SY/T 0529-1993 Analysis of C1～C12, N2, CO2 components in oilfield gas by gas chromatography SY/T0529-1993 Standard download decompression password: www.bzxz.net

Petroleum and Natural Gas Industry Standard of the People's Republic of China SY/T0529--93
C~C12, N2, CO in Oilfield Gas
Component Analysis
Correlation Normalization Gas Chromatography
Published on January 6, 1994
China National Petroleum Corporation
Implementation on June 1, 1994
1 Subject Content and Scope of Application
Petroleum and Natural Gas Industry Standard of the People's Republic of China C~C2, NCO, Component Analysis in Oilfield Gas
Correlation Normalization Gas Chromatography
SY/T0529-93
This standard specifies the analytical method for determining C,~C12, N2CO2 components in oilfield gas by correlation normalization gas chromatography. This standard applies to the component analysis of oilfield gas and similar gas mixtures. 2 Reference standards
GB/T13609 Sampling method of natural gas
3 Summary of the method
The gas sample does not need to be enriched, but is directly injected into the gas chromatograph, separated by two or more filling columns and a capillary rod, detected by a thermal conductivity detector (TCD) and a hydrogen flame detector (FID), and the spectrum is recorded by an automatic integrator. Quantitative calculation by normalization method. 4 Reagents and materials
4.1 Carrier gas and auxiliary gas
a. Hydrogen or nitrogen, with a purity of not less than 99.99% b. Nitrogen purity of not less than 99.99%,
c. Compressed air: dried and deoiled.
4.2 Reagents and materials used in the preparation of chromatographic columns The reagents and materials used in the preparation of chromatographic columns are now in Appendix A (reference) or Appendix B (reference). 5 Instruments and Equipment
5.1 Gas Chromatograph
Any gas chromatograph that meets the following technical specifications can be used. 5.1-1 Process Box
The column box should be able to simultaneously install at least two packed columns and one capillary column. It can be programmed to increase the temperature, with the highest operating temperature not lower than 350℃ and a temperature control accuracy of ±0.2℃. If one chromatograph cannot meet the requirements, two can be used. The column box is preferably equipped with a six-way valve or a ten-way valve, which may not be installed if a double-column parallel gas line is used. 5.1.2 Detectors
5.1.2.1 The sensitivity of the thermal conductivity cell detector is higher than 1000mVmL/mg (benzene). 5.1.2.2 The detection limit of the oxygen-hydrogen flame ionization detector is less than 5×10~1″g/s. 5.1.2.3 The temperature of the detector should be kept constant during the whole analysis process, and the temperature control accuracy should be ±0.1°C. 5.1.3 Carrier gas control system
During the whole analysis process, the carrier gas flow rate should be kept constant, and its change should be within 1%. 5.2 Chromatographic column
The material of the filling column must be resistant to the components in the sample and non-adhesive. Stainless steel should be preferred, and the filling material in the column should be able to achieve a satisfactory separation effect on the components to be detected. Approved by China National Petroleum Corporation on January 6, 1994 and implemented on June 1, 1994
5.2.1 Adsorption column
SY/T 0529-93
The adsorption column must be able to completely separate the peaks of ON and C, and the valleys of the two adjacent peaks must return to the baseline. 5.2.2 Distribution consumption
The distribution column must be able to separate (O2+N2+C1), CO2C2~nC, and each component. 5.2.3 Capillary column
The capillary column is used to separate each component between C3 and C12, including isomers. 5.3 Recording system
The chromatographic data processor with signal switching function or dual channels is required to be able to record chromatograms and response values. Input voltage: -5mV~1V, repeatability: ±0.1%.
6 Operation steps
6.1 Instrument preparation
6.1.1 Install the chromatographic column according to the selected process (see Figure A1 or Figure B1) and strictly check for leaks. 6.1.2 Connect the voltage regulator and stabilize the voltage at 220±2V. 6.1.3 Set the chromatographic conditions to make the instrument in the best working state. Including carrier gas, fuel gas, auxiliary gas and supplementary gas flow, detector, injector and column box temperature, as well as the running time programming of each. 6.2 Sample preparation
Sampling is carried out in accordance with GB/T13609. If the temperature of the gas source is higher than the room temperature of the laboratory, the sample must be heated before injection to restore it to the state at the time of sampling. bzxZ.net
6.3 Injection
Both the packed column and the capillary column use a six-way valve fixed coil or a syringe for injection. The injection volume of the capillary column is based on the complete separation of C.~C, and the ear-heavy component has enough integral value.
Qualification and carbon number classification
Ci~Cs, O2:N2, CO2 are qualitatively analyzed one by one according to the retention time (refer to the chromatogram, see Figure A2 or Figure B2). When there is no special requirement, the heavy components above mCs are divided according to the carbon number based on the normal alkane. The components between two normal alkanes are all classified into the components with higher carbon numbers. For example, the components between nCs and nC are all classified into C: (refer to the chromatogram in Figure A3 or Figure B3). 8 Quantitative calculation
Select the components that can be picked up by TCD and TID as the related components. You can choose one of the components to calculate the K value, or choose several components to calculate the K value and then calculate the average value. Now take iCs and nCs as an example to calculate the K value (C4 can also be used). For the convenience of formula expression, the oilfield gas components are numbered in the order of Table 1.
Calculate the correlation coefficient K
K=(Ara+Aro
In the formula, ATs, Aria——respectively the peak areas of iCs and nCs detected on TCD, and AFgArn——respectively the peak areas of iCs and nCs detected on FID.E. 2
8.2 Calculation of component content
8.2.1 Mixed peak treatment
SY/T 0529—93
O2, N2 and C cannot be separated in the distribution column and are detected as a mixed peak. The area of ​​the mixed peak is often not equal to the sum of the areas of the three peaks in the adsorption column. The mixed peak must be distributed into the areas of each component according to formulas (2), (3) and (4). A
Ao+AN+Ac
Ao,+An2+Acl
Ao+A+Ac
In the formula, Ar1A.A:4—is the peak area of ​​OV2 and Ci after distribution, All——the mixed peak area detected by TCD of the distribution column, Aα2, An2Ac,————are the peak areas of ON2 and C detected by TCD of the adsorption column. 8.2.2 Correction for air pollution
During the sampling and chromatographic injection process, the sample is easily contaminated by air. When calculating the air-free content, oxygen and the corresponding nitrogen should be deducted. The local air is used as the sample for actual measurement. The area ratio of nitrogen to oxygen is calculated by deducting the nitrogen mixed in the sample from the measured oxygen peak area in the sample gas. The calculation formula is:
At,—Ar,-
Wherein, A, Ar are the peak areas of nitrogen and oxygen measured using local air as the sample, ATI is the peak area of ​​oxygen after distribution in the sample gas, A is the peak area of ​​nitrogen after distribution in the sample gas, and AT2 is the actual peak area of ​​nitrogen in the sample gas. 8.2.31-2~~8 content calculation
8.2.4=9~17 content calculation
Aaifri
Z(AF) +E(KAriFT)
Z(ATF) +E(AFiF)
In the above two formulas: C, — concentration of component i, mol%, 19
AT;——peak area of ​​component detected on TCI, X100
FT——peak area of ​​component detected on FID, its value is shown in Appendix C (reference): Ai component peak area detected on FID, K——correlation coefficient.
9 Precision
Use the following criteria to judge whether the results are reliable (95% confidence level). 9.1 Repeatability
The difference between two results repeatedly determined by the same operator should not be greater than the values ​​in Table 2. 9.2 Reproducibility
The difference between two results proposed by different laboratories should not be greater than the values ​​in Table 2. (5)
Component content
SY/T0529—93
Reproducibility
Take repeated measurements The arithmetic mean of the two results is taken as the analysis result. Reproducibility
SY/T0529—93
Appendix A
HP5880A/5890A Gas Chromatography Analysis Operating Conditions (Reference)
A1 Analysis of Na(Oz), COs, Ct~Cat components in oilfield gas A1.1 Reagents and materials used in the preparation of chromatographic columns a. Vinylmethylpolysilane stationary phase, 10% LCW-982 coated on chromP, particle size 0.175-~0.147rm (80~100 days)
b. Tandem polysiloxane stationary phase, 30% DC-200 coated on clromI, particle size 0.175~0.147mm (80~100 mesh) c. Polystyrene type (Porapak-Q) chromatographic stationary phase, 0.175~~0.1471um (80~100), d, molecular sieve, 5A or 13X, particle size 0.246~~0.175mm (60-~80 months). A1.2 Apparatus
HP5890A gas chromatograph (with thermal conductivity detector, gas flow chart see Figure A1). A1.3 Chromatographic column
See Figure A2 for reference spectrum.
TCD gas flow chart
Figure A25890ATCD detection reference chromatogram
SY/T0529--93
a Column I: 03×500mm stainless steel packed column, filled with vinylmethylpolysilane stationary phase, used for cutting step separation of mC, subsequent components!
b. Column I: 3×3000mm stainless steel packed column, filled with chiral polysiloxane stationary phase, used for separation of monomer hydrocarbons of Ca-Cs,
Column: 3×2000mm stainless steel packed column, filled with Porapak-Q, used for separation of CO2, C2 c.
d. Column, ±3×2000mm stainless steel packed column, filled with 5A or 13X molecular sieve, used for separation of F02, Nz and C. A1.4 Operating conditions
a. Column box temperature, 90℃ constant humidity
b. Detector temperature, 110℃,
c. Injector temperature: 100℃s
d, carrier gas flow rate, 30mL/mins
e, injection temperature, 1mLi
f. Paper speed: 0.5cm/min
g. The operation time of the four-column three-valve C+ backflush system is shown in Table A1. Table A1
Operation pair
A2 Oilfield gas C, C13 component analysis
2,
A2.1 Instrument
HP5880A gas chromatograph (with hydrogen flame ionization detector). A2.2 Chromatographic column
OV-101 domain SE-30 elastic capillary column, column length 25-50m, reference chromatogram is shown in Figure A3. A2.3 Operating conditions a. Column box temperature: initial temperature 40°C, heating rate 5°C/min, final temperature 240°C b. Detector temperature, 300°C c. Injector temperature: 250 d. Carrier gas flow rate, 1~2mL/mins e. Auxiliary gas flow rate: 400mL/mins f. Fuel gas flow rate: 40mL/mins g. End gas flow rate: 30mL/min h. Split ratio: 50 1~100:1 i. Paper speed, lcn/nin# i. Recording system, HP3394 SY/T 0529-93 k. Injection volume: 1m Use a syringe to directly inject the gas sample into the capillary injection port. According to the separation of C, the injection volume can be appropriately increased or decreased. Accurate measurement is not required. c
Figure A35880 Reference chromatogram for FID detection
SY/T 0529-93
Appendix B
VISTA6000/6500 gas chromatograph analysis operating conditions (reference material)
B1 Analysis of constant components of N2(O2), CO2, Cr~Cs in oilfield gas B1.1 Reagents and materials used for preparing chromatographic columns a. Molecular sieve, 5A or 13X, particle size 0.246~0.175mm (60~80 months) b, 8, β\-oxydipropionitrile, analytical grade: c. Dibutyl phthalate, analytical grade, D, 6201 as or other suitable carrier, particle size 0.246 ~ 0.175mm (60 ~ 80 mm). B1.2 Instrument
VISTA6500 gas chromatograph (with thermal conductivity detector, gas flow chart see Figure B1). B1.3 Chromatographic column
Reference chromatogram see Figure B2.
a, Column I, Φ3×6000mm stainless steel packed column, the ratio of the filling material in the column is phthalic acid ester: B, 1,2-dipropionitrile: 6201 twist equal to 40:20:100 (mass ratio), used to separate (O2+N2+C), CO2 and C2-~C components b. Column I, Φ3×1200mm stainless steel packed column, filled with 5A or 13X molecular sieve, used to separate Oz,,, and C. B1.4 Operating conditions
a: Column box temperature: 45℃ constant temperature
b. Detector temperature, 120℃, bridge flow: 200m A, c. Injector temperature, 80°C,
d, carrier gas flow, 40mL/minz
e, injection volume: 0.25mLs
f. Paper speed: lcm/mins
9. Recording system: VISTA402 or A4800. B2
Analysis of C-C12 components in oil and gas
VISTA6000 gas chromatograph (with flame ionization detector): B2.2 Chromatographic column
SE-30 or OV-101 elastic quartz capillary tube, column length 25~50m. See Figure B3 for the chromatogram. B2.3 Operating conditions
a, Column box temperature, initial temperature 45°C, heating rate 5~10°C/min, end temperature 240°C; b. Detector temperature: 300°C
c, Injector temperature: 250Cs
d, Carrier gas flow rate: 1~2mL/min
e. Gas flow rate: 30mL/mins
f, Auxiliary gas flow rate, 300mL/min
g. Tail gas flow rate, 30nL/min#
h, Split ratio: 50:1 ～100:1,
i, paper speed: lcm/miny
j. Recording system, VTSTA402 or A4800, SY/T0529-93
k, injection volume: 1 L. Use a syringe to directly inject the gas sample into the capillary inlet. According to the separation of C, the amount of escaped sample can be appropriately increased or decreased, and no precise measurement is required. A
TCD gas path diagram
Figure R2TCD detection reference chromatogram
Figure B3FID detection reference chromatogram
Red component name
SY/T 0529—93
Appendix C
Reference molar correction factor for thermal conductivity cell
(reference)
Molar mass
114,22
128,25
Correction factor
Additional instructions
This standard is proposed by China National Petroleum Corporation. SY/T 0529--93
This standard is under the jurisdiction of the Planning and Design Institute of China National Petroleum Corporation. This standard was drafted by the Exploration and Development Research Institute of Jiangwen Petroleum Administration Bureau and the North China Petroleum Exploration and Design Institute. The drafters of this standard are Dong Shusheng and Hu Guoping.3 Operating conditions a. Column box temperature: initial temperature 40°C, heating rate 5°C/min, final temperature 240°C b. Detector temperature, 300°C c. Injector temperature: 250°C d. Carrier gas flow rate, 1~2mL/mins e. Auxiliary gas flow rate: 400mL/mins f. Fuel gas flow rate: 40mL/mins g. End gas flow rate: 30mL/min h. Split ratio: 50 1~100:1 i. Paper speed, lcn/nin# i. Recording system, HP3394 SY/T 0529-93 k. Injection volume: 1m Use a syringe to directly inject the gas sample into the capillary injection port. According to the separation of C, the injection volume can be appropriately increased or decreased. Accurate measurement is not required. c
Figure A35880 Reference chromatogram for FID detection
SY/T 0529-93
Appendix B
VISTA6000/6500 gas chromatograph analysis operating conditions (reference material)
B1 Analysis of constant components of N2(O2), CO2, Cr~Cs in oilfield gas B1.1 Reagents and materials used for preparing chromatographic columns a. Molecular sieve, 5A or 13X, particle size 0.246~0.175mm (60~80 months) b, 8, β\-oxydipropionitrile, analytical grade: c. Dibutyl phthalate, analytical grade, D, 6201 as or other suitable carrier, particle size 0.246 ~ 0.175mm (60 ~ 80 mm). B1.2 Instrument
VISTA6500 gas chromatograph (with thermal conductivity detector, gas flow chart see Figure B1). B1.3 Chromatographic column
Reference chromatogram see Figure B2.
a, Column I, Φ3×6000mm stainless steel packed column, the ratio of the filling material in the column is phthalic acid ester: B, 1,2-dipropionitrile: 6201 twist equal to 40:20:100 (mass ratio), used to separate (O2+N2+C), CO2 and C2-~C components b. Column I, Φ3×1200mm stainless steel packed column, filled with 5A or 13X molecular sieve, used to separate Oz,,, and C. B1.4 Operating conditions
a: Column box temperature: 45℃ constant temperature
b. Detector temperature, 120℃, bridge flow: 200m A, c. Injector temperature, 80°C,
d, carrier gas flow, 40mL/minz
e, injection volume: 0.25mLs
f. Paper speed: lcm/mins
9. Recording system: VISTA402 or A4800. B2
Analysis of C-C12 components in oil and gas
VISTA6000 gas chromatograph (with flame ionization detector): B2.2 Chromatographic column
SE-30 or OV-101 elastic quartz capillary tube, column length 25~50m. See Figure B3 for the chromatogram. B2.3 Operating conditions
a, Column box temperature, initial temperature 45°C, heating rate 5~10°C/min, end temperature 240°C; b. Detector temperature: 300°C
c, Injector temperature: 250Cs
d, Carrier gas flow rate: 1~2mL/min
e. Gas flow rate: 30mL/mins
f, Auxiliary gas flow rate, 300mL/min
g. Tail gas flow rate, 30nL/min#
h, Split ratio: 50:1 ～100:1,
i, paper speed: lcm/miny
j. Recording system, VTSTA402 or A4800, SY/T0529-93
k, injection volume: 1 L. Use a syringe to directly inject the gas sample into the capillary inlet. According to the separation of C, the amount of escaped sample can be appropriately increased or decreased, and no precise measurement is required. A
TCD gas path diagram
Figure R2TCD detection reference chromatogram
Figure B3FID detection reference chromatogram
Red component name
SY/T 0529—93
Appendix C
Reference molar correction factor for thermal conductivity cell
(reference)
Molar mass
114,22
128,25
Correction factor
Additional instructions
This standard is proposed by China National Petroleum Corporation. SY/T 0529--93
This standard is under the jurisdiction of the Planning and Design Institute of China National Petroleum Corporation. This standard was drafted by the Exploration and Development Research Institute of Jiangwen Petroleum Administration Bureau and the North China Petroleum Exploration and Design Institute. The drafters of this standard are Dong Shusheng and Hu Guoping.3 Operating conditions a. Column box temperature: initial temperature 40°C, heating rate 5°C/min, final temperature 240°C b. Detector temperature, 300°C c. Injector temperature: 250°C d. Carrier gas flow rate, 1~2mL/mins e. Auxiliary gas flow rate: 400mL/mins f. Fuel gas flow rate: 40mL/mins g. End gas flow rate: 30mL/min h. Split ratio: 50 1~100:1 i. Paper speed, lcn/nin# i. Recording system, HP3394 SY/T 0529-93 k. Injection volume: 1m Use a syringe to directly inject the gas sample into the capillary injection port. According to the separation of C, the injection volume can be appropriately increased or decreased. Accurate measurement is not required. c
Figure A35880 Reference chromatogram for FID detection
SY/T 0529-93
Appendix B
VISTA6000/6500 gas chromatograph analysis operating conditions (reference material)
B1 Analysis of constant components of N2(O2), CO2, Cr~Cs in oilfield gas B1.1 Reagents and materials used for preparing chromatographic columns a. Molecular sieve, 5A or 13X, particle size 0.246~0.175mm (60~80 months) b, 8, β\-oxydipropionitrile, analytical grade: c. Dibutyl phthalate, analytical grade, D, 6201 as or other suitable carrier, particle size 0.246 ~ 0.175mm (60 ~ 80 mm). B1.2 Instrument
VISTA6500 gas chromatograph (with thermal conductivity detector, gas flow chart see Figure B1). B1.3 Chromatographic column
Reference chromatogram see Figure B2.
a, Column I, Φ3×6000mm stainless steel packed column, the ratio of the filling material in the column is phthalic acid ester: B, 1,2-dipropionitrile: 6201 twist equal to 40:20:100 (mass ratio), used to separate (O2+N2+C), CO2 and C2-~C components b. Column I, Φ3×1200mm stainless steel packed column, filled with 5A or 13X molecular sieve, used to separate Oz,,, and C. B1.4 Operating conditions
a: Column box temperature: 45℃ constant temperature
b. Detector temperature, 120℃, bridge flow: 200m A, c. Injector temperature, 80°C,
d, carrier gas flow, 40mL/minz
e, injection volume: 0.25mLs
f. Paper speed: lcm/mins
9. Recording system: VISTA402 or A4800. B2
Analysis of C-C12 components in oil and gas
VISTA6000 gas chromatograph (with flame ionization detector): B2.2 Chromatographic column
SE-30 or OV-101 elastic quartz capillary tube, column length 25~50m. See Figure B3 for the chromatogram. B2.3 Operating conditions
a, Column box temperature, initial temperature 45°C, heating rate 5~10°C/min, end temperature 240°C; b. Detector temperature: 300°C
c, Injector temperature: 250Cs
d, Carrier gas flow rate: 1~2mL/min
e. Gas flow rate: 30mL/mins
f, Auxiliary gas flow rate, 300mL/min
g. Tail gas flow rate, 30nL/min#
h, Split ratio: 50:1 ～100:1,
i, paper speed: lcm/miny
j. Recording system, VTSTA402 or A4800, SY/T0529-93
k, injection volume: 1 L. Use a syringe to directly inject the gas sample into the capillary inlet. According to the separation of C, the amount of escaped sample can be appropriately increased or decreased, and no precise measurement is required. A
TCD gas path diagram
Figure R2TCD detection reference chromatogram
Figure B3FID detection reference chromatogram
Red component name
SY/T 0529—93
Appendix C
Reference molar correction factor for thermal conductivity cell
(reference)
Molar mass
114,22
128,25
Correction factor
Additional instructions
This standard is proposed by China National Petroleum Corporation. SY/T 0529--93
This standard is under the jurisdiction of the Planning and Design Institute of China National Petroleum Corporation. This standard was drafted by the Exploration and Development Research Institute of Jiangwen Petroleum Administration Bureau and the North China Petroleum Exploration and Design Institute. The drafters of this standard are Dong Shusheng and Hu Guoping.Recording system, VTSTA402 or A4800, SY/T0529—93
k, injection volume: 1 L. Use a syringe to directly inject the gas sample into the capillary inlet. According to the separation of C, the amount of sample can be appropriately increased or decreased, and no precise measurement is required. A
TCD gas circuit diagram
Figure R2TCD detection reference chromatogram
Figure B3FID detection reference chromatogram
Red component name
SY/T 0529—93
Appendix C
Thermal conductivity cell reference molar correction factor
(reference)
Molar mass
114,22
128,25
Correction factor
Additional instructions
This standard is proposed by China National Petroleum Corporation. SY/T 0529--93
This standard is under the jurisdiction of the Planning and Design Institute of China National Petroleum Corporation. This standard was drafted by the Exploration and Development Research Institute of Jiangwen Petroleum Administration Bureau and the North China Petroleum Exploration and Design Institute. The main drafters of this standard are Dong Shusheng and Hu Guoping.Recording system, VTSTA402 or A4800, SY/T0529—93
k, injection volume: 1 L. Use a syringe to directly inject the gas sample into the capillary inlet. According to the separation of C, the amount of sample can be appropriately increased or decreased, and no precise measurement is required. A
TCD gas circuit diagram
Figure R2TCD detection reference chromatogram
Figure B3FID detection reference chromatogram
Red component name
SY/T 0529—93
Appendix C
Thermal conductivity cell reference molar correction factor
(reference)
Molar mass
114,22
128,25
Correction factor
Additional instructions
This standard is proposed by China National Petroleum Corporation. SY/T 0529--93
This standard is under the jurisdiction of the Planning and Design Institute of China National Petroleum Corporation. This standard was drafted by the Exploration and Development Research Institute of Jiangwen Petroleum Administration Bureau and the North China Petroleum Exploration and Design Institute. The main drafters of this standard are Dong Shusheng and Hu Guoping.
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