WO2014161119A1 - Filtrate reducer for calcium phosphate cement - Google Patents

Filtrate reducer for calcium phosphate cement Download PDF

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WO2014161119A1
WO2014161119A1 PCT/CN2013/001495 CN2013001495W WO2014161119A1 WO 2014161119 A1 WO2014161119 A1 WO 2014161119A1 CN 2013001495 W CN2013001495 W CN 2013001495W WO 2014161119 A1 WO2014161119 A1 WO 2014161119A1
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parts
calcium phosphate
phosphate cement
acid
fluid loss
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PCT/CN2013/001495
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French (fr)
Chinese (zh)
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曾建国
孙富全
高永会
邹建龙
李鹏晓
王翀
刘爱萍
侯薇
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中国石油天然气集团公司
中国石油集团海洋工程有限公司
天津中油渤星工程科技有限公司
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Publication of WO2014161119A1 publication Critical patent/WO2014161119A1/en

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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
    • C09K8/487—Fluid loss control additives; Additives for reducing or preventing circulation loss
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
    • 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
    • C04B28/34—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 containing cold phosphate binders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/46—Water-loss or fluid-loss reducers, hygroscopic or hydrophilic agents, water retention agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]

Definitions

  • the invention relates to a cement admixture for oil and gas well cementing, in particular to a water loss agent for calcium orthoate cement.
  • acrylamide/2-acrylamido-2-methylpropanesulfonic acid/acrylic acid terpolymer acrylamide/2-acrylamido-2-methyl is well applied in silicate oil well cement slurry system.
  • the propanesulfonic acid/acrylic acid/maleic anhydride tetrapolymer could not effectively control the water loss of the calcium phosphate cement slurry.
  • the object of the present invention is to provide a fluid loss agent suitable for calcium acid cement, which is lost.
  • the water agent is added to the calcium acid cement slurry, and the water loss of the cement slurry can be controlled within 50 ml / 30 min in the range of 50 to 150 °C.
  • the calcium phosphate cement fluid loss reducing agent according to the present invention is a pentapolymer, and the comonomer of the pentapolymer is unsaturated amide, 2-acrylamido-2-methylpropanesulfonic acid, and one yuan is not Saturated carboxylic acid, methylene bis acrylamide and allyl polyoxyethylene ether; parts by weight of five monomers: 20 ⁇ 50 parts of unsaturated amide monomer, 2-acrylamido-2-methyl
  • the propane sulfonic acid is 30 to 50 parts, the monounsaturated carboxylic acid is 1 to 10 parts, the methylene bis acrylamide is 0.05 to 0.5 parts, and the allyl polyoxyethylene ether is 1 to 20 parts.
  • the preferred five-copolymer calcium phosphate cement fluid loss reducing agent is divided into five parts by weight: unsaturated amide monomer is 30 ⁇ 50 parts, 2-acrylamido-2-methylpropane sulfonic acid is 30 ⁇
  • the unsaturated amide monomer is one of acrylamide and hydrazine, ⁇ '-dimethyl acrylamide.
  • the monounsaturated carboxylic acid monomer is one of acrylic acid and methacrylic acid.
  • the cement slurry was prepared according to the GB/T 19139-2003 standard, and the water loss, free water amount and compressive strength of the sample #1_16# in the test sample 1 and the comparative test formulation were evaluated according to the standard.
  • the calcium phosphate cement formulation of the present invention is: aluminate cement (CA60) 100 + sodium polyphosphate 10.5 + fly ash 100, the same applies hereinafter.
  • Evaluation of the fluid loss agent formulation 100 parts calcium phosphate cement + 1 part of the fluid loss agent of the invention + 1 part retarder tartaric acid + 1 part retarder citric acid + 45 parts water.
  • the experimental results are shown in Table 3. Considering that the 9#-16# sample has poor control of water loss at 50 °C, it is not necessary to carry out higher temperature water loss, free water and compressive strength experiments.
  • the water loss agent 1#_8# sample provided by the invention can control the water loss within 50ml/30min within 50 ⁇ 150°C, the cement slurry free liquid is less, and the cement stone compressive strength is greater than 14MPa, which is beneficial to Improve cementing quality.
  • the fluid loss agent provided by the invention is added to the calcium phosphate cement slurry, and the cement slurry is 50 ⁇ 150
  • the amount of water loss in the range of °0 is within 50ml/30min.
  • the water loss control ability of the calcium orthosilicate slurry system is significantly better than that of the commercially available hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, polyvinyl alcohol, acrylamide/2 acrylamide. 2-methylpropanesulfonic acid/acrylic acid terpolymer, acrylamide/2_acrylamido-2-methylpropanesulfonic acid/acrylic acid/maleic anhydride tetrapolymer and Chinese patent (ZL200810226689. 4 ) Reported fluid loss agent.
  • the water loss control ability of the fluid loss reducing agent provided by the present invention is superior to that of the 3-chloro-2-hydroxytrimethylammonium chloride ether reported by the US patent (US 6, 846, 357 B2).
  • Cationic starch formed by the formation of starch see Table 4).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention relates to a filtrate reducer for a calcium phosphate cement. The filtrate reducer is a five-element copolymer. Comonomers of the five-element copolymer are an unsaturated acidamide monomer, 2-acrylamido-2-methylpropane sulfonic acid, unsaturated monocarboxylic acid, methylene-bisacrylamidem, and allyl polyoxyethylene ether. The five monomers are as follows by weight ratios: the unsaturated acidamide monomer is 20 to 50 parts, the 2-acrylamido-2-methylpropane sulfonic acid is 30 to 50 parts, the unsaturated monocarboxylic acid is 1 to 10 parts, the methylene-bisacrylamidem is 0.05 to 0.5 parts, and allyl polyoxyethylene ether is 1 to 20 parts. The filtrate reducer for the calcium phosphate cement controls the water loss of the calcium phosphate cement within 50 ml/30 min at a temperature of 50 to 150 degrees centigrade.

Description

- -种磷酸钙水泥降失水剂  - - Calcium phosphate cement fluid loss agent
技术领域 Technical field
本发明涉及一种油气井固井用水泥外加剂， 具体的是一种隣酸钙水泥 的降失水剂。  The invention relates to a cement admixture for oil and gas well cementing, in particular to a water loss agent for calcium orthoate cement.
背景技术 Background technique
文献 (US 5, 900, 053， US 6， 796, 378以及 2012年固井技术研讨会论 文集， 108-116页）研究表明， 通过酸碱反应制备的磷酸钙水泥作为一种 耐 C02腐蚀的特种水泥， 可用于含 C02腐蚀气体的油气田固井。 但是， 在 固井施工时， 磷酸钙水泥浆在压力下经过高渗透地层时将发生 "渗滤"， 水泥浆滤液大量进入地层， 导致水泥浆流动性变差， 危及施工安全， 甚 至造成固井事故。 同时， 滤液进入储层会对储层形成不同程度的伤害。 因此， 通常在固井作业时需要使用降失水剂。 Document (US 5, 900, 053, 6, 796, 378 and US cementing technology Symposium 2012, pages 108-116) showed that calcium phosphate prepared by acid-base reaction cement as a corrosion resistant C0 2 Special cement, which can be used for oil and gas field cementing with C0 2 corrosive gas. However, during cementing, the calcium phosphate cement slurry will undergo "percolation" when it passes through the high-permeability formation under pressure. The cement slurry filtrate enters the formation in large quantities, resulting in poor fluidity of the cement slurry, endangering construction safety, and even causing cementing. accident. At the same time, the filtrate entering the reservoir will cause different degrees of damage to the reservoir. Therefore, it is common to use a fluid loss additive during cementing operations.
磷酸钙水泥作为一种非硅酸盐基的化学结合材料， 其表面性质与水 化过程与硅酸盐基的油井水泥差别大， 因此， 常见的适用硅酸盐水泥的 降失水剂对磷酸钙水泥浆失水控制能力较差。 美国专利 （US 6, 846, 357 B2 ) 报道， 在 82. 2°C ( 180T ) 下， 占水泥重量 1%的降失水剂羟乙基纤 维素、 羧甲基羟乙基纤维素、 淀粉按 API (美国石油协会）标准测试的失 水量均为 1200ml/30min。 此外， 在硅酸盐油井水泥浆体系应用效果良好 的丙烯酰胺 /2-丙烯酰胺基 -2-甲基丙磺酸 /丙烯酸三元共聚物、 丙烯酰胺 /2_丙烯酰胺基- 2-甲基丙磺酸 /丙烯酸 /马来酸酐四元共聚物均不能有效 的控制磷酸钙水泥浆的失水。 而在固井作业中， 一般要求水泥浆的失水 量不超过 250ml/30min， 特殊情况下 （如尾管固井）， 要求水泥浆的失水 量不超过 50ml/30min。 发明内容  As a non-silicate-based chemical bonding material, calcium phosphate cement has different surface properties and hydration process than silicate-based oil well cement. Therefore, the common water-reducing agent for Portland cement is phosphoric acid. Calcium cement slurry has poor water loss control ability. U.S. Patent (US 6, 846, 357 B2) reports that at 82.2 ° C (180 T), the water-reducing agent hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, starch, which accounts for 1% by weight of the cement. The water loss tested according to the API (American Petroleum Institute) standard was 1200 ml / 30 min. In addition, acrylamide/2-acrylamido-2-methylpropanesulfonic acid/acrylic acid terpolymer, acrylamide/2-acrylamido-2-methyl is well applied in silicate oil well cement slurry system. The propanesulfonic acid/acrylic acid/maleic anhydride tetrapolymer could not effectively control the water loss of the calcium phosphate cement slurry. In cementing operations, it is generally required that the water loss of the cement slurry does not exceed 250 ml/30 min. Under special circumstances (such as tail pipe cementing), the water loss of the cement slurry is required to not exceed 50 ml/30 min. Summary of the invention
本发明的目的是提供一种适用于憐酸钙水泥的降失水剂， 将本降失 水剂添加到隣酸钙水泥浆中，可以在 50〜150°C范围内将水泥浆的失水量 控制在 50ml /30min以内。 The object of the present invention is to provide a fluid loss agent suitable for calcium acid cement, which is lost. The water agent is added to the calcium acid cement slurry, and the water loss of the cement slurry can be controlled within 50 ml / 30 min in the range of 50 to 150 °C.
本发明所述的磷酸钙水泥降失水剂是一种五元共聚物， 该五元共聚 物的共聚单体为不饱和酰胺、 2-丙烯酰胺基 -2-甲基丙磺酸、 一元不饱和 羧酸、 亚甲基双丙烯酰胺和烯丙基聚氧乙烯醚； 五种单体的按重量份为： 不饱和酰胺单体为 20〜50份， 2-丙烯酰胺基 -2-甲基丙磺酸为 30〜50份， 一元不饱和羧酸为 1〜10份， 亚甲基双丙烯酰胺为 0. 05〜0. 5份， 烯丙 基聚氧乙烯醚为 1〜20份。 较好的五元共聚物磷酸钙水泥降失水剂五种单体按重量份为： 不饱 和的酰胺单体为 30〜50份， 2-丙烯酰胺基 -2-甲基丙磺酸为 30〜50份， 一元不饱和羧酸为 2〜8份， 亚甲基双丙烯酰胺为 0. 1〜0. 5份， 烯丙基 聚氧乙烯醚 3〜15份。  The calcium phosphate cement fluid loss reducing agent according to the present invention is a pentapolymer, and the comonomer of the pentapolymer is unsaturated amide, 2-acrylamido-2-methylpropanesulfonic acid, and one yuan is not Saturated carboxylic acid, methylene bis acrylamide and allyl polyoxyethylene ether; parts by weight of five monomers: 20~50 parts of unsaturated amide monomer, 2-acrylamido-2-methyl The propane sulfonic acid is 30 to 50 parts, the monounsaturated carboxylic acid is 1 to 10 parts, the methylene bis acrylamide is 0.05 to 0.5 parts, and the allyl polyoxyethylene ether is 1 to 20 parts. The preferred five-copolymer calcium phosphate cement fluid loss reducing agent is divided into five parts by weight: unsaturated amide monomer is 30~50 parts, 2-acrylamido-2-methylpropane sulfonic acid is 30份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份。
所述的不饱和酰胺单体为丙烯酰胺和 Ν, Ν' —二甲基丙烯酰胺的一 种。  The unsaturated amide monomer is one of acrylamide and hydrazine, Ν'-dimethyl acrylamide.
所述的一元不饱和羧酸单体为丙烯酸和甲基丙烯酸的一种。  The monounsaturated carboxylic acid monomer is one of acrylic acid and methacrylic acid.
所述的烯丙基聚氧乙烯醚单体为 C =C (R) CH20 (C C 0) nH， 其中， R 为甲基或氢， n值的范围为 5〜20， 较好的 n值范围为 6〜12。 具体实施方式 The allyl polyoxyethylene ether monomer is C = C (R) CH 2 0 (CC 0) n H, wherein R is methyl or hydrogen, and the value of n ranges from 5 to 20, preferably The value of n ranges from 6 to 12. detailed description
按表 1和表 2配方称取丙烯酰胺 （或 Ν，Ν' —二甲基丙烯酰胺）、 2- 丙烯酰胺基 -2-甲基丙磺酸、 （甲基） 丙烯酸、 亚甲基双丙烯酰胺、 烯丙 基聚氧乙烯醚以及氢氧化钠溶于去离子水中， 然后将上述溶液加入到四 口瓶反应器内， 并保持搅拌 （转速 170rpm) ，在氮气保护下升温至 75°C， 加入 10g重量浓度为 10%的过硫酸铵溶液引发聚合反应， 75°C下恒温反应 4h， 得到五元共聚物溶液， 产物经干燥、 粉碎制成粉剂。  Weigh acrylamide (or hydrazine, Ν'-dimethyl acrylamide), 2-acrylamido-2-methylpropane sulfonic acid, (meth)acrylic acid, methylene bis propylene according to the formula of Table 1 and Table 2. The amide, allyl polyoxyethylene ether and sodium hydroxide were dissolved in deionized water, and then the above solution was added to a four-necked reactor, kept stirring (speed 170 rpm), and heated to 75 ° C under nitrogen atmosphere. 10 g of a 10% by weight ammonium persulfate solution was added to initiate polymerization, and the reaction was carried out at 75 ° C for 4 h under constant temperature to obtain a pentad copolymer solution. The product was dried and pulverized to prepare a powder.
表 1 磷酸钙水泥降失水剂配方 编号 {# 2 ； , 7ύ Hi: 丙烯酰胺 30.0 40.0 40.0 50.0 0 0 0 0Table 1 Calcium phosphate cement fluid loss formula No. {# 2 ; , 7ύ Hi: Acrylamide 30.0 40.0 40.0 50.0 0 0 0 0
N，V —二 N, V - two
甲基丙烯 0 0 0 0 30.0 40.0 40.0 50.0 酰胺  Methacrylic 0 0 0 0 30.0 40.0 40.0 50.0 Amide
2-丙烯酰  2-acryloyl
胺基 -2 -甲 50.0 40.0 40.0 40.0 50.0 40.0 40.0 40.0 基丙磺酸 Amino -2 - A 50.0 40.0 40.0 40.0 50.0 40.0 40.0 40.0 Propanesulfonic acid
丙烯酸 6.0 0 0 4.0 6.0 0 0 4.0 甲基丙烯  Acrylic 6.0 0 0 4.0 6.0 0 0 4.0 Methyl propylene
0 8.0 8.0 0 0 8.0 8.0 0 酸  0 8.0 8.0 0 0 8.0 8.0 0 Acid
亚甲基双  Methylene double
0.2 0.1 0.1 0.5 0.2 0.1 0.1 0.5 丙烯酰胺  0.2 0.1 0.1 0.5 0.2 0.1 0.1 0.5 acrylamide
烯丙基聚  Allyl polymerization
氧乙烯醚 13.8 0 11.9 0 13.8 0 11.9 0 (η=6)  Oxyethylene ether 13.8 0 11.9 0 13.8 0 11.9 0 (η=6)
烯丙基聚  Allyl polymerization
氧乙烯醚 0 11.9 0 5.5 0 11.9 0 5. δ (η=12)  Oxyethylene ether 0 11.9 0 5.5 0 11.9 0 5. δ (η=12)
过硫酸铵  Ammonium persulfate
10 10 10 10 10 10 10 10 溶液 (10%)  10 10 10 10 10 10 10 10 solution (10%)
NaOH 13.0 11.4 11.4 9.9 13.0 11.4 11.4 9.9 0 377 378.6 378.6 380.1 377 378.6 378.6 380.1  NaOH 13.0 11.4 11.4 9.9 13.0 11.4 11.4 9.9 0 377 378.6 378.6 380.1 377 378.6 378.6 380.1
对比试验配方 Comparative test formula
编号 9# 10ft 1W 12# 13# 14# 15# 16# 丙烯酰胺 0 0 0 0 40 30 0 0 No. 9# 10ft 1W 12# 13# 14# 15# 16# Acrylamide 0 0 0 0 40 30 0 0
Ν, N' 一二 Hey, N' one two
甲基丙烯 40.0 60.0 40 60.0 0 0 40 50 酰胺  Methyl propylene 40.0 60.0 40 60.0 0 0 40 50 amide
2-丙烯酰  2-acryloyl
胺基 -2-甲 100.0 100.0 100.0 100.0 40 50 40 40 基丙磺酸 丙烯酸 6.0 8.0 7.2 . () 0 6.0 0 4 甲基丙烯 Amino-2-methyl 100.0 100.0 100.0 100.0 40 50 40 40 propyl propane sulfonic acid Acrylic 6.0 8.0 7.2 . () 0 6.0 0 4 Methyl propylene
0 0 0 0 8 0 8 0 酸  0 0 0 0 8 0 8 0 Acid
衣康酸 6.0 8.0 6.0 0 0 0 0 0 马来酸酐 0 0 0 6.0 0 0 0 0 亚甲基双  Itaconic acid 6.0 8.0 6.0 0 0 0 0 0 Maleic anhydride 0 0 0 6.0 0 0 0 0 Methylene double
0.5 0. 1 0.5 0. 1 0. 1 0.2 0. 1 0. δ 丙烯酰胺  0.5 0. 1 0.5 0. 1 0. 1 0.2 0. 1 0. δ Acrylamide
过硫酸铵  Ammonium persulfate
3 3 3 3 10 10 10 10 溶液 (10%)  3 3 3 3 10 10 10 10 solution (10%)
NaOH 24.4 26.0 24.4 26.0 11.4 13.0 11.4 9.9 NaOH 24.4 26.0 24.4 26.0 11.4 13.0 11.4 9.9
¾0 717.0 689.0 717.0 689.0 378.6 377 378.6 380. 1 3⁄40 717.0 689.0 717.0 689.0 378.6 377 378.6 380. 1
按 GB/T 19139-2003标准制备水泥浆， 并按该标准评价表 1和对比 试验配方中的 1#_16#样品的失水量、游离水量和抗压强度。 由于国内不 存在商品化的由酸碱反应制备的磷酸钙水泥， 本发明中磷酸钙水泥配方 为： 铝酸盐水泥 （CA60) 100 + 多聚磷酸钠 10.5 +粉煤灰 100， 以下 同。 评价降失水剂配方： 100份磷酸钙水泥 + 1份本发明的降失水剂 + 1份缓凝剂酒石酸 + 1份缓凝剂柠檬酸 + 45份水。 实验结果如表 3所 示。 考虑到 9#-16#样品在 50°C时具有较差的控制失水能力， 因此， 没 必要开展更高温度的失水量、 游离水量和抗压强度实验。 The cement slurry was prepared according to the GB/T 19139-2003 standard, and the water loss, free water amount and compressive strength of the sample #1_16# in the test sample 1 and the comparative test formulation were evaluated according to the standard. Since there is no commercially available calcium phosphate cement prepared by acid-base reaction, the calcium phosphate cement formulation of the present invention is: aluminate cement (CA60) 100 + sodium polyphosphate 10.5 + fly ash 100, the same applies hereinafter. Evaluation of the fluid loss agent formulation: 100 parts calcium phosphate cement + 1 part of the fluid loss agent of the invention + 1 part retarder tartaric acid + 1 part retarder citric acid + 45 parts water. The experimental results are shown in Table 3. Considering that the 9#-16# sample has poor control of water loss at 50 °C, it is not necessary to carry out higher temperature water loss, free water and compressive strength experiments.
表 3 合成降失水剂性能实验结果 失水量， 24h抗压强度， 样品编号 温度， c 游离液， ml  Table 3 Experimental results of synthetic fluid loss agent performance Water loss, 24h compressive strength, sample number temperature, c free solution, ml
ml/30min Pa  Ml/30min Pa
50 28 0.2 22.5 50 28 0.2 22.5
90 34 0.2 24.290 34 0.2 24.2
W W
130 44 0.3 25.8  130 44 0.3 25.8
150 48 0.4 26.3 150 48 0.4 26.3
Figure imgf000006_0001
Figure imgf000006_0001
S6M00/CT0ZN3/X3d 6ΠΪ9Ϊ/ 0Ζ OAV 50 22 0 21.8 S6M00/CT0ZN3/X3d 6ΠΪ9Ϊ/ 0Ζ OAV 50 22 0 21.8
90 30 0 24.590 30 0 24.5
8# 8#
130 34 0.2 24.4  130 34 0.2 24.4
150 38 0.2 25.2 150 38 0.2 25.2
9# 50 1260 0.1 21.1 9# 50 1260 0.1 21.1
10# 50 1400 0.1 20.8 lltt 50 1346 0.1 19.7 10# 50 1400 0.1 20.8 lltt 50 1346 0.1 19.7
12# 50 1280 0.1 20.2 12# 50 1280 0.1 20.2
13 50 1420 0.1 20.9 13 50 1420 0.1 20.9
14U 50 1382 0.1 22.4 14U 50 1382 0.1 22.4
50 1248 0.1 18.4 50 1248 0.1 18.4
16# 50 1482 0.1 19.4 16# 50 1482 0.1 19.4
从表 3可以得出结论： From Table 3, we can conclude that:
(1)本发明提供的降失水剂 1#_8#样品在 50〜150°C内可将失水量 控制在 50ml/30min以内，水泥浆游离液少，水泥石抗压强度大于 14MPa， 有利于提高固井质量。  (1) The water loss agent 1#_8# sample provided by the invention can control the water loss within 50ml/30min within 50~150°C, the cement slurry free liquid is less, and the cement stone compressive strength is greater than 14MPa, which is beneficial to Improve cementing quality.
(2) 按同样合成工艺合成的对比试验 9#-16ft样品不能有效的控制 磷酸盐水泥浆体系失水量。  (2) Comparative test synthesized by the same synthesis process The 9#-16ft sample cannot effectively control the water loss of the phosphate cement slurry system.
将 7#样品与巿售的油井水泥降失水剂羟乙基纤维素、 羧甲基羟乙基 纤维素、 聚乙烯醇、 丙烯酰胺 /2-丙烯酰胺基 -2-甲基丙磺酸 /丙烯酸共聚 物、 丙烯酰胺 /2_丙烯酰胺基 -2-甲基丙磺酸 /丙烯酸 /马来酸酐共聚物以 及按 ZL200810226689.4实施例 1-4合成的样品（分别记为 17#、 18#， 19# 和 20#)进行同等条件下性能比较试验（按 GB/T 19139- 2003进行失水试 验）， 实验配方： 100份磷酸钙水泥 + 1份降失水剂 + 1份缓凝剂酒石酸 + 1份缓凝剂柠檬酸 + 45份水。 试验结果如表 4所不。The 7# sample and the sold oil well cement fluid loss agent hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, polyvinyl alcohol, acrylamide/2-acrylamido-2-methylpropanesulfonic acid / Acrylic copolymer, acrylamide/2-acrylamido-2-methylpropanesulfonic acid/acrylic acid/maleic anhydride copolymer and samples synthesized according to Examples 1-4 of ZL200810226689.4 (respectively recorded as 17#, 18#) , 19# and 20#) performance comparison test under the same conditions (dehydration test according to GB/T 19139-2003) Test), experimental formula: 100 parts of calcium phosphate cement + 1 part of water loss agent + 1 part of retarder tartaric acid + 1 part of retarder citric acid + 45 parts of water. The test results are shown in Table 4.
Figure imgf000008_0001
Figure imgf000008_0001
Figure imgf000008_0002
Figure imgf000008_0002
*为美国专利 (US 6, 846, 357 B2 ) 报道数据。  * Reported data for US patents (US 6, 846, 357 B2).
从表 4可以得出结论， 本发明提供的磷酸钙降失水剂对水泥桨的失 水控制能力优于表 4所列的其它类型的降失水剂。  From Table 4, it can be concluded that the calcium phosphate fluid loss agent provided by the present invention has superior dehydration control ability to cement paddles than the other types of fluid loss agents listed in Table 4.
工业实用性  Industrial applicability
本发明提供的降失水剂加入到磷酸钙水泥浆中， 水泥浆在 50〜150 °0范围内失水量在 50ml/30min以内。 采用本发明降失水剂对隣酸钙水泥 浆体系的失水控制能力显著优于市售的羟乙基纤维素、 羧甲基羟乙基纤 维素、 聚乙烯醇、 丙烯酰胺 /2 丙烯酰胺基 -2-甲基丙磺酸 /丙烯酸三元共 聚物、 丙烯酰胺 /2_丙烯酰胺基 -2-甲基丙磺酸 /丙烯酸 /马来酸酐四元共 聚物以及中国专利 （ZL200810226689. 4 ) 报道的降失水剂。 此外， 在同 等条件下， 本发明提供的降失水剂的失水控制能力优于美国专利 （US 6， 846, 357 B2 )报道的由 3_氯 _2_羟基三甲基氯化铵醚化淀粉而形成的阳 离子淀粉 （见表 4)。 The fluid loss agent provided by the invention is added to the calcium phosphate cement slurry, and the cement slurry is 50~150 The amount of water loss in the range of °0 is within 50ml/30min. The water loss control ability of the calcium orthosilicate slurry system is significantly better than that of the commercially available hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, polyvinyl alcohol, acrylamide/2 acrylamide. 2-methylpropanesulfonic acid/acrylic acid terpolymer, acrylamide/2_acrylamido-2-methylpropanesulfonic acid/acrylic acid/maleic anhydride tetrapolymer and Chinese patent (ZL200810226689. 4 ) Reported fluid loss agent. In addition, under the same conditions, the water loss control ability of the fluid loss reducing agent provided by the present invention is superior to that of the 3-chloro-2-hydroxytrimethylammonium chloride ether reported by the US patent (US 6, 846, 357 B2). Cationic starch formed by the formation of starch (see Table 4).

Claims

权 利 要 求 书 Claim
1. 一种磷酸钙水泥降失水剂， 是一种五元共聚物， 其特征在于： 该五 元共聚物的共聚单体为不饱和的酰胺单体、 2 丙烯酰胺基 -2-甲基丙磺 酸、 一元不饱和羧酸、 亚甲基双丙烯酰胺和烯丙基聚氧乙烯醚。  A calcium phosphate cement fluid loss additive, which is a pentapolymer, characterized in that: the comonomer of the pentapolymer is an unsaturated amide monomer, 2 acrylamido-2-methyl Propanesulfonic acid, monounsaturated carboxylic acid, methylene bis acrylamide and allyl polyoxyethylene ether.
2. 根据权利要求 1所述的磷酸钙水泥降失水剂， 其特征在于： 五种单 体按重量份比为： 不饱和的酰胺单体为 20〜50份， 2-丙烯酰胺基 -2-甲 基丙磺酸为 30〜50份， 一元不饱和羧酸为 1〜10份， 亚甲基双丙烯酰胺 为 0. 05〜0. 5份， 烯丙基聚氧乙烯醚 1〜20份。  2. The calcium phosphate cement fluid loss reducing agent according to claim 1, wherein: the five monomers are in a ratio by weight: unsaturated amide monomer is 20 to 50 parts, 2-acrylamido-2 5份,的均聚聚氧乙烯的1〜20份。 Methyl propane sulfonic acid is 30~50 parts, monounsaturated carboxylic acid is 1~10 parts, methylene bis acrylamide is 0. 05~0. 5 parts, allyl polyoxyethylene ether 1~20 parts .
3. 根据权利要求 1 所述的磷酸钙水泥降失水剂， 其特征在于： 不 饱和的酰胺单体为 30〜50份， 2-丙烯酰胺基 -2-甲基丙磺酸为 30〜50 份， 一元不饱和羧酸为 2〜8份， 亚甲基双丙烯酰胺为 0. 1〜0. 5份， 烯 丙基聚氧乙烯醚 3〜15份。 3. The calcium phosphate cement fluid loss reducing agent according to claim 1, wherein the unsaturated amide monomer is 30 to 50 parts, and the 2-acrylamido-2-methylpropanesulfonic acid is 30 to 50. 1份。 The portion of the monounsaturated carboxylic acid is 2 to 8 parts, the methylene bis acrylamide is 0. 1~0. 5 parts, allyl polyoxyethylene ether 3 to 15 parts.
4. 根据权利要求 1所述的磷酸钙水泥降失水剂， 其特征在于： 所述的 不饱和的酰胺单体为丙烯酰胺或 N， N' —二甲基丙烯酰胺的一种。  The calcium phosphate cement fluid loss reducing agent according to claim 1, wherein the unsaturated amide monomer is one of acrylamide or N,N'-dimethylacrylamide.
5. 根据权利要求 1所述的磷酸钙水泥降失水剂， 其特征在于： 所述的 一元不饱和羧酸单体为丙烯酸或甲基丙烯酸的一种。  The calcium phosphate cement fluid loss reducing agent according to claim 1, wherein the monounsaturated carboxylic acid monomer is one of acrylic acid or methacrylic acid.
6. 根据权利要求 1所述的磷酸钙水泥降失水剂， 其特征在于： 所述的 烯丙基聚氧乙烯醚单体为 C =C (R) C 0 (C C 0)„H， 其中， R为甲基或氢， n值的范围为 6〜12。  The calcium phosphate cement fluid loss reducing agent according to claim 1, wherein the allyl polyoxyethylene ether monomer is C = C (R) C 0 (CC 0) „H, wherein , R is methyl or hydrogen, and the value of n ranges from 6 to 12.
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