Bio Fuels Blending & Technology

July 2008 Presented N McHardy

Contents
Terms What are Biofuels ? SA Government Strategy and Feedstock Blending of Biofuels ethanol in petrol (specifications) bio diesel in diesel (specifications) Bio Fuels Technologies first generation others

Units (1)
Measure Percentage ppm ppb Comparison Calculation

How many in onex/100 hundred? How many in onex/1 000 000 million How many in onex/1 000 000 000 billion (US)

Approximate values

Terms (1)
RVP Reid Vapour Pressure (Volatility) kPa Kilopascal unit of measure for pressure m/m mass per mass comparison v/v volume per volume comparison mg milligram (one gram divided by one thousand) Pb Symbol for lead L Symbol for litre BOB or RBOB Special refinery blend intended to be blended with alcohol to make on specification petrol

Terms (2)
Paraffin Saturated straight chain hydrocarbon Aromatics compounds based on a benzene ring C(6)H(6) and its derivatives typically toluenes and xylenes. Olefins unnatural in that they have two less hydrogen molecules C(n)H(2n) than a saturated paraffin. Alcohols hydrocarbons that include an OH molecule atom combination Ethers any two hydrocarbon molecules linked by an oxygen molecule Oxygenates alcohols or ethers or both of these FAME fatty acid methyl ester (bio diesel B100)

Terms (3)
Fungible fully interchangeable product in any ratio of blends. Example A = B and X%A + Y%B = A =B even though A and B can be distinguished from each other. RON research octane number characteristic of petrol MON motor octane number characteristic of petrol Octane Straight chain normal C8H18 Cetane Number- characteristic of diesel fuel (engine test) Cetane Index characteristic of diesel fuel (calculated) Cetane Straight chain normal C10H22 Petrol engine spark ignition Diesel engine compression ignition

Terms (4)
Blend Component - a substance that is added in significant quantity because of its properties that are required in final product. The component may or may not be useful as a stand alone product. Additive a substance that is added to enhance specific properties of the final product but is added in volume that are insignificant in the total volume. The additives are usually not useful stand alone

What are Bio Fuels? What are Fossil Fuels?

What Are Biofuels?

Simply and broadly fuels derived from (renewable) organic materials
Wood Fermentable Sugar, Starch or cellulose Vegetable Oils Animal Oils Dung Biomass Charcoal Biogas often in form of Methane Bio ethanol from fermentation process Bio diesel from esterification of oil

Common products are

Fossil Fuel
Fossil fuels are those that are broadly derived from (non renewable) sources
Coal, anthracite, peat Crude oil Natural gas Methyl hydrates

Fossil Fuel
Common refined products are
Liquid Petroleum Gas (LPG) Petrol Diesel Jet fuel Paraffin Heavy fuel oil (bunkers) Asphalt bitumen and tar

Role of Renewables Big Picture

Independent energy supply Contribution to CO2 emission reduction Extend fossil fuel volumes Political tool in respect of potential subsidies Potential to increase agricultural production with impacts on land use, water use and food production. Potential to influence technology (flexfuels vehicles) Today all countries that are significant producers or users of biofuels have large subsidies in place except Brazil. Tax payers and energy users pay for biofuels.

RSA Biofuels strategy

A ten-year overview
Kyoto Protocol 2008-12 Developed countries must reduce green house gas emissions by 5% of 1990 levels Energy Policy White Paper Sets energy policy direction Acknowledges bio fuels Transport Fuels Audit DST: Biofuels need gvt support, more research needed WSSD Obligation to develop renewable energy technologies Kyoto Protocol SA accedes, access to CDM, DNA established Fuel Levy exemption 30% Depreciation allowance: 50:30:20 Renewable Energy White Paper 10 000GWh by 2013 To be reviewed in 2008 Petroleum Products Amendment Act 2003 Vehicle emission strategy Kyoto Protocol Becomes legally binding REFSO 2006/7: 16.7c/l subsidy for ethanol, 27.3c/l for biodiesel R20m max Enviro taxes paper Cabinet authorises strategy development Fuel Levy exemption 40%/100% Regulations under PPA Agricultural CEO Forum: Gvt intervention BEE facilitation Incentives Cleaner Fuels Programme Unleaded petrol Low sulphur diesel Commercial bio projects Draft strategy for public comment

Dec 2007 Revised Biofuels strategy

1997

1998

2001

2002

2003

2005

2006

Biofuels Industrial Strategy (Dec 2007) overview

Five year time frame - Two percent biofuels in liquid fuels target for 2013 with tax supports in place Intentions
Attract investment to rural areas Promote agricultural development Import substitution Overcome trade distortions related to developed world subsidised agriculture Ethanol from sugar cane and sugar beet Biodiesel from sunflower, canola (rape seed) and soya bean Maize banned for bioethanol production Targets require that 1.4% of arable RSA land convert to Biofuels RSA has only 14% arable land

Crops

NATIONAL STRATEGY A brief overview

Contract to be signed between biofuel producer and oil companies but no arbitrage between agri and biofuels for crop pricing. Mandated upliftment not desirable Deregulated ethanol in petrol pricing contemplated Government biofuels task team to address implementation.

RSA Agriculture
Approximate values 2005 a good year
Crop Maize Wheat Barley Canola Sugarcane Sunflower Soya 460 000 150 000 Area Ha 270 000 800 000 92 000 15 000 ton 7 600 000 2 000 000 250 000 50 000 22 000 000 620 000 270 000 Probable Bio Product Bio ethanol Bio ethanol Bio ethanol Bio Diesel Bio ethanol Bio Diesel Bio Diesel

RSA Bio Fuel First Generation Technology

Approximate values - 100 percent RSA Bio Fuel Supply
Crop Yield Litres Need tons per Ton 420 18 29 000 000 RSA ton 2005 7 600 000 Probable Bio Product 12 Billion Litres Ethanol 8 Billion Litres Bio Diesel

Maize Soya

450 000 000 270 000

RSA typically imports 600 000 ton Soya per year Conceptually Ethanol much easier to produce than Bio Diesel for RSA

RSA Bio Fuel First Generation Technology

Approximate values - 100 percent RSA Bio Fuel Supply
Crop Yield Litres Need tons per Ton 420 18 29 000 000 RSA ton 2005 7 600 000 Probable Bio Product 12 Billion Litres Ethanol 8 Billion Litres Bio Diesel

Maize Soya

450 000 000 270 000

RSA typically imports 600 000 ton Soya per year Conceptually Ethanol much easier to produce than Bio Diesel for RSA

Arable land RSA versus Brazil

Land (Million Hectares) Brazil Total Area 850 (100%) RSA 120 (100%)

Preserved area and other 510 (60%) use Arable Land soya maize sugar cane (all) sugar cane (ethanol) pastures 340 (40%) 21 (2.5%) 14 (1.5%) 8 (1%) 4 (0.5%) 200 (24%) 14 (13%) 0.15 (-) 0.27 (-) 0.44 (0.5%)

Rough numbers for comparison only Rainfall and irrigation limited for RSA

Bio Fuels Petrol & Ethanol

PETROL
Specifications Ethanol Blending Ethanol Technology Other Oxygenates
Butanol Ethers
ETBE MTBE TAME DIPE

Automotive petrol
Petrol is a complex blend of many components and additives Petroleum Products Act 1977 regulations 23 June 2006
Permitted metal free unleaded petrol grades must conform to SANS 1598 Permitted metal containing unleaded petrol grades must conform to SANS 1598

Regulated Road Octane grades

Grade Low RON Med RON 93 93 93 High RON 95 95 95

Unleaded & Un-metalled91 Unleaded Metalled Lead Replacement 91 91

All grades allowed coastal and inland but different vapour pressure MON will be ten numbers lower than RON except if alcohol is used at greater than 2% then MON will be eight numbers lower than RON.

Petrol specifications SANS 1598 (1)

Component Sulphur RVP Volatility index Aromatics v/v Benzene v/v Oxygen m/m Inland Coastal Comment

500 ppm 500 ppm Max 45 to 75 45 to 75 89 (94) 50% 5% 3.7% 95 (100) 50% 5% 2.8% Kpa Summer (Winter) Max Max Max

Petrol specifications (2)

Component Lead mg Pb/L Contamination Manganese mg/L Potassium mg/l Phosphorus mg/L Iron mg/L LRP 13 36 10 14 ? MULP 13 18 0 0 0 ULP 13 0 0 0 0 Comment Max additive Max additive Max additive Max additive Max

A manufacturer may only add one metal/LRP additive type to a batch

Oxygenate comparison (1)

Oxygenate RON MON Boil RVP Point (c) kPa 55 72 86 78 55 28 10 124 Solubility in water <5% <5% <5% 100%

MTBE ETBE TAME Ethanol

118 118 109 130

101 102 99 96

Note - These are approximate values - Blending values can be nonlinear.

Bio Ethanol SANS 456 ( ASTM D 4806)

Denatured fuel ethanol for blending with gasolines for use in automotive spark engines

Component Ethanol Methanol Solvent washed gum Water Denaturant (usually petrol) Inorganic chloride Copper content Acidity

Measure 92,1 0,5 5,0 1 1,96 4,76 40 0,1 0,007

Comment Min % v/v Min % v/v mg/100ml Max % v/v % v/v Max mg/ Kg Max mg/Kg Max mg/Kg

Typical Distillation Curves

450 400 350 300 Celcius 250 200 150 100 50 0 0 10 20 30 40 50 60 70 80 90 100 % Recovered Diesel Petrol

Petrol solubility
Non oxygenated petrol and alcohol are soluble to 100% in each other
Perfect miscibility and limited natural separation

Non oxygenated petrol and ethers are soluble to 100% in each other
Perfect miscibility and limited natural separation

Alcohols and ethers are soluble up to 100% in each other

Perfect miscibility and limited natural separation

Petrol and water

Conventional petrol does not dissolve in water
Poor miscibility and natural separation

Ethers have low solubility (approx 4%) in water

Poor miscibility and natural separation If ether petrol and water are mixed then some ether can migrate into water

Alcohols (ethanol) is 100% soluble in water

Perfect miscibility and no natural separation If alcohol petrol and water are mixed then the alcohol prefers to migrate into the water

Bio Fuel - simple blending ethanol

Petrol +Ethanol = Off Spec Stuff Refinery Blend +Ethanol = On-Spec Petrol Stock Out +Ethanol = No Petrol Refinery Blend +Stock Out = No Petrol
Refinery blend may or may not contain Ethers Alcohols + olefins = ethers. These can be manufactured in refineries Ethanol does not add to refinery petrol volume output

Fuels Blending

Bio Ethanol blending - Petrol

Key parameters
RON MON Vapour pressure and distillation curve Dilution of components Polarity of components (related to non linear blending) Non linear blend characteristics (1+2=5 and or 3+5=6)??? Displacement of refinery light ends and net refinery volume Altered distillation curve and fuel performance Each refinery will have different optimal solution

Key issues

Effect of Ethanol on Petrol Vapour Pressure

84 82
RVP KPA

80 78 76 74 0 2 4 6 Volume % Ethanol 8 10 12

Push Out Some Light Components

Ethanol blending
Significant challenge is where and how to blend.
In refinery (best optimisation but double transport?) In depots (sub optimal refineries but lower transport and give away?) Storage of additional blend components? Transport and logistics issues Minimise loss of value in supply chain Fit for purpose product to customer (standby generators and in tank fungibility?)

Ethanol Logistics and Depots

Some restrictions on pipeline use
No petrol alcohol mix with more than 2% alcohol (Wet or Dry) permitted in multiproduct pipeline that is used for JET Existing pipeline and coastal shipping is WET PAM not fungible with non alcohol petrol BOBs (Blend for oxygenate) not fungible?

If depot blending need tanks and equipment

Manage two products to be in stock to keep market wet Must get suitable blend stock from other manufacturers Recovery for unplanned shutdowns

Ethanol Marketing Issues

Motorist perceptions (green, power, economy?) Product & Performance differentiation at regulated price Fungibility and corrosion in customers tank Ethanol and/or Ether wrt water Continuity/Security of supply Fire fighting special precautions Ethanol permeates plastics/rubber Lube change interval The SAME?

Bio Fuels Diesel & FAME

DIESEL
Specifications FAME Blending Technology

Automotive diesel
Petroleum Products Act 1977 regulations
Effective 23 June 2006 Where maximum biodiesel differs from SANS 342 the regulations apply Standard grade diesel maximum 500mg / Kg sulphur max 5% v/v biodiesel Standard grade B10 -----10% biodiesel Standard grade B20 , B30 , B50 Low sulphur grade diesel max 50mg / Kg sulphur max 5% v/v biodiesel Low sulphur grade B10 -----10% biodiesel Low sulphur grade B20 , B30 , B50 Biodiesel B100 which must be 100% v/v biodiesel

Automotive diesel
A complex blend of many components and additives Automotive diesel fuel SANS 342
After storage for a period of 12 months after receipt under conventional conditions the diesel will conform to requirements of table 1 Grades are maximum 500 ppm and 50 ppm sulphur Grade may contain maximum 5% biodiesel that conforms to SANS 1935

Automotive biodiesel fuel - SANS 1935

similar to EN 14214 (Euro Std) but permits higher iodine value (wider range of oils) Fuel comprising of long chain methyl ester of vegetable oil Fuel shall be clear and free of water visible water, sediment or suspended matter and any other contaminant

Diesel Specifications SANS 342

Property Sulphur ppm (max) Cetane Number Flash Point Celsius (min) Copper strip corrosion (max 3h@100C) CFPP max (Summer Winter) Water max v/v Oxidation Stability mg/100ml Bio Diesel SANS 1935 B100 max Shelf Life 500 / 50 45 55 1 3 or -4 C 0.05% 2.0 5% 12 mths

Diesel comparison
Parameter Ash content % m / m Flash point Cetane number Carbon residue Cold filter plugging point Density Oxidation Stability SANS 342 SANS 1935 0,01 55 45 0,2 -4 or 3 800 2,0 0,02 120 51 0,3 -4 or 3 860 to 900 6,0 Comment IP 4 / ISO 3987 Celsius Min IP 154 Win / Sum Kg/m3 IP 388/ EN 14112

Biodiesel parameters (1)

Parameter Ester content % m / m Kinematic viscosity Sulphur content Total contamination Acid value Iodine Value Methanol content SANS 1935 96,5% 3,5 5,0 10 24 0,5 140 0,2 Comment EN 14103 mm2/s ppm (Max) ppm m / m mg KOH /100g g / 100g %m/m

Biodiesel parameters (2)

Parameter Monoglyceride Diglyceride Triglyceride Free glycerol Total glycerol Total group 1 metals Total group 2 metals Phosphorous content SANS 1935 0,8 0,2 0,2 0,02 0,25 5,0 5,0 0,2 Comment EN 14103 mm2/s ppm (Max) m / m ppm mg KOH /100g m / m ppm m / m ppm m / m ppm

Diesel solubility and Diesel with water

Diesel and bio diesel are soluble to 100% in each other
Perfect miscibility and limited natural separation

Neither Diesel nor Bio diesel will dissolve significantly in water. ( In the ppm range 150 to 350 ppm )
Poor miscibility and natural separation

Simple Blending Bio Diesel

Refinery Diesel Stock Out Refinery Diesel + Bio Diesel = Diesel (B5?) + Bio Diesel = B100 =? + Stock Out = B0 = OK

Bio Diesel Marketing issues

Impact on vehicle emissions?
Long chain molecules high boiling point Decrease combustion temperature and exhaust temperature Increase particulate matter

Impact on Oil Changes?

Suggested shorten lube change Esters increase wash down of diesel to sump Esters oxidise change lube viscosity Esters are effective solvents loosen gum and rust Higher likelihood of gelling when stored Keep oxygen out Keep cool Use only quality esters

Impact on fuel handling and storage

Bio Fuels - Process Technology

Overview of Bio Fuel Processes

Biological tend to be slow and deliver a well defined product that can be purified Thermal Tend to be rapid but deliver a mixed product that is more difficult to process or purify than from biological process. For all processes it is vital to evaluate full cycle of all components required especially energy, water, and carbon. Refer to carbon content of ground under favourable and unfavourable agricultural conditions. Affects net CO2 in atmosphere.

Overview of Processes
Starch and Sugars Residues Lignocellulose Oil plants Residues

Biological conversion Thermal conversion Ethanol Butanol Chemicals Synthetic biofuels ethanol, butanol, methanol, chemicals and hydrocarbons

Esterification

Biodiesel, Chemicals

Bio Diesel FAME basics

100 ml Methanol + 1 000 ml Vegetable oil + catalyst = 1 000 ml FAME + 100 ml Glycerol + 15ml unrecoverable Glycerol can be feedstock to pharmaceuticals and soaps (typically about 80% pure from initial process) Oil seed cake may be suitable for animal feed Full laboratory tests currently cost about R15 000 per batch but if only essential indicators about R1 000 ISO 9000 type process facility can reduce cost and frequency of tests

Bio Ethanol basics

Fermentation
Enzymes plus starch = dextrose
Dextrose plus yeast = raw ethanol about 10% v/v

Yeast plus sucrose = raw ethanol about 10% v/v

Initial distillation approx 95% ethanol plus water

Azeotrope ( WET) marginally stable if added to petrol

Secondary Distillation / Molecular sieve - >99% pure

Anhydrous Ethanol (DRY) stable if added to petrol

Relatively sophisticated plant

requires heat input, moderate pressure and multiple distilling.

Bio Ethanol (Cellulosic)

This is hope for future
Processes viable at laboratory scale No commercial scale Strong research in USA Potential to yield ethanol from grass , wood any available cellulose. Often Enzyme dependant. Low demand on agriculture as cellulose grows quicker and more easily than starch or sugar

Gulf Ethanol
Vortex implosion disintegrator High pressure high velocity turns biomass into cellulose powder. Low demand on agriculture as cellulose grows quicker and more easily than starch or sugar

Bio Ethanol (Cellulosic)

Coskata Process
Biomass is gasified to syngas (not feedstock dependant) Micro organisms produce Ethanol Low water and low energy input

Bio Butanol
BP have just launched this product
Very small volumes UK only Fermentation process (slow) Proprietary enzymes (restricted availability) Better blending properties than ethanol ( energy, octane, vapour pressure) May present challenges for bio degradability? Caution needed regarding sustainability of full cycle as no material returns to agriculture

Bio to Furfural Family

Another hope for the future
Process viable at laboratory scale No pilot plants or commercial scale Strong research in USA Potential to convert sugars to bio fuel precursors using synthesized oligosaccharides from bacteria
Glucose to 5-hydroymethylfurfural Fructose to 2,5 -dimethylfuran

potentially good petrol blend products

Summary

Summary
Yes oil industry can blend types of grades (petrol and diesel) envisaged in the strategy (but it costs). Yes local industry can produce the volumes of biofuel envisaged in the strategy (but it costs). Much work is required to get appropriate specifications and regulations in place to enable efficient industry (agri/bio/oil). Must consider full supply scope
Crude availability and type of refineries Car parc and fuel specifications Product fitness for purpose Subsidies/ equalization slate and return on investment to participants Price to end user Fitness for purpose

References
South African National Standards (www.stansa.co.za) The Royal Society (www.royalsociety.org) The Scientific American (www.SciAm.com) The Chemical Engineer (www.tcetoday.com) International Fuel Quality Centre (www.ifqc.org) Nature of South Africas Soil Resources (www.environment.gov.za/nssd )

Thank you