Utilization of Biotechnology for the Development of Functional and Bioactive Lipid-Based Products

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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 40-180oC
• Kerosine (paraffin oil) A mixture of
  hydrocarbons containing 11-12 carbon atoms,
  boiling point 160-250oC
• Diesel oil A mixture of hydrocarbons containing
  13-25 carbon atoms, boiling point 220-350oC

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 doesnt 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.

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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 http//www.biodieselcommunity.or
g/safety/ http//www.biodiesel.org/pdf_files/fuelf
actsheets/MSDS.pdf
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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 CO2 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 0.850 129,500
• Biodiesel (B100) 0.880 118,296
  8.65
• 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)

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Triacylglyceride
8
Fatty Acid Molecular Structure
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Saturated Fatty Acids
10
Monounsaturated Fatty Acids
11
Polyunsaturated Fatty Acids
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Esterification
R - COOH R1- OH R COO - R1
H2O Fatty Acid Alcohol
Catalyst Ester/biodiesel Water
Methanol safety http//www.biodiesel.org/resource
s/reportsdatabase/reports/gen/20060401_GEN-370.pdf
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Transesterification
Triacylglyceride Alcohol
Esters/Biodiesel Glycerine
R1, R2, R3 are hydrocarbon chains on fatty
acids and R is the alkyl group on an alcohol
molecule
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Homogeneous Catalysis Acid or Base Catalysis
Dryer
Biodiesel
Oil/fat
Reactor
Biodiesel
Alcohol/ catalyst
Separator
Wash Column
Glycerine Alcohol
Water
Alcohol
Glycerine Recovery
Glycerine Water Alcohol
Alcohol Recovery
Glycerine
Glycerine Water
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Homogeneous Catalyst Options

• Base Catalysts NaOH, KOH, Na/K-Methoxide
• Acid Catalysts H2SO4, H3PO4, CaCO3
• Lipase Enzymes

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Base Catalyzed Conversions

• Base catalyzed processes dominate current
  commercial production
• Sensitive to water and free fatty acids
• Typical alcohol to oil ratio varies between 61
  and 101 (mole ratio)
• Typical catalyst concentrations (w/w, )
• NaOH/KOH 0.3-1.4
• Na-Methoxide 0.5 or less

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Acid Catalyzed Conversions

• Direct esterification, oils with high free fatty
  acid content or for making esters from soap stock
• Requires water removal
• Requires high alcoholfree fatty acid ratio, i.e.
  401
• Requires large amount of catalyst (5-25)

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Homogeneous Catalysis Two-Step Process
Dryer
Biodiesel
Alcohol Catalyst
Alcohol Base Catalyst
Oil/fat
Biodiesel
Acid Reactor
Alcohol/ Acid catalyst
Separator
Base Reactor
Wash Column
Glycerine Alcohol
Water
Alcohol
Glycerine Recovery
Glycerine Alcohol Water
Alcohol Recovery
Glycerine
Glycerine Water
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Heterogeneous Catalysis
Biodiesel
Alcohol
Glycerine
Glycerine
Alcohol
Oil/fat
Glycerine
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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 gt SrO gt CaO gt MgO

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Heterogeneous Esterfip-H Process Highlights

• http//www.Axens.net
• Continuous technology based on solid catalyst
• High glycerol purity gt98
• 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

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Enzymatic Conversion
Reactor
Enzyme
Biodiesel
Oil Alcohol
Separator
Glycerine

• Lipases are used as catalyst
• Immobilized or free enzymes

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Comparison of Enzyme and Base Catalysis

• Catalyst Base Enzyme
• Reaction temperature 60-70C 30-4OoC
• 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

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Batch vs Continuous System

• Batch process is better suited to smaller plants
  (lt1 million gallons/year)
• Batch process provides operation flexibility
• Continuous process allows use of high volume
  separation systems hence increases throughput

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Transesterification Time

• At ambient temperature (70F and 21oC) 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 (65oC)
• High shear mixing and co-solvent use accelerates
  reaction rates

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Non-Catalytic Conversions

• Supercritical fluids
• Co-solvent systems

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Non-Catalytic ConversionSupercritical Methanol
Biodiesel
Alcohol
Oil/fat
High pressure temperature reactor
Separator
Alcohol
Separator
Glycerine

• 350-400oC,
• 85-100 atm (1200-1500 psi),
• alcoholoil 421
• 3-5 min reaction time

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Non-Catalytic ConversionCo-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
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Phase Separation
Required density difference for phase separation
0.1 Specific Gravity Methanol 0.79 Biodiesel
0.88 Soybean oil 0.92 Catalyst 0.97 Glycerine
1.28 Good reaction as much methanol as
possible Good phase separation min. methanol
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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.
• http//www.nrcan.gc.ca/es/etb/cetc/cetc01/htmldocs
  /pdfs/supercetane_e.pdf

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• AVRO Diesel TM Process
• (http//www.nrcan.gc.ca/es/etb/cetc/cetc01/htmldoc
  s/pdfs/avro_diesel_e.pdf) combines mild thermal
  cracking with esterification. This process is
  being patented by the CANMET Energy Technology
  Centre Ottawa.
• 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.

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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.

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Biodiesel DryWashTM

• Adsorbent purification
• Magnesium Silicate (Magnesol D-Sol)
• Removes both particles and soluble impurities
• Excess methanol flash evaporated
• http//www.dallasgrp.com/biodiesel.pdf

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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.
• http//www.greenlineindustries.com/ProcessDesc_1.h
  tm

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Technology Providers

• Desmet Ballestra North America
• Westfalia Separator, Inc.
• Crown Irons Works
• Lurgi PSI 

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• Reading Material
• http//www.southeastdiesel.org/Photos/Library/Ag/E
  ng_AspectsCh1.pdf
• http//www.fapc.okstate.edu/factsheets/fapc149.pdf
  
• http//www.fapc.okstate.edu/factsheets/fapc150.pdf
  
• http//www.uidaho.edu/bioenergy/biodieselED/public
  ation/01.pdf
• University of Idaho-Questions
• http//www.uidaho.edu/bioenergy/top10q_s.htm

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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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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
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Biodiesel Industry Expansion
Largest Capacity100 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
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• Planning
• Location
• Biodiesel Marketing
• Feedstock Sourcing
• Glycerine Outlet
• Process Plant Size
• Chris Mitchell Biodiesel Product Manager
  Desmet Ballestra North America

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• 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 (H2O, 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 (gt90
  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
59
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• 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
61
(No Transcript)
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• 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
64
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• 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
66
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• 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 10-15 mgy biodiesel
  plants are typically in the range of
  1.00-0.75 / annual gallon.
• Total capital costs for 30-90 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 SpecificationASTM D 6751-06
Property Method Min Max
Flash point, ºC ASTM D 93 130.0
Water sediment, vol ASTM D 2709 0.050
Kin. Viscosity (40ºC), mm²/s ASTM D 445 1.9 6.0
Sulfated ash, mass ASTM D 874 0.020
Sulfur, mass ASTM D 5453 0.0015 (S15) 0.05 (S500)
Copper strip corrosion ASTM D 130 No. 3
Cetane number ASTM D 613 47
Cloud point, ºC ASTM ASTM D 2500 Report
ASTM American Society of Testing and  Materials.
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Biodiesel Fuel SpecificationASTM D 6751-06
Property Method Min Max
Carbon residue, mass ASTM D 4530 0.050
Acid no., mg KOH/g ASTM D 664 0.50
Free glycerin, mass ASTM D 6584 0.020
Total glycerin, mass ASTM D 6584 0.240
Phosphorus, mass ASTM D 4951 0.001
Distillation temp., ºC Atm. equiv. temp., 90 recovered ASTM D 1160 360
Sodium potassium, combined, ppm UOP 391 5
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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

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Biodiesel Quality AssuranceBQ-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

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Biodiesel Quality AssuranceBQ-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

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Biodiesel Quality AssuranceBQ-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

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Biodiesel Quality AssuranceBQ-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
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Biodiesel Quality AssuranceBQ-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