WO2023016329A1 - 一种液体减轻剂及其制备和应用 - Google Patents

一种液体减轻剂及其制备和应用 Download PDF

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Publication number
WO2023016329A1
WO2023016329A1 PCT/CN2022/110216 CN2022110216W WO2023016329A1 WO 2023016329 A1 WO2023016329 A1 WO 2023016329A1 CN 2022110216 W CN2022110216 W CN 2022110216W WO 2023016329 A1 WO2023016329 A1 WO 2023016329A1
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liquid
optionally
hollow microspheres
water
lightening agent
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PCT/CN2022/110216
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English (en)
French (fr)
Inventor
马春旭
房恩楼
宋维凯
肖伟
王伟
田野
侯亚伟
符军放
王学春
马小康
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中海油田服务股份有限公司
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Publication of WO2023016329A1 publication Critical patent/WO2023016329A1/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
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
    • C09K8/473—Density reducing additives, e.g. for obtaining foamed cement compositions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08—Flue dust, i.e. fly ash
    • C04B18/082—Cenospheres
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02—Treatment
    • C04B20/023—Chemical treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1018—Coating or impregnating with organic materials
    • C04B20/1022—Non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1055—Coating or impregnating with inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • This article relates to but not limited to the density adjustment of cement slurry, especially relates to but not limited to a liquid suspension alleviating agent for well cementing.
  • Cementing is a key link in the drilling process. It serves the purpose of supporting the casing and isolating the formation.
  • low-density cement slurry is usually used for cementing.
  • the waiting setting strength is low, which cannot meet the needs of rapid drilling in the next step; another method is to add hollow low-density materials such as hollow microspheres, floating beads, and expanded perlite to reduce the density of cement slurry, which can effectively reduce the water-cement ratio.
  • the embodiment of the present application provides a lightening agent that can reduce density and can be added in liquid form.
  • the suspension alleviating agent provided by the embodiment of the present application can be stored stably for a long time.
  • the liquefied addition of the lightening agent is realized, thereby realizing the flexible preparation of low-density cement slurry, and providing convenience for the preparation of low-density cement slurry on site.
  • the embodiment of the present application provides a liquid lightening agent, including water, hollow microspheres, high molecular polymer and dispersant, the weight ratio of the water, hollow microspheres, high molecular polymer and dispersant is (40 to 60 ):(26 to 56):(0.5 to 2):(0.5 to 2).
  • the liquid lightening agent further includes an antifreeze agent.
  • the weight ratio of the hollow microspheres to the antifreeze is (26 to 56): (0 to 10); the weight ratio of the hollow microspheres to the antifreeze It can also be (26 to 56):(5 to 10).
  • the high molecular polymer is selected from the group consisting of methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, starch, xanthan gum, gelatin, carrageenan, warm Any one or more of Len gum, polyvinyl alcohol, polymers with 2-acrylamide-2-methylpropanesulfonic acid (AMPS) as the main monomer, polyurethane thickener and polyacrylamide.
  • methyl cellulose carboxymethyl cellulose, hydroxyethyl cellulose, starch, xanthan gum, gelatin, carrageenan, warm Any one or more of Len gum, polyvinyl alcohol, polymers with 2-acrylamide-2-methylpropanesulfonic acid (AMPS) as the main monomer, polyurethane thickener and polyacrylamide.
  • AMPS 2-acrylamide-2-methylpropanesulfonic acid
  • the degree of polymerization of the methyl cellulose is 300-500.
  • the degree of polymerization of the carboxymethyl cellulose is 300-500.
  • the degree of polymerization of the hydroxyethyl cellulose is 200-400.
  • the gelatinization temperature of the starch is 80°C to 90°C.
  • the number average molecular weight of the xanthan gum is 6 million to 9 million.
  • the gelatin has a number average molecular weight of 50,000 to 100,000.
  • the number average molecular weight of the carrageenan is 200,000 to 400,000, and it is ⁇ -type.
  • the number average molecular weight of the Wenlun gum is 3 million to 5 million.
  • the degree of polymerization of the polyvinyl alcohol is 2400-3000.
  • the polymer whose main monomer is 2-acrylamide-2-methylpropanesulfonic acid (AMPS) has a number average molecular weight of 300,000 to 500,000.
  • the polyurethane thickener is a polyurethane thickener with improved associative rheology.
  • the polyacrylamide has a number average molecular weight of 16 million to 18 million.
  • the dispersant is selected from any one or more of polycarboxylic acid containing polyether side chains, sodium pyrophosphate, sodium lignosulfonate and sulfonated formaldehyde acetone polycondensate Various.
  • the antifreeze is selected from any one or more of alcohol compounds, fatty acid amide compounds and nitrite; in one embodiment provided by the application , the alcohol compound is selected from any one or more of methanol, ethylene glycol, isopropanol and diethylene glycol; in one embodiment provided by the application, the fatty acid amide compound is selected from two Any one or more of methylformamide, formamide and acetamide.
  • the salinity of the water is less than 1 g/L.
  • the hollow microspheres are selected from borosilicate hollow glass microspheres
  • the borosilicate hollow glass microspheres include but are not limited to HGS series products of Minnesota Mining and Manufacturing Corporation (3M Company), H series products of Sinosteel Maanshan, D series products of Zhongke Huaxing New Materials Co., Ltd. or Anhui HGS series products of Kaisheng Basic Materials Technology Co., Ltd.
  • the hollow glass microspheres are coated with nano-SiO 2 .
  • nano-SiO 2 coats the method for the hollow glass microspheres, comprising the steps of:
  • step 2) Adding the hollow microspheres treated in step 1) into a mixed liquid made of a weak base, an alcoholic solvent, and water, the ratio of the weak base, the alcoholic solvent, and water is in the volume ratio (0.05 to 0.20):(1 to 5):(2 to 10), the ratio of the hollow microspheres to the mixed liquid is the weight ratio (1 to 3):(20 to 50);
  • step 2) Mix the mixed liquid obtained in step 2) with the silicon source, and treat for 3h to 10h to obtain a mixture.
  • the weight ratio of the silicon source to the mixed liquid obtained in step 2) is (0.8 to 1.8): (10 to 30) ;
  • step 3 The solid-liquid separation of the mixture in step 3), washing and filtering with ethanol and water respectively, and calcining the solid material at 120°C to 150°C for 1h to 3h to obtain coated modified hollow microspheres .
  • the weak base includes any one or more of ammonia water, aluminum hydroxide, sodium acetate and sodium formate.
  • the alcohol solvent includes any one or more of methanol, ethanol, ethylene glycol and glycerol.
  • the silicon source includes any one or more of ethyl orthosilicate, tetramethylsilicate and butyl orthosilicate.
  • the present application provides the preparation method of the above-mentioned liquid lightening agent, comprising the following steps: adding the high molecular polymer into water, mixing uniformly, adding the hollow microspheres, mixing uniformly, adding a dispersant and antifreeze, mixing After uniformity, the liquid lightening agent is obtained.
  • the present application provides the application of the above-mentioned liquid lightening agent in cement slurry, the liquid lightening agent accounts for 8wt.% to 40wt.% (BWOC) of the cement slurry.
  • BWOC 80wt.% to 40wt.%
  • the performance of the cement slurry added with the liquid lightening agent of the present application is good, which can meet the needs of cementing operations.
  • the technical solution provided by this application can effectively prepare hollow microbead lightening materials with high solid phase content, which has the characteristics of low density and high strength.
  • the prepared low-density cement slurry has good performance and adjustable thickening time, which can satisfy most
  • the liquid addition of lightening agent can be realized to effectively reduce the density of cement slurry.
  • the free adjustment of cement slurry density from 1.1g/cm 3 to 1.6g/cm 3 is realized.
  • This application can form a stable liquid lightening agent, which can realize the liquid addition of solid lightening materials, and is suitable for LAS system (Liquid Additives System liquid additive automatic feeding system);
  • the solid content of the liquid lightening agent described in this application can reach 50% to 120% of the solvent, and the density is 0.35g/cm 3 to 0.90g/cm 3 . Adding a small amount can effectively reduce the density of cement slurry; it can adjust the cement slurry The density is between 1.1g/cm 3 and 1.6g/cm 3 , and the water-cement ratio of the cement slurry can be up to 2; the cement slurry containing the liquid lightening agent of this application has the characteristics of good anti-channeling performance, high strength, and short coagulation time.
  • the performance of the finished product is stable, the stability and temperature resistance are good, the floating phenomenon is weakened, and it can exist stably for no less than 3 months. Even if it loses stability, it can still return to its original state after high-speed stirring;
  • the production process only involves high-speed stirring, the process is simple and mature, the production speed is fast, and it is easy for industrial production.
  • the high molecular polymer is methyl cellulose, and the degree of polymerization of methyl cellulose is 300 to 500, purchased from Dacheng Yibo Chemical Co., Ltd.;
  • the high molecular polymer is carboxymethyl cellulose
  • the polymer of carboxymethyl cellulose is 300 to 500, purchased from Yibo Chemical Co., Ltd., Dacheng County.
  • the high molecular polymer is starch
  • the gelatinization temperature of starch is 80°C to 90°C, purchased from Shandong Gaoyi New Material Technology Co., Ltd.
  • the high molecular polymer is xanthan gum
  • the number average molecular weight of xanthan gum is 6 million to 9 million, purchased from Ordos Zhongxuan Biochemical Co., Ltd.
  • the high molecular polymer is gelatin
  • the gelatin has a number average molecular weight of 50,000 to 100,000, purchased from Henan Laimeiyuan Biotechnology Co., Ltd.
  • the high molecular polymer is carrageenan
  • the number average molecular weight of carrageenan is 200,000 to 400,000, ⁇ -type, purchased from Henan Laimeiyuan Biotechnology Co., Ltd.
  • the high molecular polymer is polyvinyl alcohol with a degree of polymerization of 2400 to 3000, purchased from Guangzhou Huida Chemical Co., Ltd.
  • the polymer is a polymer with 2-acrylamide-2-methylpropanesulfonic acid (AMPS) as the main monomer, and the degree of polymerization of the polymer is a number average molecular weight of 300,000 to 500,000.
  • AMPS 2-acrylamide-2-methylpropanesulfonic acid
  • the high molecular polymer is a polyurethane thickener, the brand name is HTK-2020, purchased from Shanghai Hongtu Industrial Co., Ltd.
  • the high molecular polymer is polyacrylamide
  • the polyacrylamide has a number average molecular weight of 16 million to 18 million, purchased from Shandong Gaoyi New Material Technology Co., Ltd.
  • the hollow microspheres are processed as follows:
  • the hollow microspheres were purchased from Sinosteel Ma'anshan Mining Institute New Material Technology Co., Ltd., model H6000;
  • step 2) Add the mixed liquid made of ammonia, ethanol and water to the hollow microspheres treated in step 1), and process for 0.5h; the weight ratio of the hollow microspheres to the mixed liquid is 2.2:15.6; the mixture of ammonia, ethanol and water The volume ratio is 0.1:2:6;
  • step 2) Mix the mixed liquid obtained in step 2) with ethyl orthosilicate, and treat for 4 hours to obtain a mixture, and the weight ratio of the mixed liquid obtained in step 2) to ethyl orthosilicate is 0.93:12.4;
  • step 3) The mixture in step 3) was separated from solid and liquid, washed with ethanol and water for several times, filtered, and calcined at 120° C. for 2 hours to obtain coated modified hollow microspheres.
  • the high molecular polymer is Wenlun glue, the number average molecular weight is 3 million to 5 million, purchased from Hebei Xinhe Biochemical Co., Ltd.;
  • the salinity of water is 0.8g/L
  • polycarboxylate dispersant containing polyether side chains is polycarboxylate acrylate, purchased from Tianjin Zhonghai Oilfield Chemical Co., Ltd., and the brand name is PC-F44L;
  • Antifreeze is ethylene glycol, purchased from Jinan Luke Chemical Co., Ltd.;
  • the preparation method of the liquid lightening agent of this embodiment is as follows: add the high molecular polymer into water, stir for 20 minutes at a speed of 1000r/min, add the hollow microspheres after mixing evenly, add polycarboxylic acid containing polyether side chains after mixing evenly And antifreeze, after mixing evenly, the liquid lightening agent is obtained.
  • the hollow microspheres are processed as follows:
  • the hollow microspheres were purchased from Zhongke Huaxing New Material Co., Ltd., model D4000;
  • step 2) adding ammonia, ethanol, and water to the hollow microspheres treated in step 1) for 0.5 hours; the weight ratio of the hollow microspheres to the mixed liquid is 1.8:19.8; The volume ratio is 0.05:4:6;
  • step 3 Mix the mixed liquid obtained in step 2) with ethyl orthosilicate, and treat for 4 hours to obtain a mixture, the weight ratio of ethyl orthosilicate to the mixture is 0.86:13.4;
  • step 4) The mixture in step 3) is separated from solid and liquid, and the solid matter is calcined at 130° C. for 2 hours to obtain coated modified hollow microspheres.
  • the high molecular polymer is hydroxyethyl cellulose, purchased from Renqiu Pengyu Chemical Co., Ltd.; the number average degree of polymerization of the hydroxyethyl cellulose is 200 to 400;
  • the salinity of water is 0.8g/L
  • polycarboxylate dispersant containing polyether side chains is polycarboxylate acrylate, purchased from Tianjin Zhonghai Oilfield Chemical Co., Ltd., and the brand name is PC-F44L;
  • Antifreeze is ethylene glycol, purchased from Jinan Luke Chemical Co., Ltd.;
  • the preparation method of the liquid lightening agent of this embodiment is as follows: add the high molecular polymer into water, stir for 20 minutes at a speed of 1000r/min, add the hollow microspheres after mixing evenly, add polycarboxylic acid containing polyether side chains after mixing evenly And antifreeze, after mixing evenly, the liquid lightening agent is obtained.
  • the hollow microspheres are processed as follows:
  • the hollow microspheres were purchased from Zhongke Huaxing New Material Co., Ltd., model D4000;
  • step 2) adding ammonia, ethanol, and water to the hollow microspheres treated in step 1) for 0.5 hours; the weight ratio of the hollow microspheres to the mixed liquid is 1.8:19.8; The volume ratio is 0.05:4:6;
  • step 2) Mixing the mixed liquid obtained in step 2) with ethyl orthosilicate, and treating it for 4 hours to obtain a mixture, the mass specific weight ratio of the ethyl orthosilicate to the mixture is 0.86:13.4;
  • step 4) The mixture in step 3) is separated from solid and liquid, and the solid matter is calcined at 130° C. for 2 hours to obtain coated modified hollow microspheres.
  • the high molecular polymer is xanthan gum
  • the number average molecular weight of xanthan gum is 6 million to 9 million, purchased from Ordos Zhongxuan Biochemical Co., Ltd.;
  • the salinity of water is 0.8g/L
  • the dispersant is a polycondensate of sulfonated formaldehyde and acetone, purchased from Tianjin COSL Chemical Co., Ltd., with the brand name PC-F40L;
  • Antifreeze is ethylene glycol, purchased from Jinan Luke Chemical Co., Ltd.;
  • the preparation method of the liquid lightening agent of this embodiment is as follows: add high molecular polymer into water, stir at 1000r/min speed for 20min, add the hollow microspheres after mixing evenly, add dispersant and antifreeze after mixing evenly, A liquid lightener is obtained.
  • the hollow microspheres are processed as follows:
  • the hollow microspheres were purchased from Sinosteel Ma'anshan Mining Institute New Material Technology Co., Ltd., model H6000;
  • step 2) Add the mixed liquid made of ammonia, ethanol and water to the hollow microspheres treated in step 1), and process for 0.5h; the weight ratio of the hollow microspheres to the mixed liquid is 2.2:15.6; the mixture of ammonia, ethanol and water The volume ratio is 0.1:2:6;
  • step 2) Mix the mixed liquid obtained in step 2) with ethyl orthosilicate, and treat for 4 hours to obtain a mixture, the weight ratio of ethyl orthosilicate to the mixed liquid obtained in step 2) is 0.93:12.4;
  • step 3) The mixture in step 3) was separated from solid and liquid, washed with ethanol and water for several times, filtered, and calcined at 120° C. for 2 hours to obtain coated modified hollow microspheres.
  • the high molecular polymer is gelatin, and the number average molecular weight of gelatin is 50,000 to 100,000, purchased from Henan Laimeiyuan Biotechnology Co., Ltd.;
  • the salinity of water is 0.8g/L
  • the dispersant is sodium lignosulfonate, purchased from Jinan Shengshi Chuangfu Chemical Co., Ltd., industrial grade, item number 668;
  • Antifreeze is ethylene glycol, purchased from Jinan Luke Chemical Co., Ltd.;
  • the preparation method of the liquid lightening agent of this embodiment is as follows: add high molecular polymer into water, stir at 1000r/min for 20min, add the hollow microspheres after mixing uniformly, add dispersant and antifreeze after mixing uniformly, A liquid lightener is obtained.
  • the hollow microspheres are processed as follows:
  • the hollow microspheres were purchased from Zhongke Huaxing New Material Co., Ltd., model D4000 (borosilicate hollow glass microspheres);
  • step 2) adding ammonia, ethanol, and water to the hollow microspheres treated in step 1) for 0.5 hours; the weight ratio of the hollow microspheres to the mixed liquid is 1.8:19.8; The volume ratio is 0.05:4:6;
  • step 2) Mix the mixed liquid obtained in step 2) with ethyl orthosilicate, and treat for 4 hours to obtain a mixture, and the mass ratio of ethyl orthosilicate to the mixture is 0.86:13.4;
  • step 4) The mixture in step 3) was separated from solid to liquid, and the solid material was calcined at 130° C. for 2 hours to obtain coated modified hollow microspheres.
  • the high molecular polymer is methyl cellulose, and the degree of polymerization of methyl cellulose is 300 to 500, which is purchased from Yibo Chemical Co., Ltd., Dacheng County; another high molecular polymer is carboxymethyl fiber Primer, the polymer of carboxymethyl cellulose is 300 to 500, purchased from Yibo Chemical Co., Ltd., Dacheng County; the ratio of the two polymers is 1:1 (weight ratio).
  • the salinity of water is 0.8g/L
  • the dispersant is a polycondensate of sulfonated formaldehyde and acetone, purchased from Tianjin COSL Chemical Co., Ltd., with the brand name PC-F40L;
  • Antifreeze is ethylene glycol, purchased from Jinan Luke Chemical Co., Ltd.;
  • the preparation method of the liquid lightening agent of this embodiment is as follows: add high molecular polymer into water, stir at 1000r/min for 20min, add the hollow microspheres after mixing uniformly, add dispersant and antifreeze after mixing uniformly, A liquid lightener is obtained.
  • the hollow microspheres are processed as follows:
  • the hollow microspheres were purchased from Zhongke Huaxing New Material Co., Ltd., model D4000;
  • step 2) adding ammonia, ethanol, and water to the hollow microspheres treated in step 1) for 0.5 hours; the weight ratio of the hollow microspheres to the mixed liquid is 1.8:19.8; The volume ratio is 0.05:4:6;
  • step 2) Mix the mixed liquid obtained in step 2) with ethyl orthosilicate, and treat for 4 hours to obtain a mixture, and the mass ratio of ethyl orthosilicate to the mixture is 0.86:13.4;
  • step 4) The mixture in step 3) is separated from solid and liquid, and the solid matter is calcined at 130° C. for 2 hours to obtain coated modified hollow microspheres.
  • the high molecular polymer is starch
  • the gelatinization temperature of starch is 80°C to 90°C, purchased from Shandong Gaoyi New Material Technology Co., Ltd.
  • another high molecular polymer is carrageenan, carrageenan
  • the number average molecular weight is 200,000 to 400,000, ⁇ -type, purchased from Henan Laimeiyuan Biotechnology Co., Ltd.; the ratio of the two polymers is 1:3 (weight ratio).
  • the salinity of water is 0.8g/L
  • the dispersant is a polycondensate of sulfonated formaldehyde and acetone, purchased from Tianjin COSL Chemical Co., Ltd., with the brand name PC-F41L;
  • Antifreeze is calcium nitrite, purchased from Shandong Xuxiang Chemical Co., Ltd.;
  • the preparation method of the liquid lightening agent of this embodiment is as follows: add high molecular polymer into water, stir at 1000r/min speed for 20min, add the hollow microspheres after mixing evenly, add dispersant and antifreeze after mixing evenly, A liquid lightener is obtained.
  • Example 1 The only difference between this comparative example and Example 1 is that the amount of dispersant is 0.2 parts, the amount and source of other raw materials and the preparation process of this comparative example are exactly the same as those of Example 1.
  • Example 1 The only difference between this comparative example and Example 1 is that no high molecular polymer is involved, the amount and source of other raw materials and the preparation process of this comparative example are exactly the same as those of Example 1.
  • clay was used as a lightening material.
  • the clay was purchased from Shijiazhuang Xinhui Mineral Products Co., Ltd., and was sodium bentonite for drilling fluid.
  • Prehydration is required during use. Prehydration is about 16 hours, and the amount added is about 3% to 6% of the cement amount. It can be used to prepare cement slurry with a density of 1.50g/cm 3 to 1.75g/cm 3 to form The strength of cement stone is low, generally less than 7MPa.
  • sodium silicate was used as the lightening material, which was purchased from Jinan Xinshuo Chemical Co., Ltd., and was industrial sodium silicate.
  • the strength is relatively high, but it can only be used at low temperature. When the temperature is higher than 50°C, the thickening time is difficult to adjust;
  • hollow microspheres were directly used as lightening materials, which were purchased from Sinosteel Maanshan Mining Institute New Material Technology Co., Ltd., model H6000;
  • cement slurry of 1.20g/cm 3 to 1.60g/cm 3 . It has the characteristics of low density and high strength, but it needs to be dry mixed with cement in advance, which is inconvenient to use and cannot be added in liquefaction.
  • Example 1 Under the condition of minus 20°C ⁇ 50°C, it can exist stably for more than 3 months
  • Example 2 Under the condition of minus 20°C ⁇ 50°C, it can exist stably for more than 3 months
  • Example 3 Under the condition of minus 20°C ⁇ 50°C, it can exist stably for more than 2 months
  • Example 4 Under the condition of minus 20°C ⁇ 50°C, it can exist stably for more than 2 months
  • Example 5 Under the condition of minus 20°C ⁇ 50°C, it can exist stably for more than 2 months
  • Example 6 Under the condition of minus 20°C ⁇ 50°C, it can exist stably for more than 2 months Comparative example 1
  • Comparative example 2 Obvious stratification appeared in about a month, the lower part was clear water, and the upper part was accumulation of hollow microbeads
  • Example 1 and Example 2 of the present application As can be seen from the above table 1, the stability of the liquid lightening agent prepared as a whole by each component and its respective content in Example 1 and Example 2 of the present application is far better than that in Comparative Example 1 and Comparative Example 2.
  • the components and their respective levels as a whole prepare the stability of the liquid lightening agent.
  • BWOC is by weight of cement, that is, the percentage of the weight of the cement slurry; the fluid loss reducer is G80L and the defoamer X60L, both purchased from Tianjin COSL Chemical Co., Ltd.; Example 1 and Example 2, Wet mixing method is used to add.
  • the soil of Comparative Example 3 needs to be pre-hydrated for 16 hours in advance.
  • the water glass of Comparative Example 4 can be added by wet mixing method.
  • the hollow microspheres of Comparative Example 5 need to be pre-mixed with cement on the shore. Increase premix cost.
  • the strength of the low-density cement paste prepared in Example 1 and Example 2 can reach more than 14MPa, which meets the requirements of on-site construction; the strength of the low-density cement paste prepared in Comparative Example 3 and Comparative Example 4 is lower, generally It can only be used as filling slurry; comparative example 5 has higher strength, but it is generally carried out by dry mixing, which is inconvenient to use.
  • the liquid lightening agent of the present application can prepare high-performance, low-density, high-strength cement slurry, is suitable for wet mixing, and is convenient to use.

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Abstract

本申请公开了一种液体减轻剂及其制备和应用。所述液体减轻剂，包括水、空心微珠和高分子聚合物，所述水、空心微珠和高分子聚合物的重量比为(40至60):(26至56):(0.5至2)。本申请提供的减轻剂既可以起到降低密度的作用、又是一种可以以液体形式添加的减轻材料。实现了减轻材料的液体化添加，从而实现低密度水泥浆的灵活配制，为现场低密度水泥浆的配制提供便利。此外，本申请提供的减轻剂可以长期稳定存储。

Description

一种液体减轻剂及其制备和应用 技术领域
本文涉及但不限于水泥浆的密度调节，尤其涉及但不限于一种固井用液体悬浮减轻剂。
背景技术
固井是钻井过程中的一个关键环节，起到支撑套管和封隔地层的目的，当地层破裂压力较窄时，为防止压裂地层，通常采用低密度水泥浆进行固井。常用的低密度水泥浆方法主要是两种：一种是采用搬土浆、水玻璃等悬浮材料，通过提高水泥浆的水灰比来实现，但这种方式制备的水泥浆起强度慢、24h候凝强度低，无法满足下一步快速钻进的需求；另一种方法是加入空心微珠、漂珠、膨胀珍珠岩等中空低密度材料，降低水泥浆的密度，可以有效降低水灰比，提高水泥石的强度，但是缺点是此类中空材料由于加量大，一般需要在灰站提前与水泥进行干混，而一旦进行干混后，因比例确定，水泥浆的密度很难进一步调节，而且通常在作业准备过程中，一般需要进行常规密度水泥浆和低密度水泥浆的固体灰的存储，也会增加储罐数量，另外，在海上固井作业时，由于海风的影响，固体材料尤其是低密度材料，吹灰过程中易造成损失，不利于后期密度的稳定。
发明概述
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请实施例提供了一种既可以起到降低密度、又可以以液体形式添加的减轻剂。本申请实施例提供的悬浮减轻剂可以长期稳定存储。
通过液体减轻剂的制备，实现减轻剂的液体化添加，从而实现低密度水泥浆的灵活配制，为现场低密度水泥浆的配制提供便利。
本申请实施例提供了一种液体减轻剂，包括水、空心微珠、高分子聚合物和分散剂，所述水、空心微珠、高分子聚合物和分散剂的重量比为(40至 60):(26至56):(0.5至2):(0.5至2)。
在本申请提供的一种实施方式中，所述液体减轻剂还包括防冻剂。
在本申请提供的一种实施方式中，所述空心微珠和所述防冻剂的重量比为(26至56):(0至10)；所述空心微珠和所述防冻剂的重量比还可以为(26至56):(5至10)。
在本申请提供的一种实施方式中，所述高分子聚合物选自甲基纤维素、羧甲基纤维素、羟乙基纤维素、淀粉、黄原胶、明胶、角叉莱胶、温伦胶、聚乙烯醇、以2-丙烯酰胺-2-甲基丙磺酸(AMPS)为主要单体的聚合物、聚氨酯增稠剂和聚丙烯酰胺中的任意一种或更多种。
在本申请提供的一种实施方式中，所述甲基纤维素的聚合度为300至500。
在本申请提供的一种实施方式中，所述羧甲基纤维素的聚合度为300至500。
在本申请提供的一种实施方式中，所述羟乙基纤维素的聚合度为200至400。
在本申请提供的一种实施方式中，所述淀粉的糊化温度为80℃至90℃。
在本申请提供的一种实施方式中，所述黄原胶的数均分子量为600万至900万。
在本申请提供的一种实施方式中，所述明胶的数均分子量为5万至10万。
在本申请提供的一种实施方式中，所述角叉莱胶的数均分子量为20万至40万，κ-型。
在本申请提供的一种实施方式中，所述温伦胶的数均分子量为300万至500万。
在本申请提供的一种实施方式中，所述聚乙烯醇的聚合度为2400至3000。
在本申请提供的一种实施方式中，所述2-丙烯酰胺-2-甲基丙磺酸(AMPS)为主要单体的聚合物，数均分子量为30万至50万。
在本申请提供的一种实施方式中，所述聚氨酯增稠剂为缔合型流变性改 进的聚氨酯增稠剂。
在本申请提供的一种实施方式中，聚丙烯酰胺为数均分子量1600万至1800万。
在本申请提供的一种实施方式中，所述分散剂选自含有聚醚侧链的聚羧酸、焦磷酸钠、木质素磺酸钠和磺化甲醛丙酮缩聚物中的任意一种或更多种。
在本申请提供的一种实施方式中，所述防冻剂选自醇类化合物、脂肪酸酰胺类化合物和亚硝酸盐的中的任意一种或更多种；在本申请提供的一种实施方式中，所述醇类化合物选自甲醇、乙二醇、异丙醇和二甘醇中的任意一种或更多种；在本申请提供的一种实施方式中，所述脂肪酸酰胺类化合物选自二甲基甲酰胺、甲酰胺和乙酰胺中的任意一种或更多种。
在本申请提供的一种实施方式中，所述水的矿化度为小于1g/L。
在本申请提供的一种实施方式中，所述空心微珠选自硼硅酸盐空心玻璃微珠；
所述硼硅酸盐空心玻璃微珠，包含但不限于Minnesota Mining and Manufacturing Corporation(3M公司)的HGS系列产品、中钢马鞍山的H系列产品、中科华星新材料有限公司的D系列产品或安徽凯盛基础材料科技有限公司的HGS系列产品。
在本申请提供的一种实施方式中，所述空心玻璃微珠被纳米SiO 2包覆。
在本申请提供的一种实施方式中，纳米SiO 2包覆所述空心玻璃微珠的方法，包括如下步骤：
1)将所述空心微珠在pH值为11至13的溶液中处理1h至3h，处理后中和所述空心微珠表面的碱性物质并干燥；
2)将步骤1)处理后的所述空心微珠加入弱碱、醇类溶剂、水配成的混合液体，所述弱碱、所述醇类溶剂和水的比例范围为体积比(0.05至0.20):(1至5):(2至10)，空心微珠与混合液体的比例为重量比(1至3):(20至50)；
3)将步骤2)得到的混合液体与硅源混合，处理3h至10h，得到混合物，所述硅源与步骤2)得到的混合液体的重量比为(0.8至1.8):(10至30)；
4)对步骤3)中的混合物固液分离，分别使用乙醇和水多次洗涤、过滤 后，将固体物质在120℃至150℃下煅烧处理1h至3h，即得包覆改性空心微珠。
在本申请提供的一种实施方式中，所述弱碱包括氨水、氢氧化铝、醋酸钠和甲酸钠中的任意一种或更多种。
在本申请提供的一种实施方式中，所述醇类溶剂包括甲醇、乙醇、乙二醇和丙三醇中的任意一种或更多种。
在本申请提供的一种实施方式中，所述硅源包括正硅酸乙酯、硅酸四甲酯和正硅酸丁酯中的任意一种或更多种。
又一方面，本申请提供了上述的液体减轻剂的制备方法，包括以下步骤：将高分子聚合物加入水中，混合均匀后加入所述空心微珠，混合均匀后加入分散剂和防冻剂，混合均匀后即得液体减轻剂。
又一方面，本申请提供了上述的液体减轻剂在固井水泥浆中的应用，所述液体减轻剂的占所述固井水泥浆的8wt.％至40wt.％(BWOC)。加入本申请液体减轻剂水泥浆各项性能良好，可以满足固井作业需求。
本申请提供的技术方案可以有效制备高固相含量的空心微珠减轻材料，具有密度低、强度高的特点，配制的低密度水泥浆各项性能良好，稠化时间可调，可以满足大多数井况下的低密度固井作业需求，实现减轻剂的液体添加，有效降低水泥浆密度。实现了使用同一种固体基材料的基础上，水泥浆密度在1.1g/cm 3至1.6g/cm 3的自由调节。
本申请的有益效果如下：
1、本申请可以形成稳定的液体减轻剂，可以实现了固体减轻材料的液体化添加，适用于LAS***(Liquid Additives System液体添加剂自动加料***)；
2、本申请所述液体减轻剂固体含量可达溶剂的50％至120％，密度在0.35g/cm 3至0.90g/cm 3，加入少量就可以有效降低水泥浆的密度；能够调节水泥浆密度在1.1g/cm 3至1.6g/cm 3，水泥浆水灰比最大可以为2；包含本申请液体减轻剂的水泥浆防窜性能好、强度高、混凝时间短等特点。
3、成品性能稳定，稳定性和耐温性能良好，上浮现象减弱，可以稳定存 在不短于3个月，即使失稳后，重新高速搅拌后，仍可以恢复原状；
4、生产工艺仅涉及高速搅拌，工艺简单成熟，生产速度快，易于工业化生产。
本申请的其它特征和优点将在随后的说明书中阐述，并且，部分地从说明书中变得显而易见，或者通过实施本申请而了解。本申请的其他优点可通过在说明书中所描述的方案来发明实现和获得。
详述
下文对本申请的实施例进行详细说明。需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互任意组合。
在一种实施方式中，高分子聚合物为甲基纤维素，甲基纤维素的聚合度为300至500，购自大城县亦博化工有限公司；
在一种实施方式中，高分子聚合物为羧甲基纤维素，羧甲基纤维素的聚合物为300至500，购自大城县亦博化工有限公司。
在一种实施方式中，高分子聚合物为淀粉，淀粉的糊化温度为80℃至90℃，购自山东高益新材料科技有限公司。
在一种实施方式中，高分子聚合物为黄原胶，黄原胶的数均分子量为600万至900万，购自鄂尔多斯市中轩生化股份有限公司。
在一种实施方式中，高分子聚合物为明胶，明胶的数均分子量为5万至10万，购自河南来莱美源生物科技有限公司。
在一种实施方式中，高分子聚合物为角叉莱胶，角叉莱胶的数均分子量为20万至40万，κ-型，购自河南来莱美源生物科技有限公司。
在一种实施方式中，高分子聚合物为聚乙烯醇，聚乙烯醇的聚合度为2400至3000，购自广州辉达化工有限公司。
在一种实施方式中，高分子聚合物为2-丙烯酰胺-2-甲基丙磺酸(AMPS)为主要单体的聚合物，聚合物的聚合度为数均分子量为30万至50万。
在一种实施方式中，高分子聚合物为聚氨酯增稠剂，牌号为HTK-2020，购自上海宏图实业有限公司。
在一种实施方式中，高分子聚合物为聚丙烯酰胺，聚丙烯酰胺为数均分子量1600万至1800万，购自山东高益新材料科技有限公司。
实施例1
本实施例中空心微珠经过如下处理：
所述空心微珠购自中钢集团马鞍山矿院新材料科技有限公司，型号为H6000；
1)将所述空心微珠在pH值为12的溶液中处理2h，处理后中和所述空心微珠表面的碱性物质并干燥；
2)将步骤1)处理后的所述空心微珠加入氨水、乙醇、水配成的混合液体，处理0.5h；空心微珠与混合液体的重量比为2.2:15.6；氨水、乙醇和水的体积比为0.1:2:6；
3)将步骤2)得到的混合液体与正硅酸乙酯混合，处理4h，得到混合物，所述正硅酸乙酯与步骤2)得到的混合液体的重量比为0.93:12.4；
4)对步骤3)中的混合物固液分离，分别使用乙醇和水多次洗涤、过滤后，将固体物质在120℃下煅烧处理2h，即得包覆改性空心微珠。
在本实施例中，高分子聚合物为温伦胶，数均分子量为300万至500万，购自河北鑫合生物化工有限公司；
水的矿化度为0.8g/L；
含有聚醚侧链的聚羧酸分散剂为聚羧酸系丙烯酸盐，购自天津中海油服化学有限公司，牌号为PC-F44L；
防冻剂为乙二醇，购自济南鲁科化工有限公司；
取包覆改性的空心微珠35重量份、高分子聚合物0.6重量份、水57.6重量份、含有聚醚侧链的聚羧酸分散剂0.8重量份、防冻剂6重量份。
本实施例的液体减轻剂制备方法如下：将高分子聚合物加入水中，1000r/min速度下搅拌20min，混合均匀后加入所述空心微珠，混合均匀后加入含有聚醚侧链的聚羧酸和防冻剂，混合均匀后即得液体减轻剂。
实施例2
本实施例中空心微珠经过如下处理：
所述空心微珠购自中科华星新材料有限公司，型号为D4000；
1)将所述空心微珠在pH值为11的溶液中处理3h，处理后中和所述空心微珠表面的碱性物质并干燥；
2)将步骤1)处理后的所述空心微珠加入氨水、乙醇、水配成的混合液体，处理0.5h；空心微珠与混合液体的重量比为1.8:19.8；氨水、乙醇和水的体积比为0.05:4:6；
3)将步骤2)得到的混合液体与正硅酸乙酯混合，处理4h，得到混合物，所述正硅酸乙酯与混合物的重量比为0.86:13.4；
4)对步骤3)中的混合物固液分离，将固体物质在130℃下煅烧处理2h，即得包覆改性空心微珠。
在本实施例中，高分子聚合物为羟乙基纤维素，购自任丘市鹏宇化工有限公司；所述羟乙基纤维素的数均聚合度为200至400；
水的矿化度为0.8g/L；
含有聚醚侧链的聚羧酸分散剂为聚羧酸系丙烯酸盐，购自天津中海油服化学有限公司，牌号为PC-F44L；
防冻剂为乙二醇，购自济南鲁科化工有限公司；
取包覆改性的空心微珠30重量份、高分子聚合物1.4重量份、水60重量份、含有聚醚侧链的聚羧酸0.6重量份、防冻剂8重量份。
本实施例的液体减轻剂制备方法如下：将高分子聚合物加入水中，1000r/min速度下搅拌20min，混合均匀后加入所述空心微珠，混合均匀后加入含有聚醚侧链的聚羧酸和防冻剂，混合均匀后即得液体减轻剂。
实施例3
本实施例中空心微珠经过如下处理：
所述空心微珠购自中科华星新材料有限公司，型号为D4000；
1)将所述空心微珠在pH值为11的溶液中处理3h，处理后中和所述空心微珠表面的碱性物质并干燥；
2)将步骤1)处理后的所述空心微珠加入氨水、乙醇、水配成的混合液体，处理0.5h；空心微珠与混合液体的重量比为1.8:19.8；氨水、乙醇和水的体积比为0.05:4:6；
3)将步骤2)得到的混合液体与正硅酸乙酯混合，处理4h，得到混合物，所述正硅酸乙酯与混合物的质量比重量比为0.86:13.4；
4)对步骤3)中的混合物固液分离，将固体物质在130℃下煅烧处理2h，即得包覆改性空心微珠。
在本实施例中，高分子聚合物为黄原胶，黄原胶的数均分子量为600万至900万，购自鄂尔多斯市中轩生化股份有限公司；
水的矿化度为0.8g/L；
分散剂为磺化甲醛丙酮缩聚物，购自天津中海油服化学有限公司，牌号为PC-F40L；
防冻剂为乙二醇，购自济南鲁科化工有限公司；
取包覆改性的空心微珠26重量份、高分子聚合物0.5重量份、水40重量份、分散剂0.5重量份、防冻剂8重量份。
本实施例的液体减轻剂制备方法如下：将高分子聚合物加入水中，1000r/min速度下搅拌20min，混合均匀后加入所述空心微珠，混合均匀后加入分散剂和防冻剂，混合均匀后即得液体减轻剂。
实施例4
本实施例中空心微珠经过如下处理：
所述空心微珠购自中钢集团马鞍山矿院新材料科技有限公司，型号为H6000；
1)将所述空心微珠在pH值为12的溶液中处理2h，处理后中和所述空心微珠表面的碱性物质并干燥；
2)将步骤1)处理后的所述空心微珠加入氨水、乙醇、水配成的混合液体，处理0.5h；空心微珠与混合液体的重量比为2.2:15.6；氨水、乙醇和水的体积比为0.1:2:6；
3)将步骤2)得到的混合液体与正硅酸乙酯混合，处理4h，得到混合物，所述正硅酸乙酯与步骤2)得到的混合液体的重量比为0.93:12.4；
4)对步骤3)中的混合物固液分离，分别使用乙醇和水多次洗涤、过滤后，将固体物质在120℃下煅烧处理2h，即得包覆改性空心微珠。
在本实施例中，高分子聚合物为明胶，明胶的数均分子量为5万至10万，购自河南来莱美源生物科技有限公司；
水的矿化度为0.8g/L；
分散剂为木质素磺酸钠，购自济南盛世创富化工有限公司，工业级，货号668；
防冻剂为乙二醇，购自济南鲁科化工有限公司；
取包覆改性的空心微珠56重量份、高分子聚合物2重量份、水60重量份、分散剂2重量份、防冻剂10重量份。
本实施例的液体减轻剂制备方法如下：将高分子聚合物加入水中，1000r/min速度下搅拌20min，混合均匀后加入所述空心微珠，混合均匀后加入分散剂和防冻剂，混合均匀后即得液体减轻剂。
实施例5
本实施例中空心微珠经过如下处理：
所述空心微珠购自中科华星新材料有限公司，型号为D4000(硼硅酸盐空心玻璃微珠)；
1)将所述空心微珠在pH值为11的溶液中处理3h，处理后中和所述空心微珠表面的碱性物质并干燥；
2)将步骤1)处理后的所述空心微珠加入氨水、乙醇、水配成的混合液体，处理0.5h；空心微珠与混合液体的重量比为1.8:19.8；氨水、乙醇和水的体积比为0.05:4:6；
3)将步骤2)得到的混合液体与正硅酸乙酯混合，处理4h，得到混合物，所述正硅酸乙酯与混合物的质量比重量比为0.86:13.4；
4)对步骤3)中的混合物固液分离，将固体物质在130℃下煅烧处理2h， 即得包覆改性空心微珠。
在本实施例中，高分子聚合物为甲基纤维素，甲基纤维素的聚合度为300至500，购自大城县亦博化工有限公司；另一种高分子聚合物为羧甲基纤维素，羧甲基纤维素的聚合物为300至500，购自大城县亦博化工有限公司；两种聚合物比例为1:1(重量比)。
水的矿化度为0.8g/L；
分散剂为磺化甲醛丙酮缩聚物，购自天津中海油服化学有限公司，牌号为PC-F40L；
防冻剂为乙二醇，购自济南鲁科化工有限公司；
取包覆改性的空心微珠35重量份、高分子聚合物1.8重量份、水44重量份、分散剂0.5重量份、防冻剂8重量份。
本实施例的液体减轻剂制备方法如下：将高分子聚合物加入水中，1000r/min速度下搅拌20min，混合均匀后加入所述空心微珠，混合均匀后加入分散剂和防冻剂，混合均匀后即得液体减轻剂。
实施例6
本实施例中空心微珠经过如下处理：
所述空心微珠购自中科华星新材料有限公司，型号为D4000；
1)将所述空心微珠在pH值为11的溶液中处理3h，处理后中和所述空心微珠表面的碱性物质并干燥；
2)将步骤1)处理后的所述空心微珠加入氨水、乙醇、水配成的混合液体，处理0.5h；空心微珠与混合液体的重量比为1.8:19.8；氨水、乙醇和水的体积比为0.05:4:6；
3)将步骤2)得到的混合液体与正硅酸乙酯混合，处理4h，得到混合物，所述正硅酸乙酯与混合物的质量比重量比为0.86:13.4；
4)对步骤3)中的混合物固液分离，将固体物质在130℃下煅烧处理2h，即得包覆改性空心微珠。
本实施例中，高分子聚合物为淀粉，淀粉的糊化温度为80℃至90℃，购 自山东高益新材料科技有限公司；另一种高分子聚合物为角叉莱胶，角叉莱胶的数均分子量为20万至40万，κ-型，购自河南来莱美源生物科技有限公司；两种聚合物比例为1:3(重量比)。
水的矿化度为0.8g/L；
分散剂为磺化甲醛丙酮缩聚物，购自天津中海油服化学有限公司，牌号为PC-F41L；
防冻剂为亚硝酸钙，购自山东旭祥化工有限公司；
取包覆改性的空心微珠35重量份、高分子聚合物1.2重量份、水44重量份、分散剂0.5重量份、防冻剂5重量份。
本实施例的液体减轻剂制备方法如下：将高分子聚合物加入水中，1000r/min速度下搅拌20min，混合均匀后加入所述空心微珠，混合均匀后加入分散剂和防冻剂，混合均匀后即得液体减轻剂。
对比例1
本对比例与实施例1的区别仅在于，分散剂的用量为0.2份，其他原料的用量和来源以及本对比例的制备过程与实施例1完全相同。
对比例2
本对比例与实施例1的区别仅在于，不涉及高分子聚合物，其他原料的用量和来源以及本对比例的制备过程与实施例1完全相同。
对比例3
本对比例使用搬土作为减轻材料，所述搬土购自石家庄市鑫汇矿产品有限公司，为钻井液用钠基膨润土。
使用过程中需要预水化，预水化约16h，加量约在水泥加量的3％至6％，可以用于配制密度为1.50g/cm 3至1.75g/cm 3的水泥浆，形成的水泥石强度较低，一般小于7MPa。
对比例4
本对比例使用水玻璃作为减轻材料，购自济南鑫硕化工有限公司，为工业泡花碱。
可以液体添加，加量约在水泥加量的4wt.％至15wt.％(占水泥重量比)，可以用于配制1.5g/cm 3至1.75g/cm 3的水泥浆，形成的水泥石的强度相对较高，但是只能用于低温下，温度高于50℃后，稠化时间难以调节；
对比例5
本对比例直接使用空心微珠作为减轻材料，购自中钢集团马鞍山矿院新材料科技有限公司，型号为H6000；
可以用于配制1.20g/cm 3至1.60g/cm 3的水泥浆，具有低密度、高强度的特点，但是需要提前与水泥进行干混，使用不方便，无法液体化添加。
测试例1：
表1实施例与对比例制备的早强剂的稳定性测试结果
实施例1 零下20℃～50℃条件下，可以稳定存在3个月以上
实施例2 零下20℃～50℃条件下，可以稳定存在3个月以上
实施例3 零下20℃～50℃条件下，可以稳定存在2个月以上
实施例4 零下20℃～50℃条件下，可以稳定存在2个月以上
实施例5 零下20℃～50℃条件下，可以稳定存在2个月以上
实施例6 零下20℃～50℃条件下，可以稳定存在2个月以上
对比例1 不能将空心微珠全部混入水中，产品太稠，无法形成悬浮液
对比例2 一个月左右出现明显分层，下部为清澈的水，上部为空心微珠堆积
从上表1可以看出，本申请实施例1和实施例2中的各组分及其各自的含量作为整体制备的液体减轻剂的稳定性远远优于对比例1和对比例2中的各组分及其各自的含量作为整体制备的液体减轻剂的稳定性。
测试例2：
表2本申请的实施例和常规减轻材料配制的低密度水泥浆的测试结果
Figure PCTCN2022110216-appb-000001
Figure PCTCN2022110216-appb-000002
表1中，BWOC为by weight of cement，即占水泥浆重量的百分比；降失水剂为G80L和消泡剂X60L，均购自于天津中海油服化学有限公司；实施例1和实施例2，采用湿混方式添加，对比例3的搬土需要提前预水化16h，对比例4的水玻璃可以采用湿混方式添加，对比例5的空心微珠，需要在岸基与水泥进行预混，增加预混成本。
由表1结果可以看出，实施例1和实施例2配制的低密度水泥浆强度可以达到14MPa以上，满足现场施工要求；对比例3和对比例4配制的低密度水泥浆强度较低，一般只能作为填充浆使用；对比例5强度较高，但一般采用干混方式进行，使用不便。本申请的液体减轻剂可以配制高性能的低密度高强度水泥浆，适合湿混，使用便捷。
上述水泥浆的配制及性能评价按照美国石油协会API RP 10B-2 2013标准开展。
虽然本申请所揭露的实施方式如上，但所述的内容仅为便于理解本申请而采用的实施方式，并非用以限定本申请。任何本申请所属领域内的技术人员，在不脱离本申请所揭露的精神和范围的前提下，可以在实施的形式及细节上进行任何的修改与变化，但本申请的保护范围，仍须以所附的权利要求书所界定的范围为准。

Claims (10)

  1. 一种液体减轻剂，包括水、空心微珠、高分子聚合物和分散剂，所述水、空心微珠、高分子聚合物和分散剂的重量比为(40至60):(26至56):(0.5至2):(0.5至2)。
  2. 根据权利要求1所述的液体减轻剂，其中，所述液体减轻剂还包括防冻剂；
    可选地，所述空心微珠和所述防冻剂的重量比为(26至56):(0至10)；优选地，所述空心微珠和所述防冻剂的重量比为(26至56):(5至10)。
  3. 根据权利要求2所述的液体减轻剂，其中，所述高分子聚合物选自甲基纤维素、羧甲基纤维素、羟乙基纤维素、淀粉、黄原胶、明胶、角叉莱胶、温伦胶、聚乙烯醇、以2-丙烯酰胺-2-甲基丙磺酸(AMPS)为主要单体的聚合物、聚氨酯增稠剂和聚丙烯酰胺中的任意一种或更多种。
  4. 根据权利要求3所述的液体减轻剂，其中，所述甲基纤维素的聚合度为300至500；可选地，所述羧甲基纤维素的聚合物为300至500；可选地，所述羟乙基纤维素的聚合度为200至400；可选地，所述淀粉的糊化温度为80℃至90℃；可选地，所述黄原胶的数均分子量为600万至900万；可选地，所述明胶的数均分子量为5万至10万；可选地，所述角叉莱胶的数均分子量为20万至40万，κ-型；可选地，所述温伦胶的数均分子量为300万至500万；可选地，所述聚乙烯醇的聚合度为2400至3000；可选地，所述2-丙烯酰胺-2-甲基丙磺酸(AMPS)为主要单体的聚合物，数均分子量为30万至50万；可选地，聚丙烯酰胺为数均分子量1600万至1800万。
  5. 根据权利要求2至4中任一项所述的液体减轻剂，其中，所述分散剂选自含有聚醚侧链的聚羧酸、焦磷酸钠、木质素磺酸钠和磺化甲醛丙酮缩聚物中的任意一种或更多种；
    可选地，所述防冻剂选自醇类化合物、脂肪酸酰胺类化合物和亚硝酸盐的中的任意一种或更多种；
    可选地，所述水的矿化度为小于1g/L。
  6. 根据权利要求5所述的液体减轻剂，其中，
    所述醇类化合物选自甲醇、乙二醇、异丙醇和二甘醇中的任意一种或更多种；
    所述脂肪酸酰胺类化合物选自二甲基甲酰胺、甲酰胺和乙酰胺中的任意一种或更多种。
  7. 根据权利要求1至4中任一项所述的液体减轻剂，其中，所述空心微珠选自硼硅酸盐空心玻璃微珠；
    可选地，所述空心玻璃微珠被纳米SiO 2包覆。
  8. 根据权利要求7所述的液体减轻剂，其中，纳米SiO 2包覆所述空心玻璃微珠的方法，包括如下步骤：
    1)将所述空心微珠在pH值为11至13的溶液中处理1h至3h，处理后中和所述空心微珠表面的碱性物质并干燥；
    2)将步骤1)处理后的所述空心微珠加入弱碱、醇类溶剂、水配成的混合液体，所述弱碱、所述醇类溶剂和水的比例范围为体积比(0.05至0.20):(1至5):(2至10)，空心微珠与混合液体的比例为重量比(1至3):(20至50)；
    3)将步骤2)得到的混合液体与硅源混合，处理3h至10h，得到混合物，所述硅源与步骤2)得到的混合液体的重量比为(0.8至1.8):(10至30)；
    4)对步骤3)中的混合物固液分离，分别使用乙醇和水多次洗涤、过滤后，将固体物质在120℃至150℃下煅烧处理1h至3h，即得包覆改性空心微珠；
    可选地，所述弱碱包括氨水、氢氧化铝、醋酸钠和甲酸钠中的任意一种或更多种；
    可选地，所述醇类溶剂包括甲醇、乙醇、乙二醇和丙三醇中的任意一种或更多种；
    可选地，所述硅源包括正硅酸乙酯、硅酸四甲酯和正硅酸丁酯中的任意一种或更多种。
  9. 根据权利要求2至8中任一项所述的液体减轻剂的制备方法，包括以下步骤：将高分子聚合物加入水中，混合均匀后加入所述空心微珠，混合均匀后加入分散剂和防冻剂，混合均匀后即得液体减轻剂。
  10. 根据权利要求1至8中任一项所述的液体减轻剂在固井水泥浆中的应用，所述液体减轻剂的占所述固井水泥浆的8wt.％至40wt.％。
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030101911A1 (en) * 2001-12-03 2003-06-05 Brothers Lance E. Methods, well cement compositions and lightweight additives therefor
US6626991B1 (en) * 1999-07-29 2003-09-30 Schlumberger Technology Corp Low-density and low-porosity cementing slurry for oil wells or the like
US20050241538A1 (en) * 2004-04-28 2005-11-03 Vargo Richard F Jr Methods of making cement compositions using liquid additives containing lightweight beads
CN102002263A (zh) * 2010-11-01 2011-04-06 上海大学 一种空心玻璃微珠包覆二氧化钛的制备方法
CN103666407A (zh) * 2012-09-12 2014-03-26 中国石油化工股份有限公司 钻井液及其制备方法
US20180355236A1 (en) * 2016-02-09 2018-12-13 Halliburton Energy Services, Inc. Surfactants for use in liquid suspensions of lightweight beads
AU2016428908A1 (en) * 2016-11-10 2019-03-07 Halliburton Energy Services, Inc. Storable liquid suspension of hollow particles
CN109679456A (zh) * 2019-01-09 2019-04-26 深圳市欧科力科技有限公司 集装箱用高效隔热防腐面漆的制备方法
CN110846008A (zh) * 2019-12-16 2020-02-28 天津市康盛科技开发有限公司 一种油井水泥减轻外掺料
CN211499249U (zh) * 2019-10-14 2020-09-15 北京志盛威华化工有限公司 一种复合反射保温涂层结构
CN113621355A (zh) * 2021-08-09 2021-11-09 中海油田服务股份有限公司 一种液体减轻剂及其制备和应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103665747B (zh) * 2012-08-30 2015-10-21 中国石油化工股份有限公司 一种复合空心微球及其制备方法和应用
FR3039145A1 (fr) * 2015-07-23 2017-01-27 Saint-Gobain Weber Procede de preparation d'un beton ou mortier allege contenant de la glycerine

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6626991B1 (en) * 1999-07-29 2003-09-30 Schlumberger Technology Corp Low-density and low-porosity cementing slurry for oil wells or the like
US20030101911A1 (en) * 2001-12-03 2003-06-05 Brothers Lance E. Methods, well cement compositions and lightweight additives therefor
US20050241538A1 (en) * 2004-04-28 2005-11-03 Vargo Richard F Jr Methods of making cement compositions using liquid additives containing lightweight beads
CN102002263A (zh) * 2010-11-01 2011-04-06 上海大学 一种空心玻璃微珠包覆二氧化钛的制备方法
CN103666407A (zh) * 2012-09-12 2014-03-26 中国石油化工股份有限公司 钻井液及其制备方法
US20180355236A1 (en) * 2016-02-09 2018-12-13 Halliburton Energy Services, Inc. Surfactants for use in liquid suspensions of lightweight beads
AU2016428908A1 (en) * 2016-11-10 2019-03-07 Halliburton Energy Services, Inc. Storable liquid suspension of hollow particles
CN109679456A (zh) * 2019-01-09 2019-04-26 深圳市欧科力科技有限公司 集装箱用高效隔热防腐面漆的制备方法
CN211499249U (zh) * 2019-10-14 2020-09-15 北京志盛威华化工有限公司 一种复合反射保温涂层结构
CN110846008A (zh) * 2019-12-16 2020-02-28 天津市康盛科技开发有限公司 一种油井水泥减轻外掺料
CN113621355A (zh) * 2021-08-09 2021-11-09 中海油田服务股份有限公司 一种液体减轻剂及其制备和应用

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