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ICS 75.160.20

E 31

National Standard of the People’s Republic of China

GB/T 23799-2009

Issued on May 18, 2009 Implemented on Dec 1, 2009 General Administration of Quality Supervision, Insp ection and Q u a r a n t i n e o f P e o p l e ' s R e p u b l i c o f C h i n a Issued by Standardization Administration of the Peo ple's R e p u b l i c o f C h i n a

Issued by

GB/T 23799-2009

2

Preface

Compared with ASTM D 5797：2007, this standard has major followings differences:

Standard specification ASTM D 5797:2007 "Methanol gasoline for motor vehicles for

spark-ignition engine" (M70 ~ M85) (English version) is adopted to revise this standard,

which is compared with articles in ASTM D 5797:2007 (See Appendix D).

Compared with ASTM D 5797:2007, this standard has major followings differences:

——When this standard used ASTM D 5797:2007 quoted standard, national standards

and standards of petrochemical industry have adopted corresponding national standards

or standards of petrochemical industry, while ASTM D 5797:2007 quoted standard is

stilled adopted in the case of absence of corresponding standard.

——Appoint arbitral test method

——Cancel the grade of methanol fuel (M70~M85), which is specified in accordance with

geographical distribution and ambient temperature, and only set a grade for methanol

gasoline for motor vehicles (M85).

——Limit of vapor pressure of methanol fuel (M85) in original standard will be revised as

"November 1~April 30: ≤78kpa, May 1~Oct 31: ≤80mg/kg "

——Limit value of sulfur content index of methanol fuel (M85) in original standard will be

modified from original "≤160 mg / kg" to "≤80mg/kg";

——Cancel phosphorus content index in original standard, add sodium content index and

its determination method;

——Increase the Mn content limit value for the "≤ 2.9 mg / L";

——Add Mn content limit value of ≤2.9 mg/L” ;

——Add note of table: " Effective metal corrosion inhibitor and detergent for automobile

gasoline (comply with GB 19592) shall be added” and “Don’t manually add

halogen-containing additive, which is harmful to reliability of the vehicle and

post-processing system, and additives containing, iron, lead and phosphorous”.

should be added to an and effectively in line with GB 19592" motor vehicle gasoline, and

"no man-made vehicles to join of harmful ".

——Add chapters such as "Inspection rule", "Symbol, packaging, transportation and

storage" and "Safety";

——Revise Appendix A1 and A2 in original standard to normative Appendix A and B in this

standard; Add in normative Appendix C and informative Appendix D;

——Remove chapter of key , Appendix A3, X1 and X2.

Appendix A, B and C in this standard are normative appendices, while Appendix D is

informative appendix.

This standard was proposed by National Technical Committee on Petroleum Products and

Lubricants of Standardization Administration of China (SAC/TC 280)

This standard is under the jurisdiction of Subcommittee on Petroleum Fuels and

Lubricants of National Technical Committee on Petroleum Products and Lubricants of

Standardization Administration of China (SAC/TC 280 1)

Drafting unit of this standard: Shanghai Internal Combustion Engine Research Institute,

Shenzhen Jimmy Chemical Technology Co., Ltd., Shanghai Coking Co., Ltd., Technology

Center of SAIC Group, China National Offshore Oil Corporation, Shanxi Jiaxin Energy &

GB/T 23799-2009

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Chemical Co., Ltd., Beijing Xiongtao Weiye Energy Technology Development Co., Ltd..

Units of participating in the drafting: Xinao Group Co., Ltd., Shaanxi Yanchang Zhongli

New Energy Co., Ltd., Shanxi Wharton Industrial Co., Ltd., Shanghai Maple Automobile

Co., Ltd., Jiangsu Nanda High Technology Industry Co., Ltd. , Century Petrochemical Co.,

Ltd. In Xinjiang Uygur Autonomous Region.

, Xinjiang Uygur Autonomous Region Century Petrochemical Co., Ltd..

Major drafters of this standard: Lan Zhibo, Yang Youwen, Qi Hongyuan, Li Ruibo, Xie

Zhenhua, Shi Lei, Tang Chien, Liu Fanghua, Song Jinzhong, Wang Jianzhong.

GB/T 23799-2009

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Methanol gasoline for motor vehicles (M85)

1. Scope This standard stipulates terms, definitions, abbreviations, requirements, reagents, test

methods, inspection rules, symbols, packaging, transportation, storage and safety for

methanol gasoline for motor vehicles (M85), which is blended by 84%~86% (volume

fraction) methanol, 16%~14% (volume fraction) gasoline for motor vehicles (comply with

GB17930) and additive with improved service performance.

Products belonging to this standard are applicable to being used as the fuels for the

vehicle adopting methanol gasoline for motor vehicles (M85) of spark-ignition engine

vehicle.

Molecular formula of methanol is CH3OH.

2. Cited Normative Documents

Clauses of the following documents become the clauses of this standard through citation in this

standard. All amendment lists (not including errata) of cited documents or revisions indicated with

date or are not applicable to this standard; however, it is encouraged for all parties reaching

agreement according to this standard to study whether the latest version of those documents can

be used. The latest versions of all cited documents indicated with no date are applicable to this

standard.

GB 190 Labels for packages of dangerous goods

GB/T 4756 Petroleum liquids--Manual sampling (GB/T 4756-1998, eqv ISO 3170:1988)

GB/T 6283 Chemical products—Determination of water Karl·fischer method(general

method) (GB/T 6283-2008, ISO 760:1978, NEQ)

GB/T 6682 Water for analytical laboratory use - Specification and test methods (GB/T

6682-2008, ISO 3696: 1987, MOD)

GB/T 8019 Motor gasoline and aviation fuels; Determination of existent gum; Jet

evaporation method

GB/T 8020 Gasoline; Determination of lead content; Atomic absorption spectrometry

GB/T 9725-2007 Chemical reagent—General rule for potentiometric titration

GB/T 11140 Standard test method for sulfur in petroleum products by wavelength

dispersive X - ray fluorescence spectrometry

GB 12268 List of dangerous goods

GB 13690 Classification and labels of dangerous chemical substances sommonly used

GB/T 16483 Safety data sheet for chemical products—Content and order of sections

GB/T 17476 Standard test method for determination of additive elements,wear

metals,and contaminants in used lubricanting oils and determination of selected elements

in base oils by inductively coupled plasma atomic emission spectrometry (ICP-AES)

GB 17930 Gasoline for motor vehicles

GB/T 18612 Determination of organic chloride content in crude oil by combustion and

microcoulometry

GB 19592 Detergent additive fore vehicular gasoline

GB/T 23799-2009

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SH 0164 Rules for the Packing, Storage, Transportation and Inspection upon Delivery

of Petroleum products

SH/T 0253 Determination method for total sulfur content in light petroleum products

(coulometric method)

SH/T 0663 Detemination Of some alcohol and ether in petrol(gasoline)-gas

chromatography method

SH/T 0689 Standard test method for determination of total sulfur in light hydrocarbons

motor fuels and oils by ultraviolet fluorescence

SH/T 0711 Standard test method for manganese in gasoline- by atomic absorption

spectroscopy

SH/T 0794 Standard test method for determination of vapor pressure of petroleum

products

ASTM D512 Standard Test Methods for Chloride Ion In Water

ASTM D872 Test Method for Sulfonation Index of Road Tars

ASTM D1613 Standard Test Method for Acidity in Volatile Solvents and Chemical

Intermediates Used in Paint, Varnish, Lacquer, and Related Products

ASTM D4626 Standard Practice for Calculation of Gas Chromatographic Response

Factors

ASTM D5059 Standard Test Methods for Lead in Gasoline by X-Ray Spectroscopy

ASTM E203 Standard Test Method for Water Using Volumetric Karl Fischer Titration

3. Terms and definitions, abbreviations Following terms and definitions, abbreviations are applicable to this standard.

3.1 Aliphatic ether

It refers to an ash-free organic compound containing an oxygen atom, which is between

two carbon atoms on the organic groups. Its molecular formula is and n=5~8.

According to this standard, aliphatic ether only refers to the saturated compound.

3.2 Methanol gasoline (M85) for motor vehicles

It refers to a product blended by methanol and gasoline for motor vehicles.

Note: methanol addition amount of 84%~86% (volume fraction).

3.3 Higher alcohols

It refers to fatty alcohol with carbon number of 2~8 and molecular formula of .

3.4 Hydrocarbon

It refers to the compound, which only contains carbon and hydrogen. In methanol gasoline

(M85) for motor vehicles, this compound is from gasoline for motor vehicles--a blending

component.

3.5 Low-volume connector

A connector without dead volume.

Special device connecting 2 pipelines with inner diameter of 1.6mm and thinner pipeline.

3.6 Split ratio

It’s ratio between total flow of carrier gas at the sample injection port and that of carrier

gas entering into the chromatograph.

3.7 TCEP

1,2,3-tris-(2-cyano-ethoxy) propane: Stationary liquid for gas chromatography.

GB/T 23799-2009

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3.8 WCOT

It’s the abbreviation of capillary column type and refers to the capillary column with

coating on the inner wall. A thin layer of stationary liquid is coated on the inner wall of this

type of capillary column.

4. Requirements and test method Technical requirements and test method for methanol gasoline (M85) for motor vehicles

are shown in Table 1.

Table 1 Technical requirements and test method for methanol gasoline (M85) for motor

vehicles Item Quality index Test method Appearance Orange-red transparent liquid

without layering. It doesn’t contain suspensions and deposited mechanical impurities.

Visual inspection a

Methanol+ higher alcohols (volume fraction)/%

84~86 Appendix A (determine methanol), SH/T (determine higher alcohols)

Hydrocarbon+ aliphatic ether b

(volume fraction)/% 14~16 Appendix B

Vapor pressure/kPa Nov, 1 to April, 20, ≤ May, 1 to Oct, 31, ≤

78 68

SH/T 0794

Lead content c /(mg/L), ≤ 2.5 GB/T 8020, ASTM D5059 Sulfur content d /(mg/kg), ≤ 80 GB/T 11140, SH/T 0253, SH/T

0689 Higher alcohols(volume fraction)/% , ≤

2 SH/T 0663

Acidity (calculated as acetic acid)/(mg/kg), ≤

50 ASTM D1613

Actual colloid (mg/100mL), ≤ 5 GB/T 8019 Unwashed colloid (mg/100mL), ≤ 20 GB/T 8019 Organic chlorine content /(mg/kg), ≤ 2 GB/T 18612 Inorganic chlorine content e (calculated as Cl-1)/(mg/kg), ≤

1 Appendix C, ASTM D512 (method C)

Na content, ≤ 2 GB/T 17476 Moisture f (mass ratio) /% , ≤ 0.5 ASTM E203, GB/T 6283 Mn content g /(mg/L), ≤ 2.9 SH/T 0711 Note: " Effective metal corrosion inhibitor and detergent for automobile gasoline (comply with GB 19592) shall be added” and “Don’t manually add halogen-containing additive, which is harmful to reliability of the vehicle and post-processing system, and additives containing, iron, lead and phosphorous” shall be added. a. Inject the sample into a 100mL glass cylinder for observation. It shall be orange-red transparent liquid without layering and doesn’t contain suspensions and deposited mechanical impurities. When there is dispute, determined result obtained via the method in GB/T 511 is used as the basis. Orange-red color occurs due to addition of candle red dye (alias Sudan IV) in the methanol gasoline (M85) for motor vehicles. Addition amount of red candle shall be 8 ~ 10mg/kg and its Index No. is CISolvent Red 24 (26105). Other types of dye can’t be added. b. "Hydrocarbon + aliphatic ether" is the gasoline for motor vehicles complying with GB 17930. Content of "Hydrocarbon+ aliphatic ether" can also be obtained by reducing the sum of contents of methanol, other alcohols and water. However, determined result via the method in Appendix B is used as the basis when there is dispute. c. Determined result via the method in GB/T 8020 is used as the basis when there is dispute. When using test method in ASTM D5059, methanol (AR reagent) shall be used as the solvent to prepare calibration solution in order to prevent error caused by larger difference of carbon hydrogen ratio. d. Determined result via the method in SH/T 0689 is used as the basis when there is dispute.

GB/T 23799-2009

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When using test method in GB/T 11140, methanol (AR reagent) shall be used as the solvent to prepare calibration solution in order to prevent error caused by larger difference of carbon hydrogen ratio. e. Determined result via the method in Appendix C is used as the basis when there is dispute. f. Determined result via the method in ASTM E203 is used as the basis when there is dispute. g. Mn content is introduced after blending gasoline for motor vehicles. It refers to total Mn content existing in the form of methyl cyclopentadienyl manganese tricarbonyl. Other types of Mn-containing additives can’t be manually added.

5. Inspection rule 5.1 Classification and items of inspection

Inspection for products belonging to this standard is factory inspection, whose items are

all the items specified in technical requirements in Chapter 4.

5.2 Rule for grouping and batching

Under the same condition of material and process, each drum or kettle of product is a

batch.

5.3 Sampling

5.3.1 Sampling

Sampling shall be conducted in accordance with GB/T 4756. Take 2g sample for test and

reservation.

5.3.2 Brown glass container shall be used for sampling. If the metal container is used,

then it shall not be welded because welding will be corroded and dissolved into methanol

fuel, resulting in contamination of sample. Use of plastic container is prohibited.

5.4 Judgment rule

If results of factory inspection comply with the regulations in technical requirements in

Chapter 4, then determine the batch of product is judged as qualified.

5.5 Re-inspection rule

If factory inspection results don’t comply with the regulations in technical requirements in

Chapter 4, double amount of sample shall be taken for re-inspection according to GB/T

4756. If an items in results of factory inspection still can’t comply with the regulations in

technical requirements in Chapter 4, then the batch of product is judged as unqualified.

6. Symbol、packaging、transportation and storage 6.1 Methanol gasoline (M85) for motor vehicles is flammable liquids and toxic goods. It’s

irritative. Its symbol, packaging, transportation, and storage and acceptance of delivery

shall be carried out in accordance with SH0164, GB 12268, GB 13690 and GB 190 out.

6.2 "Methanol gasoline (M85) for motor vehicles" shall be marked on the fuel pumps and

the containers, which use methanol gasoline (M85) for motor vehicles complying with this

standard and are sold to the customers. Moreover, the symbol of flammable liquids and

toxic goods shall be marked on the place that is easily visualized the driver.

6.3 During transportation and storage process for methanol gasoline (M85) for motor

vehicles complying with this standard, special pipelines, containers and pumps shall be

used. Sealing parts and materials for these storage tanks, pumps, pipelines and meters

should be appropriate for the requirements of methanol gasoline (M85) for motor vehicles.

During transportation and storage process, ensure that the entire system is clean and

GB/T 23799-2009

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doesn’t contain water. Meanwhile, strictly prevent absorption of water from outside and

breather valve carrying desiccant must be equipped on the storage tank for finished

product. If phase separation occurs, special treatment shall be conducted.

6.4 Use of unprotected aluminum devices in the distribution and metering equipment for

methanol gasoline (M85) for motor vehicles can result in entry of insoluble aluminum

compound into the fuel and lead to the blockage of the filter screen for the automobile fuel.

Moreover, the conductivity of fuel can increase due to contact between fuel and

distribution hose even with protective aluminum device is adopted, which aggravates the

corrosion effect. Therefore, unprotected aluminum material and nitrile rubber distribution

hose without lining shall be avoided to use in the distribution and metering equipment for

methanol gasoline (M85) for motor vehicles.

7. Safety 7.1 Material Safety Data Sheet of the product shall include data and information of safety

involving links such as transportation, storage, use and accident handling. Manufacturer

or supplier shall provide Material Safety Data Sheet of its product, which is prepared in

accordance with GB/T 1643.

7.2 Methanol vapor from methanol gasoline (M85) for motor vehicles has stimulating

effect on the nervous system and can cause blindness and poisoning after having been

inhaled in the human body. Therefore, volatilization of vapor of methanol gasoline (M85)

for motor vehicles shall be minimized during handling and refueling. Prohibit the product of

contacting with mouth, eyes and skin. Avoid inhaling vapor of methanol gasoline (M85) for

motor vehicles. Preventive measures shall be accordingly conducted for the personnel of

preparation, handling and refueling to prevent excessive inhalation of harmful vapor.

7.3 When methanol gasoline (M85) for motor vehicles splashes on the skin and the eye,

promptly wash with plenty of clean water and rapidly conduct medical care.

7.4 Inhalation of methanol gasoline (M85) for motor vehicles by the mouth is prohibited.

Forbid using methanol gasoline (M85) for motor vehicles to wash hands, scrub clothes

and machine parts and fill lighter, as well as use of the fuel for blowtorch.

7.5 When methanol gasoline (M85) for motor vehicles is on fire, sand, anti-solvent

fluoro-protein foam extinguishing agent and asbestos cloth shall be used to extinguish the

fire. When methanol gasoline (M85) for motor vehicles spills, special treatment shall be

conducted.

7.6 Methanol gasoline (M85) for motor vehicles specified by this standard is only

applicable to spark-ignition engine of using methanol gasoline for motor vehicles and can’t

be used for any other purposes.

GB/T 23799-2009

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Appendix A (normative Appendix)

Determination method for methanol content in methanol gasoline (M85) for motor vehicles

A.1 Scope This method is to determine methanol content in the methanol gasoline (M85) for motor

vehicles via gas chromatograph. This method is applicable to determining methanol

content (within range of 70~95%) in the methanol gasoline (M85) for motor vehicles

(volume fraction).

A.2 Overview of the method A.2.1 Add internal standard tertiary amyl alcohol into the sample and then introduce it into

gas chromatograph equipped with two columns and a column switching valve. Firstly

make sample pass through the first column (polar TCEP column), empty light hydrocarbon,

retain heavy hydrocarbon components and oxygen-containing compound.

A.2.2 Switch the valve for blowback after methyl cyclopentane flows from the polar column

and before methanol flows from the polar column, while oxygen-containing compound

enters into non-polar WCOT column. Before heavy hydrocarbon components flow out,

methanol and internal standard flow out in the sequence of boiling points.

A.2.3 After internal standard has flowed out from non-polar column, switch column

switching valve to its initial position to blow heavy hydrocarbon compound back. Detect

outflow components with flame-ionization detector or TCD, record the response value of

detector that is proportional to component concentration, determine peak area and

calculate the concentration of each component with reference to internal standard.

A.3 Implication and application A.3.1 Information about methanol content is requested for production ofA.3.1 methanol

gasoline (M85) for motor vehicles to guarantee quality of qualified commercial fuel

products, because methanol content in methanol gasoline (M85) for motor vehicles has

impact on the performance of the vehicle using this fuel.

A.3.2 In addition to production control for methanol gasoline (M85) for motor vehicles, this

method can also be used to determine contaminants in fuel.

A.4 Instruments A.4.1 Gas chromatograph

As for exact description and definition, refer to ASTM E355.

A.4.1.1 Operate gas chromatograph in accordance with the conditions given in Table A.1.

Connection between switching valve and blowback system is shown in Figure A.1.

Required ratio of flow rate of carrier gas shall be obtained in the flow control system of the

carrier gas (See Table A.1), while pressure control device and pressure gauge shall meet

the requirements in Table A.2.

Table A.1 Analytical condition of gas chromatography

Item Analytical condition Temperature of column box 60 Sample injector 200 Detector

TCD 200 Flame-ionization detector 250

Temperature/

Valve 60

GB/T 23799-2009

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Flow rate of injected sample 75 Column 5 Auxiliary gas 3

Flow rate

Supplemental gas 18 Carrier gas Helium Injection volume 1 Split ratio 15:1 Blowback time/min 0.2~0.3 Reset time for the valve /min 8~10 Analysis time /min 18~20

Table A.2 Retention characteristics of TECP/WCOP column based on the conditions listed

in Table A.1

Component Retention time/min Relative retention time/min

Methanol 3.21 0.44

Tertiary amyl alcohol 7.30 1.00

A.4.1.2 Detector

Both TCD and FID can be used. The system shall have sufficient sensitivity and stability to

meet the response when actual concentration changes by 0.01% (volume fraction) or the

internal standard changes by 50% (volume fraction).

A.4.1.3 Switching and blowback valve

A 10-way valve, which is located on the box of gas chromatographic column, to complete

functions in A.8 and relevant instruction in Figure A.1. Design of small dead volume shall

be conducted for the valve and severe distortion of chromatographic peak won’t be

induced.

A.4.1.4 Use automatic valve switching device as possible to guarantee repetition of

switching time. The device is synchronized with time of sample injection and data

acquisition. If there is no such device, use a stopwatch to begin to record switching time of

the valve during sample injection.

A.4.1.5 Sample injection system

The system is a split injection device. Split injection shall ensure that actual sample

quantity entering into the column is within calibrated amount, optimum response of the

detector and linear range.

Valve at reset position

Polar (TCEP) column

Detector

Non-polar (WCOT) column

Adjustable current limiter

Flow controller

Emptying of the column

Back pressure regulator

Bypass injection port

GB/T 23799-2009

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Valve at blowback position

Figure A.1 Chromatograph system

A.4.1.6 Sample delivery system

To repeatedly introduce the sample into any system of the split injection device,

micro-sampler, automatic sampler and injection valve for the liquid sample can be used.

A.4.2 Data processing and computing system

A.4.2.1 Recorder or computer

A.4.1.2

Recording of spectrum and data processing shall meet the requirements in A.4.1.2, while

peak height and area can be measured with computer and electronic integrator or via

manual method.

A.4.3 Chromatographic column

Any column that complies with or is better than chromatographic columns and selectivity

described in A.4.3.1.1 can be used. Column shall be operated in accordance with the

temperature required in A.4.3.2. Within the same range of boiling point, the column can

complete separation between volatile hydrocarbon and oxygen-containing compound.

Reserved oxygen-containing compound and heavy hydrocarbon can be blown back to the

non-polar column.

A.4.3.1.1 TCEP micro-packed column：

Peak height=560mm, external diameter=1.6mm, internal diameter=0.38mm，stainless

pipe. Fill with 0.14~0.15g g 20% TCEP fixed phase and the carrier is 150~180 μm

(100/80 mesh) red diatomite P (AW). This column is used to study precision and deviation

data in A.13.

A.4.3.2 Non-polar column (column for analysis)

Any column that is equivalent to or better than chromatographic columns and selectivity

described in A.4.3.2.1 and Figure A.2 can be used.

A.4.3.2.1 WCOT methyl silane column: Length = 30m, inner diameter = 0.53mm. WCOT

capillary quartz column is coated with cross-linked methyl silane with thickness of 2.65µm.

The column is used to study data of precision and deviation in A.13.

Emptying of the column Adjustable current limiter

Polar (TCEP) column

Back pressure regulator

Bypass injection port

Flow controller

Non-polar (WCOT) column

Detector

GB/T 23799-2009

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Figure A.2 Example of chromatographic results

A.5 Reagents and materials A.5.1 Carrier gas: Carrier gas complies with the requirements of detector type and its

purity (volume fraction) isn’t less than 99.995%.

Note: Helium can be used.

A.5.2 Methanol: Purity (volume fraction)=99.9%. It can be used for determination of

retention time and quantitative calibration. Its content is known. Moreover, there is no

other compound for analysis.

Caution: It's combustible and has hazard to the health.

A.5.3 Dichloromethane: Reagent grade. Non-volatile residue.

A.5.4 N2: Purity (volume fraction) =99.998%. It can be used for preparation of TCEP

micro-packed column.

Caution: Pressurized Gas

A.5.5 Tertiary amyl alcohol (2-methyl-2-butanol): Purity (volume fraction)>99 %. It can be

used as the internal standard.

Caution: It’s combustible and has hazard to the health.

A.6 Packing and preparation of column A.6.1 Preparation of TCEP packed column

A.6.1.1 If it can retain methanol and tertiary amyl alcohol (internal standard) in the

methanol gasoline (M85) for motor vehicles from hydrocarbon components with same

boiling range, the chromatographic column can be used.

A.6.1.2 Dissolve 10g TCEP in 100mL dichloromethane add 40g 150 ~ 180 m1 (100/80

mesh) red diatomite carrier P into above solution, rapidly transfer above mixture into an

evaporating dish, place it into a fume hood (Wiping of residual filler deposited on the

container isn’t required), continuously and gently stir the filler until the solvent is

completely evaporated. Filler in the column can be directly used to prepared TCEP

column.

A.6.2 Filling of TCEP micro-packed column

A.6.2.1 Use to wash a stainless column tube with height of 560mm and external diameter

Methanol

Ethanol

Tertiary amyl alcohol

GB/T 23799-2009

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of 1.6mm (internal diameter=0.3mm). Then dry it with compressed N2.

A.6.2.2 Insert a cluster of silver-plated wire (6~12 threads) or a plug made by stainless

web into one end of the column tube. Slowly add 0.14 ~ 0.15g filler into another end of the

column, gently shake the column to tightly pack the filler during filling process and insert

the plug at charging end. When using wire or stainless web plug to block the column,

6.4mm shall be left at two ends of the column to ensure that filler doesn’t flow out.

A.6.2.3 Aging of column

Before use, simple aging shall be conducted for both TCEP column and WCOT column. In

the box of gas chromatographic column, connect the column to the valve (see A.8.1),

adjust flow of carrier gas in accordance with A.8.3 and put the valve on the reset position.

After a few minutes, increase box temperature to 120 ℃, maintain for 5 ~ 10min and cool

the column to 60 ℃ before shutting off the carrier gas.

A.7 Sampling A.7.1 To obtain representative sample for the test, conduct sampling in accordance with

the regulations specified in GB/T 4756.

A.7.2 Before analysis, sample of methanol gasoline (M85) for motor vehicles shall be

stored in the refrigerator before analysis until sampling and analysis for the test. If analysis

can’t be immediately conducted, the sample shall be placed in the refrigerator.

A.7.3 Before sampling for analysis, sample container shall be fully vibrated and particles

can precipitate on the bottom of the container. Observe if obvious phase separation

occurs in the sample. If phase separation happens, the sample will be discarded and

re-sampling be required.

A.8 Preparation of instruments and determination of conditions A.8.1 Assembly

Use connector with small dead volume and the pipe with small diameter to connect

WCOT column to the valve system. It is important that the dead volume of connecting the

chromatographic system be minimized. Otherwise, the value of chromatographic peak will

become wide.

A.8.2 Adjust operating conditions (if TCD is used, don't open the circuit of the detector) in

accordance with Table A.1. The system shall be detected before operation.

A.8.3 Adjustment of split ratio

See Figure A.1.

A.8.3.1 Set the valve to reset position, install a bubble flowmeter at the vent of the column,

adjust the pressure at injection port until flow rate reaches 5.0mL/min.

A.8.3.2 Install the flowmeter at the vent of split opening, use flow controller on the gas

path A to control the flow to 70 mL/min. If necessary, re-check the flow from outlet in

accordance with A.8.3.1.

A.8.3.3 Switch the valve to blowback position and adjust resistance valve to make the flow

from outlet of the column be equal to that in A.8.3.1, which is necessary for minimizing

change of flow when switching the valve.

A.8.3.4 Switch the valve to reset position for sample injection, adjust flow controller B to

make flow at the outlet of detector reach 3.0~3.2 mL/min. According to the exact

requirement of the instrument, add supplement gas or TCD flow to make total flow at the

outlet of detector reach 3.0~3.2 mL/min.

GB/T 23799-2009

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A.8.4 When using TCD, open thermal-conductivity and bridge-current circuit system to

make the detector reach balance. When using FID, set flow of H2 and air, ignite the flame

and then open the electrometer.

A.8.5 Switching time

Time of switching the valve from blowback position to reset position time causes small

change of each column system. It shall be determined in the lab in accordance with the

following methods. Start-up time of integrator and valve timer shall be kept synchronized

with time of sample injection and blowback to accurately repeat blowback time.

A.8.5.1 Prepare mixed solution containing 40% (volume fraction) methanol, 10% (volume

fraction) gasoline and 50% (volume fraction) tertiary amyl alcohol (internal standard).

A.8.5.2 Initially set blowback time of the valve to 0.23min. When the valve is at reset

position, inject 1µL mixed solution. After 0.23min since sample injection, switch the valve

to blowback position until recognized internal standard completely flows out. Record this

time and use it as reset time, which is the time when the valve returns to the reset

position.

When reserved hydrocarbon is completely blown back, signal will return to the stable

baseline and the system is preparing for next analysis. Chromatograph shows the same

spectrum as Figure A.2.

A.8.5.3 It is very important to optimize switching time of the valve through analysis for

mixed solution prepared in A.8.5.1，. Accurate blowback time can be determined within

switching time of the valve (0.2~0.3min)。If the valve is switched too early，C5 and light

hydrocarbons will be blown back and their peaks appear along with that of

oxygen-containing compound. If the valve is switched too late, some methanol may be

evacuated, which leads to incorrect determined result of methanol.

A.9 Correction and calculation

A.9.1 Prepare at least 3 different blended samples of gasoline and methanol. The

gasoline doesn’t contain methanol and tertiary amyl alcohol. For preparation of blended

sample, please refer to procedure in ASTM D4307. Volume fraction (%) of each

component is calculated at constant temperature. These blended samples with known

concentrations contain some methanol with given concentrations.

A.9.2 Analyze each kind of mixture for correction in accordance with A.10.

A.9.3 Use manual method or integrator to determine peak areas of methanol and internal

standard. Calculate relative response factor of internal standard.

A.10 Test procedure

A.10.1 Take the sample from the refrigerator and analyze in accordance with A.7.3.

Sample and internal standard for use, as well as any container for weighing the sample,

are used for balance at a certain temperature.

Precisely add internal standard sample (tertiary amyl alcohol) with given volume into the

sample with given volume and accurately determine sample volume.

Note: Internal standard is generally 40~60% (volume fraction).

A.10.2 Chromatographic analysis Inject representative sample containing internal standard into chromatograph and

determine in accordance with switching time. Note: Split ratio=15:1, sample quantity=1 µL.

GB/T 23799-2009

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A.10.3 Description of chromatogram Compare analysis results of sample and calibration. Identify methanol and internal standard.

Where:

V(M)= Methanol content (volume fraction), %;

V(S)= Volume of internal standard (tertiary amyl alcohol). The unit is mL;

V(F)= Sampling volume of methanol gasoline (M85) for motor vehicles. The unit is mL;

A(M)= Peak area or peak height of methanol;

A(S)= Peak area or peak height of internal standard (tertiary amyl alcohol) ;

RRv(M)= Relative correction factor of methanol (related to internal standard)

A.12 Report

Methanol content (volume fraction) is reported and accurate to 0.1%.

A.13 Precision and deviation

Precision of methanol in methanol gasoline (M85) for motor vehicles, which is determined

by this method, isn’t determined yet.

A.14 Deviation

As there is no suitable reference material to determine the deviation of methanol in the

methanol gasoline (M85) for motor vehicles, the deviation of this method can’t be

determined.

GB/T 23799-2009

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Appendix B

(normative Appendix)

Determination method for contents of hydrocarbon and aliphatic ether in methanol

gasoline (M85) for motor vehicles

B.1 Scope

This method is applicable to determination for contents of hydrocarbon and aliphatic ether

in methanol gasoline (M85) for motor vehicles.

B.2 Overview of the method

Add methanol gasoline (M85) for motor vehicles into NaCl solution, add distilled water for

phase separation among hydrocarbon, aliphatic ether and methanol. Then conduct visual

inspection in Bobcock emulsifiable concentrate bottle.

B.3 Implication and application

Maintaining a specific ratio among hydrocarbon, aliphatic ether and methanol in the

methanol gasoline (M85) for motor vehicles is very important for the performance of

start-up, operation and emission of the vehicle, as well as generation of visible flame

during combustion process of methanol gasoline (M85) for motor vehicles.

B.4 Instrument

B.4.1 Bobcock emulsifiable concentrate bottle, made by borosilicate glass, 165mm, 18g.

See ASTM D872.

B.4.2 Disposable syringe or clean pipette, 10mL 0.1mL.

B.4.3 Centrifuge: It can fix Bobcock emulsifiable concentrate bottle and rotate at 1500

r/min.

B.5 Reagents and materials.

If other specifications aren’t specified, all the reagents used in this test method are

analytically pure.

B.6 Test procedure

Add 20mL 10% NaCl solution (mass fraction) into Bobcock emulsifiable concentrate bottle

(8%), transfer 10mL methanol gasoline (M85) for motor vehicles into Bobcock emulsifiable

concentrate bottle, cover the bottle mouth and shake for 1min. Then add enough distilled

water until the reading on the scale reaches 7.5~8.0, cover the bottle mouth, put it into the

centrifuge and rotate for 5min at 1500 r/min. Directly read and record the reading on the

bottle neck, subtract the reading of the curved liquid surface at liquid-liquid boundary,

multiply by 2 and obtain volume percentages of hydrocarbon and aliphatic ether in the

methanol gasoline (M85) for motor vehicles (for test).

B.7 Precision and deviation

B.7.1 Precision of this test method is obtained through test results in several labs.

B.7.2 Repeatability

The difference between two results of repeated determination, obtained through analyzing

the same sample on the same instrument by the same analyst in the same lab, should not

exceed 1.4% (volume fraction):

B.7.3 Reproducibility

There is no obvious deviation between actual methanol content and determined value

when using this test method to determine blended methanol gasoline (M85) for motor

vehicles. The result is consistent with the actual value and within the specified range of

GB/T 23799-2009

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the precision.

GB/T 23799-2009

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Appendix C

(normative Appendix)

Determination method for inorganic Cl- content in methanol gasoline (M85) for motor

vehicles

C.1 Scope

This method is applicable to determination for inorganic Cl- content in methanol gasoline

(M85) for motor vehicles. The range of Cl- content in the methanol gasoline (M85) for

motor vehicle determined by this method is (0~100.0)mg/kg. When Cl- content in the

methanol gasoline (M85) for motor vehicles≥4.0 mg/kg, use direct titration method to

determine Cl- content; When Cl- content in methanol gasoline (M85) for motor vehicles

<4.0 mg/kg, use standard addition method to determine Cl- content.

C.2 Overview of the method

Use silver ion complex electrode as working electrode and adopt automatic potentiometric

titration. Use standard AgNO3 titration solution to titrate Cl- in methanol gasoline (M85) for

motor vehicles. The point with largest dU/dV (volume change rate: ratio of potential to

titrant volume) is its titration endpoint. Calculate Cl- content in methanol gasoline (M85) for

motor vehicles in accordance with consumption of standard AgNO3 titration solution.

C.3 Instrument and device

C.3.1 Automatic potentiometric titrator: Type: Titrando Metrohm; resolution=0.1mV;

accuracy=0.2%.

C.3.2 Electrode: Silver ion complex electrode: Ag/AgCl, 6.0726, 100 Metrohm.

C.3.3 Magnetic stirring rod: equipped with stirring bar.

C.3.4 Micro burette: 10mL.

C.3.5 Volumetric flask: 10 mL, 1000 mL.

C.3.6 Pipette

C.4 Reagents and solutions

If other specifications aren’t specified, all the reagents used in this test method are

analytically pure. The water for use follows specifications of second-grade water or higher

specifications in GB/T 6682.

C.4.1 HNO3 solution (1+3): Weigh concentrated HNO3 and water (volume ratio=1:3), mix

well.

C.4.2 Standard NaCl solution: 100mg/L (calculated as Cl-), weigh 0.1648g NaCl

(reference reagent), which has been calcinated to constant weight at 500~600℃, dissolve

it in small amount of water, completely transfer into a 1000mL volumetric flask, dilute to

volume with water and shake well for use.

C.4.3 Standard AgNO3 titration solution [c(AgNO3)=16.99g/L]

C.4.3.1 Preparation

Weigh 17.5g AgNO3, dissolve it in small amount of water, completely transfer into a

1000mL volumetric flask, dilute to volume with water, shake well and store in a brown

reagent bottle.

C.4.3.2 Calibration

Conduct calibration in accordance with the regulations in GB/T 9725-2007. Weigh 0.22g

NaCl (reference reagent), which has been calcinated to constant weight at 500~600℃,

GB/T 23799-2009

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and add 70mL water to completely dissolve it. Add 10mL starch solution (10g/L), use

216-type silver electrode as indicator electrode and 217-type double salt bridge saturated

calomel electrode as reference electrode. Use prepared standard AgNO3 titration solution

for titration. The point with largest dU/dV (volume change rate: ratio of potential to titrant

volume) is its titration endpoint. Calculate consumed volume of standard AgNO3 titration

solution (V) at titration endpoint in accordance with the regulations in 6.2.2 of GB/T

9725-2007.

C.4.3.3 Calculate actual concentration of standard AgNO3 titration solution in accordance

with with formula (C.1):

Where:

c(AgNO3)——Mass concentration of standard AgNO3 titration solution. The unit is g/L;

m——Accurate value of NaCl quality. The unit is g;

v——Consumed volume of standard AgNO3 titration solution (V) at titration endpoint. The

unit is mL;

58.442——Molar mass of NaCl. The unit is g/mol;

169.869——Molar mass of AgNO3. The unit is g/mol;

C.5 Operating procedure

C.5.1 When Cl- content in the sample≥4.0 mg/kg, use direct titration method to determine

Cl- content. Operating procedure is as follows:

Use 50mL pipette to weigh and transfer 50mL test sample into a 100mL beaker, add

0.2mL HNO3 solution (1+3), mix well and begin to titrate with standard AgNO3 titration

solution. The point with largest dU/dV (volume change rate: ratio of potential to titrant

volume) is its titration endpoint. Record consumed volume of standard AgNO3 titration

solution (V) at titration endpoint. During determination process, concentration of standard

AgNO3 titration solution can be adjusted in accordance with Cl- content in the sample.

C.5.2 When Cl- content in methanol gasoline (M85) for motor vehicles <4.0 mg/kg, use

standard addition method to determine Cl- content. Operating procedure is as follows:

Use 50mL pipette to respectively weigh several equivalent test samples (50mL) into

100mL beaker, respectively add 2, 3, 4, ... Vi, Vn mL standard NaCl solution (100g/mL),

add 0.2mL HNO3 solution (1+3), mix well and begin to titrate each sample with standard

AgNO3 titration solution. The point with largest dU/dV (volume change rate: ratio of

potential to titrant volume) is its titration endpoint. Record consumed volume of standard

AgNO3 titration solution (V) at titration endpoint and draw curve of consumed volume of

standard AgNO3 titration solution (V) against addition amount of standard NaCl solution

(see Figure C.1). If the test sample doesn’t contain Cl-, curve shall pass through the origin.

If the curve doesn’t pass through the origin, the solution contains Cl-. Extended curve

intersects with the abscissa. The distance from the intersection point to the origin (see

Figure C.1) is the equivalence of Cl- to volume of standard Cl-solution (V0).

GB/T 23799-2009

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Series 1

——Linearity (Series 1)

C.1 Curve for determination of Cl- in the sample via standard addition method

C.5.3 Use 10mL volumetric flask (quality is known) to weigh 10mL test sample (accurate

to 0.0001g), record mass of test sample (m) and calculate its density.

C.6 Calculation

C.6.1 When content of determined element in the test sample≥4.0 mg/kg, calculate Cl-

content in accordance with formula (C.2).

Where:

c(Cl-)——Cl- content in the test sample. The unit is mg/kg;

35.5——Molar mass of chlorine. The unit is g/mol;

169.869——Molar mass of AgNO3. The unit is g/mol;

V (AgNO3)——Consumed volume of standard AgNO3 titration solution (V) at titration

endpoint. The unit is mL;

c(AgNO3)——Mass concentration of standard AgNO3 titration solution. The unit is g/L;

Vsample——Sample volume for titration. The unit is mL;

ρsample——Sample density. The unit is g/mL;

m——Accurate value of NaCl quality. The unit is g;

C.6.2 When content of determined element in the test sample<4.0 mg/kg, calculate Cl-

content in accordance with formula (C.3).

c(Cl-)=V0X c0/ (Vsample Xρsample)………………………………(C.3)

Where:

c(Cl-)——Cl- content in the test sample. The unit is mg/kg;

c0——Mass concentration of added standard Cl-. The unit is mg/L;

V0——Its value is distance from the intersection point of curve of standard addition

method and X axis to the origin. The unit is mL.

Vsample——Sample volume for titration. The unit is mL;

ρsample——Sample density. The unit is g/mL;

Vsample ρsample

Addition volume of standard Cl- solution/mL

Vol

ume

of

stan

dard

A

gNO

3 tit

ratio

n so

lutio

n/m

L

GB/T 23799-2009

21

C.6.3 Calculate sample density in accordance with formula (C.4).

ρsample =m/V (C.4)

ρsample——Sample density. The unit is g/mL;

m——Sample mass. The unit is g/mL;

V——Sample volume. The unit is mL.

C.7 Repeatability

Repeatability: The difference between two results of repeated determination, obtained

through analyzing the same sample on the same instrument by the same analyst in the

same lab, should not exceed following values:

Cl- content/(mg/kg) Permissible error/(mg/kg)

0~10.0 0.2

10.1~50.0 0.4

50.1~100.0 0.5

C.8 Report

Take arithmetic mean of two results of repeated determination as the determination result

of sample (accurate to 0.1 mg/kg).

GB/T 23799-2009

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Appendix D

(informative Appendix)

Comparison of structural difference between numbering of section in this standard and

that in ASTM D5797:2007

Table D.1 shows comparison of structural difference between numbering of section in this

standard and that in ASTM D5797:2007

Table D.1 Comparison of structural difference between numbering of section in this

standard and that in ASTM D5797:2007

Numbering of section in this standard Corresponding numbering of section in foreign standard

1 1.1

— 1.2~1.3

2 2. Reference standard

3.1 3.1

3.2~3.5 3.2.1~3.2.4

4 Table 1 in 4.1, 6.1.1~6.1.7, 6.1.9~6.1.11

— 4.1.1~4.1.2

5.1~5.2, 5.4~5.5 —

5.3.1 5.2, 5.4

5.3.2 5.3

— 5.1

6.1~6.3 —

6.4 4.1.3

— 6.1.8

7 —

— 7

Appendix A Appendix A1

Appendix B Appendix A2

Appendix C Appendix A3

Appendix D —

— Appendix X1

— Appendix X2

Reference

ASTM D4307 Standard Practice for Preparation of Liquid Blends for Use as Analytical

Standards

ASTM E355 Standard Practice for Gas Chromatography Terms and Relationships

GB/T 23799-2009

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