P.1 

OAR Box 1846 

Prepped by Ollie Stewart 

Document Number: 

63) ll-J-6 

Docket Number: 

A-90-07 

Printed 11/18/2008 7:30:16 AM Sheet 63 of 93 
P.2 

A-96-cn -tX-5-0^) 

California Air Resources Board 

Staff Report 

MI033X{| 

\w— . Vvu 

EPA WBD2SS!'1 

Proposed Specifications for Alternative 

Fuels for Motor Vehicles 

Release Date: October 28, 1991 

State of California 

Air Resources Board 
P.3 

State of California 

AIR RESOURCES BOARD 

Stationary Source Division 

STAFF REPORT: INITIAL STATEMENT OF REASONS FOR RULEMAKING 

Public Hearing to 

Consider Adoption of Specifications for 

Alternative Fuels for Motor Vehicles 

Date of Release: October 28, 1991 

Scheduled for Consideration: December 12, 1991 

This report has been reviewed by the staff of 

the California Air Resources Board and approved for publication. 

Approval does not signify that the contents necessarily 

reflect the views and policies of the Air Resources Board, 

nor does mention of trade names or commercial products 

constitute endorsement or recommendation for use. 
P.4 

ACKMOWLFDeyCtlTS 

This report was prepared with the assistance and support from the other 

divisions and offices of the A1r Resources Board. In addition, we would 

like to acknowledge the assistance and cooperation that we have received 

from many Individuals and organizations. In particular, we would like to 

thank members of the American Society for Testing and Materials committees, 

the California Energy Commission, the California Natural Gas Vehicle 

Coalition, the California Renewable Fuels Council, the Division of 

Measurement Standards of the California Department of Food and Agriculture, 

the Motor Vehicle Manufacturers Association, the Western Liquid Gas 

Association, and the Western States Petroleum Association. 

Principal Author; 

Stephen R. Francis 

Office of legal Affairs: 

Tom Jennings 

With Special Thanki for Clerical Support To: 

Theresa Dade 

Marline Hicks 

Reviewed and Approved Bv: 

Peter D. Venturlnl, Chief, Stationary Source Division 

Ronald A. Frlesen, Assistant Chief, Stationary Source Division 

Dean C. Simeroth, Chief, Criteria Pollutants Branch 

Robert D. Fletcher, Manager, Fuels Section 
P.5 

TABLE OF CONTENTS 

CjmifinU £agi 

I. INTRODUCTION 1 

A. Introduct ion 1 

B. Summary 2 

C. Recommendation 8 

II. DISCUSSION OF THE PROPOSED REGULATIONS 10 

A. Overview of the Regulations 10 

B. Basic Prohibitions 11 

C. Proposed Specifications for Methanol 12 

D. Proposed Specifications for Ethanol 18 

E. Proposed Specifications for Natural Gas 23 

F. Proposed Specifications for Liquified Petroleum Gas 31 

G. Proposed Specifications for Hydrogen 33 

III. ENVIRONMENTAL AND ECONOMIC IMPACTS 35 

A. Emission Reductions 35 

B. Costs 35 

C. Small Business Impacts 36 

D. Other Environmental Impacts 36 

E. Global Warming and Ozone Depletion Impacts.. 37 

F. Public Safety Impacts 37 

REFERENCES 39 

APPENDICES 

Appendix A: Proposed Regulation Order-Proposed Amendments to 

Section 1960.l(k), 1956.8(b), and 1956.8(d), Title 13, 

California Code of Regulations, and Proposed Adoption of 

Sections 2290 - 2292.7, Title 13, California Code of 

Regulations 

Appendix B: Proposed Amendments to the California Exhaust Emission 

Standards and Test Procedures for 1988 and Subsequent Model 

Passenger Cars, Light-duty Trucks, and Medium-duty Vehicles 

Appendix C: 

Appendix D: 

Proposed Amendments to the California Exhaust Emission 

Standards and Test Procedures for 1985 and Subsequent Model 

Heavy-duty Diesel Engines and Vehicles 

Proposed Amendments to the California Exhaust Emission 

Standards and Test Procedures for 1987 and Subsequent Model 

Heavy-duty Otto-cycle Engines and Vehicles 
P.6 

Appendix E: ASTM Draft Compression Ignition Methanol Fuel Specification 

7/91-1 

Appendix F: ASTM D-2 Proposal P-232. Draft 8-9-91: Fuel Methanol (M-85) 

for Automotive Spark-ignition Engines 

Appendix G: Proposed M-85 Certification Fuel Specification from the Motor 

Vehicle Manufacturers Association of the United States, Inc. -

7/23/91 

Appendix H: ASTM D 4806-88 Standard Specification for Denatured Fuel 

Ethanol for Blending with Gasolines for Use as Automotive 

Spark-ignition Engine Fuel 

Appendix I: ASTM D 1835-89 Standard Specification for Liquified Petroleum 

Gases 
P.7 

I. 

INTRODUCTION 

A. INTRODUCTION 

This report presents the staff's proposed specifications for 

alternative motor vehicle fuels. The proposed specifications are part of 

the efforts of the Air Resources Board (ARB or Board) to promote the 

development of cleaner motor vehicles by adopting regulations that consider 

the combined effects of vehicle emission control technology and clean fuels. 

In September 1990, the ARB adopted regulations to phase-in more 

stringent exhaust emission standards for vehicles as well as make 

alternative clean fuels for vehicles available to motorists. These 

regulations are referred to as the low emission vehicle/clean fuels 

regulations. As part of this effort, the ARB staff identified the need to 

develop specifications for alternative motor vehicle fuels including 

methanol, ethanol, compressed natural gas (CNG), liquified petroleum gas 

(LPG), and hydrogen. For the purposes of this report, the staff is 

considering any motor vehicle fuel other than gasoline or diesel fuel as an 

alternative motor vehicle fuel. The specifications are necessary to ensure 

that motor vehicles designed to use alternative fuels will have fuels 

available that are of consistent quality and produce the expected emission 

benefits. The proposed regulatory action is in response to this identified 

need. 

In developing the proposed specifications, the staff held two 

workshops. The staff also considered the information presented by fuel 

producers and sellers, vehicle manufacturers, the Environmental Protection 

Agency (EPA), the American Society for Testing and Materials (ASTM), the 

California Renewable Fuels Council, the California Natural Gas Vehicle 

Coalition, and other interested parties. The staff has considered the 

effects of the specifications on emissions, any safety considerations, and 

the feasibility and cost of producing alternative fuels. 

The following section summarizes the staff's proposal. 

-1-
P.8 

B. SUMMARY 

1. What is tha staff proposing? 

The staff is proposing to establish new specifications for the 

commercial use of the alternative motor vehicle fuels listed in Table 1. 

These specifications are referred to as commercial fuel specifications. 

Commercial fuel specifications apply to fuel sold or supplied in California 

for use in motor vehicles beginning January 1, 1993. 

Fuel 

Methanol 

M-100 

M-85 

Ethanol 

E-100 

E-85 

Table 1 

Summary of Alternative Fuels for which New 

Commercial Specifications are Being Proposed 

Fuel Description 

Nominal 100 volume percent methanol 

Nominal 85 volume percent methanol; 

15 volume percent gasoline 

Nominal 100 volume percent ethanol 

Nominal 85 volume percent ethanol; 

15 volume percent gasoline 

Natural Gas 

Compressed Natural Gas 

Liquified Natural Gas 

Liquified Petroleum Gas 

Hydrogen 

Nominal 88 mole percent methane 

Nominal 88 mole percent methane 

Nominal 80 volume percent propane 

Nominal 98 mole percent hydrogen 

The staff 1s also proposing to amend existing fuel specifications for 

the certification of motor vehicles using methanol, natural gas, or 

liquified petroleum gas. These specifications are referred to as 

certification fuel specifications. Certification fuel specifications apply 

to fuel used by motor vehicle manufacturers when performing motor vehicle 

emission testing to demonstrate compliance with emission standards. The 

proposed specifications would be applicable beginning with the 1994 model 

year vehicles. 

-2-
P.9 

2. Why Hr>»s the ARB need to establish specifications for alternative 

fuels? 

In September 1990, the Board adopted the low emission vehicle/clean 

fuels regulations to reduce emissions of criteria pollutants and toxic air 

contaminants. These reductions will assist the state and local air 

pollution control districts in demonstrating progress toward the attainment 

of state and federal ambient air quality standards. The need for emission 

reductions, and the benefits of the low emission vehicle/clean fuels 

program, are discussed in the ARB Staff Report entitled "Proposed 

Regulations for Low Emission Vehicles and Clean Fuels," dated August 13, 

1990. Commercial fuel and certification fuel specifications are necessary 

to ensure that the benefits of this program will be achieved. 

The Division of Measurement Standards (DMS), within the California 

Department of Food and Agriculture, typically sets commercial fuel 

specifications for use in motor vehicles. These commercial fuel 

specifications are based on specifications approved by the American Society 

for Testing and Materials (ASTM). The only alternative fuel for which ASTM 

has issued a specification is liquified petroleum gas. Since none of the 

alternative fuels listed in this Staff Report have been used extensively in 

California, DMS has not yet adopted commercial fuel specifications. 

Therefore, commercial fuel specifications currently do not exist In 

California law for any of the alternative fuels identified in Table 1 above. 

The staff believes that there Is now a need to adopt commercial fuel 

specifications for alternative fuels to ensure that these meet consistent 

standards for quality. Fuels of inferior or inconsistent quality may cause 

the vehicles to operate improperly, resulting in adverse impacts on both 

public acceptance of low emission vehicles and emissions. 

We expect that a substantial percentage of low emission vehicles will 

be designed as fuel-flexible or dual-fuel vehicles operating on either an 

alternative fuel or gasoline. However, unless these vehicles use 

alternative fuels, the full emission benefits from these vehicles may not be 

achieved. Therefore, the staff believes that it is necessary to assure the 

quality of commercial alternative fuels so that operators of these vehicles 

will be encouraged to purchase the alternative fuel. 

The staff also proposes amendments which would revise the alternative fuel 

specifications currently established for motor vehicle emission 

certification testing. These certification specifications cover M-100 fuel 

methanol, M-85 fuel methanol, compressed and liquified natural gas, and 

liquified petroleum gas. The certification specifications are being revised 

so that they will be consistent with the commercial specifications. 

Certification fuel specifications are not being proposed at this time for E100 fuel ethanol, E-85 fuel ethanol and hydrogen, because the ARB does not 

currently have emission test procedures for these fuels. The certification 

fuel specifications are normally Included in the emission test procedure 

documents. 

-3-
P.10 

3. What in the staff proposing for methanol? 

The staff is proposing commercial and certification specifications for 

two types of methanol fuels: M-100 and M-85. The M-100 designation refers 

to fuel that contains nominally 100 percent methanol. The M-85 designation 

refers to fuel that Is nominally 85 percent methanol and 15 percent 

gasoline. 

The proposed M-100 commercial fuel specifications are based on the 

proposed ASTM specification for methanol used in compression ignition 

engines. The staff is proposing that the minimum methanol content be 

96 volume percent. The staff is also proposing standards for distillation 

range, other alcohols and ethers, hydrocarbons, and the visibility of any 

flames (referred to as flame luminosity). Additional standards are included 

to ensure that the fuel is free of contaminants and suitable for use as a 

motor vehicle fuel. The M-100 fuel is likely to be used initially as a 

replacement for diesel fuel 1n heavy-duty vehicles, and eventually as a fuel 

for light-duty vehicles. The proposed specifications for M-100 fuel are 

presented in proposed section 2292.1 of Title 13 (Appendix A) . 

The proposed commercial specifications for M-85 are based on the fuel 

specifications that have been approved as the interim ASTM specifications. 

The staff 1s proposing that the M-85 fuel contain a minimum methanol content 

of 85 volume percent and an unleaded gasoline content of about 15 volume 

percent. Standards are also proposed for higher alcohols, vapor pressure, 

and flame luminosity. Additional standards are Included to ensure that the 

fuel is free of contaminants and suitable for use as a motor vehicle fuel. 

The M-85 fuel 1s currently used in light-duty vehicles with spark-ignition 

(Otto-cycle) engines. The proposed commercial specifications for M-85 fuel 

are presented in proposed section 2292.2 of Title 13 (Appendix A) . 

The staff's proposed specifications for M-100 and M-85 certification 

fuels are identical to the proposed commercial specifications for M-100 fuel 

and M-85 fuel, respectively. However, the certification test procedures 

allow motor vehicle manufacturers to use gasoline that is used to certify 

gasoline-powered motor vehicles as the blending gasoline to meet the 

15 percent requirement for M-85 fuel. This option is identified in the 

three test procedures referenced by Title 13, CCR, which set forth the 

vehicle certification procedures for light and medium-duty vehicles 

(Appendix B), heavy-duty diesel engines and vehicles (Appendix C), and 

heavy-duty otto-cycle engines and vehicles (Appendix D) . 

4. What is tha staff proposing for ethanol? 

The staff is proposing commercial specifications for two types of 

ethanol fuels: E-100 fuel and E-85 fuel. The E-100 designation refers to 

fuel that contains nominally 100 percent ethanol. The E-85 designation 

refers to fuel that 1s nominally 85 volume percent ethanol and 15 volume 

percent unleaded gasoline. 

-4-
-EJJ-, 

There has not been as much work done in the area of fuel specifications 

for ethanol fuels as there has been with the methanol fuels. Therefore, the 

staff based the proposed commercial fuel specifications on the M-100 and M85 fuel specifications. In addition, the staff has consulted with ASTM 

members, the California Renewable Fuels Council, and other interested 

parties, incorporating their comments as appropriate. 

The proposed commercial specifications for E-100 fuel are presented in 

proposed section 2292.3 of Title 13 (Appendix A) . The proposed commercial 

specifications for E-85 fuel are presented in proposed section 2292.4 of 

Title 13 (Appendix A) . 

The proposed E-100 and E-85 fuel specifications require the use of 

denatured ethanol. This is actually a federally mandated requirement to 

denature ethanol that will not be used in alcoholic beverages. The 

denaturant gives the alcohol an unpleasant odor and taste and/or increases 

the toxicity level substantially over the toxicity of the base ethanol. The 

denatured fuel ethanol specification is based in large part on the ASTM D 

4806-88 specification. The denatured fuel ethanol specification has been 

incorporated into the E-100 and E-85 fuel specifications in sections 2292.3 

and 2292.4 of Title 13, CCR, rather than being Included as a separate 

specification. 

The staff 1s not proposing specifications for E-100 and E-85 

certification fuels at this time since no corresponding vehicle 

certification procedures exist. 

5. What is tha staff proposing for natural gas? 

The staff Is proposing commercial and certification specifications for 

two types of natural gas: compressed natural gas (CNG) and liquified 

natural gas (LNG). The staff expects differences in fuel composition 

between these two fuels to be small. Therefore, the staff is proposing that 

CNG and LNG meet the same specifications for commercial fuel and 

certification fuel. 

The proposed CNG and LNG commercial specifications were developed in 

consultation with the California Natural Gas Vehicle Coalition (which 

includes Pacific Gas and Electric, Southern California Gas, and San Diego 

Gas and Electric), and other interested parties. The specifications include 

standards for methane content at a minimum of 88 mole percent and ethane 

content at a maximum of six mole percent. Additional standards are included 

to ensure that the fuel is free of contaminants and suitable for use as a 

motor vehicle fuel. 

The proposed methane content of 88 mole percent has been set to reflect 

survey data on gas supply and emission results. The survey data demonstrate 

that nearly all of the natural gas utilities in the United States could meet 

the 88 mole percent specification. The available emission results show 

-5-
P.12 

negligible differences 1n emissions In the range of these specifications. 

The proposed CNG and LNG specifications are set forth in proposed 

section 2292.5 of Title 13, CCR (Appendix A) . 

The staff is proposing to amend the existing certification 

specification to be Identical to the proposed commercial fuel specification. 

6. What Is tha <t»ff proposing for liquified petroleum oas? 

The staff is proposing that the commercial specifications for liquified 

petroleum gas contain standards for propane at a minimum of 80 volume 

percent and propene at a maximum of 10 volume percent. Additional standards 

are included to ensure that the fuel is free of contaminants and suitable 

for use as a motor vehicle fuel. 

The commercial fuel specifications are the same as the existing ARB 

certification specifications, with one exception. To avoid eliminating a 

major portion of refinery-produced LPG>from the market, the staff is 

proposing to raise the propene standard from five volume percent to 10 

volume percent. High propene content fuel may increase the reactivity of 

vehicle exhaust and refueling emissions, lower the octane rating, cause 

other vehicle durability and performance problems, and possibly indicate the 

presence of other undesirable impurities. However, the staff believes that 

the ten volume percent propene limit is not high enough to cause these 

problems and has determined that this change will not result in any adverse 

impacts on emissions or vehicle driveability. The proposed specifications 

for liquified petroleum gas are presented in proposed section 2292.6 of 

Title 13, CCR (Appendix A) . 

The staff 1s proposing to amend the existing certification fuel 

specifications to be identical to the proposed commercial fuel 

specifications. 

7. What Is tha staff proposing for hydrogen? 

The staff 1s proposing that the commercial fuel specification for 

hydrogen be set at 98 mole percent hydrogen. Additional standards are 

included to ensure that the fuel is free of contaminants and suitable for 

use as a motor vehicle fuel. The proposed hydrogen specifications are 

included in the proposed section 2292.7 of Title 13, CCR (Appendix A) . 

The staff is not proposing specifications for hydrogen certification 

fuel at this time since no corresponding vehicle certification procedures 

exist. 

8. Why 1s tha staff proposing that the commercial and certification 

specifications ba tha same? 

The staff believes commercial and certification specifications need to 

be the same to ensure that certified motor vehicles will perform the same 

-6-
P.13 

during normal use as they did during certification testing; consistent 

performance is necessary to ensure that the expected benefits are achieved. 

The staff believes that the proposed specifications are sufficiently 

stringent to meet motor vehicle manufacturers needs for a certification fuel 

that provides consistent testing results, and the ARB's needs for a 

commercial fuel that can be made readily available to motorists. 

9. When must fuel producers comply with the proposed specifications? 

The staff is proposing that the alternative fuels must comply with the 

listed commercial specifications by January 1, 1993. This date will provide 

fuel producers sufficient lead time to prepare for the distribution of fuels 

which can comply with the specifications. 

The staff is proposing that the certification fuel specifications apply 

beginning with the 1994 model year. However, a vehicle manufacturer that 

wishes to certify a 1992 model year alternative fuel vehicle using the 

proposed specifications may do so as an option. This date will provide 

motor vehicle manufacturers with sufficient lead time to design future motor 

vehicles to use the specified alternative fuel. 

10. How did tha staff address safety issues? 

The staff has determined that the relative safety of the alternative 

fuels is important in promoting the use of the fuels. Vapor space 

flammability and flame visibility associated with the methanol and ethanol 

fuels have emerged as two safety issues. 

Because of the lower vapor pressure of the alcohol fuels, higher vapor 

pressure components must be present. A higher vapor pressure is necessary 

so that ignition 1s not possible at ambient temperatures. If a higher vapor 

pressure cannot be used, some other mechanism must be used to avoid 

ignition. The unleaded gasoline that will be added to both the E-85 and M85 fuels will increase the vapor pressure of the fuel and decrease vapor 

space flammability. The proposed specifications will ensure that enough 

gasoline or other vapor pressure increasing components, or both, are present 

in the M-85 and E-85 fuels to serve these purposes. In addition, the vapor 

space flammability of the M-85 and E-85 fuels will be minimized by 

incorporating a minimum Reid vapor pressure limit of the final blend. 

Vehicle manufacturers and retrofitters using M-100 and E-100 fuels will 

have to address the problem of vapor space flammability. The staff believes 

these problems can be solved using improved fuel storage system technology. 

This issue is not directly addressed by these regulations, but instead falls 

under the purview of agencies that certify vehicle safety. 

Methanol burns without a visible flame. As a result, a safety hazard 

is created if fires are not immediately noticed. Unleaded gasoline added to 

M-85 fuel will Increase flame visibility (luminosity). M-100 will not be 

able to rely on gasoline for flame luminosity. Therefore, fuel producers 

-7-
P.14 

and vehicle manufacturers are in the process of developing additives that 

could be added in small quantities to enhance flame luminosity. The 

proposed specifications require compliance with the flame luminosity by 

January 1, 1994. The M-100 California fleet currently consists only of 

heavy-duty vehicles, which are refueled by experienced drivers, or fleet 

maintenance personnel. This limits the threat to safety posed by M-100 fuel 

fires. The staff believes that the additional time is needed to develop 

acceptable flame luminosity additives. 

Ethanol fuels have flames that are sufficiently visible so that 

visibility enhancing additives are not required. 

ll. What are, the costs of the proposal? 

Implementation of the proposed regulations could impact the vehicle and 

fuel industries, as well as consumers. The overall costs of using 

alternatively-fueled vehicles In place of gasoline-fueled vehicles was 

covered in the Staff Report for the low-emission vehicle/clean fuels 

regulations. The staff expects no significant impact on the cost of 

alternative fuels to result from the implementation of the proposed 

specifications. 

The staff has determined that small businesses should not be adversely 

affected by the specifications since no increase in the cost of producing 

the fuels is anticipated. 

C. RECOMMENDATION 

The staff recommends that the Board amend or adopt as appropriate the 

following sections of Title 13, California Code of Regulations, and amend 

the specified test procedures which are incorporated by reference into 

Title 13. The proposed regulation order is included as Appendices A - D. 

o Section 1960.1. - Exhaust Emission Standards and Test Procedures -

1981 and Subsequent Model Passenger Cars, Light-Duty Trucks, and 

Medium-Duty Vehicles. 

o Section 1956.8 - Exhaust Emission Standards and Test Procedures -

1985 and Subsequent Model Heavy -Duty Engines and Vehicles. 

o Section 2290 - Definitions 

o Section 2291 - Basic Prohibitions 

o Section 2292.1 - Specifications for M-100 Fuel Methanol 

o Section 2292.2 - Specifications for M-85 Fuel Methanol 

o Section 2292.3 - Specifications for E-100 Fuel Ethanol 

o Section 2292.4 - Specifications for E-85 Fuel Ethanol 

-8-
P.15 

o Section 2292.5 - Specifications for Compressed and Liquified 

Natural Gas 

o Section 2292.6 - Specifications for Liquified Petroleum Gas 

o Section 2292.7 - Specifications for Hydrogen 

o California Exhaust Emission Standards and Test Procedures for 1988 

and Subsequent Model Passenger Cars, Light-duty Trucks, and Mediumduty Vehicles 

o California Exhaust Emission Standards and Test Procedures for 1985 

and Subsequent Model Heavy-duty Diesel Engines and Vehicles 

o California Exhaust Emission Standards and Test Procedures for 1987 

and Subsequent Model Heavy-duty Otto-cycle Engines and Vehicles 

-9-
P.16 

II. 

DISCUSSION OF THE PROPDSFD REGULATIONS 

A. OVERVIEW OF THE REGULATIONS 

The staff is proposing new regulations which would establish 

specifications for certain alternative fuels sold or supplied for use in 

motor vehicles (commercial fuel specifications). The regulations for 

commercial fuel specifications would be applicable January 1, 1993. An 

alternative motor vehicle fuel is defined as any fuel which is commonly or 

commercially known or sold as one of the following: M-100 fuel methanol, M85 fuel methanol, E-100 fuel ethanol, E-85 fuel ethanol, compressed and 

liquified natural gas, liquified petroleum gas, or hydrogen. 

These regulations would be Included in a new proposed Article 3, 

Subchapter 5, Title 13, California Code of Regulations, as sections 2290, 

2291, and 2292.1 through 2292.7. 

The staff 1s also proposing to amend the alternative fuel 

specifications currently established for motor vehicle emission 

certification testing (certification fuel specifications). These 

specifications cover M-100 fuel methanol, M-85 fuel methanol, compressed and 

liquified natural gas, and liquified petroleum gas. The staff is proposing 

that the certification fuel specifications be identical to the proposed 

commercial fuel specifications. The amended specifications would apply 

starting with 1994 model year vehicles. 

These changes regarding certification fuel specifications would be 

effected by amendments to sections 1960.l(k), 1956.8(b), and 1956.8(d) in 

Article 1, Chapter 1 of Title 13, California Code of Regulations, and the 

following certification test procedures incorporated by reference in these 

sections: 

o California Exhaust Emission Standards and Test Procedures for 1988 

and Subsequent Model Passenger Cars, Light-duty Trucks, and Mediumduty Vehicles; 

-10-
P.17 

o California Exhaust Emission Standards and Test Procedures for 1985 

and Subsequent Model Heavy-duty Diesel Engines and Vehicles; and 

o California Exhaust Emission Standards and Test Procedures for 1987 

and Subsequent Model Heavy-duty Otto-cycle Engines and Vehicles. 

The changes to the above three incorporated procedures are related to 

the alternative fuel specifications used in the certification of motor 

vehicles for sale in California, and to alternative fuel specifications for 

mileage accumulation vehicles used by vehicle manufacturers to produce 

durability data. 

The proposed regulation order is included as Appendix A for the 

proposed additions and changes to Title 13, and Appendices B, C, and D for 

the proposed changes to the certification procedures. 

B. BASIC PROHIBITIONS 

The proposed amendments to Title 13, California Code of Regulations, 

would prohibit the sale, offer for sale or supply of an alternative fuel 

intended for use in motor vehicles in California unless it conforms with the 

applicable commercial specifications. Most of the fuel characterized in 

this report as "alternative fuel" is currently used in applications other 

than motor vehicles. A quantity of alternative fuel clearly not Intended 

for use in motor vehicles would not be subject to the prohibitions. In 

order to help assure that fuels likely to be made available to motorists 

will meet the specifications, the regulations would specifically identify 

three instances in which alternative fuels will be deemed to be Intended for 

use in motor vehicles. These Include all instances when the alternative 

fuel is stored at a facility which is equipped and used to dispense that 

type of fuel to motor vehicles, and when the fuel is delivered or intended 

for delivery to such a facility. In these two Instances there is a 

substantial likelihood that the fuel will be made available for use in motor 

vehicles, and it is therefore appropriate that the seller comply with the 

proposed specifications. The third instance involves the sale or supply of 

alternative fuel to a person engaged in the distribution of motor vehicle 

fuels to motor vehicle fueling facilities. However, in this situation the 

person selling or supplying the fuel would not be subject to the 

requirements upon a demonstration that the person has taken reasonably 

prudent precautions to assure that he fuel will not be used a a motor 

vehicle fuel in California. 

To help assure the applicability of the Health and Safety Code Section 

43016 "per vehicle" penalties, the regulations would provide that each 

retail sale of alternative fuel for use In a motor vehicle shall also be 

deemed a sale or supply by any person who previously sold or supplied the 

alternative fuel 1n violation of the standards. This approach is similar to 

language in several other ARB motor vehicle fuels regulations, Including 

Title 13, California Code of Regulations, section 2261.5(a)(5). 

-11-
P.18 

Beginning with the 1994 model year vehicles, motor vehicle 

manufacturers must use fuel meeting the proposed certification 

specifications when conducting tests to demonstrate that motor vehicles 

comply with California emission standards. 

C. PROPOSED SPECIFICATIONS FOR METHANOL 

For methanol, the staff 1s proposing specifications for two types of 

fuels: M-100 fuel and M-85 fuel. The staff uses the designation M-100 to 

refer to fuel methanol that contains nominally 100 volume percent methanol. 

The M-85 designation refers to fuel that is nominally 85 volume percent 

methanol and 15 percent unleaded gasoline. 

1. M-lOO Fual Specifications 

The M-100 fuel methanol specifications presented in Table 2, and 

included in the proposed Section 2292.1 of Title 13 (Appendix A) , are 

derived from the draft proposed ASTM specification for methanol fuel used in 

compression ignition engines. The ASTM draft proposed specifications are 

included as Appendix E. 

Currently, M-100 fuel 1s used mostly in heavy-duty applications in 

compression ignition, or converted compression Ignition engines, hence the 

specification designation by ASTM for compression ignition engines. 

FEV of America and others are developing light-duty engines which utilize 

M-100 as a fuel. The application being developed by FEV is also a converted 

compression ignition engine. The M-100 fuel specifications are intended to 

have enough flexibility to apply to heavy and light-duty compression 

ignition, converted compression Ignition, and spark ignition (Otto-cycle) 

engines. 

The 96 volume percent methanol specification in the ARB proposed 

specifications for M-100 fuel allows less pure, less expensive methanol to 

be used in the future. The impurities that may come from the fuel 

manufacturer include higher alcohols and ethers. The impurities that may 

come from the distribution system may include petroleum-related hydrocarbons 

and water. In addition, the ARB has set an acidity specification of 0.003 

mass percent, instead of the ASTM listed specification of 0.03 mass percent. 

The acidity specification was set in order to be consistent with the M-85 

fuel specification, and ensure a minimum of corrosive effects from the fuel. 

A major concern for compression ignition engines is ignition 

improvement. Methods for ignition improvement include the addition of 

chemical additives to Improve ignition, or the conversion of the engine from 

compression ignition to hot surface ignition. A flame luminosity 

requirement has been added to the specification for safety purposes, which 

must be met by January 1, 1994. This requirement will also mean the 

introduction of luminosity-enhancing additives into the fuel in small 

quantities. 

-12-
P.19 

The M-100 specification does not directly address the issue of vapor 

space flammability. The staff expects that vehicle manufacturers and 

retrofitters will design fuel storage systems to prevent vapor ignition in 

the fuel tank. 

The rationale for the remaining ASTM M-100 specifications is contained 

in the appendix to the ASTM Draft Compression Ignition Methanol Fuel 

Specification 7/91-1 Included as Appendix E of this staff report. 

•13-
P.20 

Table 2 

Proposed Commercial and Certification Specifications 

for M-100 Fuel Methanol 

Specification 

Methanol 

Distillation 

Other alcohols and 

ethers 

Hydrocarbons, 

gasoline or 

diesel fuel 

derived 

96 vol. t (min.) 

4.0°C (range) 

2 mass t (max.) 

2 mass 1 (max.) 

Luminosity 

Specific gravity 0.792 ± 0A002 

Test Method 

As determined by the 

distillation range below 

ASTM D 1078-86. At 95X by 

volume distilled. Must 

include 64.6 + 0.1 C 

ASTM D 4815-89 

ASTM D 4815-89, and then 

subtract concentration of 

alcohols, ethers and 

water from 100 to obtain 

percent hydrocarbons 

Shall produce a luminous 

flame throughout the 

entire burn duration. 

Applicable 1/1/94. 

ASTM D 891-89 

Acidity as acetic 

a d d 

Total chlorine as 

chloride 

Lead 

Phosphorus 

Sulfur 

Gum, heptane washed 

Total particulates 

Water 

Appearance 

a 20/20uC 

0.003 mass t (max.) ASTM D 1613-85 

0.0002 mass t (max. 

2 mg/1 (max.) 

0.2 mg/l (max.) 

0.01 mass t (max.) 

5 mg/100 ml (max.) 

5 mg/1 (max.) 

0.5 mass t (max.) 

Free of turbidity, 

suspended matter 

and sediment 

)ASTM 0 2988-86 

ASTM D 

ASTM D 

ASTM D 

ASTM D 

ASTM D 

ASTM E 

Visual 

at 2! 

3237-90 

3231-89 

3120-87 

381-86 

2276-89 

203-75 

ly determined 

>°C by Proc. A 

of ASTM D 4176-86 

-14-
P.21 

2. H-P* *"*• Specifications 

The proposed specifications for M-85 fuel are included in section 

2292.2 of Title 13 (Appendix A) and are presented in Table 3. These fuel 

specifications are based on the ASTM M-85 fuel specifications for automotive 

spark-ignition engines that have been approved as the interim ASTM 

specifications (Appendix F), and California Energy Commission specifications 

which closely resemble the ASTM specifications. The ASTM specifications are 

classified as interim if there has not been adequate development and 

verification of the specifications and associated test procedures to satisfy 

all parties in the ASTM review process. This process allows the 

specifications to be put in place, and additional work to be performed over 

time to verify or correct all aspects of the specifications. 

The primary difference between M-100 fuel and M-85 fuel is in the 

blending of approximately 15 volume percent gasoline into the M-85 fuel. 

The gasoline Improves cold-starting to enhance driveability by raising the 

vapor pressure, as represented by the Reid vapor pressure (RVP). The upper 

RVP limit has been set to be equivalent to the gasoline specification and 

addresses evaporative emissions. A minimum RVP limit has been added 

primarily to address Industry concerns about decreased driveability at low 

RVP. The gasoline blended into the M-85 fuel also has safety advantages by 

increasing flame luminosity and lowering the vapor space flammability limit 

in the fuel tank. 

The ARB's proposed specifications differ from the ASTM specifications 

by requiring that the blending hydrocarbon be commercial unleaded gasoline 

instead of simply hydrocarbons. Using commercial unleaded gasoline will 

help to ensure fuel consistency. The unleaded gasoline requirement also 

helps to ensure that ARB enforcement officials will not be faced with 

situations where large stocks of off-specification unleaded gasoline are 

claimed by producers or importers to be blending stock for alcohol fuels and 

thus delaying enforcement action. The ARB's proposed specifications also 

differ from the ASTM specifications by requiring a heptane washed gum 

specification instead of a nonvolatile matter specification. The staff is 

proposing the heptane washed gum specification to minimize potential 

interferences from gasoline additives. 

The Motor Vehicle Manufacturers Association has proposed certification 

specifications for M-85 fuel (Appendix G) which are similar to the 

certification and commercial specifications currently proposed by the ARB. 

The major difference 1s that the specifications proposed by the Motor 

Vehicle Manufacturers Association provide for the use of chemical grade 

methanol. Due to the higher cost of chemical grade methanol, separate 

commercial and certification fuels would be necessary. The staff believes 

that the proposed M-85 fuel specifications will produce a certification fuel 

of adequately consistent properties. Therefore, the staff did not include 

the requirement for the use of chemical grade methanol in the certification 

fuel specifications. 

15-
P.22 

One of the motor vehicle manufacturers has requested a conductivity 

specification of 3 microSiemens/cm and a tightening of the chloride 

specification from 0.0002 mass percent to 0.0001 mass percent to reduce 

corrosion of engine components. In addition, they have requested a 

tightening of the total particulates specification from 5 milligrams/liter 

to 0.2 milligram/liter, for the purposes of reducing filter plugging. The 

staff is not proposing to adopt these recommendations at this time because 

the staff has not had sufficient time to review the recommendations. The 

staff will reconsider the need to incorporate these specifications after 

further analysis. 

There are no differences between the proposed commercial and 

certification specifications for M-85 fuel. However, the certification test 

procedures allow motor vehicle manufacturers the option of using 

certification gasoline as the blending gasoline for M-85 certification fuel. 

This option is contained in the three certification test procedures 

referenced by Title 13, CCR, which set forth the vehicle certification 

procedures for light and medium-duty vehicles (Appendix B) , heavy-duty 

diesel engines and vehicles (Appendix C) , and heavy-duty otto-cycle engines 

and vehicles (Appendix D) . 

-16-
Table 3 

Proposed Commercial and Certification Specifications 

for M-85 Fuel Methanol 

constituent Specification 

Methanol 

Gasoline, 

Unleaded, 1/ 

Higher alcohols 

(C2 - C8) 

Hydrocarbons • 

aliphatic ethers 

Vapor pressure, dry 

Luminosity 

Acidity as acetic 

acid 

Total chlorine 

as chlorides 

Lead 

Phosphorus 

Sulfur 

Gum, heptane washed 

Total particulates 

Water 

Appearance 

85 vol. % (min.) 

14.5 • .5 vol. * 

2 vol. % (max.) 

13-15 vol. i 

Final blend must meet 

vapor pressure 

requirements for 

commercial unleaded 

gasoline of the area 

in which it will be 

sold, with a 

minimum RVP of 6.5 

psi 

Test Method 

Annex Al to the ASTM D-2 

Proposal P-232 

Must meet local specifications 

for commercial unleaded 

gasoline, except for RVP 

ASTM D 4815-89 

ASTM D 4815-89, and then 

subtract concentration of 

alcohols, ethers and water 

from 100 to obtain percent 

hydrocarbons 

Methods contained in Title 13, 

Section 2262, CCR, must be 

used. ASTM D 4953-90 is an 

alternative method, however, 

in case of dispute about the 

vapor pressure, the value 

determined by the methods 

contained in section 2262 

shall prevail over the value 

calculated by ASTM D 4953-90, 

including its precision 

statement 

Shall produce a luminous flame 

throughout the entire burn 

duration 

0.003 mass t (max.) 

0.0002 mass t (max.) 

0.002 g/1 (max.) 

0.0002 g/1 (max.) 

0.015 mass t (max.) 

5 mg/100 ml (max.) 

5 mg/l (max.) 

0.5 mass t (max.) 

Free of turbidity, 

suspended matter 

and sediment 

ASTM D 1613-85 

ASTM D 3120-87 modified for 

the det. of organic 

chlorides, and 

ASTM D 2988-86 

ASTM D 3237-90 

ASTM 0 3231-89 

ASTM D 3120-87 

ASTM D 381-86 

ASTM D 2276-89 

ASTM E 203-75 

Visually determined at 

25°C by Proc. A of 

ASTM D 4176-86 

a./ Adjustment of RVP must be performed using common blending components 

from the gasoline stream. 

-17-
P.24 

D. PROPOSED SPECIFICATIONS FOR ETHANOL 

1. Denatured Ethanol Specification 

The proposed E-100 and E-85 fuel specifications require the use of 

denatured ethanol. This 1s actually a federally mandated requirement to 

denature ethanol that will not be used in alcoholic beverages. The 

denaturant gives the alcohol an unpleasant odor and taste and/or increases 

the toxicity level substantially over the base ethanol toxicity. 

There are several types of denatured ethanol used 1n industry, which 

differ mostly in the types and amounts of denaturants used. Gasoline, 

methanol, and various hydrocarbons are often used in amounts that are 

typically from two to five parts denaturant per hundred parts ethanol by 

volume. Use of different types of denatured ethanol might significantly 

affect the driveab1lity/durab111ty of the vehicle, and possibly have adverse 

emission impacts. 

To minimize possible adverse impacts from the use of denaturants, the 

staff is proposing to include the ASTM D 4806-88 specification for denatured 

alcohol in both the E-100 and E-85 fuel specifications. The ASTM 

specification is entitled "Standard Specification for Denatured Fuel Ethanol 

for Blending with Gasolines for Use as Automotive Spark-ignition Engine 

Fuel," and is included as Appendix H. 

The staff 1s, however, proposing the following modifications to the 

ASTM method: 

o limiting the type of denaturant to unleaded gasoline; 

o narrowing the allowable range of added denaturant to four to five 

parts gasoline to 100 parts ethanol by volume; 

o tightening the chloride ion content specification from 0.004 mass 

percent to 0.0004 mass percent; 

o adjusting the copper content from 0.03 milligrams per liter to 0.07 

milligrams per liter. 

The limitation on the type and amount of denaturant used contributes to 

consistency in the final blend and limits possible problems associated with 

introducing denaturants with markedly different properties into the fuel. 

The tighter limit on the chloride ion content will minimize corrosion 

problems. The copper content had been initially set incorrectly at 

0.03 milligrams per liter. 

The staff has Incorporated the denatured fuel ethanol specifications 

into the E-100 and E-85 fuel specifications. 

•18-
P.25 

2. F-tnn Fuel Specifications 

E-100 fuel has not been used extensively as a fuel in the United 

States. Brazil has a large amount of experience with E-100 fuels. However, 

the staff has been unable to acquire useable data on standard specifications 

for the ethanol fuel. Therefore, the proposed E-100 commercial fuel 

specifications shown in Table 4, and included in Section 2292.3 of Title 13 

(Appendix A) , are based on the proposed ARB M-100 fuel specifications and 

the ASTM D 4806-88 specification for denatured alcohol. The staff has also 

relied on discussions with representatives of the ethanol industry, 

automobile manufacturers, and other Interested parties. 

The staff 1s proposing a minimum ethanol specification of 92 volume 

percent. This specification allows for the denaturants and for less pure, 

less expensive fuel ethanol in the future, as well as accommodating some 

contamination resulting from distribution of the fuel. The impurities that 

may come from the fuel manufacturer include other alcohols and water. The 

impurities that may come from the distribution system may include petroleumrelated hydrocarbons and water. 

The proposed specifications also include standards for sulfur, 

phosphorus, lead, and appearance that have been directly carried over from 

the M-100 specifications. The water, chloride ion content, and acidity 

specifications were derived from the ASTM D 4806-88 specification. The 

rationale for the remaining E-100 specifications is derived from the 

appendix to the ASTM Draft M-100 specifications 7/91-1, Included as Appendix 

E of this staff report, and from the ASTM D 4806-88 specification, included 

as Appendix H. 

E-100 fuels share some of the problems of M-100 fuels related to cold 

starting (when used In Otto-cycle engines) and vapor space flammability. 

These problems are not addressed by these specifications. The staff 

believes that any vapor space flammability problems can be solved by 

fuel storage system technology. Flame luminosity, which is a major concern 

for methanol fuels, 1s not considered a major problem for ethanol fuels. 

Modern techniques allow alcohol to be produced commonly with .1 percent 

water or less. Ethanol that has low water content is referred to as 

anhydrons ethanol. Alcohol with less than 5 percent water is commonly 

referred to as anhydrous ethanol. For ethanol fuels, substantial cost 

benefits may be possible by the use of ethanol containing water (referred to 

as hydrous ethanol) instead of anhydrous ethanol. Although there has been 

some promising research directed towards the use of hydrous ethanol, most of 

the ethanol fuel development work in the United States has concerned 

anhydrous fuel ethanol. Therefore, the staff is only proposing 

specifications for anhydrous ethanol at this time. 

-19-
P.26 

Table 4 

Proposed Commercial Specifications for E-100 Fuel Ethanol 

Snecifleation 

Ethanol 

Denatured fuel 

ethanol 

Other alcohols and 

ethers 

Hydrocarbons, 

gasoline or diesel 

fuel derived 

Acidity as acetic ad d 

Total chlorine 

as chloride 

Copper 

Lead 

Phosphorus 

Sulfur 

Gum, heptane washed 

Total particulates 

Water content 

Appearance 

Value 

92 vol. % (min.) 

98 vol. % (min.) 

2 mass t (max.) 

5 mass % (max.) 

0.007 mass t (max.) 

0.0004 mass I (max.) 

0.07 mg/1 (max.) 

2 mg/1 (max.) 

0.2 mg/1 (max.) 

0.01 mass 1 (max.) 

5 mg/100 ml (max.) 

5 mg/1 (max.) 

1.25 mass t (max.) 

Free of turbidity, 

suspended matter 

and sediment 

Test Method 

ASTM D 3545-90 

a/ 

ASTM D 4815-89 

ASTM D 4815-89, and 

then subtract 

concentration of 

alcohols, ethers 

and water from 100 

to obtain percent 

hydrocarbons 

ASTM D 1613-85 

ASTM D 3120-87 

modified for the 

det. of organic 

chlorides, and 

ASTM D 2988-86 

ASTM D 1688-90 as 

modified in ASTM D 

4806-88 

ASTM D 3237-90 

ASTM 0 3231-89 

ASTM D 3120-87 

ASTM 0 381-86 

ASTM D 2276-89 

ASTM E 203-75 

Visually determined 

at 25°C by Proc. A 

of ASTM D 4176-86 

a./ Must meet the ASTM D 4806-88 specification for denatured fuel ethanol, 

except the denaturant must be representative of unleaded gasoline that 

is commercially available blended at a maximum of 4 to 5 parts gasoline 

to 100 parts by volume fuel ethanol (including water) to form the 

denatured fuel ethanol. The final blend specifications for E-100 fuel 

take precedence over the ASTM D 4806-88 specification. 

.20-
P.27 

3. f-flff Fuel Specifications 

The E-85 fuel has not been used extensively as a fuel in the United 

States. Therefore, the staff has developed the specifications using the 

proposed specifications for M-85 fuel and discussions with members of 

various ASTM committees, the California Renewable Fuels Council, and other 

interested parties. 

The proposed E-85 fuel specifications are listed in Table 5, and 

included 1n Section 2292.4 of Title 13 (Appendix A) . The proposed 

81 percent ethanol requirement would be a rigid specification, while the 

gasoline fraction would be based upon meeting the local commercially 

available unleaded gasoline specifications, with the exception of the RVP 

specifications. The overall blend would be required to meet the vapor 

pressure requirements of gasoline in the area in which it is to be sold. 

Because of the problem of butane loss due to weathering, butane is not 

required to be used as the vapor pressure adjusting component. A lower 

limit on RVP has been added to avoid potential driveability problems and to 

minimize problems of vapor space flammability: 

The proposed E-85 fuel specifications include standards for gum, 

sulfur, phosphorus, lead, and appearance that have been directly carried 

over from the M-85 fuel specifications. The water, chlorine as chloride, 

and acidity specifications were derived from the ASTM D 4806-88 (Appendix H) 

specification. The RVP requirement for E-85 fuel should be the same as that 

for M-85 fuel and gasoline. 

The staff Is not proposing specifications for E-100 or E-85 

certification fuels at this time since no corresponding vehicle 

certification procedures exist. 

-21-
Table 5 

Proposed Commercial Specifications for E-85 Fuel Ethanol 

Specification 

Ethanol 

Denatured fuel 

ethanol 

Other alcohols 

Gasoline, unleaded 

Hydrocarbons • 

aliphatic ethers 

Value 

81 vol. t (min.) 

85 vol. i (min.) 

2 vol. 1 (max.) 

14.5 • .5 vol. t 

13-19 vol. t 

Test Method 

ASTM D 3545-90 

A/ 

ASTM D 4815-89 

V 

ASTM D 4815-89 

Vapor pressure, dry 

Acidity 

Total chlorine 

as chloride 

Copper 

Lead 

Phosphorus 

Sulfur 

Gum, heptane washed 

Total Particulates 

Water 

Appearance 

Final blend must meet 

vapor pressure 

requirements for 

commercial unleaded 

gasoline of the area 

1n which it will be 

sold, with a minimum 

RVP of 6.5 psi 

0.007 mass t (max.) 

0.0004 mass 1 (max.) 

0.07 mg/1 (max.) 

0.002 g/1 (max.) 

0.0002 g/1 (max.) 

0.015 mass I (max.) 

5 mg/100 ml (max.) 

5 mg/l (max.) 

1.25 mass I (max.) 

Free of turbidity, 

suspended matter 

and sediment 

subtract concentration of 

alcohols, ethers and water 

from 100 to obtain percent 

hydrocarbons. The denaturant 

is included in this percentage 

Methods contained in Title 13, 

Section 2262, CCR, must be 

used. ASTM 0 4953-90 1s an 

alternative method. However, 

in case of dispute about the 

vapor pressure, the value 

determined by the methods 

contained 1n Title 13, 

section 2262 shall prevail 

over the value calculated by 

ASTM D 4953-90, Including its 

precision statement 

ASTM D 1613-85 

ASTM D 3120-87 modified 

the det. of organic 

chlorides, and 

ASTM D 2988-86 

for 

ASTM D 1688-90 as modified in 

ASTM D 4806-88 

ASTM D 3237-90 

ASTM D 3231-89 

ASTM D 3120-87 

ASTM D 381-86 

ASTM D 2276-89 

ASTM E 203-75 

Visually determined at 

25 C by proc. A of 

ASTM D 4176-86 

-22-
P.29 

i/ Must meet the ASTM D 4806-88 specification for denatured fuel ethanol, 

except the denaturant must be commercially available unleaded gasoline, 

which 1s then blended in a range of 4 to 5 parts gasoline to 100 parts 

by volume fuel ethanol (including water) to form the denatured fuel 

ethanol. The final blend specifications for E-85 fuel take precedence 

over the ASTM D 4806-88 specifications. 

by The denaturant for the denatured fuel ethanol is not included as a part 

of this percentage, but is included as a part of the total blend volume 

for percent calculation. The gasoline specified here (not denaturant) 

must meet local specifications for commercial unleaded gasoline, except 

for RVP. The adjustment of RVP must be performed using common blending 

components from the gasoline stream. 

E. PROPOSED SPECIFICATIONS FOR NATURAL GAS 

The staff is proposing specifications for compressed natural gas (CNG) 

and liquified natural gas (LNG). Compressed natural gas differs from LNG in 

the manner in which the natural gas is transported and stored; CNG is 

typically transported and stored at high pressures and ambient temperatures, 

whereas LNG Is transported and stored at lower pressures and temperatures. 

The staff expects differences in fuel composition between these two fuels to 

be small, and 1s proposing the same specifications be set for both CNG and 

LNG. The staff 1s also proposing that the commercial and certification 

specifications be the same. 

Natural gas normally contains methane as the predominant species, along 

with small amounts of ethane, propane, butane, nitrogen, water, carbon 

dioxide, and other compounds (L1ss, 1991). Natural gas composition can be 

variable, and 1s processed when necessary to remove hydrogen sulfide, water, 

inert gases, and heavier hydrocarbons. 

The proposed specifications are listed in Table 6, and included in the 

commercial CNG and LNG specifications set forth in proposed section 2292.5 

of Title 13 (Appendix A) . The proposed specifications are based on the 

certification fuel specifications that are already a part of the California 

Exhaust Emission Standards and Test Procedures for 1985 and Subsequent Model 

Heavy-duty Diesel-Engines and Vehicles (Appendix C) and the California 

Exhaust Emission Standards and Test Procedures for 1987 and Subsequent Model 

Heavy-duty Otto-cycle Engines and Vehicles (Appendix D) . In developing 

these specifications, the staff has also relied upon comments provided by 

the California Natural Gas Vehicle Coalition, motor vehicle manufacturers, 

and other interested parties. 

The staff 1s proposing several changes to the the existing ARB 

specifications. The values in the proposed regulations are listed as mole 

percent, rather than percent of organic carbon, the Wobbe number 

specification has been dropped, and specifications for inert compounds have 

been added. In addition, the specifications for water and particulate 

matter have been made more enforceable by setting quantifiable limits. 

-23-
P.30 

Table 6 

Proposed Commercial and Certification Specifications 

for Compressed and Liquified Natural Gas 

Specification 

Hydrocarbons (expressed as 

Methane 

Ethane 

C, and higher HC 

Cg and higher HC 

Other species (expressed as 

Hydrogen 

Carbon monoxide 

Oxygen 

Inert gases 

Sum of CO. and N9 

Water

 c c 

Particulate matter 

Value 

mole percent) 

88.Ot (min.) 

6.01 (max.) 

3.0f (max.) 

0.2* (max.) 

mole percent unless 

0.lt (max.) 

0.11 (max.) 

0.51 (max.) 

5.01 (max.) 

A/ 

y 

Test Method 

ASTM D 1945-81 

ASTM D 1945-81 

ASTM D 1945-81 

ASTM D 1945-81 

otherwise indicated) 

ASTM D 2650-88 

ASTM D 2650-88 

ASTM D 1945-81 

ASTM D 1945-81 

a./ The dewpoint at vehicle fuel storage container pressure shall be at 

least 10 F below the 99.01 winter design temperature listed in Chapter 

24, Table 1, Climatic Conditions for the United States, in the American 

Society of Heating, Refrigerating and Air Conditioning Engineer's 

(ASHRAE) Handbook, 1989 fundamentals volume. Testing for water vapor 

shall be in accordance with ASTM 0 1142-90, utilizing the Bureau of 

Mines apparatus. 

b/ The compressed or liquified natural gas shall not contain dust, sand, 

dirt, gums, oils, or other substances in an amount sufficient to be 

Injurious to the fueling station equipment or the vehicle being fueled. 

•24-
P.31 

1. repressed Natural Gas 

Compressed natural gas is transported primarily in pipelines on a 

continuous basis. Since natural gas use in motor vehicles will initially be 

a very small fraction of the total natural gas utilized in California, the 

specifications for the pipeline gas are important to review. 

For natural gas to be feasible in the near future, the specifications 

for the current supply need to be acceptable for vehicle use. Fortunately, 

the natural gas supplies from the three major natural gas companies in 

California are fairly uniform. Tables 7, 8, and 9 show the quality of the 

pipeline gas for Pacific Gas and Electric, San Diego Gas and Electric, and 

Southern California Gas, respectively. As shown in these tables, the 

methane content 1s typically greater than 90 percent. 

Motor vehicles using CNG may be driven in other regions of the country. 

Since vehicle manufacturers would be more likely to manufacturer CNG 

vehicles 1f they could be sold and used anywhere in the United States, the 

staff believes that the ARB specifications should be consistent with 

specifications for natural gas available in the rest of the United States. 

Table 10 presents the results of a study, sponsored by the Gas Research 

Institute, on variations in natural gas composition throughout the United 

States (Liss, 1991). The data were collected In ten major cities throughout 

the United States, including California. 

The reference on the table to propane/air peakshavlng relates to a 

practice by some utilities to Inject propane and air into their systems 

during times when these areas experience problems meeting demand for natural 

gas. The peakshavlng can also be accomplished with liquified natural gas. 

Therefore, the staff has determined that the effects of propane/air 

peakshavlng should not be included in the analysis. The cities without 

peakshavlng can be seen to have methane contents as low as 74 mole percent, 

and ethane contents as high as 14.7 mole percent. However, the mean values 

of 93.2 mole percent methane, 3.6 mole percent ethane, and the 0.8 mole 

percent propane as well as the inert gases (C02 • N2) at 2.7 mole percent, 

all fall within the specifications, as do the tenth and nintieth 

percentiles. 

Clearly, at least for the non propane-air peak-shaving cities, the 

specifications as proposed do not pose any major problems. The staff 

expects that certain suppliers of natural gas in other states may have some 

difficulty meeting the specifications, but it is not unreasonable to expect 

that they would be able to make the adjustments required to meet them. For 

example, liquified natural gas can be used for peak-shaving, rather than 

propane, as is already done in some locations. 

-25-
Table 7 

Qas Composition Standard Deviations 

Pacific Qas & Electric Company 

COMPONENT 

i 

ro 

' CARBON DIOXIDE 

NITROGEN 

METHANE 

ETHANE 

PROPANE 

1 BUTANE 

N-BUTANE 

IPENTANE 

NPENTANE 

HEXANES-tTotal 

CAUFORNIA 

PRODUCERS 

AVERAQE 

(mol%) 

.151 

5.795 

91.871 

1.319 

.505 

.097 

.116 

.045 

.041 

.060 

100.000 

STD DEV 

(+/) 

.163 

5 558 

6.132 

2.086 

.932 

.130 

.208 

.054 

.044 

.082 

OUT-OF-STATE 

PRODUCERS 

AVERAQE 

(mo)%) 

.792 

1.035 

94.585 

2.940 

.518 

.052 

.028 

.020 

.012 

<029_ 

100.000 

STD DEV 

(47) 

.420 

.075 

1.985 

1.190 

.374 

.031 

.028 

.006 

.004 

.000 

SYSTEM-WIDE 

AVERAQE 

(mol%) 

.662 

1.975 

94.040 

2614 

.513 

.059 

.082 

.023 

.015 

£0*. 

100.000 

STD DEV 

(+/•) 

.369 

1.172 

2.814 

1.369 

.486 

.051 

.064 

.016 

.012 

.016 

NOTES: 1. This data Is based on 1989 annual natural gas deliveries Into the PQ&E gas system. 

2. California producers represent 20% of total natural gas deliveries Into the PG&E system. 

3. Out-of-state producers represent 80% of total natural gas deliveries Into the PQ&E system. 

(Provided to the ARB by the California Natural Gas Vehicle Coalition) 
Table 8 

Gas Composition Standard Deviations 

San Diego Gas arid Electric 

COMPONENT MISSION OCEANSIDE SYSTEM-WIDE 

i 

IV) 

I 

METHANE 

ETHANE 

C3 

CB 

mm 

Total 

AVERAQE 

ftnol*) 

93.533 

3.061 

0.723 

0.051 

£&2 

100.000 

STD DEV 

I+/-1 

0253 

0.178 

0.070 

0.004 

0.147 

AVERAGE 

fmottM 

92432 

3.421 

1.193 

0.096 

285Q 

00.000 

STD DEV 

(+/-) 

0.600 

0.193 

0.160 

0.014 

0.330 

AVERAQE 

fmol%i 

93019 

3.231 

0.942 

0.072 

zm 

100.000 

STD DEV 

(+/•) 

0.371 

0.142 

0.106 

.010 

0.222 

NOTES: 1. This data Is based on June 1, to July 19, 1991 natural gas deliveries Into the SDG&E gas system. 

2 Some of the gas deliveries Into the SDG&E system ara transported through the SoCal gas system, and some are delivered directly 

by out-of-state transporters. Exact quantities from each source were not available for this data. 

(Provided to the ARB by the California Natural Gas Vehicle Coalition) 
Table 9 

Gas Composition Standard Deviations 

Southern California Gas Company 

COMPONENT 

-28-

CARBON DIOXIDE 

NITROGEN 

METHANE 

ETHANE 

PROPANE 

IBUTANE 

N BUTANE 

1PENTANE 

N-PENTANE 

HEXANES+ 

Total 

CAUFORNIA 

PRODUCERS 

AVERAGE 

(mol%) 

1.68 

0.76 

90.64 

4.48 

1.66 

0.20 

037 

0.08 

0.06 

0.07 

100.00 

STD DEV 

(+/-) 

1.31 

1.24 

6.41 

3.39 

1.57 

0.26 

0.55 

0.13 

0.10 

0 12 

OUT-OF-STATE 

PRODUCERS 

AVERAGE 

(mol %) 

0.73 

2.12 

91.77 

4.09 

0.86 

0 09 

0.16 

0.05 

0.04 

0.09 

100.00 

STD DEV 

(+/-) 

0.28 

0.67 

1.20 

0.43 

0.26 

0.04 

0.08 

0.02 

0 02 

0.05 

SYSTEM WIDE 

AVERAGE 

(mol%) 

0.82 

1.98 

91.65 

4.13 

0 95 

0.10 

0.19 

0.05 

0.04 

0.09 

100.00 

STD DEV 

(+/) 

0.58 

0.85 

2.37 

1.16 

0.61 

0.10 

0 20 

0.05 

0.04 

006 

NOTES: 1. This data to based on June 1990 natural gas deliveries Into the SoCal gas system. 

2. California producers represent 10% of total natural gas deliveries Into the SoCal gas system. 

3. Out-of-state producers represent 90% of total natural gas deHverles Into the SoCal gas system. 

(Provide d to the ARB by the Californi a Natura l Ga s Veliicle Coalition ) 
P.35 

Table 10 

Weighted National Statistics For Natural Gas In 

Ten Major Urban Areas Of The U.S. With and Without Propane/Air Peaksharing 

Methane (Mole S) 

Ethane (Mole %) 

Propane (Mole %) 

C4+ (Mole St) 

CO, + N, (Mole *) 

Heating Value (MJ/m>) 

Heating Value (BTU/tcf) 

Specific Gravity 

Wobbe Number (MJ/m*) 

Wobbe Number 

Air/Fuel Ratio (Mass) 

Mean 

93.2 

3.6 

0.8 

0.5 

2.7 

38.64 

1037 

0.603 

49.85 

1338 

16.3 

Minimi! 

With P/A 

55.8 

0.7 

0.0 

0.0 

0.1 

36.14 

970 

0.566 

44.64 

1198 

12.7 

Minimum 

W/O P/A 

74.0 

0.70 

0.0 

0.0 

0.1 

36.14 

970 

0.566 

44.64 

1198 

13.6 

Maximum 

With P/A 

98.1 

14.7 

23.7 

2.1 

15.1 

45.01 

1208 

0.883 

52.24 

1402 

17.1 

Maximum 

W/O P/A 

98.1 

14.7 

2.4 

2.1 

10.0 

42.10 

1130 

0.695 

52.24 

1402 

17.1 

10 th 

*-Tiie 

88.5 

1.8 

0.3 

0.1 

1.0 

38.12 

1023 

0.578 

48.89 

1312 

15.7 

90 th 

%-Tile 

96.4 

5.0 

1.3 

0.6 

4.7 

39.12 

1050 

0.628 

50.56 

.1357 

16.8 

(Liss, 1991) 

-29-
P.36 

The Southwest Research Institute has conducted preliminary studies on a 

single cylinder engine that indicate that natural gas fuel compositions 

varying within the range of the proposed specifications do not have a major 

effect on criteria pollutant emission levels (Ryan, 1990). 

High ethane and propane content in natural gas can cause lower knock 

limited compression ratios, and even engine damage. Therefore, the staff 

has limited the concentrations of these components in the proposed 

specification for natural gas. The staff has also limited the 

concentrations of higher hydrocarbons due to their tendency to increase 

reactivity, and due to concerns about hydrocarbon dewpoint. There is a 

possibility of higher hydrocarbons condensing out of the compressed gas at 

the point where the high pressure gas leaves the regulator and the 

temperature of the gas decreases abruptly. If this occurs, there may be 

some loss in fuel metering control. 

The inert gas specifications have been added due to the effects on 

combustion and vehicle performance. The water specification was set at a 

level that should help avoid corrosion of steel storage tanks due to low 

temperature (approximately OF ) and high pressure (approximately 4000 psi). 

The National Fire Protection Association (NFPA) 52 document, in Appendix A1-4.7 (of the NFPA document) notes that if water content has been limited, 

the other potentially corrosive components do not pose a major problem 

(NFPA, 1988). The particulate matter specification Is intended to avoid 

engine damage, including plugging of the fuel delivery system. 

2. Llaulfled Natural fias 

The LN6 specifications would be set the same as the CNG specifications. 

The staff assumes that the LNG would be produced from the same sources as 

the CNG. Liss (1991) noted that the differences between most CNG and most 

LNG compositions relate to the extremely low levels of carbon dioxide, 

nitrogen, and water, along with heavier molecular weight hydrocarbons in LNG 

as compared to CNG. However, the staff does not expect these differences to 

be significant. 

-30-
P.37 

F. PROPOSED SPECIFICATIONS FOR LIQUIFIED PETROLEUM GAS 

The proposed specifications for liquified petroleum gas (LPG) presented 

in Table 11, and included in the proposed Section 2292.6 of Title 13 

(Appendix A) , are based on the special-duty propane specifications contained 

in the ASTM D 1835-89 Standard Specification for Liquified Petroleum Gases 

included as Appendix I of this report. Special-duty propane is a relatively 

consistent fuel whose fuel composition rationalization is covered in the 

appendix to ASTM 0 1835-89. The staff is proposing that the commercial fuel 

and certification fuel specifications be the same. 

The staff is proposing to include a minimum propane content of 80.0 

volume percent in the proposed specifications, which is not included in 

the ASTM D 1835-89 special-duty propane specifications. The staff believes 

that a minimum specification is necessary to ensure consistent fuel quality. 

The proposed ARB specifications for LPG also differ from the 

ASTM 0 1835-89 specifications for special-duty propane in that the staff 1s 

proposing that the maximum propene content be raised from five volume 

percent in the ASTM specifications to ten percent for the ARB proposed 

specifications. 

The propene content of LPG is a concern with respect to its high 

reactivity, its tendency to lower the knock limited compression ratio, and 

its impact on other durability and driveability problems. Most of the 

research on the driveability and vehicle durability effects of varying LPG 

fuel compositions was performed in the early 1960's. One of the studies 

included detailed Information on the effects of different propene levels 

indicating that, even for severe-duty engines, variations were not that 

pronounced in the five volume percent to ten volume percent propene range 

(Brower et al, 1962). 

Limiting the propene content to five volume percent as is done in the 

ASTM 0 1835-89 specifications could exclude an estimated 50 percent of the 

California refinery-produced LPG from the vehicle fuel marketplace (Moyer, 

1991). Refinery-produced LPG has been estimated to account for 

approximately 60 percent of the current LPG supply in California (Gawronskl, 

1991). Therefore, limiting the propene to five volume percent could result 

in an estimated 30 percent of the currently available LPG being excluded 

from the California motor vehicle fuel market. This could possibly lead to 

higher prices, and decreased motor vehicle fuel availability. For these 

reasons, and the fact that there is no compelling evidence that raising the 

propene specification to ten volume percent would have major emissions or 

vehicle dr1ve«bjl1ty or durability effects, the staff 1s proposing to 

include a prepenf specification of ten volume percent. At this level, the 

staff estimates that 12 percent of the California refinery-produced LPG or 

seven percent,of currently available LPG would be excluded from the 

California motor vehicle fuel marketplace (Moyer, 1991). 

-31-
P.38 

Table 11 

Proposed Commercial and Certification Specifications 

for Liquified Petroleum Gas 

Specification Value Test Method 

Propane 80.0 vol. % 

(min.) ASTM 0 2163-87 

Vapor„pressure at 

100° F 208 psig (max.) ASTM 0 1267-89 or 

ASTM D 2598-88 a/ 

Volatility residue: 

evaporated temp., 

95* -37°F (max.) ASTM D 1837-86 

or 

butane & heavier 2.5 vol. 1 

(max.) ASTM D 2163-87 

Propene 10.0 vol. t 

(max.) ASTM J) 2163-87 

Residual matter: ~ 

residue on evap. 

of 100 ml 0.05 ml (max.) ASTM D 2158-89 

oil stain observ. pass ASTM 0 2158-89 

Corrosion, copper, 

strip No. 1 (max.) ASTM 0 1838-89 

Sulfur 123 ppmw (max.) ASTM D 2784-89 

Moisture content pass ASTM 0 2713-86 

i/ In case of dispute about the vapor pressure of a product, the value 

actually determined by Test Method ASTM D 1267-89 shall prevail over the 

value calculated by Practice ASTM 0 2598-88. 

fc/ An acceptable product shall not yield a persistent oil ring when 0.3 ml 

of solvent residue mixture is added to a filter paper, in 0.1 ml 

increments and examined in daylight after 2 min. as described in Test 

Method ASTM D 2158-89. 

-32-
P.39 _, 

G. PROPOSED SPECIFICATIONS FOR HYDROGEN 

The specifications for hydrogen presented in Table 12, and included in 

the proposed Section 2292.7 of Title 13 (Appendix A) , are partially based 

on the Compressed Gas Association's CGA G-5.3 - 1990 specification Type IA 

for gaseous hydrogen (CGA, 1990). The proposed specifications apply to 

hydrogen fuel used in internal combustion engines. As fuel cell technology 

develops, separate specifications for hydrogen used in fuel cell technology 

may need to be developed. The staff is not proposing specifications for 

hydrogen certification fuel at this time since no corresponding vehicle 

certification procedures exist. 

Hydrogen industry representatives have commented that a stringent 

hydrogen specification is unnecessary from an air quality perspective, and 

that technologies such as solar produced hydrogen, electrolytically produced 

hydrogen, and biologically produced hydrogen would have to further purify 

their gas (an added cost) in order to remove, for the most part, oxygen 

(Lynch, 1991) (Stuart, 1991). Researchers at the German Aerospace Research 

Establishment have set an approximate 98 volume percent hydrogen purity 

specification for shutting off their solar powered hydrogen production 

process (Brinner 1990). The presence of oxygen at less than two mole 

percent 1s not an explosion concern, nor does it present any"known problem 

as far as emissions are concerned. Therefore, the staff is proposing a 

minimum hydrogen content of 98 mole percent, with a minimum combined 

hydrogen, water, nitrogen, and oxygen specification of 99.9 mole percent. 

The 98 mole percent hydrogen purity requirement 1n the proposed 

specification allows developing hydrogen production technologies, such as 

solar powered electrolysis, to act as suppliers of vehicle hydrogen. The 

Impurities, 1n the amounts shown, should not cause excess emissions for 

internal combustion hydrogen engines. The staff does not believe that the 

other specifications should be a problem for any anticipated hydrogen 

production technology. The total hydrocarbon specification is set low 

enough that emissions of reactive compounds should be produced at levels 

lower than that attributable to the engine lubricants. The particulate 

matter specification is intended to avoid engine damage, including plugging 

of the fuel delivery system. 

-33-
P.40 

Table 12 

Proposed Commercial Fuel Specifications for Hydrogen 

Specification 

Hydrogen 

Combined hydrogen, water, 

oxygen and nitrogen 

Total hydrocarbons 

Particulate matter 

Value 

98.0 mole t (min) 

99.9 mole t (min.) 

0.01 mole % (max.) 

A/ 

Tftirt Method 

ASTM D 1946-90 

ASTM D 1946-90 for 

hydrogen, 

nitrogen and 

oxygen; ASTM 0 

1142-90 for water 

using the Bureau 

of Mines 

apparatus 

ASTM 0 1946-90 

&/ The hydrogen shall not contain dust, sand, dirt, gums, oils, or other 

substances in an amount sufficient to be injurious to the fueling 

station equipment or the vehicle being fueled. 

-34-
P.41 

III. 

ENVIRONMENTAL AMD ECONOMIC IMPACTS 

A. EMISSION REDUCTIONS 

The emission reductions resulting from the implementation of the 

proposed regulations would result from ensuring the quality £f fuel used as 

a result of the low emission vehicle/clean fuels regulatlons^adopted 1n 

September 1990. An analysis of the emission reductions to be expected from 

the use of low emission vehicles was included as part of the Staff Report 

for these earlier regulations. The staff has limited data on the effects of 

varying constituents in the fuels. Therefore, the actual emission 

reductions achievable from the implementation of these particular 

specifications are not quantifiable. The staff believes that the proposed 

specifications will help assure that motorists have alternative fuels 

available that are of consistent quality and result in the expected benefits 

identified in the low emission vehicle/clean fuels regulations. 

B. COSTS 

The overall costs of operating low emission vehicles in place of 

gasoline-fueled vehicles were covered in the Staff Report for the lowemission vehicle/clean fuels regulations adopted in September 1990. This 

discussion will focus on only those costs which might be attributed to any 

differences between the fuel specifications as proposed, and fuel which 

might be sold as certification or commercial fuel if such specifications 

were not adopted. For the reasons discussed below, the proposed 

specifications are not expected to result in any increase in costs. 

Methanol currently manufactured can easily meet the proposed M-100 and 

M-85 fuel specifications. The fuel methanol purity specifications allow for 

impurities due to possible future lower cost methanol manufacturing 

processes. There are also provisions in the specifications for impurities 

due to transport of methanol through pipelines. The gasoline to be used in 

M-85 fuel blending will be the commonly available commercial unleaded fuel. 

-35-
P.42 

The denatured ethanol required by the proposed specifications for the 

E-100 and E-85 fuels, with minor modifications is commonly available, and 

currently utilised for gasohol. The staff expects that other specifications 

for E-100 and E-86 fuels should also be easily met. The blending gasoline 

for E-85 fuel will be the common commercially available unleaded gasoline as 

was the case for M-85 fuel. 

Studies are now on-going to determine the effects of varying CNG fuel 

composition on emissions. Results are not conclusive to date, and so costeffectiveness values are not possible at this time. However, the CNG 

specifications proposed, which have been developed in close consultation 

with the natural gas industry, should allow all of the major California 

natural gas utilities to supply natural gas for vehicles, given their 

current fuel quality. Thus, the commercial specification should add no 

additional cost to the current cost of CNG fuel in California. Since the 

sources for LNG and CNG are assumed to be the same, and the specifications 

will be the same, the discussion for CNG also applies for LNG. 

The specification of a ten volume percent propene limit will possibly 

exclude about seven percent of the currently available LPG from the 

vehicular fuel market. However, the "off-spec" LPG could be ^utilized for 

purposes other than 1n vehicle internal combustion engines. "The ten volume 

percent propene limit will exclude much less LPG from the market than the 

estimated 30 percent excluded 1f the ASTM D 1835-89 special-duty propane 

specification, which has a five volume percent propene limit, was adopted 

instead. While there may be some difficulties encountered in segregating 

the fuel supplies, the staff does not expect that there will be a need to 

install new storage facilities, or Incur any other significant costs. 

The staff expects that the fuel specifications proposed for hydrogen 

can be easily met by the current commercial scale hydrogen producing 

industries. In addition, the approximately 98 mole percent hydrogen level 

also allows such future supply sources as solar to be used, where oxygen 

levels can be somewhat higher. 

C. SMALL BUSINESS IMPACTS 

Smell businesses are defined by Government Code Section 11342 et seq. 

The Code requires the ARt to discuss how complying with a proposed 

regulation could adversely affect small businesses. The staff does not 

believe that adoption of tht proposal would result in significant, adverse 

impacts on small businesses. 

D. OTHER ENVIRONMENTAL IMPACTS 

Implementation of the proposal would have an overall positive impact on 

the environment by reducing undesirable vehicle emissions, as the setting of 

the specifications would serve to promote the production of low emission 

vehicles. Although the proposal could result in increased production and 

use of alternative fuels, the staff does not believe that 1t would result in 

any increase in overall fuel demand. The production, distribution, and 

.36. 
P.43 

narketing of alternative fuels cause emissions of air pollutants. However, 

the emissions from alternative fuels production and use would replace the 

emissions that would have been associated with a comparable amount of 

gasoline. The specifications will help prevent lower quality fuel from 

being used, which could compromise vehicle emission systems, and may 

contribute to increased criteria pollutants and toxic pollutants. 

The tighter specifications alone should not force any new fuel 

production installations to be built. However, should modifications to 

existing facilities be required in order to produce the tighter 

specification clean fuels, permits would be required from the appropriate 

local air district to modify an existing facility. 

The staff does not expect that the proposed specification will result 

in any significant adverse environmental impacts. 

E. GLOBAL WARMING AND OZONE DEPLETION IMPACTS 

The setting of clean fuel specifications is not expected to increase 

emissions of greenhouse gases that may contribute to global warming or 

pollutants that may contribute to stratospheric ozone depletion. 

F. PUBLIC SAFETY IMPACTS 

The staff has determined that the relative safety of the alternative 

fuels is important in promoting the use of the fuels. Vapor space 

flammability and flame visibility associated with the methanol and ethanol 

fuels have emerged as two safety Issues associated with these fuels. 

Corrosion .of fuel tanks 1s another potential safety problem associated with 

natural gas. 

1. Safety Issues Assodated With Alcohol Fuels 

Because of the lower vapor pressure of the alcohol fuels, higher vapor 

pressure components must be present. A higher vapor pressure is necessary 

so that ignition is not possible at ambient temperatures. If a higher vapor 

pressure cannot be used, some other mechanism must be used to avoid 

ignition. The unleaded gasoline that will be added to both the E-85 and M85 fuels will Increase the vapor pressure of the fuel and decrease vapor 

space flammability. The proposed specifications will ensure that enough 

gasoline or other vapor pressure increasing components, or both, are present 

in the M-85 and E-85 fuels to serve these purposes. In addition, the vapor 

space flammability of the M-85 and E-85 fuels will be minimized by 

incorporating a minimum Reid vapor pressure Umit of the final blend. 

Vehicle manufacturers and retrofitters using M-100 and E-100 fuels will 

have to address the problem of vapor space flammability. The staff believes 

these problems can be solved using improved fuel storage system technology. 

This issue is not directly addressed by these regulations, but instead falls 

under the purview of agencies that certify vehicle safety. 

-37-
P.44 

Methanol burns without a visible flame. As a result, a safety hazard 

is created if fires are not immediately noticed. Unleaded gasoline added to 

M-85 fuel will increase flame visibility (luminosity). M-100 will not be 

able to rely on gasoline for flame luminosity. Therefore, fuel producers 

and vehicle manufacturers are in the process of developing additives that 

could be added in small quantities to enhance flame luminosity. The 

proposed specifications require compliance with the flame luminosity by 

January 1, 1994. The M-100 California fleet currently consists only of 

heavy-duty vehicles, which are refueled by experienced drivers, or fleet 

maintenance personnel. This limits the threat to safety posed by M-100 fuel 

fires. The staff believes that the additional time is needed to develop 

acceptable flame luminosity additives. 

Ethanol fuels have flames that are sufficiently visible so that 

visibility enhancing additives are not required. 

2. Safety Issue Associated With Natural Gas 

For compressed natural gas, corrosion of steel storage tanks can lead 

to failure. The NFPA has determined that preventing water condensation 

inside the storage tank is the most effective way to prevent^thls corrosion 

(NFPA, 1988). The CNG fuel specification has been designed to prevent water 

condensation. 

-38-
P.45 

REFERENCES 

ARB, 1990a. Proposed Regulations for Low Emission Vehicles and Clean Fuels. 

A1r Resources Board Staff Report, August 13, 1990. 

ARB, 1990b. Proposed Regulations for Low Emission Vehicles and Clean Fuels. 

Air Resources Board Technical Support Document, August 13, 1990. 

Brinner, A., H. Bussman, W. Seeger and H. Steeb, 1990. Operation Results of 

a lOkW PV-Electrolvsis System in Different Coupling Modes. Proceedings 

of the 8th World Hydrogen Energy Conference, July 22-27, 1990. 

Brower, G.K., E.F. Mezera and R.F. Najt, 1962. LP Gas Engine Fuel: "To Be 

Or Not To Be: That is the Question". Presentation at the 1962 Annual 

Meeting of the Gas Processors Association. 

CGA, 1990. Commodity Specification for Hydrogen. G-5.3-1990, Compressed Gas 

Association, Inc. 

Gawronski, J.L., 1991. Written correspondence to Steve Francis, April 24, 

1991. 

Herrbrich, B., 1991. Written correspondence to Steve Francis, June 10, 

1991. 

Johnson, W.H., 1985. Written correspondence to Ron Cannon, July 11, 1985. 

Liss, W.E., 1991. Natural Gas As A Stationary Engine and Vehicle Fuel. SAE 

Paper No. 912364, to be presented in the Fall of 1991. 

Lynch, F.E., 1991. Written correspondence to Steve Francis, May 29, 1991. 

Moyer, N.A., 1991. Written correspondence to Robert Fletcher, 

July 15, 1991. 

NFPA, 1988. National Fire Protection Association, NFPA 52 Compressed 

Natural Gas fCNGl Vehicular Fuel System. 1988 Edition. June 8, 1988. 

Ryan III, T.W., 1991. Variable Gas Composition Experiments. SwRI Project 

No. 03-3178, Phase 209. 

Stuart, A.K., 1991. Written correspondence to Robert Fletcher, April 23, 

1991. 

-39-
P.46 

APPENDICES 
APPENDIX A 

PROPOSED REGULATION ORDER 

Proposed Amendments to Section 1960.l(k). 1956.8(b). and 1956.8(d). 

Title 13. California Code of Regulations, and Proposed Adoption 

of sections 2290 - 2292.7, Title 13, California Code of Regulations 
P.48 

PROPOSED REGULATION ORDER 

Note: Proposed new language is shown in italics and proposed deletions 

are shown in stp4keeut. 

Amend section 1960.l(k), Title 13, California Code of Regulations to read as 

follows: 

1960.1. Exhaust Emission Standards and Test Procedures - 1981 and 

Subsequent Model Passenger Cars, Light-Duty Trucks, and Medium-Duty 

Vehicles. 

(a) through (j) [No change] *" 

(k) The test procedures for determining compliance with these standards 

are set forth in "California Exhaust Emission Standards and Test Procedures 

for 1981 through 1987 Model Passenger Cars, Light-Duty Trucks, and MediumDuty Vehicles", adopted by the State Board on November 23, 1976, as last 

amended May 20, 1987, and in "California Exhaust Emission Standards and Test 

Procedures for 1988 and Subsequent Model Passenger Cars, Light-Duty Trucks, 

and Medium-Duty Vehicles", adopted by the state board on May 20, 1987, as 

last amended Ju4y 12T 4991 [Insert date of amendment], both of which are 

incorporated herein by reference. 

(1) through (o) [No Change] 

NOTE: Authority cited: Sections 39600, 39601, 43013, 43018, 43101 and 

43104, Health and Safety Code. Reference: Sections 39002, 39003, 39667, 

43000, 43013, 43018, 43100, 43101, 43101.5, 43102, 43103, 43104, 43106 and 

43204, Health and Safety Code. 

A-l 
P.49 

Amend Title 13, California Code of Regulations, section 1956.8(b) and 

(d) to read as follows: 

1956.8. Exhaust Emission Standards and Test Procedures - 1985 and 

Subsequent Model Heavy-Duty Engines and Vehicles. 

(a) [No Change] 

(b) The test procedures for determining compliance with standards 

applicable to 1985 and subsequent heavy-duty diesel engines and vehicles are 

set forth in the "California Exhaust Emission Standards and Test Procedures 

for 1985 and Subsequent Model Heavy-Duty Diesel Engines and Vehicles", 

adopted April 8, 1985, as last amended Ju4y 42T 1991 [insert date of 

amendment], which is incorporated herein by reference. 

(c) [No Change] 

(d) The test procedures for determining compliance with standards 

applicable to 1987 and subsequent model heavy-duty otto-cycto engines and 

vehicles are set forth in the "California Exhaust Emission Standards and 

Test Procedures for 1987 and Subsequent Model Heavy Duty Otto-Cycle Engines 

and Vehicles," adopted April 25, 1986, as last amended Ju4y 42T 1994 

[insert date of amendment], which is incorporated herein by reference. 

(e) through (h) [No Change] 

NOTE: Authority cited: Sections 39600, 39601, 43013, 43018, 43101, 43103, 

and 43104 Health and Safety Code. Reference: Sections 39002, 39003, 43000, 

43013, 43018, 43100, 43101, 43101.5, 43102. 43103, 43104, 43106, and 43204, 

Health and Safety Code. 

Adopt new Article 3, sections 2290 - 2292.7, Chapter 5, Title 13, California 

Code of Regulations, to read as follows: 

Article 3. Specifications for Alternative Motor Vehicle Fuels 

2290. Definitions 

(a) For the purposes of this article, the following definitions apply: 

A-2 
P.50 

(1) "Alternative fuel" means any fuel which is commonly or commercially 

known or sold as one of the following: M-100 fuel methanol, M-85 fuel 

methanol, E-100 fuel ethanol, E-85 fuel ethanol, compressed natural gas, 

liquified natural gas, liquified petroleum gas, or hydrogen. 

(2) "ASTM" means the American Society for Testing and Materials. 

(3) "Motor vehicle" has the same meaning as defined in section 415 of 

the Vehicle Code. 

(4) "Supply" means to provide or transfer a product to a physically 

separate facility, vehicle, or transportation system. 

NOTE: Authority cited: sections 39600, 39601, 43013, 43018, and 43101, 

Health and Safety Code; and Vestern Oil and Gas Ass'n. v. Orange County Air 

Pollution Control District. 14 Cal. 3d 411, 121 Cal. Rptr. 249 (1975). 

Reference: sections 39000, 39001, 39002, 39003, 39010, 39500, 40000, 43000, 

43016, 43018, and 43101, Health and Safety Code; and Western Oil and Gas 

ASS'il* v. Orange County Air Pollution Control District. 14 Cal. 3d 411, 121 

Cal. Rptr. 249 (1975). 

2291. Basic Prohibittons. 

(a) Starting January 1, 1993, no person shall sell, offer for sale or 

supply an alternative fuel intended for use in motor vehicles in California 

unless it conforms with the applicable specifications set forth in this 

article 3. 

(b) An alternative fuel shall be deemed to be intended for use in motor 

vehicles in California if it is: 

(1) stored at a facility which is equipped and used to dispense that 

type of alternative fuel to motor vehicles, or 

(2) delivered or intended for delivery to a facility which is equipped 

and used to dispense that type of alternative fuel to motor vehicles, or 

(3) sold, offered for sale or supplied to a person engaged in the 

distribution of motor vehicle fuels to motor vehicle fueling facilities, 

unless the person selling, offering or supplying the fuel demonstrates 

that he or she has taken reasonably prudent precautions to assure that 

the fuel will not be used as a motor vehicle fuel in California. 

(c) For the purposes of this section, each retail sale of alternative 

fuel for use in a motor vehicle, and each supply of alternative fuel into a 

A-3 
P.51 

motor vehicle fuel tank, shall also be deemed a sale or supply by any person 

who previously sold or supplied such alternative fuel in violation of this 

section. 

NOTE: Authority cited: sections 39600, 39601, 43013, 43018, and 43101, 

Health and Safety Code; and Western Oil and Gas Ass'n. v. Orange County Air 

Pollution Control District. 14 Cal. 3d 411, 121 Cal. Rptr. 249 (1975). 

Reference: sections 39000, 39001, 39002, 39003, 39010, 39500, 40000, 43000, 

43016, 43018, and 43101, Health and Safety Code; and Western Oil and Gas 

ASS'n. v. Orange County Air Pollution Control District. 14 Cal. 3d 411, 121 

Cal. Rptr. 249 (1975). 

2292.1. Specifications for M-100 Fuel Methanol 

The following standards apply to M-100 fuel methanol 

(The identified test methods are incorporated herein by reference): 

Specifications for M-100 Fuel Methanol 

Specification 

Methanol 

Distillation 

Other alcohols and 

ethers 

Hydrocarbons, 

gasoline or 

diesel fuel 

derived 

Luminosity 

Value 

96 vol. X (min.) 

4.0 °C (range) 

2 mass % (max.) 

2 mass X (max.) 

Specific gravity 0.792 * 0.002 

9 20/20°C 

Test Method 

As determined by the 

distillation range 

below 

ASTM D 1078-86. At 

95X by volume 

distilled. Must 

include 64.6 * 

0.1bC 

ASTM D 4815-89 

ASTM D 4815-89, and 

then subtract 

concentration of 

alcohols, ethers 

and water from 100 

to obtain percent 

hydrocarbons 

Shall produce a 

luminous flame 

throughout the 

entire burn 

duration. 

Applicable 1/1/94 

ASTM D 891-89 

A-4 
P.52 

Acidity as acetic 

acid 

Total chlorine as 

chloride 

Lead 

Phosphorus 

Sulfur 

Gum, heptane washed 

Total particulates 

Water 

Appearance 

0.003 mass % (max.) ASTM D 1613-85 

0.0002 mass X (max.) 

2 mg/l (max.) 

0.2 mg/l (max.) 

0.01 mass X (max.) 

5 mg/100 ml (max.) 

5 mg/l (max.) 

0.5 mass X (max.) 

Free of turbidity, 

suspended matter 

and sediment 

ASTM D 2988-86 

ASTM D 3237-90 

ASTM D 3231-89 

ASTM D 3120-87 

ASTM 0 381-86 

ASTM D 2276-89 

ASTM E 203-75 

Visually determined 

at 25 C by proc. A 

of ASTM 0 4176-86 

NOTE: Authority cited: sections 39600, 39601, 43013, 43018, and 43101, 

Health and Safety Code; and Western Oil and Gas Ass'n. v. Orange County Air 

Pollution Control District. 14 Cal. 3d 411, 121 Cal. Rptr. 249 (1975). 

Reference: sections 39000, 39001, 39002, 39003, 39010, 39500, 40000, 43000, 

43016, 43018, and 43101, Health and Safety Code; and Western Oil and Gas 

ASS'n. v. Oranae County Air Pollution Control District. 14 Cal. 3d 411, 121 

Cal. Rptr. 249 (1975). 

2292.2. Specifications for M-85 Fuel Methanol 

The following standards apply to M-85 fuel methanol 

(The identified test methods are incorporated herein by reference): 

Specifications for M-85 Fuel Methanol 

Specification 

Methanol 

Gasoline, 

unleaded aJ 

Higher alcohols 

(C2 - C8) 

Hydrocarbons * 

aliphatic ethers 

Yilue 

85 vol. X (min.) 

14.5 ± .5 vol. X 

2 vol. X (max.) 

13-15 vol. X 

Vapor pressure, dry Final blend must 

meet vapor pressure 

requirements for 

Test Method 

/tone* Al to the ASTM 0-2 

Proposal P-232, Draft 

8-9-91 

Must meet local specifications 

for commercial unleaded 

gasoline, except for RVP 

ASTM D 4815-89 

ASTM D 4815-89, and then 

subtract concentration of 

alcohols, ethers and water 

from 100 to obtain percent 

hydrocarbons 

Methods contained in Title 13, 

Section 2262 must be used. 

ASTM D 4953-90 is an 

A-5 
Luminosity 

Acidity as acetic 

acid 

Total chlorine 

as chloride 

Lead 

Phosphorus 

Sulfur 

Gum, heptane washed 

Total particulates 

Water 

Appearance 

commercial unleaded 

gasoline of the area 

in which it will be 

sold, with a minimum 

RVP of 6.5 psi 

0.003 mass X (max.) 

0.0002 mass X (max.) 

0.002 g/1 (max.) 

0.0002 g/1 (max.) 

0.015 mass X (max.) 

5 mg/100 ml (max.) 

5 mg/l (max.) 

0.5 mass X (max.) 

Free of turbidity, 

suspended matter 

and sediment 

alternative method, however, 

in case of dispute about the 

vapor pressure, the value 

determined by the methods 

contained in Title 13, Section 

2262 shall prevail over the 

value calculated by ASTM D 

4953-90, including its 

precision statement 

Shall produce a luminous flame 

throughout the entire burn 

duration 

ASTM D 1613-85 

ASTM D 3120-87 modified for 

the det. of organic 

chlorides, and 

ASTM D 2988-86 

ASTM D 3237-90 

ASTM 0 3231-89 

ASTM D 3120-87 

ASTM 0 381-86 

ASTM D 2276-89 

ASTM E 203-75 

Visuallv determined 

at 25 C by Proc. 

A of ASTM D 4176-86 

Adjustment of RVP must be performed using common blending 

components from the gasoline stream. 

NOTE: Authority cited: sections 39600, 39601, 43013, 43018, and 43101, 

Health and Safety Code; and Western Oil and Gas Ass'n. v. Orange County Air 

Pollution Control District. 14 Cal. 3d 411, 121 Cal. Rptr. 249 (1975). 

Reference: sections 39000, 39001, 39002, 39003, 39010, 39500, 40000, 43000, 

43016, 43018, and 43101, Health and Safety Code; and Western Oil and Gas 

ASS'n. v. Orange County Air Pollution Control District. 14 Cal. 3d 411, 121 

Cal. Rptr. 249 (1975). 

A-6 
P.54 

2292.3. Specifications for E-100 Fuel Ethanol 

The following standards apply to E-100 fuel ethanol: 

(The identified test methods are incorporated herein by reference): 

Specifications for E-100 Fuel Ethanol 

Specification 

Ethanol 

Denatured fuel 

ethanol 

Other alcohols and 

ethers 

Hydrocarbons, 

gasoline or 

diesel fuel 

derived 

Acidity as acetic 

acid 

Total chlorine as 

chloride 

Copper 

Lead 

Phosphorus 

Sulfur 

Gum, heptane washed 

Total particulates 

Water 

Appearance 

Value 

92 vol. X (min.) 

98 vol. X (min.) 

2 mass X (max.) 

5 mass X (max.) 

0.007 mass X (max.) 

0.0004 mass X (max.) 

0.07 mg/l (max.) 

2 mg/l (max.) 

0.2 mg/l (max.) 

0.01 mass X (max.) 

5 mg/100 ml (max.) 

5 mg/l (max.) 

1.25 mass X (max.) 

Free of turbidity, 

suspended matter 

and sediment 

Test Method 

ASTM 0 3545-90 

a/ 

ASTM D 4815-89 

ASTM D 4815-89, and 

then subtract 

concentration of 

alcohols, ethers 

and water from 100 

to obtain percent 

hydrocarbons 

ASTM D 1613-85 

ASTM D 3120-87 

modified for the 

determination of 

organic chlorides, 

and ASTM 0 2988-86 

ASTM D 1688-90 as 

modified in ASTM 0 

4806-88 

ASTM D 3237-90 

ASTM D 3231-89 

ASTM D 3120-87 

ASTM D 381-86 

ASTM D 2276-89 

ASTM E 203-75 

Visually determined 

at 25°C by Proc. A 

of ASTM D 4176-86 

1/ Must meet the ASTM 0 4806-88 specification for denatured fuel 

ethanol, except the denaturant must be representative of unleaded 

gasoline that is commercially available blended in a range of 4 to 

5 parts by volume gasoline to 100 parts by volume fuel ethanol 

(including water) to form the denatured fuel ethanol. The final 

A-7 
P.55 

blend specifications for E-100 take precedence over the ASTM 0 

4806-88 specifications 

NOTE: Authority cited: sections 39600, 39601, 43013, 43018, and 43101, 

Health and Safety Code; and Western Oil and Gas Ass'n. v. Orange County Air 

Pollution Control District. 14 Cal. 3d 411, 121 Cal. Rptr. 249 (1975). 

Reference: sections 39000, 39001, 39002, 39003, 39010, 39500, 40000, 43000, 

43016, 43018, and 43101, Health and Safety Code; and Western Oil and Gas 

ASS'n. v. Orange County Air Pollution Control District. 14 Cal. 3d 411, 121 

Cal. Rptr. 249 (1975). 

2292.4. Specifications for E-85 Fuel Ethanol 

The following standards apply to E-85 fuel ethanol 

(The identified test methods are incorporated herein by reference): 

Specifications for E-85 Fuel Ethanol 

Specification 

Ethanol 

Denatured fuel 

ethanol 

Other alcohols 

Gasoline, unleaded 

Hydrocarbons + 

aliphatic ethers 

Vapor pressure, dry 

Acidity as acetic 

acid 

Total chlorine 

Value 

81 vol. X (min.) 

85 vol. X (min.) 

2 vol. X (max.) 

14.5 t .5 vol. X 

13-19 vol. X 

Final blend must 

meet vapor pressure 

requirements for 

commercial unleaded 

gasoline of the area 

in which it will be 

sold, with a minimum 

RVP of 6.5 psi 

Test Method 

ASTM D 3545-90 

aJ 

ASTM 0 

bj 

4815-89 

ASTM D 4815-89, and then 

subtract concentration of 

alcohols, ethers and water 

from 100 to obtain percent 

hydrocarbons. The denaturant 

is included in this 

percentage. 

Methods contained in Title 13, 

Section 2262 must be used. 

ASTM D 4953-90 is an 

alternative method, however, 

in case of dispute about the 

vapor pressure, the value 

determined by the methods 

contained in Title 13, Section 

2262 shall prevail over the 

value calculated by ASTM 0 

4953-90, including its 

precision statement 

0.007 mass X (max.) ASTM D 1613-85 

A-8 
P.56 

as chloride 

copper 

Lead 

Phosphorus 

Sulfur 

Gum, heptane washed 

Total particulates 

Water 

Appearance 

0.0004 mass X (max.) 

0.07 mg/l (max.) 

0.002 g/1 (max.) 

0.0002 g/1 (max.) 

0.015 mass X (max.) 

5 mg/100 ml (max.) 

5 mg/l (max.) 

1.25 mass X (max.) 

Free of turbidity, 

suspended matter 

and sediment 

ASTM 0 3120-87 modified for 

the det. of organic 

chlorides, and 

ASTM D 2988-86 

1688-90 as modified in 

D 4806-88 

3237-90 

3231-89 

3120-87 

381-86 

2276-89 

203-75 

Visuallv determined 

at 25 C by proc. 

A of ASTM D 4176-86 

ASTM D 

ASTM 

ASTM D 

ASTM 

ASTM 

ASTM 

ASTM 

ASTM 

D 

D 

D 

D 

E 

aJ Must meet the ASTM D 4806-88 specification for denatured fuel 

ethanol, except the denaturant must be commercially available 

unleaded gasoline, which is then blended in a range of 4 to 5 parts 

by volume gasoline to 100 parts by volume fuel ethanol (including 

water) to form the denatured fuel ethanol. The final blend 

specifications for E-85 take precedence over the ASTM D 4806-88 

specifications. 

bj The denaturant for the denatured fuel ethanol is not included as a 

part of this percentage, but is included as a part of the total 

blend volume for percent calculation. The gasoline specified here 

(not denaturant) must meet local specifications for commercial 

unleaded gasoline, except for RVP. Adjustment of RVP must be 

performed using common blending components from the gasoline 

stream. 

NOTE: Authority cited: sections 39600, 39601, 43013, 43018, and 43101, 

Health and Safety Code; and Western Oil and Gas Ass'n. v. Orange County Air 

Pollution Control District. 14 Cal. 3d 411, 121 Cal. Rptr. 249 (1975). 

Reference: sections 39000, 39001, 39002, 39003, 39010, 39500, 40000, 43000, 

43016, 43018, and 43101, Health and Safety Code; and Western Oil and Gas 

ASS'n, v. Oranae County Air Pollution Control District. 14 Cal. 3d 411, 121 

Cal. Rptr. 249 (1975). 

2292.5. Specifications for Compressed and Liquified Natural Gas 

The following standards apply to compressed and liquified natural gas 

(The identified test methods are incorporated herein by reference): 

A-9 
P.57 

Specifications for Compressed and Liquified Natural Gas 

Specification Value Test Method 

Hydrocarbons (expressed as mole percent) 

Methane 88.OX (min.) ASTM D 1945-81 

Ethane 6.OX (max.) ASTM D 1945-81 

Cr. and higher HC 

Ci and higher HC 

Other species (expressed 

Hydrogen 

Carbon monoxide 

Oxygen 

Inert gases 

Sum of COy and N? 

Water £ c 

Particulate matter 

3.OX (max.) 

0.2X (max.) 

as mole percent unl 

0.1X (max.) 

0.1X (max.) 

0.5X (max.) 

5.OX (max.) 

aJ 

bJ 

ASTM D 1945-81 

ASTM D 1945-81 

ess otherwise indicated) 

ASTM D 2650-88 

ASTM D 2650-88 

ASTM D 1945-81 

ASTM D 1945-81 

i/ The dewpoint at vehicle fuel storage container pressure shall be at 

least 10 F below the 99.OX winter design temperature* listed in 

Chapter 24, Table 1, Climatic Conditions for the United States, in 

the American Society of Heating, Refrigerating and Air Conditioning 

Engineer's (ASHRAE) Handbook, 1989 fundamentals volume. Testing 

for water vapor shall be in accordance with ASTM D 1142-90, 

utilizing the Bureau of Mines apparatus. 

bJ The compressed or liquified natural gas shall not contain dust, 

sand, dirt, gums, oils, or other substances in an amount sufficient 

to be injurious to the fueling station equipment or the vehicle 

being fueled. 

NOTE: Authority cited: sections 39600, 39601, 43013, 43018, and 43101, 

Health and Safety Code; and Western Oil and Gas Ass'n. v. Oranae County Air 

Pollution Control District. 14 Cal. 3d 411, 121 Cal. Rptr. 249 (1975). 

Reference: sections 39000, 39001, 39002, 39003, 39010, 39500, 40000, 43000, 

43016, 43018, and 43101, Health and Safety Code; and Western Oil and Gas 

ASS'n, v. Oranae County Air Pollution Control District. 14 Cal. 3d 411, 121 

Cal. Rptr. 249 (1975). 

2292.6. Specifications for Liquified Petroleum Gas 

The following standards apply to liquified petroleum gas 

(The identified test methods are incorporated herein by reference): 

A-10 
P.58 

Specifications for Liquified Petroleum Gas 

Specification 

Propane 

Vapor.pressure at 

100° F 

Volatility residue: 

evaporated temp., 

95X 

or 

butane & heavier, 

Propene 

Residual matter: 

residue on evap. 

of 100 ml 

oil stain observ. 

Corrosion, copper, 

strip 

Sulfur 

Moisture content 

Value 

80.0 vol. X 

(min.) 

208 psig (max.) 

-37°F (max.) 

2.5 vol. X 

(max.) 

10.0 vol. X 

(max.) 

0.05 ml (max.) 

pass t/ 

No. 1 (max.) 

123 ppmw (max.) 

pass 

Test 

Method 

ASTM D 2163-87 

ASTM D 1267-89 

ASTM D 2598-88 §./ 

ASTM D 1837-86 

ASTM D 2163-87 

ASTM D 2163-87 

ASTM D 2158-89 

ASTM-D 2158-89 

ASTM D 1838-89 

ASTM D 2784-89 

ASTM D 2713-86 

a/ In case of dispute about the vapor pressure of a product, the value 

actually determined by Test Method ASTM D 1267-89 shall prevail 

over the value calculated by Practice ASTM D 2598-88. 

h./ An acceptable product shall not yield a persistent oil ring when 

0.3 ml of solvent residue mixture is added to a filter paper, in 

0.1 ml increments and examined in daylight after 2 min. as 

described in Test Method ASTM D 2158-89. 

NOTE: Authority cited: sections 39600, 39601, 43013, 43018, and 43101. 

Health and Safety Code; and Western Oil and Gas Ass'n. v. Orange County Air 

Pollution Control District. 14 Cal. 3d 411, 121 Cal. Rptr. 249 (1975). 

Reference: sections 39000. 39001, 39002, 39003. 39010, 39500, 40000, 43000, 

43016, 43018, and 43101, Health and Safety Code; and Western Oil and Gas 

ASS'n, v. Orange County Air Pollution Control District. 14 Cal. 3d 411, 121 

Cal. Rptr. 249 (1975). 

2292.7. Specifications for Hydrogen 

The following standards apply for hydrogen 

(The identified test methods are incorporated herein by reference): 

A-11 
P.59 

Specifications for Hydrogen 

Specification 

Hydrogen 

Combined hydrogen, water, 

oxygen and nitrogen 

Total hydrocarbons 

Particulate matter 

Yalue 

98.0 mole X (min.) 

99.9 mole X (min.) 

0.01 mole X (max.) 

d/ 

Test 

Method 

ASTM D 1946-90 

ASTM D 1946-90 for 

hydrogen, 

nitrogen and 

oxygen; ASTM D 

1142-90 for water 

using the Bureau 

of Mines 

apparatus 

ASTM D 1946-90 

ay The hydrogen shall not contain dust, sand, dirt, gums, oils, or 

other substances in an amount sufficient to be injurious to the 

fueling station equipment or the vehicle being fueled. 

NOTE: Authority cited: sections 39600, 39601, 43013, 43018, and 43101, 

Health and Safety Code; and Western 011 and Gas Ass'n. v. Orange County Air 

Pollution Control District. 14 Cal. 3d 411, 121 Cal. Rptr. 249 (1975). 

Reference: sections 39000, 39001, 39002, 39003, 39010, 39500, 40000, 43000, 

43016, 43018, and 43101, Health and Safety Code; and Western Oil and Gas 

ASS'h. v. Oranae County Air Pollution Control District. 14 Cal. 3d 411, 121 

Cal. Rptr. 249 (1975). 

A-12 
P.60 

APPENDIX B 

Proposed Amendments to the California Exhaust Emission 

Standards and Test Procedures for 1988 and Subsequent Model 

Passenger Cars, Light-duty Trucks, and Medium-duty Vehicles 
P.61 

PROPOSED 

State of California 

AIR RESOURCES BOARD 

CALIFORNIA EXHAUST EMISSION STANDARDS 

AND TEST PROCEDURES FOR 1988 

AND SUBSEQUENT MODEL PASSENGER CARS, 

LIGHT-DUTY TRUCKS, AND MEDIUM-DUTY VEHICLES 

Adopted: May 20, 1987 

Amended: December 20, 1989 

Amended: January 22, 1990 

Amended: December 26, 1990 

Amended: July 12, 1991 

Amended: 
P.62 

NOTE: Amendments to the standards and test procedures made in this rulemaking 

are shown in underline to indicate additions to the text and stp4keebfe 

to indicate deletions. 

The symbol "#####" means that the remainder of the text of these 

procedures for a specific section, which is not shown in this amendment 

document, has not been changed. 

The numbering convention employed in this document, in order of 

priority, is: l.a.I.i.A. Any references within specific sections in 

the Code of Federal Regulations are denoted in order of priority as: 

(*)(!)(i)(A) - the same numbering system employed in the Code of Federal 

Regulations. 
P.63 

# # # # # 

CALIFORNIA EXHAUST EMISSION 

STANDARDS AND TEST PROCEDURES 

FOR 1988 AND SUBSEQUENT MODEL 

PASSENGER CARS, LIGHT-DUTY TRUCKS 

AND MEDIUM-DUTY VEHICLES 

# # # # # 

9. Test Requirements 

a. Fuel Specifications 

In paragraph 86.113-90: 

1. Add subparagraph (a)(1)(i) which reads: 

(1) For 1992 and subsequent model-year Otto-cycle vehicles, 

gasoline having the specifications listed below may be used in 

exhaust and evaporative emission testing as an option to the 

specifications referred to in subparagraph (a). 

Research Octane, minimum 93 

Sensitivity, minimum 7.5 

Lead (organic), maximum, g/US gal 0.050 

Distillation Range 

IBP, degrees F 75-100 

10 pet. point, degrees F 120-140 

50 pet. point, degrees F 200-230 

90 pet. point, degrees F 300-325 

EP, maximum 415 

Sulfur, maximum weight pet. 0.03 

Phosphorous, maximum, g/US gal 0.005 

RVP, ps1 7.5-8.0 

Hydrocarbon composition 

Olefins, maximum pet. 10 

Aromatics, maximum pet. 35 

Saturates remainder 

# # # # # 

10. Replace subparagraph (d) with: 

(d) Methanol-Gasoline Fuel SpecifIcationsr for 1993 Model-Year 

Vehicles. 

Various methanol-gasoline fuel blends will be used according to 

the type of methanol-fueled vehicle being certified and the 

particular aspect of the certification procedure being 

conducted, as specified below. Gasoline used for blending fuel 

for use in mileage accumulation shall b© representative of 

commercial regular unleaded gasoline which will be generally 

B-1 
P.64 

available through retail outlets. Gasoline used for blending 

fuel for use in emission testing shall conform with the unleaded 

gasoline specification noted in paragraph (a) above. 

Fuel additives and ignition improvers intended for use in 

methanol test fuels shall be subject to the approval of the 

Executive Officer. In order for such approval to be granted, a 

manufacturer must demonstrate that emissions will not be 

adversely affected by the use of the fuel additive or ignition 

improver. 

(1) Otto-cycle methanol vehicles and hybrid electric vehicles, 

which use otto-cycle methanol engines 

Mileage-accumulation fuel: For methanol vehicles and hybrid 

electric vehicles, which use otto-cycle methanol engines a 

methanol-gasoline blend composed of 85-percent methanol 

which is representative of commercially available methanol 

and 15-percent unleaded gasoline as noted above. 

Emission-testing fuel: For vehicles certifying on methanol, a 

methanol-gasoline blend composed of 85 percent chemical 

grade methanol and 15-percent unleaded gasoline as noted 

above. 

(2) Methanol-fueled diesel vehicles and hybrid electric 

vehicles which use methanol-fueled diesel engines 

Mileage-accumulation fuel: For methanol vehicles and hybrid 

electric vehicles which use methanol-fueled diesel engines, 

commercially available methanol fuel. 

Emission-testing fuel: chemical grade methanol. 

(3) Fuel-flexible vehicles 

Mileage-accumulation fuel: For both durability-data vehicles 

and emission-data vehicles, mileage accumulation shall be 

conducted with one fuel. For vehicles designed to operate 

on methanol, a methanol-gasoline blend composed of 85-

percent methanol and 15-percent unleaded gasoline both of 

which are representative of commercially available fuels 

shall be used. 

Emission-test fuel: Case (1) For regular emission testing, 

methanol-gasoline blend composed of 85-percent chemical 

grade methanol and 15-percent unleaded gasoline. 

Case (2) For the testing required under 6.a.22.(D). of 

these procedures, exhaust emission tests (exhaust OMHCE for 

non-TLEVs, non-LEVs, and non-ULEVs, exhaust NMOG for TLEVs, 

LEVs, and ULEVs, exhaust formaldehyde, exhaust CO, and 

exhaust NO ) shall be conducted at the specified mileage 

intervals Qsing 85-percent chemical grade methanol and 15-

percent unleaded gasoline, and 35-percent chemical grade 

methanol and 65-percent unleaded gasoline. In addition, 

complete sets of emission tests shall be conducted »i 5,000 

B-2 
P.65 

miles, 50,000 miles and the final mileage point with 

unleaded gasoline. 

(4) Other methanol fuels may be used for testing and service 

accumulation provided: (i) they are commercially available; 

(ii) information, acceptable to the Executive Officer, is 

provided to show that only the designated fuel would be used in 

customer service; (iii) use of a fuel listed in this section 

would not have a detrimental effect on emissions or durability; 

(iv) written approval from the Executive Officer of the fuel 

specifications must be provided prior to the start of testing. 

(5) The specification of the fuels to be used under paragraphs 

(d)(1), (d)(2), and (d)(3) of this section shall be reported in 

accordance with 86.090-21(b)(3) or 86.091-21(b)(3). 

XI) The specifications set forth in subparagraph (e) mav be 

used as an option for 1993 model-year vehicles. 

I L Add new subparagraph fe) to read: 

l&} Methanol-Gasoline Fuel Specifications £or 1994 and 

Subsequent Model-Year VehiclesVarious methanol-gasoline fuel blends will be used according to 

the type of methanol-fueled vehicle being certified and the 

particular aspect of the certification procedure being 

conducted, as specified below. 

Fuel additives and ignition Improvers intended for use in 

methanol test fuels shall be subject to the approval of the 

Executive Officer. In order for such approval to be granted, a 

manufacturer must demonstrate that emissions will not be 

adversely affected by the use of the fuel additive or ignition 

improver. 

U O Otto-cvcle methanol vehicles and hybrid electric vehicles 

which use otto-cvcle methanol engines 

Mileaoe-accumulation and emission-testing fuel: For methanol 

vehicles and hybrid electric vehicles which use otto-cvcle 

methanol engines, fuel which meets the specifications 

listed in Title 13. CCR. Section 2292.1 or 2292.2 as 

applicable. 

U J Methanol-fueled diesel vehicles and hybrid electric 

vehicles which use methanol-fueled diesel engines 

Mileaoe-accumulation and emission-testing fuel: For methanol 

vehicles and hybrid electric vehicles which use methanolfueled diesel engines, fuel which meets the specifications 

listed in Title 13. CCR. Section 2292.1 or 2292.2 as 

applicable. 

(3) Fuel-flexible vehicles 

Mileaoe-accumulation fuel: For both durabilitv-data vehicles 

and emission-data vehicles, mileage accumulation shall be 

B-3 
P.66 

conducted with one fuel. For vehicles designed to operate 

on methanol, a fuel that meets the specifications listed in 

Title 13. CCR. Section 2292.? shall be used. 

Fmission-test fuel: Case fl) For regular emission testing, fuel 

that meets the specifications listed in Title 13. CCR. 

Section 2292.2. 

Case (2) For the testing reguired under 6.a.3.(D). of 

these procedures, exhaust emission tests fexhaust QMHCE for 

non-TLEVs. non-LEVs. and non-ULEVs. exhaust NMOG for TLEVs. 

LEVs. and ULEVs. exhaust formaldehyde, exhaust CO. and 

exhaust NO ) shall be conducted at the specified mileage 

intervals flsing: fi) fuel that meets the specifications 

listed in Title 13. CCR. Section 2292.2 where 85 percent 

methanol fuel is required: and Mi ) a blend of fuel that 

meets the specifications listed in Title 13. CCR. Section 

2292.2 and commercially available unleaded gasoline, such 

that the final blend is composed of 35 volume percent 

methanol (plus or minus 1 volume percent of total blend) 

where 35 percent methanol fuel is reouired. In addition, 

complete sets of emission tests shall be conducted at 5.000 

miles. 50.000 miles and the final mileage point with 

commercially available unleaded gasoline. Gasoline meeting 

the specifications in paragraph fa) mav be used in the 

place. Qf any gasoline required in Case 2. 

(4) Alternative Blending gasoline. Gasoline as specified in 

paragraph fa) mav be used as an alternative for the blending 

gasoline specified in Section 2292.2 of Title 13. CCR. The Reid 

vaoor pressure specification for the gasoline specified in 

paragraph fa) mav be disregarded: however, the final blend test 

fuel for all testing reouiring fuel as specified in Section 

2292.2 of Title 13. CCR. must meet the Reid vaoor pressure 

reouirement as specified in Title 13. CCR. Section 2292.2. 

XI) The specification of the fuels to be used under paragraphs 

(e)(1). fe)f2). fe)f3) and fe)f4) of this section shall be 

reported in accordance with 86.090-21(b)f3) or 86.091-21fb)f3). 

12. Add new subparagraph (ef) to read: 

ff) Gaseous Fuel Specifications for 1988 Through 1993 Model 

Year Vehicles. 

(1) Gaseous fuels representative of commercial gaseous fuels 

which will be generally available through retail outlets in 

California or liquid petroleum gas having the ASTM D1835 or NGPA 

HD-5 specification shall be used in service accumulation. 

(2) Liquid petroleum gas having the ASTM D1835 or NGPA HD-5 

specification shall be used for exhaust and evaporative emission 

testing. 

(3) Natural gas representative of commercial natural gas which 

will be generally available through retail outlets in California 

shall be used for exhaust emission testing. 

B-4 
P.67 

(4) Written approval from the Administrator of the fuel 

specifications must be provided prior to the start of the 

testing. 

(5) For dedicated gaseous- and dual-fueled vehicles and for 

hybrid electric vehicles which use gaseous-fueled engines, the 

mileage accumulation fuel for both durability-data vehicles and 

emission-data vehicles shall be conducted with one fuel. For 

vehicles designed to operate on natural gas, natural gas which 

meets the requirements of (3) shall be used. For vehicles 

designed to operate on liquified petroleum gas, liquified 

petroleum gas which meets the requirements of (2) shall be used. 

f6) The specifications set forth in subparagraph fg) mav be 

used as an option for 1993 model-vear vehicles. 

13. Add new subparagraph fg) to read: 

Xi) Gaseous Fuel Specifications for 1994 and Subsequent Model 

Year Vehicles. 

Xl) Liouified petroleum gas meeting the specifications listed 

in Title 13. CCR. Section 2292.6 shall be used in service 

accumulation and for exhaust and evaporative emission testing. 

f2) Natural gas meeting the specifications listed in Title 13. 

CCR. Section 2292.5 shall be used in service accumulation and 

for exhaust emission testing. 

XI) For dedicated gaseous- and dual-fueled vehicles and for 

hybrid electric vehicles which use gaseous-fueled engines, the 

mileage accumulation fuel for both durabi1itv-data vehicles and 

emission-data vehicles shall be conducted with one fuel. F_Q£_ 

vehicles designed to operate on natural gas, natural gas which 

meets the requirements of (2) shall be used. For vehicles 

designed to operate on liouified petroleum gas, liouified 

petroleum gas which meets the requirements of fl) shall be used. 

B-5 
P.68 

APPENDIX C 

Proposed Amendments to the California Exhaust Emission 

Standards and Test Procedures for 1985 and Subsequent Model 

Heavy-duty Diesel Engines and Vehicles 
P.69 

PROPOSED 

State of California 

AIR RESOURCES BOARD 

CALIFORNIA EXHAUST EMISSION STANDARDS AND TEST PROCEDURES 

FOR 1985 AND SUBSEQUENT MODEL 

HEAVY-DUTY DIESEL-ENGINES AND VEHICLES 

Adopted: 

Amended: 

Amended: 

Amended: 

Amended: 

Amended: 

Amended: 

April 8, 1985 

July 29, 1986 

January 22, 1990 

May 15, 1990 

December 26, 1990 

July 12, 1991 
P.70 

NOTE: This document is printed in a style to indicate amendments to the 

existing standards and test procedures. The amendments made in the present 

rulemaking are shown in under 1ine to indicate additions to the text and 

stMkeeat to indicate deletions. 

This document incorporates by reference various sections of the Code of 

Federal Regulations, some with modifications. The symbol "*****" means that 

the remainder of the federal text for a specific section, which is not shown 

in these procedures, has been included by reference, with only the printed 

text changed. The symbols "#####" mean that the remainder of the text of 

these procedures for a specific section, which is not shown in this 

amendment document, has not been changed. 
P.71 

CALIFORNIA EXHAUST EMISSION STANDARDS AND TEST PROCEDURES 

FOR 1985 AND SUBSEQUENT MODEL 

HEAVY-DUTY DIESEL-ENGINES AND VEHICLES 

# # # # # 

86.1313-90 Fuel specifications. April 11, 1989. 

# # # # # 

(b)(4)X_U Methanol fuel used in service accumulation of 1991 through 

1993 model-vear methanol-fueled diesel engines shall be representative 

of commercially available methanol fuel. Methanol used in fuel for 

exhaust emission testing of 1991 through 1993 model-vear methanolfueled diesel engines shall be chemical grade methanol._Ih£_ 

specifications set forth in subparagraph fb)f4)fii) mav be used as an 

option for 1993 model-vear engines. 

fbWaUii ) Methanol fuel used in service accumulation and exhaust 

emission testing for 1994 and subsequent model-vear methanol-fueled 

diesel engines shall meet the specifications in Title 13. CCR. 

sections 2292.1 or 2292.2 as applicable. Gasoline as specified in 

subparagraph 9fa) of the California Exhaust Emission Standards and 

Test Procedures for 1988 and Subsequent Model Passenger Cars. Lightdutv Trucks, and Med1um-dutv Vehicles mav be used as an alternative 

for the blending gasoline as specified in Section 2292.2 of Title 13. 

£TJL The Reid vaoor pressure specification for the blending gasoline 

mav be disregarded, however, the final blend test fuel for all testing 

reouirlno fuel as specified in Title 13. CCR. Section 2292.2 must meet 

the Reid vaoor pressure requirements as specified in Title 13. CCR. 

Section 2292.2. 

fb)f4Uii1) Fuel additives and ignition improvers intended for use in 

methanol test fuels shall be subject to the approval of the Executive 

Officer. In order for such approval to be granted, a manufacturer 

must demonstrate that emissions will not be adversely affected by the 

use of the fuel additive or Ignition improver. 

ADD SUBPARAGRAPH (Ee.) TO READ: 

(e) Natural Gas and Liquefied Petroleum Gas Test Fuel. 

(e)(1) Natural Gas Test Fuel. 

feUlU D Natural gas used in service accumulation for 1990 through 

1993 model-vear diesel engines shall be representative of commercial 

natural gas which is generally available. Natural gas meeting the 

specifications below, or substantially equivalent specifications 

approved by the Executive Officer, shall be used in exhaust emission 

testing for 1990 through 1993 model-vear diesel engines. The 

specifications set forth in subparagraph feUlUii ) mav be used as an 

option for 1993 model-vear engines. 

C-l 
P.72 

Natural Gas Emission Test Fuel Specification 

Specification 

Wobbe Number 

Value Tolerance 

1350 •/- 0.51 

Calculation 

Method 

ASTM D 1945 Using 

AGA Bulletin No. 

36 

Hydrocarbons (expressed as percent of total organic carbon present) 

Methane 881 •/- 0.51 

Ethane 81 •/- 0.31 

C~ and higher HC 41 +/- 0.21 

Cc and higher HC 0.51 maximum 

Total unsaturated HC 0.51 maximum 

Other Species (expressed as mole percent) 

ASTM D 

ASTM D 

ASTM D 

ASTM D 

ASTM D 

1945 

1945 

1945 

1945 

2650 

Hydrogen 

Carbon Monoxide 

Other Requirements 

0.11 

0.11 

maximum 

maximum 

ASTM 0 2650 

ASTMT) 2650 

1. Free from liquids over the entire range of temperatures and 

pressures encountered In the engine and fuel system. 

2. Free from solid particulate matter. 

feUlUI D Natural gas used 1n service accumulation and exhaust 

emission testing for 1994 and subsequent model-vear diesel engines 

shall meet the specifications listed in Title 13. CCR. Section 2292.5, 

(e)(2)Xil 

Liquefied Petroleum Gas Test Fuel, Liquefied petroleum gas used in 

service accumulation for 1990 through 1993 model-vear diesel engines 

shall be representative of commercial liquefied petroleum gas which is 

generally available through retail outlets. Liquefied petroleum gas 

used 1n exhaust and evaporative emission testing for 1990 through 1993 

model-year diesel engines shall conform to NGPA HD-5 specification. 

The specifications set forth in subparagraph fe)fl)fii) mav be used as 

an option for 1993 model-vear engines. 

(e)(2)(H) Liquefied petroleum gas used in service accumulation and in 

exhaust and evaporative emission testing for 1994 and subsequent modelvear diesel engines shall meet the specifications listed in Title 13. 

CCR. Section 2292.6. 

(e)(3) 

The specification range of the fuels to be used under paragraphs 

(e)(1) and (e)(2) of this section shall be reported in accordance with 

86.090-21(b)(3). 

C-2 
P.73 

APPENDIX D 

Proposed Amendments to the California Exhaust Emission 

Standards and Test Procedures for 1987 and Subsequent Model 

Heavy-duty Otto-cycle Engines and Vehicles ^ 
P.74 

PROPOSED 

State of California 

AIR RESOURCES BOARD 

CALIFORNIA EXHAUST EMISSION STANDARDS AND TEST PROCEDURES 

FOR 1987 AND SUBSEQUENT MODEL 

HEAVY-DUTY OTTO-CYCLE 

ENGINES AND VEHICLES 

Adopted: 

Amended: 

Amended: 

Amended: 

Amended: 

Amended: 

Amended: 

April 25, 1986 

June 2, 1988 

January 22, 1990 

May 15, 1990 

December 26, 1990 

July 12, 1991 
P.75 

NOTE: This document is printed in a style to indicate amendments to the 

standards and test procedures. The amendments made in the present 

rulemaking are shown in underline to indicate additions to the text and 

stF4keeut to indicate deletions. 

This document incorporates by reference various sections of the Code of 

Federal Regulations, some with modifications. The symbol "*****" means that 

the remainder of the federal text for a specific section, which is not shown 

in these procedures, has been included by reference, with only the printed 

text changed. The symbols "#####" mean that the remainder of the text of 

these procedures for a specific section, which is not shown in this 

amendment document, has not been changed. 
P.76 

CALIFORNIA EXHAUST EMISSION STANDARDS AND TEST 

PROCEDURES FOR 1987 AND SUBSEQUENT MODEL HEAVY-DUTY 

OTTO-CYCLE ENGINES AND VEHICLES 

# # # # # 

Subpart N, Emission Regulations for New Otto-cycle and Diesel Heavy-Duty 

Engines; Gaseous and Particulate Exhaust Test Procedures 

# # # # # 

86.1313-90 Fuel specifications. April 11, 1989. 

**** * 

(AU^M.- Methanol-Gasoline Fuel Specifications for 1993 Model-Year 

Engines. Methanol fuel used in service accumulation of methanolfueled otto-cycle engines shall be representative of commercially 

available methanol fuel. Methanol used in fuel for exhaust emission 

testing shall be chemical grade methanol. For fuel-flexible vehicles 

and engines, the gasoline used for blending fuel for use in service 

accumulation shall be representative of commercial regular unleaded 

gasoline which will be generally available through retail outlets. 

Gasoline used for blending fuel for use in emission testing shall 

conform with the unleaded gasoline specification noted in paragraph 

(a) above. The requirements set forth in subparagraph fa)(3)fii) mav 

be used as an option for 1993 model-vear vehicles. 

faU3UH ) Methanol-Gasoline Fuel Specifications for 1994 and 

Subsequent Model-Year Engines. Methanol fuel used in service 

accumulation and exhaust emission testing of methanol-fueled ottocvcle engines shall meet the specifications listed in Title 13. CCR. 

sections 2292.1 or 2292.2 as applicable. For fuel-flexible vehicles 

and engines, the gasoline used for blending fuel for use in service 

accumulation and emission testing, except for that gasoline used to 

create the fuel blend as specified in Title 13. CCR. Section 2292.2. 

shall be representative of commercial unleaded gasoline which will be 

generally available through retail outlets. Gasoline as specified in 

paragraph fa) above mav be used as an alternative for the blending 

gasoline specified in Section 2292.2 of Title 13. CCR. The Reid 

vaoor pressure specification for the gasoline specified in paragraph 

fa) above mav be disregarded: however, the final blend test fuel for 

all testing requiring fuel as specified in Section 2292.2 of Title 

13. CCR. must meet the Reid vaoor pressure requirement as specified 

in Title 13. CCR. Section 2292.2. 

fa)f3)(111) Fuel additives and ignition improvers intended for use in 

methanol test fuels shall be subject to the approval of the Executive 

Officer. In order for such approval to be granted, a manufacturer 

must demonstrate that emissions will not be adversely affected by the 

use of the fuel additive or ignition Improver. 

ADD SUBPARAGRAPH (e) TO READ: 

(e) Natural Gas and Liquefied Petroleum Gas Test Fuel 

D-1 
P.77 

(e)(l)Xi). Natural Gas Test Fuel. Natural gas used in service 

accumulation for 1990 through 1993 modal-year engines shall be 

representative of commercial natural gas which is generally 

available. Natural gas meeting the specifications below, or 

substantially equivalent specifications approved by the Executive 

Officer, shall be used in exhaust emission testing for 1990 through 

1993 model-vear engines. The SPeClfJCfltJQnS Set forth in 

subparagraph fe)fl)fii) mav be used as an option for 1993 model-vear 

vehicles. 

Natural Gas Emission Test Fuel Specification 

Specification Value Tolerance Calculation 

Method 

Wobbe Number 1350 •/- 0.51 ASTM 0 1945 

Using AGA 

Bulletin 

No. 36 

Hydrocarbons (expressed as percent of total organic carbon present) 

Methane 

Ethane 

C, and higher HC 

Cg and higher HC 

Total unsaturated HC 

881 

81 

41 

0.51 

0.51 

•/- 0.51 

•/- 0.31 

•/- 0.21 

max imum 

maximum 

Other Species (expressed as mole percent) 

Hydrogen 

Carbon Monoxide 

0.11 

0.11 

maximum 

maximum 

ASTM 

ASTM 

ASTM 

1945 

1945 

1945 

ASTM 0 1945 

ASTM D 2650 

ASTM D 2650 

ASTM D 2650 

Other Requirements 

1. Free from liquids over the entire range of temperatures and 

pressures encountered 1n the engine and fuel system. 

2. Free from solid particulate matter. 

felMHi n Natural gas used 1n service accumulation and in exhaust 

emission testing for 1994 and subsequent model-vear engines shall 

meet the specifications listed in Title 13. CCR. Section 2292.5. 

(e)(2)XU 

Liquefied Petroleum Gas Test Fuel. Liquefied petroleum gas used in 

service accumulation for 1990 through 1993 model-vear engines shall 

be representative of commercial liquefied petroleum gas which is 

generally available through retail outlets. Liquefied petroleum gas 

used in exhaust and evaporative emission testing for 1990 through 

1993 model-vear engines shall conform to NGPA HD-5 specification. 

The specifications set forth in subparagraph feU2)M1 ) mav be used 

as an option for 1993 model-vear vehicles. 

D-2 
P.78 

fe)f?)fii) Liquefied petroleum gas fuel that will be used in service 

accumulation and in exhaust and evaporative emission testing for 1994 

and subsequent model-vear engines shall meet the specifications 

listed in Title 13. CCR. Section 2292.6. 

(e)(3) 

The specification range of the fuels to be used under paragraphs 

(e)(1) and (e)(2) of this section shall be reported in accordance 

with 86.090-21(b)(3). 

# # # # # 

D-3 
P.79 

APPENDIX E 

ASTM Draft Compression Ignition Methanol Fuel Specification 7/91-1 
P.80 

:ompression Ignition Methanol Fuel Specification, '91-1, ?aae 1 

This document is part of the ASTM standards process and is 

for ASTM committee use only. It shall not be reproduced 

j ^ ,-jt -Gsirj* or circulated or quoted, in whole or in part, outside the 

|§3r *ft B* •

 AS TM committee activities except with the approval of the 

'*^. j^.2 U chairman of the committee having jurisdiction or the 

L' '" President of the Society 

Committee D02.E2 Draft 3.0 Date 7/01/91 

PROPOSED STANDARD SPECIFICATION FOR , 

COMPRESSION IGNITION METHANOL BASED FUEL* 

1. SCOPE 

1.1 This proposed standard specification covers a compression 

ignition methanol fuel which contains less than 2% hydrocarbons. 

The significance of this specification is shown in Appendix XI. 

1.2. This specification is intended for use by purchasing 

agencies in formulating specifications for purchases of compression 

ignition methanol fuel for fleet use. 

1.3 This specification, unless othervise provided by agreement 

between the purchaser and the supplier, prescribes the required 

properties of compression ignition methanol fuel at the time and 

place of delivery. 

2. REFERENCED DOCUMENTS 

2.1 ASTM Standards 

D 56 Test Method for Flash Point by Tag Closed Tester2 

D 381 Test Method for Existent Gum in Fuels by Jet Evaporation2 

1. This proposed specification is under the jurisdiction of ASTM 

Committee D02 on Petroleum Products and Lubricants and is the 

direct responsibility of D02.E on Diesel, Burner and Turbine Fuels 

2. Annual Book of Standards, Volume 5.01 
P.81 

:cmpression Ignition Methanol Fuel Specification. ~

/9l-l. Pace 2 

3 391 Test Method for Specific Gravity, Apparent, of liquid 

Industrial Chemicals3 

D 1078 Test Method for Distillation Range of Volatile 

4 Organic Liquids 

4 D 1152 Standard Specification for Methanol 

D 1613 Test Method for Acidity in Volatile Solvents and Chemical 

Intermediates Used in Paint, Varnish, Lacquer, and Related 

4 

Products 

D 2276 Test Methods for Particulate Contaminant in Aviation 

2 

Turbine Fuels 

D 2622 Test Method for Sulfur in Petroleum Products (X-ray 

Spectrographic Method) 

D 2988 Test Method for Water-Soluble Halide Ion in 

5 

Halogenated Organic Solvents and Their Admixtures 

D 3231 Test Method for Phosphorus in Gasoline 

D 3237 Test Method for Lead in Gasoline by Atomic Absorption 

Spectrometry 

D 3244 Standard Practice for Utilization of Test Data to Determine 

2 

Conformance with Specifications 

D 4057 Standard Practice for Manual Sampling of Petroleum Products 

D 4176 Test Method for Free Water and Particulate Contamination in 

Distillate Fuels (Clear and Bright Pass/Fail Proceedings'

3 

D 4815 Test Method for Determining Cl or C4 Alcohols and MTBE in 

3 

Gasoline by Gas Chromatography 

1 Annual Book of Standards, Volume 5.01 

2 Annual Book of Standards, Volume 5.02 

3 Annual Book of Standards, Volume 5.03 

4 Annual Book of Standards, Volume 6.03 

5 Annual Book of Standards, Volume 15,05 

DRAFT 
P.82 

Compression Ignition Methanol Fuel Specification. ~/°l-l. Page 2 

Z 2 03 Test Method for Water Using Karl Fischer Reagent* 

Z 3 00 Recommended Practice for Sampling Industrial Chemicals" 

2.TERMINOLOGY 

3.1 Definitions: 

3.1.1 Methanol (99.85% grade) with impurities and water as 

defined in D1152, Standard Specification for Methanol 

(Methyl alcohol). 

3.2 Description of Terms Specific to this Proposed Specification 

3.3.1 Compression Ignition - a process of rapid oxidation 

(combustion) of a fuel as a result of being injected into 

the high temperature, pressure conditions of the 

combustion chamber of an internal combustion engine. 

3.2.2 Compression Ignition Methanol Fuel - methanol 

containing a performance and safety additive, and 

impurities including water. Nominally 96%, by volume, 

minimum methanol content. 

4. MATERIALS AND MANUFACTURE 

4.1 Additives may be added to methanol for purposes of 

identification and safety, and to enhance engine durability and 

performance. Additive packages may be classified by function as 

performance and safety, and might, for example, contain the 

following types of components: 

1 Annual Book of Standards, Volume 6.03 

2 Annual Book of Standards, Volume 15.05 

DRAFT 
P.83 

Compression Ignition Methanol Fuel Specification."" '91-1. ?aae 4 

4.1.1 Performance Additives 

4.1.1.1 Detergent 

4.1.1.2 Corrosion Inhibitor 

4.1.1.3 Fuel System Lubricant 

4.1.2 Safety Additives 

4.1.2.1 Coloring Agent 

4.1.2.2 Odorous additive 

4.1.2.3 Taste bittering compound 

4.1.2.4 Luminosity additive 

4.2 In transportation and storage, compression ignition 

methanol fuel should not be exposed to those plastics, polymers, or 

other materials known to be swollen or dissolved by methanol. The 

use of any material for storage or transport which is leachable by 

methanol, such as phthalate esters, must be avoided. 

5. CHEMICAL COMPOSITION AND PHYSICAL PROPERTIES 

5.1 Compression ignition methanol fuel shall conform to the 

requirements listed in Table 1 as supplied at the time and place of 

delivery. The Specified Limits of Table 1 are based on a single 

determination and are to be considered as Critical Specifications by 

D 3244. 
P.84 

Compression Ignition Methanol Fuel Specification, "/91-1, Page = 

TABLE 1 

DETAILED CHEMICAL AND PHYSICAL PROPERTIES 

OF COMPRESSION IGNITION METHANOL FUEL 

CONSTITUENT 

Distillation Range 

C, max, at 95% by 

volume distilled 

Other alcohols and 

Ethers, m%, max 

Hydrocarbons, Gasoline 

or Diesel Fuel Derived 

m %, max 

SPECIFIED LIMIT 

4.0 

(Must include 64.6 - 0.1

 WC) 

Flash Point, °C 

Specific Gravity, 

Apparent 

Appearance 

Acidity, ra %, max 

Water, m%, max 

Total Particulates, 

mg/L, max 

Gum, heptane washed, 

mg/L, max 

Total Chlorine, as 

Chloride, mg/L, max 

Lead, mg/L, max 

Phosphorus, mg/L, max 

Sulfur, m %, max 

Additives 

10 + 2 

ANALYTICAL 

METHOD 

D 1078 

D 4815 

Test Method 

being Developed 

D 56 

0.792 i 0.002 @ 20/20 °C 

Free of Turbidity, Suspended 

Suspended Matter and Sediment 

0.03, as Acetic Acid 

0.30 

2 

2 

0.2 

0.01 

See Note 2 

D 891 

See Note 1 

D 

E 

D 

1613 

203 

2276 

D 381 

D 2988 

D 3237 

D 3231 

D 3120 

1. Visually determined at 25 °C by Procedure A of D 4176 unless 

otherwise agreed upon between buyer and seller. 

2. Additives may be added to compression ignition methanol fuel 

to enhance performance and safety aspects. See Section 4.1. 

DRAFT 
Compression ignition Methanol Fuel Specification, ~/91-l. Page 5 

5. SAMPLING 

6.1 Sample in accordance with ASTM Z 3 00 for simple liquids. 

Additional sampling instructions may be found in the sections cf 

ASTM 4057 pertaining to gasoline and distillate fuels, however 

certain containers specified in these Practices should not be used 

due to metal contamination. The only approved container material 

for sampling methanol is glass. 

6.2" A minimum sample size of about 1 L or 1 U.S. qt is 

recommended. 

7. NUMBER OF TESTS AND RETESTS 

7.1 The Specified Limits of this specification are based on a 

single test analysis and are to be considered as critical 

specifications based upon the criteria of D 3244. Resolution of 

disputes over whether a material lot conforms to this specification 

may be made using this Standard Practice. 

7.2 The number of samples and resamples taken is dependent upon 

the method of delivery (tank truck, railcar, or pipeline, for 

example), the size and configuration of the tankage, and by 

agreement of the supplier and user. 

DRAFT 
P.86 

Compression Ignition Methanol Fuel Specification, "/91-1, Page 7 

3. TEST METHODS 

3.1 The properties described in this proposed specification 

shall be determined in accordance with the following methods. 

NOTE 1 ASTM test methods have not yet been developed for all the 

properties specified. In addition, the appropriateness of 

some test procedures at the constituent concentrations 

required has not been fully demonstrated. 

8.1.1 Distillation Range - Test Method D1078. Report 

corrected temperatures for initial and 95% volume off boiling 

points. The temperature range must include the the standard boiling 

point of methanol. 

8.1.2 other Alcohols and Ethers - Test Method D 4815. 

Although primarily applicable to gasoline blends, the test method 

may be used satisfactorily, without modification, for compression 

ignition methanol. 

3.1.3 Hydrocarbons, Gasoline or Diesel Fuel Derived - The 

test method for this property is based on gas chromatography, 

however the specific methodology is being developed. 

8.1.4 Specific Gravity, Apparent - Test Method D 891. This 

test method includes both hydrometer and pycnometer methods. While 

both provide adequate precision for this specification, the 

pycnometer will be considered the referee method. 

DRAFT 
Compression Ignition Methanol Fuel Specification. "V91-1. ?aae S 

8.1.5 Appearance - Test Method D 417 6. Other procedures may 

be used, however, D4176, Procedure A will be considered the referee 

method. 

8.1.6 Acidity - Test Method D 1613 

8.1.7 Water Content - Test Method E 203 

8.1.8 Total Particulates - Test Method D 2276. This method 

must be modified for methanol analysis. The cellulose acetate 

membrane filter specified by the method is replaced with a nylon 

filter. Pore size continues to be 0.8 micron. 

NOTE 2: Cellulose acetate dissolves in methanol. 

8.1.9 Existent Gum in Fuels by Jet Evaporation - Test Method 

D 3 81. This test method provides for determination of existent and 

unwashed grams in motor gasoline and aircraft fuel. For this 

specification, the procedure for heptane washed existent gums in 

motor gasoline should be followed. 

8.1.10 Total Chlorine as Chloride - Test Method D 2988. 

This method requires verification of it's appropriateness with 

methanol. 

8.1.11 Lead - Test Method D 3237. This test method provides 

for the determination of lead in gasoline. Blanks and calibration 

standards should be prepared in methanol. 

DRAFT 
P.88 

Compression Ignition Methanol Fuel Specification. ~/9l-l. Paoe 9 

8.1.12 Phosphorus - Test Method D 3 231 

3.1.13 Sulfur - Test Method D 2622 or D 3120. Sulfur may be 

determined by Method D 2 622 however calibration standards and blanks 

should be prepared in methanol. This method may not be applicable 

at the low levels specified in Table 1. Method D 312 0 is directly 

applicable and is considered the referee method. 

9 KEYWORDS 

9.1 Compression Ignition Engine Fuel 

9.2 Methanol Fuel 

9.3 Diesel Engine Fuel 

9.4 Alternate Fuel 

9.5 Specification 

DRAFT 
_E£9_ 

Compression Ignitio n Methanol Fuel Specification . "-'91-i. Page 10 

APPENDIX 

(Nonmandatory Information) 

XI SIGNIFICANCE OF PROPOSED ASTM SPECIFICATION FOR COMPRESSION 

IGNITION METHANOL FUEL 

Xl.l Introduction 

XI.1.1 A primary consideration in the development of the 

compression ignition methanol fueled engine was the capability to 

drastically reduce the exhaust particulate emissions compared to 

diesel fuel compression ignition engines. This specification .was 

developed to provide a fuel purity sufficient to maintain low 

exhaust emissions ahd provide maximum engine durability. Some 

impurities, such as hydrocarbons and other alcohols are less 

critical to these objectives and are therefore permitted at higher 

levels. Conversely, certain impurities, such as water, have been 

found to dramatically reduce engine fuel system durability, and 

therefore necessitating a lower specified limit. The intent of this 

specification is to provide a fuel of sufficient purity without 

requiring the higher purity levels associated with a chemical grade 

product such as specified in D 1152. 

DRAFT 
P.90 

Compression Ignition Methanol Fuel Specification. ~/9l-l. Page 11 

XI.2 Properties 

XI.2.1 The Distillation Range of compression ignition methanol 

fuel specifies a boiling range which is dependent upon methanol 

content. The nominal boiling point of methanol is 

64.6 C. A 4 C temperature range is permitted to be consistent 

with other specified limits. 

XI.2.2 Other alcohols and ethers are permitted up to 2% mass 

maximum. Small amounts of various alcohols and ethers are 

anticipated in the manufacturing process. At the specified limit 

not detriment has been observed toward emissions or engine 

durability. 

XI.2.3 Hydrocarbon impurities are generally associated with 

handling practices. Compression ignition methanol fuel is 

frequently distributed through the same pipeline or bulk delivery 

system as other fuel products. Hydrocarbons above 2%, mass 

adversely impacts the particulate exhaust emission characteristics 

of the compression ignition methanol engine. If present, these 

hydrocarbon impurities are restricted to gasoline or diesel fuels. 

High boiling hydrocarbons such as from crude oil or lubricating oils 

are not permissible due to fuel injection system fouling and 

combustion deposits. 

XI.2.4 Flash point is important from a safety standpoint. 

Large quantities of highly volatile impurities such as gasoline can 

reduce flash point thereby increasing the flamability hazards. 

DRAFT 
P.91 

Compression Ignition Methanol Fuel Specification. 7/91-1, Page 12 

XI.2.5 Specific gravity provides a fast and relatively simple 

test for purity of compression ignition methanol fuel. The presence 

of water will tend to increase specific gravity, while other 

impurities will reduce it. This test alone, however, is not 

sufficient to determine whether the fuel meets this specification. 

Specific gravity is also important to engine operation, as the fuel 

is delivered to the combustion chamber volumetrically. A low 

specific gravity may result in a lower engine power output. 

XI.2.6 The visual appearance of compression ignition methanol 

fuel indicates the presence of impurities. Turbidity, 

discoloration, or sediment are indication of poor fuel quality and 

may adversely effect the operation of the engine. 

XI.2.7 Acidity is a measure of the concentration of low 

molecular weight organic acids such as acetic and formic acids 

which, when combined with water, are highly corrosive to many 

metals. Analysis of typical methanol fuel samples has shown acidity 

content as high as 0.005 % mass. The specification permits 0.03 % 

mass maximum which represents a level estimated to have a potential 

impact on engine fuel system durability. 

XI.2.8 Water is the most critical impurity identified as 

impacting engine durability and operation. Laboratory testing has 

revealed that methanol fuel containing water contents above 0.3 0% 

have 

DRAFT 
Compression Ignition Methanol Fuel Specification. 7/91-1. Page 13 

7 to 3 times the potential of plugging fuel injector tips than water 

contents below this concentrations. In field engines reduced 

injector life due to plugging has been identified when water 

contents exceed 0.30%. 

XI.2.9 Total Particulates content represent insoluble material 

which may be introduced through distribution, storage, or handling. 

Particulate impurities greater than the amounts specified will 

result in shorter fuel filter life. 

XI.2.10 Residues remaining in fuel methanol after evaporation 

may be determined by the Test Method for Existent Gums. Such 

residues represent impurities introduced through the methanol fuel 

distribution system, specifically, from hoses, tanks, and linings. 

They are generally materials of relatively high boiling points which 

have been found to foul engine fuel injectors in field engines. 

XI.2.11 Chlorine containing impurities, whether inorganic, 

chlorides, or organic are corrosive to many metals in very low 

concentrations. 

XI.2.12 Lead and Phosphorus have been found to poison exhaust 

aftertreatment catalysts used in gasoline fueled vehicles. It is 

anticipated that such devices will also be utilized on methanol 

fueled vehicles to further control exhaust emissions. 

XI.2.13 Sulfur content is controlled to protect against engine 

wear, deterioration of engine oil, corrosion of exhaust system 

?arts, and exhaust catalyst deactivation. 

DRAFT 
P.53 

APPENDIX F 

ASTM D-2 Proposal P-232, Draft 8-9-91: 

Fuel Methanol (M-85) for Automotive Spark-ignition Engines 
P.94 

Draft 8-9-91 

D-2 Proposal PXXX This document is part of the 

ASTM standards process and is for 

ASTM committee use only. It shall 

not be reproduced or circulated 

or quoted, in whole or in part 

outside of ASTM committee 

activities except with the approval 

of the chairman of the committee 

having jurisdiction or the President 

of the Society. 

This proposed specification has no status as an ASTM standard and is published 

on behalf of the sponsoring committee for information only for a maximum of two 

years. Comments are solicited and should be addressed to the American Society 

for Testing and Materials, 1916 Race St. , Philadelphia, Pa 19103. When 

referencing this document, the word Proposal must precede the P designation. 

Proposed specification for 

FUEL METHANOL (M85) FOR AUTOMOTIVE SPARK-IGNITION ENGINES 1 

1. Scope 

1.1 This proposed specification covers a fuel blend, nominally 85% by 

volume methanol and 15% by volume hydrocarbons for use in ground vehicles with 

automotive spark-ignition engines. Appendix XI discusses the significance 

of the properties specified. Appendix X2 presents the current status in 

the development of a luminosity test procedure for M85. 

1 .2 The values stated in SI units are the standard. 

1 .3 The following safety hazard caveat pertains only to the test method 

portions, Annexes Al , A2, A3 and Appendix X2 of this proposed specification. 

This proposed specification does not purport to address all of the safety 

problem associated with its use. It is the responsibility of the user this 

proposed specification to establish appropriate safety and health practices 

and determine the applicability of regulatory limitations prior to use. 

2. Referenced Documents 

2.1 ASTM Standards: 

D 86 Method for Distillation of Petroleum Products 2 

D 130 Method for Detection of Copper Corrosion from Petroleum Products 
P.95 

by the Copper Strip Tarnish Test 2 

D 512 Standard Test Methods for Chloride Ion in Water 7 

D 525 Test Method for Oxidation Stability of Gasoline (Induction Period 

Method) 2 

D 1193 Specification for Reagent Water 7 

D 1266 Test Method for Sulfur in Petroleum Products (Lamp Method) 2,3 

D 1353 Test Method for Nonvolatile Matter in Volatile Solvents for 

Use in Paint, Varnish, Lacquer, and Related Products 5 

D 1613 Test Method for Acidity in Volatile Solvents and Chemical 

Intermediates Used in Paint, Varnish, Lacquer and Related Products 5 

D 2622 Test Method for Sulfur in Petroleum Products by X-Ray Spectrometry 3 

D 2988 Test Method for Water-Soluble Halide Ion in Halogenated Organic 

Solvents and Their Admixtures 6 

D 3116 Test Method for Trace Amounts of Lead in Gasoline 3 

D 3120 Test Method for Trace Quantities of Sulfur in Light Liquid 

Petroleum Hydrocarbons by Oxidative Microcoulometry 3 

D 3229 Test Method for Low Levels of Lead in Gasoline by X-Ray 

Spectrometry 3 

D 3231 Test Method for Phosphorus in Gasoline 3 

D 3237 Test Method for Lead in Gasoline by Atomic Absorption 

Spectrometry 3 

D 4057 Practice for Manual Sampling of Petroleum and Petroleum Products.4 

D 4177 Standard Method for Automatic Sampling of Petroleum and Petroleum 

Products 4 

D 4307 Practice for Preparation of Liquid Blends for use as Analytical 

Standards 

D 4626 Practice for Calculation of Gas Chromatographic Response Factors 

D 4814 Standard Specification for Automotive Spark-Ignition Engine Fuel 4 

D 4815 Test Method for Determination of Cl to C4 Alcohols and MTBE 

in Gasoline by Gas Chromatography 4 

D 4953 Test Method for Vapor Pressure of Gasoline and Gasoline-Oxygenate 

Blends (Dry Method) 4 

E 203 Test Method for Water Using Karl Fischer Reagent 6 

E 355 Practice for Gas Chromatography Terms and Relationships 

E 1145 Standard Specification for Denatured Ethyl Alcohol, Formula 3A 

ES 14 Emergency Standard Test Method for Vapor Pressure of Petroleum 

Products (Automatic Method) 

ES 15 Emergency Standard Test Method for Vapor Pressure of Petroleum 

Products (Mini Method) 

RR D-2-1007 Manual on Determining Precision Data for ASTM Methods on 

Petroleum Products and Lubricants 

3. Terminology 

3.1 Definitions: 

3.1.1 methanol, n-- methyl alcohol, the chemical compound CH30H. 

3.2 Description of Terms Specific to this Specification: 

DRAFT 
P.96 

•_V -t3.2.1 hydrocarbon--the hydrocarbon component in a methanol-hydrocarbon 

blend. 

3.2.2 fuel methanol (M85)-- a blend of methanol and hydrocarbons of which 

the methanol portion is nominally 85 volume %. 

3.2.3 higher alcohols — aliphatic alcohols of the general formula 

°CnH(2 n + l)OH with n being 2 to 8. 

4. M85 Fuel Performance Requirements 

4.1 Fuel Methanol (M85) shall conform to the following requirements. 

Methanol plus higher alcohols, minimum, volume 

Higher Alcohols (C2-C8) maximum, volume % 

Hydrocarbon/aliphatic ether blends containing 

up to 2.7 wt% oxygen, volume % 

Vapor Pressure, kPa (psi) 

Luminosity 

Acidity, as acetic acid, maximum, mass % 

Nonvolatile Matter, maximum, mg/100 mL 

Total Chlorine as Chlorides, maximum, mass % 

Lead, maximum, grams/litre 

Phosphorus, maximum, grams/litre 

Appearance 

Water, maximum, mass % 

Sulfur, maximum, mass ° 

85 

2 

13-15 

Summer 48-62 (7.0-9.0) 

Intermediate 62-75 (9.0-11.0) 

Winter 75-90 (11.0-13.0) 

Shall produce a luminous 

flame throughout the entire 

burn duration. 

0.005 

5 

0.0002 

0.002 

0.0002 

The product shall be visibly 

free of suspended or 

precipitated contaminants 

(clear and bright). This 

shall be determined at indoor 

ambient temperatures unless 

otherwise agreed upon between 

the supplier and the 

purchaser. 

0.5 

0.01 

Note 1 Most of the requirements cited are based on the best technical 

information currently available. Requirements for Sulfur, Phosphorus, and Lead 

are based on the use of gasoline defined in Specification D 4814 at the 15 

volume % level and the understanding that control of these elements will 

affect catalyst lifetime, especially if base metal catalysts are used with 

dedicated M85 vehicles. As greater experience is gained from field use of 

M85 vehicles, it is expected that many of these requirements will change 

to better reflect performance requirements. 

DRAFT 
_P.9Z_ 

4.1.1 Summer class volatility shall be used in those geographical areas 

and times indicated for A, A/B, B/A and B volatility class fuels in Table 2 of 

Specification D 4814. Intermediate class volatility shall be used in 

those areas and times for B/C, C/B, C, C/D and D/C volatility fuels. Winter 

class shall be used for those geographical areas and times indicated for 

D, D/E, E/D and E volatility fuels. 

4.1.2 The hydrocarbons used shall have a final maximum boiling point of 

225 deg C by Method D 86, oxidation stability of 240 minutes minimum 

by Test Method D 525 and No.l maximum copper strip corrosion by Method D 130. 

The hydrocarbons may contain aliphatic ethers as blending components as are 

customarily used for motor fuel. 

Note 2 Use of gasoline containing 30 volume % aromatics of typical carbon 

number distribution for the non-methanol portion of the M85 has been generally 

demonstrated to meet the luminosity requirement. Some commercially available 

gasolines at 30 volume o aromatics level have been shown not to meet the 

luminosity requirement. 

5. Sampling 

5.1 Sample in accordance with Practice D 4057, except that water displacement 

(10.3.1.8 of Practice D 4057) must not be used. 

5.2 Where practical, M85 should be sampled in glass containers. If samples 

must be collected in metal containers, do not use soldered metal 

containers. This is because the soldering flux in the containers 

and lead in the solder can contaminate the sample. Plastic containers 

should be avoided. 

5.3 A minimum sample size of about 1 L or 1 U.S. qt is recommended. 

G. Test Methods 

6.1 The requirements enumerated in this proposed specification shall be 

determined in accordance with the following methods: 

Note 3 The appropriateness of ASTM methods cited has not been demonstrated 

for use with M85. In addition, test methods proposed in the Annexes and 

Appendices are in the developmental stages or lack precision determinations. 

6.1.1 Methanol- Annex Al . Verification of the appropriateness of this method 

is underway. A draft procedure for the method as proposed for Fuel Methanol 

(M85) is attached as Annex A1 . 

DRAFT 
P.98 

6.1.2 Hydrocarbon- Test Method D 4815 has been used to determine higher 

alcohols, methyl tertiary butyl ether (MTBE), and water, if the GC 

is equipped with a thermal conductivity detector. As an alternative, 

water can be determined by Karl Fischer (see 6.1.10). The 

concentration of methanol, other alcohols, MTBE and water can be added, 

and the sum subtracted from 100 to get the percent of hydrocarbons. 

An alternative method which yields the sum of hydrocarbons and MTBE 

is contained in Annex A2. 

6.1.3 Vapor Pressure- Test Methods D 4953, ES 14, or ES 15. 

6.1.4 Luminosity- Appendix X2 contains a procedure for measuring 

the luminosity of M85 fuel. However, lack of a suitable criteria 

for establishing the relevancy of the procedure makes it unusable 

as the basis of a specification at this time. It is intended that a 

test will be developed which will alleviate the necessity of a compositional 

criteria in order to meet the luminosity requirement. 

6.1.5 Acidity- Test Method D 1613. 

6.1.6 Nonvolatile Matter- Test Method D 1353. 

6.1.7 Total Chlorine as Chloride- Test Method D 3120 modified to utilize 

a chloride sensitive microcoulometric detector has been used for total 

chlorine at the levels specified in this specification. Inorganic Chloride 

can be determined by Test Methods D 512 C or D 2988. An alternate method 

for inorganic chloride is found in Annex A3. 

6.1.8 Lead - Test Methods D 3116, D 3237 or D 3229. With Test Method 

D 3229, the calibration standards shall be prepared using methanol as the 

solvent to prevent errors caused by large differences in carbon-hydrogen 

ratios. 

6.1.9 Phosphorus- Test Method D 3231. 

6.1.10 Water- Test Method E 203. 

6.1.11 Sulfur- Test Methods D 1266, D 2622, or D 3120. With Test Method 

D 2622, the calibration standards shall be prepared using methanol as the 

solvent to prevent carbon-hydrogen ratio caused errors. 

7. Key Words 

7.1 automotive spark-ignition engine fuel; methanol; M85; copper corrosion; 

oxidation stability; sulfur; acidity; water; chloride; total chlorinephosphorus; vapor pressure; lead; hydrocarbon; luminosity; 

nonvolatile matter; alcohol; oxygenates; MTBE; volatility; 

DRAFT 
P.99 

fuel methanol (M85) for automotive spark-ignition engines, ether 

1. This proposed specification is under the jurisdiction of Committee D-2 on 

Petroleum Products and Lubricants and is the direct responsibility of 

Subcommittee D02.A on Gasoline. Reference to the following documents is to 

the latest issue unless otherwise specified. 

2. Annual Book of ASTM Standards, Vol 05.01. 

3. Annual Book of ASTM Standards, Vol 05.02. 

4. Annual Book of ASTM Standards, Vol 05.03. 

5. Annual Book of ASTM Standards, Vol 06.03. 

6. Annual Book of ASTM Standards, Vol 15.05. 

7. Annual Book of ASTM Standards, Vol 11.01. 

JMD:jmd 

August 9, 1991 

Doc# DRAFT D0710005 

RAFT 
P.1 

Annexes 

(Mandatory Information i 

Al. PROPOSED TEST METHOD FOR DETERMINATION OF METHANOL 

IN FUEL METHANOL (M85) FOR AUTOMOTIVE SPARK-IGNITION ENGINES8 

Al.l. Scope 

A1.1.1. This proposed test method covers a procedure for determination of methanol in fuel methanol (M85) 

by Gas Chromatography. This proposed test method is appropriate for fuels containing 75 to 95 

volume & methanol. 

Al.1.2. The values stated in acceptable SI units are io be regarded as the standard. 

A 1.2. Terminology 

A 1.2.1. Descriptions of Terms Specific to this Proposed Test Method 

Al.2.1.1. Low Volume Connector - special union for connecting two lengths of tubing 1.6mm I.D. and 

smaller also referred to as a zero dead volume union. 

A 1.2.1.2. Split Ratio - in gas chromatography using capillary columns, the ratio of the total flow of the 

carrier gas to the sample inlet vs the flow of carrier gas to the capillary column. 

Al.l 1.3. WCOT - abbreviation for a type of capillary column, wall coated open tubular, used in gas 

chromatography. This type of column is prepared by coaung the inside of the capillary with 

a thin film of stationary phase. 

A 1.2.1.4. TCEP - 123-tris-2-cyanoethoxypropane. a gas chromatographic liquid phase. 

A 1.3. Summary of Proposed Test Method 

A 1.3.1. An internal standard, tertiary amyl alcohol, is added to the sample which is then introduced into a 

gas chromatograph equipped with two columns and a column switching valve. The sample passes 

into the first column, a polar TCEP column that elutes lighter hydrocarbons to vent and retains the 

oxygenated and heavier hydrocarbons. 

8

 This proposed test method is under the jurisdiction of ASTM Committee D-2 on Petroleum Products and 

Lubricants and is the direct responsibility of Subcommittee D02.04 on Hydrocarbon Analysis. 

DRAFT 
P.2 

Methanol in Methanol-Based Fuels Page 2 

A 1.3.2. After methvicvclopentane. but before methanol elutes from the polar column, the valve is switched 

to backflush the oxygenates onto a WCOT non-polar column. The methanol and internal standard 

elute from the non-polar column in boiling point order, before elution of any major hydrocarbon 

constituents. 

A 1.3.3. After the internal standard elutes from the non-polar column, the column switching valve is switched 

back to its original position to backflush the heavy hydrocarbons. The eluted components are 

detected by a flame ionization or thermal conductivity detector. The detector response, proportional 

to the component concentration, is recordei the peak areas are measured: and the concentration of 

methanol is calculated with reference to the internal standard. 

A 1.4. Significance and Use 

Al.4.1. The production of fuel methanol (M85) requires knowledge of tne methanol content to insure 

acceptable commercial fuel quality. The methanol content of M85 affects the performance of an 

automobile designed to run on M85. 

A 1.4.2. This proposed test method is applicable to both quality control in the production of fuel methanol 

(M85) and for the determination of fuel contamination. 

A 1.5. Apparatus 

Al.5.1. Chromatograph (see E 355 for specific descriptions and definitions) 

A 1.5.1.1. Gas chromatographic instrument operable at the conditions given in Table Al.l. and having a 

column switching and backflushing system equivalent to Figure Al.l. Carrier gas flow 

controllers must be designed for use at the required flow rates (Table Al.l). Pressure control 

devices and gauges must be designed for use at the pressures required. 

A 1.5.1.2. Detector - either a thermal conductivity detector (TCD) or flame ionization detector (FID) may 

be used. The system must have sufficient sensitivity and stability to sense absolute concentration changes of 0.01 volume percent of methanol or internal standard at me 50 volume 

percent level. 

Al.5.1.3. Switching and Backflushing Valve - A 10-pon valve, to be located within the gas chromatographic column oven, capable of performing the functions described in Section A 1.9 and illustrated in Figure Al.l. The valve must be of low volume design and not contribute significantly 

to chromatographic deterioration.9 

Al.5.1.4. Automatic valve switching device (strongly recommended to insure repeatable switching 

times) - a device synchronized with injection and data collection times. If no such device is 

A Valeo Model #CM-VSV-10-HT valve with 1.6 mm (1/16 in) fittings has been found satisfactory for 

this purpose. This is the valve being used in the majority of the analyses for the development of data for 

Section A1.13. A Valeo Model #C10W with 0.8 mm (1/32 in) fittings is recommended for use with 

columns of 0.32 mm I.D. and smaller. 
P.3 

Methanol in Methanol-Based Fuels * Page 3 

available, a stopwatch, started at the time of injecuon. should be used to indicate the proper 

valve switching ume. 

A 1.5.1.5. Injection System • a splitting-type inlet device. Split injection is necessary to maintain the 

actual chromatographed sample size within the limits of column and detector optimum 

efficiency and linearity. 

A 1.5.1.6. Sample Introduction System • any system capable of introducing a representative sample into 

the split inlet device. Microlitre syringes, automatic syringe injectors, and liquid sampling 

valves have been used successfully. 

A 1.5.2. Data Presentation or Calculation System: 

A 1.5.2.1. Recorder - a recording potentiometer or equivalent with a full scale deflection of 1 mV or less, 

and full scale response time of 1 second or less, with sufficient sensitivity and stability to meet 

the requirements of A 1.5.1.2. 

Al.5.2.2. Integrator or computer - devices capable of meeting the requirements of Al.5.1.2. and 

providing graphic and digital presentation of the chromatographic data. Peak heights or areas 

can be measured by computer, electronic integration or manual techniques. 

Al.5.3. Columns. Two columns are used. 

A1.5.3.1. Polar column - Any column with equivalent or better chromatographic efficiency and selectivity 

to that described in Al.5.3.1.1 can be used. The column must perform at the same temperature 

as required for the column in Al.5.3.2. This column performs a pre-separation of the 

oxygenates from volatile hydrocarbons in the same boiling point range. The oxygenates and 

remaining hydrocarbons are backflushed onto the non-polar column in Al.5.3.2. 

Al.5.3.1.1. TCEP micro-packed column10 - 560 mm (22 in) x 1.6 mm (1/16 in) O.D. x 

0.38 mm (0.015 in) ID stainless steel tube packed with 0.14 to 0.15 g of 20% 

(wt/wt) TCEP on 80/100 mesh Chromosorb P(AW). This column is being used to 

develop Precision and Bias dau for Section A 1.13. 

Al.5.3.2. Non-polar (analytical) column - Any column with equivalent or better chromatographic 

efficiency and selectivity to that described in Al.5.3.2.1 and illustrated in Figure A12 can be 

used. 

Al.5.3.2.1. WCOT methyl silicone column - 30 meter (1.181 in) long x 0.53 mm (0.021 in) ID 

fused silica WCOT column with a 2.6 um film thickness of crosslinked methyl 

siloxane. This column is being used to develop Precision and Bias data for Section 

A1.13. 

10 Available from Hewlett j*acks«i' Ccmpaiiy. Avondale. PA. 

DRAFT 
P.4 

Methanol in Methanol-Based Fuels Page 4 

A 1.6. Reagents and Materials 

A1.6.1. Carrier Gas - Carrier gas appropriate to the type of detector used. Helium has been used successfuUy. 

The minimum purity of the carrier gas used must be 99.995 mol%. 

A 1.6.2. Methanol • 99.9% purity. Required to establish identification by retention time and for calibration. 

Must be of known purity and free of the other components to be analyzed. (WARNING • Flammable. Health hazard.) 

Al.6.3. tertiary-Amyl alcohol (2-Methyi-2-Butanol) - 99% purity. Used as the internal standard. 

(WARNING • Flammable. Health hazard.) 

A 1.6.4. Methylene chloride - Used for column preparation. Reagent grade, free of non-volatile residue. 

(WARNING - Health hazard.) 

A 1.6.5. Nitrogen - 99.998 mol%. Used to prepare tubing for the micro-packed TCEP column. 

(WARNING - gas under pressure.) 

A 1.7. Preparation of Column Packing 

A1.7.1. Preparation of TCEP Column Packing 

A 1.7.1.1. Any satisfactory method, used in the practice of the art that will produce a column capable of 

retaining methanol and tertiary amyl alcohol (internal standard) from hydrocarbon components 

of the same boiling point range in a fuel methanol (M85) sample may be used. The following 

procedure has been used successfully. 

Al.l 1.2. Completely dissolve lOgofTCEPin 100 mL of methylene chloride. Next add 40 g of 80/100 

mesh Chromosorb P(AW) to the TCEP solution. Quickly transfer this mixture to an 

evaporating dish, in a fume hood, without scraping any of the residual packing from the sides 

of the container. Constantly, but gently, stir the packing until all of the solvent has evaporated. 

This column packing can be used immediately to prepare the TCEP column. 

A 1.7.2. Packing of Micro-packed TCEP Column 

A 1.7.2.1. Wash a straight 560 mm length of 1.6 mm O.D. (0.38 mm I.D.) stainless steel tubing with 

methanol and dry with compressed nitrogen. 

A 1.7.2.2. Insert 6-12 strands of silvered wire, a small mesh screen or stainless steel frit inside one end 

of the tube. Slowly add 0.14 to 0.15 g of packing material to the column and gently vibrate 

to settle the packing inside the column. When strands of wire are used to retain the packing 

material inside (he column, leave 6.4 mm (0.25 in.) of space at the top of the column. Place 

wire or screen in column to retain packing. 

A 1.7.2.3. Column Conditioning - Both the TCEP and WCOT columns are to be briefly conditioned 

before use. Connect the columns to the valve (see A 1.9.1) in the chromatographic oven. 

Adjust the carrier gas flows as in A 1.9.3 and place the valve in the RESET position. After 

DRAFT 
P.5 

Methanol in Methanol-Based Fuels Page 5 

several minutes, increase the column oven temperature to 120°C and maintain these conditions 

for 5 to 10 minutes. Cool the columns below 60°C before shuttinc off the earner flow. 

A 1.8. Sampling 

Al.8.1. To obtain samples for this proposed test method, use procedures outlined in Practice D 4057 or 

Method D 4177 except that water displacement (paragraph 10.3.1.8 of Practice D 4057) must not 

be used. 

A 1.8.2. Fuel samples must be stored under refrigeration until the laboratory sub-sample is taken for analysis. 

Any laboratory sub-samples must also be refrigerated if they are not to be analyzed immediately. 

A 1.8.3. Thoroughly shake the sample container prior to withdrawing any sub-sample for analysis. Allow 

any particulate matter to settle to the bottom of the sub-sample container. Inspect the sub-sample 

for evidence of phase separation. If phase separation is detected, the sample is invalid and a new 

sample must be requested. 

A 1.9. Preparation of Apparatus and Establishment of Conditions 

A 1.9.1. Assembly - Connect the WCOT column to the valve system using low volume connectors and 

narrow bore tubing. It is important to minimize the volume of the chromatographic system that 

comes in contact with the sample, otherwise peak broadening will occur. 

Al.9.2. Adjust the operating conditions to those listed in Table Al.l. (If a TCD is being used do not turn 

on the detector circuits.) Check the system for leaks before proceeding further. 

Al.9.3. Row Rate Adjustment (see Figure Al.l) 

A 1.9.3.1. Attach a flow measuring device to the column vent widi the valve in the RESET position and 

adjust the pressure to the injection port to give 5.0 mL/min flow < 14 psig). Soap bubble flow 

meters are suitable. 

Al.9.3.2. Attach a flow measuring device to the split injector vent and adjust the flow from the split vent 

using the A flow controller to give a flow of 70 mL/min. Recheck the column vent flow set 

in A 1.9.3.1 and adjust if necessary. 

Al.9.3.3. Switch the valve to the BACKFLUSH position and adjust the variable restrictor to give the 

same column vent flow set in Al.9.3.1. This is necessary to minimize flow changes when the 

valve is switched. 

A 1.9.3.4. Switch the valve to the inject position RESET and adjust the B flow controller to give a flow 

of 3.0-3.2 mL/min at the detector exit. When required for the particular instrumentation used, 

add makeup flow or TCD switching flow to give a total of 21 mL/min at the detector exit. 

A 1.9.4. When a thermal conductivity detector is used, turn on the filament current and allow the detector to 

equilibrate. When a flame ionization detector is used, set the hydrogen and air flows, ignite the 

flame, and tum on the electrometer. 

DRAFT 
P.6 

Methanol in Methanol-Based Fuels Page 6 

A1.9.5. Valve Switch Times - The times for switching the valve to the BACKFLUSH position and then back 

to the RESET position will vary slightly for each column system and must be determined experimentally as follows. The start time of the integrator and valve timer must be synchronized with the 

injection to accurately reproduce the backflush time. 

Al.9.5.1. Prepare a blend consisting of. approximately, 40 volume% methanol. 10 volume% gasoline 

(methanol-free). and 50 volume% tertiary-amyl alcohol (internal standard.) 

A 1.9.5.2. Initially assume a valve BACKFLUSH time of 0.23 minute. With the valve in the RESET 

position, inject 1 uL of the blend prepared above. At 0.23 minute after the injection, rotate 

the valve to the BACKFLUSH position and leave it there until the complete elution of internal 

standard is realized. Note this time as the RESET time and return the valve to the RESET 

position. When all of the remaining hydrocarbons are backflushed. the signal will return to a 

stable baseline and the system is ready few another analysis. The chromatogram should appear 

similar to that illustrated in Figure A 1.2. 

Al.9.5.3. It is necessary to optimize the valve BACKFLUSH time by analyzing the blend prepared in 

Al.9.5.1. The correct BACKFLUSH time is determined experimentally by using valve 

switching times between 0.2 and 0.3 minute. When the valve is switched too soon. C5 and 

lighter hydrocarbons will be backflushed and will co-elute in the oxygenate section of the 

chromatogram. When the valve BACKFLUSH is switched too late, part or all of the methanol 

will be vented resulting in an incorrect methanol measurement. 

ALIO. Calibration 

A1.10.1. Prepare at least three different blends of methanol in gasoline which is known to be free of methanol 

and tertiary-amyl alcohol. Refer to Practice D 4307 for preparation of liquid blends. Volume 

percent concentrations for each component must be calculated at the temperature of interest. These 

blends must be at known concentrations bracketing the methanol concentrations of interest. 

A 1.10.2. Analyze each calibration blend as described in Section Al.l 1. 

A 1.10.3. Measure the peak areas of methanol and of the internal standard by either manual methods or an 

electronic integrator. Calculate the relative volume response factor for metiianol relative to the 

internal standard, according to Practice D 4626. 

Al.l 1. Procedure 

Al.l 1.1. Preparation of Sample - Remove the sample from refrigeration and withdraw a sub-sample for 

analysis as described in A 1.8.3. Allow the sub-sample, internal standard, and any volumetric 

apparatus employed to equilibrate at the temperature of interest Accurately add a known volume 

of the internal standard, tertiary-amyl alcohol, to an accurately measured volume of sample. 

Concentrations of forty (40) to sixty (60) volume percent have been used successfully. 

Al.l 1.2. Chromatographic Analysis - Introduce a representative aliquot of die sample, containing internal 

standard, into the chromatograph and use the valve switch times determined in A 1.9.5. An injection 

volume of luL with a 15:1 split ratio has been used successfully. 

DRAFT 
P.7 

Methanol in Methanol-Based Fuels Page 7 

A 1.11.3. Interpretation of Chromatogram - Compare the results of sample analyses to those of calibration 

analyses to determine identification of methanol and internal standard present. 

A 1.12. Calculation 

A 1.12.1. After identifying the methanol peak, measure its area and that of die internal standard. Calculate the 

volume percent of methanol as follows: 

RRV (M)xV(S)xA(M) (Al.l) 

V(M) = 100 x . 

A(S)xV(F) 

V(M) = Volume percent of metiianol. 

V(S) = Volume of internal standard (tertiary-amyl alcohol) added. 

V(F) = Volume of fuel sample taken. 

A(M) = Peak area or height of methanol. 

A(S) = Peak area or height of the internal standard 

(tertiary-amyl alcohol). 

RRV(M) = relative volume response factor for metiianol 

(relative to the internal standard). 

Al.12.2. Report the volume percent of metiianol to the nearest 0.1 volumes. 

A1.13. Precision and Bias 

A 1.13.1. Precision - The precision of this proposed test method for measuring methanol in methanol-based 

fuels is being determined. 

Al.13.2. Bias - The bias of this proposed test method has not been determined. 

A 1.14. Key Words 

A 1.14.1. Alcohols: Gas Chromatography: Fuel Methanol: M85: Methanol: Oxygenates. 

DRAFT 
P.8 

Methanol in Methanol-Based Fuels Paee 8 

Table Al.l. Chromatographic Operating Conditions 

Temperatures: 

Column Oven 60°C 

Injector 200°C 

Detector -TCD 200°C 

- FID 250°C 

Valve 60°C 

Flows: mL/min 

to Injector 

Column 

Auxiliary 

Makeup 

75 

5' 

3 

18 

Carrier Gas: Helium 

Sample size. uL i 

Split ratio 15:1 

Backflush. min 0.2 - 0.3 

Valve reset time, min 8-1 0 

Total analvsis time, min 18 - 20 

Table A 1.2. Retention Characteristics for TCEP/WCOT Column Set 

Conditions as in Table Al.l. 

Component 

Methanol 

t-Amyl Alcohol 

Retention 

Time, min 

3.21 

7.30 

Relative Retention Time 

(t-Amyl Alcohol = 1.00) 

0.44 

1.00 

DRAFT 
P.9 

Methanol in Methanol-Based Fuels Paee9 

COLUMN 

VENT 

DETECTOR 

ADJUSTABLE RESTRICTOR 

<-

POLAR CTCEPD 

COLUMN 

n—^—&-> 

BACKPRESSURE 

REGULATOR 

NON-POLAR 

CWCOT^ 

COLUMN 

4 i _ 

rTVsPLIT 

NJECTOR 

_x 

FLOW 

CONTROLLERS 

Valv e i n RESET Positio n 

COLUMN 

VENT 

DETECTOR 

ADJUSTABLE RESTRICTOR 

POLAR CTCEP^ 

COLUMN 

NON-POLAR 

CWCOT} 

COLUMN 

4 ^ _ FLOW 

rf\sPLiT 

INJECTOR 

_ 1 

BACKPRESSURE 

REGULATOR 

CONTROLLERS 

Valve in BACKFLUSH Position 

Figure Al.l. Schematic of Chromatographic System 

RAFT 
P.10 

Methanol in Methanol-Based Fuels Page 10 

terriarv-Amvl Alcohol 

Methanol 

i 

Ethanol MTBE 

Figure A1.2. Example of Chromatographic Results 

4 min 5 min 6 min 7 min 8 min 9 min 

DRAFT 
P.11 

A2. PROPOSED TEST METHOD FOR DETERMINATION OF HYDROCARBON CONTEN 

OF FUEL METHANOL (M85) FOR SPARK-IGNITION ENGINES 

A2.1 Scope 

A2.1.1 This Proposed Test Method describes a procedure to determine the 

hydrocarbon content of Fuel Methanol (M85). 

A2.1.2 The values in SI units are the standard. 

A2.2 Summary of the Proposed Test Method 

A2.2.1 The Proposed Test Method is based on the Babcock test for butter in 

milk products. It consists of addition of Fuel Methanol (M85) to a sodium 

chloride solution followed by addition of water to cause phase separation of 

the hydrocarbons which is then visually measured in the Babcock flask. 

A2.3 Significance and Use 

A2.3.1 Maintenance of a specified proportion of hydrocarbon to methanol 

has importance in the starting, operation and emission performance of 

vehicles designed to operate on Fuel Methanol (M85) and the production 

of a visible flame in the event of a fuel fire involving Fuel Methanol (M85). 

A2.4 Apparatus 

A2.4.1 Babcock Flask, Babcock Milk Bottle (Borosilicate glass to meet 

Association of Official Analytical Chemists (AOAC) specifications, 165 mm, 

18 gram). 

A2.4.2 Disposable syringes or clean pipettes, 10 mL +/" 0.1 mL. 

A2.4.3 Centrifuge capable of holding Babcock flasks and operating at 

1500 rpm. 

A2.5 Reagents and Materials 

A2.5.1 10 weight % Sodium Chloride (NaCl) solution. 

A2.5.2 Distilled water, Specification D 1193, Type IV. 

A2.6 Procedure 

A2.6.1 Place 20 mL of a 10 weight °u NaCl solution into an 8°d Babcock flask. 

Introduce 10 mL of the test Fuel Methanol (M85) with use of a pipette or 

syringe. Stopper and shake for 1 minute. Add water sufficient to read between 

7.5 and 8.0 on the Babcock scale. Place the stoppered flask into a centrifuge 

for 5 minutes at 1500 rpm. Read and record the volume percentage 

directly from the neck of the Babcock bottle. This is done by subtracting 
P.12 

the reading at the liquid/liquid interface from that of the upper meniscus. 

Multiply by 2 to obtain the % hydrocarbon by volume in the test Fuel 

Methanol (M85). 

A2.7 Precision and Bias 

A2.7.1 The precision of this Proposed Test Method for measuring the 

hydrocarbon content of fuel methanol (M85) is being determined. 

A2.7.2 The bias of this Proposed Test Method has not been determined. 

A2.8 Key Words: 

A2.8.1 hydrocarbon content; fuel methanol (M85); spark-ignition engines; 

phase separation; Babcock test. 

JMD:jmd 

August 9, 1991 

Docs DRAFT ANNX2 

DRAFT 
P.13 

A3. PROPOSED TEST METHOD FOR DETERMINATION OF INORGANIC CHLORID 

IN FUEL METHANOL (M85) FOR AUTOMOTIVE SPARK-IGNITION ENGINES 

A3.1 Scope 

A3.1.1 This proposed test method covers a procedure to determine 

inorganic chloride in Fuel Methanol in the range of concentrations 0.4 

to 2.0 ppm. 

A3.1.2 The values stated in SI units are the standard. 

A3.2 Summary of the Proposed Test Method 

A3.2.1 The sample is concentrated, acidified and treated with silver 

nitrate. The turbidity is visually compared with standards. 

A3.3 Significance and Use 

A3.3.1 Because of the corrosive nature of inorganic chloride to the fuel 

systems of internal combustion engines, a means to measure low levels of 

inorganic chloride in Fuel Methanol is required. 

A3.4 Apparatus 

A3.4.1 Distillation apparatus - 500 mL distillation flask, condenser and 

250 mL graduated cylinder as collector. 

A3.4.2 Nessler tubes, 100 mL, matched, tall form. 

A3.5 Reagents and Materials _hfvO.-

A3.5.1 Nitric Acid (HN03 f solution (1 part 15.7 M acid to 1 part 

demineralized water). (WARNING-corrosive. Health Hazard.) 

A3.5.2 Silver Nitrate solution, 0.1 M. (WARNING. Health hazard.) 

A3.5.3 Methanol, halide and sulfide free by distillation. (WARNINGflammable. Health hazard.) 

A3.5.4 Demineralized water, halide and sulfide free. 

A3.5.5 Sodium Chloride (NaCl). 

A3.6 Standards 

A3.6.1 Dissolve 0.845 g of dr y Sodium Chloride (NaCl) in halide 

and sulfide free water and dilute to one litre in a volumetric flask. 

Mix thoroughly and label solution A (0.5 mg CI/mL). 

DRAFT 
P.14 

A3.6.2 Pipet 10 mL of solution A into a 1 litre volumetric flask. Dilute 

to volume with halide and sulfide free water. Mix thoroughly and label 

solution B (0.005 mg CI/mL). 

A3.6.3 In matching Nessler tubes, prepare the following standards: 

Blank 1 2 3 4 5 

Soln B, mL (pipet) 0.0 1.0 2.0 3.0 4.0 5.0 

Methanol, mL CCl-free) 80 80 80 80 80 Q0 

A3.6.4 For each standard follow steps of 3.7.4 to 3.7.8 of Procedure. 

A3.6.5 The turbidity standards are affected by light and are not stable. 

Prepare fresh standards (from solution B) for each group of samples. 

A3.7 Procedure / r '

r

 ^7: 

•j, 

A3.7.1 Clean ail glassware wjth IM HN03 and rinse with demineralized water 

and halide and sulfide free methanol. 

A3.7.2 Measure 320 mL of sample in a graduated cylinder and put into the 

distillation flask, add boiling beads. Distill the sample into a graduated 

cylinder until 240 mL of the distillate is obtained. Use 4 mL of the 

concentrated residue from the distillation flask as follows. 

A3.7.3 Add a 4 mL sample to a 100 mL Nessler tube. 

A3.7.4 Add 80 mL of halide and sulfide free methanol to the sample in the 

Nessler tube. 

A3.7.5 Dilute the contents of all tubes (sample and standards) to the 

100 mL mark with halide and sulfide free water. 

A3.7.6 Pipet 2 mL of Nitric Acid solution (1 part 15.7 M acid to 1 

part demineralized water) into each tube. 

A3.7.7 Pipet 1 mL of 0.1 M silver nitrate solution into each tube. 

A3.7.8 Stopper and mix thoroughly by inverting. 

A3.7.9 Allow the tubes to stand in the dark for 5 minutes. Visually 

compare the sample to the standard solutions while looking vertically against 

a black background. Record the millilitres of standard solution B which 

matches the sample. 

A3.8 Calculations 

(A)(B)(0.001)(10qq0Q0)/(320/80)(f).(0.79) = ppm Cl (A3.1) 

Where: 

A= mL of Soln B which matched sample 

B= mg CI/mL of Sbln B •--•• • 

0.001 = mg["'to "g 

320/80 = concentration factor 

4 = mL of sample 

0.79 = relative density of Methanol 

A3.9 Precision and Bias 

DRAFT 
P.15 

APPENDIX 

(Nonmandatory Information) 

XI. SIGNIFICANCE OF PROPOSED SPECIFICATION FOR FUEL METHANOL 

FOR AUTOMOTIVE SPARK-IGNITION ENGINES (M85) 

XI.1 Methanol 

XI.1.1 The methanol content of M85 is a crucial parameter 

as it affects the capability of the fuel metering system of the M85 

vehicle to establish the proper air/fuel ratio for optimum vehicle 

operation. This is much less of a concern for multi-fuel-capable 

vehicles than for dedicated M85 vehicles. Methanol content affects 

the lubrication properties of the fuel and affects the water 

tolerance of the M85. 

XI. 1.2 The inclusion of impurities and contaminants, except 

for the deliberately added hydrocarbons and/or additives, can 

impact adversely on the properties and performance of fuel methanol 

(M85) as an automotive spark-ignition engine fuel. The quantities 

of some of these materials are limited by specified property 

limits. Trace amounts of unspecified materials including higher 

alcohols, methyl formate, acetone, and dimethyl ether can be 

present. The maximum limit on water, the maximum limit on higher 

alcohols, and minimum-maximum limits on hydrocarbon content control 

the amount of some impurities and contaminants. 

XI.2 Hydrocarbon 

XI.2.1 Hydrocarbons are deliberately added to provide 

improved cold startability and cold-start and warmup driveability. 

The addition of hydrocarbons also contributes to flame visibility 

(luminous flame), nonexplosive air/fuel mixtures in storage tanks 

(rich mixture vapor space), and denaturation (malodorant and taste 

deterrent). The hydrocarbon portion of the fuel must be unleaded. 

XI.2.2 The proposed specification does not control the 

composition of the hydrocarbons added to the fuel methanol. 

However, the hydrocarbons shall be stable, noncorrosive, and be in 

the boiling range of spark-ignition engine fuel as specified in 

D 4814. No minimum aromatics content is specified because the 

luminosity limit controls flame visibility. 

XI.3 Vapor Pressure 

XI.3.1 The addition of volatile hydrocarbons improves cold 

startability. The addition of too much volatile hydrocarbon*---^n 

cause hot fuel handling problems. Higher vapor pressures are 

DRAFT 
P.16 

A3.9.1 The precision of this proposed test method for measuring inorganic 

chloride in fuel methanol is being determined. 

A3.9.2 The bias of this proposed test method has not been determined. 

A3.10 Key Words 

A3.10.1 fuel methanol (M85); spark-ignition engines; chloride; inorganic 

chloride; turbidit y standards; turbidity ; silver nitrate. 

JMD:jmd 

August 12, 1991 

Doc# DRAFT ANNX4 

RAFT 
P.17 

required in the wintertime for cold starting and lower vapor 

pressures are needed in the summertime to prevent hot fuel handling 

problems. Excessive vapor pressure for a given ambient condition 

can contribute to evaporative emissions. Lower and upper limits on 

vapor pressure for three volatility classes are used to define the 

acceptable range of the volatile components to insure proper 

vehicle performance. 

XI.4 Luminosity 

XI.4.1 When pure methanol burns, it produces a blue, 

smokeless, nonluminous flame which is nearly invisible in daylight. 

Thus, it is difficult to know when a fire exists and to fight such 

a fire. To make the flame visible, materials such as aromatic 

hydrocarbons are added to methanol. A key requirement is to 

maintain the clearly visible flame throughout the duration of the 

burn. It would be very hazardous for the visible flame to 

disappear before the fire was extinguished. 

XI.4.2 In general, it has been established that unleaded 

gasoline having greater than 3 0 volume % aromatics content when 

used as the hydrocarbon portion of M85 will result in an M85 fuel 

which will meet the key requirement of a clearly visible flame 

throughout most of a burn. However, the luminosity performance is 

dependent on the types of aromatics present in the hydrocarbon 

portion. 

XI.5 Acidity 

XI.5.1 Very dilute aqueous solutions of low molecular weight 

organic acids such as formic acid are highly corrosive to many 

metals. It is therefore necessary to keep such acids at a very low 

level. 

XI.6 Nonvolatile Matter 

XI.6.1 This requirement controls high boiling impurities, 

nonvolatile matter, and contaminants which can contribute to engine 

deposits. 

XI.7 Total Chlorine 

XI.7.1 Ionic (inorganic) and organic chlorine are corrosive 

to many metals and it is desirable to minimize these compounds in 

M85. 

DRAFT 
P.18 

XI.8 Lead 

XI.8.1 Most modern gasoline-powered vehicles are equipped 

with exhaust catalytic converters to control emissions of 

hydrocarbons, carbon monoxide, and oxides of nitrogen. Most fuel 

methanol vehicles are also equipped with exhaust catalysts which 

control emissions of formaldehyde as well as the regulated 

emissions. Lead compounds deactivate the catalysts and are limited 

to trace amounts to prevent this problem. 

XI.9 Phosphorus 

XI.9.1 Like lead, phosphorus deactivates exhaust catalysts 

and is limited to trace amounts. 

XI.10 Appearance 

XI.10.1 Turbidity, phase separation, or evidence of 

precipitation normally indicates contamination. 

XI.ll Water 

XI. 11.1 The solubility of hydrocarbons in fuel methanol 

decreases with lowering temperature and increasing water content. 

Separation of the hydrocarbon from the fuel will adversely affect 

cold starting and driveability, luminosity, and denaturing. Water 

may affect the calibration of some types of composition sensors of 

flexible-fuel vehicles. Water also reduces the energy content of 

the fuel and thus adversely affects fuel economy and power. 

Because some degree of water contamination is practically 

unavoidable in transport and handling, and because the fuel 

methanol is miscible with water, the water content of fuel methanol 

is limited to reduce the potential for problems. 

XI.12 Sulfur 

XI.12.1 The limit on sulfur content is included to protect 

against engine wear, deterioration of engine oil, corrosion of 

exhaust system parts, and exhaust catalyst deactivation. 

DRAFT 
P.19 

X 2. PROPOSED TEST METHOD FOR LUMINOSITY OF FUEL METHANO 

(M85) FOR AUTOMOTIVE SPARK-IGNITION ENGINES 

X2.1 Scope 

X2.1. 1 This proposed test method covers a procedure to determine if a Fuel 

Methanol (M85) composition meets the requirement that it produce a luminous 

flame throughout the duration of a burn by comparing its luminosity 

performance under controlled conditions to that of ethanol. This test method, 

while not adequate for use in its present form is included here for information 

as it represents the current state of development for a luminosity procedure. 

It is hoped that its inclusion will solicit positive efforts toward 

development of a viable luminosity test procedure. 

X2.1.2 The values stated in SI units are the standard. An exception is 

footcandles, lumens/square foot which is a hybrid unit and the unit used for 

the calibration of the optometer. 

X2.2 Summary of the Proposed Test Method 

X2.2.1 The sample of Fuel Methanol is measured into a Petri dish resting 

on a digital scale under a daylight spectrum source (achieved by the use of 

two Daylight Spectrum Fluorescent buJbs) in a fume hood. The 

sample is ignited and the output of an optometer and the decreasing 

output of the scale are recorded on a 2 pen recorder. A video 

tape recording of the event is also recommended. A comparison is then 

made to ethanol under the same conditions. 

X2.3 Significance and Use 

X2.3. 1 Potentially low luminosity (invisible) methanol fires are a 

major safety consideration. Assuring that the Fuel Methanol burns with a 

visible flame over the entire duration of a burn allows visual recognition of a 

hazardous situation. This test method measures a property related to such 

visual recognition. 

X2.4 Apparatus 

X2.4. 1 Digital Scale having an accuracy of 0.1 gram. 

X2.4. 2 Clean borosilicate Petri dishes 100 mm diameter x 20 mm high, one per 

sample. 

DRAFT 
P.20 

X2.4. 3 Disposable syringes or clean pipettes, 10 mL +/-0.1 mL. 

X2.4. 4 Optometer with photometric (400-700 nm) filter. 11 

X2.4. 5 Two Channel pen recorder. 

X2.4. 6 Color video camera and video cassettes 

X2.4. 7 Daylight Spectrum fluorescent bulbs. 

11. The United Detector Technology Model 40X optometer has been found to be 

suitable. An equivalent may be used. 

X2.5 Reagents and Materials 

X2.5. 1 Ethanol, Specification for Denatured Ethyl Alcohol, Formula 3A, 

E 1145. (WARNING-flammable. Health hazard. Denatured alcohol cannot 

be made non-toxic.) 

X2.6 Procedure 

X2.6. 1 In a laboratory hood equipped with two 30 watt Daylight Spectrum 

fluorescent bulbs, introduce a 10 ml fuel sample from a clean 10 mL pipette 

or syringe into a borosilicate Petri dish resting on the pan of a 

tared digital balance. A standard grey background is recommended if a video 

recorder is used. The optometer sensing head is positioned on a 45 degree 

angle pointed toward the center of the Petri dish, 41 cm (16.1 inches) from the 

vertical center line of the Petri dish, see Figure X2.1 . After zeroing the 

amplifier with the Daylight Spectrum fluorescent bulbs on, the amplifier scale 

is adjusted to 1.0 footcandle (10.8 lumens/square meter) for burning Ethanol 

(Denatured Ethyl Alcohol, Formula 3A, E 1145) in the lighted hood. 

X2.6. 2 An ordinary wooden match is struck and waved over the 

test sample, initiating burning at time zero, at which point the 

video timer graphics and chart feed are simultaneously started. Flame 

luminosity, measured in footcandles (lumens/square foot = 10.8 lumens/square 

meter) and weight decrease are recorded concurrently on the chart. Termination 

of the burn is evidenced by the scale's return to zero weight. The base 

luminosity value is obtained by continuing the trace after the burn. 

The entire apparatus is shown in Figure X2.2. 

X2.7 Interpretation of Results 

X2.7. 1 The output of the optometer and scale as recorded on the dual 

pen recorder (and the video if recorded) shall be reviewed to assure acceptable 

luminosity over the entire burn duration. Figures X2.3 thru X2.6 illustrate 

traces which are typical of the results obtained with this technique. 

DRAFT 
P.21 

A numerical result obtained by mathematical comparison of the ethanol standard 

burn to that of the M85 burn , which would assure a visible flame for the entire 

duration of the burn is desirable but unavailable at this time. 

X2.7. 2 The video recording of the burn is important because luminosity by 

this proposed test method does not measure the flame color, which is 

available upon review of the video. Flame color in addition to luminosity are 

important in assessing the visibility of a flame. 

X2.7. 3 Correlation with actual vehicle fires has not been established. 

X2. 8 Precision and Bias 

X2.8. 1 The precision of this proposed test method for measuring 

the luminosity of fuel methanol (M85) is being determined. 

X2.9.1 The bias of this proposed test method has not been determined. 

X2.9 Key Words 

X2.9.1 automotive spark-ignition engine fuel; luminosity; standard 

daylight spectrum source; flame; duration of a burn ; luminous flame; M85; 

methanol; illuminance; video; daylight spectrum fluorescent bulb; ethanol. 

JMD:jmd 

August 13, 1991 

Doc# DRAFT ANNX3 
Optometer Sensing Head 

\ \ 

. \ 

P.22 

Hood Surface 

100mm Diam x 20 mm 

High Borosilicate Petri 

Dish 

Fischer Catalog 

No. 03-743D 

or Equivalent 

^ . /• 

Figure X2.1, Optometer Sensing Head Position 

DRAFT 
P.23 

FLAT BLACX 

OR GREY 

3ACXGHOUNO I 

ENTIRE SET4JF 

IN VENTED HOOD 

U simuiateo 

sumight 

lamp 

MODEL 248 UN9ROBE 

N a 111 FILTER (PHOTOMETRIC) 

NO. 112 COSINE OimjSER 

(1.61 kmph Air Flow) 

RECORDER FOOT CANOL£S VS. TIME 

Figure X2.2, Luminosity Test Apparatus Schematic 

RAFT 
•iiim' ijli!' 

;i 

—;•:•"••••!! tr 

• . 1 

Ii! Illi|l 

iiil 

Nil 

!:l 

:i 

'. I1 

:ji 

::ll | 

'Ml 

.i.:jlii!ilii:;!i-iiLU:.i:::;i!:i!l 

•••.;l^il;!" : • •!;!!::!•!: : : ' i II I 

,1!!i!H;J!i;iii;.i.:';:!!l 

:;;!"• !7,;ii71-':;!, 

i;!ii"!!ll | 

• I ' I I 

IIIII:1.! 

Mlili... 

"<H:,, . 

i.illh. -

:M 

l!i:r;i iiiiiiiii 

•mils.! 

iiinii 

:m 

!l!l|i| | 

'iiiii II .l'llllll|HI| l|| 

II-I|I>IHII!!I I 

illilllli 

i::i|iii i 

'-"it"'" ' f , : l 

ii;.|l'il|ii;'l;;!.l.! ' 

••• '" ••lll l /.mil l 

ill! 

IliS'.iil 

' I- '» •' :. I> ,, M I 

iilpi1!

11!!!"'!! 

•illiiii!::":: 

:ii!i.' 

Iii 

H I 1: , n 

iilllii}! 

:i • 

II, . 

illli l 

MM85/GAS

 :; i " 

, „ . • I|1 |;;i:;!:i !: ;:!::i!!i:lii i 

;••'. ::!ilil!i:. I • "";:i , i .::::i:i;i | 

'••'•iM'iii!:.! i :•••.:; : 

. 1 I ••'•- . 

: : ; i | 

iili'-ii.jiii.i:!:-!--.- j 

ji^ij;^:!;:!;;.:' 

j!i:!: " i... i . •• ':• • 

, ^h"iiiii!'7;:.•iii::"7 

:r;'":i; ' 

U-I rr i n: .. ! : ' r ' I 

I : i M I '" ' 

Hi 

ii::i,' 

'liih.i; 

l!'l 

ii'i;-!:!:,:',! i!j:i: :il.::: i 

>M 

l l -

nl n 

•I 

i I. I 

' < i 

i.' u 

I T !;|ihi 

il!i7--7|:!!||!;i:ii:|i!: 

iiiiiii'iiiiij Iiiiiiiiii 

!||-H 

llllllll.'llli'l'M ' 

:

ii::i,,.Iiillllll ' 

, ..Ii 1'!'! ' '"I'l| : 

.„!!iiiiiii;:i!!:iiiliil! 

l''M|i'"i': i 't "T.;•• 

' !!lll: | •; • I ' • 

,,: i-iiiii ilii-n r 

:|:l •! i:ii Ilintllf^rlP1 

Hi'1!!':; | •; Jlf a (IS L 

--. Time (sec), 

Figure X2.3, Luminosity Trace of M85, 30% Aromatic 

Qasoline 

liSIiiiisljiiiiSliiSE 

::!>:! . :|...i;:'i|ii!!;|: :

 : -^[-ri |-.^!:|!||!|||i:

| i :M 

• ; i : '. . :i : :." i • 

|...n : 

•!!!! • 

: f 

Inii i • • n I-I-. : • i •• ,.l.lil,,. • 

I;:;:.:_.I-.::::L I i.i:u...:::,,.i.ii : 

1

 • " i I . ' • i I •; i I i • 1 1 •' 111 " i I : I ! -' 

mil l :. p .!•:: I . .•:"-..I.• • (• I•! •• 

.'•!-:.

:

 J'::|::'•'!:' , h.iiiiiijjlji 

-iii-jiiiiiii^Hfiiiiiiiiiiiiiii 

'"'• ' ' ' '"'I'liti , i'M|l''i" ' "Hj i |"| t 

:

iiiii!i! 

:!!illlli 

:;!iii!; 

ill:. -.'I'M: 

in: •'-'•ii 

i.i:h:!;|' i 

I'lji'l'H 

i;.i. 

! .j -

..;;;:!ili7;:77r!!l|7:'!i'iiH' 

M.liii^i;77-:;.i":':|!r-i"; !!:" 

I:. I 

l :' ! 

'•'Ij!' 

illli 

H!: 

. = .:«•-:•# -:;tn: I • :j.|ll|ll l 

__,._. ! ;-lk:..l ;. :::: i'-..li.i 

"••!

 ! l :'!' :

- l '

 ;: i- I'!:'!'!: 

' 7"7i-;;::i 

::;!!!!!.r:! 

.i.. , i.e 

'I'-Ti ui'"-:. 

-!•-;: • .-iii:::" 

• I 

'•:.:!iinii .••::::ii"'H| 

;; ; ••!»:• » .-...._,...i.. , 

.i ; :|'-h!,l'-I— j;.! 1' ! 

;;ili--'-;'-i;;i:l;i:'!,!; i;;;'!m 

!:;;, MS5/ Pentane ii"; 

: • 'IIIII;!! , ., - • | •••• • 

.-!•• • • ; ':.|| ; • . , ..Ii -

• i " -•!!! ! •.:::;:•; 

!."?:.; I.vlllji 

,.iL!.::iiiii 

•• i in . i i 

: I I "I ' i: : r-i-v n 

, I 1111M : iII.. . 

.1.1.i.m;:.I :n. : 

• I i ii-i-n . ! 

I-i i i • I m i- I " 

•i'.:;i!. . i.-i.ii v 

..,,. •nl 1

' l''- T ' ' |l'|..-- ' • I,:- I 

mm 

~!7.L.;::;;!;;r'""l^i;"';" "ft \'\ .'• ui\ 

'1,1 

'l. l 

Figuro X2.6. Lumm <"!«> +• 

— i ime lieci 

' mm. am ^ -* 1 \ 
iiiiii! 

•3 Time (sec) 

Figure X2.5, Luminosity Trace of M100 

miliiMmmiiM 

!

n7!hm!r" ISI!!!!!III| | II |||!! !!!!{ ||. 

illl.'lllllll! i! Iiiii illll i 

}UIII!!|III ll!!:|:i:J!L|: 

iniiiiUni U.i: j-llH-

«:pi:i!:i!! illi :i"iilj! 

i|'|i{'ijii ill! uliiH'i 

|lll|ii i 

i~ 

;i»!l l 

Time (sec) 

riaur© X2.4. Luminosity Trace M cin o 
P.26 

APPENDIX 6 

Proposed M-85 Certification Fuel Specification from the Motor Vehicle 

Manufacturers Association of the United States, Inc. - 7/23/91 
P.27 

Motor Vehicle Manufacturers Association 

of the United States, Inc. 

CERTIFICATION 

nes SPECIFICATION 

FOR EMISSIONS TEST 

Methanol meeting ASTM 85 

specification D 1152, 

volume %,minimum 

(ASTM D 4815) 

•Gasoline, volume % 14.5 +/- 0.5 

(Emission Test Fuel, e.g. 

Indolene) 

Vapor Pressure, psi dry 7.5 - 8.5 

(ASTM D 4953, ES14, ES15) 

** Aromatics, volume %, 35 

maximum (ASTM D 1319) 

** Olefins, volume %, maximum 10 

(ASTM D1319) 

Ac dity, weight %, maximum 0.003 

(ASTM 1613) 

Distillation Residue, volume %, 0.5 

maximum 

(ASTM D 86 or D 1078) 

Total Chloride Content, ppm, maximum 1 

(organic and inorganic) 

(ASTM D 3120, modified for organic 

chlorides or ASTM D 2988) 

Lead Content, g/l, maximum 0.001 

(ASTM D 3237, D 3229, D 3116) 

* Gasoline volume % - 100 - (methanol + other oxygenates + 

water) 

** Note: The aromatics and olefins specifications apply only to 

the gasoline portion of the fuel. 
P.28 

Phosphorus Content, g/l, maximum 0.0001 

(ASTM D 3231) 

Sulfur Content, ppm, maximum 

(ASTM D 1266, D 2622, D 3120 

D 3246) 

50 

Particulate Contaminants, g/l, 0.001 

maximum (ASTM 2276) 

Water, weight %, maximum 0.5 

(ASTM, E 203) 
P.29 

APPENDIX H 

M^I ? ° 4 !!!!i8 s*

andard Specification for Denatured Fuel Ethanol for 

Blending with Gasolines for Use as Automotive Spark-ignition Engine Fuel 
P.30 

Designation: D 4806 - 88 An American National Stanoarc 

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 D 4806: 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 eosilon Iii indicates an editorial change since the last revision or reapprova!. 

1. Scope 

1.1 This specification covers nominally anhydrous denatured fuel ethanol intended to be blended with unleaded or 

leaded gasolines at 5 to 10 volume % for use as a sparkignition automotive engine fuel. The significance of this 

specification is shown in Appendix XI. 

1.2 The values stated in SI units are to be regarded as the 

standard. The values given in parentheses are for information only. 

1.3 The following precautionary caveat pertains only to 

the test method portions. Annex A1: This specification may 

involve hazardous materials, operations, and equipment. 

This specification does not purport to address all of the safety 

problems associated with its use. It is the responsibility of the 

user of this specification to establish appropriate safety and 

health practices and determine the applicability of regulatory 

limitations prior to use. 

2. Referenced Documents 

2.1 ASTM Standards: 

D86 Method for Distillation of Petroleum Products2 

D439 Specification for Automotive Gasoline2 

D512 Test Methods for Chloride Ion in Water3 

D891 Test Methods for Specific Gravity of Liquid 

Industrial Chemicals4 

D1152 Specification for Methanol (Methyl/Alcohol)5 

D 1193 Specification for ReageTlt Water3 

D 1353 Test Method for Non-Volatile Matter in Volatile 

Solvents for Use in Paint. Varnish, Lacquer and Related 

Products5 

D 1613 Test Method for Acidity in Volatile Solvents and 

Chemical Intermediates Used in Paint. Varnish. Lacquer, and Related Products5 

D 1688 Test Methods for Copper in Water3 

D3505 Test Method for Density or Relative Density of 

Pure Liquid Chemicals5 

D4057 Practice for Manual Sampling of Petroleum and 

Petroleum Products6 

E 203 Test Method for Water Using Karl Fischer Reagent4 

' This specification is under the jurisdiction of ASTM Committee D-2 on 

Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.A on specifications. 

Current edition approved March 25. 1988. Published May 1988. 

:

 Annual Book of ASTM Standards. Vol OS.Ol. 

1

 Annual Book of ASTM Standards. Vol 11.01. 

* Annual Book of ASTM Standards. Vol 13.0!. 

5

 Annual Book of ASTM Standards. Vol 06.03. 

* Annual Book of ASTM Standards. Vol 05.03. 

E 260 Practice for Packed Column Gas Chromatography" 

E 300 Practice for Sampling Industrial Chemicals4 ? 

E 355 Practice for Gas Chromatography Terms and 

Relationships7 

2.2 Other Standards: 

United States Code of Federal Regulations. Title 27. Pans 

211 and2128 

United States Federal Specification O-E-760b Ethyl Alcohol (Ethanol): Denatured Alcohol: and Proprietary 

Solvent9 

3. Terminology 

3.1 Definitions: 

3.1.1 ethanol. n—ethvl alcohol, the chemical compound 

C2H,OH. 

3.J.2 gasoline-ethanol blend, n—a spark-ignition automotive engine fuel containing denatured fuel ethanol in a base 

gasoline that may be leaded or unleaded as defined in 

Specification D 439. 

3.1.3 oxygenate, n—an oxygen-containing ashless, organic compound, such as an alcohol or ether, which may be 

used as a fuel or fuel supplement. 

3.2 Description of Terms Specific to this Proposed Specification: 

3.2.1 base gasoline—the gasoline component of a gasoline-ethanol blend, but generally excluding gasoline added to 

fuel ethanol as denaturant. 

3.2.2 denaturants—in fuel ethanol. toxic or noxious materials added to make it unfit for beverage use. 

3.2.3 denatured fuel ethanol—fuel ethanol made unfit for 

beverage use by the addition of denaturants. 

3.2.4 fuel ethanol—ethanol with impurities (including 

water but excluding denaturants). 

3.2.5 impurities—in commercially produced fuel ethanol 

compounds other than ethanol or denaturants present such 

as methanol and fusel oil (for example, amyl and isoamyl 

alcohols). 

4. Properties 

4.1 Denatured Fuel Ethanol—When fuel ethanol is denatured as specified in Section 5. it shall conform to the 

following requirements at the time of blending with a 

gasoline. 

7

 Annual Book of ASTM Standards. Vol 14.01. 

'Order as Code of Federal Regulations Title 27 Parts 200-End: from 

Superintendent of Oocuments. VS. Government Printing Office. Washington. DC 

20402. 

* Order from Supennteft&nt cf D^-umen's. \)S. Government Printing Office 

Washington. OC 20402 

s

- 7 : 
P.31 

D4806 

Water content, max. mass 5 

Nonvolatile maner. max. 

mg/IOOmL 

Chloride ion content, max. 

mass ppm (mg/L) 

Copper content, max. mass 

ppm <mg/L) 

Acidin las aceu.' acid 

CH,COOHi. max. mass

 r

.

: 

Img/Ll 

Appearance 

1.25 (Note 1) 

5 

40(32) 

0.1 (0.03) 

0.007 (56HNote 3 

Visibly free of sus 

precipitated contaminants 

iclear and bright) 

NOTE I—ln some cases, a lower water content may be necessary to 

avoid phase separation of a gasoline-ethanol blend at very low temperatures. This reduced water content, measured at the time of delivery. 

shall be agreed upon between the supplier and purchaser. 

NOTE 2—If denatured fuel ethanol is prepared by the addition of 

denaturants to undenatured fuel ethanol after it has been produced 

rather than during the dehydration process, the 15.56*C/15.56*C (60T/ 

60T) specific gravity in air of the undenatured fuel ethanol shall be in 

the range from 0.7937-0.797"'. 

NOTE 3—Denatured fuel ethanol may contain additives such as 

corrosion inhibitors and detergents that may affect the utratable acidity 

(acidity as acetic acid) of the finished fuel ethanol. Although the base 

fuel ethanol may meet the acidity specification, the effect of these 

additives may produce an apparent high utratable acidity of the finished 

product. Contact the ethanol supplier if there is a question regarding the 

utratable acidity of your denatured fuel ethanol to verify that the base 

ethanol meets the acidity requirements of 4.1. 

4.2 Ethanol Purity—The fuel ethanol component of denatured fuel ethanol excluding water shall be 98 volume % 

minimum ethanol (C2H?OH). and shall not contain more 

than 0.5 volume % methanol or total ketones, or both. The 

addition of materials other than fuel ethanol or the permitted 

hydrocarbon denaturants and minor amounts of commercially acceptable additives such as corrosion inhibitors is 

prohibited. Materials noted in 5.2 may be present in trace 

amounts only. 

4.3 Ethanol Content—Total fuel ethanol content of denatured fuel ethanol. including impurities as limited in 4.2. 

must be not less than 95 volume %. 

4.4 Other Propenies—Limits more restrictive than those 

specified above, or the specification of additional properties 

such as color, may be agreed-apon* between the supplier and 

the purchaser. 

5. Denaturants 

5.1 The only denaturants used for fuel ethanol shall be 

unleaded gasoline or rubber hydrocarbon solvent at a minimum concentration of 2 parts by volume per 100 parts by 

volume of fuel ethanol. as defined by Formula CDA 20 of 

the Bureau of Alcohol. Tobacco, and Firearms (BATF) of the 

U.S. Treasury Department. This specification prohibits the 

use of hydrocarbons with an end boiling point higher than 

225*C (437T) as determined by Method D 86. although they 

may be permitted by BATF regulations. Some kerosines. for 

instance, promote piston scuff in automotive engines. The 

denaturants permitted by this specification may be included 

as pan of the 10 volume To denatured fuel ethanol blended 

with a gasoline if they do not exceed 5 parts by volume per 

100 parts by volume of fuel ethanol. This is permitted in the 

United States by law. Any pan of these denaturants that are 

present at concentrations higher than 5 parts by volume per 

100 parts by oi are considered as part of 

the base gasoline. 

NOTE 4— BATF reguiauons concerning the preparation, use. and 

handling of denatured ethanols are published in the United States Code 

of Federal Reguiauons. Title 27. Pans 211 and 212. Pan 211 contains 

primarily legal and administrative information, and Pan 212 contains 

technical information on denaturants and denatured ethanols. 

5.2 Prohibited Denaturants—Although this specification 

permits only hydrocarbons in the gasoline boiling range to be 

used as denaturants. specific mention must be made of some 

materials that have extremely adverse effects on fuel stability. 

automotive engines and fuel systems. These materials shall 

not be used as denaturants for fuel ethanol under an> 

circumstances. They are as follows: methanol which does not 

meet Specification D 1152, pyrroles, turpentine, ketones and 

tars (high-molecular weight pyrolysis products of fossil or 

nonfossil vegetable matter). While any significant amount of 

methanol will lower the water tolerance and increase the 

vapor pressure of a gasoline-ethanol blend, these effects 

become more serious when methanol is present at more than 

2.5 pans by volume per 100 parts by volume of fuel ethanol. 

Also, methanol which does not meet Specification D 1152 

frequently contains impurities such as turpentine and tars. 

Similarly, ketone denaturants tend to degrade fuel stability 

or increase the tendency of a gasoline-ethanol blend to 

corrode metals and attack elastomers. These effects become 

more serious if the concentration of a ketone such as 

4-methyl pentanone (methyl isobutyl ketone) exceeds one 

pan by volume per 100 parts by volume of fuel ethanol. 

There is no information available on the effects of denaturants other than those mentioned above, but unless a denaturant. such as a higher aliphatic alcohol or ether, is known 

to have no adverse effect on a gasoline-ethanol blend or on 

automotive engines or fuel systems, it shall not be used. 

6. Sampling 

6.1 Samples may be obtained by an appropriate procedure of Practice D 4057 or Practice E 300. Do not use 

soldered metal containers although they are specified in 11.7 

of Practice E 300. because the soldering flux in the containers may contaminate the sample. Some soldered cans, 

such as those conforming to the requirements of 7.1 of 

Practice D4057 are acceptable, but because they cannot 

readily be distinguished from cans which do not meet this 

specification, the use of metal containers are to be avoided. 

6.2 Sample Size—A minimum of about 1 L or 1 U.S. qt is 

recommended. If specific gravity is to be determined by a 

hydrometer method, additional volume may be required. 

This depends on the size of the hydrometer. 

6.3 L.OI Size—A lot shall normally consist of the amount 

contained in a tanker compartment or other bulk container 

in which it is delivered. If this definition does not apply, the 

definition of a lot must be agreed upon between the supplier 

and purchaser. 

NOTE 5—See Sections 5. 6. and 7 of Practice E 300 ror a detailed 

discussion of the statistics oi sampling. 

7. Test Methods 

7.1 ASTM test methods have not yet been developed for 

all of the properties specified. For insunce. to determine 

ethanol content, see the proposed test method in Annex A1. 

The use of this method is not required and other suitable 

methods mav be used. 

576 
P.32 

D4806 

7.2 Water Content—lest Method E 203. 

7.3 Nonvolatile Matter—Test Method D 1353. 

7.4 Acidity— Test Method D 1613. 

7.5 Appearance—The product shall be visibly free of 

susp-v.ided or precipitated contaminants (clear and bright). 

i'his shall be determined at indoor ambient temperature 

unless otherwise agreed upon between the supplier and the 

purchaser. 

7.6 Specific Gravity—Test Method D891. Procedure B 

(hydrometer) is normally used. No formal precision statement is available, but practical experience indicates that 

precision is no better than 0.0005. Test Method D891 

Procedure C (pyenometen. with an interlaboratory precision 

(reproducibility) of 0.0002. should be used as a referee 

method. 

7.7 Chloride Ion Content—Modification of Test Method 

D512. Procedure C. 

7.7.1 The modification of Test Method D 512. Procedure 

C consists of using 5 mL of sample diluted with 20 mL of 

water in place of the 25 mL sampie specified in the standard 

procedure. The water shall meet Specification D 1193. Type 

II. The volume of the sample prepared by this modification 

will be slightly larger than 25 mL. To allow for the dilution 

factor, repon the chloride ion present in the fuel ethanol 

sample as the chloride ion present in the diluted sample 

multiplied by five. 

7.7.2 The precision of this modified method has not been 

determined, but for the actual amount of chloride ion found 

in the diluted sample, it is expected to be similar to the 

precision of Test Method D 512. Procedure C. 

7.8 Copper Content—Modification of Test Method 

D 1688. Procedure D. 

7.8.1 The modification of Test Method D 1688. Procedure D (atomic absorption) consists of mixing reagent grade 

ethanol (which may be denatured according to the U.S. 

Bureau of Alcohol. Tobacco, and Firearms (BATF) of the 

U.S. Treasury Department Formula 3A or 30) in place of 

water as the solvent or diluent for the preparation of reagents 

and standard solutions. However, this must not be done to 

prepare the stock copper solution described in 38. J of Test 

Method D1688. Because a violent reaction may occur 

between the acid and the ethanol. use water, as specified, in 

the acid solution pan of the procedure to prepare the stock 

copper solution. Use ethanol for the rinse and final dilution 

only. 

7.8.2 The precision of this modified method has not been 

determined but it is expected to be similar to the precision of 

Test Method D 1688. Procedure D. 

7.9 Ethanol Content—See Annex A1 for a proposed tesi 

method. 

Al. PROPOSED TEST METHOD FOR THE DETERMINATION OF ETHANOL CONTENT OF DENATURED 

FUEL ETHANOL BY GAS CHROMATOGRAPHY 

Al.l Scope 

A 1.1.1 This proposed test method covers the determination of the amount of ethanol in denatured fuel ethanol and 

may also be used to determine the amounts of other C, 

through C« alcohols. This test method does not determine 

water content: Test Method E 203 is recommended for the 

determination of water. 

A 1.1.2 The interpretation of this procedure shall be 

guided by the provisions of E 286 and E 355. 

A1.2 Summary of Test Method 

A 1.2.1 A two column chromatographic system connected 

to a thermal conductivity detector is used. A measured 

volume of sample is injected into the first column containing 

a polar liquid phase. The light hydrocarbons through 

methvicvclopentane are vented to the atmosphere as they 

elute. The column is backflushed immediately after tbe 

elution of methvicvclopentane. and the components remaining are directed into the second column, which contains 

an active solid. In this column, the alcohols elute before the 

remaining hydrocarbons. Immediately after the alcohols of 

interest have eluted. the flow through this solid-packed 

column is reversed to backflush the remaining hydrocarbons. 

Quantitative results are obtained by comparison of the areas 

of the recorded alcohol peaks with those obtained from the 

analysis of mixtures of known alcohol content. 

Al .3 Significance and Use 

A 1.3.1 Denatured fuel ethanol consists of ethanol. water. 

and denaturants and may contain impurities such as methanol, isopropyl alcohol, tertiary butyl alcohol. 1-pentanol 

(amyl alcohol), and 3-methyl-l-butanol (isoamyl alcohol). 

This proposed test method provides information on the 

purity of denatured fuel ethanol in order to help determine 

its suitability for blending with gasoline for use as an 

automotive spark-ignition engine fuel. 

A1.4 Apparatus 

A 1.4.1 Gas Chromatograph—A gas chromatograph 

equipped with a thermal conductivity detector with provision for installing a valve in the column oven or other heated 

zone. Provision must be made to operate a second column at 

a higher temperature than the first column and the valve. 

A 1.4.2 Valve, eight-port rotary or equivalent. 

A 1.4.3 Integrator—Electronic integration is recommended. 

A 1.4.4 Recorder—A 1-mV recorder with a 1-s full-scale 

response. If electronic integration is not used, minimum 

chart width of 250 mm (10 in.) and a minimum chart speed 

of 1 cm/min (0.4 in./min) are required. 

A 1.4.5 Column 1—A stainless steel column 2.4-m (3-fti 

long. 3.5-mm (0.138-in.) inside diameter, approximate!) 

4.75-mm (Vi«-in.) (outside diameter packed with 80 to 100 

mesh Chromosorb P coated to a 25 mass % level with 

tetracyanoethylated pentaerythritol (TCEPE). 

A 1.4.6 Column 2—K stainless steel column 4.6 m (15 ft i 

long. 3.5-mm (0.138-in.) inside diameter, approximate^ 
P.33 

D4806 

4.75-mm (V.6-in.) outside diameter packed with 80 to 100 

mesh Porapak P. 

A1.5 Reagents and Materials 

A 1.5.1 Calibration Mixture—Mix known amounts, approximately equal to the concentrations expected in the fuel 

to be tested of the following: 

A 1.5.1.1 Methanol—For the calibration mixture, use 

about 1 volume % 

NOTE Al.l: Methanols-tving—Flammable. May be fatal or cause 

blindness if swallowed. Vapor harmful. 

A 1.5.1.2 Ethanol—For the calibration mixture, use about 

90 volume Tc. 

NOTE A 1.2: £//ujno/-Wamiiig—Flammable. Denatured alcohol 

cannot be made nontoxic Eye irritant. Skin irritant on repeated contact. 

A 1.5.1.3 Amyl Alcohol—For the calibration mixture, use 

about 1 volume %. 

NOTE A1.3: /4mW ^/coAo/-W«niiiig— Flammable. Moderately toxic. 

May be absorbed through the skin. Irritating to skin, eyes, and mucous 

membranes. 

A 1.5.1.4 Jsoamyl Alcohol—For the calibration mixture, 

use about 1 volume %. 

NOTE A 1.4: hoamvt Alcohol-Mi umag—Flammable. Moderately 

toxic. May be absorbed through skin. Irritating to skin. eyes, and 

mucous membranes. 

A 1.5.1.5 The mixture must also contain a measured 

amount, approximately 7 volume %, of methyl 

cyclopentane. 

A 1.5.1.6 Methylcyclopentane. 

NOTE A1.5: Methylcydopmane-Vltnm,—Extremely flammable. 

Harmful if inhaled. Skin irritant on repeated contact Aspiration hazard. 

A 1.5.1.7 It is recommended that the mixture be prepared 

by weighing the components. The conversion to volume 

percent by use of their densities may involve inaccuracies 

due to volume change when the components are mixed. The 

purity of the compounds used must be at least 99 %. This 

mixture contains highly volatile components and will not 

retain its stability over a long period, and shall be handled 

accordingly. 

A 1.5.2 Carrier Gas—Chromatographic grade helium. 

A 1.6 Preparation of Apparatus 

A 1.6.1 Install the valve and columns as shown in Fig. 

Al.l. 

A 1.6.2 Place Column 2 in a separate heated zone. Any 

necessary connecting lines shall be of minimum diameter 

and length and must also be heated. 

A1.6.3 The restrictor shown in Fig. A1.1 is optional and is 

used to reduce baseline disruption when the valve is operated. It consists of a short length of 0.25-mm inside diameter 

stainless steel capillary tubing which should approximate the 

resistance to flow of Column 2. 

A 1.6.4 Establish the instrument parameters shown in 

Table Al.l. 

A1.7 Calibration 

A 1.7.1 Procedure: 

A 1.7.l.l Chromatograph a calibration blend prepared as 

in A 1.5.1 with the valve in the inject K~::*-o

 ,?,<i

 -*e 

Deiecioiniect'd: 

oc: 

FICJV\ cnrmo'if " • ' t t ?<Ov, •.ontrO'*e' -T 

Analyze position 

OetecioI—Z. 1 I | Dtvfiow rnnnollp' »1 t t fio*. cnni'iw« -

R G. A1.1 Diagram ef Apparatus 

TABLE A1.1 Operating Conditions Carrier gas 

Carrier gas (tow rate 

Detector type 

Detector temperature 

Infection port temperature 

Column 1 temperature 

VUve temperature 

Column 2 temperature 

Sample size 

rtaium 

60mwmm 

thermal conductivity 

200*C(392»F) 

170»C (338*F) 

115*C dothermal (239*F) 

IIS'CfZB'F) 

200*C isothermal (392*F) 

2.5 uL (reprodudtte) 

detector on polarity B. Determine the time in seconds 

required for the complete elution of the methylcyclopentane. 

Call this time 77,. 

A1.7.1.2 Chromatograph another equal volume sample-of 

the reference mixture with the detector on polarity A. At 

time 7", switch the valve to the analyze position. When the 

last oxygenate of interest has eluted, switch the valve to the 

inject position. Call this time T2. See Fig. A 1.2. 

A 1.7.2 A typical chromatogram is shown in Fig. A 1.2. 

Amyl alcohol and isoamyl alcohol elute after ethanol. but 

hydrocarbons elute in this region and may prevent the 

quantitative determination of these alcohols. 

A 1.7.3 Measure the areas of the alcohol peaks. Calculate 

tbe response factor (mass or volume percent per unit of area) 

to an accuracy of at least three significant figures for each of 

these components as follows: 

F=L/A 

where: 

F - response factor, 

A = area under the peak for the component, and 

L = mass or volume % concentration of the component. 

A l i Determination 

Al.8.1 Chromatograph the samples using the procedure 

578 
P.34 

D4806 

2 TimeT1 Ethanol Time T2 

7 

o o 

u C 

5 ° 

>. < 

m. < 

A7\J V . 

-Hydrocarbon Deneturant • 

6.30 12.60 16.90 25.20 31.50 

Retention Time, Minutes 

RG. A1.2 Typical Chromatogram 

37.60 44.10 50.40 

of A1.7.1. The volume of sample must be exactly the same as 

that used in calibration. 

A 1.8.2 Calculate the amount of alcohols present from the 

areas under their peaks as follows: 

La-FC 

where: 

La *- mass or volume percent of each alcohol, 

C - area for tbe particular alcohol, and 

F = response factor 

A 1.8.3 The amount of hydrocarbon denaturant can be 

estimated bv subtracting the sum total of the alcohols from 

100. 

A1.9 Report 

A 1.9.1 Report the concentrations of the individual 

alcohols on an absolute basis to the nearest 0.1 %. 

ALIO Precision and Bias 

A 1.10.1 Precision—The precision of this proposed test 

method has not been determined. 

A 1.10.2 Bias—There being no criteria for measuring bias 

in these test-product combinations, no statement of bias can 

be made. 

APPENDIX 

(Nonmandatory Information) 

XI. SIGNIFICANCE OF SPECIFIED PROPERTIES 

XI.1 Denatured Fuel Alcohol 

X1.1.1 Water Content—Karl Fischer analysis is generally 

the only consistently reliable procedure for the determination of water in denatured ethanol. Test Method E203 

describes the modifications required to run the test in the 

presence of alcohols. Specific gravity methods such as D 891 

and D 3505. are generally unsuitable for the reasons given in 

X 1.2.1. Blends of fuel ethanol and gasoline have a limited 

solvency for water. This solvency will vary with the ethanol 

content, the temperature of the blend, and the aromatic 

content of the base gasoline. A fuel made by blending 10 

.ulume % fuel ethanol with a gasoline containing 14 volume 

>o aromatics and 0.6 mass % dissolved water (about 0.5 

volume %), will separate into a lower alcohol-rich aqueous 

pnase and an upper hydrocarbon phase if cooled to about 

7*C (45*F). As normal spark-ignition engines will not run on 

the aqueous phase material, such a separation is likely to 

cause serious operating problems. Because some degree of 

water contamination is practically unavoidable in transport 

and handling, and because gasoline-ethanol blends are hygroscopic, the water content of the denatured fuel ethanol 

must be limited when it is blended with gasoline to reduce 

the risk of phase separation. 

XI. 1.2 nonvolatile Matter—This requirement controls a 

wide range of impurities and contaminants. 

XI. 1.3 Chloride Ion Content—Low concentrations of 

chloride ions are corrosive to many metals. 

XI. 1.4 Copper Content—Copper is a very active catalyst 

for the low-temperature oxidation of hydrocarbons. Experimental work has shown that copper concentration: higher 

579 
P.35 

D4806 

than 0.012 mass ppm in commercial gasolines may significantly increase the rate of gum formation. 

XI. 1.5 Acidity— Very dilute aqueous solutions of lowmolecular weight organic acids such as acetic (CH3COOH) 

are highly corrosive to many metals. It is therefore necessary 

to keep such acids at a very low level. 

XI. 1.6 Appearance—Turbidity or evidence of precipitation normally indicates major contamination. 

X1.1.7 Ethanol Purity—The presence of even small quantities of some organic oxygen compounds other than ethanol 

may adversely affect the properties of fuel ethanol-gasoline 

blends. 

X1.2 Undenatured Ethanol: 

X 1.2.1 Specific Gravity—The density of a water-ethanol 

mixture is primarily a function of its water content. Normal 

U.S. industry practice and Federal regulations call for the use 

of the 15.56'C/15.56'C (60T/60*F) specific gravity in air as 

the control method for water content of undenatured 

ethanol. Because the addition of denaturants will normalh 

affect specific gravity, specific gravity methods are generalh 

not suitable for determining the water content of denatured 

ethanols. 

Tne American Society tor Testing and Materials takes no position respecting tne valksity ol any patent rigms asserted in connection 

with any item mentioned In this standard. Users ot this standard are expressly advised that determination ot the validity of any such 

patent rights, and the risk ot infringement ot such rights, are entirely their own responsibility. 

This standard is suOtect ro revision at any time by the responsible technical committee and must be reviewed every live years ana 

it not revised, either reapproved or withdrawn. Your comments are invited either tor revision ot this standard or tor additional stanoaras 

and should be addressed to ASTM Headquarters. Your comments will receive caretui consideration at a meeting ot the responsible 

technical committee, which you may attend tl you fee/ that your comments have not received a tair hearing you should make your 

views known to the ASTM Committee on standards. 1916 Race St.. Philadelphia, PA 19103. 

580 
P.36 

APPENDIX I 

ASTM D 1835-89 Standard Specification for Liquified Petroleum Gases 
Designation: D 1835 - 89 An American National SianoaStandard Specification for 

Liquefied Petroleum (LP) Gases1 

This sundard is issued under the fixed designation D 1835: the number immediately following the designation indicates the year of 

ongmal adoption or. in the case of revision, the vear of last revision. A number in parentheses indicates the year oi last reapproval. A 

superscript eosiion I.I indicates an editorial change since the last revision or reapproval. 

I. Scope 

1.1 This specification covers those products commonly 

referred to as liquefied petroleum gases. 

1.2 This specification is applicable to products intended 

for use as domestic, commercial, industrial, and engine fuels. 

1.3 This specification is for use in formulating specifications for required properties of liquefied petroleum gases at 

the time of deliverv in bulk. 

2. Referenced Documents 

2.1 ASTM Standards: 

D1265 Practice for Sampling Liquefied Petroleum (LP) 

Gases: 

D126" Test Method for Vapor Pressure of Liquefied 

Petroleum (LP) Gases (LP-Gas Methods 

D1657 Test Method for Density or Relative Density of 

Light Hydrocarbons by Pressure Thermohydrometer 

D 1837 Test Method for Volatility of Liquefied Petroleum 

(LP) Gases2 

D1838 Test Method for Copper Strip Corrosion by 

Liquefied Petroleum (LP) Gases: 

D 2158 Test Method for Residues in Liquefied Petroleum 

(LP) Gases3 

D2163 Test Method for Analysis of Liquefied Petroleum 

(LP) Gases and Propane Concentrates by Gas Chromatography-' 

D 2598 Practice for Calculation of Certain Physical Properties of Liquefied Petroleum TLP) Gases from Compositional Analvsis;

' 

1

 This specification is under the jurisdiction of ASTM Committee D-2 on 

Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.H on Liquefied Petroleum Gas 

Current edition approved March 31. 1989. Published May 1989. Originall> 

published as D 1835 - 61 T. Last previous edition D 1835 - 8" 

:

 Annual ba<>h of ASTM Sianaards. Vol 05.01. 

' Annual Book of ASTM Standards. Vol 05.02. 

D2713 Test Method lor Drvness of Propane (Valve Freeze 

Method)3 

D2784 Test Method for Sulfur in Liquefied Petroieun-. 

Gases (Oxy-Hydrogen Burner or Lamp)' 

D 3700 Practice for Containing Hydrocarbon Fluid Samples Using a Floating Piston Cylinder4 

2.2 Other Document: 

GPA Sundard 21405 

3. Types 

3.1 Four basic types of liquefied petroleum gases are 

provided to cover the common use applications, as follows: 

3.1.1 Commercial Propane—A hydrocarbon product lor 

use where high volatility is required. Commercial propane is 

suitable for certain low severity internal combustion engine 

applications. 

3.1.2 Commercial Butane—A hydrocarbon product lor 

use where low volatility is required. 

3.1.3 Commercial PB Mixtures—Mixtures of propane 

and butane for use where intermediate volatility is required. 

3.1.4 Special-Duty Propane—A high-quality product 

composed chiefly of propane, which exhibits superior antiknock characteristics when used as an internal combustion 

engine fuel. 

4. Detail Requirements 

4.1 The four types of liquefied petroleum gases shall 

conform to the requirements prescribed in Table 1. 

5. Sampling 

5.1 Proper sampling of liquefied gases is extremely important if the tests are to be significant. Samples for compositional analysis should be obtained in accordance with 

Practice D 3700. Samples for other required tests should be 

obtained in accordance with Practice D 1265. 

4

 Annual Book ol ASTM Sianaards. Vol 05.03. 

5

 Available from Oas Processors Assn.. 6526 E. 60th St.. Tulsa. OK 7414: 

70." 
# D 1835 

TABLE 1 Detail Requirements for Liquefied Petroleum Gates 

Vapor pressure at 100°F (37.8°C). 

kPa 

Volatile residue 

max 

evaporated temperature. 95 %. max.' 

°C 

or 

butane and heavier, max. vol % 

pentane and heavier, max. vol S 

Propylene content, max. vol S 

Residual matter: 

residue on evaporation 100 mL. 

oil stain observation 

Relative density at 60/ 

60'F (15.6/15.6#C) 

Corrosion, copper, strip, max 

Sulfur, ppmw 

Moisture content 

Free water content 

max. 

.pa9 

»F 

mL 

Commercial 

Propane 

208 

1430 

-37 

-38.3 

2.5 

0.05 

oass-

-

No. 1 

185 

pass 

Commercial 

Butane 

70 

485 

36 

2.2 

2.0 

0.05 

pass0 

c 

No. 1 

140 

none' 

Product Designation 

Commercial 

PB Mixtures 

s 

36 

2.2 

2.0 

0.05 

pass0 

£ 

NO. 1 

140 

none' 

Spedal-Outy 

Propane* 

208 

1430 

-37 

-38.3 

2.5 

5.0 

0.05 

pass0 

No. 1 

123 

pass 

ASTM Test Methods 

(see Section 2) 

D 1267 or 

D2598c 

D1837 

D2163 

D2163 

D2163 

D2156 

D2158 

0 1657 or 

D2596 

D1838 

D2784 

0 2713 

* Eamvaient to Prooane HD-5 of GPA Standard 2140. 

8

 The permissible vapor pressures ot products classified as PB mixtures must not exceed 208 psig (1430 kPa> and additionally must not exceed mat calculated from 

me totiowmg relationship between me observed vapor pressure and tne ooserved relative density: 

Vapor pressure, ma* » 1167 - 1880 (relative density 60/60'F) or 1167 - 1880 (density at 15»C) 

A soecrtic mixture Shan De designated try tne vapor pressure at 100°F in pounds per souare inch gage. To comply with tne Designation, me vapor pressure ot tne mixture 

shanoewitrtm+Oto-IOpsiot tne vapor pressure specified. 

" in cawof dispute aoout tne vapor pressure ot a product, tne value actually determined by Test Method D1267 snail prevail over tne vaue calculated try Practice 

D 2598 

<- An acceptable product snail not yield a persistent on nng wnen 0.3 mL ot solvent residue mixture is added to a inter paoer. in O.i-rnL increments ana examined in 

fiavhant after 2 mm as descnoed in Test Method 0 2158 

« Aitnougn not a specific retirement, tne relative density must oe determined for other purposes and should be reported. Additionally, the relative densrtv ol PB. mixture 

is needed to establish tne perrrttsOie maiomum vapor pressure isee Footnote fi). . , 

' Tne presence or absence ot water shall oe uetermined oy visual nspectxxi of the samples on which the relative density is determmed. 

APPENDIX 

(Nonnuuidatory Information) 

XI. SIGNIFICANCE OF ASTM SPECIFICATIONS FOR LIQUEFIED PETROLEUM (LP) GASES 

Xl.l General 

X l. I. I Liquefied petroleum gas products are composed of 

those readily liquefiable hydrocarbon compounds which are 

produced in the course of processing natural gas and also in 

the course of the conventional refining of crude oil. The 

composition of liquefied gases can vary widely depending 

upon the source and the nature of the treatment to which the 

products have been subjected. 

X l. 1.2 There are many uses for liquefied petroleum gases. 

Important uses are. (7) as domestic, commercial, and industrial fuels. (2) as a carbon source material in metal treating 

operations, (i) as refinery raw materials for synthetic gasoline production, and (4\ as petrochemical raw materials. The 

nature of the needs dictates the required composition characteristics in these various applications. Since the last threiuses of those listed are in the category ol specialty applications which involve special requirements, they are excluded 

from consideration in the specifications. 

Xl.l.3 ln substance, the ASTM Specifications for Liquefied Petroleum Gases are designed to properly define acceptable products for domestic, commercial, and industrial uses. 

ln many cases it will be found that products meeting the 

specifications will also be usable in applications other than 

the ones for which they were designed. The following can be 

accepted as a general guide in the more common use 

applications of the three types of fuels: 

X l. 1.3.1 Commercial Propane—This fuel type is the one 

preferred for domestic, commercial, and industrial use. 

particularly in geographical areas and in seasons where low 

ambient temperatures are common, and where uniformity of 

fuel is an important consideration. Commercial propane is 

suitable for certain low severity internal combustion engine 

applications. 

X1.1.3.2 Commercial PB Mixtures—This fuel type, since 

it covers a broad range of mixtures, permits the tailonng of 

fuels to specific needs. The various mixtures find application 

as domestic, commercial, and industrial fuel in areas and at 

times when low ambient temperature conditions are less 

frequently encountered. 

XI. 1.3.3 Commercial Butane—This fuel type finds limited application as a domestic fuel in areas of warmer 

climates. It is similarly used in industrial applications where 

problems of fuel vaporization are not present. 

XI. 1.3.4 Special-Duty Propane—This fuel type is a spe704 
P.39 

# D 1835 

cial iiquefied petroieum gas product tailored to meet the 

restricts e needs of internal combustion engines operating 

under moderate to high engine severity. Fuel products of this 

type will be less variable in composition and combustion 

characteristics than the other products covered by this 

'.per. '"ication. 

M.2 Significance and Use 

XI.2.1 Since commercial liquefied petroleum gases are 

essentially either singie component products, depending 

upon fuel type, it follows that all of the important behavior 

characteristics of such products can be defined and controlled by a relatively few simpie measurements. The specification tests which are provided achieve the desired result. 

The significance of the various tests as they can apply to 

consumer problems is summarized here. 

X l .2.1.1 I apor Pressure. I olatility. and Relative Density 

(</i I'anor Press-tin- is an indirect measure of the mo?: 

extreme low-temperature conditions under which initial 

vaporization can be expected to take place. It can be 

considered as a semiquantitative measure of the amount of 

the most volatile material present in the product. It can alsr 

be used as a means for predicting the maximum pressures 

which may be experienced at fuel tank temperatures. Vapor 

Dressure becomes more significant when it is related n 

volatility. 

(/>> Volatility, expressed in terms of the 95

 r

c evaporated 

temperature of the product, is a measure of the amount of 

least volatile fuel component present in the product. Coupled with a vapor pressure limit, it serves to assure essentially 

single-component products in the cases of commercial propane and commercial butane fuel types. When volatility is 

coupled with a vapor pressure limit which has been related to 

gravity, as in the case of the commercial PB-mixture type of 

fuels, the combination serves to assure essentially two 

component mixtures for such fuels. When coupled with z. 

proper vapor pressure limit, this measurement serves tc 

assure that special-duty propane products will be composed 

chiefly of propane and propylene and that propane will bt 

the major constituent. 

ic) Relative Density, by itself, has little significance. I; 

becomes of value only when related to vapor pressure and 

volatility. Since relative density is of importance in meeting 

transportation and storage requirements it is always determined for all liquefied petroleum gas products. 

XI.2.!.2 Other Proaua Characteristics—While the vaporization and combustion characteristics of commercial 

liquefied gas products are completely defined for the norma! 

use applications by vapor pressure, volatility, and relative 

density, as given in XI.2.1.1, there are other items which 

either affect or might affect the results obtained in some 

specific use applications. For that reason, limits are specified 

for residue content, copper corrosion, sulfur content, moisture content, and free water content to provide assurance of 

product dependability under the more extreme conditions of 

use. 

ia) Residue (End Point Index) is a measure of the concentration of combustible hydrocarbon materials present in the 

product which are substantially less volatile than the liquefied petroleum gas hydrocarbons. Control over residue 

content is of considerable importance in use applications 

where the fuel is used in liquid feed systems, ln such cases. 

failure to limit the permissible concentration of residue 

materials may result in troublesome deposits. It is also o\" 

importance where the fuel vapors are withdrawn from the 

top of the storage container, ln such applications, regulating 

equipment tends to become fouled up if excessive amounts 

of residue are present in the field. 

(b) Copper Corrosion limits are for the purpose of providing assurance that difficulties will not he experienced i;. 

the deterioration of the copper and copper-alloy fittings and 

connections which are commonly used in many types of 

utilization, storage, and transportation equipment. The 

copper corrosion test will detect the presence of hydrogen 

sulfide, which is highly toxic. Therefore the copper corrosion 

limits also provide assurance that the LP-Gas will not 

contain hydrogen sulfide in such quantities as to present :: 

health and safety hazard. In addition. Test Method D 2420 is 

recommended as a field test and added safeguard to ensure 

that LP-Gas does not contain detectable amounts of hydrogen sulfide. 

ic) Sulfur Content limits are provided primarily for the 

purpose of more completely defining liquefied petroleum gas 

products since these products are inherently much lower in 

sulfur content than other petroleum-derived fuels. In the 

normal fuel use applications for liquefied petroleum gas. 

sulfur content is considered to be of limited significance if 

the other product characteristics are within the specified 

iimits. 

(cl) Moisture Content is a measure of the aporoximaie 

percentage saturation of the product with water. This measurement is a requirement only on the commercial ant: 

special duty propane types of liquefied petroleum gas. The 

purpose of moisture content control is to provide assurance 

that pressure reducing regulators and similar equipment will 

operate consistently without troublesome freeze-ups caused 

by the distillation of dissolved water from the product. 

le) Free Water Content is of importance only on the 

commercial PB-mixtures and commercial butane type products. These two types of products are normally used under 

ambient conditions which are mild and. as a consequence 

the only requirement is vigilance to assure that no free wateris present. 

Tne American Society lor Testing and Materials taxes no position respecting tne validity o' anv patent ngnts asserted in connecticwitn anv item mentionea in tnis stanoard. users ol tnis stanoaro are enpressiv aavisea mat oeterminanon or tne validity or any su:-

patent ngnts. ana tne nsr, ol intnngement ot sucn ngnts. are entireiv tneir own resoonsipiiii, 

Tnis stanoaro is subiect to revision at any time by tne resoonsibie technical committee ana must be reviewed every live years anc 

it not reviseo eitner reapproveo or witnorawn. rour comments are invited either tor revision ol this stanoaro or lor additional stanoarai 

ana snouia De aaoressea to ASTM heaaauaners. Your comments win receive caretui consioeration at a meeting ol tne resoonsio^ 

technical committee whicn vou mav attena. n vou teei mat vour comments nave not receivea a lair neanng you snouia mane youviews xnown to tne ASTM Commmee on Stanaarss. 1916 Race S:. Phiiaaeipnia. PA 19103 

"05