CN118056880A - Synthetic main emulsifier, preparation method thereof and high-temperature-resistant oil-based drilling fluid - Google Patents
Synthetic main emulsifier, preparation method thereof and high-temperature-resistant oil-based drilling fluid Download PDFInfo
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- 238000005553 drilling Methods 0.000 title claims abstract description 106
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 105
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920000962 poly(amidoamine) Polymers 0.000 claims abstract description 19
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 15
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- -1 compound sulfonate Chemical class 0.000 claims description 36
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- 239000004927 clay Substances 0.000 claims description 9
- 239000003077 lignite Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
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- 239000011734 sodium Substances 0.000 claims description 8
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- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 239000000440 bentonite Substances 0.000 claims description 6
- 229910000278 bentonite Inorganic materials 0.000 claims description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012267 brine Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007957 coemulsifier Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000003784 tall oil Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
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- 238000004090 dissolution Methods 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 4
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- 239000004698 Polyethylene Substances 0.000 claims description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical group [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 3
- 239000010428 baryte Substances 0.000 claims description 3
- 229910052601 baryte Inorganic materials 0.000 claims description 3
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- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 230000000996 additive effect Effects 0.000 claims 1
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- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
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Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention relates to the technical field of drilling fluid, in particular to a synthetic main emulsifier, a preparation method thereof and high-temperature resistant oil-based drilling fluid, wherein the synthetic main emulsifier comprises, by mass, 2 to 6 parts of long carbon chain polyamidoamine type emulsifier, 2 to 6 parts of composite sulfonate and 1 to 3 parts of stearate, and the carbon chain length of the long carbon chain polyamidoamine type emulsifier is C 10 to C 14. The synthetic main emulsifier disclosed by the invention has low viscosity effect and high demulsification voltage, is a high-efficiency main emulsifier, can play a good role in emulsification, wetting and dispersion in oil-based drilling fluid, has good rheological property, electrical stability, sedimentation stability and system performance stability, and can meet the requirements of high-clay mineral reservoir section drilling operation and high-temperature high-pressure reservoir drilling operation.
Description
Technical Field
The invention relates to the technical field of drilling fluid, in particular to a synthetic main emulsifier, a preparation method thereof and high-temperature resistant oil-based drilling fluid taking the synthetic main emulsifier as a raw material.
Background
Petroleum is taken as non-renewable resource and has important importance in the fields of industry, national defense and the like. The oil-based drilling fluid is rapidly developed in petroleum exploitation and gradually becomes an important means for drilling high-temperature deep wells, high-inclination directional wells, horizontal wells, various complex well sections and protecting reservoirs with high difficulty. Compared with developed countries, china is seriously lagged in research and application of oil-based drilling fluid systems, and most of the oil-based drilling fluid systems have the defects of poor temperature resistance, difficult maintenance and treatment, high cost and the like.
As the key point of domestic and foreign exploration and development, the deep ultra-deep oil and gas reservoir is positioned in a stratum with high temperature of 150 ℃ to 200 ℃ and high pressure of 105MPa to 140MPa, and the burial depth can reach 9000m. Geological conditions faced by deep hydrocarbon reservoir development are also more complex, such as 2 to 3 sets of salt layers in front of the Tarim mountain and a plurality of sets of pressure systems combined below the south edge of the Songer basin. Deep well ultra-deep well drilling is the field with the greatest technical challenges, the greatest complexity of underground accidents and the greatest concentration of difficult problems at present. In recent years, the oil-based drilling fluid is increasingly applied to the field of deep wells with complex geological conditions on land such as Tarim basin, sichuan basin, and Song's basin, wherein the well depth reaches more than 8000m, such as gram depth 21 well depth 8098m, the temperature reaches more than 200 ℃, such as Tasheng 1 well, the stratum temperature is 203 ℃, the density reaches more than 2.60g/cm 3, such as Lesheng 1 well, and the drilling fluid density is 2.68g/cm 3. The problems faced by the drilling fluid under the ultra-high temperature and high pressure are mainly the deterioration and failure of the performance of the treating agent caused by the high-temperature environment, the balance of the rheological property of the high-density fluid caused by the ultra-high pressure stratum, and the difficulty in regulating and controlling the performance of the drilling fluid caused by the complex geological conditions, such as the pollution of a huge thick salt paste layer, the stability of a well wall with a high and steep structure, and the like. Therefore, the ultra-high temperature high-density oil-based drilling fluid with strong pollution resistance and good rheological property is a key for improving the safe and efficient drilling of the complex deep ultra-high temperature high pressure stratum.
The chinese patent publication No. CN105907382B discloses an emulsifier based on oil-based drilling fluids, which comprises tall oil fatty acid, polyamine, chloroacetic acid amide, surfactant and organic solvent, and also provides a method for preparing the emulsifier based on oil-based drilling fluids. The emulsifier based on the oil-based drilling fluid is an integrated emulsifier, and has the characteristics of stable emulsion and high demulsification voltage. But the problems faced by drilling fluids at high temperature and pressure are still not solved.
Disclosure of Invention
The invention provides a synthetic main emulsifier and high-temperature resistant oil-based drilling fluid, which overcomes the defects of the prior art, and can effectively solve the problems of deterioration and failure of the conventional drilling fluid in the high-temperature environment.
One of the technical schemes of the invention is realized by the following measures: the synthetic main emulsifier comprises, by mass, 2 to 6 parts of a long-carbon-chain polyamidoamine type emulsifier, 2 to 6 parts of a compound sulfonate, 1 to 3 parts of stearate, and the long-carbon-chain polyamidoamine type emulsifier has a carbon chain length of C 10 to C 14.
The following are further optimizations and/or improvements to one of the above-described inventive solutions:
The synthetic main emulsifier is prepared by the following method: the long carbon chain polyamidoamine emulsifier comprises 2 to 6 parts of long carbon chain polyamidoamine emulsifier, 2 to 6 parts of compound sulfonate and 1 to 3 parts of stearate, wherein the carbon chain length of the long carbon chain polyamidoamine emulsifier is C 10 to C 14.
The long carbon chain polyamidoamine emulsifier is prepared by the following method:
Firstly, filling refined tall oil acid into a reactor, heating to 85-90 ℃, adding polyethylene polyamine, heating to 180-190 ℃ under the condition of introducing nitrogen, and reacting at constant temperature for 3-4 h;
secondly, when no water drop appears in the water knockout drum for 10min to 15min or the liquid level in the reactor is not increased, regulating the flow rate of nitrogen, raising the temperature to 240 ℃ to 250 ℃, and carrying out constant-temperature reaction for 3h to 4h;
And thirdly, when no water drop appears in the water separator or the liquid level is not increased, adding solvent oil D140, cooling to 180-190 ℃, adding an organotin compound catalyst with the mass of maleic anhydride and 0.1% of the total reactant, reacting for 5 hours at constant temperature, adding an alcohol ether solvent for dissolution, and cooling to room temperature to obtain the long carbon chain polyamide amine type emulsifier.
The compound sulfonate is prepared by uniformly stirring and mixing petroleum ferric sulfonate, sodium alkyl benzene sulfonate and sodium alkyl succinate sulfonate at a high speed at 60 ℃.
The stearate is polyoxyethylene stearate.
The second technical scheme of the invention is realized by the following measures: the preparation method of the synthetic main emulsifier comprises the following steps: mixing required amount of long carbon chain polyamidoamine type emulsifier, composite sulfonate and stearate, and reacting for 3-7 hours at the temperature of 120-210 ℃ to obtain the synthetic main emulsifier.
The third technical scheme of the invention is realized by the following measures: the high temperature resistant oil-based drilling fluid comprises, by mass, 1-3% of a synthetic main emulsifier, 1-3% of an auxiliary emulsifier, 0.8-2% of organic soil, 0.5-1% of calcium oxide, 1-3% of a filtrate reducer, 5-40% of a weighting agent, and the balance of a mixed solution of base oil and calcium chloride brine.
The following is a further optimization and/or improvement of the third aspect of the present invention:
The auxiliary emulsifier is a mixture of polyoxy diene dioleate with an HLB value of 7.5 and polyoxypropylene stearate with an HLB value of 8, and the weight ratio of the polyoxy diene dioleate to the polyoxypropylene stearate is 1:1-3.
The organic clay is oleophylic clay formed by bentonite after being treated by quaternary ammonium salt surfactant.
The filtrate reducer is lignite.
The weighting agent is barite with density of more than 4.25g/cm 3.
The base oil is diesel oil, the concentration of calcium chloride salt water is 20-30wt%, and the volume ratio of the base oil to the calcium chloride salt water is 70:30-90:10.
The synthetic main emulsifier has low viscosity effect and high demulsification voltage, can play a role in good emulsification, wetting and dispersion in oil-based drilling fluid, has good rheological property, electrical stability, sedimentation stability and system performance stability and strong inhibition, can stabilize a well wall, prevent collapse, has good protection performance on oil-gas layers, particularly water-sensitive stratum, has good high-temperature (240 ℃) resistance and lubricating performance, can cope with shale collapse-prone stratum, deep well thick salt paste layer, complex stratum and the like, and is suitable for deep well and large inclined shaft drilling. The high-temperature resistant oil-based drilling fluid has good inhibition performance, and can meet the requirements of drilling operation of a high-clay mineral reservoir section. In addition, the high-temperature-resistant oil-based drilling fluid also has good pollution resistance, and can meet the requirements of high-temperature and high-pressure reservoir drilling operation.
Drawings
FIG. 1 is a graph showing the sedimentation stability performance of the oil-based drilling fluid with high temperature resistance according to example 13 of the present invention.
Fig. 2 is a chart of the inhibition performance test of the high temperature resistant oil-based drilling fluid of example 13 of the present invention.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments can be determined according to the technical scheme and practical situations of the present invention. The various chemical reagents and chemical supplies mentioned in the invention are all commonly known and used in the prior art unless specified otherwise; the percentages in the invention are mass percentages unless specified otherwise; the room temperature and the room temperature in the present invention generally refer to temperatures ranging from 15 ℃ to 25 ℃, and are generally defined as 25 ℃.
The invention is further described below with reference to examples:
Example 1: the synthetic main emulsifier comprises, by mass, 2 to 6 parts of long-carbon-chain polyamidoamine-type emulsifier, 2 to 6 parts of compound sulfonate, 1 to 3 parts of stearate, and the carbon chain length of the long-carbon-chain polyamidoamine-type emulsifier is C 10 to C 14.
Example 2: as an optimization of the above examples, the synthetic main emulsifier was prepared by the following method: mixing required amount of long carbon chain polyamidoamine type emulsifier, composite sulfonate and stearate, and reacting for 3-7 hours at the temperature of 120-210 ℃ to obtain the synthetic main emulsifier. Under the above conditions, long carbon chain polyamidoamine emulsifier, composite sulfonate and stearate undergo addition reaction; unsaturated vinyl of stearate provides free radical, long carbon chain polyamidoamine type emulsifier and composite sulfonate are respectively added to two ends of vinyl, and the synthetic main emulsifier is obtained through reaction.
Example 3: as an optimization of the above examples, the long carbon chain polyamidoamine type emulsifier was prepared by the following method:
Firstly, filling refined tall oil acid into a reactor, heating to 85-90 ℃, adding polyethylene polyamine, heating to 180-190 ℃ under the condition of introducing nitrogen, and reacting at constant temperature for 3-4 h;
secondly, when no water drop appears in the water knockout drum for 10min to 15min or the liquid level in the reactor is not increased, regulating the flow rate of nitrogen, raising the temperature to 240 ℃ to 250 ℃, and carrying out constant-temperature reaction for 3h to 4h;
And thirdly, when no water drop appears in the water separator or the liquid level is not increased, adding solvent oil D140, cooling to 180-190 ℃, adding an organotin compound catalyst with the mass of maleic anhydride and 0.1% of the total reactant, reacting for 5 hours at constant temperature, adding an alcohol ether solvent for dissolution, and cooling to room temperature to obtain the long carbon chain polyamide amine type emulsifier.
Example 4: as optimization of the embodiment, the compound sulfonate is prepared by uniformly stirring and mixing petroleum ferric sulfonate, sodium alkyl benzene sulfonate and sodium alkyl succinate sulfonate at a high speed at 60 ℃. The composite sulfonate prepared by the method is a good oil-soluble emulsifier and dispersant.
Example 5: as an optimization of the above examples, the stearate was polyoxyethylene stearate. The polyoxyethylene stearate has good thermal stability.
Example 6: the high-temperature resistant oil-based drilling fluid comprises, by mass, 1 to 3% of a synthetic main emulsifier, 1 to 3% of an auxiliary emulsifier, 0.8 to 2% of organic soil, 0.5 to 1% of calcium oxide, 1 to 3% of a filtrate reducer, 5 to 40% of a weighting agent, and the balance of a mixed solution of base oil and calcium chloride brine.
Example 7: as an optimization of the above examples, the co-emulsifier was a mixture of a polyoxyalkylene dioleate having an HLB value of 7.5 and a polyoxypropylene stearate having an HLB value of 8, the weight ratio of polyoxyalkylene dioleate to polyoxypropylene stearate being 1:1 to 3.
Example 8: as an optimization of the above examples, the organic clay is a lipophilic clay formed by bentonite after being treated with a quaternary ammonium salt surfactant.
Example 9: as an optimization of the above embodiment, the filtrate reducer is lignite.
Example 10: as an optimization of the above examples, the weighting agent was barite with a density greater than 4.25g/cm 3.
Example 11: as an optimization of the above examples, the base oil was diesel oil, the calcium chloride salt water concentration was 20wt% to 30wt%, and the volume ratio of the base oil to the calcium chloride salt water was 70:30 to 90:10 in the mixed liquid of the base oil and the calcium chloride salt water.
The high temperature resistant oil-based drilling fluid system comprises base oil, organic soil, an emulsifying agent, a filtrate reducer, calcium oxide, brine and a weighting agent, has strong inhibition property compared with water-based slurry, can stabilize a well wall, prevent collapse, has good protection performance on oil and gas layers, particularly water-sensitive stratum, and has good high temperature resistant (240 ℃) performance and lubricating performance, and is mainly used for coping with shale easy-collapse stratum, deep well thick salt paste layer, complex stratum and the like, and is suitable for drilling deep wells and large inclined wells. The high-temperature-resistant oil-based drilling fluid system is beneficial to improving the temperature resistance, lubricity and inhibition of the drilling fluid, enhancing the suspension stability of the system and ensuring that the weighting material has good sedimentation stability.
Example 12: preparation of synthetic main emulsifier:
① Preparation of long carbon chain polyamidoamine type emulsifier:
Firstly, installing a four-neck flask on a liftable oil bath pot, configuring a water separator, a stirrer, a thermometer, reduced pressure distillation and a nitrogen pipeline, loading refined tall oil acid into the four-neck flask, heating to 87 ℃, adding triethylene tetramine, heating to 185 ℃ under the condition of introducing nitrogen, and carrying out constant-temperature reaction for 3-4 hours;
Secondly, when no water drop appears in the water knockout drum for 10min to 15min or the liquid level in the reactor is not increased, the flow rate of nitrogen is regulated, the temperature is increased to 245 ℃, and the constant temperature reaction is carried out for 3h to 4h;
And thirdly, when no water drop appears in the water separator or the liquid level is not increased, adding solvent oil D140, cooling to 185 ℃, adding an organotin compound catalyst with the mass of maleic anhydride and 0.1% of the total reactant, reacting for 5 hours at constant temperature, adding an alcohol ether solvent for dissolution, and cooling to room temperature to obtain the long carbon chain polyamide amine type emulsifier.
② Preparation of complex sulfonate: and (3) uniformly stirring and mixing the three raw materials of petroleum ferric sulfonate, sodium alkyl benzene sulfonate and sodium alkyl succinate sulfonate at a weight ratio of 2:1:1 at a high speed at 60 ℃ to obtain the modified magnesium sulfonate.
③ Mixing the prepared long carbon chain polyamidoamine type emulsifier, the compound sulfonate and the stearate according to the proportion in the table 1, and reacting for 3 to 7 hours at the temperature of 120 to 210 ℃ to obtain the synthetic main emulsifier No. 1 to No. 4 respectively. The synthetic main emulsifiers No. 1 to No. 4 were added to oil-based drilling fluid with a density of 1.8g/cm 3, respectively, and the mixture was thermally rolled at 150℃for 16 hours, and the performance of the synthetic main emulsifiers No. 1 to No. 4 was evaluated at 65℃with the results of the parametric tests shown in Table 1. In Table 1, AV is apparent viscosity, and is measured by a six-speed rotational viscometer brookfield DV-III, with reference to GB/T161782-1997. PV is the plastic viscosity, measured with a six-speed rotational viscometer brookfield DV-III, see GB/T161782-1997. YP is the dynamic shear force, measured with a six-speed rotational viscometer brookfield DV-III, see GB/T161782-1997. ES is the demulsification voltage, measured by an electric stabilizer DWY, with reference to GB/T161782-1997. As can be seen from Table 1, the synthetic main emulsifiers No. 1 to No. 4 have better performance, and meanwhile, the synthetic main emulsifier No. 4 has the optimal effect, which indicates that the viscosity effect of the main emulsifier is low, the demulsification voltage is high, and the high-efficiency main emulsifier is formed, so that the high-efficiency main emulsifier can play a good role in emulsifying, wetting and dispersing in oil-based drilling fluid.
Example 13: the high-temperature resistant oil-based drilling fluid comprises 1% of organic soil by mass percent; 2% of a main emulsifier (main emulsifier is main emulsifier No. 4 obtained in example 12); 3% of a co-emulsifier; 0.5% calcium oxide; 1% of a filtrate reducer; 20% weighting agent; and (3) mixing the diesel oil and the calcium chloride brine (30 wt%) with the ratio of 4:1 by volume, stirring at a high speed for more than 1h, and uniformly mixing to obtain the high-temperature resistant oil-based drilling fluid. Wherein the organic soil is oleophylic clay formed by bentonite after being treated by trimethyl ammonium bromide (long-chain quaternary ammonium salt cation) with carbon chain length of C 12 -C 16; the auxiliary emulsifier is mixed by polyoxy diene dioleate with HLB value of 7.5 and polyoxy propylene stearate with HLB value of 8 according to the proportion of 1:2; the filtrate reducer is lignite; the weighting agent is heavy stone.
Example 14: the high-temperature-resistant oil-based drilling fluid comprises the following raw materials in percentage by mass: 0.8% of organic soil; 1.5% of a main emulsifier (main emulsifier is main emulsifier No. 4 obtained in example 12); 2.2% of a co-emulsifier; 1% of calcium oxide; 3% of filtrate reducer; 30% weighting agent; 60.5% of diesel oil and 25% of calcium chloride salt water mixture, wherein the volume ratio of the diesel oil to the calcium chloride salt water mixture is 5:1, and the components are mixed and stirred at a high speed for more than 1h, and the high-temperature resistant oil-based drilling fluid is obtained after uniform mixing. Wherein the organic soil is oleophylic clay formed by bentonite after being treated by trimethyl ammonium bromide with carbon chain length of C 12 -C 16; the auxiliary emulsifier is mixed by polyoxy diene dioleate with HLB value of 7.5 and polyoxy propylene stearate with HLB value of 8 according to the proportion of 1:2; the filtrate reducer is lignite; the weighting agent is heavy stone.
Example 15: the high-temperature-resistant oil-based drilling fluid comprises the following raw materials in percentage by mass: 0.5% of organic soil; 2.5% of a main emulsifier (main emulsifier is main emulsifier No. 3 obtained in example 12); 2.2% of a co-emulsifier; 1% of calcium oxide; 2% of filtrate reducer; 38% weighting agent; 53.3 percent of diesel oil and 35 percent of calcium chloride salt water mixture with the concentration of 35 percent by weight, wherein the volume ratio of the diesel oil to the calcium chloride salt water mixture is 6:1, and the components are mixed and stirred for more than 1 hour at high speed, and the high temperature resistant oil-based drilling fluid is obtained after uniform mixing. Wherein the organic soil is oleophylic clay formed by bentonite after being treated by trimethyl ammonium bromide with carbon chain length of C 12 -C 16; the auxiliary emulsifier is polyoxy diene dioleate with HLB value of 7.5 and polyoxy propylene stearate with HLB value of 8 which are mixed uniformly according to the proportion of 1:2; the filtrate reducer is lignite; the weighting agent is heavy stone.
Example 16: the high-temperature-resistant oil-based drilling fluid comprises the following raw materials in percentage by mass: 0.3% of organic soil; 2.7% of a main emulsifier (main emulsifier is main emulsifier No. 4 obtained in example 12); 2.0% of a co-emulsifier; 1.2% calcium oxide; 2% of filtrate reducer; 45% weighting agent; 48.3% of diesel oil and 37% of calcium chloride salt water mixture, wherein the volume ratio of the diesel oil to the calcium chloride salt water mixture is 7:1, and the components are mixed and stirred at a high speed for more than 1h, and the high-temperature resistant oil-based drilling fluid is obtained after uniform mixing. Wherein the organic soil is oleophylic clay formed after long-chain quaternary ammonium salt cations are trimethyl ammonium bromide with carbon chain lengths of C 12 -C 16; the auxiliary emulsifier is mixed by polyoxy diene dioleate with HLB value of 7.5 and polyoxy propylene stearate with HLB value of 8 according to the proportion of 1:2; the filtrate reducer is lignite; the weighting agent is heavy stone.
The high temperature resistant oil-based drilling fluids prepared according to system examples 13 to 16 were each thermally rolled at 240 ℃ for 16 hours, and performance parameter tests were performed, and the parameter test results are shown in table 2. Wherein, the rheological property test temperature is 65 ℃ +/-2 ℃, the ES test temperature is 50 ℃ +/-2 ℃, and the HTHP test temperature is 240 ℃ +/-2 ℃. The G10' '/10' parameters were initial and final cut, measured with a six-speed rotational viscometer brookfield DV-III, see GB/T161782-1997. HTHP parameter is high temperature and high pressure filtration loss, and is measured by GGS71-B high temperature and high pressure filtration loss instrument with reference to GB/T161782-1997. As can be seen from Table 2, the main emulsifier prepared in example 12 is suitable for oil-based drilling fluids with different densities, has good rheological property, electrical stability and 240 ℃ high temperature resistance, and has stable performance of the whole system.
Impact of ambient temperature on high temperature oil-based drilling fluid rheology:
The winter climate in deep well and ultra-deep well areas in China is cold, the surface and shallow layer temperatures can reach-10 ℃ to-20 ℃, even lower, the heat exchange speed of drilling fluid and the environment is rapid, and the influence on the rheological property is large. The rheology of the high temperature resistant oil-based drilling fluid obtained in example 13 was continuously measured using a continuous temperature reduction device in a rotational viscometer, and the test results are shown in table 3. It can be seen from table 3 that the environmental temperature has a greater effect on the rheology of the high temperature resistant oil-based drilling fluids of the present invention. The reading values of phi 100 and phi 6 increase slowly when the test temperature is reduced from 65 ℃ to 30 ℃; when the test temperature was reduced from 30℃to 20℃to 10℃the reading values of phi 100 and phi 6 increased rapidly, indicating a sharp decrease in flowability.
Impact of settling stability against high temperature oil-based drilling fluids:
In general, a high-density drilling fluid system has a certain sedimentation phenomenon after aging at a high temperature, so that the overall performance of the drilling fluid system is affected, and therefore, it is very important to evaluate the sedimentation stability of the high-density drilling fluid system. The sedimentation stability of the high temperature resistant oil-based drilling fluid obtained in example 13 was evaluated by measuring the upper and lower density differences ρ after aging of the drilling fluid, and the evaluation results are shown in fig. 1. As can be seen from FIG. 1, after the high-temperature-resistant oil-based drilling fluid is aged at different temperatures, the upper and lower densities rho are between 0.0212g/cm 3 and 0.032g/cm 3, and no obvious sedimentation occurs in the aged drilling fluid system, so that the drilling fluid system has good sedimentation stability.
Evaluation of inhibition performance of drilling fluid system:
The influence of the inhibition performance of the drilling fluid system on the drilling construction is very important, and the good inhibition performance of the drilling fluid is particularly important for reservoirs with high clay mineral content. Thus, the target reservoir interval cuttings were used indoors and compared by measuring the inhibition of cuttings by rolling fluid in the high temperature resistant oil based drilling fluid obtained in example 13, aging conditions were 16 hours at 240 ℃, and the experimental results are shown in fig. 2. As can be seen from FIG. 2, the rolling recovery rate of the rock debris in the target reservoir section in clear water is only about 42%, the rolling recovery rate in the conventional water-based drilling fluid system is about 78%, and the rolling recovery rate in the high-temperature-resistant high-density oil-based drilling fluid system can reach more than 98%, which shows that the high-temperature-resistant oil-based drilling fluid has good inhibition performance and can meet the requirements of drilling operation of the high-clay mineral reservoir section.
Testing the pollution resistance of the high-temperature oil-based drilling fluid:
In the drilling process, the drilling fluid inevitably contacts with other fluids of the stratum and solid-phase substances such as rock debris, so that the drilling fluid is damaged by water invasion, salt invasion, rock debris pollution and the like, and the performance of the drilling fluid system can be influenced to a certain extent, therefore, the drilling fluid system has good anti-pollution performance, and the stability of the performance of the drilling fluid system can be ensured. The anti-pollution performance of the high temperature oil-based drilling fluid of example 13 was evaluated indoors by adding fresh water, calcium chloride and cuttings to the drilling fluid system, the aging condition was 240 ℃ for 16 hours, and the experimental results are shown in table 4. As shown in Table 4, after adding contaminants such as fresh water, calcium chloride and rock debris into the high-temperature-resistant oil-based drilling fluid, the viscosity and shear force of the drilling fluid system are not changed greatly, and the demulsification voltage value is basically maintained at about 1000V, so that the high-temperature high-pressure fluid loss is small, which indicates that the high-temperature-resistant oil-based drilling fluid has good anti-pollution capability and can meet the requirements of high-temperature high-pressure reservoir drilling operation.
And (3) testing the protection performance of the high-temperature-resistant oil-based drilling fluid reservoir:
The reservoir protection effect of the high temperature and high density oil-based drilling fluid system was evaluated by indoor simulation using natural core, the reservoir protection performance of the drilling fluid was evaluated by measuring the core permeability change before and after the pollution of the high temperature oil-based drilling fluid of example 13, and the experimental results are shown in table 5. As can be seen from Table 5, after the natural rock core of the reservoir is polluted by the developed high-temperature-resistant high-density oil-based drilling fluid, the permeability is reduced to a certain extent, but the reduction range is not large, the final permeability recovery value can still be more than 90%, and the natural rock core has good reservoir protection performance, and can ensure that the reservoir is not seriously damaged in the drilling process.
Preferred evaluation of fluid loss additives:
The high-temperature resistant oil-based drilling fluid needs to have a good fluid loss reducing effect so as to meet the requirement of safe drilling of high-temperature and high-pressure stratum. The filtration-reducing effect of several filtration-reducing agents in the high-temperature-resistant oil-based drilling fluid is evaluated, and the basic formula of the high-temperature-resistant oil-based drilling fluid is as follows: 0.3% of organic soil, 2.7% of main emulsifier, 2.0% of auxiliary emulsifier, 1.2% of calcium oxide, 2% of filtrate reducer, 45% of weighting agent, 48.3% of mixture of diesel oil and calcium chloride brine (37 wt%) (the volume ratio of the two is 7:1), and the experimental ageing conditions are 16 hours at 240 ℃, and the experimental results are shown in table 6. As can be seen from Table 5, after different types of filtrate reducers are added into the base slurry, the high-temperature high-pressure filtrate loss is reduced to different degrees, wherein the filtrate reduction effect of the polymer filtrate reducer lignite is best, and when the addition amount of the polymer filtrate reducer lignite is 2.0%, the high-temperature high-pressure filtrate loss of the oil-based drilling fluid can be reduced to 5.6mL, so that a good filtrate reduction effect is achieved.
The addition of the emulsifier is preferably evaluated:
As the water content of the water-in-oil drilling fluid system increases, the emulsion system becomes less stable, and therefore, it is necessary to add an emulsifier having excellent properties to maintain good stability of the emulsion system. The addition of the developed high temperature resistant emulsifier (main emulsifier and auxiliary emulsifier) is subjected to a preferred evaluation experiment, and the experimental method is as follows: different amounts of main emulsifier and auxiliary emulsifier are added into 320mL of diesel oil and 80mL of CaCl 2 saline, after stirring for 20min at high speed, the emulsion state is observed after the mixture is placed at 240 ℃ for 8h, and the demulsification voltage value is measured, and the experimental result is shown in Table 7. As is clear from the results in Table 7, the amounts of the main emulsifier and the auxiliary emulsifier were 2.7% and 2.0% respectively, and the amounts of the main emulsifier and the auxiliary emulsifier were 2.7% and 2.0% respectively, based on the total consideration of the economical factors and the emulsion properties, as the emulsion state was better and the emulsion breaking voltage was higher.
In conclusion, the oil-based drilling fluid prepared by the invention has high temperature resistance, good rheological property, electrical stability, sedimentation stability, stable system performance and strong inhibition performance, can meet the actual requirements of high-temperature high-salt oil reservoirs, also reduces the occurrence probability of drilling engineering accidents, and reduces the pollution of the drilling fluid to hydrocarbon reservoirs as a target hydrocarbon reservoir protection technology.
The technical characteristics form the embodiment of the invention, have stronger adaptability and implementation effect, and can increase or decrease unnecessary technical characteristics according to actual needs so as to meet the requirements of different situations.
Claims (10)
1. The synthetic main emulsifier is characterized by comprising, by mass, 2 to 6 parts of a long-carbon-chain polyamidoamine emulsifier, 2 to 6 parts of a compound sulfonate, 1 to 3 parts of stearate, and the long-carbon-chain polyamidoamine emulsifier has a carbon chain length of C 10 to C 14.
2. The synthetic main emulsifier according to claim 1, characterized by being prepared by the following method: mixing required amount of long carbon chain polyamidoamine type emulsifier, composite sulfonate and stearate, and reacting for 3-7 hours at the temperature of 120-210 ℃ to obtain the synthetic main emulsifier.
3. The synthetic main emulsifier according to claim 1 or 2, characterized in that the long carbon chain polyamidoamine-type emulsifier is prepared by the following method:
Firstly, filling refined tall oil acid into a reactor, heating to 85-90 ℃, adding polyethylene polyamine, heating to 180-190 ℃ under the condition of introducing nitrogen, and reacting at constant temperature for 3-4 h;
secondly, when no water drop appears in the water knockout drum for 10min to 15min or the liquid level in the reactor is not increased, regulating the flow rate of nitrogen, raising the temperature to 240 ℃ to 250 ℃, and carrying out constant-temperature reaction for 3h to 4h;
And thirdly, when no water drop appears in the water separator or the liquid level is not increased, adding solvent oil D140, cooling to 180-190 ℃, adding an organotin compound catalyst with the mass of maleic anhydride and 0.1% of the total reactant, reacting for 5 hours at constant temperature, adding an alcohol ether solvent for dissolution, and cooling to room temperature to obtain the long carbon chain polyamide amine type emulsifier.
4. The synthetic main emulsifier according to claim 1, 2 or 3, wherein the composite sulfonate is prepared by uniformly stirring and mixing petroleum iron sulfonate, sodium alkylbenzenesulfonate and sodium alkyl succinate sulfonate at a high speed at 60 ℃.
5. A synthetic main emulsifier according to any one of claims 1 to 4, characterized in that the stearate is polyoxyethylene stearate.
6. A process for the preparation of a synthetic main emulsifier according to claim 1 or 3 or 4 or 5, characterized by the following steps: mixing required amount of long carbon chain polyamidoamine type emulsifier, composite sulfonate and stearate, and reacting for 3-7 hours at the temperature of 120-210 ℃ to obtain the synthetic main emulsifier.
7. A high temperature resistant oil-based drilling fluid which is prepared from the synthetic main emulsifier as claimed in claims 1 to 5, and is characterized in that the raw materials comprise, by mass, 1% to 3% of the synthetic main emulsifier, 1% to 3% of the auxiliary emulsifier, 0.8% to 2% of organic soil, 0.5% to 1% of calcium oxide, 1% to 3% of a filtrate reducer, 5% to 40% of a weighting agent, and the balance of a mixed solution of base oil and calcium chloride brine.
8. The high temperature resistant oil-based drilling fluid according to claim 7, wherein the co-emulsifier is a mixture of polyoxydienodioleate having an HLB value of 7.5 and polyoxypropylene stearate having an HLB value of 8, the weight ratio of polyoxydienodioleate to polyoxypropylene stearate being 1:1 to 3; or/and the organic soil is oleophilic clay formed by bentonite after being treated by quaternary ammonium salt surfactant.
9. The high temperature resistant oil-based drilling fluid according to claim 7 or 8, characterized in that the fluid loss additive is lignite; or/and the weighting agent is barite with density of more than 4.25g/cm 3.
10. The high temperature resistant oil-based drilling fluid according to claim 7 or 8 or 9, characterized in that the base oil is diesel oil, the calcium chloride salt water concentration is 20 to 30wt%, and the volume ratio of base oil to calcium chloride salt water in the mixed fluid of base oil and calcium chloride salt water is 70:30 to 90:10.
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