ENGINEERING ASPECTS OF

BIODIESEL PRODUCTION PROCESS

Nurhan Turgut Dunford
Oklahoma State University Department of Biosystems and Agricultural Engineering

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

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 160250oC Diesel oil: A mixture of hydrocarbons containing 1325 carbon atoms, boiling point 220-350oC

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.

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.org/safety/ http://www.biodiesel.org/pdf_files/fuelfactsheets/M SDS.pdf

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 Biodiesel (B100) B20 Blend (B20) B2 Blend (B2)

0.850 0.880 0.856* 0.851*

129,500 118,296 127,259* 129,276*

8.65 % 1.73 %* 0.17 %*

* Calculated Values from those of No. 2 Diesel and Biodiesel (B100)

Triacylglyceride

OH H

HOOCR

OH H OH H

HOOCR

3H2O

HOOCR H

GLYCEROL

FATTY ACIDS

TRIGLYCERIDES

WATER

Fatty Acid Molecular Structure

Saturated Fatty Acids

Monounsaturated Fatty Acids

Polyunsaturated Fatty Acids

Esterification

R - COOH + R1- OH
Fatty Acid Alcohol Catalyst

R COO - R1 + H2O
Ester/biodiesel Water

Methanol safety: http://www.biodiesel.org/resources/reportsdatabas e/reports/gen/20060401_GEN-370.pdf

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

Homogeneous Catalysis Acid or Base Catalysis

Dryer
Biodiesel

Oil/fat

Biodiesel
Alcohol/ catalyst

Reactor

Separator
Glycerine + Alcohol

Wash Column
Water

Alcohol

Glycerine + Water +Alcohol

Alcohol Recovery
Glycerine + Water

Glycerine Recovery
Glycerine

Homogeneous Catalyst Options

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

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 0.3-1.4% Na-Methoxide 0.5% or less

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%)

Homogeneous Catalysis Two-Step Process

Dryer
Alcohol + Catalyst Alcohol + Base Catalyst Biodiesel

Oil/fat

Biodiesel
Alcohol/ Acid catalyst Acid Reactor Base Reactor Separator

Wash Column

Glycerine + Alcohol Alcohol

Water

Alcohol Recovery

Glycerine + Alcohol + Water

Glycerine Recovery
Glycerine

Glycerine + Water

Heterogeneous Catalysis
Biodiesel

Alcohol

Glycerine Glycerine Alcohol Glycerine

Oil/fat

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

Heterogeneous Esterfip-H Process Highlights

http://www.Axens.net 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

Enzymatic Conversion
Reactor

Enzyme

Biodiesel
Oil + Alcohol Separator

Glycerine

Lipases are used as catalyst Immobilized or free enzymes

Comparison of Enzyme and Base Catalysis

Catalyst
Reaction temperature Free fatty acids in raw materials Water in raw materials Yield of methyl esters

Base
60-70C Saponified products (soap formation) Interference with the reaction Normal

Enzyme
30-4OoC Methyl esters

No influence Higher

Recovery of glycerol
Purification of methyl esters Catalyst cost

Difficult
Repeated washing Cheap

Easy
None Relatively expensive

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

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

Non-Catalytic Conversions
Supercritical fluids Co-solvent systems

Non-Catalytic Conversion Supercritical Methanol

Alcohol Biodiesel Oil/fat
High pressure & temperature reactor

Separator Separator

Alcohol

350-400oC, 85-100 atm (1200-1500 psi), alcohol:oil 42:1 3-5 min reaction time

Glycerine

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

Phase Separation
Required density difference for phase separation Specific Gravity Methanol Biodiesel Soybean oil Catalyst Glycerine 0.1

0.79 0.88 0.92 0.97 1.28 as much methanol as possible min. methanol

Good reaction Good phase separation

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/sup ercetane_e.pdf

AVRO Diesel TM Process

/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.

(http://www.nrcan.gc.ca/es/etb/cetc/cetc01/htmldocs

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.

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

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.htm

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

Reading Material
http://www.southeastdiesel.org/Photos/Library/Ag/Eng_ AspectsCh1.pdf http://www.fapc.okstate.edu/factsheets/fapc149.pdf http://www.fapc.okstate.edu/factsheets/fapc150.pdf http://www.uidaho.edu/bioenergy/biodieselED/publicati on/01.pdf University of Idaho-Questions http://www.uidaho.edu/bioenergy/top10q_s.htm

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

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

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

Planning*

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

Location*
Minimizing the freight cost for feedstock
and biodiesel will be critical to survive. mile radius?

How much biodiesel can be sold in a 200 How much competition or potential
* Chris Mitchell Biodiesel Product Manager Desmet
Ballestra North America

competition exists in a 200 mile radius?

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? suppliers to insure adequate feedstock? rail, and at what frequency?

Can you sign a long-term contract with one of these

Will the feedstock suppliers in the area deliver by truck or

* Chris Mitchell Biodiesel Product Manager Desmet

Ballestra North America

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? or rail, and at what frequency?

Will the glycerin refiners in the area want delivery by truck

Do you need to install your own glycerin refinery?

* Chris Mitchell Biodiesel Product Manager Desmet Ballestra North America

Process Plant Size*

What plant size will meet the short and long term
needs of the local biodiesel market? size?

How does local feedstock availability limit plant 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

* Chris Mitchell Biodiesel Product Manager Desmet Ballestra
North America

build the plant, and how much capacity can that buy?

Plant Site Selection*

Transportation Proximity Utility Connections Specific Parcel of Land Shared Infrastructure
* Chris Mitchell Biodiesel Product Manager Desmet Ballestra
North America

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

Utility Connections*
Does the site have sufficient power supply available? Does the site have sufficient water supply available (to
meet fire protection demand)? the plant waste water?

Does the site have a sewer connection that can take

Does the plant have natural gas supply available?

* Chris Mitchell Biodiesel Product Manager Desmet Ballestra

North America

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?
sufficient number of cars?

Is the site long enough for the rail siding to hold a Any environmental & construction permitting issues?
* Chris Mitchell Biodiesel Product Manager Desmet Ballestra
North America

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

Critical Parameters*

Safety
Quality Downtime/Uptime Operating Costs Capital Costs
* Chris Mitchell Biodiesel Product Manager Desmet Ballestra
North America

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 (NFPANational 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

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

Quality*
All biodiesel leaving the facility must meet ASTM (American
Society of Testing and Materials) specs at a minimum. to with the buyer.

Biodiesel leaving the facility should meet specs as agreed

Biodiesel should also be transported in clean vessels.

* Chris Mitchell Biodiesel Product Manager, Desmet Ballestra

North America

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

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

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

Total Operating Costs

CHEMICALS MANPOWER 11% 85% 1% 1% 0% 0% 2% UTILITIES MAINTENANCE TAXES & INSURANCE DEPRECIATION FEEDSTOCK

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

Conversion Costs
(approximately $0.33/gallon)

$0.030 CHEMICALS $0.029 $0.221 $0.010 $0.010 $0.031 MANPOWER UTILITIES MAINTENANCE TAXES & INSURANCE DEPRECIATION

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

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

Capital Cost -- Process Building

3%

20% grading/concrete structural/building 12% process equipment equipment setting piping electrical 8% automation insulation 6% 10% 3%

38%

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

Capital Cost -- Complete facility

4% 3% SITE WORK PROCESS BUILDING 65% 18% UTILITY BUILDING OFFICE BUILDING TANK FARM

10%

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

Biodiesel Fuel Specification ASTM D 6751-06

Property
Flash point, C
Water & sediment, %vol Kin. Viscosity (40C), mm/s Sulfated ash, %mass Sulfur, %mass Copper strip corrosion Cetane number Cloud point, C ASTM

Method
ASTM D 93
ASTM D 2709 ASTM D 445 ASTM D 874 ASTM D 5453 ASTM D 130 ASTM D 613 ASTM D 2500

Min
130.0
1.9 47

Max

0.050 6.0 0.020 0.0015 (S15) 0.05 (S500) No. 3 Report

ASTM: American Society of Testing and Materials.

Biodiesel Fuel Specification ASTM D 6751-06

Property
Carbon residue, %mass Acid no., mg KOH/g Free glycerin, %mass Total glycerin, %mass Phosphorus, %mass Distillation temp., C Atm. equiv. temp., 90% recovered Sodium & potassium, combined, ppm

Method
ASTM D 4530 ASTM D 664 ASTM D 6584 ASTM D 6584 ASTM D 4951 ASTM D 1160

Min

Max
0.050 0.50 0.020 0.240 0.001 360

UOP 391

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

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

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

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

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

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