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中华人民共和国质量监督检验检疫总局中华人民共和国质量监督检验检疫总局中华人民共和国质量监督检验检疫总局中华人民共和国质量监督检验检疫总局 发发发发
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
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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 &
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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
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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.
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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
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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.
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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
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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
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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
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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
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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.
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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
15
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
19
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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