WO2016107054A1

WO2016107054A1 - Crosslinking agent preparation method, and crosslinking agent and profile control agent preparation method

Info

Publication number: WO2016107054A1
Application number: PCT/CN2015/079338
Authority: WO
Inventors: 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
Original assignee: 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; 中国石油集团工程技术研究院
Priority date: 2014-12-29
Filing date: 2015-05-20
Publication date: 2016-07-07
Also published as: CN104498006B; CN104498006A

Abstract

The present invention relates to the technical field of gels. Disclosed are a crosslinking agent preparation method, and crosslinking agent and profile control agent preparation method, for addressing the technical problem in the prior art of a shorter shelf life of the crosslinking agent, the method comprising: dissolving at least one of resorcinol and hydroquinone in ethanol to form an ethanol solution having a total concentration of the resorcinol or the hydroquinone at 40-45% therein; heating and melting phenol, and then mixing and agitating the same with the ethanol solution with the mass ratio of the ethanol solution to the phenol being 1:10-1:20; mixing and agitating hexamethylene tetramine, sodium humate, lignosulfonate and a reducing agent, and then adding the mixture of the phenol and the ethanol solution to react and obtain a solid state product, namely, the solid state product is the crosslinking agent, and the mass ratio of solid reactants to liquid reactants is 1:0.8-1.2. The present invention lengthens the shelf life of the crosslinking agent.

Description

Method for producing cross-linking agent, cross-linking agent and method for producing profile control agent

Technical field

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.

Background technique

In the middle and late stages of oilfield development, replenishing stratigraphic energy by water injection is the main measure adopted by most oilfields in China. Due to the heterogeneity of the oil layer, the phenomenon of “protrusion” and “turbulence” of water in the oil layer may occur, which seriously affects the development effect of the oil field. In order to improve the water injection effect and the ultimate oil recovery of the oilfield, it is necessary to take timely measures of water shutoff and profile control. 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. Among them, 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.

Summary of the 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.

In a first aspect, the present invention provides a method for producing a crosslinking agent, comprising:

Dissolving at least one of resorcinol or hydroquinone in ethanol, and further configured as an ethanol solution, wherein the total concentration of the resorcinol or hydroquinone in the ethanol solution is 40% to 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 1:0.81.2, 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.

Optionally, the reducing agent is specifically one or more of anhydrous sodium sulfite, sodium thiosulfate, and thiourea.

In a second aspect, 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.

In a third aspect, 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.

Optionally, the reaction temperature of the base liquid is: 60 ° C to 80 ° C.

Optionally, the crosslinking assistant is one or more of ammonium chloride, citric acid, formic acid, and acetic acid.

Optionally, the polymer has a molecular weight of 17 million to 22 million and a degree of hydrolysis of less than 25%.

The beneficial effects of the present invention are as follows:

In the embodiment of the present invention, there is provided 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%;

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 hexamethylenetetramine, sodium humate, lignosulfonate, and A mixture of reducing agents, specifically a mixture of the phenol and the ethanol solution. 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.

DRAWINGS

Various other advantages and benefits will become apparent to those skilled in the art from a The drawings are only for the purpose of illustrating the preferred embodiments, and It is not considered to be a limitation of the invention. Throughout the drawings, the same reference numerals are used to refer to the same parts. In the drawing:

1 is a flow chart showing a method of manufacturing a crosslinking agent according to an embodiment of the present invention;

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.

detailed description

Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While the embodiments of the present invention have been shown in the drawings, the embodiments Rather, these embodiments are provided so that this disclosure will be more fully understood and the scope of the disclosure will be fully disclosed.

The general idea of the embodiment of the present invention is as follows:

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;

For a better understanding of the above technical solutions, the technical solutions of the present invention will be described in detail below through the accompanying drawings and specific embodiments. It should be understood that the specific features of the embodiments and the embodiments of the present invention are the detailed description of the technical solutions of the present invention, and The technical features of the embodiments of the present invention and the embodiments may be combined with each other without conflict.

In a first aspect, 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.

In 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.

In a second aspect, based on the same inventive concept, 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.

In a third aspect, based on the same inventive concept, 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.

Optionally, the reaction temperature of the base liquid is: 60 ° C ~ 80 ° C.

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.

In order to enable those skilled in the art to further understand the solutions of the embodiments of the present invention, the following will be introduced based on the practical application of the solutions introduced in the embodiments of the present invention.

Example 1:

Prepare 0.4% polymer solution, add 0.3% 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.

Example 2:

Prepare 0.4% polymer solution, add 0.25% 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.

Example 3:

Prepare 0.4% polymer solution, add 0.2% cross-linking agent, 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.

One or more embodiments of the present invention have at least the following beneficial effects:

In the embodiment of the present invention, there is provided 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 phenol and the ethanol solution. 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;

While the preferred embodiment of the invention has been described, it will be understood that Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and the modifications and

It is apparent that those skilled in the art can make various modifications and variations to the invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the invention are within the scope of the invention

The invention is also intended to cover such modifications and variations within the scope of the equivalents.

Claims

A method for producing a crosslinking agent, comprising:

Dissolving at least one of resorcinol or hydroquinone in ethanol, and further configured as an ethanol solution, wherein the total concentration of the resorcinol or hydroquinone in the ethanol solution is 40% to 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 hexamethylenetetramine, sodium humate, lignosulfonate, and A mixture of reducing agents, specifically a mixture of the phenol and the ethanol solution.
The method according to claim 1, wherein the reducing agent is specifically one or more of anhydrous sodium sulfite, sodium thiosulfate, and thiourea.
A crosslinking agent produced by the method of claim 1 or 2.
A method for producing 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 copolymer, the crosslinking agent is the crosslinking agent according to claim 3, 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.
The method according to claim 4, wherein the reaction temperature of the base liquid is from 60 ° C to 80 ° C.
The method according to claim 4, wherein the crosslinking assistant is one or more of ammonium chloride, citric acid, formic acid, and acetic acid.
The method of claim 4 wherein said polymer has a molecular weight of from 17 million to 22 million and a degree of hydrolysis of less than 25%.