CRI - TCBiomass2011


Published on

CRI/Criterion has deployed high-throughput tools for formulation of new catalyst compositions, and for testing the performance of the catalysts in several applications. This ability allows for screening of a large number of catalysts in a very short amount of time, significantly reducing the time required for catalyst development. The high-throughput screening ability has been proven in several areas of CRI/Criterion’s businesses, including chemicals and refining. High-throughput screening tools are equally, if not more, valuable in speedy deployment of biofuels and biochemicals from the lab to the market. Here we provide an overview of a program for rapid catalyst and process development to convert a mixed alcohol feed into gasoline and kerosene range hydrocarbons.

Published in: Technology, Business
  • Be the first to comment

  • Be the first to like this

No Downloads
Total views
On SlideShare
From Embeds
Number of Embeds
Embeds 0
No embeds

No notes for slide

CRI - TCBiomass2011

  1. 1. Speeding up the Deployment of Biofuels: Rapid Catalyst and Process Optimization with CRI/Criterion’s High-Throughput Tools Vikrant Urade, Alan Del Paggio, Laxmi Narasimhan CRI Catalyst
  2. 2. An Outline of the Presentation <ul><li>CRI and “Enhanced Experimentation” at CRI </li></ul><ul><li>Success Stories in Catalyst Development using High Throughput Tools </li></ul><ul><li>Biofuels and the Role of CRI as a Catalyst Company </li></ul><ul><li>Case Study </li></ul><ul><ul><li>Application of Enhanced Experimentation for Rapid Catalyst and Process Screening for Biofuels Production </li></ul></ul><ul><li>Conclusions </li></ul>09/22/11
  3. 3. High-Throughput Workflow 09/22/11 <ul><li>Catalyst Testing </li></ul><ul><li>Multiple parallel reactors </li></ul><ul><li>Small reactor volume (<1 mL) </li></ul><ul><li>Gas and liquid feeds </li></ul><ul><li>Automated operation </li></ul><ul><li>Data mining and analysis </li></ul><ul><li>Catalyst Synthesis </li></ul><ul><li>Using robotic catalyst preparation tools </li></ul><ul><li>Impregnations </li></ul><ul><li>Precipitations </li></ul><ul><li>Hydrothermal synthesis </li></ul>Catalyst Preparation Parallel pelletizing, crushing and sieving tools
  4. 4. Success Story: EO Catalyst <ul><li>Ten sets of screenings experiments in 5 months to optimize S-888 formulation, resolve manufacturing issues & establish IP </li></ul><ul><li>12-18 months of conventional testing would have been required to test as many variations </li></ul><ul><li>Conventional microreactor testing confirmed EE results </li></ul><ul><li>Scale-up, commercialization and deployment five Shell-owned EO plants around the world in record time </li></ul>09/22/11
  5. 5. Improved Dehydrogenation Catalyst <ul><li>February 2006: New formulation testing started, 600 formulations tested </li></ul><ul><li>October 2006: Dopant selected for optimization. 3X improvement in selectivity over target and no loss of activity </li></ul><ul><li>June 2007: Pittsburgh plant commercial trial successfully completed </li></ul><ul><li>Nov 2007: AstraCat series of catalysts introduced to the market </li></ul><ul><li>Jan 2008: AstraCat select sold to BASF, for delivery in June 2008 </li></ul>09/22/11
  6. 6. Role of CRI in the Bio-Domain 09/22/11 Lignocellulosic Biomass “ Front End” Biochemical or Thermochemical Oxygenate-rich Liquid Hydrocarbon Liquid (Gasoline/Jet/Diesel) <ul><li>Fermentation, pyrolysis or gasification based </li></ul><ul><li>Produces a liquid (alcohols, acids, ketones etc.) </li></ul><ul><li>Front end processes are still evolving: Optimization to increase yields, improve downstream process-ibility </li></ul><ul><li>CRI expertise in this area is in application of inorganic catalysis (e.g. IH 2 ) </li></ul><ul><li>Catalytic processing: Strong CRI expertise </li></ul><ul><li>A variety of catalysts and processes are possible </li></ul><ul><li>Catalytic upgrading can evolve simultaneously with front end processes: increase speed to market </li></ul><ul><li>Challenges are presence of microconstituents, high acidity, water, CO/CO 2 formation </li></ul> “ Back End” Catalytic Upgrading
  7. 7. Biofuels Pathways and CRI’s Catalyst Portfolio 09/22/11
  8. 8. Introducing IH 2 <ul><li>Advantages </li></ul><ul><li>Feedstock flexible </li></ul><ul><li>Differentiators </li></ul><ul><li>Exothermic </li></ul><ul><li>Lower capital </li></ul><ul><li>Low pressure </li></ul><ul><li>Non-corrosive Oil </li></ul><ul><li>Natural phase separation </li></ul><ul><li>Cellulosic HC fuel stock </li></ul><ul><li>Higher BTU content </li></ul><ul><li>Integrated green H 2 </li></ul><ul><li>90% GHG reduction </li></ul><ul><li>OK off grid </li></ul><ul><li>Highly scalable </li></ul><ul><li>Integration of existing techs </li></ul><ul><li>Rapid implementation </li></ul>09/22/11 Biomass Sizing , Drying & Feed Hydropyrolysis Hydroconversion Cellulosic Hydrocarbon Product Very Low O Pyrolysis Oil Light Gases IH 2 ISBL Bubbling Fluidized Bed Proprietary Catalyst Green H 2 500-600°C < 500 psig Fixed Bed Hydrotreater Proprietary Catalyst Green H 2 < 500 psig Green H 2
  9. 9. Conversion of mixed alcohols to gasoline <ul><li>Case Study </li></ul>09/22/11
  10. 10. Problem Statement <ul><li>CRI’s JDA partner produces mixed alcohol feed by fermentation of lignocellulosic biomass </li></ul><ul><li>Target: upgrade to gasoline by dehydration and oligomerization; establish a process flow scheme and economics </li></ul><ul><li>CRI’s approach: </li></ul><ul><ul><li>Identify promising solid acid catalysts based on literature survey and previous internal data </li></ul></ul><ul><ul><li>Develop a systematic design of experiments for process and catalyst screening over a broad range of parameters (temperature, space velocity, pressure) </li></ul></ul><ul><ul><li>Use high-throughput tools to generate data rapidly and establish full mass balance at each condition to understand reaction mechanism </li></ul></ul>09/22/11
  11. 11. Screening Statement <ul><li>Systematic Design of Experiments covering parameter space of interest </li></ul><ul><li>16-barrel once through fixed bed catalyst screening tool </li></ul><ul><li>Catalyst volume ~ 0.1-0.4 mL </li></ul><ul><li>Extensive analysis to establish full mass balance </li></ul><ul><li>Overall reaction scheme: Dehydration followed by oligomerization, cyclization, aromatization and cracking with increasing process severity </li></ul><ul><li>Alcohols  Olefins + Water  Hydrocarbons (n-Olefins, iso-Olefins, naphthenes, aromatics) </li></ul><ul><li>150 conditions analyzed and 5000+ ‘responses’ generated in 3 months of net instrument time and with only 3 lit of alcohol feed </li></ul><ul><li>Data subjected to rigorous statistical analysis to understand trends </li></ul>09/22/11
  12. 12. Power of EE: Rapid Process Optimization 09/22/11 Total olefin yield Decrease @ high T Increase @ low T WHSV Temperature Region 2 Region 3 Region 1: Incomplete dehydration Region 2: Complete dehydration but little further reaction Region 3: Complete dehydration and further oligomerization, alkylation and isomerization to a mixture of gasoline and jet fuel WHSV Temperature Region 1 Use of EE tools is a must to bring down process optimization time!
  13. 13. Yield Patterns 09/22/11 Temperature Temperature WHSV Aromatics WHSV Propylene WHSV Gasoline yield Temperature Temperature H 2 :Liquid Naphthenes
  14. 14. Flexibility in Product Slate 09/22/11 Increasing process severity Predominantly gasoline VGO+ Hydrocarbon layer Starting with the same mixed alcohols feed, products from gasoline to VGO boiling range can be made by changing process severity
  15. 15. Product Profile: SIMDIS 09/22/11 Liquid product of alcohol oligomerization is a smooth boiling mixture of gasoline, jet fuel and diesel
  16. 16. Conclusions <ul><li>Alcohol dehydration and oligomerization: Change of product slate using catalyst and process severity as knobs </li></ul><ul><li>Highly isomeric gasoline with low aromatics & practically no benzene produced and scaled up using larger unit (~100 kg processing) </li></ul><ul><li>Established overall gasoline yield, mass balance under optimal conditions </li></ul><ul><li>Helped JDA partner arrive at process economics, capex, preliminary process scheme </li></ul><ul><li>Broadly, catalysts are indispensible in deployment of advanced, hydrocarbon biofuels </li></ul><ul><li>CRI’s catalyst expertise and enhanced experimentation workflow help to develop and deploy application-specific catalysts in record time </li></ul>09/22/11
  17. 17. Questions 09/22/11