This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

Designation: D4806 − 19a

Standard Specification for

Denatured Fuel Ethanol for Blending with Gasolines for Use
as Automotive Spark-Ignition Engine Fuel1
This standard is issued under the fixed designation D4806; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope* mendations issued by the World Trade Organization Technical

1.1 This specification covers nominally anhydrous dena- Barriers to Trade (TBT) Committee.
tured fuel ethanol intended to be blended with unleaded or 2. Referenced Documents
leaded gasolines at 1 % to 15 % by volume for use as automo-
tive spark-ignition engine fuel covered by Specification D4814 2.1 ASTM Standards:2

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as well as other fuel applications or specifications involving D86 Test Method for Distillation of Petroleum Products and
ethanol. The significance of this specification is shown in Liquid Fuels at Atmospheric Pressure
Appendix X1. D381 Test Method for Gum Content in Fuels by Jet Evapo-
ration
1.2 Jurisdictions may vary in their regulatory requirements D1298 Test Method for Density, Relative Density, or API
for the allowable or prohibited types of denaturants, chemical Gravity of Crude Petroleum and Liquid Petroleum Prod-
composition of the denaturant or concentration of denaturant ucts by Hydrometer Method
needed to denature the ethanol. The user is advised to check D1613 Test Method for Acidity in Volatile Solvents and
with the national and regional regulatory agencies where the Chemical Intermediates Used in Paint, Varnish, Lacquer,
ethanol is denatured and used. and Related Products
1.2.1 Specific regulatory requirements for denatured fuel D1688 Test Methods for Copper in Water
ethanol and acceptable denaturants from various jurisdictions D2622 Test Method for Sulfur in Petroleum Products by
are given in Appendixes for information. Wavelength Dispersive X-ray Fluorescence Spectrometry
1.3 The values stated in SI units are to be regarded as D3120 Test Method for Trace Quantities of Sulfur in Light
standard. Liquid Petroleum Hydrocarbons by Oxidative Microcou-
1.3.1 Exception—Values given in parentheses are provided lometry
for information only. Non-SI units are shown in the Appendix D4052 Test Method for Density, Relative Density, and API
if they are in a direct quotation from government regulations. Gravity of Liquids by Digital Density Meter
In most cases, U.S. federal regulations specify non-SI units. D4057 Practice for Manual Sampling of Petroleum and
Petroleum Products
1.4 The following safety hazards caveat pertains only to the
D4175 Terminology Relating to Petroleum Products, Liquid
method modification in 8.7 of this specification: This standard
Fuels, and Lubricants
does not purport to address all of the safety concerns, if any,
D4177 Practice for Automatic Sampling of Petroleum and
associated with its use. It is the responsibility of the user of this
Petroleum Products
standard to establish appropriate safety, health, and environ-
D4306 Practice for Aviation Fuel Sample Containers for
mental practices and determine the applicability of regulatory
Tests Affected by Trace Contamination
limitations prior to use.
D4814 Specification for Automotive Spark-Ignition Engine
1.5 This international standard was developed in accor-
Fuel
dance with internationally recognized principles on standard-
D5453 Test Method for Determination of Total Sulfur in
ization established in the Decision on Principles for the
Light Hydrocarbons, Spark Ignition Engine Fuel, Diesel
Development of International Standards, Guides and Recom-
Engine Fuel, and Engine Oil by Ultraviolet Fluorescence
D5501 Test Method for Determination of Ethanol and
Methanol Content in Fuels Containing Greater than 20%
1
This specification is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
2
Subcommittee D02.A0.02 on Oxygenated Fuels and Components. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Sept. 15, 2019. Published September 2019. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1988. Last previous edition approved in 2019 as D4806 – 19. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D4806-19A. the ASTM website.

*A Summary of Changes section appears at the end of this standard

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 D4806 − 19a
Ethanol by Gas Chromatography 3. Terminology
D5580 Test Method for Determination of Benzene, Toluene, 3.1 For general terminology, refer to Terminology D4175.
Ethylbenzene, p/m-Xylene, o-Xylene, C9 and Heavier
Aromatics, and Total Aromatics in Finished Gasoline by NOTE 1—The user is advised that the definitions used by various
industries, marketers, and regulatory bodies can differ from those specific
Gas Chromatography
to this specification. It is the responsibility of the user to ensure that the
D5854 Practice for Mixing and Handling of Liquid Samples terms used in a particular context are clearly understood.
of Petroleum and Petroleum Products
3.2 Definitions:
D6423 Test Method for Determination of pHe of Denatured
3.2.1 denaturants, n—materials added to ethanol to make it
Fuel Ethanol and Ethanol Fuel Blends
unsuitable for beverage use under a formula approved by a
D6550 Test Method for Determination of Olefin Content of
regulatory agency to prevent the imposition of beverage
Gasolines by Supercritical-Fluid Chromatography
alcohol tax.
D7039 Test Method for Sulfur in Gasoline, Diesel Fuel, Jet
3.2.1.1 Discussion—Denaturants are only those materials
Fuel, Kerosine, Biodiesel, Biodiesel Blends, and
added by the denaturer to comply with the approved formula;
Gasoline-Ethanol Blends by Monochromatic Wavelength
any materials absorbed later are not denaturants.
Dispersive X-ray Fluorescence Spectrometry
D7318 Test Method for Existent Inorganic Sulfate in Ethanol 3.2.2 denatured fuel ethanol, n—fuel ethanol made unfit for
by Potentiometric Titration beverage use by the addition of denaturants under formula(s)
D7319 Test Method for Determination of Existent and Po- approved by the applicable regulatory agency to prevent the
tential Sulfate and Inorganic Chloride in Fuel Ethanol and imposition of beverage alcohol tax.
Butanol by Direct Injection Suppressed Ion Chromatog- 3.2.3 ethanol, n—ethyl alcohol, the chemical compound
raphy CH3CH2OH.
D7328 Test Method for Determination of Existent and Po- 3.2.4 fuel ethanol, n—a grade of ethanol with other compo-
tential Inorganic Sulfate and Total Inorganic Chloride in nents common to its production (including water) that do not
Fuel Ethanol by Ion Chromatography Using Aqueous affect the use of the product as a component for automotive
Sample Injection spark-ignition engine fuels.
D7347 Test Method for Determination of Olefin Content in
Denatured Ethanol by Supercritical Fluid Chromatogra- 3.2.4.1 Discussion—The common components do not in-
phy clude denaturant.
D7576 Test Method for Determination of Benzene and Total 3.2.5 gasoline, n—a volatile mixture of liquid
Aromatics in Denatured Fuel Ethanol by Gas Chromatog- hydrocarbons, generally containing small amounts of
raphy additives, suitable for use as a fuel in spark-ignition, internal
D7757 Test Method for Silicon in Gasoline and Related combustion engines. D4814
Products by Monochromatic Wavelength Dispersive 3.2.6 gasoline blendstock, n—a liquid hydrocarbon compo-
X-ray Fluorescence Spectrometry nent suitable for use in spark-ignition engine fuels.
D7795 Test Method for Acidity in Ethanol and Ethanol
Blends by Titration 3.2.6.1 Discussion—Examples of gasoline blendstock in-
D7923 Test Method for Water in Ethanol and Hydrocarbon clude natural gasoline, raffinate, reformate, conventional gaso-
Blends by Karl Fischer Titration line blendstock for oxygenate blending (CBOB), and reformu-
E29 Practice for Using Significant Digits in Test Data to lated gasoline blendstock for oxygenate blending (RBOB).
Determine Conformance with Specifications 3.2.7 gasoline-ethanol blend, n—a fuel consisting primarily
E203 Test Method for Water Using Volumetric Karl Fischer of gasoline along with a substantial amount (more than 0.35 %
Titration by mass oxygen) of denatured fuel ethanol.
E300 Practice for Sampling Industrial Chemicals 3.2.8 oxygenate, n—an oxygen-containing, ashless, organic
E1064 Test Method for Water in Organic Liquids by Coulo- compound, such as an alcohol or ether, which may be used as
metric Karl Fischer Titration a fuel or fuel supplement. D4814
2.2 Government Regulations: 3.2.9 pHe, n—a measure of the acid strength, defined by
United States Code of Federal Regulations, Title 27, Parts Test Method D6423, of ethanol-hydrocarbon blends. D6423
19, 20, and 213 3.2.9.1 Discussion—This measurement is sometimes
United States Code of Federal Regulations, Title 40, Part 80 thought to be analogous to the traditional pH measurement of
California Code of Regulations, CCR Title 13, §2260 – hydrogen ion activity in aqueous systems but the measure-
§22984 ments done in Test Method D6423 are in a nearly anhydrous
environment.
3.3 Abbreviations:
3
A printed copy of the Code of Federal Regulations may be purchased from the 3.3.1 CCR—California Code of Regulations
U.S. Government Printing Office Superintendent of Documents, 732 N. Capitol St.,
NW, Mail Stop: SDE, Washington, DC 20401 or the online store at http:// 3.3.2 CFR—U.S. Code of Federal Regulations
bookstore.gpo.gov/. The Code of Federal Regulations may be browsed online at 3.3.3 DFE—Denatured Fuel Ethanol
http://www.gpoaccess.gov/cfr/index.html.
4
California regulations are available online at http://government.westlaw.com. 3.3.4 EPA—The U.S. Environmental Protection Agency
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 D4806 − 19a
TABLE 1 Performance Requirements
Property Limit Method
Ethanol, % by volume, min 92.1 D5501
Methanol, % by volume, max 0.5 D5501
Solvent-washed gum content, mg/100 mL, max 5 D381
Water, % by volume (% by mass), max 1.0 (1.26) D7923, E203, or E1064
Inorganic Chloride, mg/kg (mg/L), max 6.7 (5) D7319 or D7328
Copper, mg/kg, max 0.1 D1688
Acidity (as acetic acid CH3COOH) mg/kg, (% by mass) [mg/L], max 70 (0.0070) [56] (Note 2) D7795
pHe 6.5 to 9.0 D6423
Sulfur, mg/kg, max 30. D2622, D3120, D5453, or D7039
Existent sulfate, mg/kg, max 4 D7318, D7319, or D7328

3.3.5 IRS—U.S. Internal Revenue Service 5.1.1.1 This specification is specific to denatured fuel etha-
3.3.6 RBOB—reformulated blendstock for oxygenate blend- nol as a blendstock in spark-ignition engine fuel. Denaturants
ing that could provide satisfactory performance for other uses
could cause damage to spark-ignition engines. The fuel ethanol
3.3.7 RIN—Renewable Identification Number
formulas approved by the alcohol regulatory agency for fuel
3.3.8 TTB—The Alcohol and Tobacco Tax and Trade Bureau use could include denaturing materials which are not allowed
of the U.S Department of Treasury by this ASTM specification. It is the denaturer’s responsibility
to consult the regulations to ensure legal denaturing of the fuel
4. Performance Requirements (Table 1) ethanol and to ensure compliance with this specification with
4.1 Denatured Fuel Ethanol—After fuel ethanol is dena- regard to allowed denaturants.
tured as specified in Section 5, it shall conform to the following 5.1.2 The natural gasoline, gasoline blendstock, or unleaded
requirements at the time of blending with gasoline. gasoline used as denaturant should not contain materials at
NOTE 2—Denatured fuel ethanol may contain additives, such as
concentrations that can separate from solution at the expected
corrosion inhibitors and detergents, that can affect the titratable acidity temperatures of blending, storage, and use. If drag reducing
(acidity as acetic acid) of the finished denatured fuel ethanol. Although the agent (additive) (DRA) is used in the distribution system, it
base fuel ethanol may meet the acidity specification, the effect of these should not be present in the product delivered to be used as a
additives can produce an apparent high titratable acidity of the finished denaturant at a concentration or shear condition that can
product. Contact the ethanol supplier if there is a question regarding the
titratable acidity of the denatured fuel ethanol to verify that the base fuel
separate from the denatured fuel ethanol under those condi-
ethanol meets the acidity requirements in Table 1. tions.
5.1.3 Prohibited Denaturants—This specification prohibits
4.2 Other Properties—Limits more restrictive than those
the use of hydrocarbons with an end boiling point higher than
specified above, or the specification of additional properties
225 °C as determined by Test Method D86, although they may
such as color, may be agreed upon between the supplier and the
be permitted by some regulations. Some kerosines, for
purchaser.
instance, promote piston scuff in automotive engines. Specific
4.3 For purposes of determining conformance with the mention must be made of some materials that have extremely
specified limits in Table 1, an observed value or a calculated adverse effects on fuel stability, automotive engines, and fuel
value shall be rounded “to the nearest unit” in the last righthand systems. These materials shall not be used as denaturants for
digit used in expressing the specification limit, in accordance fuel ethanol under any circumstances. They are as follows:
with the rounding method of Practice E29, unless otherwise methanol, pyrroles, turpentine, ketones, and tars (high-
specified. molecular weight pyrolysis products of fossil or nonfossil
vegetable matter). Ketone denaturants tend to degrade fuel
5. Denaturant and Regulatory Information stability or increase the tendency of a gasoline-ethanol blend to
5.1 General Requirements—This specification provides corrode metals and attack elastomers. These effects become
general information for the denaturants to be used in denatured more serious if the concentration of a ketone such as 4-methyl
fuel ethanol and the concentration of denaturant to be added. pentanone (methyl isobutyl ketone) exceeds one part by
Jurisdictions may vary in their regulatory requirements for the volume per 100 parts by volume of fuel ethanol. There is no
allowable or prohibited types of denaturants, chemical compo- information available on the effects of denaturants other than
sition of the denaturant or concentration of denaturant needed those mentioned above. Therefore, the only denaturants that
to denature the ethanol. shall be used are those listed in 5.1.1.
5.1.1 Allowable Denaturants—The only denaturants al- 5.1.4 Denaturant Level—A buyer may ask the denaturer to
lowed for the denatured fuel ethanol defined by this specifica- denature within a specific range (for example, 1.96 % to 2.5 %
tion are natural gasoline, gasoline blendstocks, or unleaded by volume). A buyer may also ask the denaturer to certify the
gasoline. Small amounts of the same or similar hydrocarbons range used for the denaturant addition. A buyer or distributor
absorbed by the denatured fuel ethanol as it moves through the may commingle receipts certified within the same range and
distribution system is not denaturant. A jurisdiction can main- provide a certification of conformance with the product from
tain approved formulas to denature alcohol for fuel use. that commingling. The blender may use this certification of
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 D4806 − 19a
conformance for the product to demonstrate compliance with 7.3 The correct sample volume and appropriate container
the denaturant limits. If the product is shipped directly from a selection are important decisions that can impact test results.
denaturer to a blender, the initial certification from the dena- Refer to Practice D4306 for aviation fuel container selection
turer may be used to demonstrate compliance. Compliance for tests sensitive to trace contamination. Refer to Practice
with the denaturant limit cannot be determined analytically. D5854 for procedures on container selection and sample
Compliance shall be based on the information from the original mixing and handling. All sampling and storage containers
denaturer. The maximum concentration of denaturant allowed should be evaluated for durability, compatibility, and contami-
in this specification is 5 % by volume. nation of denatured fuel ethanol prior to use. If samples must
5.2 Regulatory Information for Denaturants and Denatured be collected in metal containers, do not use soldered metal
Fuel Ethanol: containers. Soldering flux in the containers and the lead in the
5.2.1 Users of this specification are advised to consult with solder can contaminate the sample.
the applicable regulatory agency for specific requirements for 7.4 Sample Size—A minimum of about 1 L is recommended.
denaturants (types, composition, and amounts) and denatured If specific gravity is to be determined by a hydrometer method,
fuel ethanol in their jurisdictions. The requirements can be additional volume may be required. This depends on the size of
covered by regulations specific to a jurisdiction or by multiple the hydrometer.
regulations due to overlapping jurisdictions. Appendixes have

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7.5 Lot Size—A lot shall normally consist of the amount
been developed to provide information for several jurisdictions contained in a tanker compartment or other bulk container in
describing the requirements within the designated jurisdiction: which it is delivered. If this definition does not apply, the
5.2.1.1 Appendix X2, Regulatory Requirements for Califor- definition of a lot must be agreed upon between the supplier
nia. and purchaser.
5.2.1.2 Appendix X3, Regulatory Requirements for the
United States. NOTE 5—See Sections 5, 6, and 7 on Significance, Safety, and
Statistical Considerations, respectively, of Practice E300 for a detailed
discussion of the statistics of sampling.
6. Workmanship
6.1 At the point of custody transfer, the denatured fuel 8. Test Methods
ethanol shall be visually free of sediment, suspended, or
8.1 The scope of some of the test methods listed below do
undissolved matter. It shall be clear and bright at the product
not include denatured fuel ethanol. The precisions of those test
temperature at the point of custody transfer or at a lower
methods can differ from the reported precisions when testing
temperature agreed upon by the purchaser and seller.
denatured fuel ethanol.
NOTE 3—Fuel components should be resistant to phase separation or
undissolved matter at the lowest temperatures to which it is likely to be 8.2 Water—Test Methods D7923, E203, or E1064.
subjected, dependent on the time and place of its intended use. See 8.3 Solvent-Washed Gum Content—Test Method D381, air
Specification D4814 Table X8.1 for guidance. jet apparatus.
NOTE 4—Solubility is temperature dependent. As this fuel component
cools, some high molecular weight additives can become insoluble. 8.4 Acidity—Test Method D7795.
6.2 The product shall be free of any adulterant or contami- 8.5 pHe—Test Method D6423.
nant that can render the material unacceptable for its com-
8.6 Inorganic Chloride—Test Methods D7319 or D7328.
monly used applications.
6.2.1 Manufacturers, importers, and others denaturing fuel 8.7 Copper—Modification of Test Methods D1688, Test
ethanol shall avoid ethanol (for example, improperly recycled Method A.
ethanol) or denaturants contaminated by silicon-containing 8.7.1 The modifications of Test Methods D1688, Test
materials, or both. Silicon contamination of gasoline- Method A (atomic absorption, direct) consists of mixing
oxygenate blends has led to fouled vehicle components (for reagent-grade ethanol (which can be denatured in accordance
example, spark plugs, exhaust oxygen sensors, catalytic con- with TTB Formula 3A or 30) in place of water as the solvent
verters) requiring parts replacement and repairs. Test Method or diluent for the preparation of reagents and standard solu-
D7757 is a procedure for determining silicon content but no tions. However, this must not be done to prepare the stock
specification limits have been established for this silicon. copper solution described in the section on Copper Solution,
Stock in Test Method D1688. Because a violent reaction can
7. Sampling, Containers, and Sample Handling occur between the acid and the ethanol, use water, as specified,
7.1 The user is strongly advised to review all intended test in the acid solution part of the procedure to prepare the stock
methods prior to sampling to understand the importance and copper solution. Use ethanol for the rinse and final dilution
effects of sampling technique, proper containers, and special only.
handling required for each test method. 8.7.2 The precision of this modified method has not been
determined, but it is expected to be similar to the precision of
7.2 Correct sampling procedures are critical to obtain a Test Method D1688, Test Method A.
sample representative of the lot intended to be tested. Use
appropriate procedures in Practice D4057 or Practice E300 for 8.8 Ethanol and Methanol—Test Method D5501.
manual method sampling and in Practice D4177 for automatic 8.9 Sulfur—Test Methods D2622, D3120, D5453, or
method sampling, as applicable. D7039. California specifies that compliance with the California

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 D4806 − 19a
sulfur standard for denatured ethanol shall be determined using ethanol volumes) at the time of denaturing. There is no
Test Method D5453 – 93. EPA allows Test Methods standardized test procedure or calculation to directly or indi-
D3120 – 06ε1, D5453 – 08a, or D7039 – 07 for measuring rectly determine the denaturant content in denatured fuel
sulfur in gasoline as long as these alternative test method ethanol.
results are correlated to the EPA designated Test Method
D2622 – 05 when determining compliance with Federal EPA 9. Keywords
sulfur standards.
9.1 acidity; automotive spark-ignition engine fuel; base
8.10 Existent Sulfate—Test Methods D7318, D7319, or gasoline; chloride ion; copper; corrosion inhibitors; denatur-
D7328. ants; denatured fuel ethanol; ethanol; fuel; fuel ethanol; gaso-
8.11 Denaturant—The denaturant content is determined by line; gasoline-ethanol blend; oxygenate; solvent-washed gum
the ratio of (metered denaturant) to (metered denaturant and content; sulfate ion; sulfur; water

APPENDIXES

(Nonmandatory Information)

X1. SIGNIFICANCE OF SPECIFIED PROPERTIES

X1.1 Denatured Fuel Alcohol X1.1.2 Solvent-Washed Gum Content:

X1.1.1 Water—Karl Fischer analysis is generally the only X1.1.2.1 The test for solvent-washed gum content measures
consistently reliable procedure for the determination of water the amount of residue after evaporation of the fuel and
in denatured ethanol. Test Method E203 describes the modifi- following a heptane wash. The heptane wash removes the
cations required to run the test in the presence of alcohols. heptane-soluble, nonvolatile material such as additives, carrier
Relative density or specific gravity is needed to convert the oils used with additives, and diesel fuels. Solvent-washed gum
Karl Fischer water determination from E203 and E1064 from consists of heptane-insoluble gum. The fuel-insoluble portion
a percent by mass to a percent by volume. Methods D1298 and can clog fuel filters. Both can be deposited on surfaces when
D4052 are recommended for determination of relative density. the fuel evaporates.
X1.1.1.1 Methods and tables exist to determine the water X1.1.2.2 Solvent-washed gum can contribute to deposits on
content of ethanol/water mixtures based on the specific gravity the surfaces of carburetors, fuel injectors, and intake
of the mixture. These methods do not work for water determi- manifolds, ports, valves, and valve guides. The impact of
nation after the denaturant has been added. solvent-washed gum from pure alcohols such as ethanol on
malfunctions of modern engines is not known. The test method
X1.1.1.2 Blends of denatured fuel ethanol and gasoline or
is used essentially to detect the presence of high boiling,
similar hydrocarbons have a limited solvency for water. This
heptane-insoluble impurities.
solvency will vary with the ethanol content, the temperature of
the blend, and the aromatic content of the base gasoline. A fuel X1.1.2.3 Because the precision statements for Test Method
made by blending 10 % by volume denatured fuel ethanol with D381 were developed using only data on hydrocarbons, they
a gasoline containing 14 % by volume aromatics and 0.6 % by are not applicable to denatured fuel ethanol.
mass dissolved water (about 0.5 % by volume), will separate X1.1.3 Chloride Ion—Low concentrations of chloride ions
into a lower alcohol-rich aqueous phase and an upper hydro- are corrosive to many metals.
carbon phase if cooled to about 7 °C. As normal spark-ignition
X1.1.4 Copper—Copper is a very active catalyst for the
engines will not run on the aqueous phase material, such a
low-temperature oxidation of hydrocarbons. Experimental
separation is likely to cause serious operating problems. The
work has shown that copper concentrations higher than
phase separation of gasoline-ethanol blends is affected by the
0.012 mg ⁄kg in commercial gasolines can significantly in-
total water content of the mixture. This includes the water
crease the rate of gum formation.
content from the ethanol and gasoline hydrocarbons blended at
the rack and the water adsorbed from the transportation and X1.1.5 Acidity—Very dilute aqueous solutions of low-
storage infrastructure for the blended fuel. All water sources molecular weight organic acids such as acetic acid
should be identified, monitored and controlled to prevent phase (CH3COOH) are highly corrosive to many metals. It is
separation of the blended fuel. Denatured fuel ethanol is therefore necessary to keep such acids at a very low level.
hygroscopic and can pick up water from the atmosphere during X1.1.5.1 The acidity method is intended to determine the
long-term storage. Prudent precautions to reduce water expo- concentration of organic acids in ethanol. However, carbon
sure and monitor the product should be considered if long term dioxide gas is very soluble in ethanol, and in the presence of
storage is expected. available water, a small portion of the gas converts to carbonic
X1.1.1.3 Test Method D7923 may be used to measure water acid. In denatured fuel ethanol, the water content is very low
content in denatured fuel ethanol in concentrations 0.05 % to and the ethanol molecules will combine with the water leaving
5.0 % by mass. very little water available for the carbon dioxide molecule. One
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 D4806 − 19a
step in the test method is to add a significant quantity of water ethanol will vary based on levels of denaturant, water and the
to the sample allowing a greater fraction of the dissolved gas to minor components common to ethanol production.
become carbonic acid. Another step of the test method is the
X1.1.9 Existent Sulfate—The presence of small amounts of
addition of an aqueous base to perform the titration. The base
inorganic sulfates in denatured fuel ethanol under the right
addition will shift the equilibrium from the carbonic acid to the
conditions can contribute to turbine meter deposits and the
carbonate salt resulting in more of the dissolved carbon dioxide
premature plugging of fuel dispensing pump filters in the fuel
being converted into carbonic acid. By the end of the titration
distribution system. The sulfates also have been shown to
all of the dissolved gas will have been converted to the
cause fuel injector sticking resulting in engine misfiring and
carbonate salt.
poor driveability in automobiles.
X1.1.5.2 Dissolved carbon dioxide is a known interference
and can cause a false high reading when using Test Method X1.1.10 Denaturant—Section 5 discusses the denaturants
D1613. Prior to 2018, Test Method D1613 was included in the that are allowed or prohibited and the denaturing levels for
standard. Due to the CO2 interference, a number of false high product meeting this specification. Denaturant is added in the
acidity values were reported causing disruptions in the mar- specified concentration range to comply with TTB and IRS
ketplace. The problems with using Test Method D1613 led to requirements. The content is set by volumetric addition during
the development of Test Method D7795 with a purge step the denaturing process. Standard analytical methods do not
which removed the CO2 interference. Test Method D1613 has exist to directly or indirectly determine the denaturant content
been removed as an appropriate test method for this standard. or acceptability of the denaturant beyond that point.
X1.1.6 pHe—When the pHe of ethanol used as a fuel for X1.1.11 Sulfur—The Federal Tier 2 Motor Vehicle and
automotive spark-ignition engines is below 6.5, fuel pumps can Emissions Standards and Gasoline Sulfur Control Require-
malfunction as a result of film forming between the brushes ments establish sulfur standards for refineries and importers
and commutator, fuel injectors can fail from corrosive wear, producing reformulated gasoline, Reformulated Blendstock for
and excessive engine cylinder wear can occur. When the pHe Oxygenate Blending (RBOB), and conventional gasoline. EPA
is above 9.0, fuel pump plastic parts can fail. has established gasoline sulfur content standards for gasoline
X1.1.7 Appearance—Turbidity or evidence of precipitation and denatured fuel ethanol blended into gasoline. Sulfur
normally indicates contamination. contaminates the catalytic converter necessary for reducing
X1.1.7.1 Fuel components can encounter conditions in the emissions of hydrocarbons (HC), carbon monoxide (CO), and
bulk distribution system that could cause the material to fail a nitrogen oxides (NOx).
workmanship visual evaluation. Some fuel components can X1.1.12 Methanol—Small amounts of methanol can be
contain dirt or rust particles during distribution. Terminals or produced in the ethanol production process. Methanol at high
bulk plants can address these issues with proper operating concentrations can be corrosive to components of the fuel
procedures; for example, by allowing sufficient time for the dirt system and has a greater effect on increasing vapor pressure
or particles to settle in the tank, by filtration or by other means. than does ethanol. The limit is set to prevent methanol
X1.1.8 Ethanol—The ethanol content is important in deter- corrosion and the incremental effect on vapor pressure. The
mining the blend ratios for adding denatured fuel ethanol into limit is also to prevent methanol from being used as a
the finished gasoline. The ethanol content of denatured fuel denaturant.

X2. CALIFORNIA ETHANOL REQUIREMENTS

X2.1 California Ethanol Requirements TABLE X2.1 California Denatured Ethanol Standards
(In Addition to the Performance Requirements in ASTM
X2.1.1 While the following requirements are believed to be D4806 – 99)
accurate at the time of publication, users should consult the Specification
Property Test Method
relevant authority to confirm the current regulations and Limit
requirements. The information provided about the regulations Sulfur, mg/kg, max 10 D5453 – 93
is for information only. In case of conflict, the text of current Benzene, % by volume, max 0.06 D7576 – 10
Olefins, % by volume, max 0.5 D7347 – 071
regulations takes precedence. Aromatics, % by volume, max 1.7 D7576 – 10
X2.1.2 The California Air Resources Board has approved
standards for denatured ethanol to be field-blended with
California Reformulated Gasoline Blendstock for Oxygenate
Blending (CARBOB) to make California Phase 3 Reformu- X2.1.3 The California standards for denatured ethanol set
lated Gasoline (CaRFG3). Standards also have been specified maximum limits on sulfur, benzene, olefins, and aromatics
for the denaturant. These California standards for denatured contents as shown in Table X2.1, and also require the dena-
ethanol and denaturant became effective Dec. 31, 2003, and tured ethanol to comply with the performance requirements in
were amended on Aug. 29, 2008. Specification D4806 – 99.

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 D4806 − 19a
TABLE X2.2 California Denaturant Standards the test results are multiplied by the decimal fraction repre-
Property
Specification
Test Method
senting the percent denaturant.
Limit
Benzene, % by volume, 1.10 D5580 – 02 (2007) X2.1.5 California allows an exception to the limits shown in
max Table X2.1 where the denatured ethanol supplier takes reason-
Olefins, % by volume, max 10.0 D6550 – 10
Aromatics,% by volume, 35.0 D5580 – 02 (2007)
ably prudent precautions to ensure the denatured ethanol that
max exceeds these limits will only be added to a specially designed
CARBOB which has been designated to be blended with such
denatured ethanol. Documentation is required to support the
X2.1.4 California specifies that compliance with the sulfur transfer of denatured ethanol. All CaRFG3 requirements for the
standard shall be determined by testing the denatured ethanol final blend shall be met.
using Test Method D5453 – 93. California specifies that com-
X2.1.6 California specifies the standards for the denaturant
pliance with the standards for benzene, olefins, and aromatics
used in denatured ethanol as shown in Table X2.2. Also shown
contents shall be determined by direct analysis of the denatured
are the test methods required to determine compliance.
fuel ethanol (Table X2.1) or by testing a sample of the
denaturant using the test methods specified for CARB gasoline X2.1.7 California standards allow higher amounts of
(Table X2.2), and then calculating the content of those com- benzene, olefins, and aromatics in the denaturant if the supplier
pounds in the denatured ethanol, multiplying the test value by takes necessary precautions to ensure that when added to the
0.0500. However, where it is demonstrated that the denatured ethanol, the level is less than 5.00 % by volume and the limits
ethanol contains less than 5.00 % by volume denaturant, then in Table X2.1 are met.

X3. U.S. FEDERAL REQUIREMENTS FOR DENATURED FUEL ETHANOL

X3.1 While the following requirements are believed to be with the rounding method described in the ASTM standard
accurate at the time of publication, users should consult the practice, ASTM E29 – 02ε1, entitled, ‘Standard Practice for
relevant authority to confirm the current regulations and Using Significant Digits in Test Data to Determine Confor-
requirements. The information provided about the regulations mance with Specifications’”. The denaturant concentration in
is for information only. In case of conflict, the text of current the denatured fuel ethanol is not determined by an analytical
regulations takes precedence. test method but is calculated from the metered volumes by the
denaturer.
X3.2 U.S. EPA Requirements for Denaturant in Dena-
tured Fuel Ethanol X3.2.1.3 The following portions of Practice E29 – 13 ad-
dress the EPA denaturant limit.
X3.2.1 There are two EPA regulations impacting the dena-
6.4 Rounding Procedure—The actual rounding procedure shall be as follows:
turant concentration in denatured fuel ethanol. 6.4.1 When the digit next beyond the last place to be retained is less than 5,
X3.2.1.1 In the definition for Renewable Fuel (40 CFR § retain unchanged the digit in the last place retained.
6.4.2 When the digit next beyond the last place to be retained is greater than 5,
80.1401) the EPA states “(2) Ethanol covered by this definition increase by 1 the digit in the last place retained.
shall be denatured as required and defined in 27 CFR parts 19 6.4.3 When the digit next beyond the last place to be retained is 5, and there
through 21. Any volume of denaturant added to the undena- are no digits beyond this 5, or only zeros, increase by 1 the digit in the last
place retained if it is odd, leave the digit unchanged if it is even. Increase by 1
tured ethanol by a producer or importer in excess of 2 volume the digit in the last place retained, if there are non-zero digits beyond this 5.
percent shall not be included in the volume of ethanol for
purposes of determining compliance with the requirements X3.2.1.4 For rounding purposes only, if the records from the
under this subpart.” The U.S. Environmental Protection denaturant addition system indicate the denaturant concentra-
Agency regulations stipulate that denaturant added in excess of tion is between 1.5 % by volume to 2.5 % by volume, then
2 % by volume shall not be considered when determining using the rounding method in Practice E29 – 02ε1, the dena-
volumes for the purposes of compliance with the Renewable tured fuel ethanol is deemed to contain 2 % by volume
Fuel Standard. This absolute limitation includes volumes for denaturant for EPA purposes only.
Renewable Identification Number (RIN) generation. The limits X3.2.2 Beginning January 1, 2017, under the U.S. EPA Tier
for the denaturant addition are shown in Table X3.1. 3 fuel program, “the concentration of all denaturants used in
X3.2.1.2 The EPA also has a procedure to follow when DFE [denatured fuel ethanol] is limited to a maximum of 3.0
determining compliance with this regulation. Regulation 40
volume percent” (40 CFR 80.1610(a)(4)).
CFR § 80.9, “Rounding a test result for determining confor-
mance with a fuels standard,” states “for purposes of determin- X3.2.3 Denatured fuel ethanol “must be composed solely of
ing compliance with the fuel standards of 40 CFR Part 80, a carbon, hydrogen, nitrogen, oxygen and sulfur” (40 CFR
test result will be rounded to the nearest unit of significant 80.1610(a)(2)), and “only previously certified gasoline (includ-
digits specified in the applicable fuel standard in accordance ing previously certified blendstocks for oxygenate blending),

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 D4806 − 19a
TABLE X3.1 U.S. Federal Limits on Denaturants and Denatured Fuel Ethanol
Limits on Denaturant Content of Denatured Fuel Ethanol
Limit, volume % Source Requirement
1.96 minA TTBB TTB Formulas require a minimum of two parts of approved denaturant to 100 parts of
ethanol with a minimum of 195 proof ethanol.

2 maxC,D EPAD The maximum amount of denaturant the EPA allows for RIN generation in denatured fuel
ethanol under the national Renewable Fuels Standard Program.

3.0 maxC EPAE The maximum amount of denaturant the EPA allows in denatured fuel ethanol for use as a
gasoline blendstock.
Chemical Limits on Denatured Fuel Ethanol
Property Specification Limit Test Method
Sulfur, mg/kg, max 10F D2622, D3120, D5453, D7039
A
For purposes of determining conformance with this limit, the Absolute Method in Practice E29 should be used.
B
See X3.4 for information on this TTB limit.
C
For purposes of determining conformance with this limit, the Rounding Method in Practice E29 should be used.
D
See X3.2.1.1 for additional information on this EPA limit.
E
See X3.2.2 for additional information on this EPA limit.

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F
See X3.3.1 for additional information on this EPA limit.

gasoline blendstocks, or natural gas liquids may be used as are published in the United States Code of Federal Regulations,
denaturants” (40 CFR 80.1610(a)(3)). Title 27, Parts 19, 20, and 21. The denatured fuel ethanol
allowed by this specification shall contain a minimum of 1.96
X3.3 U.S. EPA Requirements for Sulfur in Denatured % by volume denaturant.
Fuel Ethanol
X3.3.1 Beginning January 1, 2017, under the U.S. EPA Tier X3.4.2 To avoid imposition of the beverage excise tax, TTB
3 fuel program, “the sulfur content must not be greater than 10 regulations require the denaturer to add specific quantities of
ppm” (10 mg/kg) (40 CFR 80.1610(a)(1)). approved denaturants to the ethanol prior to shipping. The
denaturant content is determined by the ratio of metered
X3.3.2 There are additional EPA federal requirements for denaturant and ethanol volumes at the time of denaturing. The
producers and importers of certified denaturant to be used for
TTB regulations stipulate the record keeping requirements for
the manufacture of denatured fuel ethanol: The sulfur content
the denaturer. These regulations include records of the quanti-
of the denaturant for use in the manufacture of denatured fuel
ties of ethanol and denaturant added in the denaturing process.
ethanol “must not be greater than 330 ppm” (40 CFR
The TTB periodically audits the denaturing facilities and
80.1611(a)(1)). “The ethanol denaturant “must be composed
solely of carbon, hydrogen, nitrogen, oxygen and sulfur” (40 associated records for compliance with these regulations. The
CFR 80.1611(a)(2)). “Only previously certified gasoline (in- regulations do not require the receiver to analytically verify
cluding previously certified blendstocks for oxygenate that the material added was an approved denaturant or that it
blending), gasoline blendstocks, or natural gas liquids may be was added within the necessary concentration range. Approved
used as denaturants” (40 CFR 80.1611(a)(3)). analytical methods or calculations do not exist to permit any
the following: (1) to confirm compliance with this section of
X3.4 U.S. Alcohol and Tobacco Tax and Trade Bureau the specification after the denaturing process, (2) to determine
Requirements on Denatured Fuel Ethanol that the denaturant used was approved by the TTB or allowed
X3.4.1 In the United States, ethanol is rendered unfit for in this specification, (3) to quantify the ratio of denaturant
beverage use by the addition of denaturants under formulas added during the denaturing process, or (4) to distinguish
approved by the Alcohol and Tobacco Tax and Trade Bureau between the hydrocarbons added as part of the denaturing
(TTB) of the U.S. Treasury Department that allow the dena- process and those absorbed later in the distribution system.
tured alcohol to ship from the denaturer free of beverage excise There is no ASTM approved test method for determining
tax and to be distributed and used as a fuel component without denaturant concentration in denatured fuel ethanol, although
TTB permits. TTB regulations concerning the preparation, regulatory agencies may use non-ASTM methods for investi-
handling, distribution and use of denatured ethanol formulas gative purposes.

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 D4806 − 19a
SUMMARY OF CHANGES

Subcommittee D02.A0 has identified the location of selected changes to this standard since the last issue
(D4806 – 19) that may impact the use of this standard. (Approved Sept. 15, 2019.)

(1) Revised subsection 3.2.9; moved term from “Definitions of

Terms Specific to this Standard” to “Definitions.”

Subcommittee D02.A0 has identified the location of selected changes to this standard since the last issue
(D4806 – 18a) that may impact the use of this standard. (Approved March 1, 2019.)

(1) Revised Table 1.

Subcommittee D02.A0 has identified the location of selected changes to this standard since the last issue
(D4806 – 18) that may impact the use of this standard. (Approved Dec. 1, 2018.)

(1) Revised subsections 3.2.3 and 3.2.4.

(2) Added new subsection 5.1.2 to Section 5, Denaturant,
under subsection 5.1, General Requirements, to include warn-
ings about using additive materials that are not compatible with
ethanol blends.

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