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TRENDS IN TECHNOLOGY FOR PRODUCTION OF BIOFUELS AND BIO-DERIVED CHEMICALS

Bio-fuels Biodiesel and Bio-lubricantsBiodiesel production increased over 1000% in the past decadeBiodiesel capacity Worldwide in 2012: 5,670 MMgpyBiodiesel earns $1.50 per gallon under the U.S. RFS program1st GENERATION BIODIESEL PLANTSTransesterificationHomogeneous catalystsPoor Glycerin QualityHigh Feedstock CostEmissions issues2nd GENERATION BIODIESEL PLANTSTransesterificationHeterogeneous catalystsDifficult Separation of GlycerinLower Feedstock costHigh Capital Investment3rd GENERATION BIODIESEL PLANTSHydrolysis followed by Esterification using Catalytic DistillationHeterogeneous catalystsEasy separation of high quality GlycerinLowest Feedstock costLower Capital InvestmentOILFFA CONTENTRELATIVE PRICEPRICE( / #)PFAD (Palm Fatty Acid Distillate)85-90%Low 27Beef Tallow: choice prime5-6%Medium32Beef Tallow: Special10%Medium30Beef Tallow: No. 1,2,310-35%Low31GreaseWhite A,BYellowHouseBrown (trap)8-10%15%20%50%MediumMediumLowLow32282625Poultry Fat30Algae Oil4-15%Medium?Soybean Oil2-3%High39Biodiesel and Bio-lubricants

Biodiesel and Bio-lubricantsGreen DieselConsidered a drop-in hydrocarbon replacement for DieselEarns $1.65 per gallon under the U.S. RFS programOnly a few operational plants currentlySPLITTING TO MAKEFATTY ACIDSTRANS-ESTERIFICATIONHYDROGENATION15 mols H2/mol triglycerideParrafinic BiodieselLOW TO MEDIUMFATTY ACID CONTAINING OILSMEDIUM TO HIGHFATTY ACID CONTAINING OILSBIODIESEL/BIOLUBRICANTSFatty Acid Methyl Ester BiodieselMILD HYDROCRACKING/ ISOMERIZATIONBiojet FuelNATURALTRIGLYCERIDESCATALYTIC DISTILLATIONDECARBOXYLATION1 mol CO2 removed/mol fatty acidParrafinic BiodieselBIODIESEL/BIOLUBRICANTSFatty Acid Methyl Ester BiodieselGLYCEROLGREEN DIESELCatalyst volume will change as a function of catalyst type and whether the catalyst is incorporated within structured catalytic packing or whether the catalyst is conventionally charged Pilot PlantReactor TypeVolume of CatalystDesign PressureDesign Temp. Liquid FeedsGas FeedsFeedstockProductTransesterificationPacked Bed2,000 ml100 bar(1500 psig)300C(575F)21TriglyceridesBiodiesel / BiolubricantsGreen Diesel Hydrodeoxidation (HDO)Packed BedMolten Salt Bath Furnace250 ml70 bar(1000 psig)375C(700F)12TriglyceridesDiesel range parrafinsCatalytic DistillationHeterogeneous Catalyst Loaded Column2x20 ft.50 bar(750 psig)200C(400F)21Fatty acidsBiodiesel / BiolubricantsCatalytic Decarboxylation (CDC)Packed Bed 5 zone electric heater50 ml30 bar(450 psig)350C(650F)12Fatty acidsDiesel range parrafinsHydrothermal DecarboxylationPacked Bed 5 zone electric heater50 ml180 bar(2600 psig)350C(650F)20TriglyceridesGreen DieselMild Hydrocracking/ IsomerizationPacked bed 5 zone electric furnace50 ml100 bar(1500 psig)375C(700F)12Biodiesel range parrafinsBio-SPK (biojet fuel)Alcohols for fuel additivesWorldwide ethanol production in 2012: 28,000 MMgpy10% blend wall reached in US. Projected gasoline consumption 133 billion gallonsTraditional ethanol earns $0.95 per gallon under the U.S. RFS program1st GENERATIONCorn from ethanolFood v. fuel debateCannot be put in pipelineLow energy density (70,000 Btu/gal 19.6 MJ/L)Corrosion issues2nd GENERATIONCellulosic ethanolSolves debateEarns higher credit Same issues as traditional ethanol3rd GENERATIONN-Butanol from waste starch or sweet sorghumSolves debateCan be put into pipelineEnergy density closer to gasoline (110,000 Btu/gal 29.2 MJ/L)No Corrosion issuesCan be put into diesel as well.Blend wall is increased to 12%OPPORTUNITIES FOR N-BUTANOLMore toxic to the organisms. Lower yields make batch process un-economicalMost organisms make iso-butanoln-butanol is used as a chemical intermediate for the production of a number of valuable chemicals such as: Butyl Acetate, Butyl Acrylate, Glycol Ethers, etc.Expected to be a 9.4 billion per year market by 2018.China currently consumes 35% of the n-butanol producedCHALLENGES FOR N-BUTANOLAlcohols for fuel additives AQUEOUS SEPARATORFEED FROM FERMENTER SOLVENT COLUMNMIXED ALCOHOLBUTANOLWATER100C117C DECANTERSolution: Immobolized organism with continuous removal of butanolJet FuelsCurrent Jet fuel demand is 5 million barrels per day.Now earns RIN credits of $1.50 - $1.65 per gallon under RFSFuel costs are approximately 35 45% of an airlines cost. Volatility is damaging.Modularity

The concept of modularity for the design of pilot plants, demonstration plants and small commercial plants was pioneered by our group. This concept now has found universal acceptance in terms of maintaining QA/QC controls, assembly procedures and reducing overall project costs .Aspen Plus Simulation+Heat & Material Balances+Process Flow DiagramsProcess & Instrumentation Diagrams+Equipment Specs+Instrument Specs+Control PhilosophyDetailed Engineering +3D Plant Design Procurement+Construction+Field TestingPhase 1Phase 2Phase 3Phase 4Project Implementation Sequence

Catalyst Research Systems

The basic requirement in the analysis of catalytic reactors is a rate expression for the reaction concern.

The choice of a suitable reactor for carrying out experiments under conditions where meaningful kinetic rate expressions can be obtained is of very great importance.

Unitel: Breadth of ApplicationCatalyst Research

Petro-chemicalsEnergy Research

Misc. Unit Operations

Pharmaceutical & NutraceuticalPEGasificationPetroleum Refining

PolymerizationEnvironmentalTransesterification

Green Diesel HydroDeOxidation(HDO) Pilot PlantGreen Diesels consist of diesel-range (C12-C18) paraffins of high cetane numbersDeoxygenation by hydrogenation of triglyceridesNo glycerin byproductNiMo catalystsHydrotreat/hydrocrack the trigylcerides remove O (Oxygen) atoms as H2O

Very high hydrogen consumptionYield = 50-60% Big H2 plant investment; or incorporated into a refineryC57H104O6 + 15H2 6H2O + C3H8 + 3 C18H38 triglyceride hydrogen water propane diesel

CO2 + H2 CO + H2O CO + 3H2 CH4 + H2OCO2 + 4H2 CH4 + 2H2OThe Chemistry Biodiesels Catalytic DistillationFatty AcidsR1 C OH + OH CH2 HOOO MethanolWater Methyl EsterR1 C O CH2 H + H2O OOOR2 C O CH2 H + H2O R3 C O CH2 H + H2O R2 C OH + OH CH2 HR3 C OH + OH CH2 HCatalytic DeCarboxylation(CDC) Pilot PlantDecarboxylation the critical step towards jet fuel

Catalytic DeCarboxylation(CDC) Pilot Plant

Mild Hydrocracking Isomerization Pilot PlantOptimizing the jet fuel

Heterogeneous CatalystR1H ParaffinicHydrocarbonn-C17H34C10-C15 BranchedParaffinsMild Hydrocracking & HydroisomerizationMild Hydrocracking Isomerization Pilot Plant

Our Current ProjectsAt the present time, some of the projects that we are working on are strange and interesting. Some examples are:Recirculating fluidized bed based pyrolysis of biomass to produce pyoilMonetization of natural gas into methanol using modular construction technologiesMonetization of natural gas into DME using catalytic distillationsConversion of triglycerides into jet fuels using catalytic decarboxylation and catalytic hydroisomerizationPilot plant to study and optimize next generation CO2 absorbing technologiesEight reactor hydrotreating pilot plantBiomass oxyblown gasification for syngas productionUpgrading of tar sand derived bitumens

Why Pilot Plants?Commit your blunders on a small scale and make your profit on a large scale.Pilot and demo plants represent the intermediate state between laboratory studies and industrial plants.The pilot and demo plant must be understood not as a scale-up of laboratory units but as a small scale simulation of the future industrial plant.

xxxThe objectives of a pilot plant, therefore, can differ depending on the specific circumstances of each project, and the decision for its construction can include one or several of the following objectives:

To optimize the operating parameters of the process,To study the effects of recirculating process streams and of accumulation of impurities over long periods,To obtain process information necessary to specify and design the full scale plant,To test process control systems and procedures,To test materials of construction,To optimize the design of the equipment,To obtain sufficient information to prepare detailed and reliable estimates of capital and operating costs and to prepare a reliable economic evaluation of the project,To gain operating experience. and to train the personnel that will operate the full scale plant, To identify hazards in the process and ensure safety in design and operation, including the disposal of radioactive wastes,To produce a reasonable amount of uranium concentrate for characterization and for use in subsequent stages of the nuclear fuel cycle.Catalyst charge: 50 mLReactor internal volume: 100 mLMaximum system pressure: 30 bar (~450 psig)Maximum system temperature: 350C (~650F)Number of liquid feeds: 1Maximum LHSV of liquid feed: 2Number of gas feeds: 32 high pressure, 1 low pressure

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411 Business Center Drive, Suite 111Mt. Prospect, IL 60056 USAwww.uniteltech.com

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