SY/T 5613-2000 Test methods for physical and chemical properties of shale
Some standard content:
ICS 75.020
Registration No.: 6972—2000
Petroleum and Natural Gas Industry Standard of the People's Republic of ChinaSY/T 56132000
Methods for testing shale physics and chemistry properties2000-03-31Published
State Administration of Petroleum and Chemical Industry
2000-10-01Implementation
SY/T 5613-2000
This standard is a revision of SY/T5613-93 "Test Methods for Physical and Chemical Properties of Shale". This standard modifies the shale adsorption isotherm experiment in the original standard and adds the formula for calculating the cation exchange capacity (CEC) and bentonite equivalent (MBT) of shale in Chapter 7 "Cation Exchange Capacity of Shale - Methylene Blue Test" in the original standard. This standard replaces SY/I5613-93 from the date of entry into force. This standard is proposed by China National Petroleum Corporation. This standard is under the jurisdiction of the Petroleum Drilling Engineering Professional Standardization Committee. The drafting unit of this standard: Petroleum Engineering Department of Southwest Petroleum Institute. The main drafters of this standard are Luo Xingshu, Cui Maorong, Zhang Xiaohua and Yang Bo. This standard was first issued in July 1989, and this version is the first revision. 1 Scope
Petroleum and Natural Gas Industry Standard of the People's Republic of China Methods for testing shale physics and chernistry properties
Methods for testing shale physics and chernistry propertiesSY7T 5613—2000
Replaces SY/T5613—93
This standard specifies the test methods for density determination, expansion test, dispersion test, cation exchange capacity determination, adsorption isotherm test, water-soluble salt analysis, etc. of shale. This standard is applicable to the physical and chemical properties test of shale. 2 Referenced standards
The provisions contained in the following standards constitute the provisions of this standard through reference in this standard. When this standard is published, the versions shown are valid. All standards will be revised, and parties using this standard should explore the possibility of using the latest versions of the following standards. GB/T5005—1994 Barite powder for drilling fluid GB/T16783—1997 Field test procedure for water-based drilling fluid 3 Collection and preparation of shale samples
3.1 Collection of shale samples
Shale samples are selected from cores or drill cuttings. When measuring the representative physical and chemical properties of shale, it is recommended to use cores. When analyzing water-soluble salts, cores must be used. When more shale samples are needed to evaluate the shale inhibition capacity, drill cuttings can be used. The collected shale samples must be marked with cores or cuttings, and the sampling structure, layer, well number, depth and sampling time must be marked. 3.2 Preparation of shale samples
3.2.1 Core
Scrape off the surface of the core that is contaminated by drilling fluid and place it in a ventilated room with ten winds. Crush the core on a clean plastic or steel plate, and sieve with a double-layer sample sieve with a hole side length of 3.2mm and 2.0mm respectively. Collect 500g of core particles that pass the 3.2mm sieve but not the 2.0mm sieve, and store them in a wide-mouth bottle for later use (with a label). Dry the part that does not pass the 3.2mm sieve and passes the 2.0mm sieve in a constant temperature oven at 10573t for at least 4h. Crush, collect 1kg of rock powder that passes through the sieve with a hole length of 0.149mm, and store it in a wide-mouth bottle for later use (core powder can also be made directly from the core, without having to sieve it with a double-layer sieve first) 3.2.2 Drill Cuttings
Collect drill cuttings from the specified layer on the drilling fluid vibrating screen, use the drilling fluid to wash away the drill cuttings soil, try to remove the mixed rock cuttings from other layers, wash once with a 3% hydrogen peroxide solution, put it in a ventilated room, and sieve it with a double-layer sample sieve with hole lengths of 3.2mm and 2.0mm respectively. Collect the drill cutting particles that pass through the sieve with a hole length of 3.2tmm but not through the sieve with a hole length of 2.0mm, and store them in a wide-mouth bottle for later use. Put the drill cuttings that do not pass through the sieve with a hole length of 3.2mm and pass through the sieve with a hole length of 2.0mm in a constant temperature oven at 105℃±3℃ to dry for at least 4h. Crush, collect 1kg of drill cuttings powder that passes through the sieve with a hole side length of 0.149tmn, and store it in a bottle for later use (drill cuttings powder can also be made directly from drill cuttings, without having to sieve it with a double-layer sieve first). In the sample preparation process, avoid contamination of rock samples by foreign substances, and pay attention to maintaining the representativeness of rock samples. Approved by the State Administration of Petroleum and Chemical Industry on March 31, 2000, implemented on October 1, 2000
4 Determination of density of shale
SY/T5613—2000
Weigh 55.00~60.00g (accurate to 0.01g), dry the core powder prepared according to 3.2.1 or the drill cutting powder prepared according to 3.2.2 at 105℃±3℃ for 4h and cool to room temperature, and determine it according to 2.3.2 of GB/T5005—1994. 5 Shale expansion test
5.1 Instruments
a) NP-01 shale expansion tester: including a complete set of equipment including a host, a recorder and a press; b) Balance: with an accuracy of 0.01g;
c) Vernier caliper, etc.
5.2 Operation steps
5.2.1 Sample core preparation
a) Place a layer of filter paper inside the bottom cover of the measuring tube and tighten the bottom cover of the measuring tube. b) Weigh 10g±0.01g of core powder prepared according to 3.2.1 or drill cuttings powder prepared according to 3.2.2, which has been dried at 105℃±3℃ for 4h and cooled to room temperature, and put it into the measuring tube to flatten the rock powder. c) Install the sealing ring on the plug rod, insert the plug rod into the measuring tube, and place them on the press to apply pressure evenly until the pressure gauge indicates 4053kPa (40atm), and keep the pressure steady for 5min
d) Remove the pressure, remove the measuring tube, slowly remove the plug rod from the measuring tube, and use a vernier caliper to measure the original thickness of the sample core. 5.2.2 Expansion test
a) Turn on the power, start the instrument, and preheat for 15min. b) Install the measuring tube with the sample core installed between the two connecting rods of the main machine and put it in the right position. Put the measuring rod (hole plate) into the measuring tube so that it is in close contact with the sample core, and insert the sensor center rod at the upper end of the measuring rod. Adjust the adjusting nut on the center rod so that the digital meter displays 0.00. c) Adjust the recorder measurement range to 1V (full scale is equivalent to 10mm), the recording paper feed speed to 0.01mm/s (do not start the paper feed switch), and adjust the recorder adjustment knob so that the recording pointer is aligned with the 0 line of the recording paper. d) Fill the measuring tube with distilled water and start the recorder switch at the same time. The digital meter displays the linear expansion R of the sample core at any time, and the recorder draws the relationship curve between the linear expansion and time (expansion curve). e) After the instrument has been working for 16 hours, turn off the power, remove the measuring tube and measuring rod, clean them, and store them for future use. 5.3 Calculation formula
Calculate the linear expansion rate of 2h and 16h according to formula (1): VH
Where: V is the linear expansion rate of shale at time t: R is the linear expansion amount at time t, mm;
is the original thickness of the sample core, mm.
1 When measuring the original thickness of the sample core, use a vernier caliper to measure the height of the measuring tube before filling the rock powder (measure four orthogonal points and take the average value). After the sample core is made, use the same method to measure the height of the measuring tube without the sample core. The difference between the two times is the thickness of the sample core. 2 Start recording the expansion of 2h and 16h while filling the measuring tube with distilled water. 6 Shale dispersion test
6.1 Instruments
a) Roller furnace;
b) High-temperature tank;
c) Sampling sieve with a hole side length of 0.420 nm; d) Balance: accuracy of 0.1 g;
e) Electric heating blast constant temperature drying box.
6.2 Operation steps
SY/T 5613-2000
6.2.1 Weigh 50.0g (accurate to 0.1g) of core particles prepared according to 3.2.1 or drill cuttings particles prepared according to 3.2.2, and put them into a high-temperature tank containing 350mL of distilled water, and cover it tightly. 6.2.2 Place the high-temperature tank filled with samples in a drilling fluid roller furnace at 80℃±3℃, and roll for 16hc6. 2.3 After rolling at constant temperature for 16h, take out the high-temperature tank and cool it to room temperature. Pour all the liquid and rock samples in the tank onto a sample sieve with a side length of 0.42mm, and wet-sieve and wash in a trough filled with rice water for 1min. 6.2.4 Place the remaining rock samples in a blast constant temperature drying oven at 105℃=3℃ and dry them for 4h. Take out and cool, and place it in the air for 24 hours, then weigh it (accurate to 0.1g). 6.3 Calculation formula
Calculate the 16h fresh water recovery rate according to formula (2): × 100%
The side length of the hole is 0.42mm shale recovery rate; where: R—
hole side length is 0.42mm screen residue, g
1The experimental conditions for wet screening should be kept consistent as much as possible. 2 The humidity of the air after standing for 24 hours should be as consistent as possible with the humidity of the storage environment of the wind-rock sample. 3 In order to reduce accidental errors, each shale sample should be tested at least 3 to 4 times in parallel, and the average value should be taken as the report result. 7 Cation exchange capacity of shale - Methylene blue test 7.1 Operation steps
Weigh 100.0g of the core powder prepared according to 3.2.1 or the drill cuttings powder prepared according to 3.2.2 that has been cooled to room temperature and placed in a 250mL measuring cylinder, add distilled water to extract the total volume to 200ml. Mix well and stir at high speed on a high-speed stirrer for 15min. Use a syringe without a needle to measure 2.0mL of the shaken shale slurry (if the volume of the consumed methylene blue solution exceeds 12mL, 1.0mL of slurry can be measured), according to GB/16783- 1997, 6.2-6.3. 7.2 Calculation formula
Calculate the cation exchange capacity (CEC) and the bentonite equivalent (MBT) value of shale according to formula (3) and formula (4) respectively:
Wherein: CEC—cation exchange capacity of shale, mmol (monovalent ions)/kg (dry shale); - the number of milliliters of sub-basic blue solution consumed in titration; 6- the number of grams of shale taken in titration;
MBT—bentonite equivalent of shale, g (bentonite equivalent)/kg (ten shale); 0.70
-refers to the cation exchange capacity per 1g of bentonite, mmol (monovalent ions)/g (bentonite). 8 Shale adsorption isotherm
8. 1 Instruments and reagents
a) Analytical balance: accuracy of 0.1mg; (3)
b) Electric blast constant temperature drying oven;
) Flat weighing bottle, ordinary dryer;
SY/T5613-2000
d) Zinc chloride, calcium chloride, calcium nitrate, sodium chloride, potassium dihydrogen phosphate, all analytically pure. 8.2 Operation steps
8.2.1 Weigh 2.0~3.0g (accurate to 0.1mg) of core powder prepared according to 3.2.1 or 5 portions of drill cuttings powder prepared according to 3.2.2, respectively, and place them into 5 flat weighing bottles that have been washed and dried to constant weight at 105℃±3℃, and then place them in a constant temperature drying oven at 105℃±3℃ to constant weight (the difference between the two weights should not exceed 1mg), and record. The exact mass of each bottle of dry mud shale powder (mi). 8.2.2 Prepare 300 mL of saturated solutions of the above five salts, such as zinc chloride and calcium chloride (use distilled water, and always keep a small amount of undissolved salt in the solution), and put them into five clean desiccators respectively, and label them. 8.2.3 Put the above five portions of dry mud shale powder together with weighing bottles into five desiccators containing different saturated salt solutions, open the weighing bottle caps, and cover the desiccator caps. Let it stand for 6 days in an environment of 24℃±1C. 8.2.4 After 6 days, open the desiccator, cover the weighing bottle, and immediately weigh it accurately on the analytical balance. 8.2.5 From the difference between the two masses of the flat weighing bottles that have been dried to constant weight in 8.2.4 and 8.2.1, the mass of shale when water absorption reaches equilibrium at the specified relative humidity (m2) is obtained.
8.3 Calculation formula
8.3.1 Calculate the equilibrium adsorption capacity of shale at different relative humidity according to formula (5): m2-ml×100%
Wherein: EA
Equilibrium adsorption capacity of shale at different relative humidity; mass of dry shale, g,
Mass of shale after absorbing water at a certain relative humidity, g. m2
8.3.2 With the equilibrium adsorption capacity as the ordinate and the relative humidity as the abscissa, draw the adsorption isotherm of shale on the coordinate paper. The relative humidity of various saturated salt solutions at 24℃ is as follows: Salt
Zinc chloride
Calcium chloride
Calcium nitrate
Sodium chloride
Potassium dihydrogen phosphate
1Controlled at a constant temperature of 24℃±1℃2Each shale sample is averaged at 5 relative temperatures 9 Analysis of water-soluble salts in shale
9.1 Extraction of water-soluble salts in shale
9.1.1 Instrument
Relative humidity (p/po)
Equilibrium adsorption capacity should be measured in duplicate, and the average value of the results should be plotted. a) High-speed stirrer: load speed is 11000r/min±300r/min; b) Buchner funnel and vacuum pump, or electric centrifuge (4000r/min, centrifuge tube volume is 50mL). 9.1.2 Operation steps
a) Weigh 200.0g of the core powder prepared according to 3.2.1 or the drill cuttings powder prepared according to 3.2.2, put it into a 1L beaker, add 1L of distilled water to remove carbon dioxide, stir well, put it into 3 high-stirring containers respectively, and stir it on a five-axis stirrer for 5 minutes at high speed. b) Pour the shale slurry in the 3 containers back into the 1L beaker, stir well, and immediately filter it with a Buchner funnel (using slow filter paper). If the filtrate is turbid, it should be filtered again until a clear leaching solution is obtained. Store the filtrate in a clean glass bottle or plastic bottle. If filtration is not required, centrifugal separation or pressure filtration with a water loss instrument can also be used. The separated leaching solution must still be clear and transparent. Note: Distilled water for leaching needs to be boiled for 15 minutes to remove carbon dioxide, and used immediately after cooling. 9.2 Determination of drying residue and total amount of water-soluble salt 9.2.1 Instruments and reagents
a) Electric heating plate, water bath;
b) Desiccator, porcelain evaporating dish;
c) 12% (mass fraction) sodium carbonate solution; d) 15% (mass fraction) hydrogen peroxide solution. 9.2.2 Operation steps
a) Use a pipette to draw 50mL or 100mL (depending on the amount of salt) of clear leaching solution, put it into a porcelain evaporator III of known mass, transfer it to a water bath to evaporate to dryness, and then put it into a 105℃±3℃ constant temperature box to dry for 4h. b) Take out the evaporating dish, cool it in a desiccator for 30min, weigh it on an analytical balance, and dry it for another 2h. Use the same method to cool and weigh it until constant weight is reached (the difference between the two masses does not exceed 1mg). Calculate the total amount of drying residue. c) Add 15% hydrogen peroxide solution to the dried residue to moisten it, and then evaporate it in a water bath. Repeat this process until the residue turns completely white. Dry it in a constant temperature oven, cool it, and weigh it until it reaches a constant weight according to the above method. 9.2.3 Calculation formula
Calculate the total amount of dried residue and the total amount of water-soluble salt according to formula (6) and formula (7) respectively: RQ
m3mo×100%
m5-mo×100%
-total amount of dried residue;
Where: RQ
total amount of water-soluble salt;
mass of evaporated blood, g; bZxz.net
mass of dried residue and evaporated blood, g
the amount of shale equivalent to the extracted leaching solution, g; the mass of water-soluble salt and evaporating dish, g.
1 If the residue contains a lot of magnesium sulfate and calcium sulfate, it is difficult to achieve constant weight when dried at 105℃±3℃, so it should be dried at 180℃ instead. (6)
2 If the residue contains a lot of calcium chloride and magnesium chloride, it is easy to absorb moisture. You can first add 10.0mL of 12% sodium carbonate solution to the leaching solution, evaporate it to form carbonate, and then dry it at 105℃±3℃ or 180℃ for 2h to achieve constant weight. The amount of sodium carbonate added should be subtracted from the total amount of salt. 3 Salt (especially magnesium salt) should be cooled and weighed at the same time and conditions. The drying, cooling and weighing conditions of the empty porcelain evaporating dish should be consistent with the conditions during the measurement.
4 When adding hydrogen peroxide to treat the residue, just moisten the residue to avoid excessive foaming during the decomposition of hydrogen peroxide, which may cause the salt to splash out. 5 When the total amount of water-soluble salt exceeds 1%, the composition analysis of water-soluble salts in 9.3, 9.4, 9.5 and 9.6 shall be carried out. 9.3 Determination of carbonate and bicarbonate
Use a pipette to draw 25ml or 50ml of clear leaching solution and measure according to A6 in Appendix A of GB/T16783-1997. 9.4 Determination of chloride
Use a pipette to draw 25ml of clear leaching solution and measure according to 8.3 in GB/T16783-1997. 9.5 Determination of sulphate
Use a pipette to draw 25ml or 50ml of clear leaching solution and measure according to A3 in Appendix A of GB/T16783-1997. 5
9.6 Determination of calcium and magnesium
SY/T 5613—2000
Use a pipette to draw 25tnL of the clear leaching solution and perform the determination according to A1 and A2 in Appendix A of GB/T 16783-1997. 10 Determination of exchangeable calcium and magnesium in shale
10.1 Instruments and Materials
8) Electric centrifuge: rated speed 4000r/min, centrifuge tube volume 50mL or 100mL; b) Ammonia buffer solution: dissolve 67.5g analytical pure ammonium chloride in 100mL water, add 570mL analytical pure concentrated nitrogen water (15mol/L concentration), and dilute to 1mL with water;
c) K-B indicator: 0.5g acid chrome blue K and 0.1g naphthol green B with 100g Grind together the sodium chloride dried at 105±3℃ and store in a brown bottle;
(d) 0.01nal/.EDTA standard solution:
e) 2mol/L sodium hydroxide solution and calcium indicator:f) 1:3 hydrochloric acid solution (volume fraction);
g) 1:1 ammonia solution (volume fraction);h) 1mol/L ammonium acetate solution (pH value is 7.0): dissolve 77.09g ammonium acetate in water and dilute to nearly 1 L, adjust the pH value to 7.0 with 1:1 hydrogen water or dilute acetic acid, and dilute to 1L. 10.2 Operation steps
10.2.1 Weigh 2.00-5.00g of core powder prepared according to 3.2.1 or drill cuttings powder prepared according to 3.2.2, put it into a 50mL or 100mL centrifuge tube, add a small amount of 1mol/L ammonium acetate solution along the tube wall, stir it with a rubber rod to form a uniform mud state, add 1mol/L ammonium acetate to a total volume of about 40mL, and stir it thoroughly. Wash the rubber-headed glass rod with a small amount of 1mol/ ammonium acetate, and collect the solution in the centrifuge tube. Place the centrifuge tubes in pairs on the two plates of the scale, add 1A ammonium acetate to make the two tubes equal in mass, put them symmetrically into the centrifuge and centrifuge at a speed close to 4000r/min for 5 minutes, collect the supernatant in a 250mL volumetric flask, and then treat it with 1mol/L ammonium acetate solution for 3 to 5 times until the final leaching liquid is free of calcium ions. Finally, dilute it to the scale with 1mal/L ammonium acetate solution, shake 10.2.2, and use a pipette to draw 25ml of the liquid, two portions, and put them in 200ml beakers respectively, and evaporate at low temperature. Add 3-5 drops of 1:3 hydrochloric acid to the dried beaker to dissolve the residue, and rinse the inner wall of the beaker with a small amount of water, and add water to a total volume of 40mL. 10.2.3 For one portion, use 1:1 nitrogen water to neutralize (pH test paper), add 5mL of ammonia buffer solution, mix well, add a little KB indicator, and titrate with 0.0imol/EDTA standard solution until the solution changes from wine red to blue (end point), and record the number of milliliters of EDTA consumed (V). At the same time, do a blank test and record the number of milliliters of EDTA consumed (V). 10.2.4 For the other portion, add 2-9mL of 2rmol/L sodium hydroxide solution to make the solution pH reach 12, add a little calcium indicator, and titrate with 0.01mol/EDTA standard solution. When approaching the end point, add drop by drop, shake well, until the solution changes to pure vegetable color. Record the milliliters of EDTA consumed (V2). At the same time, do a blank test and record the milliliters of EDTA consumed (V). 10.3 Calculation formula
Calculate the total amount of water-soluble and exchangeable calcium and magnesium according to formula (8) and formula (9): Caz+ - me(Vz - Vo)
2×1000
Mg M(Vi- Vo)=(V- ) × 000
Wherein: Ca+ - total amount of water-soluble and exchangeable calcium, mmol/kg (calculated shale); Mg+ - total amount of water-soluble and exchangeable magnesium, mmol/kg (dry shale); m6 - mass of shale equivalent to the absorbed leaching solution, g; V - amount of FDTA dissolved in the determination of calcium ions, mL; Vo - amount of EDIA solution consumed in the blank test, mL; M - liquid density of EDTA standard solution, mol/L: 6
SY/T5613-2000
- The amount of EDTA solution consumed when determining calcium and magnesium ions, mL. Then subtract the water-soluble calcium and magnesium content measured in 9.6 from the total amount of water-soluble and exchangeable calcium and magnesium to obtain the exchangeable calcium and magnesium. 10.4 Precautions
10.4.1 If there is floating organic matter in the ammonium acetate leachate, it should be filtered before determination, otherwise the calcium and magnesium in the organic matter will enter the solution when acid is added and dissolved after evaporation, affecting the determination results of exchangeable calcium and magnesium. 10.4.2 Method for checking calcium ions in the leachate: Take about 1mL of the leachate and put it in a test tube, add 2 drops of 2mol/L sodium hydroxide, add a little calcium indicator, and shake well. If the solution is blue, it means there is no calcium ion; if it is purple, it means there is calcium ion.2 Method for checking calcium ions in the leachate: take about 1 mL of the leachate and put it in a test tube, add 2 drops of 2 mol/L sodium hydroxide, add a little calcium indicator, and shake well. If the solution is blue, it means there is no calcium ion; if it is purple, it means there is calcium ion.2 Method for checking calcium ions in the leachate: take about 1 mL of the leachate and put it in a test tube, add 2 drops of 2 mol/L sodium hydroxide, add a little calcium indicator, and shake well. If the solution is blue, it means there is no calcium ion; if it is purple, it means there is calcium ion.
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