WO2019010771A1 - 一种深井聚磺钻井液及其制备方法 - Google Patents

一种深井聚磺钻井液及其制备方法 Download PDF

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Publication number
WO2019010771A1
WO2019010771A1 PCT/CN2017/100133 CN2017100133W WO2019010771A1 WO 2019010771 A1 WO2019010771 A1 WO 2019010771A1 CN 2017100133 W CN2017100133 W CN 2017100133W WO 2019010771 A1 WO2019010771 A1 WO 2019010771A1
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Prior art keywords
weight
parts
barite
content
acrylamide
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PCT/CN2017/100133
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English (en)
French (fr)
Inventor
白杨
罗平亚
林凌
梁大川
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西南石油大学
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Application filed by 西南石油大学 filed Critical 西南石油大学
Priority to PCT/CN2017/100133 priority Critical patent/WO2019010771A1/zh
Priority claimed from CN201710565459.XA external-priority patent/CN107245329B/zh
Priority to US15/795,792 priority patent/US9926482B1/en
Publication of WO2019010771A1 publication Critical patent/WO2019010771A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/14—Clay-containing compositions
    • C09K8/18—Clay-containing compositions characterised by the organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/14—Clay-containing compositions
    • C09K8/18—Clay-containing compositions characterised by the organic compounds
    • C09K8/22—Synthetic organic compounds
    • C09K8/24—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/14—Clay-containing compositions
    • C09K8/16—Clay-containing compositions characterised by the inorganic compounds other than clay
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504—Compositions based on water or polar solvents
    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
    • C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
    • E21B21/06—Arrangements for treating drilling fluids outside the borehole
    • E21B21/062—Arrangements for treating drilling fluids outside the borehole by mixing components

Definitions

  • the invention relates to the field of deep well drilling fluid, in particular to a deep well polysulfide drilling fluid and a preparation method thereof, and is particularly suitable for drilling deep and ultra deep wells.
  • the commonly used deep well and ultra-deep well drilling fluids have two major categories: water-based and oil-based.
  • oil-based drilling fluid has the advantages of high temperature resistance, salt and calcium resistance, and stability of the well wall relative to the water-based drilling fluid, the preparation cost of the oil-based drilling fluid is much higher than that of the water-based drilling fluid, and the well is used when it is used.
  • the ecological environment near the site has a serious impact, and the rate of mechanical drilling is generally low.
  • the water-based drilling fluid has the advantages of low cost, simple configuration and maintenance, wide source of treatment agent, various types, and easy control of performance; therefore, water-based drilling fluid is mainly used in China.
  • High-density drilling fluid system rheology is difficult to control: In order to ensure low-temperature HTHP water loss in high-temperature drilling fluid, the type and amount of high-temperature drilling fluid fluid loss additive need to be greatly increased in the system, so that the drilling fluid base slurry viscosity Significantly increase, after the base pulp is aggravated, the viscosity of the barite particles is greatly increased due to the presence of a large amount of barite particles. If the soil volume in the drilling fluid is slightly controlled, when the temperature is high, the viscosity and shear force increase greatly, resulting in fluidity. Loss (high temperature gelation and high temperature cure). At present, the anti-temperature and salt-resistant viscosity reducing agents continuously developed have been mainly used for clay, and the clay content in the high-density drilling fluid system is limited, so that it is difficult to reduce viscosity.
  • the high-temperature salt water drilling fluid treatment agent above 180 °C has many varieties, the amount is large, and the system is very complicated, which will inevitably make it difficult to maintain and handle once the performance is unstable.
  • the treatment agent consumption increase is 50%; when the temperature is increased from 121 °C to 148.9 °C
  • the treatment agent consumption increase value is 100%; when the temperature is increased from 148.9 ° C to 176.7 ° C, the treatment agent consumption increase value is 100%.
  • domestic high-temperature high-density brine drilling fluids also have the above characteristics.
  • the total amount is more than 25%, and the total amount of organic treatment agent in the system is much more than 30%.
  • the purpose of the invention is to aim at the excessive use of the high-density and high-density brine drilling fluid in China, and the amount of the treatment agent is too large, and the amount of the HTHP is difficult to control after the drilling fluid is aged, and the preparation cost and the maintenance cost are high.
  • the problem is that the deep well polysulfide drilling fluid and the preparation method thereof are provided.
  • the deep well polysulfide drilling fluid solves the problem that the high density drilling fluid has high viscosity, the HTHP loses water, and is difficult to control.
  • a deep well polysulfonate drilling fluid wherein the deep well polysulfonate drilling fluid contains water, bentonite, sodium carbonate, sulfomethylphenolic resin, sulfonated brown coal, halogenated salt, and descending Fluid loss agent, Sodium polyacrylate, sodium hydrogen sulfite and barite, and the content of the bentonite is 3.5 to 5 parts by weight, and the content of the sodium carbonate is 0.15 to 0.35 parts by weight based on 100 parts by weight of water,
  • the content of the sulfomethylphenol resin is 6-8 parts by weight
  • the content of the sulfonated brown coal is 6-8 parts by weight
  • the content of the halogenated salt is 7.5-12 parts by weight
  • the content of the fluid loss agent is
  • the content of the sodium polyacrylate is 0.8 to 1.7 parts by weight
  • the content of the sodium hydrogen sulfite is 3-5 parts by weight
  • the content of the bentonite is 4-4.8 parts by weight
  • the content of the sodium carbonate is 0.2-0.24 parts by weight
  • the content of the sulfomethyl phenolic resin is 6.5-7.8 based on 100 parts by weight of water.
  • the content of the sulfonated lignite is 6.5-7.8 parts by weight
  • the content of the halogenated salt is 9-10.8 parts by weight
  • the content of the fluid loss additive is 0.75-0.9 parts by weight
  • the sodium polyacrylate The content is from 1.2 to 1.44 parts by weight
  • the content of the sodium hydrogen sulfite is from 3.5 to 4.2 parts by weight
  • the content of the barite is from 260 to 290 parts by weight.
  • the fluid loss additive is acrylamide/dimethyldiallylammonium chloride binary copolymer and/or acrylamide/dimethyldiallylammonium chloride/2-acrylamide-2 - a methyl propanesulfonic acid terpolymer.
  • the fluid loss additive is acrylamide/dimethyldiallylammonium chloride binary copolymer and acrylamide/dimethyldiallylammonium chloride/2-acrylamide-2- Combination of methacrylic acid terpolymer, and acrylamide/dimethyldiallylammonium chloride binary copolymer and acrylamide/dimethyldiallylammonium chloride/2-acrylamide-
  • the weight ratio of the 2-methylpropanesulfonic acid terpolymer was (0.6-0.8):1.
  • the halogenated salt is sodium chloride and/or potassium chloride.
  • the halogenated salt is a combination of sodium chloride and potassium chloride, and the weight ratio of the sodium chloride to the potassium chloride is (0.6-0.96):1.
  • the barite is barite A and/or barite B
  • the barite A has a particle size of 50-70 microns
  • the barite B has a particle size of 1-1.2 microns. .
  • the barite is a combination of barite A and barite B, and the weight ratio of the barite A to the barite B is (1-4):1.
  • the deep well polysulfonate drilling fluid has a pH of 8-9, and the deep well polysulfonate drilling fluid has a density of 2.30-2.45 g/cm 3 .
  • Another aspect of the present invention also provides a method for preparing a deep well polysulfonate drilling fluid, wherein the preparation method comprises the following steps:
  • the bentonite is used in an amount of 3.5 to 5 parts by weight
  • the sodium carbonate is 0.15 to 0.35 parts by weight
  • the sulfomethylphenol resin is used in an amount of 6 to 8 parts by weight based on 100 parts by weight of water.
  • the sulfonated brown coal is used in an amount of 6-8 parts by weight
  • the halogenated salt is used in an amount of 7.5-12 parts by weight
  • the fluid loss additive is used in an amount of 0.5-1.2 parts by weight
  • the sodium polyacrylate The amount is 0.8 to 1.7 parts by weight
  • the content of the sodium hydrogen sulfite is 3-5 parts by weight
  • the amount of the barite is 250 to 300 parts by weight.
  • the bentonite is used in an amount of 4 to 4.8 parts by weight
  • the sodium carbonate is contained in an amount of 0.2 to 0.24 parts by weight
  • the sulfomethyl phenolic resin is used in an amount of 6.5 to 7.8, based on 100 parts by weight of water.
  • the sulfonated brown coal is used in an amount of 6.5-7.8 parts by weight
  • the halogenated salt is used in an amount of 9-10.8 parts by weight
  • the fluid loss additive is used in an amount of 0.75-0.9 parts by weight
  • the sodium polyacrylate is from 1.2 to 1.44 parts by weight
  • the sodium hydrogen sulfite is from 3.5 to 4.2 parts by weight
  • the barite is used in an amount of from 260 to 290 parts by weight.
  • the fluid loss additive is acrylamide/dimethyldiallylammonium chloride binary copolymer and/or acrylamide/dimethyldiallylammonium chloride/2-acrylamide-2 - a methyl propanesulfonic acid terpolymer.
  • the fluid loss additive is acrylamide/dimethyldiallylammonium chloride binary copolymer and acrylamide/dimethyldiallylammonium chloride/2-acrylamide-2- Combination of methacrylic acid terpolymer, and acrylamide/dimethyldiallylammonium chloride binary copolymer and acrylamide/dimethyldiallylammonium chloride/2-acrylamide-
  • the weight ratio of the 2-methylpropanesulfonic acid terpolymer was (0.6-0.8):1.
  • the halogenated salt is sodium chloride and/or potassium chloride.
  • the halogenated salt is a combination of sodium chloride and potassium chloride, and the weight ratio of the sodium chloride to the potassium chloride is (0.6-0.96):1.
  • the barite is barite A and/or barite B
  • the barite A has a particle size of 50-70 microns
  • the barite B has a particle size of 1-1.2 microns. .
  • the barite is a combination of barite A and barite B, and the weight ratio of the barite A to the barite B is (1-4):1.
  • the conditions of the first mixing include: a temperature of 50-70 ° C, a stirring rate of 550-650 r / min, a time of 30-45 minutes; conditions of the pre-hydration treatment Including: the temperature is 50-70 ° C, the stirring rate is 550-650r / min, the time is 23-25 hours;
  • the conditions of the second mixing comprise: a temperature of 60-70 ° C, a stirring rate of 950-1000 r / min, a time of 50-70 minutes; and the third mixing conditions include : temperature is 60-70 ° C, stirring rate is 550-650r / min, time is 50-70 minutes;
  • the fourth mixing condition comprises: a temperature of 60-70 ° C, a stirring rate of 550-650 r / min, and a time of 30-40 minutes.
  • Another aspect of the present invention also provides a deep well polysulfonate drilling fluid prepared by the above preparation method.
  • the deep well polysulfonate drilling fluid has a pH of 8-9, and the deep well polysulfonate drilling fluid has a density of 2.30-2.45 g/cm 3 .
  • the deep well polysulfonate drilling fluid provided by the invention is based on the high temperature cross-linking action of the treatment agent, and NaHSO 3 is used as a high-temperature moderate crosslinking initiator, and the barite powder of different particle diameters is compounded to solve the high-density drilling fluid.
  • the viscosity is high, HTHP loses water, and it is difficult to control.
  • the developed high temperature and salt resistant high density drilling fluid has excellent performance (HTHP has low water loss and good rheology) and the type of treatment agent is small, and the total dosage is greatly reduced.
  • the aging deep well polysulfonate drilling fluid system has low viscosity (apparent viscosity AV is 61-63 mPa.s, plastic viscosity PV is 46-47 mPa.s), and HTHP (high temperature and high pressure filtration loss) has low water loss ( ⁇ 15ml) and other rare excellent performance.
  • Apparent viscosity Also known as effective viscosity or apparent viscosity, it is the ratio of shear stress to velocity gradient of drilling fluid under a certain velocity gradient. It is expressed by “AV” and the unit is m Pa. s (mPa. sec).
  • Dynamic shear force The dynamic shear stress of the drilling fluid reflects the interaction force between the clay particles and the polymer molecules during the laminar flow, that is, the strength of the network structure formed inside the drilling fluid. , expressed by "YP” or "T 0 ", the unit is Pa (Pa).
  • Static force Reflects the strength of the internal gel network when the drilling fluid is at rest.
  • the static force is expressed in Greek ⁇ , and the legal unit of measurement is Pa (Pa).
  • the magnitude of the static shear force is determined by the number of structural chains in the fluid per unit volume and the strength of the individual structural chains.
  • the internal structure of the fluid gradually tends to be stable, and the structure development tends to be perfect.
  • the cutting force also increases. Therefore, to measure the speed of gel strength growth, the static shear force must be measured twice. According to the API (American Petroleum Institute) standard, the static shear force of 10 seconds and 10 minutes is measured, which is called the initial shear force and the final cut. force.
  • the size of the static shear force reflects the ability of the suspended rock powder.
  • the density of the mud, the weighting agent barite, etc. is large.
  • the invention provides a deep well polysulfonate drilling fluid, wherein the deep well polysulfonate drilling fluid comprises water, bentonite, sodium carbonate, sulfomethylphenolic resin, sulfonated brown coal, halogenated salt, fluid loss additive, sodium polyacrylate, Sodium bisulfite and barite, and the content of the bentonite may be 3.5 to 5 parts by weight, and the content of the sodium carbonate is 0.15 to 0.35 parts by weight, based on 100 parts by weight of water, the sulfomethyl group
  • the content of the phenolic resin may be 6-8 parts by weight
  • the content of the sulfonated lignite may be 6-8 parts by weight
  • the content of the halogenated salt may be 7.5-12 parts by weight
  • the content of the fluid loss agent may be
  • the content of the sodium polyacrylate may be 0.8-1.7 parts by weight
  • the content of the sodium hydrogen sulfite may be 3-5 parts by weight
  • the deep well polysulfonate drilling fluid contains water, bentonite, sodium carbonate, sulfomethyl phenolic resin, sulfonated brown coal, halogenated salt, fluid loss additive, sodium polyacrylate, sodium hydrogen sulfite and heavy
  • the spar and in accordance with the above proportional relationship, can achieve the object of the present invention to some extent.
  • the inventors of the present invention found in the research that although it contains only water, bentonite, sodium carbonate, sulfomethyl phenolic resin, sulfonated brown coal, halogenated salt, fluid loss additive, sodium polyacrylate, sodium hydrogen sulfite and barite And the object of the present invention can be achieved in accordance with the above proportional relationship, but preferably, the content of the bentonite is 4-4.8 parts by weight, and the content of the sodium carbonate is 0.2-0.24 by weight based on 100 parts by weight of water.
  • the content of the sulfomethyl phenolic resin is 6.5-7.8 parts by weight, the content of the sulfonated brown coal is 6.5-7.8 parts by weight, and the content of the halogenated salt is 9-10.8 parts by weight, the fluid loss
  • the content of the agent is 0.75-0.9 parts by weight, the content of the sodium polyacrylate is 1.2-1.44 parts by weight, the content of the sodium hydrogen sulfite is 3.5-4.2 parts by weight, and the content of the barite is 260-290. The weight is better and the effect is better.
  • the bentonite is not particularly limited as a slurry material, and may be a conventional choice in the art.
  • it may be bentonite for drilling fluid, and its main component is clay mineral containing not less than 85% by weight of montmorillonite. .
  • the water is not particularly limited and may be tap water (clean water).
  • the sulfomethyl phenolic resin is code-named SMP-III, which is commercially available and has a molecular weight of from 200,000 to 500,000.
  • the sulfonated brown coal (viscosity reducing agent) is coded as SMC.
  • the sodium polyacrylate (viscosity reducing agent) has a molecular formula of (C 3 H 3 NaO 2 ) n and is commercially available, and has a number average molecular weight of 200,000 to 400,000.
  • the sodium carbonate and the sodium hydrogen sulfite are not particularly limited and may be commercially available products.
  • the fluid loss additive may be an acrylamide/dimethyldiallylammonium chloride binary copolymer and/or acrylamide/dimethyldiallylammonium chloride/2-acrylamide.
  • a -2-methylpropanesulfonic acid terpolymer preferably, the fluid loss additive is an acrylamide/dimethyldiallyl ammonium chloride binary copolymer and acrylamide/dimethyldiene Combination of ammonium chloride/2-acrylamide-2-methylpropanesulfonic acid terpolymer, and acrylamide/dimethyldiallylammonium chloride binary copolymer with acrylamide/dimethyldi
  • the weight ratio of allyl ammonium chloride/2-acrylamide-2-methylpropanesulfonic acid terpolymer may be (0.6-0.8):1; preferably (0.65-0.75):1; Acrylamide/dimethyldiallylammonium chloride binary copolymer (AM/DMDAAC) and the acrylamide
  • the method for synthesizing the acrylamide/dimethyldiallylammonium chloride binary copolymer comprises the following steps:
  • step (3) The product obtained in the step (2) is extracted with ethanol, chopped, and filtered, and then dried in a vacuum oven.
  • the mixing condition may be: the temperature is 49-51 ° C, the stirring rate is not specifically limited, and may be a conventional selection by those skilled in the art, for example, the stirring rate may be 280-320 rpm. /min, and nitrogen and oxygen deoxidation treatment while stirring the solution, the time may be 19-21 minutes;
  • the initiator may be a redox system, for example, may be 2,2' azabis(2-imidazoline) dihydrochloride (VA-044), 2, 2'- One or more of azobisisobutylphosphonium dihydrochloride (AIBA-2HCl)-sodium hydrogen sulfite, ammonium persulfate-sodium hydrogen sulfite, potassium persulfate-sodium hydrogen sulfite, preferably Ammonium sulfate-sodium hydrogen sulfite, and the initiator is simultaneously mixed with AM and DMDAAC after the end of the nitrogen and oxygen deoxidation treatment. Further, preferably, the initiator may be added dropwise at a dropping rate of 0.3-05 mL/min. And the mixing conditions may be: a temperature of 49-51 ° C, a time of 7.5-8.5 hours;
  • the drying treatment may be carried out at a temperature of 49-51 ° C for 23-25 hours, and after being dried to be ground into a white powder;
  • the intrinsic viscosity of the acrylamide/dimethyldiallyl ammonium chloride binary copolymer is 370-380 mL/g, Preferably 375-378 mL/g;
  • the acrylamide is contained in an amount of 75 to 85% by weight based on the total weight of the acrylamide/dimethyldiallyl ammonium chloride binary copolymer, and the dimethyl diallyl ammonium chloride is used.
  • the content is 15-25% by weight;
  • the acrylamide is present in an amount of from 78 to 82% by weight, based on the total weight of the acrylamide/dimethyldiallylammonium chloride binary copolymer, the dimethyl diallyl group
  • the content of ammonium chloride is 18-22% by weight.
  • AM/DMDAAC acrylamide/dimethyldiallyl ammonium chloride binary copolymers
  • the unit of cationicity is (mol%)
  • the unit of intrinsic viscosity is (mL.g -1 )
  • the unit of yield is (%).
  • the synthesis method of the acrylamide/dimethyldiallylammonium chloride/2-acrylamide-2-methylpropanesulfonic acid terpolymer comprises the following steps:
  • step (2) mixing the mixture of step (1) with AM, DMDAAC;
  • step (3) The product obtained in the step (3) is extracted with ethanol, chopped, and filtered, and then dried in a vacuum oven.
  • the mixing condition may be: the temperature is 29-31 ° C, and the stirring rate is not specifically limited, and may be a conventional selection by those skilled in the art, for example, may be 180-220 rpm And the pH of the mixed solution can be adjusted to neutral, and a certain concentration of NaOH solution can be selected to adjust the pH value;
  • the mixing condition may be: the temperature is 49-51 ° C, the stirring rate is not specifically limited, and may be a conventional selection by a person skilled in the art, and the nitrogen removal is performed while stirring the solution. Oxygen treatment, the time can be 19-21 minutes;
  • the initiator may be a redox system, for example, may be "ammonium persulfate” - sodium hydrogen sulfite” and “potassium persulfate - sodium hydrogen sulfite", and the weight ratio of "ammonium persulfate - sodium hydrogen sulfite” to "potassium persulfate - sodium hydrogen sulfite” is 1:1, and
  • the initiator is simultaneously mixed with AMPS, AM and DMDAAC after the end of the nitrogen deoxidation treatment; and the mixing may be carried out at a temperature of 49-51 ° C for 7.5-8.5 hours; in addition, preferably, The initiator may be added dropwise to the mixture of the step (2) at a dropping rate of 2.5 to 3.5 mL/min and mixed therewith.
  • the drying treatment may be carried out at a temperature of 49-51 ° C for 23-25 hours, and after drying, grinding into a white powder; wherein the acrylamide / two
  • the methyl diallyl ammonium chloride/2-acrylamide-2-methylpropanesulfonic acid terpolymer has an intrinsic viscosity of 340-350 mL/g, preferably 345-348 mL/g;
  • the content of the acrylamide is 50-65 wt% based on the total weight of the acrylamide/dimethyldiallylammonium chloride/2-acrylamide-2-methylpropanesulfonic acid terpolymer.
  • the content of the dimethyl diallyl ammonium chloride is 12-22% by weight, and the content of the 2-acrylamide-2-methylpropanesulfonic acid is 13-38% by weight;
  • the acrylamide content is 55-based on the total weight of the acrylamide/dimethyldiallylammonium chloride/2-acrylamide-2-methylpropanesulfonic acid terpolymer. 60% by weight, the content of the dimethyldiallylammonium chloride is 15-20% by weight, and the content of the 2-acrylamide-2-methylpropanesulfonic acid is 20-30% by weight.
  • the halogenated salt may be sodium chloride and/or potassium chloride; preferably, the halogenated salt is a combination of sodium chloride and potassium chloride, and the sodium chloride and the potassium chloride are The weight ratio may be (0.6-0.96): 1, preferably (0.7-0.8): 1.
  • the barite may be barite A and/or barite B, and the barite A may have a particle diameter of 50-70 micrometers, and the barite B
  • the particle diameter may be 1-1.2 ⁇ m; preferably, the barite is a combination of barite A and barite B, and the weight ratio of the barite A to the barite B may be ( 1-4): 1, preferably (1.5-4): 1; further, in the present invention, the main component of the barite A and the barite B is BaSO 4 , that is, the The barite A may be BaSO 4 having a particle diameter of 50 to 70 ⁇ m, and the barite B may be BaSO 4 having a particle diameter of 1 to 1.2 ⁇ m.
  • the pH of the deep well polysulfonate drilling fluid may be 8-9, preferably, the pH of the deep well polysulfonate drilling fluid is 8.4-8.6.
  • the reagent for adjusting the pH of the deep-well polysulfide drilling fluid is not particularly limited, and may be a conventional choice in the art. For example, if the pH of the deep-well polysulfide drilling fluid is raised, the selection may be selected. The adjustment is carried out by one or more of sodium hydroxide, sodium hydrogencarbonate and calcium hydroxide. If the pH of the deep well polysulfonate drilling fluid is lowered, it may be adjusted by using diluted hydrochloric acid or an acid salt.
  • the density of the deep well polysulfonate drilling fluid may be from 2.30 to 2.45 g/cm 3 , preferably from 2.35 to 2.42 g/cm 3 , and in the present invention, the deep well may be adjusted by adjusting the total amount of barite The density of the polysulfide drilling fluid is increased.
  • Another aspect of the present invention also provides a method for preparing a deep well polysulfonate drilling fluid, wherein the preparation method comprises the following steps:
  • the bentonite may be used in an amount of 3.5 to 5 parts by weight
  • the sodium carbonate may be used in an amount of 0.15 to 0.35 parts by weight
  • the sulfomethylphenol resin may be used in an amount of 6 parts by weight based on 100 parts by weight of water.
  • the sulfonated brown coal may be used in an amount of 6-8 parts by weight
  • the halogenated salt may be used in an amount of 7.5-12 parts by weight
  • the fluid loss additive may be used in an amount of 0.5-1.2 parts by weight.
  • the sodium polyacrylate may be used in an amount of 0.8 to 1.7 parts by weight
  • the sodium hydrogen sulfite may be contained in an amount of 3 to 5 parts by weight
  • the barite may be used in an amount of from 250 to 300 parts by weight.
  • the present invention in the preparation process of the deep well polysulfonate drilling fluid, as long as the bentonite and sodium carbonate are pre-hydrated, the sulfomethylphenolic resin, the sulfonated brown coal, the halogenated salt, the fluid loss additive, the sodium polyacrylate
  • the sodium hydrogen sulfite and the barite are sequentially mixed with the pre-hydrated mixture, and the above proportional relationship is satisfied to achieve the object of the present invention to some extent.
  • the inventors of the present invention found in the study that although the bentonite and sodium carbonate are pre-hydrated, the sulfomethyl phenolic resin, the sulfonated brown coal, the halogenated salt, the fluid loss additive, the sodium polyacrylate, the sodium hydrogen sulfite and the heavy
  • the purpose of the present invention is achieved by sequentially mixing the spar with the pre-hydrated mixture and meeting the above proportional relationship, but preferably, the bentonite is used in an amount of 4-4.8 based on 100 parts by weight of water.
  • the content of the sodium carbonate is 0.2-0.24 parts by weight
  • the sulfomethyl phenolic resin is used in an amount of 6.5-7.8 parts by weight
  • the sulfonated brown coal is used in an amount of 6.5-7.8 parts by weight
  • the halogenated salt is used in an amount of 6.5-7.8 parts by weight
  • the amount of the fluid loss reducing agent is from 0.75 to 0.9 parts by weight
  • the sodium polyacrylate is used in an amount of from 1.2 to 1.44 parts by weight
  • the sodium hydrogen sulfite is from 3.5 to 4.2 parts by weight.
  • the barite is used in an amount of from 260 to 290 parts by weight, more preferably by weight.
  • the bentonite is not particularly limited as a slurry material, and may be a conventional choice in the art.
  • it may be bentonite for drilling fluid, and its main component is clay containing not less than 85% by weight of montmorillonite. mineral.
  • the water is not particularly limited and may be tap water (clean water).
  • the sulfomethyl phenolic resin is code-named SMP-III, which is commercially available and has a molecular weight of from 200,000 to 500,000.
  • the sulfonated brown coal (viscosity reducing agent) is coded as SMC.
  • the sodium polyacrylate (viscosity reducing agent) has a molecular formula of (C 3 H 3 NaO 2 ) n and is commercially available, and has an average molecular weight of 200,000 to 400,000.
  • the sodium carbonate and the sodium hydrogen sulfite are not particularly limited and may be a commercially available product.
  • the fluid loss additive may be an acrylamide/dimethyldiallylammonium chloride binary copolymer and/or acrylamide/dimethyldiallylammonium chloride/2-acrylamide.
  • a -2-methylpropanesulfonic acid terpolymer preferably, the fluid loss additive is an acrylamide/dimethyldiallyl ammonium chloride binary copolymer and acrylamide/dimethyldiene Combination of ammonium chloride/2-acrylamide-2-methylpropanesulfonic acid terpolymer, and acrylamide/dimethyldiallylammonium chloride binary copolymer with acrylamide/dimethyldi
  • the weight ratio of allyl ammonium chloride/2-acrylamide-2-methylpropanesulfonic acid terpolymer may be (0.6-0.8):1; preferably (0.65-0.75):1; Acrylamide/dimethyldiallylammonium chloride binary copolymer (AM/DMDAAC) and the acrylamide
  • the halogenated salt may be sodium chloride and/or potassium chloride; preferably, the halogenated salt is a combination of sodium chloride and potassium chloride, and the sodium chloride and the potassium chloride are The weight ratio may be (0.6-0.96): 1, preferably (0.7-0.8): 1.
  • the barite may be barite A and/or barite B, and the barite A may have a particle diameter of 50-70 micrometers, and the barite B
  • the particle diameter may be 1-1.2 ⁇ m; preferably, the barite is a combination of barite A and barite B, and the weight ratio of the barite A to the barite B may be ( 1-4): 1, preferably (1.5-4): 1; further, in the present invention, the main component of the barite A and the barite B is BaSO 4 , that is, the The barite A may be BaSO 4 having a particle diameter of 50 to 70 ⁇ m, and the barite B may be BaSO 4 having a particle diameter of 1 to 1.2 ⁇ m.
  • the conditions of the first mixing include: a temperature of 50-70 ° C, a stirring rate of 550-650 r / min, a time of 30-45 minutes; the pre-hydration treatment
  • the conditions include: the temperature is 50-70 ° C, the stirring rate is 550-650 r / min, and the time is 23-25 hours;
  • the second mixing condition comprises: the temperature is 60-70 ° C, and the stirring rate is 950-1000r/min, time is 50-70 minutes; and the third mixing conditions include: temperature is 60-70 ° C, stirring rate is 550-650r / min, time is 50-70 minutes;
  • the fourth mixing condition comprises: a temperature of 60-70 ° C, a stirring rate of 550-650 r / min, and a time of 30-40 minutes.
  • the conditions of the first mixing include: a temperature of 55-65 ° C, a stirring rate of 580-620 r / min, a time of 30-35 minutes; conditions of the pre-hydration treatment Including: the temperature is 55-65 ° C, the stirring rate is 580-620 r / min, the time is 23.5-24.5 hours;
  • the conditions of the second mixing include: a temperature of 62-68 ° C, a stirring rate of 980-1000 r / min, a time of 55-65 minutes; and a condition of the third mixing Including: the temperature is 62-68 ° C, the stirring rate is 580-620 r / min, the time is 55-65 minutes;
  • the conditions of the fourth mixing include: a temperature of 62-68 ° C, a stirring rate of 580-620 r / min, and a time of 30-35 minutes.
  • Another aspect of the present invention also provides a deep well polysulfonate drilling fluid prepared by the above preparation method.
  • the pH of the deep well polysulfonate drilling fluid may be 8-9, preferably, the pH of the deep well polysulfonate drilling fluid is 8.4-8.6.
  • the reagent for adjusting the pH of the deep-well polysulfide drilling fluid is not particularly limited, and may be a conventional choice in the art. For example, if the pH of the deep-well polysulfide drilling fluid is raised, sodium hydroxide may be selected. One or more of sodium bicarbonate and calcium hydroxide are adjusted. If the pH of the deep well polysulfide drilling fluid is lowered, the diluted hydrochloric acid or acid salt may be used for adjustment.
  • the density of the deep well polysulfonate drilling fluid may be 2.30-2.45 g/cm 3 , preferably 2.35-2.42 g/cm 3 .
  • the deep well polysulfide drilling may be performed by using barite.
  • the density of the liquid increases, and the inventors of the present invention found in the study that the ratio of the weight ratio of the barite A to the barite B can be 4:1 to 3:2.
  • the polysulfonate drilling fluid was heavier to 2.30-2.45 g/cm 3 .
  • the method for preparing the deep well polysulfide drilling fluid comprises the following steps:
  • the bentonite and water are stirred at a temperature of 50-70 ° C under stirring conditions of 550-650 r / min for 5-15 minutes; then, the mixture of bentonite and water is mixed with sodium carbonate at a temperature of 50 -70 ° C is stirred at 550-650r / min for 25-35 minutes; then, pre-hydration treatment to obtain pre-hydrated soil slurry, wherein the conditions of the pre-hydration treatment include: temperature can be For 50-70 ° C, the time may be 23-25 hours; preferably, the temperature is 55-65 ° C, the time is 23.5-24.5 hours;
  • the base slurry is mixed with a sulfomethylphenol resin and a sulfonated lignite and stirred at a temperature of 60 to 70 ° C for 30 to 40 minutes under stirring at 550 to 650 r / min.
  • the recovery rate is determined by reference to the petroleum industry standard SY-T5613-2000 mud shale physical and chemical properties test method
  • Bentonite (montmorillonite) was purchased from Xinjiang Zhongfei Xiazi Street Bentonite Co., Ltd.;
  • the sulfomethyl phenolic resin was purchased from Chongqing Dafang Synthetic Chemical Co., Ltd. as the sulfomethyl phenolic resin SMP-III powder for drilling fluids;
  • Sulfonated lignite was purchased from Chengdu Chuanfeng Chemical Engineering Co., Ltd. as sulfonated lignite SMC;
  • Halogenated salts, fluid loss additives, sodium polyacrylate were purchased from Kelon Chemical Reagent Factory;
  • Raw materials such as barite are purchased from Guizhou Nano Powder Industry Co., Ltd. (a commercial product of ultrafine barium sulfate).
  • Acrylamide, dimethyldiallylammonium chloride, and 2-acrylamido-2-methylpropanesulfonic acid were purchased from Kelon Chemical Reagent Factory.
  • This preparation example is for explaining the synthesis of the acrylamide/dimethyldiallylammonium chloride binary copolymer (AM/DMDAAC).
  • a magnetic stirrer was placed in a three-necked flask, a thermometer was inserted, and the mixture was continuously stirred in a constant temperature water bath, the water temperature was set to 50 ° C, and the stirring rate was 300 rpm;
  • the white powder synthesized was an acrylamide/dimethyldiallyl ammonium chloride binary copolymer. (AM/DMDAAC), having an intrinsic viscosity of 376.24 mL/g, and based on the total weight of the binary copolymer, the content of acrylamide is 79.8% by weight, and the content of dimethyldiallyl ammonium chloride is 20.2% by weight.
  • AM/DMDAAC acrylamide/dimethyldiallyl ammonium chloride binary copolymer.
  • This preparation example is for the synthesis of the acrylamide/dimethyldiallylammonium chloride/2-acrylamide-2-methylpropanesulfonic acid terpolymer (AM/DMDAAC/AMPS).
  • initiator is "ammonium persulfate - sodium hydrogen sulfite” and “potassium persulfate - sodium bisulfite"
  • aqueous solution with deionized water
  • the acceleration rate of the drop was 3 mL/min, and the temperature was raised to 50 ° C, and the solution was uniformly stirred by stirring, and the reaction was carried out for 8 hours;
  • the white powder synthesized was acrylamide/dimethyldiallylammonium chloride/2-acrylamide-2-methylpropanesulfonic acid terpolymer (AM/DMDAAC/AMPS), and its intrinsic viscosity 347.91 mL/g, wherein the content of acrylamide is 55.9% by weight based on the total weight of the terpolymer, and the content of dimethyl diallyl ammonium chloride is 16.3% by weight, 2-acrylamide- The content of 2-methylpropanesulfonic acid was 27.8% by weight.
  • the present embodiment is used to explain the preparation method of the deep well polysulfide drilling fluid of the present invention.
  • the deep well polysulfonate drilling fluid I was prepared, and the temperature resistance was up to 220 °C.
  • the other properties of the deep well polysulfonate drilling fluid after aging are shown in Table 2; the XGRL-2 roller heating furnace was used to prepare from Example 1.
  • the rolling recovery of the deep well polysulfonate drilling fluid was measured as shown in Table 3.
  • the present embodiment is used to explain the preparation method of the deep well polysulfide drilling fluid of the present invention.
  • the soil slurry is heated to 65 ° C, and then 2.5 g of anti-temperature and salt-resistant zwitterionic fluid loss additive and 8.75 g of sodium polyacrylate are added, and then stirred at a high speed of 1000 r/min for 60 minutes, and then 10 g is added.
  • Sodium chloride and 12.5 g of potassium chloride and 0.875 g of sodium hydrogen sulfite were stirred at a low speed of 600 r/min for 60 minutes as a base slurry;
  • the deep well polysulfide drilling fluid II was prepared and the temperature resistance was as high as 220 °C.
  • the other properties of the deep well polysulfonate drilling fluid after aging are shown in Table 2.
  • a deep-well polysulfonate drilling fluid was prepared in the same manner as in Example 1, except that the amounts of the various treatment agents were different, especially the total amount of the organic treatment agent was small, specifically, based on 100 parts by weight of fresh water.
  • the bentonite is used in an amount of 3 parts by weight
  • the sodium carbonate is used in an amount of 0.2 parts by weight
  • the sulfomethylphenol resin is used in an amount of 2.5 parts by weight
  • the sulfonated brown coal is used in an amount of 2.5 parts by weight
  • the sodium chloride is used in an amount of 4 parts by weight
  • the chlorine is used.
  • the amount of potassium used is 3 parts by weight, the amount of the binary copolymer is 0.4 parts by weight, the amount of sodium polyacrylate is 2.5 parts by weight, and the amount of sodium hydrogen sulfite is used.
  • the amount of barite A used was 200 parts by weight, and the amount of barite B used was 50 parts by weight, based on 3 parts by weight.
  • the deep well polysulfonate drilling fluid was prepared in the same manner as in Example 2, except that the amount of the various treatment agents was different, especially the total amount of the organic treatment agent was used, specifically, based on 100 parts by weight of fresh water, bentonite
  • the amount is 6 parts by weight
  • the amount of sodium carbonate is 0.3 parts by weight
  • the amount of the sulfomethylphenol resin is 8.5 parts by weight
  • the amount of the sulfonated lignite is 8.5 parts by weight
  • the amount of sodium chloride is 5 parts by weight, chlorination.
  • the amount of potassium used is 6.5 parts by weight, the amount of the terpolymer is 1.8 parts by weight, the amount of sodium polyacrylate is 5 parts by weight, the amount of sodium hydrogen sulfite is 5 parts by weight, and the amount of barite A is 180 parts by weight.
  • the amount of barite B used was 120 parts by weight.
  • the deep well polysulfide drilling fluid D2 was prepared, and the temperature resistance was as high as 220 °C. Other properties are shown in Table 2.
  • a deep well polysulfonate drilling fluid was prepared in the same manner as in Example 1, except that other organic treating agents were additionally added, specifically, other organic treating agents were additionally added, specifically, 8 wt% was added.
  • the fluid loss additive AOBS/AA/polyhydroxyglycol graft copolymer HLJ-4 for drilling fluid produced by Shijiazhuang Hualai Dingsheng Technology Co., Ltd.
  • the deep well polysulfonate drilling fluid D3 was prepared, and the temperature resistance was as high as 220 °C.
  • the other properties were as shown in the performance of the drilling fluid system of Table 2 after aging at 220 °C.
  • the AV unit is (m Pa.s)
  • the PV unit is (m Pa.s)
  • the YP unit is (Pa)
  • the ⁇ (10′′) unit is (Pa)
  • the HTHP water loss unit is (ml).
  • Drilling fluid formula Experimental condition Quality of recycling (g) Recovery rate(%) Clear water +50g red soil 220°C/16h 6.23 12.46 Drilling fluid system +50g red soil 220°C/16h 48.08 96.16
  • the red layer soil is Sichuan red layer soil cuttings, which is 6-10 mesh, and the recovery rate is over 40 mesh recovery rate; the results in the table are the average of 2 experimental data.
  • the apparent viscosity of the deep well polysulfonate drilling fluid prepared in Comparative Example 1 was 84 m Pa. s, plastic viscosity up to 68m Pa. s, dynamic stress is 16Pa, ⁇ (10′′) is 4Pa, and the most serious is that HTHP loses up to 54ml, which is easy to cause complicated underground accidents;
  • the apparent viscosity of the deep well polysulfonate drilling fluid prepared in Comparative Example 2 was 79 m Pa. s, plastic viscosity up to 76m Pa. s, the dynamic stress is 13Pa, ⁇ (10′′) is 7Pa, and the most serious is that HTHP loses water up to 46ml, which is easy to cause complicated underground accidents;
  • the apparent viscosity of the deep well polysulfonate drilling fluid prepared in Comparative Example 3 was 77 m Pa. s, plastic viscosity up to 67m Pa. s, the dynamic stress is 10Pa, ⁇ (10′′) is 8Pa, and the most serious is that HTHP loses water up to 37ml, which is easy to cause complicated underground accidents.

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Abstract

一种深井聚磺钻井液，含有水、膨润土、碳酸钠、磺甲基酚醛树脂、磺化褐煤、卤化盐、降滤失剂、聚丙烯酸钠、亚硫酸氢钠和重晶石，且以100重量份的水为基准，膨润土的含量为3.5‑5重量份，碳酸钠的含量为0.15‑0.35重量份，磺甲基酚醛树脂的含量为6‑8重量份，磺化褐煤的含量为6‑8重量份，卤化盐的含量为7.5‑12重量份，降滤失剂的含量为0.5‑1.2重量份，聚丙烯酸钠的含量为0.8‑1.7重量份，亚硫酸氢钠的含量为3‑5重量份，重晶石的含量为250‑300重量份。还公开了一种深井聚磺钻井液的制备方法。

Description

一种深井聚磺钻井液及其制备方法 技术领域
本发明涉及深井钻井液领域，具体涉及一种深井聚磺钻井液及其制备方法，特别适合于深井、超深井的钻进。
背景技术
近年来，随着钻特殊井、超深井和复杂井数量的增多，深井和超深井的钻探已在国内外被看作今后钻探工业发展的一个重要方面。对钻井液工艺技术提出了更高的要求，原有的钻井液处理剂已不能完全满足钻井液工艺技术发展的需要。由于井越深，技术上的困难越多，因此，世界各国都把钻井深度和速度作为钻井工艺的重要标志。实践证明，深井、超深井钻井液质量对深井、超深井的成败、钻速、深部油气资源勘探和钻井成本有着极其重要的意义。从当前深井、超深井钻井液研究现状来看，常用的深井、超深井钻井液有水基和油基两大类。虽然油基钻井液相对水基钻井液有抗高温、抗盐钙侵、有利于井壁稳定等优点，但是与水基相比，油基钻井液的配制成本高太多、使用时会对井场附近的生态环境造成严重影响、机械钻速一般也较低。而水基钻井液具有：成本低、配置处理维护较为简单、处理剂来源广且种类多、性能容易控制等优点；所以国内以水基钻井液为主。针对水基钻井液的缺点，研制一种性能良好且稳定的水基钻井液是钻进深井、超深井的关键技术，也是国内外钻进深井、超深井的难点所在。
自70年代初三磺钻井液产生以来，一直发展到现在的聚磺钻井液体系是深井钻井液发展的必然趋势，绝大部分深井钻井液体系多数乃至绝大多数都离不开聚磺的作用，其作用原理主要是抵抗高温对处理剂的破坏作用为主，相关处理剂以提高其抗温能力作为其先决条件，抗盐能力为基础，抗温能力主要是为抵抗高温降解作用为主。
然而，目前深井高温钻井液存在的主要问题如下：
(1)高温钻井液体系失水造壁性难以控制：自从不能使用含有铬元素的处理剂以后，深井高温钻井液体系，特别是盐水钻井液的HTHP失水、老化后急剧增大是普遍现象，温度越高盐度越高越突出。因此，有效抗温抗盐降滤失剂(降HTHP失水)的研发是当前钻井液技术领域的重点。也是建立高温盐水钻井液体系的核心问题。另外，当低密度盐水钻井液HTHP失水及其热稳定性解决之后，其加重到1.50g/cm3以上，其HTHP失水明显上升，当密度大于2.0g/cm3以后，则其HTHP失水成倍增加，这样，必须花费 更多种类的降滤失剂且进一步加大用量来加以解决，从而大幅度增加了高温钻井液降滤失剂的种类和用量，也限制了对抗温、抗盐降滤失剂研发的途径。
(2)高密度钻井液体系流变性难以控制：为了保证高温钻井液具有较低的HTHP失水，则体系中需要大幅增加高温钻井液降滤失剂的种类和用量，使得钻井液基浆粘度大幅增加，基浆加重过后由于大量重晶石颗粒的存在又使其粘度大幅度增加，若钻井液中土量控制稍有不当，当高温老化后，则粘度、切力大增从而导致流动性丧失(高温胶凝和高温固化)。并且目前不断研发的抗温、抗盐降粘剂主要针对黏土进行作用，在高密度钻井液体系中黏土含量有限，从而难以有限降粘。
目前，国内对抗温抗盐钻井液研究很多，但抗高温高密度盐水钻井液体系并未完全过关，因此，“抗温200℃饱和盐水，高密度钻井液(≤2.30g/cm3)体系研究”列为十三五油气国家重大专项攻关任务和研究内容。
对于深井高密度水基钻井液来说，温度越高，处理剂品种越多，加量越大，体系越复杂；特别是180℃以上高温老化后的HTHP失水若要控制在15ml以下的难度及必须使用多种降失水剂及大幅度增大加量才能作到己成国内外泥浆界的共识。
使180℃以上高温盐水钻井液处理剂品种多，加量很大，体系十分复杂，必然造成使用中一旦性能不稳很难维护处理。据统计国外钻井液使用温度与处理剂(有机)耗量的关系，可知，当温度由93℃增至121℃时，处理剂耗量增加值为50％；当温度由121℃增至148.9℃时，处理剂耗量增加值为100％；当温度由148.9℃增至176.7℃时，处理剂耗量增加值为100％。
同样，国内高温高密度盐水钻井液同样具有以上特征，据统计抗200℃高温、高密度(2.00g/cm3)欠饱和盐水钻井液体系中通常有十种有机处理剂，仅降滤失剂总用量就大于25％，体系有机处理剂总用量更是远超过30％的情况十分普遍。
发明内容
本发明的目的是为了针对我国高温高密度盐水钻井液普遍存在的使用处理剂种类过多，加量过大，钻井液老化后HTHP造壁性和流变性难以控制，配制成本和维护成本居高不下的问题，而提供一种深井聚磺钻井液及其制备方法，该深井聚磺钻井液解决了高密度钻井液粘度高，HTHP失水大，且很难调控的难题。
为了克服现有技术存在的上述问题，提供了一种深井聚磺钻井液，其中，该深井聚磺钻井液含有水、膨润土、碳酸钠、磺甲基酚醛树脂、磺化褐煤、卤化盐、降滤失剂、 聚丙烯酸钠、亚硫酸氢钠和重晶石，且以100重量份的水为基准，所述膨润土的含量为3.5-5重量份，所述碳酸钠的含量为0.15-0.35重量份，所述磺甲基酚醛树脂的含量为6-8重量份，所述磺化褐煤的含量为6-8重量份，所述卤化盐的含量为7.5-12重量份，所述降滤失剂的含量为0.5-1.2重量份，所述聚丙烯酸钠的含量为0.8-1.7重量份，所述亚硫酸氢钠的含量为3-5重量份，所述重晶石的含量为250-300重量份。
优选地，以100重量份的水为基准，所述膨润土的含量为4-4.8重量份，所述碳酸钠的含量为0.2-0.24重量份，所述磺甲基酚醛树脂的含量为6.5-7.8重量份，所述磺化褐煤的含量为6.5-7.8重量份，所述卤化盐的含量为9-10.8重量份，所述降滤失剂的含量为0.75-0.9重量份，所述聚丙烯酸钠的含量为1.2-1.44重量份，所述亚硫酸氢钠的含量为3.5-4.2重量份，所述重晶石的含量为260-290重量份。
优选地，所述降滤失剂为丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物和/或丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物。
更优选地，所述降滤失剂为丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物和丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物的组合，且丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物与丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物的重量比为(0.6-0.8)：1。
优选地，所述卤化盐为氯化钠和/或氯化钾。
更优选地，所述卤化盐为氯化钠和氯化钾的组合，且所述氯化钠与所述氯化钾的重量比为(0.6-0.96)：1。
优选地，所述重晶石为重晶石A和/或重晶石B，所述重晶石A的粒径为50-70微米，所述重晶石B的粒径为1-1.2微米。
更优选地，所述重晶石为重晶石A和重晶石B的组合，且所述重晶石A与所述重晶石B的重量比为(1-4)：1。
优选地，所述深井聚磺钻井液的pH为8-9，以及所述深井聚磺钻井液的密度为2.30-2.45g/cm3。
本发明另一方面还提供了一种深井聚磺钻井液的制备方法，其中，该制备方法包括以下步骤：
(1)将膨润土和碳酸钠进行第一混合后再进行预水化处理；
(2)将步骤(1)预水化处理得到的混合物与降滤失剂和聚丙烯酸钠进行第二混合，然后再与卤化盐和亚硫酸氢钠进行第三混合；
(3)将步骤(2)得到的混合物与磺甲基酚醛树脂和磺化褐煤进行第四混合；
其中，以100重量份的水为基准，所述膨润土的用量为3.5-5重量份，所述碳酸钠的含量为0.15-0.35重量份，所述磺甲基酚醛树脂的用量为6-8重量份，所述磺化褐煤的用量为6-8重量份，所述卤化盐的用量为7.5-12重量份，所述降滤失剂的用量为0.5-1.2重量份，所述聚丙烯酸钠的用量为0.8-1.7重量份，所述亚硫酸氢钠的含量为3-5重量份，所述重晶石的用量为250-300重量份。
优选地，以100重量份的水为基准，所述膨润土的用量为4-4.8重量份，所述碳酸钠的含量为0.2-0.24重量份，所述磺甲基酚醛树脂的用量为6.5-7.8重量份，所述磺化褐煤的用量为6.5-7.8重量份，所述卤化盐的用量为9-10.8重量份，所述降滤失剂的用量为0.75-0.9重量份，所述聚丙烯酸钠的用量为1.2-1.44重量份，所述亚硫酸氢钠的含量为3.5-4.2重量份，所述重晶石的用量为260-290重量份。
优选地，所述降滤失剂为丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物和/或丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物。
更优选地，所述降滤失剂为丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物和丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物的组合，且丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物与丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物的重量比为(0.6-0.8)：1。
优选地，所述卤化盐为氯化钠和/或氯化钾。
更优选地，所述卤化盐为氯化钠和氯化钾的组合，且所述氯化钠与所述氯化钾的重量比为(0.6-0.96)：1。
优选地，所述重晶石为重晶石A和/或重晶石B，所述重晶石A的粒径为50-70微米，所述重晶石B的粒径为1-1.2微米。
更优选地，所述重晶石为重晶石A和重晶石B的组合，且所述重晶石A与所述重晶石B的重量比为(1-4)：1。
优选地，在步骤(1)中，所述第一混合的条件包括：温度为50-70℃，搅拌速率为550-650r/min，时间为30-45分钟；所述预水化处理的条件包括：温度为50-70℃，搅拌速率为550-650r/min，时间为23-25小时；
其中，在步骤(2)中，所述第二混合的条件包括：温度为60-70℃，搅拌速率为950-1000r/min，时间为50-70分钟；以及所述第三混合的条件包括：温度为60-70℃，搅拌速率为550-650r/min，时间为50-70分钟；
其中，在步骤(3)中，所述第四混合的条件包括：温度为60-70℃，搅拌速率为550-650r/min，时间为30-40分钟。
本发明另一方面还提供了一种由上述制备方法制备得到的深井聚磺钻井液。
优选地，所述深井聚磺钻井液的pH为8-9，以及所述深井聚磺钻井液的密度为2.30-2.45g/cm3。
通过上述技术方案，本发明提供的深井聚磺钻井液利用处理剂高温交联作用为基础，NaHSO3作为高温适度交联引发剂，同时复配不同粒径的重晶石粉以解决高密度钻井液粘度高，HTHP失水大，且很难调控的难题，研发出的抗温抗盐高密度钻井液的性能优良(HTHP失水低，流变性良好)且处理剂种类少，总用量大幅降低，且老化后的深井聚磺钻井液体系具有粘度低(表观粘度AV为61-63mPa﹒s，塑性粘度PⅤ为46-47m Pa﹒s)、HTHP(高温高压降滤失量)失水低(≤15ml)等难得的优良性能。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
在本发明中，根据GB3102.3-1993《力学的量和单位》中的规定，所述的术语“表观粘度”、“塑性粘度”以及“动切力”的定义如下：
表观粘度：又称有效粘度或视粘度，是钻井液在某一速度梯度下，剪切应力与速度梯度的比值，用“AV”表示，单位为m Pa﹒s(毫帕﹒秒)。
塑性粘度：钻井液在层流时，钻井液中固体颗粒之间、固体颗粒和液体分子之间、液体分子之间各种内摩擦力之和称为钻井液的塑性粘度，用“PV”表示，单位为m Pa﹒s(毫帕﹒秒)或cP(厘泊)，1m Pa﹒s＝1cP。
动切力：钻井液的动切应力反映的是钻井液在层流时，粘土颗粒之间及高聚物分子之间相互作用力的大小，即钻井液内部形成的网状结构能力的强弱，用“YP”或“T0”表示，单位为Pa(帕)。
静切力：反映钻井液流体在静止状态时，内部凝胶网状结构的强度。静切力以希腊字母θ表示，法定计量单位为帕(Pa)。静切力的大小决定于单位体积内流体中结构链的数目与单个结构链的强度。流体内部结构序列逐渐趋向稳定，结构发育趋向完善，静 切力也增大。因此，衡量凝胶强度增长的快慢，规定静切力必须测两次，按API(美国石油学会)标准规定是测量静止10秒和10分的静切力，分别称为初切力和终切力。静切力的大小，反应了悬浮岩粉的能力。特别是加重泥浆，加重剂重晶石等的密度大，一旦泥浆泵停止工作，冲洗液循环中断时，泥浆中粗的岩屑颗粒很快下沉而造成孔内埋钻事故。因此静切力应保持一定的数值。
本发明提供了一种深井聚磺钻井液，其中，该深井聚磺钻井液含有水、膨润土、碳酸钠、磺甲基酚醛树脂、磺化褐煤、卤化盐、降滤失剂、聚丙烯酸钠、亚硫酸氢钠和重晶石，且以100重量份的水为基准，所述膨润土的含量可以为3.5-5重量份，所述碳酸钠的含量为0.15-0.35重量份，所述磺甲基酚醛树脂的含量可以为6-8重量份，所述磺化褐煤的含量可以为6-8重量份，所述卤化盐的含量可以为7.5-12重量份，所述降滤失剂的含量可以为0.5-1.2重量份，所述聚丙烯酸钠的含量可以为0.8-1.7重量份，所述亚硫酸氢钠的含量为3-5重量份，所述重晶石的含量可以为250-300重量份。
根据本发明，所述的深井聚磺钻井液，只要含有水、膨润土、碳酸钠、磺甲基酚醛树脂、磺化褐煤、卤化盐、降滤失剂、聚丙烯酸钠、亚硫酸氢钠和重晶石，并且符合上述比例关系即可在一定程度上实现本发明的目的。
本发明的发明人在研究中发现，尽管只要含有水、膨润土、碳酸钠、磺甲基酚醛树脂、磺化褐煤、卤化盐、降滤失剂、聚丙烯酸钠、亚硫酸氢钠和重晶石并且符合上述比例关系即可实现本发明的目的，但优选情况下，以100重量份的水为基准，所述膨润土的含量为4-4.8重量份，所述碳酸钠的含量为0.2-0.24重量份，所述磺甲基酚醛树脂的含量为6.5-7.8重量份，所述磺化褐煤的含量为6.5-7.8重量份，所述卤化盐的含量为9-10.8重量份，所述降滤失剂的含量为0.75-0.9重量份，所述聚丙烯酸钠的含量为1.2-1.44重量份，所述亚硫酸氢钠的含量为3.5-4.2重量份，所述重晶石的含量为260-290重量份，效果更好。
根据本发明，所述膨润土作为配浆材料，没有具体限定，可以为本领域的常规选择，例如，可以为钻井液用膨润土，其主要成分为含有蒙脱石不少于85重量％的粘土矿物。
根据本发明，所述水没有具体限定，可以为自来水(清水)即可。
根据本发明，所述磺甲基酚醛树脂的代号为SMP-Ⅲ，可以商购得到，分子量为20-50万。
根据本发明，所述磺化褐煤(降粘剂)的代号为SMC。
根据本发明，所述聚丙烯酸钠(降粘剂)的分子式为(C3H3NaO2)n，可以商购得到，其数均分子量为20万-40万。
所述碳酸钠和所述亚硫酸氢钠没有具体限定，可以为商购产品。
根据本发明，所述降滤失剂可以为丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物和/或丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物；优选地，所述降滤失剂为丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物和丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物的组合，且丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物与丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物的重量比可以为(0.6-0.8)：1；优选为(0.65-0.75)：1；另外，所述丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物(AM/DMDAAC)和所述丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物(AM/DMDAAC/AMPS)可以为发明人自己合成制备而得，选择水溶液自由基共聚来制备，其合成方法如下所述。
根据本发明，所述丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物的合成方法包括以下步骤：
(1)将AM、DMDAAC和去离子水混合；
(2)将步骤(1)得到的混合物与引发剂混合；
(3)将步骤(2)得到的产物用乙醇抽提、剪碎以及过滤后在真空烘箱中进行干燥处理。
其中，在步骤(1)中，所述混合的条件可以为：温度为49-51℃，搅拌速率没有具体限定，可以为本领域技术人员的常规选择，例如，搅拌速率可以为280-320转/分钟，且在搅拌溶液的同时进行通氮除氧处理，时间可以为19-21分钟；
其中，在步骤(2)中，所述引发剂可以为氧化还原体系，例如可以为2,2′氮杂双(2-咪唑啉)二盐酸盐(VA-044)，2,2′-偶氮二异丁基脒二盐酸盐(AIBA-2HCl)-亚硫酸氢钠，过硫酸铵-亚硫酸氢钠，过硫酸钾-亚硫酸氢钠中的一种或多种，优选为过硫酸铵-亚硫酸氢钠，且所述引发剂在通氮除氧处理结束后同时与AM和DMDAAC混合，另外，优选地，所述引发剂可以以0.3-05mL/min的滴加速率滴加；以及所述混合的条件可以为：温度为49-51℃，时间为7.5-8.5小时；
其中，在步骤(3)中，所述干燥处理的条件可以为：温度为49-51℃，时间为23-25小时，且在经干燥处理后研磨成白色粉末；
其中，该丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物的特性黏数为370-380mL/g， 优选为375-378mL/g；以及
以该丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物的总重量为基准，所述丙烯酰胺的含量为75-85重量％，所述二甲基二烯丙基氯化铵的含量为15-25重量％；
优选地，以该丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物的总重量为基准，所述丙烯酰胺的含量为78-82重量％，所述二甲基二烯丙基氯化铵的含量为18-22重量％。
通过改变AM和DMDAAC两种单体以及引发剂的用量，能够获得不同分子结构的丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物(AM/DMDAAC)，其中，表1为不同引发剂制得的二元共聚物的性能。
表1
引发体系 反应温度 阳离子度 特性黏数 产率
VA-044 45℃ 7.73 281.93 53.87
AIBA-2HCl-亚硫酸氢钠 60℃ 9.78 430.14 64.35
过硫酸铵-亚硫酸氢钠 50℃ 10.29 345.65 84.26
过硫酸钾-亚硫酸氢钠 50℃ 10.06 338.47 73.44
注：阳离子度的单位为(mol％)，特性黏数的单位为(mL﹒g-1)，产率的单位为(％)。
根据本发明，所述丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物(AM/DMDAAC/AMPS)的合成方法包括以下步骤：
(1)将AMPS和去离子水混合；
(2)将步骤(1)的混合物与AM、DMDAAC混合；
(3)将步骤(2)得到的混合物与引发剂混合；
(4)将步骤(3)得到的产物用乙醇抽提、剪碎以及过滤后在真空烘箱中进行干燥处理。
其中，在步骤(1)中，所述混合的条件可以为：温度为29-31℃，搅拌速率没有具体限定，可以为本领域技术人员的常规选择，例如，可以为180-220转/分钟；以及可以将该混合溶液的pH值调节至中性，可以选用一定浓度的NaOH溶液来调节pH值；
其中，在步骤(2)中，所述混合的条件可以为：温度为49-51℃，搅拌速率没有具体限定，可以为本领域技术人员的常规选择，且在搅拌溶液的同时进行通氮除氧处理，时间可以为19-21分钟；
其中，在步骤(3)中，所述引发剂可以为氧化还原体系，例如可以为“过硫酸铵 -亚硫酸氢钠”和“过硫酸钾-亚硫酸氢钠”，且“过硫酸铵-亚硫酸氢钠”与“过硫酸钾-亚硫酸氢钠”的重量比为1：1，且所述引发剂在通氮除氧处理结束后同时与AMPS、AM和DMDAAC混合；以及所述混合的条件可以为：温度为49-51℃，时间为7.5-8.5小时；另外，优选地，所述引发剂可以以2.5-3.5mL/min的滴加速率滴加到步骤(2)的混合物中且与其混合。
其中，在步骤(4)中，所述干燥处理的条件可以为：温度为49-51℃，时间为23-25小时，且在经干燥处理后研磨成白色粉末；其中，该丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物的特性黏数为340-350mL/g，优选为345-348mL/g；以及
以该丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物的总重量为基准，所述丙烯酰胺的含量为50-65重量％，所述二甲基二烯丙基氯化铵的含量为12-22重量％，所述2-丙烯酰胺-2-甲基丙磺酸的含量为13-38重量％；
优选地，以该丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物的总重量为基准，所述丙烯酰胺的含量为55-60重量％，所述二甲基二烯丙基氯化铵的含量为15-20重量％，所述2-丙烯酰胺-2-甲基丙磺酸的含量为20-30重量％。
通过改变AMPS、AM和DMDAAC两种单体以及引发剂的用量，能够获得不同分子结构的丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物(AM/DMDAAC/AMPS)。
根据本发明，所述卤化盐可以为氯化钠和/或氯化钾；优选地，所述卤化盐为氯化钠和氯化钾的组合，且所述氯化钠与所述氯化钾的重量比可以为(0.6-0.96)：1，优选为(0.7-0.8)：1。
根据本发明，所述重晶石(加重剂)可以为重晶石A和/或重晶石B，所述重晶石A的粒径可以为50-70微米，所述重晶石B的粒径可以为1-1.2微米；优选地，所述重晶石为重晶石A和重晶石B的组合，且所述重晶石A与所述重晶石B的重量比可以为(1-4)：1，优选为(1.5-4)：1；另外，在本发明中，所述重晶石A和所述重晶石B的主要成分为BaSO4，也就是说，所述重晶石A可以为粒径50-70微米的BaSO4，所述重晶石B可以为粒径1-1.2微米的BaSO4。
根据本发明，所述深井聚磺钻井液的pH可以为8-9，优选地，所述深井聚磺钻井液的pH为8.4-8.6。而且在本发明中，调节该深井聚磺钻井液的pH的试剂没有具体限定，可以为本领域的常规选择，例如，如果将该深井聚磺钻井液的pH调高，则可以选 用氢氧化钠、碳酸氢钠和氢氧化钙中的一种或多种进行调节，如果将该深井聚磺钻井液的pH调低，则可以选用稀释的盐酸或者酸式盐进行调节。
根据本发明，所述深井聚磺钻井液的密度可以为2.30-2.45g/cm3，优选为2.35-2.42g/cm3，在本发明中，可以通过调节重晶石的总用量将该深井聚磺钻井液的密度增加。
本发明另一方面还提供了一种深井聚磺钻井液的制备方法，其中，该制备方法包括以下步骤：
(1)将膨润土和碳酸钠进行第一混合后再进行预水化处理；
(2)将步骤(1)预水化处理得到的混合物与降滤失剂和聚丙烯酸钠进行第二混合，然后再与卤化盐和亚硫酸氢钠进行第三混合；
(3)将步骤(2)得到的混合物与磺甲基酚醛树脂和磺化褐煤进行第四混合；
其中，以100重量份的水为基准，所述膨润土的用量可以为3.5-5重量份，所述碳酸钠的含量可以为0.15-0.35重量份，所述磺甲基酚醛树脂的用量可以为6-8重量份，所述磺化褐煤的用量可以为6-8重量份，所述卤化盐的用量可以为7.5-12重量份，所述降滤失剂的用量可以为0.5-1.2重量份，所述聚丙烯酸钠的用量可以为0.8-1.7重量份，所述亚硫酸氢钠的含量可以为3-5重量份，所述重晶石的用量可以为250-300重量份。
根据本发明，所述的深井聚磺钻井液的制备过程中，只要将膨润土和碳酸钠预水化处理，将磺甲基酚醛树脂、磺化褐煤、卤化盐、降滤失剂、聚丙烯酸钠、亚硫酸氢钠和重晶石依次序与预水化处理后的混合物混合，并且符合上述比例关系即可在一定程度上实现本发明的目的。
本发明的发明人在研究中发现，尽管只要膨润土和碳酸钠预水化处理，将磺甲基酚醛树脂、磺化褐煤、卤化盐、降滤失剂、聚丙烯酸钠、亚硫酸氢钠和重晶石依次序与预水化处理后的混合物混合，并且符合上述比例关系即可实现本发明的目的，但优选情况下，以100重量份的水为基准，所述膨润土的用量为4-4.8重量份，所述碳酸钠的含量为0.2-0.24重量份，所述磺甲基酚醛树脂的用量为6.5-7.8重量份，所述磺化褐煤的用量为6.5-7.8重量份，所述卤化盐的用量为9-10.8重量份，所述降滤失剂的用量为0.75-0.9重量份，所述聚丙烯酸钠的用量为1.2-1.44重量份，所述亚硫酸氢钠的含量为3.5-4.2重量份，所述重晶石的用量为260-290重量份，效果更好。
根据本发明，所述膨润土作为配浆材料，没有具体限定，可以为本领域的常规选择，例如，可以为钻井液用膨润土，其主要成分为含有蒙脱石不少于85重量％的粘土 矿物。
根据本发明，所述水没有具体限定，可以为自来水(清水)即可。
根据本发明，所述磺甲基酚醛树脂的代号为SMP-Ⅲ，可以商购得到，分子量为20-50万。
根据本发明，所述磺化褐煤(降粘剂)的代号为SMC。
根据本发明，所述聚丙烯酸钠(降粘剂)的分子式为(C3H3NaO2)n，可以商购得到，其平均分子量为20万-40万。
根据本发明，所述碳酸钠和所述亚硫酸氢钠没有具体限定，可以为商购产品。
根据本发明，所述降滤失剂可以为丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物和/或丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物；优选地，所述降滤失剂为丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物和丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物的组合，且丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物与丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物的重量比可以为(0.6-0.8)：1；优选为(0.65-0.75)：1；另外，所述丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物(AM/DMDAAC)和所述丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物(AM/DMDAAC/AMPS)可以为发明人自己合成制备而得，其合成方法如上所述，在此不再赘述。
根据本发明，所述卤化盐可以为氯化钠和/或氯化钾；优选地，所述卤化盐为氯化钠和氯化钾的组合，且所述氯化钠与所述氯化钾的重量比可以为(0.6-0.96)：1，优选为(0.7-0.8)：1。
根据本发明，所述重晶石(加重剂)可以为重晶石A和/或重晶石B，所述重晶石A的粒径可以为50-70微米，所述重晶石B的粒径可以为1-1.2微米；优选地，所述重晶石为重晶石A和重晶石B的组合，且所述重晶石A与所述重晶石B的重量比可以为(1-4)：1，优选为(1.5-4)：1；另外，在本发明中，所述重晶石A和所述重晶石B的主要成分为BaSO4，也就是说，所述重晶石A可以为粒径50-70微米的BaSO4，所述重晶石B可以为粒径1-1.2微米的BaSO4。
根据本发明，在步骤(1)中，所述第一混合的条件包括：温度为50-70℃，搅拌速率为550-650r/min，时间为30-45分钟；所述预水化处理的条件包括：温度为50-70℃，搅拌速率为550-650r/min，时间为23-25小时；
其中，在步骤(2)中，所述第二混合的条件包括：温度为60-70℃，搅拌速率为 950-1000r/min，时间为50-70分钟；以及所述第三混合的条件包括：温度为60-70℃，搅拌速率为550-650r/min，时间为50-70分钟；
其中，在步骤(3)中，所述第四混合的条件包括：温度为60-70℃，搅拌速率为550-650r/min，时间为30-40分钟。
优选地，在步骤(1)中，所述第一混合的条件包括：温度为55-65℃，搅拌速率为580-620r/min，时间为30-35分钟；所述预水化处理的条件包括：温度为55-65℃，搅拌速率为580-620r/min，时间为23.5-24.5小时；
优选地，在步骤(2)中，所述第二混合的条件包括：温度为62-68℃，搅拌速率为980-1000r/min，时间为55-65分钟；以及所述第三混合的条件包括：温度为62-68℃，搅拌速率为580-620r/min，时间为55-65分钟；
优选地，在步骤(3)中，所述第四混合的条件包括：温度为62-68℃，搅拌速率为580-620r/min，时间为30-35分钟。
本发明另一方面还提供了一种由上述制备方法制备得到的深井聚磺钻井液。
根据本发明，所述深井聚磺钻井液的pH可以为8-9，优选地，所述深井聚磺钻井液的pH为8.4-8.6。而且在本发明中，调节该深井聚磺钻井液的pH的试剂没有具体限定，可以为本领域的常规选择，例如，如果将该深井聚磺钻井液的pH调高，则可以选用氢氧化钠、碳酸氢钠和氢氧化钙中的一种或多种进行调节，如果将该深井聚磺钻井液的pH调低，则可以选用稀释的盐酸或者酸式盐进行调节。
根据本发明，所述深井聚磺钻井液的密度可以为2.30-2.45g/cm3，优选为2.35-2.42g/cm3，在本发明中，可以通过选用重晶石将该深井聚磺钻井液的密度增加，本发明的发明人在研究中发现，所述所述重晶石A和所述重晶石B的用量的重量比的比值为4:1至3:2时能够将该深井聚磺钻井液加重到2.30-2.45g/cm3。
根据本发明的一种优选的实施方式，该深井聚磺钻井液的制备方法包括以下步骤：
(1)首先，将膨润土与水在温度为50-70℃在550-650r/min的搅拌条件下搅拌5-15分钟；然后，将膨润土与水的混合物再与碳酸钠混合且在温度为50-70℃在550-650r/min的搅拌条件下搅拌25-35分钟；然后，再进行预水化处理得到预水化后的土浆，其中，所述预水化处理的条件包括：温度可以为50-70℃，时间可以为23-25小时；优选地，温度为55-65℃，时间为23.5-24.5小时；
(2)将预水化后的土浆加热至60-70℃，将加热后的预水化后的土浆与降滤失剂和聚丙烯酸钠混合且在950-1000r/min的搅拌条件下搅拌50-70分钟；然后，再将其混 合物与氯化钠、氯化钾和亚硫酸氢钠混合且在温度为60-70℃下在550-650r/min的搅拌条件下搅拌50-70分钟，得到的混合物作为基浆备用；
(3)将上述基浆与磺甲基酚醛树脂和磺化褐煤混合且在温度为60-70℃下在550-650r/min的搅拌条件下搅拌30-40分钟。
以下将通过实施例对本发明进行详细描述。
回收率的测定参照石油行业标准SY-T5613-2000泥页岩理化性能试验方法；
膨润土(蒙脱石)购自新疆中非夏子街膨润土有限责任公司；
磺甲基酚醛树脂购自重庆大方合成化工有限公司牌号为钻井液用磺甲基酚醛树脂SMP-III粉剂；
磺化褐煤购自成都川锋化学工程有限责任公司牌号为磺化褐煤SMC；
卤化盐、降滤失剂、聚丙烯酸钠均购自科龙化学试剂厂；
重晶石等原料均购自贵州毫微粉体工业有限公司(超微细硫酸钡的市售品)。
丙烯酰胺、二甲基二烯丙基氯化铵、2-丙烯酰胺-2-甲基丙磺酸均购自科龙化学试剂厂。
制备例1
本制备例用于说明所述丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物(AM/DMDAAC)的合成。
(1)在三口烧瓶中放入磁力搅拌子，插入温度计，置于恒温水浴锅中不断搅拌，水温设定为50℃，以及搅拌速率为300转/分钟；
(2)称取20克AM单体，用去离子水溶解后加入三口烧瓶中，再称取20克DMDAAC溶液加入到三口烧瓶中，随后，在搅拌溶液的同时进行通氮除氧处理，通氮除氧处理的时间为20分钟；
(3)以AM和DMDAAC单体总质量作为基数，称取0.048克引发剂(引发剂为过硫酸铵-亚硫酸氢钠)，用去离子水配制成水溶液，在除氧结束后滴加入三口烧瓶，其中，滴加速率为0.5mL/min，搅拌使溶液混合均匀，反应进行8小时；
(4)将产物转移至烧瓶中，用乙醇抽提2次，剪碎，过滤后在真空烘箱中于50℃下干燥24小时，然后研磨成白色粉末。
结果：合成出的白色粉末为丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物 (AM/DMDAAC)，其特性黏数376.24mL/g，且以该二元共聚物的总重量为基准，丙烯酰胺的含量为79.8重量％，二甲基二烯丙基氯化铵的含量为20.2重量％。
制备例2
本制备例用于说明所述丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物(AM/DMDAAC/AMPS)的合成。
(1)称取20克AMPS，用去离子水溶解后，转移至三口烧瓶中，在三口烧瓶中放入磁力搅拌子，插上温度计后，置于恒温水浴锅中不断搅拌，水温设定为30℃，以及搅拌速率为200转/分钟；
(2)配制一定浓度的NaOH溶液，加入三口烧瓶中，将溶液的pH值调节至中性；
(3)称取27克AM单体，用去离子水溶解后加入三口烧瓶中，再称取25克DMDAAC溶液加入到三口烧瓶中，随后，在搅拌溶液的同时进行通氮除氧处理，通氮除氧处理的时间为20分钟；
(4)称取0.13克引发剂(引发剂为“过硫酸铵-亚硫酸氢钠”和“过硫酸钾-亚硫酸氢钠”)，用去离子水配制成水溶液，在除氧结束后滴加入三口烧瓶中，滴加速率为3mL/min，并将温度升至50℃，搅拌使溶液混合均匀，反应进行8小时；
(5)将产物转移至烧瓶中，用乙醇抽提2次，剪碎，过滤后在真空烘箱中于50℃下干燥24小时，然后研磨成白色粉末。
结果：合成出的白色粉末为丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物(AM/DMDAAC/AMPS)，其特性黏数347.91mL/g，其中，以该三元共聚物的总重量为基准，丙烯酰胺的含量为55.9重量％，二甲基二烯丙基氯化铵的含量为16.3重量％，2-丙烯酰胺-2-甲基丙磺酸的含量为27.8重量％。
实施例1
本实施例用于说明本发明的深井聚磺钻井液的制备方法
(1)先量取300克的自来水将水温升至65℃，在低速600r/min电动搅拌下加入12克的钻井液用膨润土，搅拌10分钟加入0.6克Na2CO3再搅拌30分钟，常温常压下预水化24h；
(2)再将预水化后土浆升温至65℃后加入3.0克抗温抗盐两性离子降滤失剂与10.50克聚丙烯酸钠后在高速1000r/min下搅拌60分钟，再加入12克氯化钠和15.0克 氯化钾以及1.050克亚硫酸氢钠后在低速600r/min下搅拌60分钟作为基浆备用；
(3)然后在上述基浆中加入10.50克磺甲基酚醛树脂和10.50克磺化褐煤在低速600r/min下搅拌30分钟，调节钻井液体系pH值为8.5；最后用50-70微米BaSO4(200克)：1-1.2微米BaSO4(50克)＝4：1的比例将钻井液体系加重到2.30g/cm3制得本高密度深井聚磺钻井液。
结果制备得到深井聚磺钻井液I，抗温能力高达220℃，且老化后的深井聚磺钻井液的其它性能如表2所示；采用XGRL-2型滚子加热炉对由实施例1制备的深井聚磺钻井液进行了滚动回收率测定如表3所示。
实施例2
本实施例用于说明本发明的深井聚磺钻井液的制备方法
(1)先量取250克的自来水将水温升至65℃，在低速600r/min电动搅拌下加入10克的钻井液用膨润土，搅拌10分钟加入0.5克Na2CO3再搅拌30分钟，常温常压下预水化24h；
(2)再将预水化后土浆升温至65℃后加入2.5克抗温抗盐两性离子降滤失剂与8.75克聚丙烯酸钠后在高速1000r/min下搅拌60分钟，再加入10克氯化钠和12.5克氯化钾以及0.875克亚硫酸氢钠后在低速600r/min下搅拌60分钟作为基浆备用；
(3)然后在上述基浆中加入8.75克磺甲基酚醛树脂和8.75克磺化褐煤在低速600r/min下搅拌30分钟，调节钻井液体系pH值为8.5；最后用50-70微米BaSO4(180克)：1-1.2微米BaSO4(120克)＝3：2的比例将钻井液体系加重到2.45g/cm3制得本高密度深井聚磺钻井液。
结果制备得到深井聚磺钻井液II，抗温能力高达220℃，且老化后的深井聚磺钻井液的其它性能如表2所示。
对比例1
按照与实施例1相同的方法制备深井聚磺钻井液，所不同的是各种处理剂的用量不同，尤其是有机处理剂的总用量少，具体地，以100重量份的清水为基准，膨润土的用量为3重量份，碳酸钠的用量为0.2重量份，磺甲基酚醛树脂的用量为2.5重量份，磺化褐煤的用量为2.5重量份，氯化钠的用量为4重量份，氯化钾的用量为3重量份，二元共聚物的用量为0.4重量份，聚丙烯酸钠的用量为2.5重量份，亚硫酸氢钠的用量 为3重量份，重晶石A的用量为200重量份，重晶石B的用量为50重量份。
结果制备得到深井聚磺钻井液D1，抗温能力高达220℃，其它性能如表2所示。
对比例2
按照与实施例2相同的方法制备深井聚磺钻井液，所不同的是各种处理剂的用量不同，尤其是有机处理剂的总用量多，具体地，以100重量份的清水为基准，膨润土的用量为6重量份，碳酸钠的用量为0.3重量份，磺甲基酚醛树脂的用量为8.5重量份，磺化褐煤的用量为8.5重量份，氯化钠的用量为5重量份，氯化钾的用量为6.5重量份，三元共聚物的用量为1.8重量份，聚丙烯酸钠的用量为5重量份，亚硫酸氢钠的用量为5重量份，重晶石A的用量为180重量份，重晶石B的用量为120重量份。
结果制备得到深井聚磺钻井液D2，抗温能力高达220℃，其它性能如表2所示。
对比例3
按照与实施例1相同的方法制备深井聚磺钻井液，所不同的是，还额外添加了其它的有机处理剂，具体地，还额外添加了其它的有机处理剂，具体地，加入8重量％由石家庄华莱鼎盛科技有限公司生产的钻井液用降滤失剂AOBS/AA/多羟基化合物接枝共聚物HLJ-4。
结果制备得到深井聚磺钻井液D3，抗温能力高达220℃，其它性能如表2钻井液体系在220℃老化后的体系性能所示。
表2
编号 AV PV YP θ(10″) HTHP失水
实施例1 63 47 16 3 15
实施例2 61 46 15 3 14.5
对比例1 84 68 16 4 54
对比例2 79 76 13 7 46
对比例3 77 67 10 8 37
注：AV单位为(m Pa﹒s)，PV单位为(m Pa﹒s)，YP单位为(Pa)，θ(10″)单位为(Pa)，HTHP失水单位为(ml)。
表3
钻井液配方 实验条件 回收质量(g) 回收率(％)
清水+50g红层土 220℃/16h 6.23 12.46
钻井液体系+50g红层土 220℃/16h 48.08 96.16
注：红层土为四川红层土岩屑，为6-10目，回收率为过40目回收率；表中结果均为2次实验数据均值。
由表2数据可知，实施例1-2制备的深井聚磺钻井液的表观粘度为61-63m Pa﹒s，塑性粘度为46-47m Pa﹒s，动应力为15-16Pa，θ(10″)为3，以及HTHP失水均小于等于15ml；
而对比例1制备的深井聚磺钻井液的表观粘度为84m Pa﹒s，塑性粘度高达68m Pa﹒s，动应力为16Pa，θ(10″)为4Pa，而且，最为严重的是HTHP失水高达54ml，极易引起井下复杂事故的发生；
对比例2制备的深井聚磺钻井液的表观粘度为79m Pa﹒s，塑性粘度高达76m Pa﹒s，动应力为13Pa，θ(10″)为7Pa，而且，最为严重的是HTHP失水高达46ml，极易引起井下复杂事故的发生；
对比例3制备的深井聚磺钻井液的表观粘度为77m Pa﹒s，塑性粘度高达67m Pa﹒s，动应力为10Pa，θ(10″)为8Pa，而且，最为严重的是HTHP失水高达37ml，极易引起井下复杂事故的发生。
由表3数据可知，由实施例1制备的深井聚磺钻井液的滚动回收率达到96.92％，说明该钻井液具有较好的抑制性能能够有效的抑制粘土水化。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (11)

  1. 一种深井聚磺钻井液，其特征在于，该深井聚磺钻井液含有水、膨润土、碳酸钠、磺甲基酚醛树脂、磺化褐煤、卤化盐、降滤失剂、聚丙烯酸钠、亚硫酸氢钠和重晶石，且以100重量份的水为基准，所述膨润土的含量为3.5-5重量份，所述碳酸钠的含量为0.15-0.35重量份，所述磺甲基酚醛树脂的含量为6-8重量份，所述磺化褐煤的含量为6-8重量份，所述卤化盐的含量为7.5-12重量份，所述降滤失剂的含量为0.5-1.2重量份，所述聚丙烯酸钠的含量为0.8-1.7重量份，所述亚硫酸氢钠的含量为3-5重量份，所述重晶石的含量为250-300重量份。
  2. 根据权利要求1所述的深井聚磺深井聚磺钻井液，其中，以100重量份的水为基准，所述膨润土的含量为4-4.8重量份，所述碳酸钠的含量为0.2-0.24重量份，所述磺甲基酚醛树脂的含量为6.5-7.8重量份，所述磺化褐煤的含量为6.5-7.8重量份，所述卤化盐的含量为9-10.8重量份，所述降滤失剂的含量为0.75-0.9重量份，所述聚丙烯酸钠的含量为1.2-1.44重量份，所述亚硫酸氢钠的含量为3.5-4.2重量份，所述重晶石的含量为260-290重量份。
  3. 根据权利要求1或2所述的深井聚磺钻井液，其中，所述降滤失剂为丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物和/或丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物；优选地，所述降滤失剂为丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物和丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物的组合，且丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物与丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物的重量比为(0.6-0.8)：1；
    其中，所述卤化盐为氯化钠和/或氯化钾；优选地，所述卤化盐为氯化钠和氯化钾的组合，且所述氯化钠与所述氯化钾的重量比为(0.6-0.96)：1；
    其中，所述重晶石为重晶石A和/或重晶石B，所述重晶石A的粒径为50-70微米，所述重晶石B的粒径为1-1.2微米；优选地，所述重晶石为重晶石A和重晶石B的组合，且所述重晶石A与所述重晶石B的重量比为(1-4)：1。
  4. 根据权利要求1所述的深井聚磺钻井液，其中，所述深井聚磺钻井液的pH为8-9，以及所述深井聚磺钻井液的密度为2.30-2.45g/cm3。
  5. 一种深井聚磺钻井液的制备方法，其特征在于，该制备方法包括以下步骤：
    (1)将膨润土和碳酸钠进行第一混合后再进行预水化处理；
    (2)将步骤(1)预水化处理得到的混合物与降滤失剂和聚丙烯酸钠进行第二混合，然后再与卤化盐和亚硫酸氢钠进行第三混合；
    (3)将步骤(2)得到的混合物与磺甲基酚醛树脂和磺化褐煤进行第四混合；
    其中，以100重量份的水为基准，所述膨润土的用量为3.5-5重量份，所述碳酸钠的含量为0.15-0.35重量份，所述磺甲基酚醛树脂的用量为6-8重量份，所述磺化褐煤的用量为6-8重量份，所述卤化盐的用量为7.5-12重量份，所述降滤失剂的用量为0.5-1.2重量份，所述聚丙烯酸钠的用量为0.8-1.7重量份，所述亚硫酸氢钠的含量为3-5重量份，所述重晶石的用量为250-300重量份。
  6. 根据权利要求5所述的制备方法，其中，以100重量份的水为基准，所述膨润土的用量为4-4.8重量份，所述碳酸钠的含量为0.2-0.24重量份，所述磺甲基酚醛树脂的用量为6.5-7.8重量份，所述磺化褐煤的用量为6.5-7.8重量份，所述卤化盐的用量为9-10.8重量份，所述降滤失剂的用量为0.75-0.9重量份，所述聚丙烯酸钠的用量为1.2-1.44重量份，所述亚硫酸氢钠的含量为3.5-4.2重量份，所述重晶石的用量为260-290重量份。
  7. 根据权利要求5或6所述的制备方法，其中，所述降滤失剂为丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物和/或丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物；优选地，所述降滤失剂为丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物和丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物的组合，且丙烯酰胺/二甲基二烯丙基氯化铵二元共聚物与丙烯酰胺/二甲基二烯丙基氯化铵/2-丙烯酰胺-2-甲基丙磺酸三元共聚物的重量比为(0.6-0.8)：1；
    其中，所述卤化盐为氯化钠和/或氯化钾；优选地，所述卤化盐为氯化钠和氯化钾的组合，且所述氯化钠与所述氯化钾的重量比为(0.6-0.96)：1；
    其中，所述重晶石为重晶石A和/或重晶石B，所述重晶石A的粒径为50-70微米，所述重晶石B的粒径为1-1.2微米；优选地，所述重晶石为重晶石A和重晶石B的组合，且所述重晶石A与所述重晶石B的重量比为(1-4)：1。
  8. 根据权利要求5所述的制备方法，其中，在步骤(1)中，所述第一混合的条 件包括：温度为50-70℃，搅拌速率为550-650r/min，时间为30-45分钟；所述预水化处理的条件包括：温度为50-70℃，搅拌速率为550-650r/min，时间为23-25小时；
    其中，在步骤(2)中，所述第二混合的条件包括：温度为60-70℃，搅拌速率为950-1000r/min，时间为50-70分钟；以及所述第三混合的条件包括：温度为60-70℃，搅拌速率为550-650r/min，时间为50-70分钟；
    其中，在步骤(3)中，所述第四混合的条件包括：温度为60-70℃，搅拌速率为550-650r/min，时间为30-40分钟。
  9. 根据权利要求5所述的制备方法，其中，该制备方法在搅拌条件下进行，且所述搅拌条件包括：搅拌速率为500-1100转/分钟，优选为550-1000转/分钟。
  10. 由权利要求5-9中任意一项所述的制备方法制备得到的深井聚磺钻井液。
  11. 根据权利要求10所述的深井聚磺钻井液，其中，所述深井聚磺钻井液的pH为8-9，以及所述深井聚磺钻井液的密度为2.30-2.45g/cm3。
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