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ENGINEERING ASPECTS OF BIODIESEL PRODUCTION PROCESS Nurhan Turgut Dunford Oklahoma State University Department of Biosystems and Agricultural Engineering.

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Presentation on theme: "ENGINEERING ASPECTS OF BIODIESEL PRODUCTION PROCESS Nurhan Turgut Dunford Oklahoma State University Department of Biosystems and Agricultural Engineering."— Presentation transcript:

1 ENGINEERING ASPECTS OF BIODIESEL PRODUCTION PROCESS Nurhan Turgut Dunford Oklahoma State University Department of Biosystems and Agricultural Engineering

2 Outline  Introduction  Transesterification  Esterification  Homogeneous catalysis  Heterogeneous catalysis  Enzymatic conversion  Conversion without a catalyst  Lipid hydrotreating  Planning for production  Site selection

3 Petroleum  A naturally occurring oil that contains mainly hydrocarbons with some other elements such as sulphur, oxygen and nitrogen  Gasoline: A mixture of hydrocarbons containing 5-8 carbon atoms, boiling point o C  Kerosine (paraffin oil): A mixture of hydrocarbons containing carbon atoms, boiling point o C  Diesel oil: A mixture of hydrocarbons containing carbon atoms, boiling point o C

4 Petroleum Diesel  A fuel derived from the distillation of crude oil  It is heavier than gasoline but lighter than engine oil and heavy oils.  Diesel fuel is generally separated into two fuels: diesel number 1 and diesel number 2. Diesel number 1 is similar to kerosene and is lighter than diesel number 2. While diesel number 2 is sold most of the time, diesel number 1 is sold during winter in very cold climates because it doesn’t cloud or gel as easily as diesel number 2.  Diesel fuel is ignited in an internal combustion engine cylinder by the heat of air under high compression in contrast to motor gasoline, which is ignited by electrical spark.

5 Definition of Biodiesel “ A fuel comprised of mono-alkyl-ester of long chain fatty acids derived from vegetable oils or animal fat designated B100” Biodiesel safety: SDS.pdf

6 Why Biodiesel?  Can be used in existing diesel engines without modification.  Can be blended in at any ratio with petroleum diesel.  Similar Btu/gal as petroleum diesel.  Also eliminates the huge cost of revamping the nationwide fuel distribution infrastructure.  Reduces CO 2 emission. Average Density and Heating Value of Biodiesel and Diesel Fuel Fuel Density, g/cm3 Net Heating Value Avg., Btu/gal. % Difference vs. No. 2 Diesel Avg. No. 2 Diesel ,500 Biodiesel (B100) , % B20 Blend (B20) 0.856* 127,259* 1.73 %* B2 Blend (B2) 0.851* 129,276* 0.17 %* * Calculated Values from those of No. 2 Diesel and Biodiesel (B100)

7 Triacylglyceride C C C H H H H H H H H OH + HOOCR HOOCR’ HOOCR” + 3H 2 O GLYCEROL FATTY ACIDS TRIGLYCERIDES WATER

8 Fatty Acid Molecular Structure

9 Saturated Fatty Acids

10 Monounsaturated Fatty Acids

11 Polyunsaturated Fatty Acids

12 R - COOH + R 1 - OH R – COO - R 1 + H 2 O Fatty Acid Alcohol CatalystEster/biodiesel Water Esterification Methanol safety: e/reports/gen/ _GEN-370.pdf

13 Transesterification R 1, R 2, R 3 are hydrocarbon chains on fatty acids and R’ is the alkyl group on an alcohol molecule Triacylglyceride Alcohol Esters/Biodiesel Glycerine

14 Homogeneous Catalysis Acid or Base Catalysis Alcohol/ catalyst Oil/fat Reactor Separator Alcohol Recovery Glycerine + Water +Alcohol Alcohol Biodiesel Water Biodiesel Dryer Wash Column Glycerine Recovery Glycerine + Water Glycerine + Alcohol

15 Homogeneous Catalyst Options  Base Catalysts: NaOH, KOH, Na/K-Methoxide  Acid Catalysts: H 2 SO 4, H 3 PO 4, CaCO 3  Lipase Enzymes

16 Base Catalyzed Conversions  Base catalyzed processes dominate current commercial production  Sensitive to water and free fatty acids  Typical alcohol to oil ratio varies between 6:1 and 10:1 (mole ratio)  Typical catalyst concentrations (w/w, %)  NaOH/KOH %  Na-Methoxide0.5% or less

17 Acid Catalyzed Conversions  Direct esterification, oils with high free fatty acid content or for making esters from soap stock  Requires water removal  Requires high alcohol:free fatty acid ratio, i.e. 40:1  Requires large amount of catalyst (5-25%)

18 Homogeneous Catalysis Two-Step Process Alcohol/ Acid catalyst Oil/fat Acid Reactor Separator Alcohol Recovery Glycerine + Alcohol + Water Alcohol Biodiesel Water Biodiesel Dryer Wash Column Glycerine Recovery Base Reactor Glycerine + Water Alcohol + Base Catalyst Glycerine + Alcohol Alcohol + Catalyst

19 Heterogeneous Catalysis Oil/fat Alcohol Glycerine Biodiesel Alcohol

20 Heteregeneous Catalysts  Sulfated zirconia and tungstated zirconia are typical examples of superacids  Sulfonic resins such as Nafion® NR50, sulphated zirconia (SZ), and tungstated zirconia (WZ), have sufficient acid site strength to catalyze biodiesel-forming transesterification reactions as efficiently as sulfuric acid.  Many types of heterogeneous catalysts, such as alkaline earth metal oxides, various alkaline metal compounds supported on alumina or zeolite can catalyze transesterification reactions. The order of activity among alkaline earth oxide catalysts is BaO > SrO > CaO > MgO

21 Heterogeneous Esterfip-H Process Highlights   Continuous technology based on solid catalyst  High glycerol purity >98%  Very high ester yield: close to 100%  No waste production of low-value fatty acids  No waste saline streams that require disposal  Much lower catalyst requirements (per ton of FAME) compared with other processes

22 Enzymatic Conversion  Lipases are used as catalyst  Immobilized or free enzymes Oil + Alcohol Enzyme Reactor Separator Biodiesel Glycerine

23 Comparison of Enzyme and Base Catalysis CatalystBaseEnzyme Reaction temperature 60-70°C 30-4O o C Free fatty acids Saponified products Methyl esters in raw materials (soap formation) Water in raw materials Interference with No influence the reaction Yield of methyl esters Normal Higher Recovery of glycerol Difficult Easy Purification of methyl esters Repeated washing None Catalyst cost Cheap Relatively expensive

24 Batch vs Continuous System  Batch process is better suited to smaller plants (<1 million gallons/year)  Batch process provides operation flexibility  Continuous process allows use of high volume separation systems hence increases throughput

25 Transesterification Time  At ambient temperature (70F and 21 o C) reaction takes 4-8 h to reach completion  Higher temperature will decrease reaction times but this requires pressure vessel because boiling point of methanol is 148F (65 o C)  High shear mixing and co-solvent use accelerates reaction rates

26  Supercritical fluids  Co-solvent systems Non-Catalytic Conversions

27 Non-Catalytic Conversion Supercritical Methanol Oil/fat Biodiesel High pressure & temperature reactor Alcohol Glycerine Alcohol Separator  o C,  atm ( psi),  alcohol:oil 42:1  3-5 min reaction time

28 Non-Catalytic Conversion Co-Solvent Process Biox Process  Uses an inert co-solvents (tetrahydrofuran, MTBE-methyl tert-butyl ether, ) that generate an oil-rich one-phase system.  This reaction is 95% complete in ten minutes at ambient temperatures.  No catalyst is required. Alcohol Oil

29 Phase Separation Required density difference for phase separation 0.1 Specific Gravity Methanol0.79 Biodiesel0.88 Soybean oil0.92 Catalyst0.97 Glycerine1.28 “Good reaction” as much methanol as possible “Good phase separation” min. methanol

30 SuperCetane  Several reactions occur in the process, including: hydrocracking (breaking apart of large triglyceride molecules), hydrotreating (removal of oxygen), and hydrogenation (saturation of double bonds). A conventional commercial refinery hydrotreating catalyst is used in the process and hydrogen is the only other input.  Feedstocks: canola oil, soya oil, yellow grease, animal tallow and tall oil (a by-product of the kraft pulping process).  Cetane number (a measure of ignition quality) of around 100 – which is comparable to commercial cetane additives. The specific gravity of SuperCetane is similar to regular diesel while its viscosity is similar to biodiesel. It is 97% biodegradable as compared to 45% for regular diesel.  ercetane_e.pdf

31 AVRO Diesel TM Process  (http://www.nrcan.gc.ca/es/etb/cetc/cetc01/htmldocs/ pdfs/avro_diesel_e.pdf) combines mild thermal cracking with esterification. This process is being patented by the CANMET Energy Technology Centre – Ottawa.http://www.nrcan.gc.ca/es/etb/cetc/cetc01/htmldocs/ pdfs/avro_diesel_e.pdf  Feedstock: waste animal fats, cooking greases, and trap grease that are 'too contaminated' for a conventional trans-esterification process, and produces clean diesel fuel.  The process yields 65 to 75 wt% hydrocarbons/methyl-esters mixtures suitable for diesel fuel blending.

32 ConocoPhillips/Tyson Renewable Diesel  The production technology for renewable diesel uses a thermal depolymerization process to co-process animal fat with hydrocarbon feedstock.  The fuel is chemically equivalent to the diesel produced from hydrocarbon feedstocks and can be transported directly through existing pipelines to distribution terminals.

33 Biodiesel DryWash TM  Adsorbent purification  Magnesium Silicate (Magnesol D-Sol)  Removes both particles and soluble impurities  Excess methanol flash evaporated

34 Ion Exchange Dry Wash  Ion exchange resin is used for biodiesel cleaning.  Greenline & Rohm-Haas Corporation collaboration: Ion- exchange resin known as Amberlite.  Amberlite looks very much like coffee grounds and functions much like coffee grounds in a percolator. The biodiesel fuel enters the top of the percolator and trickles down through the cylinder of Amberlite.  The final product is pure and dry.  The resin needs replacing at the rate of about 1 metric ton for every 250,000 gallons of biodiesel processed.

35 Technology Providers  Desmet Ballestra North America  Westfalia Separator, Inc.  Crown Irons Works  Lurgi PSI

36 Reading Material AspectsCh1.pdf on/01.pdf University of Idaho-Questions

37 Questions  Define biodiesel  What are the three components that are required for making biodiesel?  What are the advantages and disadvantages of using ethanol instead of methanol for biodiesel production?  What are the most common catalysts (acid and base) used for biodiesel production?  Name two reactions that are used for biodiesel production and highlight differences  Compare energy contents of biodisel and petroleum diesel  Name two biodiesel production techniques which do not require a catalyst

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40 Biodiesel Production Facilities in the US Smallest capacity: 50,000 gallons/year, recycled cooking oil Largest capacity: 37.5 Million gallons/year, soybean Earth Biofuels Inc, Durant, OK, 10 Million gallons/year, multifeed stock Green Country Biodiesel Inc., Chelsea, OK, 2.5 Million gallons/year, soybean

41 Biodiesel Industry Expansion Largest Capacity:100 Million gallons/year Smallest Capacity: 250,000 gallons/year ADM, 85 Million gallons/year, canola oil Best Energy Solutions LLC, Tulsa, OK, 1 Million gallons/year

42 Planning*  Location  Biodiesel Marketing  Feedstock Sourcing  Glycerine Outlet  Process Plant Size * Chris Mitchell – Biodiesel Product Manager Desmet Ballestra North America

43 Location*  Minimizing the freight cost for feedstock and biodiesel will be critical to survive.  How much biodiesel can be sold in a 200 mile radius?  How much competition or potential competition exists in a 200 mile radius? * Chris Mitchell – Biodiesel Product Manager Desmet Ballestra North America

44 Feedstock Sourcing*  Do you have control of your own feedstock supply (as an oilseed crusher or animal fats renderer)?  If you are dependent on an external supply, how many potential suppliers are within a 200 mile radius?  Can you sign a long-term contract with one of these suppliers to insure adequate feedstock?  Will the feedstock suppliers in the area deliver by truck or rail, and at what frequency? * Chris Mitchell – Biodiesel Product Manager Desmet Ballestra North America

45 Glycerin Outlet*  Where are the closest potential buyers of glycerin?  What quality of crude glycerin (H 2 O, MeOH, soap, FFA, salt etc) will they purchase, and at what price relative to USP grade refined glycerin?  Will the glycerin refiners in the area want delivery by truck or rail, and at what frequency?  Do you need to install your own glycerin refinery? * Chris Mitchell – Biodiesel Product Manager Desmet Ballestra North America

46 Process Plant Size*  What plant size will meet the short and long term needs of the local biodiesel market?  How does local feedstock availability limit plant size?  What minimum plant size is required to provide a competitive conversion cost in the long-term?  How much equity and debt financing is available to build the plant, and how much capacity can that buy? * Chris Mitchell – Biodiesel Product Manager Desmet Ballestra North America

47 Plant Site Selection*  Transportation Proximity  Utility Connections  Specific Parcel of Land  Shared Infrastructure * Chris Mitchell – Biodiesel Product Manager Desmet Ballestra North America

48 Transportation Proximity*  Is the site adjacent to an active freight rail system?  Does the site, or can the site, have a rail siding installed with sufficient length of track?  At what frequency are rail switches possible, and how will the rail cars be moved for loading/unloading?  Is the site in close proximity to a highway? * Chris Mitchell – Biodiesel Product Manager Desmet Ballestra North America

49 Utility Connections*  Does the site have sufficient power supply available?  Does the site have sufficient water supply available (to meet fire protection demand)?  Does the site have a sewer connection that can take the plant waste water?  Does the plant have natural gas supply available? * Chris Mitchell – Biodiesel Product Manager Desmet Ballestra North America

50 Land*  Does the site have sufficient space for the process plant (with surrounding safe area), tank farm, utility building, office building, rail siding and truck route?  Does the site have sufficient extra space for a future biodiesel plant expansion or glycerine refinery?  Is the site long enough for the rail siding to hold a sufficient number of cars?  Any environmental & construction permitting issues? * Chris Mitchell – Biodiesel Product Manager Desmet Ballestra North America

51 Infrastructure*  Does the site already have a process plant staff (management, marketing, purchasing, maintenance and quality control) that can be shared to offset conversion costs?  Does the site already feedstock tanks to reduce feedstock (freight) costs?  Does the site already have utilities that can be shared? * Chris Mitchell – Biodiesel Product Manager Desmet Ballestra North America

52 Critical Parameters*  Safety  Quality  Downtime/Uptime  Operating Costs  Capital Costs * Chris Mitchell – Biodiesel Product Manager Desmet Ballestra North America

53 Safety*  Biodiesel plants use a considerable quantity of highly flammable liquid (methanol) & corrosive material (sodium methoxide).  The process plant must be designed as a hazardous area environment with the hazardous areas within and adjacent to the process building defined by NFPA-497 (NFPA- National Fire Protection Association).  The methanol and sodium methoxide storage tanks must be designed in accordance with NFPA 30. * Chris Mitchell – Biodiesel Product Manager, Desmet Ballestra North America

54 Safety*  Special Class 1, Division 1, Group D and Class 1, Division 2, Group D explosion proof electrical design is required as per NFPA-70 to minimize a source of ignition. * Chris Mitchell – Biodiesel Product Manager, Desmet Ballestra North America

55 Quality*  All biodiesel leaving the facility must meet ASTM (American Society of Testing and Materials) specs at a minimum.  Biodiesel leaving the facility should meet specs as agreed to with the buyer.  Biodiesel should also be transported in clean vessels. * Chris Mitchell – Biodiesel Product Manager, Desmet Ballestra North America

56 Quality*  Biodiesel should be analyzed before being sent to storage.  A biodiesel plant should have a fully equipped lab with a qualified chemist that understands the chemistry and unit processes in the plant well enough to trouble-shoot feedstock & process issues and give the operations staff feedback. * Chris Mitchell – Biodiesel Product Manager, Desmet Ballestra North America

57 Downtime*  Plants are often stopped for lack of feedstock, biodiesel and crude glycerine sales, sufficient storage or loading & unloading logistics.  Plants also suffer from quality problems which require significant rework, and resultant loss of production time. * Chris Mitchell – Biodiesel Product Manager, Desmet Ballestra North America

58 Uptime*  A biodiesel plant should operate a minimum of 8,000 hours per year at its design rate (>90% uptime).  The fixed costs of capital and semi-fixed costs of manpower need to be spread out upon a full production schedule to minimize conversion costs. * Chris Mitchell – Biodiesel Product Manager, Desmet Ballestra North America

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60 Operating Costs*  Approximately 85% of operating cost of a biodiesel plant is for feedstock.  Producing your own feedstock to insure supply at a fair price, and minimizing the freight to deliver the feedstock to the biodiesel plant, are both critical factors in controlling profitability.  An alternative to controlling supply is to have a flexible process to handle multiple feedstock sources (such as soybean oil, poultry fat or yellow grease). * Chris Mitchell – Biodiesel Product Manager, Desmet Ballestra North America

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62 Operating Costs*  Total conversion costs range from $0.30 to $0.50 per gallon depending on technology and plant size.  Chemical consumptions, utility consumptions and maintenance costs (50-75% of the conversion cost) are more a function of the technology than plant size.  Selecting automated, continuous or semi-continuous process technology is a critical factor in controlling plant profitability. * Chris Mitchell – Biodiesel Product Manager, Desmet Ballestra North America

63 Operating Costs*  Total conversion costs range from $0.30 to $0.50 per gallon depending on technology and plant size.  Manpower, taxes, insurance and depreciation (25-50% of conversion cost) are more a function of plant size than technology.  Selecting a plant large enough to take advantage of economy of scale (capital & manpower) is a critical factor in controlling plant profitability. * Chris Mitchell – Biodiesel Product Manager, Desmet Ballestra North America

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65 Capital Costs*  Process equipment only accounts for 25-35% of total capital cost in a typical biodiesel plant. * Chris Mitchell – Biodiesel Product Manager, Desmet Ballestra North America

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67 Capital Costs*  Total capital costs for 1-5 mgy biodiesel plants** are typically in the range of $1.75-$1.25 / annual gallon.  Total capital costs for mgy biodiesel plants** are typically in the range of $1.00-$0.75 / annual gallon.  Total capital costs for mgy biodiesel plants** are typically in the range of $0.75-$0.50 / annual gallon. ** Tank farm included / pretreatment not included. * Chris Mitchell – Biodiesel Product Manager, Desmet Ballestra North America

68 Biodiesel Fuel Specification ASTM D PropertyMethodMinMax Flash point, ºCASTM D – Water & sediment, %volASTM D 2709–0.050 Kin. Viscosity (40ºC), mm²/s ASTM D Sulfated ash, %massASTM D 874–0.020 Sulfur, %massASTM D 5453– (S15) 0.05 (S500) Copper strip corrosionASTM D 130–No. 3 Cetane numberASTM D 61347– Cloud point, ºC ASTM— ASTM D 2500–Report ASTM: American Society of Testing and Materials.

69 Biodiesel Fuel Specification ASTM D PropertyMethodMinMax Carbon residue, %massASTM D 4530–0.050 Acid no., mg KOH/gASTM D 664–0.50 Free glycerin, %massASTM D 6584–0.020 Total glycerin, %massASTM D 6584–0.240 Phosphorus, %massASTM D 4951–0.001 Distillation temp., ºC Atm. equiv. temp., 90% recovered ASTM D 1160–360 Sodium & potassium, combined, ppm UOP 391–5

70 Biodiesel Quality Assurance  Testing in accordance with fuel specifications is time consuming and expensive  In North America, the “BQ-9000” program helps assure quality in biodiesel fuel

71 Biodiesel Quality Assurance BQ-9000 Program National Biodiesel Accreditation Program  Endorsed by NBB & Canadian Renewable Fuels Association  Cooperative & voluntary program for accreditation of biodiesel producers & marketers  Open to manufacturers, marketers & distributors of biodiesel & blends in the U.S. & Canada  Combines ASTM D 6751 standard with quality systems program including practices for storage, sampling, testing, blending, shipping, distribution & fuel management

72 Biodiesel Quality Assurance BQ-9000 Program National Biodiesel Accreditation Committee (NABC) is a fully autonomous committee of NBB Designed & implemented BQ-9000 program Responsible for developing improvements Program objectives: Promote commercial success & acceptance of biodiesel Help assure biodiesel is produced to & maintained at industry standard, ASTM D 6751 Avoid redundant testing during production & distribution Provide mechanism to track biodiesel in distribution chain Reduce probability of “out of spec” fuel reaching the market

73 Biodiesel Quality Assurance BQ-9000 Program Program Accreditation  Open to companies actively or planning to produce, distribute or market biodiesel in “neat” or blended formulations  Requires formal review & audit of capacity of applicant to produce or market biodiesel that meets ASTM D 6751 standards  Once it is awarded, it is held for two years  Following two-year period, company undergoes recertification audit to extend accreditation

74 Biodiesel Quality Assurance BQ-9000 Program Accredited Producer  Entity engaged in production and/or distribution & sale of biodiesel and/or biodiesel blends of B2 or greater  Successfully met accreditation requirements Accredited Producers: AGP, Cargill, Eastman Chemical (AR Ops), Griffin Industries, Huish Detergents, Imperial Western Products, Johann Haltermann, Organic Fuels, Peter Cremer NA, SoyMor Biodiesel, West Central, World Energy Alternatives

75 Biodiesel Quality Assurance BQ-9000 Program Certified Marketer  Entity undertaking to sell or resell biodiesel or biodiesel blends  Successfully met accreditation requirements Certified Marketers: Peter Cremer NA, Sprague Energy


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