Analytical Measurement and Inspection

supporting Quality of Bio-ethanol

Kurt Tyssen, Business Development Manager

Intertek Oil, Chemical & Agri Division

total customer focus

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Bio ethanol presentation, 2009

Intertek and Bio-fuels

Intertek and Fuels:

Active in the oil industry providing Testing
and Inspection Services since 1885

Intertek and Biofuels

Analytical service provider during (i) manufacturing & processing
industry (ii) during storage & handling (iii) blending/trading

High-end (R&D) analytical support and consultancy services from
the Intertek Technology Centres (Sunbury)

Inspection and batch certification

Field sampling

Seminars and training courses
Bio Ethanol presentation, 2009

Important Criteria

The fuel should be effective in propelling a car

The fuel should not be harmful to the engine and/or
auxiliary parts

QUALITY

The fuel should be according to legislation

The fuel should be sustainable

Bio Ethanol presentation, 2009

Fuel quality standards

Specifications that a fuel needs to meet:

Gasoline
Diesel
Ethanol
Bio diesel
Heating Bio diesel

EN228 (5% ethanol volume)

EN590
EN15376 / ASTM D 4806
EN14214 / ASTM D6751
EN 14213

CEN: is contributing to the objectives of the European Union and

European Economic Area with voluntary technical
standards which promote free trade, the safety of workers
and consumers, interoperability of networks, environmental
protection, exploitation of research and development
programmes, and public procurement.
In most countries standards are now part of legislation

Bio Ethanol presentation, 2009

Options for bioethanol in Europe in automotive

Fuels
:

As component for ETBE production

In mainstream gasoline, 5 10% volume
In flexible Fuels vehicles, up to 85% volume in gasoline
As a bio component for other bio-chemicals (bio-butanol)

CEN: is contributing to the objectives of the European Union and

European Economic Area with voluntary technical
standards which promote free trade, the safety of workers
and consumers, interoperability of networks, environmental
protection, exploitation of research and development
programmes, and public procurement.
In most countries standards are now part of legislation

Bio Ethanol presentation, 2009

(Bio) Ethanol (CH3CH2OH), also called alcohol, is a substance

obtained from the fermentation of sugar cane, grains (first
generation), or cellulose (2nd generation) from biomass
New green fuels derived from a renewable source of energy,
reduce enviromental polutions.
Bio-ethanol is nothing new as In Brazil & Sweden such green
fuels (E85) already a long time are consumed as fuels for flexible
car systems

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Bio Ethanol presentation, 2009

Applications

Fuels: used in internal combustion engines and as an blend compound into

gasoline. (E5, E10, .. E 85)
Solvents: in many industrial segments such as paints and varnishes;
Raw material: for the production of ethyl acetate, glycols, acetaldehyde,
diethyl ether, neutral ethanol, quaternary ammonium,
Natural disinfectant: in the formulation of cleaning products;
Fermentation process: used as substrate in the production of vinegars and
acetic acid, due to its extremely low levels of fermentation inhibition.
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Bio Ethanol presentation, 2009

Ethanol is obtained in the first stage as hydrous alcohol.

In this form the Ethanol can find his application into the use as fuel
A further purified Ethanol (removing of some contaminants as higher
alcohols and esters, between others) also know as industrial ethanol,
is commercialized to customers with refining capacity such as ETBE
production for blending into gasoline.
Another stage of hydrous ethanol is to obtain a neutral ethanol, free of
impurities which is applied for human consumption (beverages or
pharmacy industry)
The last stage is production of Anhydrous that is obtained from
dehydration processes

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Bio Ethanol presentation, 2009

Dehydration Stages of Ethanol

Molecular Sieves How does it works?

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Bio Ethanol presentation, 2009

Denatured Ethanol
Pure ethanol and alcoholic beverages are heavily taxed. Ethanol knows
many applications that do not involve human consumption. To relieve
the tax burden on these application, most jurisdictions waive the tax
when reagents have been added to the ethanol to render it unfit for
human consumption. These include bittering agents such as denatonium
benzoate (Bitrex)or denatonium saccaride between others.
These substances are added in the alcohol to change the organolopetic
characteristic and give a bitter taste.
Concentrations between 2.5 ppm until 20 ppm are add for denaturing
process.

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Bio Ethanol presentation, 2009

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Vapor Pressures issues limitations

-Vapour pressure limit in the EU is set at 60 kPa at summer period

-Adding low volumes of ethanol will increase the vapour pressure (increase of
7kPa after adding 3-10% vol ethanol to gasoline)
-> Industry solutions to reduce vapour pressure:
1)Today (bio) ethanol is converted to (bio) ETBE
2)Removing of light components (butane) into refinery process (similar which is
happening in US) BOB
3)Implementation of a Waiver which allows higher vapour pressure for
petrol/ethanol blends (future? New version of EN 228 required.
Industry is suggesting for a an overall 10 kPa waiver

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Bio Ethanol presentation, 2009

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Intertek is member of IETHA and help the International

market to develop specifications
Technical Specifications

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Bio Ethanol presentation, 2009

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Inspection and Quality Control - Importance

Due the fact of Ethanol is a hygroscopic product it is very important to survey the quality during all
stages of transfer of the product from production, transport (vessels) , storage & handling (terminals)
& blending (depots & refineries)
.
Critical components to check depending on the quality of ethanol:
- Anhydrous European grade: analysis of water by K.F., Alcoholic Strength
-Hydrous for Dehydration: analysis of cyclohexane and other hydrocarbons by GC (plants that use
molecular sieves have restrictions to hydrocarbons), Alcoholic Strength, chlorides
- Industrial and neutral Grade : UV for benzene and other aromatics compounds, impurity components
, alcoholic strength.

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Bio Ethanol presentation, 2009

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Technical Specifications
BRAZILIAN ANP standard

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Bio Ethanol presentation, 2009

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Technical
Specifications
USA standard ASTM D.4806

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Bio Ethanol presentation, 2009

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European Quality Standard EN 15376

Method
Ethanol content
High Saturated mono alcohols
Methanol content
Water content
Acidity, as acetic acid
Sulphur content
Appearance
Copper Content
Inorganic Chloride
Phosphorus
Involatile Material

EC 2870-2000
EN 1601/EN 13132
EN 1601/EN 13132
EN 15489
EN 15491
EN 154876
Visual
EN 15488
EN 15484
EN 15487
EC 2870-2000

Value
min 98.7 % v/v
max 2,0 % v/v
max 1,0 % v/v
max 0.30 % v/v
max 0.007 %wt
max 10 mg/kg
clear and bright
max 0.1 ppm
max 20 ppm
max 0.5 ppm
max 10 mg/100ml

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Bio Ethanol presentation, 2009

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European Fuel Grade Ethanol spec

Method
Ethanol content
Higher Alcohols
Higher C3-C5 mono alcohols
Methanol content
Water content
Purity (calculated by difference)
Chlorides
Total acidity as acetic acid
Copper content
Phosphorus
Appearance
Non volatile Matter
Total Sulphur
Electrical Conductivity
Gum content Washed
Iron (Fe)
Sodium (Na)
Sum Cation content
pHe
Esters calc. as ethylacetate
Aldehydes calc as acetaldehyde
Basic Nitrogen
Methyl Sulphur

pr EN 15721
pr EN 15721
pr EN 15721
pr En 15721
ASTM D 1364
Calculate
ASTM D 5808
ASTM D 1613
ASTM D 1688A
EN 14107mod
Visual
ASTM D 1353
ASTM D 5453
ASTM D 1125
ASTM D 381
DIN 51797
DIN 57797
Calculated
EN 15490
ASTM D 94
ASTM E 411
DIN 51444
ASTM D 5623mod
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Bio Ethanol presentation, 2009

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Fuel Ethanol Tank Storage

Guidelines API Practice 1626
Standard storage mild steel tanks are completely satisfactory for the storage of

100% ethanol and ethanol/gasoline blends.

Storage tanks coated with standard, general-purpose epoxy linings are not

satisfactory for ethanol or blended storage because ethanol may soften the epoxy.

Tanks should have a fixed roof with an internal floater.

Shoretanks for ethanol should offer bottom sampling as phasing can occur
Ethanol is stored at ambient temperature.

Bio Ethanol presentation, 2009

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Fuel Ethanol Tank Storage

Ethanol will loosen rust, varnish and gums from previously

used tanks, clean all loose material from the tank before filling.
Avoid contact with soft metals.

Ensure that all tanks be clean and dry prior to filling with
ethanol. (including line systems)

They should be equipped with a 16 ounce pressure / one

ounce vacuum (P/V) vent. Make certain that the storage tank
handle this pressure.

Bio Ethanol presentation, 2009

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Transportation Equipment
Equipment used to deliver ethanol that may have prior use
delivering other commodities such as caustic soda, distillate, or
other products could contaminate the load.

Companies have, upon inspection, had to reject barges (that

had supposedly been properly cleaned) due to the presence of
caustic soda.

One company has had to reject nearly 30% of all barges

inspected.

If caustic soda or other unacceptable commodities are present,

the equipment should be rejected.

Bio Ethanol presentation, 2009

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Test Significance

Ethanol content and higher saturated alcohols

The ethanol content is specified as a minimum to ensure a correct degree of purity for
its use in automobiles.

Higher saturated (C3-C5) mono alcohols content

They assist in maintaining water in suspension and lower the RVP of ethanol blends
so they are regarded as beneficial impurities resulting from the production process
and therefore should be limited only to obtain the adequate purity of the ethanol

Methanol content
Methanol is naturally present in industrially produced ethanol in small quantities. I can
contribute to the combustion as an oxygenate but it is a toxic component.
Methanol can also be corrosive towards certain metallic and non-metallic materials

Bio Ethanol presentation, 2009

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Test Significance

Water Content
Ethanol is water absorbent and there is a risk of attracting water from air over longer
storage periods.
Blends of fuel ethanol and gasoline have a limited solvency for water. The water
content of the denatured fuel ethanol must be limited when it is blended with gasoline
to reduce the risk of phase separation. Therefore it is imperative that water is
eliminated from the systems

Solvent-Washed Gum Content

The test method is used to detect the presence of impurities that could clog fuel
systems (filter blocking)

Sulfur Content
Legislation has established gasoline sulfur controls to support vehicle emission
standards.

Bio Ethanol presentation, 2009

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Test Significance

Chloride Ion Content

Low concentrations of chloride ions are corrosive to many metals.

Copper Content
Trace levels in gasoline may significantly increase the rate of gum formation.
Copper is a very active catalyst for the low temperature oxidation of hydrocarbons

Acidity
Organic acids such as acetic are highly corrosive to many metals.

Sulfate Content
Small amounts of inorganic sulfates in denatured ethanol can contribute to turbine
meter deposits and plugging of fuel dispensing pump filters in the distribution system.
The sulfates also have been shown to cause fuel injector sticking resulting in engine
misfiring and poor drive ability.

Bio Ethanol presentation, 2009

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Introduction of BOB Grades

BOB = Blendstock for oxygenate Blending

- Refineries produces low volatile, ethanol free grade for distribution to terminals
- More expensive as attractive blend component C4 has to be reduced
- Refiners ensure BOB + 5% ethanol meets all EN 228 requirements
- BON cannot be used as fuel alone , so EtOH supply must be assured

In-line blending of BOB + ethanol at terminal rack

Provides tight control of blend ratios
Addition of corrosion inhibitor (Nace Corrosion test) to the ethanol recommended
No industry BOB standards yet. Will be demanded for comingled storage & pipeline
transport.

Bio Ethanol presentation, 2009

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Future of bio ethanol

Direct blending of ethanol will become common practice during 2009/2010

Sustainability criteria in place

Actually maximum 5% vol. In future 10% most likely (expected 2011)

Specifications available for 5% but still a long way to go for 10% specs
Ethanol needs to fulfill EN 15376 standard
Ethanol standard for E85 in draft
Specification harmonisation on a global scale between regions
Major cost impact for refiners especially on RVP and quality management
BOB specifications for pipeline transport and commingled storage to be
developed within industry
2nd generation bio ethanol (cellulose based)

Bio Ethanol presentation, 2009

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Contact us
Kurt Tyssen
EAME Biofuels Business & Analytical development Manager
Tel: +32 (0) 3 544 10 90
Fax: +32 (0) 3 542 23 44
Mobile: +32 (0) 477 37 91 84
Email: kurt.tyssen@intertek.com

Mario Van Der Ent

Tel: +31 (10) 490 27 51
Fax: 0031 (10) 472 32 25
Mobile : +31 (6) 3040 0470
Email : mario.van.der.ent@intertek.com

www.intertek.com

Bio Ethanol presentation, 2009

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