WO2024099365A1 - 乳化剂组合物及钻井液与应用 - Google Patents

乳化剂组合物及钻井液与应用 Download PDF

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WO2024099365A1
WO2024099365A1 PCT/CN2023/130496 CN2023130496W WO2024099365A1 WO 2024099365 A1 WO2024099365 A1 WO 2024099365A1 CN 2023130496 W CN2023130496 W CN 2023130496W WO 2024099365 A1 WO2024099365 A1 WO 2024099365A1
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oil
fatty acid
drilling fluid
acid
fatty
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PCT/CN2023/130496
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English (en)
French (fr)
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张现斌
张健
杨中锋
赵颖
汪倩
魏尽然
刘鑫
陈安亮
陈蕾旭
宋学文
王红芳
周涛
王力
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中国石油天然气集团有限公司
中国石油集团渤海钻探工程有限公司
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Publication of WO2024099365A1 publication Critical patent/WO2024099365A1/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
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives
    • 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
    • C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based

Definitions

  • the invention relates to the technical field of oil-based/synthetic-based drilling fluids, and in particular to an emulsifier and drilling fluid and applications thereof.
  • drilling fluid can carry cuttings, lubricate drilling tools, cool drill bits, and other important functions, and is known as the "blood of drilling projects.”
  • Oil-based/synthetic-based drilling fluid is an important type of drilling fluid. Compared with water-based drilling fluid, it has better inhibition, lubricity, high-temperature stability, pollution resistance, reservoir protection and other advantages. It is increasingly widely used in the drilling process of mudstone, thick salt-gypsum layers, shale reservoirs, and high-temperature deep layers. It is a technical field with great development potential in my country's current deep oil and gas resources, shale oil and gas resources and other fields.
  • the stability of water-in-oil emulsion is the basis of oil-based drilling fluid (water-in-oil drilling fluid) and the key core of oil-based drilling fluid. In the process of drilling deep wells, ultra-deep wells and long horizontal wells of shale gas, the stability of water-in-oil emulsion is related to the success of drilling construction.
  • emulsifiers include Span 80, fatty acids, maleated fatty polyamides, cyclohexane acid amides, calcium dodecylbenzene sulfonate, sodium rosin acid, etc.
  • CN201880053201.4 discloses the use of aminoamide as an emulsifier and the preparation of oil-based drilling fluid based on layered double hydroxide as a rheology modifier;
  • CN201610825832.6 discloses the preparation of an oil-based emulsifier based on dimer acid and long-chain alkyl monoamine, and provides An oil-based drilling fluid is provided;
  • CN201711082088.6 discloses an emulsifier for high-temperature resistant oil-based drilling fluid composed of rosin acid, white oil, alkali and alkyl sulfonate, which can resist 200°C;
  • CN201810900379.X discloses a glycidyl ether obtained by reacting cardanol and epichlor
  • CN201711453619.8 discloses heating reaction with tall oil acid, maleic anhydride, a first catalyst and a solvent to obtain a tall oil acid-maleic anhydride adduct; a second catalyst is added to the tall oil acid-maleic anhydride adduct, and hydroxyethylethylenediamine is added after heating to the temperature required for the reaction, and the heating reaction is continued for a period of time to obtain the said high-efficiency oil-based drilling fluid emulsifier.
  • CN201880084653.9 discloses the use of waste vegetable oil to prepare an alkyl ester emulsifier for the preparation of oil-based drilling fluid.
  • the oil-based/synthetic-based drilling fluid prepared with the above emulsifier has high plastic viscosity, low high-temperature stability, and poor resistance to salt water pollution, and cannot better meet the needs of safe and efficient drilling of deep wells and ultra-deep wells under complex geological conditions.
  • the present invention aims to provide a high-performance emulsifier composition suitable for oil-based/synthetic-based drilling fluids, which has a stable chemical structure, can effectively improve the emulsification stability, temperature stability and anti-pollution performance of ultra-deep well oil-based/synthetic-based drilling fluids, and can significantly improve the rheological properties of the drilling fluids, so as to at least partially solve the technical defects of the drilling fluids in the prior art under the conditions of high temperature and high pressure, extremely thick salt-gypsum layers, and highly mineralized composite salt water layers.
  • an emulsifier composition wherein the composition comprises: an effective component and a solvent, wherein the effective component comprises: di-fatty imidazoline amide, N-hydroxyethylated fatty imidazoline and maleated fatty acid, and the solvent comprises oil (environmentally friendly solvent oil) and/or alcohol ether.
  • the drilling fluid comprises the above-mentioned Emulsifier composition.
  • the drilling fluid is an oil-based or synthetic-based drilling fluid, and also includes a base oil, an aqueous phase (usually a calcium chloride solution, dispersed in the oil phase to form an oil-in-water emulsion), an organophilic modified clay mineral, a flow pattern regulator, a polymer thickener, an alkalinity regulator, an activity control agent, an organophilic modified humic acid fluid loss reducer, and a weighting material.
  • a base oil usually a calcium chloride solution, dispersed in the oil phase to form an oil-in-water emulsion
  • an organophilic modified clay mineral usually a calcium chloride solution, dispersed in the oil phase to form an oil-in-water emulsion
  • a flow pattern regulator usually a calcium chloride solution, dispersed in the oil phase to form an oil-in-water emulsion
  • an organophilic modified clay mineral usually a calcium chloride solution, disper
  • the present invention relates to the application of the above-mentioned drilling fluid in the development of deep oil and gas resources and unconventional oil and gas wells.
  • the main component of the emulsifier composition provided by the invention is transformed from conventional fatty acid polyamide to di-fatty imidazoline amide and N-hydroxyethylated fatty imidazoline; in terms of molecular structure, the hydrophilic group composition mainly in chain form is changed to a composition mainly in five-membered heterocyclic ring form; the adsorption groups of the emulsifier molecules on the oil/water interface are changed from mainly in chain form to toroidal adsorption of five-membered heterocyclic ring groups, so that it is easier to achieve full coverage on the droplets of the inverse emulsion, the repulsive force of the constructed interface film is increased, the tendency of agglomeration and flocculation between the emulsion droplets in a high-temperature environment can be reduced, and the emulsification stability is improved; at the same time, in the inverse emulsion drilling fluid, the adsorption capacity of the emulsifier composition on the solid phase surface
  • the emulsifier composition and oil-based/synthetic-based drilling fluid provided by the present invention have a temperature resistance of up to 200°C, a density of up to 2.4-2.8g/ cm3 , a salt water pollution resistance of more than 50%, and excellent drilling fluid rheological properties and sealing and plugging properties.
  • the use concentration is reduced by more than 30%, the emulsification stability is at the same level, and at the same time, the suspension capacity remains consistent, the plastic viscosity is reduced by 40%, and the rheological properties are greatly improved, which can significantly improve hydraulic efficiency, reduce circulating pressure loss, and increase mechanical drilling speed.
  • One aspect of the present invention provides an emulsifier composition, wherein the composition comprises: an effective component and a solvent, wherein the effective component comprises: di-fatty imidazoline amide, N-hydroxyethylated fatty imidazoline and maleated fatty acid, and the solvent comprises oil (environmentally friendly solvent oil) and/or alcohol ether.
  • the effective component comprises: di-fatty imidazoline amide, N-hydroxyethylated fatty imidazoline and maleated fatty acid
  • the solvent comprises oil (environmentally friendly solvent oil) and/or alcohol ether.
  • the di-fatty imidazoline amide is formed by reacting natural plant fatty acids rich in unsaturated bonds (oleic acid, linoleic acid, linolenic acid, palmitic acid and rosin acid, etc.) with polyethylene polyamines, through amidation reaction and cyclization reaction under high temperature conditions.
  • the plant fatty acid is tall oil fatty acid (Shanghai Lisen Chemical Co., Ltd., the same below) rich in oleic acid, linoleic acid and rosin acid and diethylenetriamine (Nanjing Gutian Chemical), through amidation reaction and cyclization reaction under high temperature conditions to obtain di-fatty imidazoline amide.
  • the molar ratio of the plant fatty acid (in terms of the molar number of fatty carboxylic acid, the same below) to diethylenetriamine is greater than 2:1, preferably 2-2.3:1, and more preferably 2.1:1; wherein the molar number of fatty carboxylic acid in the plant fatty acid (preferably tall oil fatty acid) is determined by measuring its acid value.
  • the temperature of the amidation reaction is 160°C-180°C, and the temperature of the cyclization reaction under the high temperature condition is 200°C-240°C.
  • the N-hydroxyethylated fatty imidazoline is formed by reacting natural plant fatty acids rich in unsaturated bonds (oleic acid, linoleic acid, linolenic acid, palmitic acid and abietic acid, etc.) with hydroxyethylethylenediamine through amidation reaction and cyclization reaction; wherein the molar ratio of the plant fatty acid to hydroxyethylethylenediamine is 1:1 or more, preferably 1-1.6:1, and more preferably 1.1:1.
  • the reaction temperature of the amidation is 160°C-180°C
  • the temperature of the cyclization reaction is 200°C-240°C;
  • the plant fatty acid and ethylenediamine are reacted to form an aliphatic imidazoline through an amidation reaction and a cyclization reaction, and then reacted with ethylene oxide to generate a hydroxyethyl or terminal hydroxyethyl polyoxyethylene group on the nitrogen atom of the aliphatic imidazoline to form an N-hydroxyethylated aliphatic imidazoline.
  • the molar ratio of the plant fatty acid to ethylenediamine is 1:1 or more, preferably 1-1.6:1, and more preferably 1.1:1.
  • the temperature of the amidation reaction is 160°C-180°C, and the temperature of the cyclization reaction is 200°C-240°C; the molar ratio of the aliphatic imidazoline to ethylene oxide is 1:1 or more, preferably 1-1.6:1, and more preferably 1.1:1, and the reaction temperature is 80-100°C (reacting with ethylene oxide).
  • the tall oil fatty acid rich in oleic acid, linoleic acid and rosin acid and hydroxyethylethylenediamine is formed by amidation and cyclization of the drug group.
  • the temperature of the amidation reaction is 160°C-180°C
  • the temperature of the cyclization reaction is 200°C-240°C.
  • the maleated fatty acid is a natural unsaturated fatty acid modified by maleic anhydride generated by diene synthesis or ene reaction of natural plant fatty acids rich in unsaturated bonds (oleic acid, linoleic acid, linolenic acid, palmitic acid and rosin acid, etc.) and maleic anhydride (maleic anhydride) under high temperature conditions, wherein the mass ratio of the plant fatty acid to maleic anhydride is 10:1-3, preferably 10:2.5.
  • the maleated tall oil fatty acid is prepared by diene synthesis or ene reaction of tall oil fatty acids rich in oleic acid, linoleic acid and rosin acid and maleic anhydride (Sinopharm Group) under high temperature conditions.
  • the mass ratio of the tall oil fatty acid to maleic anhydride is 10:1-3, preferably 10:2.5, and the temperature of the diene synthesis or ene reaction is 200°C-240°C.
  • the reaction of maleic acid with linoleic acid having conjugated double bonds is diene synthesis, and the reaction of maleic acid with oleic acid containing a single double bond is ene reaction.
  • the oil is an environmentally friendly solvent oil, which is a dearomatized solvent oil with alkanes and cycloalkanes as main components, preferably environmentally friendly solvent oil D120 (Luoyang Xinling Petrochemical Co., Ltd.).
  • the alcohol ether is a polyol ether polar organic solvent, preferably dipropylene glycol monomethyl ether (Shandong Kejian Chemical Co., Ltd.).
  • the di-fatty imidazoline amide in the emulsifier composition, is 60-80 parts by mass, the N-hydroxyethylated fatty imidazoline is 10-15 parts by mass, and the maleated fatty acid is 5-30 parts by mass.
  • the di-fatty imidazoline amide is 75-80 parts by mass, the N-hydroxyethylated fatty imidazoline is 10-15 parts by mass, and the maleated fatty acid is 10-15 parts by mass.
  • the volume ratio of the oil to the alcohol ether is 40:60-60:40, and more preferably 55:45.
  • the mass ratio of the active ingredient to the solvent is 70:30-90:10, and more preferably 85:15.
  • a drilling fluid which is an oil-based or synthetic-based drilling fluid, comprising the above-mentioned emulsifier composition. Further, it also comprises a base oil, an aqueous phase (usually a calcium chloride solution, dispersed into the oil phase to form an oil-in-water emulsion), organophilic modified clay minerals, flow pattern regulators, polymer thickeners, alkalinity regulators, activity controllers, organophilic modified humic acid fluid loss reducers and weighting materials, etc.
  • a base oil usually a calcium chloride solution, dispersed into the oil phase to form an oil-in-water emulsion
  • organophilic modified clay minerals usually a calcium chloride solution, dispersed into the oil phase to form an oil-in-water emulsion
  • flow pattern regulators usually a calcium chloride solution
  • polymer thickeners usually a calcium chloride solution
  • alkalinity regulators alkalinity regulators
  • activity controllers organophilic modified humic acid fluid loss reducer
  • the ratio of the amount of the emulsifier composition added to the total volume of the base oil and the water phase in the drilling fluid is 50-80 g/L. That is, relative to the total volume of 1 L, the amount of the emulsifier composition added is 50-80 g.
  • the volume ratio of the base oil to the water phase may be 85:15-95:5.
  • the organophilic modified clay mineral is 25-50g
  • the flow pattern regulator is 10-20g
  • the polymer thickener is 5-15g
  • the alkalinity regulator is 30-50g
  • the organophilic modified humic acid fluid loss reducer is 30-70g.
  • the weighting material such as barite and micro manganese compounded in a certain proportion is used to increase the density to the required density
  • the API grade barite of 4.35g/ cm3 can be used to increase the density of the drilling fluid to 2.6g/ cm3
  • the API grade barite of 4.35g/ cm3 can be used to increase the density of the drilling fluid to 2.6g/ cm3
  • micro manganese commercial MicroMax
  • the base oil is diesel, mineral oil or an artificially synthesized environmentally friendly base oil with ultra-low aromatic content.
  • the base oil used in some embodiments of the present invention is 0# diesel, light white oil and an artificially synthesized environmentally friendly solvent oil ESCAID 110 (produced by ExxonMobil Chemical Company).
  • the activity control agent is at least one of calcium chloride, calcium ammonium nitrate, sodium formate, and potassium formate, preferably calcium chloride, which can be a 20%-30% calcium chloride solution, and an aqueous phase and an activity control agent are provided at the same time.
  • the present invention relates to the use of the above-mentioned drilling fluid in deep oil and gas resources and unconventional oil and gas wells. applications under development.
  • the main component of the emulsifier composition provided by the invention is transformed from conventional fatty acid polyamide to fatty imidazoline amide and N-hydroxyethylated fatty imidazoline.
  • the hydrophilic group mainly composed of chains is changed to a composition mainly composed of five-membered heterocyclic rings.
  • the adsorption groups of the emulsifier molecules on the oil/water interface are changed from mainly chain distribution to annular adsorption of five-membered heterocyclic rings.
  • the adsorption capacity of the emulsifier composition on the solid phase surface of the weighting material particles is improved, and the surface lipophilic wetting performance is relatively improved, which is conducive to reducing the surface friction of the weighting material and the tendency of aggregation at high temperature, and improving the rheology of the oil-based/synthetic-based drilling fluid under the condition of high solid content and the stability of the oil-based wetting reversal of the solid phase particle surface.
  • Emulsifier composition The oil-based drilling fluid emulsifier di-fatty imidazoline amide (IMA) involved in the present invention is different in components of the emulsifier.
  • the emulsifier compositions are respectively denoted as IMA(a), IMA(b), IMA(c), etc. for comparison and explanation.
  • Organophilic modified clay minerals high temperature resistant oil-based drilling fluid viscosity increasing agent organophilic modified hexagonalite (BT38, Elementis) is used, the main component of which is hexagonalite modified by a long carbon chain quaternary ammonium salt cationic surfactant.
  • Alkalinity regulator Use commercially available calcium hydroxide or calcium oxide.
  • Oil-based drilling fluid polymer thickener polyolefin block copolymer (referred to as PRM) is used, the main composition of which is a triblock polymer of (substituted) styrene homopolymer segment-olefin copolymer segment-(substituted) styrene.
  • PRM Oil-based drilling fluid polymer thickener polyolefin block copolymer
  • the commercial product selected is G 1701 produced by Kraton.
  • Organophilic modified lignite-based fluid loss reducer oil-based drilling fluid fluid loss reducer fatty amide lignite (denoted as OLG, Shak Oil Technology Service Company organic lignite BLACKLIGO 400) is used, the main component of which is a fatty amidated lignite product prepared by the reaction of long-chain fatty amines with humic acid in lignite.
  • OLG Shak Oil Technology Service Company organic lignite BLACKLIGO 400
  • Flow pattern regulator A flow pattern regulator for oil-based drilling fluid, polymerized amide fatty acid (denoted as MOD), is used, the main component of which is a polyamide fatty acid formed by polycondensation of polyamine and mixed polybasic fatty acid (dibasic fatty acid and tribasic fatty acid), and is prepared according to CN201310684666.9. The entire contents of CN201310684666.9 are hereby introduced into this document.
  • Weighting materials Mainly commercially available API barite and ultrafine manganese powder Micromax (Shanghai Aiken).
  • Di-aliphatic imidazoline amide, N-hydroxyethylated fatty imidazoline, and maleated fatty acid were prepared according to the following methods:
  • a four-necked flask was installed on an automatic lifting oil bath, and equipped with a thermometer, a stirrer, a vacuum distillation head (connected to a water separator) and a polytetrafluoro nitrogen pipeline.
  • the ratio of the molar number of fatty carboxylic acid in tall oil fatty acid to the molar number of diethylenetriamine was 2.1:1, and the fatty acid was slightly excessive.
  • the molar number of fatty carboxylic acid in tall oil fatty acid was determined by measuring its acid value.
  • Tall oil fatty acid (Shanghai Lisen Chemical Co., Ltd.) was added to the four-necked flask, heated to 75 ⁇ 5°C under nitrogen protection, and a measured amount of diethylenetriamine (Nanjing Gutian Chemical) was added, and the temperature was raised under stirring. Stop nitrogen flow, react at 170°C ⁇ 5°C for 3.5-4.0h, amidation reaction occurs, and monitor and record the water output in the water separator; after the water output stabilizes, continue to heat to 240°C ⁇ 5°C, then carry out intramolecular dehydration cyclization reaction, control the vacuum degree at 0.06-0.09MPa, monitor and record the water output in the water separator, and react for 4.5-5.0h. When there is no more water in the water separator, pass nitrogen to purge the water vapor above the liquid surface of the reaction product, and cool to 80-90°C, discharge and cool to room temperature, and the resulting product is di-fatty imidazoline amide.
  • a four-necked flask was installed on an automatic lifting oil bath, and equipped with a thermometer, a stirrer, a vacuum distillation head (connected to a water separator) and a polytetrafluoroethylene nitrogen pipeline.
  • the materials were added in a ratio of 1.1:1 between the molar number of fatty carboxylic acid in tall oil fatty acid and the molar number of hydroxyethylethylenediamine, wherein the molar number of fatty carboxylic acid in tall oil fatty acid was 1.1:1.
  • the acid value is determined by calculation.
  • Stop nitrogen react at 170°C ⁇ 5°C for 3.5-4.0h, amidation reaction occurs, and monitor and record the water output in the water separator; after the water output stabilizes, continue to heat to 240°C ⁇ 5°C, and then carry out intramolecular dehydration cyclization reaction, control the vacuum degree at 0.06-0.09MPa, monitor and record the water output in the water separator, and react for 4.5-5.0h.
  • nitrogen is introduced to purge the water vapor above the liquid surface of the reaction product, and the reaction product is cooled to 80-90°C. The product is discharged and cooled to room temperature.
  • the obtained product is N-hydroxyethylated fatty imidazoline.
  • a three-necked flask is installed on an automatic lifting oil bath, and equipped with a thermometer and a condensing reflux device.
  • Tall oil fatty acid is added to the flask and heated to 70°C.
  • Maleic anhydride is added to the flask at a mass of 25% by mass based on the mass of tall oil fatty acid. After the addition, the mixture in the flask is heated to 220°C in stages, and maintained for about 5-6 minutes after reaching each design temperature.
  • the first heating temperature range is 70°C to 130°C; the second heating temperature range is 130°C to 160°C, the third heating temperature range is 160°C to 185°C; the fourth heating temperature range is 185°C to 205°C, and the fifth heating temperature range is 205°C to 220°C.
  • the reaction temperature is maintained at 220°C for 5 hours, and diene synthesis or ene reaction is carried out and completed.
  • the product is cooled to 80-90°C, discharged and cooled to room temperature, and the obtained product is maleated fatty acid.
  • the products obtained in Examples 1-3 were accurately weighed, and 17.6 parts by mass of a mixed solvent were added to 100 parts by mass of the mixture to make the concentration of the effective component about 85 wt %, wherein the volume ratios of environmentally friendly solvent oil D120 and dipropylene glycol methyl ether in the mixed solvent were 60:40 (Example 4), 55:45 (Example 5), 40:60 (Example 6), and 55:45 (Example 7), respectively.
  • Example 8 According to the proportion in Example 8, the products obtained in Examples 1-3 are accurately weighed, and 43 parts by mass of a mixed solvent (the mass ratio of the effective component to the solvent is 70:30) is added to 100 parts by mass of the mixture.
  • the concentration of the effective component is about 70wt%, wherein the volume ratio of environmentally friendly solvent oil D120 to dipropylene glycol methyl ether in the mixed solvent is 55:45.
  • Example 9 the products obtained in Examples 1-3 are accurately weighed, and 11 parts by mass of a mixed solvent (the mass ratio of the effective component to the solvent is 90:10) is added to 100 parts by mass of the mixture.
  • the concentration of the effective component is about 90wt%, wherein the volume ratio of environmentally friendly solvent oil D120 to dipropylene glycol methyl ether in the mixed solvent is 55:45.
  • the preparation procedure of the high temperature and high density oil-based/synthetic-based drilling fluid provided by the present invention is as follows:
  • the emulsifier compositions IMA(a), IMA(b), IMA(c), IMA(d), IMA(e), and IMA(f) in Examples 4-9 were respectively added into a white oil-in-water drilling fluid having an oil-water ratio of 90:10 and a density of 2.2 g/ cm3 , with the added amount being 50 g/L based on the total volume of oil and water.
  • the drilling fluid formula is: 204mL light white oil + emulsifier + 50g/L flow pattern regulator + 24mL CaCl 2 (20% salt solution) + 50g/L calcium hydroxide + 50g/L organophilic modified henkotite + 50g/L fluid loss reducer + 645g barite, the oil-water ratio is 90:10, and the density is 2.2g/cm 3.
  • the prepared drilling fluid is hot rolled at 150°C for 24h, and the performance of the drilling fluid before and after aging is tested according to the method recommended by GB/T 16783.2. The results are shown in Table 1 below.
  • the emulsifier composition disclosed in the present invention significantly increases the demulsification voltage after hot rolling aging.
  • the rheological properties of the drilling fluid are greatly improved, and the rheological properties before and after aging are relatively stable, which reduces the plastic viscosity, is more conducive to improving the mechanical drilling speed and reducing the circulating pressure loss.
  • the fatty acid polyamide emulsifier is added in an amount of 80g/L, and the emulsifier composition is added in an amount of 50g/L, which has the obvious characteristics of low dosage and high efficiency.
  • the content of maleated fatty acid is too high (Examples 7-9), the rheological property of the drilling fluid before aging is obviously too high, and with the increase of its added concentration (Example 9, the content of effective component is 90wt%), the rheological property after aging is obviously increased, and the static shear force is relatively high, and the development trend is relatively large (Example 9, the static shear force of 10s is 19.6Pa, and the static shear force of 10min reaches 28.8Pa); while the added concentration is low (Example 8, the content of effective component is 70wt%), the demulsification voltage of the drilling fluid is relatively low, and it is reduced to 683V after aging, and the required amount of emulsifier composition is obviously insufficient. Moreover, the effective content of the emulsifier composition is relatively low, which not only increases the amount added during application, but also increases unnecessary solvent costs and production and transportation costs.
  • the drilling fluid prepared with the emulsifier IMA (c) in Example 6 was hot-rolled at 150°C, 180°C, 200°C, and 220°C for 24 hours, and 5-15 g/L of polymer thickener was added to the drilling fluid aged at 180°C-220°C.
  • the performance of the drilling fluid before and after aging was tested according to the method recommended by GB/T 16783.2. The results are shown in Table 2.
  • the oil-based drilling fluid prepared with the emulsifier composition of the present invention maintains sufficient high-temperature emulsification stability under the condition of 150°C-220°C.
  • the rheology of the oil-based drilling fluid decreases and the filtration loss increases, which is mainly due to the attenuation of the high-temperature effect of the material providing suspension capacity in the drilling fluid.
  • the rheology of the drilling fluid is effectively maintained or increased, and the emulsification stability can be slightly improved, and the high-temperature and high-pressure filtration loss is relatively reduced. This is mainly due to the special structure of the triblock of the polymer thickener, which increases the viscosity of the base oil after being dissolved in the base oil and strengthens the grid structure in the drilling fluid.
  • Example 10 The amount of emulsifier composition IMA (c) was increased to 80 g/L, and a diesel-water drilling fluid with a density of 2.4 g/ cm3 was prepared.
  • the formula was: (oil-water ratio was 85:15): 204 mL 0# diesel + 80 g/L emulsifier IMA (c) + 36 mL CaCl2 (20% brine) + 20 g/L organophilic modified hanctolite + 30 g/L CaO + 5 g/L flow pattern regulator + 40 g/L organophilic modified humic acid fluid loss reducer + barite powder (weighted to 2.4 g/cm3).
  • the drilling fluid was hot-rolled at 160°C for 16 hours and then contaminated with 10%-80% composite brine (200 g/L sodium chloride + 100 g/L calcium chloride) of the drilling fluid volume.
  • 10%-80% composite brine 200 g/L sodium chloride + 100 g/L calcium chloride
  • the intrusion of high-mineralized salt water has a significant impact on the performance of oil-based drilling fluid.
  • the performance of the drilling fluid changes less with a lower amount of intrusion.
  • the salt water concentration is added to 30.0%, the drilling fluid thickens slightly.
  • the contamination reaches 50.0%, the viscosity increases significantly.
  • the contamination reaches 80.0%, the drilling fluid becomes seriously thickened, and the demulsification voltage reaches 176V. No water separation occurs, and the oil-in-water drilling fluid state is maintained.
  • the diesel-in-water drilling fluid developed in this paper can maintain a stable state under high contamination conditions, indicating that the drilling fluid has a high ability to resist salt water contamination. In terms of fluidity, it can still maintain a good flow state when the contamination amount is 30.0%-50.0%.
  • Example 11 (oil-water ratio is 90:10): 216 mL 0# diesel + 80 g/L emulsifier IMA (c) + 24 mL CaCl 2 (20% brine) + 25 g/L organophilic modified hanktoite + 35 g/L CaO + 15 g/L flow pattern regulator + 30 g/L organophilic modified humic acid fluid loss reducer + barite powder (weighted to a density of 2.4 g/cm 3 ) + micro manganese ore powder (weighted to a density of 2.6 g/cm 3 )
  • Example 12 (oil-water ratio of 95:5): 228 mL ESCAID 110 + 80 g/L emulsifier IMA (c) + 12 mL CaCl 2 (20% brine) + 18 g/L organophilic modified hanktoite + 35 g/L CaO + 15 g/L flow pattern regulator + 70 g/L organophilic modified humic acid fluid loss reducer + barite powder (weighted to a density of 2.4 g/cm 3 ) + micro manganese ore powder (weighted to a density of 2.8 g/cm 3 )
  • Drilling fluids were prepared according to Examples 11 and 12 and subjected to rolling aging at 160°C for 16 hours.
  • the drilling fluid properties after hot rolling are shown in Table 4.

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Abstract

本发明公开了一种乳化剂组合物及钻井液与应用。所述乳化剂组合物包括：有效组分和溶剂，其中，所述有效组分包括：双脂肪基咪唑啉酰胺、N-羟乙基化脂肪基咪唑啉和马来化脂肪酸，所述溶剂包括油和/或醇醚。本发明提供的乳化剂组合物及油基/合成基钻井液，抗温能力可达220℃，密度高达2.4-2.8g/cm3，抗盐水污染可到50％以上，钻井液流变性、致密封堵性能优良。

Description

乳化剂组合物及钻井液与应用
相关申请的交叉引用
本申请要求2022年11月11日提交的中国专利申请202211411010.5的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及油基/合成基钻井液的技术领域，具体涉及一种乳化剂及钻井液与应用。
背景技术
在油气资源勘探开发过程中，通过钻井技术，形成油气开采的必需的通道，是实现油气资源资源利用的第一阶段。因此，钻井技术对于油气资源高效开发具有决定性意义。在石油钻井工程中，钻井液能够携带岩屑、润滑钻具、冷却钻头等重要作用，被誉为“钻井工程的血液”。
油基/合成基钻井液是一类重要的钻井液类型，与水基钻井液相比，具有更好的抑制性、润滑性、高温稳定性、抗污染性、储层保护等优势，在泥页岩、巨厚盐膏层、页岩储层、高温深层钻井过程中应用越来越广泛，是我国当前深层油气资源、页岩油气资源等领域非常具有发展潜力的技术领域。
油包水乳状液的稳定性是油基钻井液(油包水钻井液)的基础，是油基钻井液的关键核心。在深井超深井和页岩气长水平井钻井过程中，油包水乳状液的稳定性关系到钻井施工的成功与否。
常用乳化剂包括司盘80、脂肪酸、马来化脂肪基聚酰胺、环烷酸酰胺、十二烷基苯磺酸钙、松香酸钠等。CN201880053201.4公开了采用氨基酰胺用作乳化剂，并基于层状双氢氧化物作为流变改进剂，制备了油基钻井液；CN201610825832.6公开了基于二聚酸和长链烷基单胺制备了油基乳化剂，并提 供了一种油基钻井液；CN201711082088.6公开了由松香酸、白油、碱和烷基磺酸盐组成的抗高温油基钻井液用的乳化剂，抗温200℃；CN201810900379.X公开了一种以腰果酚和环氧氯丙烷反应得到缩水甘油醚，再与二甲胺生成叔胺,经与1,3-丙磺酸内酯经反应得到乳化剂基料，具有较强的抗Ca2+、Mg2+等二价离子的能力，防止在高温条件下的矿化。CN201711453619.8公开了以妥尔油酸、顺丁烯二酸酐、第一催化剂以及溶剂加热反应，得到妥尔油酸-顺酐加合物；在妥尔油酸-顺酐加合物中加入第二催化剂，加热至反应所需的温度后加入羟乙基乙二胺，继续加热反应一段时间，得到所述的高效油基钻井液乳化剂。CN201880084653.9公开了利用废弃植物油制备一种烷基酯类乳化剂，用于油基钻井液的配制。用上述乳化剂配制的油基/合成基钻井液，塑性粘度较高、高温稳定性较低、抗盐水污染能力较差，不能更好地满足复杂地质条件深井超深井安全高效钻井的需求。
随着深井超深井和页岩油页岩气等非常规油气井的开发，对油基/合成基钻井液的需求也越来越多。这些井的井下温度和压力较高，并且存在高压盐水层等复杂问题，不仅要求钻井液在高温下具有良好的稳定性，而且还要具有良好的流变性、抗污染能力等要求，亟需一种高性能的乳化剂及相应的油基/合成基钻井液。
发明内容
本发明旨在提供一种适用于油基/合成基钻井液的高性能乳化剂组合物，具有稳定的化学结构，能有效提高超深井油基/合成基钻井液的乳化稳定性、抗温稳定性和抗污染性能，并能显著改善钻井液的流变性，以至少部分地解决现有技术的钻井液在高温高压、巨厚盐膏层、高矿化度复合盐水层条件下存在的技术缺陷。
作为本发明的一个方面，涉及一种乳化剂组合物，其中，所述组合物包括：有效组分和溶剂，其中，所述有效组分包括：双脂肪基咪唑啉酰胺、N-羟乙基化脂肪基咪唑啉和马来化脂肪酸，所述溶剂包括油(环保型溶剂油)和/或醇醚。
作为本发明的另一个方面，涉及一种钻井液，其中，所述钻井液包括上述的 乳化剂组合物。进一步的，所述钻井液为油基或合成基钻井液，还包括基础油、水相(通常为氯化钙溶液，分散到油相中形成油包水乳状液)、亲有机改性黏土矿物、流型调节剂、聚合物增稠剂、碱度调节剂、活度控制剂、亲有机改性腐殖酸降滤失剂和加重材料。
作为本发明的又一个方面，涉及上述钻井液在深层油气资源和非常规油气井的开发中的应用。
本发明提供的乳化剂组合物的主成分从常规脂肪酸聚酰胺为主，转型到双脂肪基咪唑啉酰胺和N-羟乙基化脂肪基咪唑啉为主；在分子结构上，将亲水基团以链状为主的组成，改变为以五元杂环为主的组成；乳化剂分子在油/水界面上的吸附基团由链状分布为主，改变为以五元杂环基团的环面状吸附，在逆乳状液的液滴上更容易达到全面覆盖，构筑的界面膜的斥力得到增加，能够在高温环境中降低乳化液滴之间聚结絮凝的趋势，提高乳化稳定性；同时，在逆乳化钻井液中，乳化剂组合物在加重材料颗粒的固相表面吸附能力得到提升，表面亲油润湿性能也相对提升，有利于降低加重材料的表面摩擦和高温下聚并的趋势，改善高固相含量条件下油基/合成基钻井液的流变性和固相颗粒表面油性润湿翻转的稳定性。
本发明提供的乳化剂组合物及油基/合成基钻井液，抗温能力可达200℃，密度高达2.4-2.8g/cm3，抗盐水污染可到50％以上，钻井液流变性、致密封堵性能优良。在相同条件下，与常规脂肪基聚酰胺类乳化剂相比，使用浓度降低30％以上，乳化稳定性到同一水平，同时，悬浮能力保持一致，塑性粘度降低40％，流变性得到大幅度改善，可以显著提高水力效率、降低循环压耗、提高机械钻速。
具体实施方式
为了使发明目的、技术方案和效果更加清晰，结合具体实施例，对本发明进行进一步的详细说明。然而，应当理解可以以多种形势实现本发明，而不应被此处阐述的实施例所限制。相反，提供这些实施例是为了更加清晰透彻地理解本发明，并且能够将本发明的技术思路清楚地介绍给本领域的技术人员。
本发明的一个方面，提供了一种乳化剂组合物，其中，所述组合物包括：有效组分和溶剂，其中，所述有效组分包括：双脂肪基咪唑啉酰胺、N-羟乙基化脂肪基咪唑啉和马来化脂肪酸，所述溶剂包括油(环保型溶剂油)和/或醇醚。
在至少一个实施例中，所述双脂肪基咪唑啉酰胺是通过富含不饱和键的(油酸、亚油酸、亚麻酸、棕榈酸和松香酸等)天然植物脂肪酸与多乙撑基多胺，经过酰胺化反应和高温条件下环化反应形成。优选所述植物脂肪酸为富含油酸、亚油酸和松香酸的妥尔油脂肪酸(上海立森化工有限公司，下同)与二乙烯三胺(南京古田化工)，经过酰胺化反应和高温条件下环化反应，制得双脂肪基咪唑啉酰胺。其中，所述植物脂肪酸(以脂肪基羧酸摩尔数计，下同)与二乙烯三胺的摩尔比大于2:1，优选为2-2.3：1，更优选为2.1:1；其中，所述植物脂肪酸(优选妥尔油脂肪酸)中脂肪基羧酸摩尔数通过测定其酸值确定。所述酰胺化反应的温度为160℃-180℃，所述高温条件下环化反应的温度为200℃-240℃。
在至少一个实施例中，所述N-羟乙基化脂肪基咪唑啉是通过富含不饱和键的(油酸、亚油酸、亚麻酸、棕榈酸和松香酸等)天然植物脂肪酸与羟乙基乙二胺，经过酰胺化反应和环化反应形成；其中，所述植物脂肪酸与羟乙基乙二胺的摩尔比为1:1以上，优选为1-1.6:1，更优选为1.1:1。所述酰胺化的反应温度为160℃-180℃，所述环化反应的温度为200℃-240℃；
或者，通过所述植物脂肪酸与乙二胺，经酰胺化反应和环化反应形成脂肪基咪唑啉，再与环氧乙烷进行反应，在脂肪基咪唑啉的氮原子上生成羟乙基或端羟乙基聚氧乙烯的基团，形成N-羟乙基化脂肪基咪唑啉。其中，所述植物脂肪酸与乙二胺的摩尔比为1:1以上，优选为1-1.6:1，更优选为1.1:1。所述酰胺化反应的温度为160℃-180℃，所述环化反应的温度为200℃-240℃；所述脂肪基咪唑啉与环氧乙烷的摩尔比为1:1以上，优选为1-1.6:1，更优选为1.1:1，所述反应的温度为80-100℃(与环氧乙烷进行反应)。
优选为所述富含油酸、亚油酸和松香酸的妥尔油脂肪酸与羟乙基乙二胺(国 药集团)经酰胺化反应和环化反应形成的N-羟乙基化脂肪基咪唑啉。所述酰胺化反应的温度为160℃-180℃，所述环化反应的温度为200℃-240℃。
在至少一个实施例中，所述马来化脂肪酸是通过富含不饱和键的(油酸、亚油酸、亚麻酸、棕榈酸和松香酸等)天然植物脂肪酸与马来酸酐(顺丁烯二酸酐)，在高温条件下发生双烯合成或烯反应，而生成的马来酸酐改性天然不饱和脂肪酸，其中，所述植物脂肪酸与马来酸酐的质量比为10：1-3，优选为10:2.5。优选为所述富含油酸、亚油酸和松香酸的妥尔油脂肪酸与马来酸酐(国药集团)在高温条件下发生双烯合成或烯反应而制成的马来化妥尔油脂肪酸。其中，所述妥尔油脂肪酸与马来酸酐的质量比为10：1-3，优选为10:2.5，所述双烯合成或烯反应的温度为200℃-240℃。其中，马来酸与具有共轭双键的亚油酸反应为双烯合成，马来酸与含有单个双键的油酸反应为烯反应。
在至少一个实施例中，所述油为环保型溶剂油，是烷烃、环烷烃为主要组分的脱芳烃溶剂油，优选为环保溶剂油D120(洛阳新岭石油化工有限公司)。
在至少一个实施例中，所述醇醚是多元醇醚类极性有机溶剂，优选为二丙二醇单甲醚(山东科建化工有限公司)。
在至少一个实施例中，所述乳化剂组合物中，双脂肪基咪唑啉酰胺为60-80质量份，N-羟乙基化脂肪基咪唑啉为10-15质量份，马来化脂肪酸为5-30质量份。优选地，双脂肪基咪唑啉酰胺为75-80质量份，N-羟乙基化脂肪基咪唑啉为10-15质量份，马来化脂肪酸为10-15质量份。
在至少一个实施例中，所述溶剂中，所述油与醇醚的体积比为40：60-60：40，进一步优选为55：45。
在至少一个实施例中，所述乳化剂组合物中，有效组分与溶剂的质量比为70：30-90：10，进一步优选为85：15。
作为本发明的另一个方面，涉及一种钻井液，为油基或合成基钻井液，包括上述的乳化剂组合物。进一步的，还包括基础油、水相(通常为氯化钙溶液，分 散到油相中形成油包水乳状液)、亲有机改性黏土矿物、流型调节剂、聚合物增稠剂、碱度调节剂、活度控制剂、亲有机改性腐殖酸降滤失剂和加重材料等。
在至少一个实施例中，油基/合成基钻井液中，所述乳化剂组合物的加入量与所述钻井液中基础油与水相的总体积的比值为50-80g/L。即，相对于1L的总体积，所述乳化剂组合物的加入量为50-80g。
在至少一个实施例中，所述基础油与水相的体积比可以为85：15-95：5。
在至少一个实施例中，以基础油和水相总体积1L计，亲有机改性粘土矿物为25-50g，流型调节剂为10-20g，聚合物增稠剂为5-15g，碱度调节剂为30-50g，亲有机改性腐殖酸降滤失剂为30-70g。在上述组成基础上，用按一定比例复合的重晶石、微锰等加重材料加重至所需密度，例如用4.35g/cm3的API级重晶石可以将钻井液密度加重到2.6g/cm3；或者用4.35g/cm3的API级重晶石可以将钻井液密度加重到2.6g/cm3后用微锰(商品MicroMax)在将钻井液密度增加至2.8g/cm3。
在至少一个实施例中，所述基础油为柴油、矿物油或人工合成的超低芳烃含量的环保型基础油。本发明一些实施例中所用的基础油为0#柴油、轻质白油和人工合成的环保型溶剂油ESCAID 110(埃克森美孚化工公司生产)。
在本发明的一些实施方式中，所述亲有机改性粘土矿物为亲有机改性的汉克托石(BT38)；所述流型调节剂为多聚酰胺基脂肪酸(MOD)；所述碱度调节剂为氢氧化钙或氧化钙；所述聚合物增稠剂为的聚烯烃嵌段聚合物(PRM)；所述亲有机改性腐殖酸降滤失剂为亲有机改性褐煤类降滤失剂(OLG)；所述加重材料为重晶石(钻井液密度加重至2.4g/cm3)，微锰(钻井液密度由2.4g/cm3加重至2.6-2.8g/cm3)。活度控制剂为氯化钙、硝酸铵钙、甲酸钠、甲酸钾中的至少一种，优选为氯化钙，可以为20％-30％的氯化钙溶液，同时提供水相和活度控制剂。
作为本发明的又一个方面，涉及上述钻井液在深层油气资源和非常规油气井 的开发中的应用。
本发明提供的乳化剂组合物的主成分从常规脂肪酸聚酰胺为主，转型到脂肪基咪唑啉酰胺和N-羟乙基化脂肪基咪唑啉为主，在分子结构上，将亲水基团以链状为主的组成改变为以五元杂环为主的组成，乳化剂分子在油/水界面上的吸附基团由链状分布为主改变为以五元杂环基团的环面状吸附，在逆乳状液的液滴上更容易达到全面覆盖，构筑的界面膜的斥力得到增加，能够在高温环境中降低乳化液滴之间聚结絮凝的趋势，提高乳化稳定性；同时，在逆乳化钻井液中，乳化剂组合物在加重材料颗粒的固相表面吸附能力得到提升，表面亲油润湿性能也相对提升，有利于降低加重材料的表面摩擦和高温下聚并的趋势，改善高固相含量条件下油基/合成基钻井液的流变性和固相颗粒表面油性润湿翻转的稳定性。
下面采用具体实施例对本发明进行详细阐述，在对本发明具体实施例做详细阐述之前，对本发明中所采用的具体材料进行说明：
乳化剂组合物：本发明所涉及的油基钻井液乳化剂双脂肪基咪唑啉酰胺(记作IMA)，为对比说明乳化剂的组分不同，乳化剂组合物分别记作IMA(a)、IMA(b)、IMA(c)等。
亲有机改性粘土矿物：采用抗高温油基钻井液提粘剂亲有机改性汉克托石(BT38，Elementis海名斯德谦)，主要组分为长碳链季铵盐阳离子表面活性剂改性的汉克托石。
碱度调节剂：采用市售氢氧化钙或氧化钙。
聚合物增稠剂：采用油基钻井液聚合物增稠剂聚烯烃嵌段共聚物(记作PRM)，主要组成为(取代)苯乙烯均聚链段-烯烃共聚链段-(取代)苯乙烯的三嵌段式聚合物，选用商业化产品为科腾公司G 1701。
亲有机改性褐煤类降滤失剂：采用油基钻井液降滤失剂脂肪基酰胺褐煤(记作OLG，沙克石油技术服务公司有机褐煤BLACKLIGO 400)，主要组分为长链脂肪胺与褐煤中腐殖酸反应制备的脂肪基酰胺化褐煤产物。
流型调节剂：采用油基钻井液用流型调节剂聚合酰胺基脂肪酸(记作MOD)，主要组分为多元胺与混合多元脂肪酸(二元脂肪酸和三元脂肪酸)缩聚而成的多酰胺脂肪酸，按CN201310684666.9制备。在此将CN201310684666.9的全部内容引入本文。
加重材料：主要采用市售的API重晶石、超微锰粉Micromax(上海艾肯)。
双脂肪基咪唑啉酰胺、N-羟乙基化脂肪基咪唑啉、马来化脂肪酸分别按照以下方法制备：
实施例1
制备双脂肪基咪唑啉酰胺
在自动升降油浴上，安装四口烧瓶，并装配有温度计、搅拌器、减压蒸馏头(接在分水器)和聚四氟氮气管线。按照妥尔油脂肪酸中脂肪基羧酸摩尔数与二乙烯三胺摩尔数之比为2.1:1投料，脂肪酸稍过量，其中妥尔油脂肪酸中脂肪基羧酸摩尔数通过测定其酸值确定。向四口烧瓶中加入妥尔油脂肪酸(上海立森化工有限公司)，在氮气保护条件下，加热至75±5℃，加入计量的二乙烯三胺(南京古田化工)，搅拌条件下升温。停止通氮气，在170℃±5℃条件下反应3.5-4.0h，发生酰胺化反应，并监测记录分水器中的出水量；待出水量稳定后，继续升温至240℃±5℃，再进行分子内脱水环化反应，控制真空度在0.06-0.09MPa，监测记录分水器中出水量，反应4.5-5.0h。当分水器中无水增加时，通入氮气，吹扫反应产物液面上方的水蒸气，并冷却至80-90℃，出料并冷却至室温，所得产物即为双脂肪基咪唑啉酰胺。
实施例2
制备N-羟乙基化脂肪基咪唑啉
在自动升降油浴上，安装四口烧瓶，并装配有温度计、搅拌器、减压蒸馏头(接在分水器)和聚四氟氮气管线。按照妥尔油脂肪酸中脂肪基羧酸摩尔数与羟乙基乙二胺摩尔数之比为1.1:1投料，其中妥尔油脂肪酸中脂肪基羧酸摩尔数通 过测定其酸值来计算确定。向四口烧瓶中加入妥尔油脂肪酸(上海立森化工有限公司)，在氮气保护条件下，加热至75±5℃，加入计量的羟乙基乙二胺(南京古田化工)，搅拌条件下升温100-110℃，保持温度搅拌1.5h，使脂肪基羧酸与羟乙基乙二胺中胺基充分成盐，提高分子间酰胺化的效果。停止通氮气，在170℃±5℃条件下反应3.5-4.0h，发生酰胺化反应，并监测记录分水器中的出水量；待出水量稳定后，继续升温至240℃±5℃，再进行分子内脱水环化反应，控制真空度在0.06-0.09MPa，监测记录分水器中出水量，反应4.5-5.0h。当分水器中无水增加时，通入氮气，吹扫反应产物液面上方的水蒸气，并冷却至80-90℃，出料并冷却至室温，所得产物即为N-羟乙基化脂肪基咪唑啉。
实施例3
制备马来化脂肪酸
在自动升降油浴上，安装三口烧瓶，并装配有温度计、冷凝回流装置，向烧瓶中加入妥尔油脂肪酸，并将其加热到70℃，向烧瓶中加入按妥尔油脂肪酸质量计25％质量的马来酸酐，加完后将烧瓶中的混合物温度分阶段加热到220℃，并在达到每个设计温度后维持约5-6min时间。第一个加热温度范围是70℃至130℃；第二个加热温度范围是130℃至160℃，第三个加热温度范围是160℃至185℃；第四个加热温度范围是185℃至205℃，第五个加热温度范围是205℃至220℃。保持反应温度为220℃至5h，进行并完成双烯合成或烯反应，产物冷却至80-90℃，出料并冷却至室温，所得产物即为马来化脂肪酸。
实施例4：IMA(a)中有效组分包括双脂肪基咪唑啉酰胺：N-羟乙基化脂肪基咪唑啉：马来化脂肪酸＝75:10:15；其中，数据为质量比，下同；
实施例5：IMA(b)中有效组分包括双脂肪基咪唑啉酰胺：N-羟乙基化脂肪基咪唑啉：马来化脂肪酸＝75:15:10；
实施例6：IMA(c)中有效组分包括双脂肪基咪唑啉酰胺：N-羟乙基化脂肪基 咪唑啉：马来化脂肪酸＝80:15:5。
实施例7：IMA(d)中有效组分包括双脂肪基咪唑啉酰胺：N-羟乙基化脂肪基咪唑啉：马来化脂肪酸＝60:10:30。
实施例8：IMA(e)中有效组分包括双脂肪基咪唑啉酰胺：N-羟乙基化脂肪基咪唑啉：马来化脂肪酸＝60:10:30。
实施例9：IMA(f)中有效组分包括双脂肪基咪唑啉酰胺：N-羟乙基化脂肪基咪唑啉：马来化脂肪酸＝60:10:30。
按照实施例4-7中的比例，准确称取实施例1-3中所得产物，混合物按100质量份计，再加入17.6质量份的混合溶剂，使有效组分的浓度约为85wt％，其中，混合溶剂中环保溶剂油D120与二丙二醇甲醚的体积比分别为60：40(实施例4)，55：45(实施例5)，40：60(实施例6)，55：45(实施例7)。
按照实施例8中的比例，准确称取实施例1-3中所得产物，混合物按100质量份计，再加入43质量份的混合溶剂(有效组分与溶剂的质量比为70：30)，有效组分的浓度约为70wt％，其中，混合溶剂中环保溶剂油D120与二丙二醇甲醚的体积比为55：45。
按照实施例9中的比例，准确称取实施例1-3中所得产物，混合物按100质量份计，再加入11质量份的混合溶剂(有效组分与溶剂的质量比为90：10)，有效组分的浓度约为90wt％，其中，混合溶剂中环保溶剂油D120与二丙二醇甲醚的体积比为55：45。
本发明所提供的的高温高密度油基/合成基钻井液的制备程序如下：
(1)量取基础油，分别加入乳化剂、流型调节剂，在11000±300RPM(转/分)搅拌5-10min；
(2)量取氯化钙溶液，缓慢加入到上述基础油中，在11000±300RPM(转/分)搅拌25-30min；
(3)加入碱度调节剂、亲有机改性粘土矿物，在11000±300RPM(转/分) 搅拌10-15min；
(4)加入聚合物增稠剂，在11000±300RPM(转/分)搅拌10-15min；
(5)加入降滤失剂、封堵剂，在11000±300RPM(转/分)搅拌10-15min；
(6)加入加重材料，在11000±300RPM(转/分)搅拌30-45min。
1.乳化剂组合物对油基钻井液性能影响的评价测试
将实施例4-9中乳化剂组合物IMA(a)、IMA(b)、IMA(c)、IMA(d)、IMA(e)、，IMA(f)分别加入到油水比为90：10、密度为2.2g/cm3的白油包水钻井液中，加量以油水总体积计50g/L。
钻井液配方为：204mL轻质白油+乳化剂+50g/L流型调节剂+24mLCaCl2(20％盐溶液)+50g/L氢氧化钙+50g/L亲有机改性汉克托石+50g/L降滤失剂+645g重晶石，油水比为90：10，密度为2.2g/cm3。将配制的钻井液在150℃条件下热滚24h，按照GB/T 16783.2推荐方法测试钻井液老化前后的性能。结果见下表1。
表1乳化剂组合物的性能

由表1中结果可知，与对比例(常规脂肪酸聚酰胺类乳化剂)相比，本发明公开的乳化剂组合物，使得热滚老化后破乳电压显著升高。钻井液的流变性大幅度改善，并且老化前后的流变性较为稳定，降低塑性粘度，更有利于提高机械钻速、降低循环压耗。加量方面，脂肪酸聚酰胺类乳化剂加量的80g/L，乳化剂组合物的加量为50g/L，具有明显的低加量、高效能的特征。乳化剂组合物中，马来化脂肪酸的含量过高(实施例7-9)，钻井液老化前的流变性明显过高，并且随着其加量浓度的增加(实施例9，有效组分的含量为90wt％)，老化后的流变性明显升高，且静切力较高，且发展趋势增加较大(实施例9，10s静切力为19.6Pa，而10min静切力达到28.8Pa)；而加量浓度低(实施例8，有效组分的含量为70wt％)，钻井液的破乳电压较低，老化后降低至683V，所需的乳化剂组合物加量明显不足。而且，乳化剂组合物的有效含量较低，不仅增加应用时的加量，而且增加了不必要的溶剂成本和生产运输成本。
2.乳化剂组合物对油基钻井液抗温能力影响的评价测试
将采用实施例6中乳化剂IMA(c)配制的钻井液经150℃、180℃、200℃、220℃条件热滚24h，并在180℃-220℃老化的钻井液中加入5-15g/L聚合物增稠剂，在按照GB/T 16783.2推荐方法测试钻井液老化前后的性能。结果见表2。
表2乳化剂组合物IMA(c)的高温稳定性评价结果

据以上结果可知，用本发明的乳化剂组合物所配制的油基钻井液，在150℃-220℃条件下，保持了足够的高温乳化稳定性。同时，由于高温作用，油基钻井液的流变性降低，滤失量增加，主要是由于钻井液中提供悬浮能力的材料高温效果衰减所致。通过在高温老化后的钻井液中，加入聚合物增稠剂，钻井液的流变性得到有效地保持或增加，并且能够使乳化稳定性略有提高，高温高压滤失量相对降低。这主要是由于聚合物增稠剂三嵌段的特殊结构，溶于基础油后，增加了基础油的粘度，强化了钻井液中的网架结构。
3.油基钻井液抗盐水污染能力的评价测试
实施例10：将乳化剂组合物IMA(c)加量提高至80g/L，配制密度为2.4g/cm3的柴油包水钻井液，配方为：(油水比为85：15)：204mL 0#柴油+80g/L乳化剂IMA(c)+36mL CaCl2(20％盐水)+20g/L亲有机改汉克托石+30g/L CaO+5g/L流型调节剂+40g/L亲有机改性腐殖酸降滤失剂+重晶石粉(加重至2.4g/cm3)，将160℃高温热滚16h后的钻井液，分别进行钻井液体积的10％-80％复合盐水(200g/L氯化钠+100g/L氯化钙)的污染，并进行高温热滚后性能参数测试，测试结果见表3。
表3乳化剂组合物IMA(c)配制的钻井液抗污染性能评价结果
高矿化度盐水的侵入污染对油基钻井液的性能影响相当显著，较低量的侵入污染，钻井液的性能变化较小，当盐水浓度加到30.0％时，钻井液略有增稠现象，当污染量达到50.0％时，粘度升高幅度较大，当污染量达到80.0％时，钻井液出现严重增稠，破乳电压将至176V，未发生析水，仍保持油包水钻井液状态。本文所研制的柴油包水钻井液，在高污染量情况下，能保持稳定的状态，表明钻井液抗盐水污染能力较高，就流动性而言，污染量为30.0％-50.0％时仍能保持较好的流动状态。
超高密度油基/合成基钻井液及其性能
实施例11：(油水比为90:10)：216mL 0#柴油+80g/L乳化剂IMA(c)+24mL CaCl2(20％盐水)+25g/L亲有机改汉克托石+35g/L CaO+15g/L流型调节剂+30g/L亲有机改性腐殖酸降滤失剂+重晶石粉(加重至密度2.4g/cm3)+微锰矿粉(加重至密度2.6g/cm3)
实施例12：(油水比为95:5)：228mL ESCAID 110+80g/L乳化剂IMA(c)+12mL CaCl2(20％盐水)+18g/L亲有机改汉克托石+35g/L CaO+15g/L流型调节剂+70g/L亲有机改性腐殖酸降滤失剂+重晶石粉(加重至密度2.4g/cm3)+微锰矿粉(加重至密度2.8g/cm3)
按照实施例11和12配制钻井液，在160℃条件下滚动老化16h后，测试 钻井液热滚后后的钻井液性能，测试结果见表4。
表4乳化剂组合组配制的超高密度钻井液性能评价结果
对于本发明而言，应进一步说明的是，以上实施例仅用以说明本发明的技术方案而非限制性的。尽管参照实施例对本发明进行了详细说明，但本领域的技术人员应当理解，对本发明的技术方案进行修改或者等同替换，都不脱离本发明技术方案的技术思路和和范围，其均应涵盖在本发明的权利要求范围当中。

Claims (14)

  1. 一种乳化剂组合物，其特征在于，所述组合物包括：有效组分和溶剂，其中，所述有效组分包括：双脂肪基咪唑啉酰胺、N-羟乙基化脂肪基咪唑啉和马来化脂肪酸，所述溶剂包括油和/或醇醚。
  2. 根据权利要求1所述的组合物，其特征在于，所述双脂肪基咪唑啉酰胺是通过富含不饱和键的植物脂肪酸与多乙撑基多胺，经酰胺化反应和环化反应而形成；
    优选地，所述植物脂肪酸为富含油酸、亚油酸和松香酸的妥尔油脂肪酸，所述多乙撑基多胺为二乙烯三胺，其中，所述植物脂肪酸与二乙烯三胺的摩尔比大于2:1。
  3. 根据权利要求1所述的组合物，其特征在于，所述N-羟乙基化脂肪基咪唑啉是通过富含不饱和键的植物脂肪酸与羟乙基乙二胺，经酰胺化反应和环化反应形成；或
    通过所述植物脂肪酸与乙二胺，经酰胺化反应和环化反应形成脂肪基咪唑啉，再与环氧乙烷反应而形成；
    其中，所述植物脂肪酸为富含油酸、亚油酸和松香酸的妥尔油脂肪酸；
    优选，所述N-羟乙基化脂肪基咪唑啉是通过所述植物脂肪酸与羟乙基乙二胺，经酰胺化反应和环化反应而形成。
  4. 根据权利要求1所述的组合物，其特征在于，所述马来化脂肪酸是通过富含不饱和键的植物脂肪酸与马来酸酐，发生双烯合成或烯反应而生成；
    其中，所述植物脂肪酸为富含油酸、亚油酸和松香酸的妥尔油脂肪酸；
    优选地，所述马来化脂肪酸是通过所述妥尔油脂肪酸与马来酸酐进行双 烯合成或烯反应而制成的马来化妥尔油脂肪酸。
  5. 根据权利要求1-4中任意一项所述的组合物，其特征在于，所述醇醚是多元醇醚类极性有机溶剂，优选为二丙二醇单甲醚。
  6. 根据权利要求1-5中任意一项所述的组合物，其特征在于，所述组合物中，双脂肪基咪唑啉酰胺为60-80质量份，N-羟乙基化脂肪基咪唑啉为10-15质量份，马来化脂肪酸为5-30质量份；
    优选，双脂肪基咪唑啉酰胺为75-80质量份，N-羟乙基化脂肪基咪唑啉为10-15质量份，马来化脂肪酸为10-15质量份。
  7. 根据权利要求1-6中任意一项所述的组合物，其特征在于，所述溶剂中，油与醇醚的体积比为40：60至60：40，优选为55：45。
  8. 根据权利要求1-7中任意一项所述的组合物，其特征在于，所述组合物中，所述有效组分与溶剂的质量比为70：30至90：10，优选为85：15。
  9. 一种钻井液，其特征在于，所述钻井液包括权利要求1-8中任意一项所述的组合物。
  10. 根据权利要求9所述的钻井液，其特征在于，所述钻井液还包括基础油、水相、亲有机改性汉克托石、流型调节剂、聚合物增稠剂、碱度调节剂、活度控制剂、亲有机改性腐殖酸降滤失剂和加重材料。
  11. 根据权利要求10所述的钻井液，其特征在于，所述组合物的加入量与所述钻井液中基础油和水相的总体积的重量体积比为50-80g/L。
  12. 根据权利要求10或11所述的钻井液，其特征在于，所述基础油与水相的体积比为85：15至95：5；
    优选地，以所述基础油和水相的总体积为1L计，所述亲有机改性汉克托石为25-50g，流型调节剂为10-20g，聚合物增稠剂为5-15g，碱度调节剂为30-50g，亲有机改性腐殖酸降滤失剂为30-70g。
  13. 根据权利要求10-12中任意一项所述的钻井液，其特征在于，所述基础油为柴油、矿物油或人工合成的超低芳烃含量的环保型基础油；所述亲有机改性粘土矿物为亲有机改性的硅酸铝锂；所述流型调节剂为多聚酰胺基脂肪酸；所述碱度调节剂为氢氧化钙或氧化钙；所述聚合物增稠剂为聚烯烃嵌段聚合物；所述亲有机改性腐殖酸降滤失剂为亲有机改性褐煤类降滤失剂。
  14. 一种权利要求9-13中任意一项所述的钻井液在深层油气资源和非常规油气井开发中的应用。
PCT/CN2023/130496 2022-11-11 2023-11-08 乳化剂组合物及钻井液与应用 WO2024099365A1 (zh)

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