WO2016107054A1 - 一种交联剂的制造方法、交联剂及调剖剂的制造方法 - Google Patents

一种交联剂的制造方法、交联剂及调剖剂的制造方法 Download PDF

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WO2016107054A1
WO2016107054A1 PCT/CN2015/079338 CN2015079338W WO2016107054A1 WO 2016107054 A1 WO2016107054 A1 WO 2016107054A1 CN 2015079338 W CN2015079338 W CN 2015079338W WO 2016107054 A1 WO2016107054 A1 WO 2016107054A1
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crosslinking agent
agent
ethanol solution
phenol
profile control
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English (en)
French (fr)
Inventor
宋有胜
张贵清
王宇宾
徐鸿志
吕光明
夏烨
郝志伟
刘婧丹
王雪莹
赵文娜
叶松滨
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China National Petroleum Corp
CNPC Offshore Engineering Co Ltd
CNPC Research Institute of Engineering Technology
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China National Petroleum Corp
CNPC Offshore Engineering Co Ltd
CNPC Research Institute of Engineering Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/244—Stepwise homogeneous crosslinking of one polymer with one crosslinking system, e.g. partial curing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504—Compositions based on water or polar solvents
    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
    • C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents

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  • the present invention relates to the field of gel technology, and discloses a method for producing a crosslinking agent, a crosslinking agent, and a method for producing a profile control agent.
  • Polymer gel is a chemical profile control agent used in oilfields. The principle is that the three-dimensional network structure formed by cross-linking of the polymer and the cross-linking agent can block the high-permeability layer (segment) to achieve oil increase. The purpose of water control.
  • Common chemical profile control agents used in most oil fields in China include chrome gel, aluminum citrate gel, and phenolic resin gel.
  • the phenolic resin gel has good gel strength and controllable reaction time, but the liquid phenolic resin cross-linking agent is irreversibly cured due to heat, and the shelf life is short, so the application of the phenolic resin gel is limited.
  • the embodiment of the invention provides a method for manufacturing a cross-linking agent, a cross-linking agent and a cross-linking polymer gel profile control agent, so as to solve the technical problem that the cross-linking period of the cross-linking agent in the prior art is short.
  • the present invention provides a method for producing a crosslinking agent, comprising:
  • the phenol is heated and melted and mixed with the ethanol solution, the mass ratio of the ethanol solution to the phenol is 1:10-20;
  • a mixture of the phenol and the ethanol solution is added to carry out a reaction to obtain a solid product, which is the solid product a crosslinking agent, wherein a mass ratio of the solid reactant to the liquid reactant is 1:0.81.2, and the solid reactant is specifically the hexamethylenetetramine, sodium humate, lignosulfonate, and A mixture of reducing agents, specifically a mixture of the phenol and the ethanol solution.
  • the reducing agent is specifically one or more of anhydrous sodium sulfite, sodium thiosulfate, and thiourea.
  • an embodiment of the present invention provides a crosslinking agent, which is introduced by any embodiment of the present invention. It is manufactured by a joint manufacturing method.
  • an embodiment of the invention provides a method for manufacturing a crosslinked polymer gel profile control agent, comprising:
  • the base solution is prepared by mixing 0.2%-0.5% polymer, 0.1%-0.3% cross-linking agent, 0.05%-0.3% auxiliary agent and water in a weight ratio, wherein the polymer is: acrylamide homopolymer or An acrylamide-containing copolymer, the crosslinking agent being the crosslinking agent described in the examples of the present invention, wherein the sum of the weight percentages of the components in the base liquid is 100%;
  • the base liquid is reacted to obtain a gel having a three-dimensional network structure, and the gel is the crosslinked polymer gel profile control agent.
  • reaction temperature of the base liquid is: 60 ° C to 80 ° C.
  • the crosslinking assistant is one or more of ammonium chloride, citric acid, formic acid, and acetic acid.
  • the polymer has a molecular weight of 17 million to 22 million and a degree of hydrolysis of less than 25%.
  • a method for producing a crosslinking agent comprising: dissolving at least one of resorcin or hydroquinone in ethanol, and further configuring an ethanol solution in the ethanol
  • the total concentration of the solution hydroquinone or hydroquinone is 40%-45%;
  • the phenol is heated and melted and mixed with the ethanol solution, the mass ratio of the ethanol solution to the phenol is 1:10-20;
  • a mixture of the phenol and the ethanol solution is added to carry out a reaction to obtain a solid product, which is the solid product a crosslinking agent, wherein a mass ratio of the solid reactant to the liquid reactant is 1:0.8 to 1.2, and the solid reactant is specifically the hexamethylenetetramine, sodium humate, lignosulfonate, and A mixture of reducing agents, specifically a mixture of the phenol and the ethanol solution.
  • the cross-linking agent produced is solid, compared with the liquid phenolic resin-based cross-linking agent, the solid cross-linking agent has limited molecular space activity, is not easy to react with each other, and is added with a reducing agent, which is not easily oxidized, and further Extending the storage time of the crosslinking agent;
  • the profile control agent base liquid prepared by the crosslinking agent has low viscosity and is easy to be pumped, and the gelation time is continuously adjustable from several hours to several days, and the components are low in cost and easy to obtain raw materials, and can be used for water well profile control. Improve the reservoir heterogeneity, thereby improving the water injection efficiency, which can be seen, thereby improving the application range and application effect of the crosslinked polymer gel profile control agent.
  • FIG. 1 is a flow chart showing a method of manufacturing a crosslinking agent according to an embodiment of the present invention
  • FIG. 2 is a flow chart showing a method of manufacturing a crosslinked polymer gel profile control agent according to an embodiment of the present invention.
  • the embodiment of the invention provides a method for manufacturing a cross-linking agent, a cross-linking agent and a cross-linking polymer gel profile control agent, so as to solve the technical problem that the cross-linking period of the cross-linking agent in the prior art is short.
  • a method for producing a crosslinking agent comprising: dissolving at least one of resorcinol or hydroquinone in ethanol, and further configuring an ethanol solution, wherein the ethanol solution is resorcinol or p-benzene.
  • the total concentration of the diphenol is 40%-45%; the phenol is heated and melted and mixed with the ethanol solution, the mass ratio of the ethanol solution to the phenol is 1:10-20; hexamethylenetetramine After mixing the sodium humate, the lignosulfonate and the reducing agent, adding a mixture of the phenol and the ethanol solution to obtain a solid product, the solid product is the crosslinking agent, wherein the solid reaction
  • the mass ratio of the reactant to the liquid reactant is 1:0.8 to 1.2, and the solid reactant is specifically a mixture of the hexamethylenetetramine, sodium humate, lignosulfonate and the reducing agent.
  • the liquid reactant is specifically: a mixture of the phenol and the ethanol solution.
  • the liquid reactant is specifically a mixture of a solution of phenol and ethanol. Since the cross-linking agent produced is solid, compared with the liquid phenolic resin-based cross-linking agent, the solid cross-linking agent has limited molecular space activity, is not easy to react with each other, and is added with a reducing agent, which is not easily oxidized, and further Extending the storage time of the crosslinking agent;
  • the profile control agent base liquid prepared by the crosslinking agent has low viscosity and is easy to be pumped, and the gelation time is continuously adjustable from several hours to several days, and the components are low in cost and easy to obtain raw materials, and can be used for water well profile control. Improve the reservoir heterogeneity, thereby improving the water injection efficiency, which can be seen, thereby improving the application range and application effect of the crosslinked polymer gel profile control agent.
  • an embodiment of the present invention provides a method for manufacturing a crosslinking agent. Referring to FIG. 1, the method includes:
  • Step S101 Dissolving at least one of resorcinol or hydroquinone in ethanol, and further configuring an ethanol solution, wherein the total concentration of the resorcinol or hydroquinone in the ethanol solution is 40%-45. %;
  • Step S102 heating and melting the phenol, and mixing and stirring with the ethanol solution, the mass ratio of the ethanol solution to the phenol is 1:10-20, wherein the melting temperature of the phenol is heated because the melting point of the phenol is 40 °C. Above 40 ° C, but because the reaction to form the cross-linking agent is an exothermic reaction, if the phenol heating temperature is too high, it is not conducive to the exothermic reaction, so in order to ensure the molten phenol while facilitating the formation of cross-linking agent, melting The temperature can be controlled between 40 ° C and 60 ° C.
  • Step S103 after mixing hexamethylenetetramine, sodium humate, lignosulfonate and a reducing agent, adding a mixture of the phenol and the ethanol solution to obtain a solid product, the solid product is The crosslinking agent, wherein the mass ratio of the solid reactant to the liquid reactant is 1:0.8 to 1.2, and the solid reactant is specifically the hexamethylenetetramine, sodium humate, and lignosulfonate. And a mixture of the reducing agents.
  • step S103 after mixing the hexamethylenetetramine, the sodium humate, the lignosulfonate and the reducing agent, adding to the solid-liquid reaction kettle, slowly adding the mixture of the phenol and the ethanol solution, and cooling the reaction by circulating water. In the kettle, the reaction heat is neutralized in time, and the above compound is compounded into a solid state, and then pulverized to obtain a crosslinking agent.
  • the reducing agent is, for example, one or more of anhydrous sodium sulfite, sodium thiosulfate, and thiourea.
  • an embodiment of the present invention provides a crosslinking agent, which is manufactured by the method for producing a crosslinking agent according to the first aspect of the present invention, which is a solid powder and is not easily oxidized. Save for a long time.
  • an embodiment of the present invention provides a method for manufacturing a crosslinked polymer gel profile control agent. Referring to FIG. 2, the method includes:
  • Step S201 mixing a weight ratio of 0.2%-0.5% polymer, 0.1%-0.3% cross-linking agent, 0.05%-0.3% auxiliary agent and water into a base liquid, wherein the polymer is: acrylamide homopolymer Or a acrylamide copolymer, the crosslinking agent is the crosslinking agent described in the first aspect of the present invention, and the sum of the weight percentages of the components in the base liquid is 100%;
  • Step S202 The base liquid is reacted to obtain a gel having a three-dimensional network structure, and the gel is a crosslinked polymer gel profile control agent.
  • reaction temperature of the base liquid is: 60 ° C ⁇ 80 ° C.
  • the crosslinking assistant is one or more of ammonium chloride, citric acid, formic acid, and acetic acid.
  • the polymer has a molecular weight of 17 million to 22 million and a degree of hydrolysis of less than 25%.
  • the profile control agent base liquid manufactured by the above scheme has low viscosity and is easy to be pumped, and the gelation time is continuously adjustable from several hours to several days, and the components are low in cost and easy to obtain raw materials, and can be used for water well profile control and improvement of reservoirs. Non Homogenization, thereby improving the efficiency of water injection, can thus be seen, thereby increasing the application range and application effect of the crosslinked polymer gel profile control agent.
  • cross-linking agent cross-linking agent from hexamethylenetetramine, sodium humate, lignosulfonate, anhydrous sodium sulfite, sodium thiosulfate, resorcinol, Recombination of hydroquinone and phenol; adding 0.1% crosslinking assistant, the crosslinking assistant is one or more of ammonium chloride, citric acid, formic acid and acetic acid, at a pH of 5-6
  • the reaction was carried out at 60 ° C to form a crosslinked polymer gel profile control agent. After gelation, the gel strength was 25065 mPa ⁇ s, and the water absorption profile was improved after implementation.
  • the crosslinked polymer gel profile control agent provided in Example 1 is suitable for use in a 60 ° C reservoir profile control plugging.
  • cross-linking agent cross-linking agent from hexamethylenetetramine, sodium humate, lignosulfonate, anhydrous sodium sulfite, sodium thiosulfate, resorcinol, a composite of hydroquinone and phenol; adding 0.1% crosslinking assistant, the crosslinking assistant is one or more of ammonium chloride, citric acid, formic acid, acetic acid, at a pH of 5-6
  • the reaction was carried out at 70 ° C to form a crosslinked polymer gel profile control agent. After gelation, the gel strength was 28144 mPa ⁇ s, and the water absorption profile was improved after the implementation.
  • the crosslinked polymer gel profile control agent provided in Example 2 is suitable for use in 70 ° C reservoir profile control plugging.
  • cross-linking agent is complex phenolic resin, from hexamethylenetetramine, sodium humate, lignosulfonate, anhydrous sodium sulfite, sodium thiosulfate, Recombination of resorcinol, hydroquinone and phenol; adding 0.1% crosslinking assistant, the crosslinking assistant is one or more of ammonium chloride, citric acid, formic acid and acetic acid at pH Between 5 and 6, the reaction was carried out at 80 ° C to form a crosslinked polymer gel profile control agent. The gel strength after gelation was 31562 mPa ⁇ s, and the water absorption profile was improved after implementation.
  • the crosslinked polymer gel profile control agent provided in Example 3 is suitable for use in 80 ° C reservoir profile control plugging.
  • a method for producing a crosslinking agent comprising: dissolving at least one of resorcin or hydroquinone in ethanol, and further configuring an ethanol solution in the ethanol
  • the solution has a total concentration of hydroquinone or hydroquinone of 40-45%; the phenol is heated and melted and mixed with the ethanol solution, the mass ratio of the ethanol solution to the phenol is 1:10-20; After mixing hexamethylenetetramine, sodium humate, lignosulfonate and a reducing agent, a mixture of the phenol and the ethanol solution is added to carry out a reaction to obtain a solid product, which is the solid product a crosslinking agent, wherein a mass ratio of the solid reactant to the liquid reactant is 1:0.8 to 1.2, and the solid reactant is specifically the sixth A mixture of hypomethyltetramine, sodium humate, lignosulfonate and the reducing agent, the liquid reactant being specifically a mixture of
  • the cross-linking agent produced is solid, compared with the liquid phenolic resin-based cross-linking agent, the solid cross-linking agent has limited molecular space activity, is not easy to react with each other, and is added with a reducing agent, which is not easily oxidized, and further Extending the storage time of the crosslinking agent;
  • the profile control agent base liquid prepared by the crosslinking agent has low viscosity and is easy to be pumped, and the gelation time is continuously adjustable from several hours to several days, and the components are low in cost and easy to obtain raw materials, and can be used for water well profile control. Improve the reservoir heterogeneity, thereby improving the water injection efficiency, which can be seen, thereby improving the application range and application effect of the crosslinked polymer gel profile control agent.

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Abstract

本发明涉及凝胶技术领域，公开了一种交联剂的制造方法、交联剂及调剖剂的制造方法，以解决现有技术中的交联剂保质期较短的技术问题，该方法包括：将间苯二酚或者对苯二酚中的至少一种溶解于乙醇，进而配置成乙醇溶液，在乙醇溶液中间苯二酚或对苯二酚的总浓度为40％-45％；将苯酚加热熔融后与乙醇溶液混合搅拌，乙醇溶液与苯酚的质量比为1∶10～1∶20；将六次甲基四胺、腐植酸钠、木质素磺酸盐和还原剂混拌之后，加入苯酚与乙醇溶液的混合物进行反应获得固态产物，固态产物即为交联剂，其中，固体反应物和液体反应物的质量比为1∶0.8～1.2。达到了延长交联剂的保质期的技术效果。

Description

一种交联剂的制造方法、交联剂及调剖剂的制造方法 技术领域
本发明涉及凝胶技术领域，公开了一种交联剂的制造方法、交联剂及调剖剂的制造方法。
背景技术
油田开发到中后期，通过注水补充地层能量是我国大部分油田所采用的主要措施。由于油层存在着非均质性，会出现水在油层中的“突进”和“窜流”现象，严重地影响着油田的开发效果。为了提高注水效果和油田的最终采收率，需要及时的采取堵水调剖技术措施。聚合物类凝胶是目前油田应用较多的化学调剖剂，其原理是聚合物与交联剂通过化学键交联所形成的三维网络结构进而封堵高渗透层(段)，以达到增油控水的目的。
我国大部分油田所用化学调剖剂常见的有铬凝胶，柠檬酸铝凝胶，酚醛树脂凝胶等。其中，酚醛树脂凝胶成胶强度较好，反应时间可控，但是由于液态酚醛树脂类交联剂极易受热发生不可逆固化，保质期较短，故而导致酚醛树脂凝胶应用受到了限制。
发明内容
本发明实施例提供一种交联剂制造方法、交联剂及交联聚合物凝胶调剖剂的制造方法，以解决现有技术中的交联剂保质期较短的技术问题。
第一方面，本发明实施提供一种交联剂的制造方法，包括：
将间苯二酚或者对苯二酚中的至少一种溶解于乙醇，进而配置成乙醇溶液，在所述乙醇溶液中间苯二酚或对苯二酚的总浓度为40％-45％；
将苯酚加热熔融后与所述乙醇溶液混合搅拌，所述乙醇溶液与所述苯酚的质量比为1∶10～20；
将六次甲基四胺、腐植酸钠、木质素磺酸盐和还原剂混拌之后，加入所述苯酚与所述乙醇溶液的混合物进行反应获得固态产物，所述固态产物即为所述交联剂，其中，固体反应物和液体反应物的质量比为1∶0.81.2，所述固态反应物具体为所述六次甲基四胺、腐植酸钠、木质素磺酸盐和所述还原剂的混合物，所述液体反应物具体为：所述苯酚与所述乙醇溶液的混合物。
可选的，所述还原剂具体为：无水亚硫酸钠、硫代硫酸钠、硫脲中的一种或多种。
第二方面，本发明实施例提供一种交联剂，由本发明任一实施例介绍的交 联剂制造方法制造而成。
第三方面，本发明实施例提供一种交联聚合物凝胶调剖剂的制造方法，包括：
将重量比为0.2％-0.5％聚合物、0.1％-0.3％交联剂、0.05％-0.3％助剂与水混合配置成基液，其中，所述聚合物为：丙烯酰胺均聚物或含丙烯酰胺共聚物，所述交联剂为本发明实施例所介绍的交联剂，所述基液中各组分重量百分比之和为100％；
所述基液通过反应得到具有三维网络结构的凝胶，所述凝胶即为所述交联聚合物凝胶调剖剂。
可选的，所述基液的反应温度为：60℃～80℃。
可选的，所述交联助剂为：氯化铵、柠檬酸、甲酸、乙酸中的一种或多种。
可选的，所述聚合物的分子量1700万～2200万，水解度小于25％。
本发明有益效果如下：
由于在本发明实施例中，提供了一种交联剂的制造方法，包括：将间苯二酚或者对苯二酚中的至少一种溶解于乙醇，进而配置成乙醇溶液，在所述乙醇溶液中间苯二酚或对苯二酚的总浓度为40％-45％；
将苯酚加热熔融后与所述乙醇溶液混合搅拌，所述乙醇溶液与所述苯酚的质量比为1∶10～20；
将六次甲基四胺、腐植酸钠、木质素磺酸盐和还原剂混拌之后，加入所述苯酚与所述乙醇溶液的混合物进行反应获得固态产物，所述固态产物即为所述交联剂，其中，固体反应物和液体反应物的质量比为1∶0.8～1.2，所述固态反应物具体为所述六次甲基四胺、腐植酸钠、木质素磺酸盐和所述还原剂的混合物，所述液体反应物具体为：所述苯酚与所述乙醇溶液的混合物。由于所制造出的交联剂为固态，相比液态酚醛树脂类交联剂，固态交联剂分子空间活动受限，相互之间不易发生反应，且其中加入了还原剂，不易被氧化，进而延长了交联剂的保存时间；
并且通过该交联剂制造而成的调剖剂基液粘度低，易于泵入，成胶时间几小时至几天连续可调，各组分成本低廉、原料易得，可用于水井调剖，改善储层非均质性，从而提高注水开采效率，由此可见，从而提高了交联聚合物凝胶调剖剂的应用范围以及应用效果。
附图说明
通过阅读下文优选实施方式的详细描述，各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的，而并 不认为是对本发明的限制。而且在整个附图中，用相同的参考符号表示相同的部件。在附图中：
图1为本发明实施例中交联剂的制造方法的流程图；
图2为本发明实施例中交联聚合物凝胶调剖剂的制造方法的流程图。
具体实施方式
下面将参照附图更详细地描述本公开的示例性实施例。虽然附图中显示了本公开的示例性实施例，然而应当理解，可以以各种形式实现本公开而不应被这里阐述的实施例所限制。相反，提供这些实施例是为了能够更透彻地理解本公开，并且能够将本公开的范围完整的传达给本领域的技术人员。
本发明实施例提供一种交联剂制造方法、交联剂及交联聚合物凝胶调剖剂的制造方法，以解决现有技术中的交联剂保质期较短的技术问题。
本发明实施例总体思路如下：
提供了一种交联剂的制造方法，包括：将间苯二酚或者对苯二酚中的至少一种溶解于乙醇，进而配置成乙醇溶液，在所述乙醇溶液中间苯二酚或对苯二酚的总浓度为40％-45％；将苯酚加热熔融后与所述乙醇溶液混合搅拌，所述乙醇溶液与所述苯酚的质量比为1∶10～20；将六次甲基四胺、腐植酸钠、木质素磺酸盐和还原剂混拌之后，加入所述苯酚与所述乙醇溶液的混合物进行反应获得固态产物，所述固态产物即为所述交联剂，其中，固体反应物和液体反应物的质量比为1∶0.8～1.2，所述固态反应物具体为所述六次甲基四胺、腐植酸钠、木质素磺酸盐和所述还原剂的混合物，所述液体反应物具体为：所述苯酚与所述乙醇溶液的混合物。
液体反应物具体为：苯酚与乙醇溶液的混合物。由于所制造出的交联剂为固态，相比液态酚醛树脂类交联剂，固态交联剂分子空间活动受限，相互之间不易发生反应，且其中加入了还原剂，不易被氧化，进而延长了交联剂的保存时间；
并且通过该交联剂制造而成的调剖剂基液粘度低，易于泵入，成胶时间几小时至几天连续可调，各组分成本低廉、原料易得，可用于水井调剖，改善储层非均质性，从而提高注水开采效率，由此可见，从而提高了交联聚合物凝胶调剖剂的应用范围以及应用效果。
为了更好的理解上述技术方案，下面通过附图以及具体实施例对本发明技术方案做详细的说明，应当理解本发明实施例以及实施例中的具体特征是对本发明技术方案的详细的说明，而不是对本发明技术方案的限定，在不冲突的情况下，本发明实施例以及实施例中的技术特征可以相互组合。
第一方面，本发明实施例提供一种交联剂的制造方法，请参考图1，包括：
步骤S101：将间苯二酚或者对苯二酚中的至少一种溶解于乙醇，进而配置成乙醇溶液，在所述乙醇溶液中间苯二酚或对苯二酚的总浓度为40％-45％；
步骤S102：将苯酚加热熔融后与所述乙醇溶液混合搅拌，所述乙醇溶液与所述苯酚的质量比为1∶10～20，其中由于苯酚的熔点为40℃，故而对苯酚进行加热熔融温度高于40℃即可，但是因为生成交联剂的反应为放热反应，所以苯酚加热温度过高的话，不利于放热反应的进行，故而为了保证熔融苯酚同时又利于生成交联剂，熔融温度可以控制在40℃～60℃之间。
步骤S103：将六次甲基四胺、腐植酸钠、木质素磺酸盐和还原剂混拌之后，加入所述苯酚与所述乙醇溶液的混合物进行反应获得固态产物，所述固态产物即为所述交联剂，其中，固体反应物和液体反应物的质量比为1∶0.8～1.2，所述固态反应物具体为所述六次甲基四胺、腐植酸钠、木质素磺酸盐和所述还原剂的混合物。
步骤S103中，在将六次甲基四胺、腐植酸钠、木质素磺酸盐和还原剂混拌之后，加入到固液反应釜，缓慢加入苯酚与乙醇溶液的混合物，采用循环水冷却反应釜，及时中和反应热，进而将上述化合物复合成固态，然后将其粉碎，就可以得到交联剂。
还原剂例如为：无水亚硫酸钠、硫代硫酸钠、硫脲中的一种或多种。
第二方面，基于同一发明构思，本发明实施例提供一种交联剂，通过本发明实施例第一方面介绍的交联剂制造方法制造而成，其为固体粉末，且不易被氧化，进而保存时间较长。
第三方面，基于同一发明构思，本发明实施例提供一种交联聚合物凝胶调剖剂的制造方法，请参考图2，包括：
步骤S201：将重量比为0.2％-0.5％聚合物、0.1％-0.3％交联剂、0.05％-0.3％助剂与水混合配置成基液，其中，聚合物为：丙烯酰胺均聚物或含丙烯酰胺共聚物，交联剂为本发明实施例第一方面介绍的交联剂，基液中各组分重量百分比之和为100％；
步骤S202：基液通过反应得到具有三维网络结构的凝胶，凝胶即为交联聚合物凝胶调剖剂。
可选的，基液的反应温度为：60℃～80℃。
可选的，交联助剂为：氯化铵、柠檬酸、甲酸、乙酸中的一种或多种。
可选的，聚合物的分子量1700万～2200万，水解度小于25％。
通过上述方案制造而成的调剖剂基液粘度低，易于泵入，成胶时间几小时至几天连续可调，各组分成本低廉、原料易得，可用于水井调剖，改善储层非 均质性，从而提高注水开采效率，由此可见，从而提高了交联聚合物凝胶调剖剂的应用范围以及应用效果。
为了使本领域所属技术人员能够进一步的了解本发明实施例的方案，下面将基于本发明实施例所介绍的方案的实际应用来对其进行介绍。
实施例1：
配制0.4％的聚合物溶液，加入0.3％交联剂，交联剂由六次甲基四胺、腐植酸钠、木质素磺酸盐、无水亚硫酸钠、硫代硫酸钠、间苯二酚、对苯二酚及苯酚的复合而成；加入0.1％交联助剂，交联助剂为氯化铵、柠檬酸、甲酸、乙酸中的一种或多种，在pH值为5～6之间，60℃温度条件下反应生成交联聚合物凝胶调剖剂，成胶后凝胶强度为25065mPa·s，实施后吸水剖面得到明显改善。
实施例1提供的交联聚合物凝胶调剖剂适用于60℃储层调剖堵水。
实施例2：
配制0.4％的聚合物溶液，加入0.25％交联剂，交联剂由六次甲基四胺、腐植酸钠、木质素磺酸盐、无水亚硫酸钠、硫代硫酸钠、间苯二酚、对苯二酚及苯酚的复合而成；加入0.1％交联助剂，交联助剂为氯化铵、柠檬酸、甲酸、乙酸中的一种或多种，在pH为5～6之间，70℃温度条件下反应生成交联聚合物凝胶调剖剂，成胶后凝胶强度为28144mPa·s，实施后吸水剖面得到明显改善。
实施例2提供的交联聚合物凝胶调剖剂适用于70℃储层调剖堵水。
实施例3：
配制0.4％的聚合物溶液，加入0.2％交联剂，交联剂为复合酚醛树脂，由六次甲基四胺、腐植酸钠、木质素磺酸盐、无水亚硫酸钠、硫代硫酸钠、间苯二酚、对苯二酚及苯酚的复合而成；加入0.1％交联助剂，交联助剂为氯化铵、柠檬酸、甲酸、乙酸中的一种或多种，在pH为5～6之间，80℃温度条件下反应生成交联聚合物凝胶调剖剂，成胶后凝胶强度为31562mPa·s，实施后吸水剖面得到明显改善。
实施例3提供的交联聚合物凝胶调剖剂适用于80℃储层调剖堵水。
本发明的一个或多个实施例，至少具有以下有益效果：
由于在本发明实施例中，提供了一种交联剂的制造方法，包括：将间苯二酚或者对苯二酚中的至少一种溶解于乙醇，进而配置成乙醇溶液，在所述乙醇溶液中间苯二酚或对苯二酚的总浓度为40-45％；将苯酚加热熔融后与所述乙醇溶液混合搅拌，所述乙醇溶液与所述苯酚的质量比为1∶10～20；将六次甲基四胺、腐植酸钠、木质素磺酸盐和还原剂混拌之后，加入所述苯酚与所述乙醇溶液的混合物进行反应获得固态产物，所述固态产物即为所述交联剂，其中，固体反应物和液体反应物的质量比为1∶0.8～1.2，所述固态反应物具体为所述六 次甲基四胺、腐植酸钠、木质素磺酸盐和所述还原剂的混合物，所述液体反应物具体为：所述苯酚与所述乙醇溶液的混合物。由于所制造出的交联剂为固态，相比液态酚醛树脂类交联剂，固态交联剂分子空间活动受限，相互之间不易发生反应，且其中加入了还原剂，不易被氧化，进而延长了交联剂的保存时间；
并且通过该交联剂制造而成的调剖剂基液粘度低，易于泵入，成胶时间几小时至几天连续可调，各组分成本低廉、原料易得，可用于水井调剖，改善储层非均质性，从而提高注水开采效率，由此可见，从而提高了交联聚合物凝胶调剖剂的应用范围以及应用效果。
尽管已描述了本发明的优选实施例，但本领域内的技术人员一旦得知了基本创造性概念，则可对这些实施例作出另外的变更和修改。所以，所附权利要求意欲解释为包括优选实施例以及落入本发明范围的所有变更和修改。
显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若本发明的这些修改和变型属于本发明权利要求及
其等同技术的范围之内，则本发明也意图包含这些改动和变型在内。

Claims (7)

  1. 一种交联剂的制造方法，其特征在于，包括：
    将间苯二酚或者对苯二酚中的至少一种溶解于乙醇，进而配置成乙醇溶液，在所述乙醇溶液中间苯二酚或对苯二酚的总浓度为40％-45％；
    将苯酚加热熔融后与所述乙醇溶液混合搅拌，所述乙醇溶液与所述苯酚的质量比为1∶10～20；
    将六次甲基四胺、腐植酸钠、木质素磺酸盐和还原剂混拌之后，加入所述苯酚与所述乙醇溶液的混合物进行反应获得固态产物，所述固态产物即为所述交联剂，其中，固体反应物和液体反应物的质量比为1∶0.8～1.2，所述固态反应物具体为所述六次甲基四胺、腐植酸钠、木质素磺酸盐和所述还原剂的混合物，所述液体反应物具体为：所述苯酚与所述乙醇溶液的混合物。
  2. 如权利要求1所述的方法，其特征在于，所述还原剂具体为：无水亚硫酸钠、硫代硫酸钠、硫脲中的一种或多种。
  3. 一种交联剂，其特征在于，通过权利要求1或2所述的方法制造而成。
  4. 一种交联聚合物凝胶调剖剂的制造方法，其特征在于，包括：
    将重量比为0.2％-0.5％聚合物、0.1％-0.3％交联剂、0.05％-0.3％助剂与水混合配置成基液，其中，所述聚合物为：丙烯酰胺均聚物或含丙烯酰胺共聚物，所述交联剂为权利要求3所述的交联剂，所述基液中各组分重量百分比之和为100％；
    所述基液通过反应得到具有三维网络结构的凝胶，所述凝胶即为所述交联聚合物凝胶调剖剂。
  5. 如权利要求4所述的方法，其特征在于，所述基液的反应温度为：60℃～80℃。
  6. 如权利要求4所述的方法，其特征在于，所述交联助剂为：氯化铵、柠檬酸、甲酸、乙酸中的一种或多种。
  7. 如权利要求4所述的方法，其特征在于，所述聚合物的分子量1700万～2200万，水解度小于25％。
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CN112441650A (zh) * 2020-11-12 2021-03-05 中国石油天然气股份有限公司 一种油田工业废水循环利用方法
CN115746229A (zh) * 2021-09-02 2023-03-07 中国石油化工股份有限公司 一种耐高温交联剂的制备方法及耐高温交联剂、油田封堵剂及其制备方法和应用
CN115197684A (zh) * 2022-07-20 2022-10-18 湖南骏泰新材料科技有限责任公司 一种基于制浆预水解液的复合堵漏剂的制备方法
CN115197684B (zh) * 2022-07-20 2024-01-16 湖南骏泰新材料科技有限责任公司 一种基于制浆预水解液的复合堵漏剂的制备方法
CN119775986A (zh) * 2025-03-13 2025-04-08 东营江源化工有限公司 一种采油用延迟交联堵水调剖剂及其制备方法

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