activation in the presence of starter and oxide – MW dependent. PO -H2O High Molecular Weight Starter Very Active Catalyst Heterogeneous Particle Size Decreases Industrial Challenge: Develop efficient process technology to use low molecular weight starters (Gly or PG) directly. Polyurethanes IMPACT™ Process Technology A more efficient process was required for commercial success. Solution was provided in an inventive process named Continuous Addition of Starter or CAOS. Semi-batch process: PO / EO CAOS process: PO / EO Gly / PG Product: 3000 MW Product: 3000 MW IMPACT™ Catalyst Starter: 700 MW made via KOH low MW polyol heel Starter: 1000 MW made via IMPACT™ ¾ CAOS is a more efficient process technology that eliminates the need for KOH products as starters. Polyurethanes CAOS – Taking Advantage of Unique Kinetics IMPACT™ Catalyst can tolerate low levels of glycerin or propylene glycol. Conventional polymer kinetics predict broad polydispersity. Example with 500 MW and 2000 MW as starter mix. ¾ KOH Catalysis as predicted by conventional polymer kinetics, Flory 500 750 1000 2000 2000 2250 2500 3500 Polyurethanes CAOS – Taking Advantage of Unique Kinetics Example with 500 MW and 2000 MW as starter mix. ¾ KOH Catalysis as predicted by conventional polymer kinetics, Flory 500 750 1000 2000 2000 2250 2500 3500 ¾ IMPACT™ Catalysis 500 1000 1500 2000 2000 2000 2000 2000 “Catch-up Kinetics” Polyurethanes “Catch-up” Kinetics Demonstration MW: 3600 2000 800 400 Weight Fraction PO Lower Molecular Weight Species React Preferentially Providing a Added Narrow Polydispersity with Continuous Addition of Starter Technology. 100% 65% 45% 36% 26% Starting Reactor Contents Polyurethanes 0% Molecular Weight PO Addition Utilizing Unique Kinetics to Optimize the Process Highly active catalyst. Ability to add low molecular weight starter during monomer feed. ¾ Ideal conditions for a continuous reactor system Polyurethanes Utilizing Unique Kinetics to Optimize the Process Highly active catalyst. Ability to add low molecular weight starter during monomer feed. ¾ Ideal conditions for a continuous reactor system Continuous Product 400000 9000000 350000 8000000 Starter EO, PO Catalyst 300000 Tank Farm GPC-Signal 250000 IMPACT KOH 7000000 6000000 5000000 200000 4000000 150000 3000000 Reactor - CSTR Cook out – PFR / CSTR 100000 2000000 50000 0 100 IMPACT™ Continuous Technology Polyurethanes 1000000 0 1000 10000 log(M) Theoretical Distributions 100000 Polyether Process Technology Comparison KOH, Semi-Batch Starter EO, PO Catalyst Solvent / Water EO, PO Salt Tank Farm Quality check Starter Reactor Reactor Neutralization or Solvent Addition IMPACT™, Continuous Distillation / Solvent Recovery Purification Saving Areas: Starter EO, PO Catalyst • Energy / Steam Tank Farm Reactor - CSTR Polyurethanes Cook out – PFR / CSTR • Waste IMPACT™ Technology – Energy Savings Solvent / Water KOH, Semi-Batch EO, PO Starter EO, PO Catalyst Salt Tank Farm Quality check Starter Reactor Reactor Neutralization or Solvent Addition Starter EO, PO Catalyst Distillation / Solvent Recovery Purification Energy Savings: EO, PO • Eliminate heat up and cool down for every batch. ¾ Reduces steam and cooling water. Starter Reactor Polyurethanes Reactor IMPACT™ Technology – Energy Savings KOH, Semi-Batch Solvent / Water EO, PO Starter EO, PO Catalyst Salt Tank Farm Quality check Starter Reactor Reactor Neutralization or Solvent Addition Distillation / Solvent Recovery Purification Energy Savings: Solvent / Water • Eliminate distillation of water and/or solvent recovery. Distillation / Solvent Recovery Polyurethanes IMPACT™ Technology – Energy Savings KOH, Semi-Batch Starter EO, PO Catalyst Solvent / Water EO, PO Salt Tank Farm Quality check Starter Reactor Reactor Neutralization or Solvent Addition Distillation / Solvent Recovery Purification IMPACT™, Continuous Energy Savings: • Steam and cooling water for batch process. • Eliminate distillation of water and/or solvent recovery. Starter EO, PO Catalyst • Potential to generate steam w/continuous process. Reactor-CSTR Cook out–PFR / CSTR Reductions – Steam = 99%, Electricity = 75% and Cooling Water = 88% Polyurethanes IMPACT™ Technology – Waste Reduction KOH, Semi-Batch Solvent / Water EO, PO Starter EO, PO Catalyst Salt Tank Farm Quality check Starter Reactor Reactor Neutralization or Solvent Addition Distillation / Solvent Recovery Purification Waste Reduction: • No aqueous waste generated from solvent removal and recovery. Solvent / Water Salt • No solid waste generated from catalyst removal. Reductions – Solid waste = 100%, Aqueous waste = 98% Polyurethanes IMPACT™ Technology – Green Highlights Case Study: Channelview, Texas facility – one KOH reactor and one continuous reactor making similar products. Easy conversion of existing KOH reactor to provide low cost capacity increase while reducing process complexity. Very consistent product quality – reliable on-line monitoring possible. Little to no by-product formation – lower volatile organic compounds (VOCs) in product. Lower un-reacted oxide inventory in the reactor during the reaction further reducing process safety risk. Wastewater reduction of 75 million pounds per year. Reduction of total energy consumption by 80 percent – this equates to a yearly reduction of 54 million pounds of CO2. Polyurethanes Summary – IMPACT™ Technology A Greener Process New Polyether Technology Developed and Commercialized. – First Significant Change in 50 Years of Production. – Technology Relies on Significant Catalyst Invention. – Commercialization Realized with Significant Process Invention. IMPACT™ Technology is a Greener Technology. – Dramatic Reduction in Energy Use and CO2 Generation. – Complete Reduction in Solid Waste. – Significant Reduction in Aqueous Waste. Development and Expansion of Technology Continuing. – – – – Licensed to all Major Polyether Producers. Approximately 50% of Bayer’s Polyether Volume has Developed Technology. Recent Extension to High and Low Molecular Weight Polyether Grades. Recent Extension to Incorporate the Use of a Renewable Based Starter (NOP). Over 3 Billion Pounds of Polyether Produced based on IMPACT™ Technology. Revolutionary Technology that Couples Positive Environmental Effects with Increased Capacity that Optimizes Existing Assets. Polyurethanes Thank You for Your Attention The authors wish to acknowledge the many scientists and engineers that have contributed to the development and commercialization of the IMPACT™ Technology. Polyurethanes Polyurethanes
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