CN107057667B - Modified phenolic crosslinking agent and preparation method and application thereof - Google Patents
Modified phenolic crosslinking agent and preparation method and application thereof Download PDFInfo
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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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
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- 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
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Abstract
The invention discloses a modified phenolic crosslinking agent, and a preparation method and application thereof, and belongs to the technical field of oilfield chemistry. The cross-linking agent comprises 90-95 parts by weight of phenolic aldehyde prepolymer and 5-10 parts by weight of stabilizer, wherein: the phenolic aldehyde prepolymer is prepared by reacting phenols and formaldehyde in a molar ratio of 2.5: 1-3: 1 under the action of an alkaline catalyst, and the content of hydroxymethyl in the phenolic aldehyde prepolymer is 18.92-23.34%; the stabilizer is amino-substituted benzoic acids. The storage period of the cross-linking agent is more than 6 months at room temperature, when the cross-linking agent is applied to the preparation of the cross-linked polymer gel profile control agent, the gelling temperature is 80-120 ℃, the gelling time is 24-120h, the formed gel system is stable, the gel viscosity is more than 8000mPa & s, the cross-linking agent is suitable for deep profile control and flooding operation treatment of an injection well, and the cross-linking agent has good application prospect in the aspect of improving the crude oil recovery ratio in the later development of a high-water-content oil field.
Description
Technical Field
The invention relates to the technical field of oilfield chemistry, and particularly relates to a modified phenolic crosslinking agent, and a preparation method and application thereof.
Background
In the middle and later stages of oil field development, the main measures adopted by most oil fields in China at present are to supplement formation energy through water injection. Due to the complexity of the oil reservoir stratum and the heterogeneity of the stratum, when the water injection amount is increased, a large amount of water is discharged from an oil well, and the water drive development effect is seriously influenced. In order to improve the water injection effect and the final recovery ratio of an oil field, the water-plugging profile control technology of an oil layer is paid attention to and developed in the development of oil and gas fields. The cross-linking agent can react with polyacrylamide polymer to obtain gel with different viscosity, and the gel is applied to the field of water shutoff and profile control of oil fields to improve the recovery ratio of the oil fields.
The existing common cross-linking agent is a water-soluble phenolic resin cross-linking agent, which is prepared by taking formaldehyde and phenol as raw materials, heating the raw materials in a reaction kettle to 50-60 ℃, and adding an alkaline catalyst for reaction. Because the content of the third-order hydroxyl phenol and the fourth-order hydroxyl phenol in the existing water-soluble phenolic resin cross-linking agent is too high, the reaction activity of the cross-linking agent is reduced; meanwhile, the water-soluble phenolic resin cross-linking agent is easy to be subjected to polycondensation, the effective period is only 1-2 months generally, and the problem of short effective period exists, so that the field application and popularization are greatly limited.
Disclosure of Invention
The invention provides a modified phenolic crosslinking agent and a preparation method and application thereof, and solves the technical problems of low reaction activity and short preservation period of a water-soluble phenolic resin crosslinking agent in the prior art.
On one hand, in order to solve the technical problems, the invention provides a modified phenolic aldehyde crosslinking agent which comprises 90-95 parts by weight of phenolic aldehyde prepolymer and 5-10 parts by weight of stabilizer, wherein:
the phenolic aldehyde prepolymer is prepared by reacting phenols and formaldehyde in a molar ratio of 2.5: 1-3: 1 under the action of an alkaline catalyst, and the content of hydroxymethyl in the phenolic aldehyde prepolymer is 18.92-23.34%;
the stabilizer is amino-substituted benzoic acids.
Further, the phenol is phenol or resorcinol.
Further, the stabilizer is one or two of o-aminobenzoic acid and p-aminobenzoic acid.
Further, the alkaline catalyst is a mixture of sodium hydroxide and barium hydroxide; the dosage of the alkaline catalyst is 1.5 to 2.5 percent of the total weight of the phenols and the formaldehyde.
In another aspect, the present invention provides a method for preparing a modified phenolic crosslinking agent, comprising:
heating phenols to 60-65 ℃, adding an alkaline catalyst, stirring and activating to obtain a mixed solution;
adding a formaldehyde solution into the mixed solution, heating to 60-65 ℃, and reacting at a constant temperature for 40-50min to obtain a phenolic aldehyde prepolymer; wherein the molar ratio of the phenols to the formaldehyde is 2.5: 1-3: 1;
uniformly mixing the phenolic aldehyde prepolymer and a stabilizer to obtain the cross-linking agent; wherein the weight parts of the phenolic aldehyde prepolymer and the stabilizer are respectively 90-95 parts and 5-10 parts; the stabilizer is amino-substituted benzoic acids.
Further, the phenol is phenol or resorcinol; the stabilizer is one or two of o-aminobenzoic acid and p-aminobenzoic acid.
Further, the alkaline catalyst is a mixture of sodium hydroxide and barium hydroxide; the dosage of the alkaline catalyst is 1.5-2.5% of the total weight of the phenols and the formaldehyde solution.
In another aspect, the invention provides the use of a modified phenolic crosslinker in the preparation of a crosslinked polymer gel profile control agent.
Further, the method of applying comprises:
mixing 0.2-0.4 wt% of polymer, 0.2-0.4 wt% of modified phenolic aldehyde crosslinking agent and water to prepare base liquid, wherein the sum of the weight percentages of all the components in the base liquid is 100%; the polymer is polyacrylamide, and the modified phenolic aldehyde crosslinking agent is prepared by mixing 90-95 parts by weight of phenolic aldehyde prepolymer and 5-10 parts by weight of stabilizer;
and reacting the base solution to obtain gel with a three-dimensional network structure, wherein the gel is the cross-linked polymer gel profile control agent.
Further, the relative molecular mass of the polymer is 2000-2500 million, and the degree of hydrolysis is less than 25%; the reaction temperature of the base liquid is 80-120 ℃.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
according to the modified phenolic aldehyde crosslinking agent provided by the embodiment of the invention, the content of third-order hydroxyl phenol and fourth-order hydroxyl phenol in the phenolic prepolymer is reduced by adding the stabilizer, so that the main components of the modified phenolic aldehyde crosslinking agent mainly comprise first-order hydroxyl phenol and second-order hydroxyl phenol, the reaction activity of the crosslinking agent and a polyacrylamide polymer is improved, meanwhile, the addition of the stabilizer slows down the self-polycondensation rate of the crosslinking agent, and the preservation period of validity is prolonged; the crosslinking agent has the storage period of more than 6 months at room temperature, can be gelled at the temperature of 80-120 ℃, the gelling time is controllable within 20-120h, and the formed gel system is stable and is suitable for deep profile control and flooding operation of an injection well.
Drawings
FIG. 1 is a flow chart of a method of making a modified phenolic crosslinker in an embodiment of the invention;
FIG. 2 is a flow chart of a method for using a modified phenolic crosslinker in the preparation of a crosslinked polymer gel profile control agent in accordance with an embodiment of the present invention.
Detailed Description
The embodiment of the invention provides a modified phenolic crosslinking agent and a preparation method and application thereof, and solves the technical problems of low reaction activity and short preservation period of validity of a water-soluble phenolic resin crosslinking agent in the prior art; the cross-linking agent has a preservation period of more than 6 months at room temperature, a gelling temperature of 80-120 ℃, gelling time of 24-120h, and a formed gel system is stable.
In order to solve the above technical problems, the general idea of the embodiment of the present invention is as follows:
the invention provides a modified phenolic aldehyde crosslinking agent which comprises 90-95 parts by weight of phenolic aldehyde prepolymer and 5-10 parts by weight of stabilizer, wherein:
the phenolic aldehyde prepolymer is prepared by reacting phenols and formaldehyde in a molar ratio of 2.5: 1-3: 1 under the action of an alkaline catalyst, and the content of hydroxymethyl in the phenolic aldehyde prepolymer is 18.92-23.34%;
the stabilizer is amino-substituted benzoic acids.
From the above contents, the main components of the modified phenolic aldehyde crosslinking agent are mainly first-order hydroxyl phenol and second-order hydroxyl phenol after the phenolic aldehyde prepolymer and the amino-substituted benzoic acid substance serving as the stabilizer act, so that the contents of third-order hydroxyl phenol and fourth-order hydroxyl phenol in the phenolic aldehyde prepolymer are reduced, and the first-order hydroxyl phenol and the second-order hydroxyl phenol have small steric hindrance and are easy to react with a polymer to form gel, so that the reaction activity of the crosslinking agent and the polyacrylamide polymer is improved; meanwhile, the addition of the stabilizer can delay the polycondensation rate of the phenolic prepolymer and prolong the preservation period of validity, thereby solving the technical problems of low reaction activity and short preservation period of validity of the water-soluble phenolic resin cross-linking agent in the prior art.
The first-order hydroxyphenol refers to phenol with one hydroxymethyl group, the second-order hydroxyphenol refers to phenol with two hydroxymethyl groups, and similarly, the third-order hydroxyphenol refers to phenol with three hydroxymethyl groups, and the fourth-order hydroxyphenol refers to phenol with four hydroxymethyl groups.
In order to better understand the technical solutions of the present invention, the technical solutions of the present invention are described in detail below with reference to the drawings and the specific embodiments, and it should be understood that the specific features in the embodiments and the embodiments of the present invention are detailed descriptions of the technical solutions of the present invention, and are not limitations of the technical solutions of the present invention, and the technical features in the embodiments and the embodiments of the present invention may be combined with each other without conflict.
On one hand, the embodiment of the invention provides a modified phenolic aldehyde crosslinking agent, which consists of 90-95 parts of phenolic aldehyde prepolymer and 5-10 parts of stabilizer in parts by weight, wherein:
the term "phenolic aldehyde prepolymer" used in the embodiment of the invention is prepared by reacting phenols and formaldehyde in a molar ratio of 2.5: 1-3: 1 under the action of an alkaline catalyst; the hydroxymethyl content of the phenolic aldehyde prepolymer is 18.92-23.34%. It should be noted that the hydroxymethyl content of the phenolic aldehyde prepolymer in the embodiment of the invention is obtained by detection according to the method GB/T14074-2006.
The phenols in the embodiments of the present invention are phenol or resorcinol, preferably phenol.
The term "stabilizer" used in the examples of the present invention means a chemical additive that slows down the polycondensation reaction of the crosslinking agent itself and prolongs the useful life of the crosslinking agent. In the embodiment of the invention, the stabilizer is one or two of o-aminobenzoic acid and p-aminobenzoic acid, and o-aminobenzoic acid is preferred.
After the phenol and the formaldehyde are reacted, the residual alkaline catalyst in the solution can still slowly catalyze the phenol and the formaldehyde to continuously react to generate the reticular cross-linked macromolecules, so that the curing failure is caused, and the stabilizer can consume the residual alkaline catalyst in the solution to prevent the reticular cross-linked macromolecules from generating on the one hand, and can form a hydrogen bond effect with hydroxymethyl carried by the cross-linking agent on the other hand, so that the self-polycondensation reaction of the cross-linking agent is slowed down, and the preservation period of validity of the cross-linking agent is prolonged. Therefore, the stabilizer and the phenolic prepolymer in the embodiment of the invention are not only simply physically mixed, but also have a chemical reaction and a mutual chemical action.
The storage life and gelling time of the cross-linking agent can be influenced by adjusting different proportions of the phenolic aldehyde prepolymer and the stabilizing agent, the using amount of the stabilizing agent is too large, the storage time of the cross-linking agent is long, and the gelling rate is relatively slow. In addition, the more the methylol content in the phenolic prepolymer, the more reactive units are, the more favorable the gelling reaction with the polymer later, but the more methylol content the crosslinking agent is, the easier it is to cure by itself. Therefore, the hydroxymethyl content, the phenolic aldehyde prepolymer and the proportion of the stabilizer can generate comprehensive influence on the reaction activity and the stability of the cross-linking agent, and research shows that: when 90-95 parts by weight of phenolic aldehyde prepolymer with 18.92-23.34% of hydroxymethyl content and 5-10 parts by weight of stabilizer are adopted, the quick gelling rate can be kept on the basis of prolonging the storage time of the cross-linking agent.
In the embodiment, the molar ratio of the phenols to the formaldehyde is 2.5: 1-3: 1, so that the phenols and the formaldehyde can be promoted to fully react, and the content of free phenols and formaldehyde in the product is reduced.
In the embodiment of the invention, the alkaline catalyst is a mixture of sodium hydroxide and barium hydroxide, and the molar ratio of the sodium hydroxide to the barium hydroxide is preferably 2: 1; further, the dosage of the alkaline catalyst is 1.5-2.5% of the total weight of the phenols and the formaldehyde. When sodium hydroxide is selected as a catalyst, para-position products are preferentially produced, more ortho-position products are produced by barium hydroxide, and the ortho-position products and the para-position products of phenol can participate in the reaction more by combining the para-position products and the ortho-position products.
On the other hand, based on the same inventive concept, the embodiment of the present invention provides a method for preparing the above modified phenolic crosslinking agent, please refer to fig. 1, which includes:
step S110: heating phenols to 60-65 ℃, adding an alkaline catalyst, stirring and activating to obtain a mixed solution;
the phenol is phenol or resorcinol, preferably phenol. Phenol can be brought into a molten state at this temperature because it has a melting point of 40 ℃. Since the reaction for generating the phenolic aldehyde prepolymer is an exothermic reaction, if the heating temperature of the phenol is too high, the exothermic reaction is not facilitated, and the heating temperature can be controlled between 40 ℃ and 60 ℃, preferably 50 ℃.
Wherein the alkaline catalyst is a mixture of sodium hydroxide and barium hydroxide, and the molar ratio of the sodium hydroxide to the barium hydroxide is preferably 2: 1; the dosage of the alkaline catalyst is 1.5-2.5% of the total weight of the phenols and the formaldehyde solution.
In step S110, the stirring activation time is preferably 20-30min, and the purpose of the stirring activation is to make phenol and sodium hydroxide fully react, so as to facilitate the next reaction.
Step S120: adding a formaldehyde solution into the mixed solution, heating to 60-65 ℃, and reacting at a constant temperature for 40-50min to obtain a phenolic aldehyde prepolymer; wherein the molar ratio of the phenols to the formaldehyde is 2.5: 1-3: 1;
preferably, the concentration of the formaldehyde solution is 36-40% by volume, but is not limited to this concentration range.
In step S120, the reaction temperature is 60 to 65 ℃, preferably 60 ℃, and the reaction is carried out under stirring; the reaction time is 40-50 min. The reaction is mild at the time and temperature, the obtained micromolecule product is a micromolecule product, the reaction is violent and difficult to control due to overhigh temperature, more polycondensation macromolecule products are generated due to overlong time, and the activity of the cross-linking agent is reduced.
The hydroxymethyl content of the phenolic prepolymer obtained by the reaction of the phenols and the formaldehyde under the molar ratio, the temperature and the time defined in the embodiment of the invention is 18.92-23.34%.
Step S130: uniformly mixing the phenolic aldehyde prepolymer and a stabilizer to obtain the cross-linking agent; wherein the weight parts of the phenolic aldehyde prepolymer and the stabilizer are respectively 90-95 parts and 5-10 parts; the stabilizer is amino-substituted benzoic acids.
Wherein the stabilizer is one or two of o-aminobenzoic acid and p-aminobenzoic acid, and o-aminobenzoic acid is preferred.
On the other hand, based on the same inventive concept, the embodiment of the invention provides the application of the modified phenolic crosslinking agent in preparing a crosslinked polymer gel profile control agent.
Referring to fig. 2, the application method includes:
step S210: mixing 0.2-0.4 wt% of polymer, 0.2-0.4 wt% of modified phenolic aldehyde crosslinking agent and water to prepare base liquid, wherein the sum of the weight percentages of all the components in the base liquid is 100%; the polymer is polyacrylamide, and the modified phenolic aldehyde crosslinking agent is prepared by mixing 90-95 parts by weight of phenolic aldehyde prepolymer and 5-10 parts by weight of stabilizer;
step S220: and reacting the base solution to obtain gel with a three-dimensional network structure, wherein the gel is the cross-linked polymer gel profile control agent.
Further, the relative molecular mass of the polymer is 2000-2500 ten thousand, and the degree of hydrolysis is less than 25%.
Further, the reaction temperature of the base solution is 80-120 ℃, and the reaction time is 24-120 h.
The profile control agent prepared by the method has the gelling temperature of 80-120 ℃, controllable gelling time of 24-120h, stable formed gel system, and gel viscosity of more than 8000mPa & s, is suitable for deep profile control and flooding operation treatment of an injection well, and has good application prospect in the aspect of improving the recovery ratio of crude oil in later development of a high water-cut oil field.
In order to enable those skilled in the art to further understand the scheme of the embodiment of the present invention, the following detailed description will be given based on the scheme described in the embodiment of the present invention.
Example 1
Putting a three-neck flask provided with a stirrer and a condenser into an electric heating constant-temperature water bath kettle, adding 235.3g of phenol, adjusting the temperature to 50 ℃, and melting the phenol into liquid; adding 4.65g of sodium hydroxide and barium hydroxide (molar ratio is 2: 1), and stirring for 20 min; adding 75.0g of formaldehyde solution (with the concentration of 40%), heating to 60 ℃, and keeping for 50 min; cooling to obtain the phenolic aldehyde prepolymer, and detecting the hydroxymethyl content of the phenolic aldehyde prepolymer to be 19.53 percent according to the GB/T14074-2006 method.
And (3) taking 90.0g of phenolic aldehyde prepolymer, adding 10.0g of anthranilic acid, and uniformly mixing to obtain the modified phenolic aldehyde crosslinking agent. The storage period of validity of the cross-linking agent is 12 months.
Preparing a partially hydrolyzed polyacrylamide solution with the mass fraction of 0.2%, curing for 24 hours, adding a modified phenolic crosslinking agent to ensure that the mass fraction is 0.2%, reacting for 24 hours at the constant temperature of 120 ℃ to generate a crosslinked polymer gel profile control agent, wherein the gel forming viscosity is 11120mPa & s.
The cross-linked polymer gel profile control agent provided in example 1 is suitable for profile control and water shutoff of a reservoir at 120 ℃.
Example 2
Putting a three-neck flask provided with a stirrer and a condenser into an electric heating constant-temperature water bath kettle, adding 263.5g of phenol, adjusting the temperature to 40 ℃, and melting the phenol into liquid; adding 6.85g of sodium hydroxide and barium hydroxide (molar ratio is 2: 1), and stirring for 30 min; adding 78.9g of formaldehyde solution (with the concentration of 38%), heating to 60 ℃, and keeping for 50 min; cooling to obtain the phenolic aldehyde prepolymer, and detecting the hydroxymethyl content of the phenolic aldehyde prepolymer to be 18.92 percent according to a GB/T14074-2006 method.
And (3) taking 90.0g of phenolic aldehyde prepolymer, adding 10.0g of anthranilic acid, and uniformly mixing to obtain the modified phenolic aldehyde crosslinking agent. The storage period of validity of the cross-linking agent is 18 months.
Preparing a partially hydrolyzed polyacrylamide solution with the mass fraction of 0.3%, curing for 24 hours, adding a modified phenolic crosslinking agent to ensure that the mass fraction is 0.2%, reacting for 120 hours at the constant temperature of 80 ℃ to generate a crosslinked polymer gel profile control agent, wherein the gel viscosity is 12156mPa & s.
The cross-linked polymer gel profile control agent provided in example 2 is suitable for profile control and water shutoff of a reservoir at 80 ℃.
Example 3
Putting a three-neck flask provided with a stirrer and a condenser into an electric heating constant-temperature water bath kettle, adding 330.3g of resorcinol, and adjusting the temperature to 60 ℃; adding 9.05g of sodium hydroxide and barium hydroxide (molar ratio is 2: 1), and stirring for 20 min; adding 81.1g of formaldehyde solution (with the concentration of 37%), heating to 65 ℃, and keeping for 50 min; cooling to obtain the phenolic aldehyde prepolymer, and detecting the hydroxymethyl content of the phenolic aldehyde prepolymer to be 21.28 percent according to a GB/T14074-2006 method.
And (3) taking 95.0g of phenolic aldehyde prepolymer, adding 5.0g of p-aminobenzoic acid, and uniformly mixing to obtain the modified phenolic aldehyde crosslinking agent. The storage period of validity of the cross-linking agent is 6 months.
Preparing a partially hydrolyzed polyacrylamide solution with the mass fraction of 0.3%, curing for 24 hours, adding a composite cross-linking agent to ensure that the mass fraction is 0.3%, reacting for 48 hours at the constant temperature of 100 ℃ to generate a cross-linked polymer gel profile control agent, wherein the gel forming viscosity is 10138mPa & s.
The cross-linked polymer gel profile control agent provided in example 3 is suitable for profile control and water shutoff of reservoirs at 100 ℃.
Example 4
Putting a three-neck flask provided with a stirrer and a condenser into an electric heating constant-temperature water bath kettle, adding 282.3g of phenol, adjusting the temperature to 50 ℃, adding 7.31g of sodium hydroxide and barium hydroxide (the molar ratio is 2: 1), and stirring for 25 min; adding 83.3g of formaldehyde solution (with the concentration of 36%), heating to 62 ℃, and keeping for 45 min; cooling to obtain the phenolic aldehyde prepolymer, and detecting the hydroxymethyl content of the phenolic aldehyde prepolymer to be 23.34 percent according to the GB/T14074-2006 method.
And taking 92.5g of phenolic aldehyde prepolymer, adding 7.5g of anthranilic acid, and uniformly mixing to obtain the modified phenolic aldehyde crosslinking agent. The storage period of validity of the cross-linking agent is 16 months.
Preparing a partially hydrolyzed polyacrylamide solution with the mass fraction of 0.2%, curing for 24 hours, adding a composite cross-linking agent to ensure that the mass fraction is 0.2%, reacting for 96 hours at the constant temperature of 100 ℃ to generate a cross-linked polymer gel profile control agent, wherein the gel forming viscosity is 12983mPa & s.
The cross-linked polymer gel profile control agent provided in example 4 is suitable for profile control and water shutoff of reservoirs at 100 ℃.
Example 5
Putting a three-neck flask provided with a stirrer and a condenser into an electric heating constant-temperature water bath kettle, adding 244.7g of phenol, adjusting the temperature to 45 ℃, and melting the phenol into liquid; adding 8.14g of sodium hydroxide and barium hydroxide (molar ratio is 2: 1), and stirring for 20 min; adding 81.1g of formaldehyde solution (with the concentration of 37%), heating to 60 ℃, and keeping for 40 min; cooling to obtain the phenolic aldehyde prepolymer, and detecting the hydroxymethyl content of the phenolic aldehyde prepolymer to be 20.37 percent according to the GB/T14074-2006 method.
And (3) taking 95.0g of phenolic aldehyde prepolymer, adding 3.0g of p-aminobenzoic acid and 2.0g of anthranilic acid, and uniformly mixing to obtain the modified phenolic aldehyde crosslinking agent. The storage period of validity of the cross-linking agent is 10 months.
Preparing a partially hydrolyzed polyacrylamide solution with the mass fraction of 0.4%, curing for 24 hours, adding a composite cross-linking agent to ensure that the mass fraction is 0.4%, reacting for 48 hours at the constant temperature of 95 ℃ to generate a cross-linked polymer gel profile control agent, wherein the gel viscosity is 11240mPa & s.
The cross-linked polymer gel profile control agent provided in example 5 is suitable for profile control and water shutoff of a reservoir at 95 ℃.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (7)
1. The modified phenolic aldehyde crosslinking agent is characterized by comprising 90-95 parts by weight of phenolic aldehyde prepolymer and 5-10 parts by weight of stabilizer, wherein:
the phenolic aldehyde prepolymer is prepared by reacting phenols and formaldehyde in a molar ratio of 2.5: 1-3: 1 under the action of an alkaline catalyst, and the content of hydroxymethyl in the phenolic aldehyde prepolymer is 18.92-23.34%;
the stabilizer is one or two of o-aminobenzoic acid and p-aminobenzoic acid;
the alkaline catalyst is a mixture of sodium hydroxide and barium hydroxide, and the molar ratio of the sodium hydroxide to the barium hydroxide is 2: 1;
the dosage of the alkaline catalyst is 1.5 to 2.5 percent of the total weight of the phenols and the formaldehyde.
2. The modified phenolic crosslinker of claim 1, wherein the phenol is phenol or resorcinol.
3. The method of preparing the modified phenolic crosslinker of claim 1 or 2, comprising:
heating phenols to 60-65 ℃, adding an alkaline catalyst, stirring and activating to obtain a mixed solution;
adding a formaldehyde solution into the mixed solution, heating to 60-65 ℃, and reacting at a constant temperature for 40-50min to obtain a phenolic aldehyde prepolymer; wherein the molar ratio of the phenols to the formaldehyde is 2.5: 1-3: 1;
uniformly mixing the phenolic aldehyde prepolymer and a stabilizer to obtain the cross-linking agent; wherein the weight parts of the phenolic aldehyde prepolymer and the stabilizer are respectively 90-95 parts and 5-10 parts; the stabilizer is amino-substituted benzoic acids.
4. The method of preparing a modified phenolic crosslinker of claim 3, wherein the phenol is phenol or resorcinol; the stabilizer is one or two of o-aminobenzoic acid and p-aminobenzoic acid.
5. Use of a modified phenolic crosslinker as claimed in claim 1 or claim 2 in the preparation of a crosslinked polymer gel profile control agent.
6. The application of claim 5, wherein the method of applying comprises:
mixing 0.2-0.4 wt% of polymer, 0.2-0.4 wt% of modified phenolic aldehyde crosslinking agent and water to prepare base liquid, wherein the sum of the weight percentages of all the components in the base liquid is 100%; the polymer is polyacrylamide, and the modified phenolic aldehyde crosslinking agent is prepared by mixing 90-95 parts by weight of phenolic aldehyde prepolymer and 5-10 parts by weight of stabilizer;
and reacting the base solution to obtain gel with a three-dimensional network structure, wherein the gel is the cross-linked polymer gel profile control agent.
7. The use of claim 6, wherein the polymer has a relative molecular mass of 2000 to 2500 ten thousand and a degree of hydrolysis of less than 25%; the reaction temperature of the base liquid is 80-120 ℃.
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| CN201710295091.XA CN107057667B (en) | 2017-04-28 | 2017-04-28 | Modified phenolic crosslinking agent and preparation method and application thereof |
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| CN201710295091.XA CN107057667B (en) | 2017-04-28 | 2017-04-28 | Modified phenolic crosslinking agent and preparation method and application thereof |
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| CN109851988B (en) * | 2019-01-24 | 2021-10-29 | 西安石油大学 | High-strength rubber plug system capable of being stored for long time at room temperature and preparation method thereof |
| CN114456784B (en) * | 2021-12-07 | 2023-06-02 | 中国海洋石油集团有限公司 | Long-storage phenolic resin crosslinking agent and high-temperature high-salt gel prepared by using same |
| CN116333704B (en) * | 2021-12-22 | 2024-05-10 | 中国石油化工股份有限公司 | Gel system for quick gel formation under high-temperature high-salt condition and preparation method thereof |
| CN116410717A (en) * | 2021-12-29 | 2023-07-11 | 中国石油天然气股份有限公司 | Profile control agent and its preparation method and application |
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