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 Comparison Calculation

Percentage How many in onex/100

hundred?
ppm How many in onex/1 000 000
million
ppb 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
• Common products are
– Charcoal
– Biogas often in form of Methane
– Bio ethanol from fermentation process
– Bio diesel from esterification of oil
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
Renewable Becomes Regulations
WSSD Energy legally under PPA
Kyoto Energy Transport
Obligation to White binding
Protocol Policy Fuels
develop Paper Agricultural
2008-12 White Audit REFSO
renewable 10 000GWh CEO Forum:
Developed Paper DST: 2006/7:
energy by 2013 Gvt intervention
countries Sets Biofuels 16.7c/l
technologies To be BEE facilitation
must energy need subsidy for
reviewed in Incentives
reduce policy gvt Kyoto ethanol,
green direction support, 2008
Protocol 27.3c/l for Cleaner Fuels
house gas Acknow- more SA accedes, biodiesel
Petroleum Programme
emissions ledges research access to R20m max
Products Unleaded petrol
by 5% of bio fuels needed CDM, DNA Amendment Low sulphur
1990 established Enviro taxes
Act 2003 diesel
levels paper

Fuel Levy Vehicle Cabinet Commercial

exemption emission authorises bio projects Dec 2007
30% strategy strategy Revised
development Draft Biofuels
Depreciation strategy for strategy
allowance: Fuel Levy
public
50:30:20 exemption
comment
40%/100%

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

• Crops
– 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
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 Area ton Probable Bio

Ha Product
Maize 270 000 7 600 000 Bio ethanol
Wheat 800 000 2 000 000 Bio ethanol
Barley 92 000 250 000 Bio ethanol
Canola 15 000 50 000 Bio Diesel
Sugarcane 22 000 000 Bio ethanol

Sunflower 460 000 620 000 Bio Diesel

Soya 150 000 270 000 Bio Diesel
RSA Bio Fuel – First Generation Technology
• Approximate values - 100 percent RSA Bio Fuel Supply

Crop Yield Litres Need tons RSA ton Probable Bio

per Ton 2005 Product

Maize 420 29 000 000 7 600 000 12 Billion Litres

Ethanol
Soya 18 450 000 000 270 000 8 Billion Litres Bio
Diesel

•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 RSA ton Probable Bio

per Ton 2005 Product

Maize 420 29 000 000 7 600 000 12 Billion Litres

Ethanol
Soya 18 450 000 000 270 000 8 Billion Litres Bio
Diesel

•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 RSA

Total Area 850 (100%) 120 (100%)

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

RON RON RON
Unleaded & Un-metalled91 93 95

Unleaded Metalled 91 93 95

Lead Replacement 91 93 95

•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 Inland Coastal Comment

Sulphur 500 ppm 500 ppm Max

RVP 45 to 75 45 to 75 Kpa

Volatility index 89 95 Summer

(94) (100) (Winter)
Aromatics v/v 50% 50% Max

Benzene v/v 5% 5% Max

Oxygen m/m 3.7% 2.8% Max

Petrol specifications (2)

Component LRP MULP ULP Comment

Lead mg Pb/L 13 13 13 Max

Contamination
Manganese mg/L 36 18 0 additive Max

Potassium mg/l 10 0 0 additive Max

Phosphorus mg/L 14 0 0 additive Max

Iron mg/L ? 0 0 additive Max

A manufacturer may only add one

metal/LRP additive type to a batch
Oxygenate comparison (1)
Oxygenate RON MON Boil RVP Solubility
Point (c) kPa in water

MTBE 118 101 55 55 <5%

ETBE 118 102 72 28 <5%

TAME 109 99 86 10 <5%

Ethanol 130 96 78 124 100%

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 Measure Comment

Ethanol 92,1 Min % v/v
Methanol 0,5 Min % v/v
Solvent washed gum 5,0 mg/100ml
Water 1 Max % v/v
Denaturant (usually petrol) 1,96 – 4,76 % v/v
Inorganic chloride 40 Max mg/ Kg
Copper content 0,1 Max mg/Kg
Acidity 0,007 Max mg/Kg
Typical Distillation Curves
450
400
350
300
Celcius

250 Diesel
200 Petrol

150
100
50
0
0 10 20 30 40 50 60 70 80 90 100
% Recovered
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)
• Key issues
– 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
Effect of Ethanol on Petrol Vapour Pressure

84

82

80
RVP KPA

78
Push Out Some Light Components
76

74
0 2 4 6 8 10 12
Volume % Ethanol
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
– BOB’s (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) 500 / 50

Cetane Number 45
Flash Point Celsius (min) 55
Copper strip corrosion (max 3h@100C) 1

CFPP max (Summer –Winter) 3 or -4 C

Water max v/v 0.05%
Oxidation Stability mg/100ml 2.0
Bio Diesel SANS 1935 B100 max 5%
Shelf Life 12 mths
Diesel comparison

Parameter SANS 342 SANS 1935 Comment

Ash content % m / m 0,01 0,02 IP 4 / ISO 3987

Flash point 55 120 Celsius

Cetane number 45 51 Min
Carbon residue 0,2 0,3 IP 154
Cold filter plugging point -4 or 3 -4 or 3 Win / Sum
Density 800 860 to 900 Kg/m3
Oxidation Stability 2,0 6,0 IP 388/ EN
14112
Biodiesel parameters (1)

Parameter SANS Comment

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

Parameter SANS Comment

1935
Monoglyceride 0,8 EN 14103
Diglyceride 0,2 mm2/s
Triglyceride 0,2 ppm (Max)
Free glycerol 0,02 m / m ppm
Total glycerol 0,25 mg KOH /100g
Total group 1 metals 5,0 m / m ppm
Total group 2 metals 5,0 m / m ppm
Phosphorous content 0,2 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 + Bio Diesel = Diesel (B5?)

• Stock Out + Bio Diesel = B100 =?
• Refinery Diesel + 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
• Impact on fuel handling and storage
– Higher likelihood of gelling when stored
– Keep oxygen out
– Keep cool
– Use only quality esters
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 Lignocellulose Oil plants

Residues Residues

Biological Esterification
conversion
Thermal conversion
Biodiesel,
Chemicals
Ethanol Synthetic biofuels
Butanol ethanol, butanol,
Chemicals methanol,
chemicals and
hydrocarbons
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 Africa’s Soil Resources
(www.environment.gov.za/nssd )
Thank you