Some standard content:
ICS 75.010
Registration number: 8191—20H01
Petroleum and natural gas industry standard of the People's Republic of ChinaSY/T 5516-2000
Chemical analysis method for carbonate rocks
Chemical analysis method for carbonate rocks2000-12-25Release
State Administration of Petroleum and Chemical Industry
2001-06-01Implementation
SY/T 5516-r-2000
Referenced standards
Reagents, solutions and materials
Instruments and equipment
5 Sample preparation
Determination of acid-insoluble matter
Determination of calcium oxide and magnesium oxide
8 Determination of the total amount of ferric oxide and aluminum oxide 9 Determination of sulfur trioxide
10 Determination of loss on ignition·
11 Quality requirements·
[2 Data processing
Appendix A (Standard Appendix)
Appendix B (Suggestive Appendix)
Preparation and calibration of solutions
Quality requirements for parallel sample analysis results expressed with uncertainty 10
SY/T5516—2000
This standard is a revision of SY551-92. The main contents of this revision are as follows: 1. Modifications were made to Chapter 1, Chapter 3, Chapter 10 and 2.1, 2.2, 6.1, 6.2, 8.1, 8.3 of the original standard; 2. The original standard 6.3, 8.3 were respectively classified into 7.1.3 and 9.1.3; 3. The original standard Chapter 12 was deleted and its content was classified into Chapter 11; 4. The ion chromatography analysis method of calcium oxide, magnesium oxide and sulfur trioxide was added, and the atomic absorption spectrometry determination method and inductively coupled plasma atomic emission spectrometry analysis method of calcium oxide and magnesium oxide were added; 5. The method of expressing the analytical quality requirements with uncertainty was added as a prompt appendix; 6. The individual words and symbols in the original standard that did not conform to the current standard were modified. Appendix A of this standard is the appendix of the standard, and Appendix B of this standard is the prompt appendix. This standard will replace SY5516-92 from the date of its entry into force. This standard is proposed by China National Petroleum Corporation. This standard is under the jurisdiction of the Petroleum Geology Exploration Professional Standardization Committee, and the drafting unit of this standard is the Exploration and Development Research Institute of Southwest Oil and Gas Field Branch of China National Petroleum Corporation. The main drafters of this standard are Tang Di, Zhang Jian, Su Zhongrui, Situ Ming, and Wang Lansheng.
This standard was first issued in November 1992, and this is the first revision. 1 Scope
Petroleum and Natural Gas Industry Standard of the People's Republic of China Chemical Analysis Method for Carbonate Rocks
Chemical Analysis Method for Carbonate Rocks This standard specifies the chemical analysis method and quality requirements for carbonate rocks. SY/T 5516—2000
Replaces SY 5516—92
This standard is applicable to the determination of acid-insoluble matter, calcium oxide, magnesium oxide, sulfur trioxide, ferric oxide, aluminum oxide, and ignition loss in carbonate rocks.
2 Referenced Standards
The provisions contained in the following standards constitute the provisions of this standard through reference in this standard. The versions shown are valid at the time of publication of this standard. All standards are subject to revision, and parties using this standard should explore the possibility of using the latest versions of the following standards. SY/T5161-87 Atomic absorption spectrometric method for determination of metal elements in rocks SY/I6404—1999 Inductively coupled plasma atomic emission spectrometric method for analysis of metal elements in sedimentary rocks 3 Reagents, solutions and materials
3.1 Reagents
a) Ammonium fluoride (analytical grade);
b) Ammonia water (analytical grade);
c) Hydrochloric acid (analytical grade);
d) Sodium hydroxide (analytical grade);
e) Triethanolamine (analytical grade);
f) Barium chloride (analytical grade);
|methanesulfonic acid (analytical grade); pure);
h) Sodium carbonate (analytical grade);
i) Sodium bicarbonate (analytical grade);
j) Chrome black T (analytical grade);
k) Calcium reagent (analytical grade);
1) Potassium sulfate (analytical grade);
m) Methyl orange (analytical grade);
n) Neutral red (analytical grade);
o) Anhydrous ethanol (analytical grade);
p) Zinc oxide (superior grade):
3.2 Solution
a) Hydrochloric acid solution: =2%:
b) Hydrochloric acid solution: 1H=50 %;
c) Sodium hydroxide solution: wNaCH=4%;
d) Triethanolamine solution: $Triethanolamine=50%: Approved by the State Administration of Petroleum and Chemical Industry on 24H0)-12-25, implemented on 2001-06-01
e) Barium chloride solution: wBac,=5%;
f) Ethanol solution: @CH,CHOH=60%
SY/T5516-2000
g) Ammonia solution: NL-HO=50%;
h) Ammonia-ammonium chloride buffer solution (pH~10.0): Weigh 27g of ammonium chloride and dissolve it in an appropriate amount of water, add 197mL of concentrated ammonia, and then dilute it with water to 1L;
i) Water for analysis: deionized water or double distilled water. Note: @ is the mass fraction of the solution; is the volume fraction of the solution. 3.3 Standard solution
a) EDTA (disodium ethylenediaminetetraacetic acid) standard titration solution: 0.0125mol/, valid for two months, preparation and calibration see Appendix A (Standard Appendix);
b) Calcium ion standard solution: should comply with the provisions of GBW (E) 080118;) Magnesium ion standard solution: should comply with the provisions of GBW (E) 080126; d) Sulfate standard solution: should comply with the provisions of GBW (E) 080267. 3.4 Ion chromatography eluent
a) Cation eluent: methane sulfonic acid concentration is 15~35mmol/: b) Anion eluent: NazCONaHCO, binary eluent concentrations are 2.0mmol/L and 3.0mmol/L respectively. 3.5 Indicators
a) Chrome black T indicator: o=5g/L (p is the mass concentration of the solution), the medium is a volume fraction of triethanolamine solution equal to 50%:
b) Calcium indicator: weigh 0.5g calcium reagent and 5g potassium sulfate in an agate mortar, grind to a particle size of 0.18mm and store in a desiccator;
c) Methyl orange indicator: e=1g/L;
d) Methyl red indicator: 0=1g/L, the medium is a mass fraction of ethanol solution equal to 60%. 3.6 Materials
a) Quantitative filter paper: $110mm;
b) Surface: $100mm;
e) Porcelain: 10mL.
4 Instruments and equipment
a) Ion chromatograph;
b) Analytical balance: sensitivity 0.1mg, sensitivity 0.1gc) Volumetric flask: 250mL, Class A;
d) Beaker: 250mL;
e) Erlenmeyer flask: 250mL;
f) Large-bellied pipette: 10mL, 25mL, 50mL, Class A;g) Acid burette: 50mL, Class A:
h) Electric hot plate: 1000W:
i) Electric furnace: 1000W:
j) Electric oven: 2400W;
k) High temperature furnace: 1200℃±10℃.
5 Sample preparation
Take 20g of the test sample, remove the dirt and grind it to a particle size of less than 0.072mm. Keep it in an oven at 105-110℃ for 2h and store it in a desiccator for later use.
6 Determination of acid-insoluble matter
6.1 Method summary
SY/T5516—2000
Carbonate rock samples are boiled in dilute hydrochloric acid solution, and the alkaline earth metal carbonates therein are decomposed into metal ions and carbon dioxide gas. Gypsum is dissolved in the liquid phase, and the insoluble matter includes silica, clay and part of pyrite. After filtering, washing, ashing and burning to a constant weight, the content of acid-insoluble matter is determined.
6.2 Analysis steps
6.2.1 Weigh 0.5g of sample to an accuracy of 0.0001g. Pour the sample into a beaker and moisten it with water. 6.2.2 Add 50 mL of hydrochloric acid solution [see 3.2a) 1 to the beaker, cover the surface with blood, place the beaker on an electric stove, and heat and boil until no carbon dioxide bubbles are generated.
6.2.3 Filter the above solution with quantitative filter paper, and transfer all the residues in the beaker to the paper, and wash the residue with hot water until there is no chloride ion. Collect the filtrate and washing water in a 250mL volumetric flask, make up to volume, shake well, and record it as filtrate A. Keep filtrate A for the determination of calcium oxide, magnesium oxide, ferric oxide, aluminum oxide, and sulfur trioxide. 6.2.4 Transfer the residue and filter paper into a constant volume, first ash on an electric furnace, then put it in a high-temperature furnace, and burn it at 800℃ for 30min; stop heating, take it out when the furnace temperature drops to 400℃, put it in a desiccator, cool it to room temperature, weigh it, and then burn it until the difference between the two weighings is less than 0.0004g.
6.3 Calculation
The calculation of the mass fraction of acid-insoluble matter (acid-insoluble matter) is shown in formula (1): ml-m2x100%
Wacid-insoluble matter
Wherein: m——the mass of the insoluble residue in the crucible, g, the mass of the sample, g;
The mass of the sample, g.
7 Determination of calcium oxide and magnesium oxide
7.1 Complexometric titration
7.1.1 Summary of the method
The total amount of calcium and magnesium ions is measured in a buffer solution with a pH value of 10, using chrome black T as an indicator and EDTA standard solution for titration. In a medium with a pII value of 12, magnesium ions are precipitated in the form of magnesium hydroxide. Using calcium reagent as an indicator, the calcium ion content is measured by titration with EDTA standard titration solution. The content of magnesium ions is obtained by subtraction. The mass fractions of calcium oxide and magnesium oxide can be obtained by calculation. Triethanolamine was used to mask the interference of iron and aluminum ions. 7.1.2 Analysis steps
7.1.2.1 Determination of calcium oxide
Use a large-bellied pipette to take 10 mL of filtrate A in a two-cornered flask, dilute it to 70 mL with water, then add 2 mL of triethanolamine solution, 10 mL of sodium hydroxide solution, and 3 mg of calcium reagent in sequence. While shaking the two-cornered flask, titrate with EDTA standard titration solution until it turns pure blue, which is the titration end point. The consumption of EDTA standard titration solution is recorded as V (mL). 7.1.2.2 Determination of the total amount of calcium oxide and magnesium oxide Use a large-bellied pipette to take 10 ml of filtrate A in a conical flask, dilute it to 70 mL with water, then add 2 mL of triethanolamine solution, 10 mL of ammonia-ammonium chloride buffer solution, and 3 to 4 drops of chrome black T indicator in sequence. While shaking the conical flask, titrate with EDTA standard titration solution until it turns pure blue, which is the titration end point. The consumption of EDTA standard titration solution is recorded as V2 (mL). 7.1.3 Calculation
The calculation of the mass fraction of calcium oxide and magnesium oxide (wco, Mao) is shown in formula (2) and formula (3) respectively: 3
SY/T 5516—2000
cV,x0.05608
×100%
c (V2- V1) ×.04030
×100%
m×250
Wherein: -—Concentration of EIYIA standard titration solution, mol/L; VI——Consumption of EDTA standard titration solution when titrating calcium oxide, IILm——Mass of sample, g;
Vz—Consumption of EDTA standard titration solution when titrating calcium oxide and magnesium oxide together, mL; (2)
0.05608, 0.04030——Respectively, the mass of calcium oxide and magnesium oxide required for complete reaction with 1.00ml.FDTA standard titration solution (cEr=1.0000mol/.), g. 7.2 Ion chromatography
Applicable to the determination of monovalent and divalent metal ions in a medium with a pH value of 2 to 3, and the minimum detection mass concentration is 0.05Tg/L. 7.2.1 Method Summary
After the sample is injected, it flows through the analytical column under the eluent. After repeated elution and exchange in the column, it is separated in the order of Na+, K+, Mg2+, C2+, and Sr2+ ions. After being measured by the conductivity detector, the computer calculates and prints out the content of each ion in the sample (mg/L).
7.2.2 Determination
7.2.2.1 Chromatographic conditions
a) Eluent: methanesulfonic acid, C(Hs0,H is 15~35mmol/L; b) Eluent flow rate: select the flow rate that can achieve baseline separation for each ion peak to be measured; ) Cation separation column:
7.2.2.2 Preparation of standard solution
In the linear range of each ion to be measured, prepare a mixed standard solution with a similar content of magnesium and calcium ions in the sample. 2.2.3 Determination
Prepare the instrument according to the chromatographic conditions. After the baseline is stable, inject the standard solution and sample respectively. The computer will compare the measured electrical signal intensity of each ion with the electrical signal intensity of the corresponding ion of the sample, calculate and print out the content of each ion in the sample (mg/L). 7.2.3 Calculation
The calculation of the mass fraction of calcium amide and magnesium oxide is shown in formula (4) and formula (5): = M* ×1.6638 ×100%
Wherein: Cma*-
20×106
c+×1.3992
×100%
-the content of magnesium ion in the sample, mg/L;
the content of calcium ion in the sample, mg/L;
m"--the mass of the sample, β:
Note: M is the relative molecular mass
7.3 Plasma spectrometry
Plasma spectrometry see SY/T6404.
7.4 Atomic absorption spectrometry
Atomic absorption spectrometry see SY/T5161.
8 Determination of the total amount of ferric oxide and aluminium oxide 8.1 Summary of the method
SY/T 5516—2000
Iron, lead and other compounds in carbonate rocks that are soluble in hot dilute hydrochloric acid solution are separated from the solution in the form of colloidal precipitation of oxides in an ammonia-ammonium chloride buffer solution. The precipitate is filtered, washed, ashed, and burned to convert into trioxide form, and then weighed.
8.2 Analysis Steps
Use a large pipette to take a fixed volume of filtrate A into a beaker, add 2 to 3 drops of methyl red indicator and 0.5 g of ammonium chloride, place the beaker on a hot plate and heat to a slight boil: while stirring continuously, add ammonia water dropwise until the solution turns yellow, add 2 drops of ammonia water, boil, and filter on quantitative filter paper while hot after a brown precipitate appears; transfer all the precipitate in the beaker to the filter paper, and wash the precipitate with hot water until the filtrate is free of chloride ions. Collect the filter cloth and washing water in a volumetric flask, adjust the volume, and record it as filtrate B. Keep filtrate B for the determination of sulfur trioxide.
Put the precipitate and filter paper in a constant volume of glass, place it on an electric furnace for incineration, and then put it into a high-temperature furnace, raise the temperature to 800℃, and keep the temperature at 30mil; stop heating, and when the furnace temperature drops to 400℃, take out the crucible and put it in a desiccator, cool it to room temperature, weigh it, and then burn it until the difference between the two weighings is less than 0.0004g.
8.3 Calculation
The total mass fraction of ferric oxide and aluminum oxide is calculated as shown in formula (6): WRO
Wherein: R,O——the total mass of FeO, and AlO; mi
the mass of the added precipitate, g;
the mass of the glass, g;
m——the mass of the sample, g
9 Determination of sulfur trioxide
9.1 Gravimetric method
9.1.1 Summary of the method
mlm2×100%
The barium sulfate precipitate formed by the reaction of sulfate radical and barium ion is filtered, washed, ashed and calcined to a constant temperature, and the sulfur trioxide content is calculated: Iron ions interfere with the determination and should be removed in advance. 9.1.2 Analysis steps
Use a large-bellied pipette to take a certain volume of filtrate B into a beaker, dilute it with water to a range of 120~150ml., add 2~3 drops of methyl red indicator, and add hydrochloric acid solution [see 3.2b)] until it becomes acidic; place the beaker on a hot plate, heat it to a slight boil, add 10hml of barium chloride solution while stirring, and let it stand for 4h at a constant temperature of about 60C; filter the above solution with quantitative filter paper, and leave all the precipitate on the filter paper.
After washing the precipitate with hot water until there is no chloride ion, put the precipitate and the filter paper into a constant-volume crucible, ash it on an electric furnace, and then put it into a high-temperature furnace, heat it to 800℃, keep the temperature constant for 30min, and stop heating. When the furnace temperature drops to 400, take out the crucible and put it into the desiccator. After cooling to room temperature, weigh it and burn it until the difference between the two weighings is less than 0.0004g. 9.1.3 Calculation
The calculation of the mass fraction of sulfur trioxide is shown in formula (7): eso
SY/T5516—2000
(ml-m2)x0.3429
0.3429—the mass of sulfur trioxide required to generate 1.0000g of barium sulfate, g. The letters in the formula have the same meaning as before.
9.2 Ion chromatography
Applicable to the determination of sulfate in a medium with a pH value of 23, with a minimum detection mass concentration of 0.05 mg/L. 9.2.1 Method summary
After the sample is injected, it flows through the anion separation column under the eluent. After repeated elution and exchange in the column, the fluorine, chlorine, bromine, and sulfate ions are separated in sequence. The ions are measured by a conductivity detector, and the content of the measured ions is calculated and printed by a computer.
9.2.2 Determination
9.2.2.1 Chromatographic conditions
a) NazCO·NaHCO, the concentrations of the binary eluents are 2.0 mmol/L and 3.0 mmol/L respectively b) Eluent flow rate: Select the flow rate that can achieve complete separation of the measured ion peaks in the sample; c) Anion separation column.
9.2.2.2 Preparation of standard solution
Within the linear range of ions, prepare a standard solution with a sulfate content similar to that in the sample. 9.2.2.3 Determination
Prepare the instrument according to the chromatographic conditions. After the baseline is stable, inject the standard solution and the sample respectively. The computer compares the measured ion signal intensity with the corresponding ion signal intensity in the sample, calculates and prints out the ion content in the sample (mg/L). 9.2.3 Calculation
The calculation of sulfur trioxide mass fraction (SO) is shown in formula (8): CSOx0.8333
-Sulfate ion content in the sample, mg Wherein CSO
The mass of the sample, g;
10 Determination of ignition loss
10.1 Summary of the method
When the rock sample is burned at high temperature, the crystal water, carbon dioxide, organic matter and a small amount of fluorine, chlorine, sulfur and part of potassium and sodium in the carbonate rock escape in gaseous form.
10.2 Analysis steps
Weigh 1g of sample, accurate to 0.0001g, place in a constant weight crucible, place in a high temperature furnace, heat to 1000%, keep constant temperature for 30min, stop heating: when the furnace temperature drops to 400℃, take out the crucible and place in a desiccator, weigh the crucible after cooling to room temperature, and then burn until the difference between the two weighings is less than 0.0004g. 10.3 Calculation
The calculation of the mass fraction of ignition loss is shown in formula (9): ignition loss
The letters in the formula have the same meaning as before.
ml-m2×100%
Quality requirements
SY/T5516—2000
The total mass fraction of each mineral to be tested should be within the range of 97.50% to 100.50%. The results of parallel sample determination in chemical method and ion chromatography analysis shall meet the quality requirements of Table 1 and Table 2 respectively. Table 1 Quality requirements for the results of chemical method determination of parallel samples Item
Acid insoluble matter
Calcium oxide
Magnesium oxide
Sulfur trioxide
Total amount of ferric oxide and
aluminum oxide
Calcium ion
Magnesium ion
Sulfate ion
Content range
>2.0~10.0bzxZ.net
>10.0~20.0
20.0~35.0
>35.0~50.0
>50.0~55.0
>1.5~ 10.0
>10.0-20.0
>5.0~10.0
>10.0~20.0
Table 2 Quality requirements for the results of parallel sample ion chromatography Content range
>50~200
>200~500
>500~800
>20~100
>100~300
>50~100
>100~500
Relative deviation
Relative deviation
12 Data processing
SY/T 5516—2000
12.1 Calcite, dolomite, and magnesite when there is no sulfate in carbonate rocks The calculation method of the mass fraction of dolomite in magnesite (α square, white, man, concave magnesite) is shown in formula (10) to (13): a square = 1.785×wca) -2.483×wMa0 white = 4.575×coMgo
w = 2.092×wMgu-1.504× wca
Wherein: 1.785
McaMgtoo
McaMg(c.2
Mc ... ×ws0,) where: mass fraction of gypsum;
McaMex
Mmeomg
McaMe(c,2
SY/T 551620000~10.0
>10.0~20.0
Table 2 Quality requirements for the results of parallel sample ion chromatography Content range
>50~200
>200~500
>500~800
>20~100
>100~300
>50~100
>100~500
Relative deviation
Relative deviation
12 Data processing
SY/T 5516—2000
12.1 Calcite, dolomite, and magnesite when there is no sulfate in carbonate rocks The calculation method of the mass fraction of dolomite in magnesite (α square, white, man, concave magnesite) is shown in formula (10) to (13): a square = 1.785×wca) -2.483×wMa0 white = 4.575×coMgo
w = 2.092×wMgu-1.504× wca
Wherein: 1.785
McaMgtoo
McaMg(c.2
Mc ... ×ws0,) where: mass fraction of gypsum;
McaMex
Mmeomg
McaMe(c,2
SY/T 551620000~10.0
>10.0~20.0
Table 2 Quality requirements for the results of parallel sample ion chromatography Content range
>50~200
>200~500
>500~800
>20~100
>100~300
>50~100
>100~500
Relative deviation
Relative deviation
12 Data processing
SY/T 5516—2000
12.1 Calcite, dolomite, and magnesite when there is no sulfate in carbonate rocks The calculation method of the mass fraction of dolomite in magnesite (α square, white, man, concave magnesite) is shown in formula (10) to (13): a square = 1.785×wca) -2.483×wMa0 white = 4.575×coMgo
w = 2.092×wMgu-1.504× wca
Wherein: 1.785
McaMgtoo
McaMg(c.2
Mc ... ×ws0,) where: mass fraction of gypsum;
McaMex
Mmeomg
McaMe(c,2
SY/T 55162000
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