WO2016134548A1 - 一种页岩气井滑溜水压裂液体系高效乳态快速水溶减阻剂 - Google Patents

一种页岩气井滑溜水压裂液体系高效乳态快速水溶减阻剂 Download PDF

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WO2016134548A1
WO2016134548A1 PCT/CN2015/073437 CN2015073437W WO2016134548A1 WO 2016134548 A1 WO2016134548 A1 WO 2016134548A1 CN 2015073437 W CN2015073437 W CN 2015073437W WO 2016134548 A1 WO2016134548 A1 WO 2016134548A1
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component
water
soluble
drag reducer
fracturing fluid
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PCT/CN2015/073437
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French (fr)
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余维初
吴军
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余维初
吴军
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Priority to US15/543,235 priority Critical patent/US10040988B2/en
Priority to PCT/CN2015/073437 priority patent/WO2016134548A1/zh
Publication of WO2016134548A1 publication Critical patent/WO2016134548A1/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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/02—Homopolymers or copolymers of vinylamine
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • 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
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/28—Friction or drag reducing additives

Definitions

  • the invention relates to a high-performance aquatic high-performance milky water-soluble drag reducing agent for shale gas well slick water fracturing fluid system with high compatibility and rapid water and characteristics. It belongs to the technical field of oilfield drag reducer.
  • the slick water fracturing technology is to add a small amount of drag reducing agent and other chemical additives and proppant as working fluid to the underground rock formation in high pressure and rapid manner, to transform the oil and gas reservoir and increase the permeability of the oil and gas layer. Increase oil and gas production capacity. Therefore, the performance of the drag reducer is directly related to whether the pressure cracking can be effectively implemented.
  • drag reducing agents are polymers of dry powder prepared from bulk via bulk polymerization. In the course of use, it has the disadvantage of being easy to form a ball and not being water-soluble, so that a lot of manpower and material resources are wasted in the process of construction.
  • the object of the present invention is to provide a green environmental protection, a good drag reduction effect, a fast dissolution rate, a convenient addition, and an advantage for the existing powder and the W/O type microemulsion slick water fracturing fluid drag reducing agent technology.
  • High-efficiency liquid drag reducing agent with the advantages of foaming, salt resistance, calcium resistance, anti-pollution, high temperature resistance, good compatibility and no need to add defoaming agent.
  • the drag reducing agent can achieve 70% drag reduction efficiency in pressure cracking, and solves the problem that the existing dry powder and W/O type microemulsion drag reducing agent are easy to form balls during use, is not easy to water, and is combined with pressure cracking liquid.
  • the shale gas well slick water fracturing fluid system high-efficiency milky fast water-soluble drag reducing agent is obtained by initiating polymerization of component A, component B and component C via a free radical initiator in water, and the value of the free radical initiator is less than 0.1% of the total weight of all reaction mixtures, the product is in the form of "milk", which is characterized by:
  • the component A is a plurality of nonionic water-soluble monomers having carbon-carbon double bonds, and the component A is composed of the following raw materials by weight:
  • the component B is a polymer stabilizer of a water-soluble monovalent cationic monomer, and the molecular weight is between 100,000 and 2,000,000, and the component B is composed of the following raw materials by weight:
  • the component C is a monovalent cationic inorganic salt, and the component C is composed of the following raw materials by weight:
  • the water is the balance.
  • the shale gas well slick water fracturing fluid system high-efficiency milky fast water-soluble drag reducing agent has the advantages of simple use, rapid water and the use of pressure cracking to achieve 70% drag reduction efficiency.
  • the invention solves the problem that the existing drag reducing agent is easy to be ball in the process of using dry powder, is not easy to water, and has poor compatibility with various ions and chemical additives in the pressure cracking liquid, and directly affects the feasibility of slick water pressure cracking. The issue of effectiveness.
  • the high-efficiency milky fast water-soluble drag reducing agent has green environmental protection, good drag reduction effect, fast dissolution speed, convenient addition, no foaming, salt resistance, calcium resistance, pollution resistance, high temperature resistance, good compatibility, and no need to add A series of advantages such as foaming agents.
  • the shale gas well slick water fracturing fluid system high-efficiency milky fast water-soluble drag reducing agent is free from component A, component B, component C
  • the base initiator is obtained by initiating polymerization in water, and the value of the radical initiator is less than 0.1% of the total weight of all the reaction mixtures, and the obtained product is in the form of "milk", which is characterized by:
  • the component A is a plurality of nonionic water-soluble monomers having carbon-carbon double bonds, and the component A is composed of the following raw materials by weight:
  • the component B is a polymer stabilizer of a water-soluble monovalent cationic monomer, and the molecular weight is between 100,000 and 2,000,000, and the component B is composed of the following raw materials by weight:
  • the component C is a monovalent cationic inorganic salt, and the component C is composed of the following raw materials by weight:
  • the water is the balance.
  • Component A 2-hydroxyethyl acrylate 1 kg, 2-hydroxyethyl methyl methacrylate 1 kg, 2-hydroxypropyl propyl 1 kg of enoate, 1 kg of 2-hydroxypropyl methacrylate, 5 kg of ethoxylated 2-hydroxyethyl acrylate, 2 kg of ethoxylated 2-hydroxyethyl methacrylate, 3 kg of methylol styrene, 1 kg of vinyl acetate, and 4 kg of acrylamide.
  • Component A accounts for 19% of the total weight of all reaction mixtures.
  • Component B 1 kg of poly[2-(methacryloyloxy)ethyl]trimethylammonium chloride, 2 kg of poly[2-(acryloyloxy)ethyl]trimethylammonium chloride, 2 kg of polyvinylbenzyltrimethylammonium chloride, 2 kg of polydimethyldiallylammonium chloride.
  • Component B represents 7% of the total weight of all reaction mixtures.
  • Component C 5 kg of sodium chloride, 10 kg of ammonium sulfate, 1 kg of potassium chloride, and 5 kg of sodium sulfate. Component C represents 21% of the total weight of all reaction mixtures.
  • a total of 47 kg of the above-mentioned component A, component B, and component C were placed in 53 kg of water and stirred, and the temperature was slowly raised to 60 ° C, and then the kneading was carried out by 10 g of ammonium persulfate, and the reaction was carried out for 10 hours. Cooling to 30 ° C, the product is a "milk"-like shale gas well slick water fracturing fluid system high-efficiency milky fast water-soluble drag reducing agent.
  • Component A 2 kg of 2-hydroxyethyl acrylate, 2 kg of 2-hydroxyethyl methacrylate, 2 kg of 2-hydroxypropyl acrylate, 1 kg of 2-hydroxypropyl methacrylate, B 4 kg of oxylated 2-hydroxyethyl acrylate, 2 kg of ethoxylated 2-hydroxyethyl methacrylate, 1 kg of hydroxymethylstyrene, 2 kg of vinyl acetate, and 3 kg of acrylamide Component A accounts for 19% of the total weight of all reaction mixtures.
  • Component B 1 kg of poly[2-(methacryloyloxy)ethyl]trimethylammonium chloride, 3 kg of poly[2-(acryloyloxy)ethyl]trimethylammonium chloride, 1 kg of polyvinylbenzyltrimethylammonium chloride, 1 kg of polydimethyldiallyl ammonium chloride.
  • Component B accounts for 6% of the total weight of all reaction mixtures.
  • Component C 5 kg of sodium chloride, 10 kg of ammonium sulfate, 5 kg of potassium chloride, 5 kg of sodium sulfate, and component C accounted for 25% of the total weight of all reaction mixtures.
  • a total of 50 kg of the above-mentioned component A, component B, and component C were placed in 50 kg of water, stirred, and slowly heated to 60 ° C, and then kneaded by 5 g of ammonium persulfate, and reacted for 10 hours. Cooling to 30 ° C, the product is a "milk"-like shale gas well slick water fracturing fluid system high-efficiency milky fast water-soluble drag reducing agent.

Abstract

本发明涉及一种叶岩气井滑溜水压裂液体系高效乳态快速水溶减阻剂，属油田减阻剂技术领域。它由组分A、组分B、组分C经由自由基引发剂在水中引发聚合获得，所述的组分A为多种具有碳碳双键的非离子型的水溶型单体，组分B为水溶的单价阳离子单体的聚合物稳定剂，组分C为单价阳离子无机盐，本发明使用简便，绿色环保，水和快速，具有溶解速度快、添加方便、不起泡、抗盐、抗钙、抗污染、抗高温、配伍性好、不需添加消泡剂等优点，在压力裂化中使用可达到70％减阻效率。解决了现有减阻剂采用干粉使用过程中容易成球，不易水和，以及与压力裂化液中的各种不同离子及化学助剂的相容性差，直接影响滑溜水压力裂化的可行性和有效性的问题。

Description

一种页岩气井滑溜水压裂液体系高效乳态快速水溶减阻剂 技术领域
本发明涉及一种高性能水生的具有高相容性和快速水和特性的页岩气井滑溜水压裂液体系高效乳态快速水溶减阻剂。属油田减阻剂技术领域。
背景技术
近年来由于页岩气田的广泛发现和开采，能提高油层通透率的滑溜水压力裂化技术也越来越受到关注。
滑溜水压裂技术是在清水或盐水中加入少量减阻剂和其它一些化学添加剂以及支撑剂作为工作液以高压快速的方式注入地下岩层，改造油气储层，增大油气层的渗透率，从而提高油气产能。因此，减阻剂的性能直接关系到压力裂化能否有效的实施。目前使用非常普遍的减阻剂是干粉的聚合物由单体经由本体聚合制备。其在使用过程中有容易成球，不易水溶的缺点，从而在施工的过程中浪费了大量的人力和物力。另外由于这种减阻剂不易分散，所以在生产过程中往往加入一定的表面活性剂以提高其分散性。然而，这种表面活性剂的加入作用有限，但副作用却很明显，就是在分散过程中起泡，需额外增加消泡剂来抑制起泡，否则将大大降低压裂液的性能，同时也增大了生产成本。另外还有一种W/O型微乳液产品的减阻剂(专利申请公布号为“CN103013488A”，名称为“滑溜水压裂液减阻剂及其制备方法”)，其在水中分散困难，在水中搅拌96小时后还是浑浊状态，严重影响滑溜水压裂液体系的性能。
发明内容
本发明的目的在于，针对现有粉末与W/O型微乳液滑溜水压裂液减阻剂技术的不足，提供一种具有绿色环保、减阻效果好、溶解速度快、添加方便、不起泡、抗盐、抗钙、抗污染、抗高温、配伍性好、不需添加消泡剂等优点的高效液体减阻剂。该减阻剂在压力裂化中使用可以达到70％减阻效率，并且解决了现有干粉与W/O型微乳液减阻剂在使用过程中容易成球，不易水和，以及与压力裂化液中的各种不同离子及化学助剂的相容性差的技术缺陷。
本发明是通过如下的技术方案来实现上述目的的：
该页岩气井滑溜水压裂液体系高效乳态快速水溶减阻剂由组分A、组分B、组分C经由自由基引发剂在水中引发聚合获得，自由基引发剂的取值为小于所有反应混合物总重量的0.1％，产品为“牛奶”状，其特征在于：
所述的组分A为多种具有碳碳双键的非离子型的水溶型单体，组分A由下述重量百分比的原料构成：
Figure PCTCN2015073437-appb-000001
所述的组分B为水溶的单价阳离子单体的聚合物稳定剂，并且分子量在100000到2000000之间，组分B由下述重量百分比的原料构成：
Figure PCTCN2015073437-appb-000002
所述的组分C为单价阳离子无机盐，组分C由下述重量百分比的原料构成：
Figure PCTCN2015073437-appb-000003
所述的水为余量。
本发明与现有技术相比的有益效果在于：
该页岩气井滑溜水压裂液体系高效乳态快速水溶减阻剂具有使用简便，快速水和的特性，在压力裂化中使用可以达到70％减阻效率。解决了现有减阻剂采用干粉使用过程中容易成球，不易水和，以及与压力裂化液中的各种不同离子及化学助剂的相容性差，直接影响滑溜水压力裂化的可行性和有效性的问题。另外本高效乳态快速水溶减阻剂具有绿色环保、减阻效果好、溶解速度快、添加方便、不起泡、抗盐、抗钙、抗污染、抗高温、配伍性好、不需添加消泡剂等一系列优点。
具体实施方式：
该页岩气井滑溜水压裂液体系高效乳态快速水溶减阻剂由组分A、组分B、组分C经由自由 基引发剂在水中引发聚合获得，自由基引发剂的取值为小于所有反应混合物总重量的0.1％，获得的产品为“牛奶”状，其特征在于：
所述的组分A为多种具有碳碳双键的非离子型的水溶型单体，组分A由下述重量百分比的原料构成：
Figure PCTCN2015073437-appb-000004
所述的组分B为水溶的单价阳离子单体的聚合物稳定剂，并且分子量在100000到2000000之间，组分B由下述重量百分比的原料构成：
Figure PCTCN2015073437-appb-000005
所述的组分C为单价阳离子无机盐，组分C由下述重量百分比的原料构成：
Figure PCTCN2015073437-appb-000006
所述的水为余量。
下面通过具体实施例对本发明做进一步的描述如下，以制取100千克的页岩气井滑溜水压裂液体系高效乳态快速水溶减阻剂为例。
实施例1：
按上述各组份的重量百分比称取组分A、组分B、组分C和水各原料。
组分A：2-羟乙基丙烯酸酯1千克，2-羟乙基甲基丙烯酸甲酯1千克，2-羟丙基丙 烯酸酯1千克，2-羟丙基甲基丙烯酸酯1千克，乙氧基化-2-羟乙基丙烯酸酯5千克，乙氧基化-2-羟乙基甲基丙烯酸酯2千克，羟甲基苯乙烯3千克，醋酸乙烯酯1千克，和丙烯酰胺4千克。组分A占所有反应混合物总重量的19％。
组分B：聚[2-(甲基丙烯酰氧基)乙基]三甲基氯化铵1千克，聚[2-(丙烯酰氧基)乙基]三甲基氯化铵2千克，聚乙烯基苄基三甲基氯化铵2千克，聚二甲基二烯丙基氯化铵2千克。组分B占所有反应混合物总重量的7％。
组分C：氯化钠5千克，硫酸铵10千克，氯化钾1千克，硫酸钠5千克。组分C占所有反应混合物总重量的21％。
水：53千克。
将上述的组分A、组分B、组分C共计47千克原料放入53千克水中搅拌，并且缓慢升温至60℃，再由过硫酸铵10克引发棸合，反应10小时后将反应物冷却到30℃，即得到产品为“牛奶”状的页岩气井滑溜水压裂液体系高效乳态快速水溶减阻剂。
实施例2：
按上述各组份的重量百分比称取组分A、组分B、组分C和水各原料。
组分A：2-羟乙基丙烯酸酯2千克，2-羟乙基甲基丙烯酸甲酯2千克，2-羟丙基丙烯酸酯2千克，2-羟丙基甲基丙烯酸酯1千克，乙氧基化-2-羟乙基丙烯酸酯4千克，乙氧基化-2-羟乙基甲基丙烯酸酯2千克，羟甲基苯乙烯1千克，醋酸乙烯酯2千克，和丙烯酰胺3千克，组分A占所有反应混合物总重量的19％。
组分B：聚[2-(甲基丙烯酰氧基)乙基]三甲基氯化铵1千克，聚[2-(丙烯酰氧基)乙基]三甲基氯化铵3千克，聚乙烯基苄基三甲基氯化铵1千克，聚二甲基二烯丙基氯化铵1千克。组分B占所有反应混合物总重量的6％。
组分C：氯化钠5千克，硫酸铵10千克，氯化钾5千克，硫酸钠5千克，组分C占所有反应混合物总重量的25％。
水：50千克。
将上述的组分A、组分B、组分C共计50千克原料放入50千克水中搅拌，并且缓慢升温至60℃，再由过硫酸铵5克引发棸合，反应10小时后将反应物冷却到30℃，即得到产品为“牛奶”状的页岩气井滑溜水压裂液体系高效乳态快速水溶减阻剂。
以上所述只是本发明的较佳实施例而已，上述举例说明不对本发明的实质内容作任何形式上的限制，所属技术领域的普通技术人员在阅读了本说明书后依据本发明的技术实质对以上具体实施方式所作的任何简单修改或变形，以及可能利用上述揭示的技术内容加以变更 或修饰为等同变化的等效实施例，均仍属于本发明技术方案的范围内，而不背离本发明的实质和范围。

Claims (1)

  1. 一种页岩气井滑溜水压裂液体系高效乳态快速水溶减阻剂，它由组分A、组分B、组分C经由自由基引发剂在水中引发聚合获得，自由基引发剂的取值为小于所有反应混合物总重量的0.1％，产品为“牛奶”状，其特征在于：
    所述的组分A为多种具有碳碳双键的非离子型的水溶型单体，组分A由下述重量百分比的原料构成：
    Figure PCTCN2015073437-appb-100001
    所述的组分B为水溶的单价阳离子单体的聚合物稳定剂，并且分子量在100000到2000000之间，组分B由下述重量百分比的原料构成：
    Figure PCTCN2015073437-appb-100002
    所述的组分C为单价阳离子无机盐，组分C由下述重量百分比的原料构成：
    Figure PCTCN2015073437-appb-100003
PCT/CN2015/073437 2015-02-28 2015-02-28 一种页岩气井滑溜水压裂液体系高效乳态快速水溶减阻剂 WO2016134548A1 (zh)

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