An Overview Of Renewable Fuels Dubrovnik,Croatia June 17, 2011


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Biodiesel, ETBE with wet ethanol and overview of Cellulose and Algae to ethanol and Biofuel

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An Overview Of Renewable Fuels Dubrovnik,Croatia June 17, 2011

  1. 1. An overview of Renewable Fuels Ethanol From Cellulose and Bio-diesel from Conventional/Algae feed and economic options for ETBE Dr. Amarjit Bakshi President Refining Hydrocarbon Technologies Texas, USA. Presented at GREEN FORUM 2 nd Green Refining & Petrochemicals Forum 17 June, 2011 Rixos Libertas, Dubrovnik, Croatia RHT
  2. 2. Ethanol as a Fuel <ul><li>Ethanol has been increasing as fuel around the World, 93 % by fermentation and 7 % from synthetic hydrocarbon feeds. </li></ul><ul><li>Domestic production reduces demand of other fuels. </li></ul><ul><li>Reduce oil demand, Trade deficits, create jobs in rural area, reduce CO 2 , reduce pollution. </li></ul><ul><li>Ethanol has 35 % oxygenates which reduces NO x and particulates. </li></ul>RHT
  3. 3. Feed used for Ethanol Sugar Feedstocks <ul><li>Fermentation of Biomass </li></ul><ul><li>Sugar Feedstocks, 6 carbon sugars, glucose and precursors to glucose are easy to convert. </li></ul><ul><li>Sugarcane is popular in Brazil and very successful </li></ul><ul><li>Beet root, sorghum and various </li></ul>RHT
  4. 4. Feed used for Ethanol Sugar Fermentation <ul><li>Fermentation of Biomass </li></ul><ul><li>Formation of a solution of fermentable sugars </li></ul><ul><li>Fermentation of these sugars to ethanol </li></ul><ul><li>Separation/distillation and purification of the ethanol, </li></ul><ul><li>Yeast ( Saccharomyces cerevisiae or known as Bakers’ yeast, used in the baking industry) used to ferment glucose to ethanol. </li></ul>RHT
  5. 5. Feed used for Ethanol Starchy Feed stocks <ul><li>Starchy molecules are made up of long chain of glucose </li></ul><ul><li>Starchy molecules can be fermented to glucose and ethanol. </li></ul><ul><li>Cereal grain, potato, cassava </li></ul><ul><li>In USA , Maize/corn and wheat is used to ferment to Ethanol </li></ul><ul><li>These feeds are hydrolyzed and go through </li></ul><ul><li>Sacchrification. Break the cells and specific enzymes which break the chemical bonds multiple times. </li></ul>RHT
  6. 6. Feed used for Ethanol Cellulose Feed stocks <ul><li>Wood, woodchips, other fibrous plant waste, Paper, Cardboard. </li></ul><ul><li>Forest Comprise75 to 85 % of world’s fibrous waste. India farming seaweed. </li></ul><ul><li>It is outside the human food chain. </li></ul><ul><li>Makes cellulose material relatively inexpensive feed stocks for ethanol production. </li></ul>RHT
  7. 7. Feed used for Ethanol Cellulose Feed stocks <ul><li>Cellulose material are made up of lignin, hemicellulose and is called lignocellulose. </li></ul><ul><li>In Brazil bagasse and vinasse and straw are being used as value-added product, for power, and fertilizer. Moving to cellulosic options for Ethanol is going to be soon. </li></ul><ul><li>The US is working on switchgrass and miscanthus; dedicated wood biomass poplar, agricultural residues, sawdust, forest slash; municipal solid waste and biomass/microalgae. </li></ul>RHT
  8. 8. Cellulose Processing to Ethanol <ul><li>Lignin are support for trees but have no sugar and enclose the sugars in Cellulose which makes it difficult to extract sugar/glucose. </li></ul><ul><li>Cellulose contains long chain glucose molecules as do starch but there is structural difference. </li></ul><ul><li>Due to lignin and structure of molecules Cellulose is difficult to hydrolyze compared to starchy feeds. </li></ul><ul><li>Hemicellulose is easily hydrolyzed as it contains polysacchrides compared to cellulose which is encompassed by lignin. </li></ul>RHT
  9. 9. Cellulose Processing to Ethanol <ul><li>Hemicellulose contains 6 carbon hexose sugars and pentose which is </li></ul><ul><li>5 carbon sugar and to enhance the efficiency pentose have to be converted to Ethanol. </li></ul><ul><li>The fermentation of hexose and pentose need different type of microorganisms. </li></ul>RHT
  10. 10. Ethanol from Cellulose (EFC) <ul><li>Three Basic EFC processes </li></ul><ul><li>Acid hydrolysis </li></ul><ul><li>Enzymatic hydrolysis </li></ul><ul><li>Thermochemical </li></ul><ul><li>Most commonly used processes are hydrolysis by any acid, sulfuric acid is predominantly used either dilute or high concentration acid. </li></ul><ul><li>Dilute acid 1 to 2 %, high temp and pressure produces 50 % glucose. 50 gallons of ethanol from 1 ton of wood/Cellulose. </li></ul>RHT
  11. 11. Ethanol from Cellulose (EFC) <ul><li>Acid hydrolysis </li></ul><ul><li>Dilute acid process efficiency is reduced, </li></ul><ul><li>once the sugar produced by secondary reaction which are poison to further fermentation step. But two step process can enhance yield to 80 gallons/ton Cellulose. </li></ul><ul><li>The dilute acid process has high reaction rates, continuous process, low efficiency and it needs small cellulose particles. </li></ul>RHT
  12. 12. Ethanol from Cellulose (EFC) <ul><li>Acid hydrolysis </li></ul><ul><li>The dilute acid process has high rate of reaction, continuous process, needs small cellulose particles. Two step process, first step under mild conditions and second step under severe conditions enhances the efficiency by reducing degradation of C 5 sugars which degrade rapidly compared C 6 Sugars. The yield is increased to 80 gallons per ton of cellulose/wood. </li></ul>RHT
  13. 13. Ethanol from Cellulose (EFC) <ul><li>Acid hydrolysis </li></ul><ul><li>The concentrated acid process uses 10%, acid at low temperature and moderate pressures, reaction rates are low. Next it is soaked in 30 to 40 % acid for additional time, and again soaked at 70 % concentration. Acid from each stage is recycled and sugars from Cellulose and hemicellulose are 90% which is 103 gallons/ton. </li></ul>RHT
  14. 14. Ethanol from Cellulose (EFC) <ul><li>ENZYMATIC HYDROLYSIS </li></ul><ul><li>Cellulose and hemicellulose are pretreated. Part is sent to grow microorganisms to produce cellulanzyme. Part is sent grow a yeast culture for fermentation. Enzymes and fermentation microorganisms are added, sugar conversion and fermentation occurs simultaneously by saccharification and co-fermentation. </li></ul><ul><li>Cost of enzymes is high, research is going on to bring down the cost of enzymes. </li></ul><ul><li>If less expensive enzymes are developed enzymatic processes hold several advantages. </li></ul>RHT
  15. 15. Ethanol from Cellulose (EFC) <ul><li>ENZYMATIC HYDROLYSIS </li></ul><ul><li>Cellulose/hemicellulose are pretreated, part is sent to grow cellulanzyme. Other part is sent grow a yeast culture for fermentation, sugar conversion and fermentation occurs simultaneously by saccharification and co-fermentation. </li></ul><ul><li>If less expensive enzymes are developed enzymatic processes hold several advantages. </li></ul>RHT
  16. 16. Ethanol from Cellulose <ul><li>Hybrid process where biomass is thermochemically gasified, gas is treated in fermenters/microorganism converts gas(CO/CO 2 /H 2 ) to ethanol by fermentation. </li></ul><ul><li>Two stage route is where biomass is thermochemically gasified, gas is catalytically converted to ethanol, yields are 50%. methanol also is catalytic converted to ethanol, enhancing yields to 80%. </li></ul>RHT THERMOCHEMICAL PROCESSES
  17. 17. Conventional Biodiesel New Developments <ul><li>RHT provides technology based on conventional vegetable oil/fats, with heterogeneous highly active catalyst, with high yield, selectivity and high on stream factor. </li></ul><ul><li>Makes no liquid or gaseous waste </li></ul><ul><li>Product meets required specifications </li></ul><ul><li>Is highly efficient and provides good economics. </li></ul>RHT
  18. 18. Conventional Biodiesel New Developments <ul><li>Simple Reaction chemistry </li></ul><ul><li>C 3 H 5 R 3 +3CH 3 OH C 3 H 5 (OH) 3 +3CH 3 R </li></ul>RHT Vegetable oil Methanol Glycerine Methyl Ester C 3 H 5 R 3 +3C 2 H 5 OH C 3 H 5 (OH) 3 +3C 2 H 5 R Vegetable oil Ethanol Glycerine Ethyl Ester Transesterification Reaction
  19. 19. Conventional Biodiesel New Developments <ul><li>Biodiesel Properties </li></ul><ul><li>Fuel Property ASTM 6751 </li></ul><ul><li>Sulfated ash w% 0.02 </li></ul><ul><li>Na+K mg/kg 5 </li></ul><ul><li>Ca+Mg mg/mg 5 </li></ul><ul><li>Acid number mgKOH/g 0.5 </li></ul><ul><li>Free / Total Glycerol w% 0.02/0.24 </li></ul><ul><li>Carbon residue w% 0.05 </li></ul><ul><li>Cetane number 47 </li></ul><ul><li>Distillation 90% C 360 </li></ul><ul><li>Flash Pt C 130 </li></ul><ul><li>Water and sediment v% 0.05 </li></ul><ul><li>Sulfur content mg/mg 15/500 </li></ul><ul><li>*ASTM 6751 above specs are not comprehensive. </li></ul><ul><li>For EU spec please see EN 14214 </li></ul>RHT
  20. 20. Figure 1 RHT- Biodiesel Process Esterification Reactor Transesterification Reactor LP Gravity Separator Methanol Triglycerides Biodiesel Biodiesel Product water wash Water Meoh/water for recovery Meoh for recovery Purification Purification Glycerine Product RHT
  21. 21. Figure 2 RHT- Biodiesel Process Esterification Reactor Transesterification Reactors LP Gravity Separator Methanol Triglycerides Biodiesel Biodiesel Product water wash Water Meoh/water for recovery Glycerine Product Meoh for recovery Gravity Separator Wash Solvent Residual Glycerine / wash solvent Purification RHT
  22. 22. Conventional Biodiesel RHT- Biodiesel <ul><li>WHY USE RHT PROCESS: </li></ul><ul><li>Highly active heterogeneous catalyst, with high yield, selectivity and high on stream factor. </li></ul><ul><li>Makes no liquid or gaseous waste </li></ul><ul><li>Product meets required specifications </li></ul><ul><li>Is highly efficient, simple to operate and provides good economics, low Capex and Opex. Provides glycerol at ~99.0 %. </li></ul>RHT
  23. 23. Conventional Biodiesel <ul><li>Provides pretreatment for FFA if required which enhances the product yields and efficiency. </li></ul><ul><li>Provides pure glycerine after purification over 99.0 % purity. </li></ul><ul><li>Simple and continuous operation. </li></ul><ul><li>Moderate pressure and temperature </li></ul><ul><li>Low Capex and Opex process for Biodiesel. </li></ul>RHT
  24. 24. Biodiesel from Algae New Developments <ul><li>Drivers of Biofuels </li></ul><ul><li>High Crude oil/fossil fuel prices make it viable for industrialist/Governments to seek alternative fuels. </li></ul><ul><li>Energy Independence </li></ul><ul><li>Tax incentives and Government mandates </li></ul><ul><li>Environmental security </li></ul><ul><li>Economic security </li></ul><ul><li>National security </li></ul>RHT
  25. 25. Biodiesel from Algae New Developments <ul><li>Algae Potential </li></ul><ul><li>Biodiesel, Aviation fuels,Ethanol, </li></ul><ul><li>Bio-Crude, Bio-gasoline </li></ul><ul><li>Production Methods </li></ul><ul><li>Open ponds, bioreactor in dark, CO2 Enhanced growth </li></ul><ul><li>Extraction/dewatering/magnetic/quantum fracturing systems and developments </li></ul><ul><li>Bio-refining technologies developments </li></ul>RHT
  26. 26. Bodiesel from Algae New Developments <ul><li>Market Potential & Products </li></ul><ul><li>Bio-diesel, Aviation fuels, Ethanol, Bio-gasoline, Bio-crude </li></ul><ul><li>Production Methods </li></ul><ul><li>Open Ponds or Bioreactor growing in dark </li></ul><ul><li>Enhanced Algae growing with CO 2 , near power plants, after N2 and Hg rejection/removal </li></ul><ul><li>Extraction/dewatering methods </li></ul><ul><li>Bio-refining advancements needed to make it viable Technology with better economics. </li></ul>RHT
  27. 27. Bodiesel from Algae New Developments <ul><li>Fastest growing biomass with CO 2 from power plants or other sources into the waste land, needs nitrogen rejection. </li></ul><ul><li>Growth of Algae can be increased thousand fold with CO 2 in water, cost effective near CO 2 sources. </li></ul><ul><li>No adverse effect on food, positive impact on environment by reducing green houses gases in atmosphere. </li></ul>RHT
  28. 28. Bodiesel from Algae New Developments <ul><li>EU Bio-fuels Targets </li></ul><ul><li>~6.0 % by 2010 and ~10 % by 2020 </li></ul><ul><li>EU can not produce enough vegetable oil </li></ul><ul><li>Algae and Cellulose have the opportunity to serve as feed stocks to meet the targets </li></ul><ul><li>USA Bio-fuels Targets </li></ul><ul><li>Federal RFS require ~36 billion gallons by 2022 </li></ul><ul><li>Over 22 billion by Algae/Cellulose </li></ul><ul><li>USA cannot produce enough oil/Corn </li></ul><ul><li>Algae and Cellulose have the opportunity to meet the difference </li></ul>RHT
  29. 29. Bodiesel from Algae New Developments <ul><li>Yields of Biodiesel </li></ul><ul><li>Most vegetable oil yields 50 to 110 US gallon/acre, except palm which is 650 US gallon/acre </li></ul><ul><li>Algae potential >10,000 US gallon/acre </li></ul><ul><li>Trend towards large scale commercial </li></ul><ul><li>plants. As the technologies are </li></ul><ul><li>commercialized together with enhancing the economics. Race is on with more than 20 major players in field. </li></ul>RHT
  30. 30. Bodiesel from Algae New Developments RHT Grow Algae Split in fat/ sugars Solvent to separate Fat and Sugars Fat /Lipids Bodiesel Bodiesel Sugars to Ethanol Ethanol ALGAE TO BIODIESEL & ETHANOL
  31. 31. Bodiesel from Algae New Developments RHT Grow Algae in Ponds/Bio-reactor Convert to Biomass Convert to Bio-crude Biocrude to Refinery CO2 Nutrients From Sludge ALGAE TO BIO-CRUDE
  32. 32. Bodiesel from Algae New Developments RHT Grow Algae in Bioreactor Dewatering Algae Biomass Bodiesel Biodiesel Ethanol Methanol ALGAE TO BIODIESEL & ETHANOL/Methanol CO2 Recycle water Ethanol Methanol Animal Food etc Animal food O2/N2 separation Light delivery Growth layers Low energy photosynthesis
  33. 33. Biodiesel from Algae <ul><li>Algae dewatering </li></ul><ul><li>Filteration </li></ul><ul><li>Centrifuging </li></ul><ul><li>Drying by unique technique </li></ul><ul><li>Spray drying </li></ul><ul><li>Lipid Extraction </li></ul><ul><li>Mechanical/thermal </li></ul><ul><li>Solvent extraction </li></ul><ul><li>Originoil claims, no dewatering before Lipid Extraction by ultrasonic frac, recycle nutrients and water, less energy consumed. </li></ul>RHT
  34. 34. Biodiesel from Algae New Developments <ul><li>Originoil Process </li></ul><ul><li>Originoil process claims reduced steps, algae is broken into lipid and sugars by ultrasonic fracturing and phases are separated and sent for purification enhancing economics. Please see there website. </li></ul><ul><li>More R &D is required to enhance the economics, major R&D effort with industry and government sponsorship is in progress. </li></ul><ul><li>RHT LLC is talking to universities for alliance </li></ul><ul><li>and hope to start R&D work soon. </li></ul>RHT
  35. 35. ETBE from Wet Ethanol Enhancing the economics <ul><li>Smart Configuration provides </li></ul><ul><li>highest conversion > 99 % above equilibrium limit. </li></ul><ul><li>Reduce the production costs by using wet ethanol, easy revamp of MTBE to ETBE. </li></ul><ul><li>Makes higher TBA, decompose TBA to IB= and water, IB= is recycled and water is rejected, producing ETBE to Spec. </li></ul><ul><li>20- 25 % savings in production costs. </li></ul>RHT
  36. 36. RHT-ETBE PROCESS Equilibrium Limits Etherification CH 3 - C = CH 3 + C 2 H 5 OH CH 3 - C - CH 3 CH 3 CH 3 OC 2 H 5 < 88% * Isobutylene Ethanol ETBE RHT * RHT overcomes equilibrium constraints. Provides IB= conversion over 99 % .
  37. 37. <ul><li>Water in ethanol reacts to TBA </li></ul><ul><li>Reaction Rate to TBA << Ether </li></ul><ul><li>RHT process does not require ethanol dehydration, saves capex and improves economics. </li></ul><ul><li>TBA is decomposed and Isobutylene recycled, water rejected. </li></ul><ul><li>Conversion over equilibrium limits > 99%. </li></ul><ul><li>Conventional catalyst low cost. </li></ul><ul><li>No special loading requirements, or single source expensive catalyst </li></ul>RHT RHT-ETBE TECHNOLOGY
  38. 38. ETBE VS MTBE Properties <ul><li> ETBE MTBE </li></ul><ul><li>C4/ROH Azeotrope, w% 1.5 - 1.7 3.5 - 4.0 </li></ul><ul><li>Boiling Point (F) 161 131 </li></ul><ul><li>RVP (PSI) 4 8 </li></ul><ul><li>Blending Octane, 112 110 </li></ul><ul><li>Oxygen Content, w% 15.7 18.2 </li></ul><ul><li>1 BBL IB= + 0.6 BBL EtOH 1.5 BBL ETBE </li></ul><ul><li>1 BBL IB= + 0.4 BBL MeOH 1.3 BBL MTBE </li></ul><ul><li>@ same IB= conversion 15 % more flow </li></ul>RHT
  39. 39. RHT Technology Advantages <ul><li>More ETBE </li></ul><ul><li>Less Ethanol in ETBE </li></ul><ul><li>No Ethanol Dehydration, lower capex enhances economics. </li></ul><ul><li>Smart Configuration allows conversion above equilibrium > 99.0 % </li></ul><ul><li>Conventional catalyst, no special loading requirements, no single source expensive catalyst </li></ul><ul><li>Water converted to TBA </li></ul>RHT
  40. 40. FIGURE 1 RHT-ETBE PROCESS C 4 4 Raffinate ETBE 4 Fixed Bed Reactor Debutanizer ETHANOL Extraction ETHANOL Recovery ETHANOL C 4 Water Water Effluent Water FEED C 4 Feed C 4 Feed Side Reactor C W C 4 /ETOH RHT ETOH Recycle
  41. 41. RHT-WET ETBE/TAEE Process Water Wash Column 1 st Reactor Debutanizer/Depentanizer Condenser Finishing Reactor Water Alcohol/ ETOH Alcohol Recycle Wash Water C 4/ C 5 feed C 4/ C LPS CW ETBE/TAEE Product CW MPS CW C 4/ C 5 Raffinate 2 3 4 9 FIGURE 2 RHT
  42. 42. RHT-ETBE/TAEE Wet Ethanol Process Debutanizer Depentanizer Bottom (from figure 2) CW LPS CW Isobutylene/Amylenes To Water Wash Column LPS ETBE/TAEE to OSBL TBA/TAA and Lights ETBE /TAEE Column FLOW SHEET 3 RHT TBA decomposition
  43. 43. Why RHT ETBE PROCESS <ul><li>Smart configuration provides 99.0 % IB= </li></ul><ul><li>conversion, above equilibrium limit. </li></ul><ul><li>LOW COST, HIGH YIELD PROCESS </li></ul><ul><li>For ETBE, no ethanol dehydration Unit required, reducing cost by a factor </li></ul><ul><li>Costs of dehydration is 20 to 30% of the ETBE unit, wet ethanol cheaper than dry ethanol. </li></ul><ul><li>No Proprietary single source catalyst and loading required. RHT USP 7,732,648 </li></ul><ul><li>Catalyst can be changed on the run/during operation </li></ul>RHT
  44. 44. RHT Portfolio <ul><li>Please see website </li></ul><ul><li>and linkedin for other details and presentations attached to profile. </li></ul><ul><li>RHT LLC provides technology for ETBE with wet ethanol, Biodiesel from vegetable oils and looking for alliances, research at universities on renewable fuel technologies Cellulose to Ethanol and Biodiesel from Algae. </li></ul><ul><li>Please contact us and look up the Patents/IP. </li></ul>RHT
  45. 45. RHT Thank You Refining Hydrocarbon Technologies LLC 20130 Chateau Bend Drive Katy ( Houston Suburb), Texas 77450 USA Dr. Amarjit Bakshi Phone 281-398-8408/281-235-7780