CN115403720B - Phenolic resin cross-linking agent and preparation method thereof - Google Patents
Phenolic resin cross-linking agent and preparation method thereof Download PDFInfo
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- CN115403720B CN115403720B CN202110576061.2A CN202110576061A CN115403720B CN 115403720 B CN115403720 B CN 115403720B CN 202110576061 A CN202110576061 A CN 202110576061A CN 115403720 B CN115403720 B CN 115403720B
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- phenolic resin
- linking agent
- resin cross
- sodium hydroxide
- phenol
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 124
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 124
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 153
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims abstract description 51
- 229910001863 barium hydroxide Inorganic materials 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000008442 polyphenolic compounds Polymers 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 50
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000008098 formaldehyde solution Substances 0.000 claims description 35
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 34
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 18
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 40
- 229920002401 polyacrylamide Polymers 0.000 abstract description 40
- 238000004132 cross linking Methods 0.000 abstract description 19
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 7
- 230000009257 reactivity Effects 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 238000004321 preservation Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 52
- 239000003795 chemical substances by application Substances 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The application discloses a phenolic resin cross-linking agent and a preparation method thereof, and belongs to the technical field of oilfield chemistry. According to the phenolic resin cross-linking agent provided by the embodiment of the application, the reaction rate among the components is improved by adding the sodium hydroxide solution and the barium hydroxide solution as the catalysts, so that the reaction is facilitated; the mutual solvent is added to be beneficial to improving the water solubility of the phenolic resin cross-linking agent and prolonging the preservation time of the phenolic resin cross-linking agent; by adding the polyhydroxy phenol, the reactivity of the phenolic resin crosslinking agent at low temperature is improved, and the crosslinking reaction of the phenolic resin crosslinking agent and polyacrylamide at low temperature is facilitated. The components exert synergistic effect, so that the phenolic resin cross-linking agent can be suitable for low-temperature oil reservoirs, thereby expanding the application range of the phenolic resin cross-linking agent.
Description
Technical Field
The application relates to the technical field of oilfield chemistry. In particular to a phenolic resin cross-linking agent and a preparation method thereof.
Background
At present, the recovery ratio of an oil field is improved mainly by injecting a profile control agent into an oil reservoir. The movable gel profile control agent is widely popularized and applied in various domestic oil fields due to simple construction process, convenient construction and wide application range. The movable gel profile control agent formed by crosslinking polyacrylamide and a water-soluble phenolic resin crosslinking agent is one of movable gel profile control agents mainly applied to domestic oil fields. The hydroxymethyl functional group on the benzene ring in the water-soluble phenolic resin crosslinking agent has stronger activity, and can be subjected to condensation reaction with the amide group in the polyacrylamide under certain conditions to form a gel with a network structure.
The water-soluble phenolic resin cross-linking agent in the related art generally reacts with polyacrylamide at a high temperature of more than 75 ℃ to generate the movable gel profile control agent.
However, the water-soluble phenolic resin in the related art is not easy to react with polyacrylamide at the low temperature of less than 75 ℃, so that the application range of the water-soluble phenolic resin is limited because the application of the water-soluble phenolic resin in a low-temperature oil reservoir of less than 75 ℃ is affected.
Disclosure of Invention
The embodiment of the application provides a phenolic resin cross-linking agent and a preparation method thereof, which can expand the application range of the phenolic resin cross-linking agent. The specific technical scheme is as follows:
on one hand, the embodiment of the application provides a phenolic resin cross-linking agent, which is prepared from the following raw materials in parts by weight:
100 parts by weight of phenol, 215-260 parts by weight of formaldehyde solution, 15-32 parts by weight of sodium hydroxide solution, 4-10 parts by weight of barium hydroxide solution, 16-32 parts by weight of mutual solvent and polyhydroxy phenol.
In one possible implementation, the polyhydric phenol includes resorcinol.
In another possible implementation, the polyhydric phenol includes hydroquinone.
In another possible implementation, the polyhydroxyphenol is present in an amount of no more than 8 parts by weight.
In another possible implementation, the sodium hydroxide solution has a mass concentration of 5% sodium hydroxide.
In another possible implementation, the barium hydroxide solution has a concentration of 5% by mass of barium hydroxide.
In another possible implementation, the total mass fraction of sodium hydroxide in the sodium hydroxide solution and barium hydroxide in the barium hydroxide solution is 1% -2% of the phenol mass fraction.
In another possible implementation manner, the mass portion of the sodium hydroxide is 75% -80% of the total mass portion of the sodium hydroxide and the barium hydroxide, and the mass portion of the barium hydroxide is 20% -25% of the total mass portion of the sodium hydroxide and the barium hydroxide.
In another possible implementation, the mutual solvent includes at least one of ethylene glycol and t-butanol.
In another aspect, the embodiment of the application provides a preparation method of a phenolic resin cross-linking agent, which comprises the following steps:
according to the mass parts of the components, placing a three-necked flask into a constant-temperature water bath, adding phenol into the three-necked flask, and heating to 40-45 ℃;
adding sodium hydroxide solution into the three-necked flask, and uniformly stirring;
dividing the formaldehyde solution into a first mass part of formaldehyde solution and a second mass part of formaldehyde solution according to the mass ratio of 7:3, adding the first mass part of formaldehyde solution into the three-neck flask within 30min, heating to 76 ℃, reacting for 30min, and cooling to 50 ℃;
adding barium hydroxide solution into the three-neck flask, adding the second mass part of formaldehyde solution, heating to 82-86 ℃, and reacting for 1.5-2 h under stirring;
cooling to room temperature, adding the mutual solvent and the polyhydroxy phenol, and stirring uniformly to obtain the phenolic resin cross-linking agent.
The technical scheme provided by the embodiment of the application has the beneficial effects that:
according to the phenolic resin cross-linking agent provided by the embodiment of the application, the reaction rate among the components is improved by adding the sodium hydroxide solution and the barium hydroxide solution as the catalysts, so that the reaction is facilitated; the mutual solvent is added to be beneficial to improving the water solubility of the phenolic resin cross-linking agent and prolonging the preservation time of the phenolic resin cross-linking agent; by adding the polyhydroxy phenol, the reactivity of the phenolic resin crosslinking agent at low temperature is improved, and the crosslinking reaction of the phenolic resin crosslinking agent and polyacrylamide at low temperature is facilitated. The components exert synergistic effect, so that the phenolic resin cross-linking agent can be suitable for low-temperature oil reservoirs, thereby expanding the application range of the phenolic resin cross-linking agent.
Detailed Description
In order to make the technical scheme and advantages of the present application more clear, the following further describes the embodiments of the present application in detail.
The embodiment of the application provides a phenolic resin cross-linking agent, which is prepared from the following components in parts by weight:
100 parts by weight of phenol, 215-260 parts by weight of formaldehyde solution, 15-32 parts by weight of sodium hydroxide solution, 4-10 parts by weight of barium hydroxide solution, 16-32 parts by weight of mutual solvent and polyhydroxy phenol.
According to the phenolic resin cross-linking agent provided by the embodiment of the application, the reaction rate among the components is improved by adding the sodium hydroxide solution and the barium hydroxide solution as the catalysts, so that the reaction is facilitated; the mutual solvent is added to be beneficial to improving the water solubility of the phenolic resin cross-linking agent and prolonging the preservation time of the phenolic resin cross-linking agent; by adding the polyhydroxy phenol, the reactivity of the phenolic resin crosslinking agent at low temperature is improved, and the crosslinking reaction of the phenolic resin crosslinking agent and polyacrylamide at low temperature is facilitated. The components exert synergistic effect, so that the phenolic resin cross-linking agent can be suitable for low-temperature oil reservoirs, thereby expanding the application range of the phenolic resin cross-linking agent.
In the embodiment of the application, the mass concentration of formaldehyde in the formaldehyde solution is 37%, the mass part of the formaldehyde solution can be 215, 220, 230, 240, 245, 250 or 260, the mass part of the sodium hydroxide solution can be 15, 20, 25, 26, 27, 28, 29, 30, 31 or 32, the mass part of the barium hydroxide solution can be 4, 5, 6, 7, 8, 9 or 10, and the mass part of the mutual solvent can be 16, 18, 20, 22, 25, 26, 28, 30 or 32.
Introduction of polyhydroxy phenols: in an embodiment of the present application, the polyhydric phenol may be benzene including two phenolic hydroxyl groups or three phenolic hydroxyl groups.
If the polyhydric phenol is benzene comprising three phenolic hydroxyl groups, the polyhydric phenol may be phloroglucinol. If the polyhydric phenol is benzene comprising two phenolic hydroxyl groups, the polyhydric phenol may be resorcinol, hydroquinone or catechol. In the examples of the present application, the polyhydric phenol is exemplified as resorcinol or hydroquinone only.
It is noted that resorcinol and hydroquinone have higher reactivity than phenol, and can undergo a crosslinking reaction with polyacrylamide at a low temperature, thereby expanding the application range of the water-soluble phenolic resin crosslinking agent.
In one possible implementation, the mass fraction of the polyhydroxy phenol is no more than 8. For example, the polyhydroxyphenol may be 0, 1, 2, 3, 4, 5, 6, 7, or 8 parts by mass.
In embodiments of the application, the polyhydric phenol may be added as needed depending on the reservoir temperature of the application. If the reservoir temperature is low, for example, the reservoir temperature is less than 75 ℃, resorcinol can be added to crosslink the water-soluble phenolic resin with polyacrylamide at low temperature, thereby increasing oil recovery. If the reservoir temperature is higher, for example, the reservoir temperature is 100-120 ℃, hydroquinone can be added, so that the high-temperature stability of the movable gel profile control agent obtained by the reaction of the water-soluble phenolic resin and the polyacrylamide is improved. If the reservoir temperature is between 75 and 100 ℃, the addition of polyhydroxy phenol is not required, thereby reducing the oil extraction cost. Therefore, the phenolic resin cross-linking agent provided by the embodiment of the application can be suitable for low-temperature and high-temperature oil reservoirs, so that the application range of the phenolic resin is widened.
Introduction of sodium hydroxide and barium hydroxide: in one possible implementation, the mass concentration of sodium hydroxide in the sodium hydroxide solution is 5%.
The sodium hydroxide as a catalyst can improve the reaction rate between the components, and is beneficial to the reaction. Sodium hydroxide solution with 5% mass concentration can make sodium hydroxide exert catalytic effect better.
In one possible implementation, the concentration of barium hydroxide in the barium hydroxide solution is 5% by mass.
Barium hydroxide is a mild catalyst, can improve the reaction rate between the components, is easy to control the reaction, and the prepared water-soluble phenolic resin has low viscosity, thereby being beneficial to fully generating crosslinking reaction with polyacrylamide. The barium hydroxide solution with the mass concentration of 5% can make the barium hydroxide perform better catalysis.
In the embodiment of the application, the mass part of the sodium hydroxide solution is 15-32, the mass part of the barium hydroxide solution is 4-10, and the total mass part of the sodium hydroxide in the sodium hydroxide solution and the barium hydroxide in the barium hydroxide solution is 1-2% of the mass part of the phenol. Wherein, the mass portion of sodium hydroxide is 75-80% of the total mass portion of the two, and the mass portion of barium hydroxide is 20-25% of the total mass portion of the two.
In the embodiment of the application, a two-step catalytic method composite alkali synthesis process with sodium hydroxide as a main component and barium hydroxide as an auxiliary component is adopted, so that the sodium hydroxide and the barium hydroxide can play a synergistic effect, the reaction rate between the components is improved together, the reaction is accelerated, the reaction time is shortened, and the reaction efficiency is improved.
Introduction of the mutual solvent: in one possible implementation, the mutual solvent includes at least one of ethylene glycol and t-butanol. In this implementation, the mutual solvent may be ethylene glycol, t-butanol or a mixture of ethylene glycol and t-butanol.
In the embodiment of the application, the ethylene glycol and the tertiary butanol are both hydrophilic organic solvents, and the water solubility of the water-soluble phenolic resin cross-linking agent can be effectively improved by adding the hydrophilic organic solvents.
In one possible implementation, the mutual solvent may also be an ether alcohol. In the embodiment of the present application, this is not particularly limited.
According to the phenolic resin cross-linking agent provided by the embodiment of the application, the reaction rate among the components is improved by adding the sodium hydroxide solution and the barium hydroxide solution as the catalysts, so that the reaction is facilitated; the mutual solvent is added to be beneficial to improving the water solubility of the phenolic resin cross-linking agent and prolonging the preservation time of the phenolic resin cross-linking agent; by adding the polyhydroxy phenol, the reactivity of the phenolic resin crosslinking agent at low temperature is improved, and the crosslinking reaction of the phenolic resin crosslinking agent and polyacrylamide at low temperature is facilitated. The components exert synergistic effect, so that the phenolic resin cross-linking agent can be suitable for low-temperature oil reservoirs, thereby expanding the application range of the phenolic resin cross-linking agent.
In another aspect, the embodiment of the application provides a preparation method of a phenolic resin cross-linking agent, which comprises the following steps:
step 1: according to the mass parts of the components, the three-necked flask is placed into a constant-temperature water bath, phenol is added into the three-necked flask, and the three-necked flask is heated to 40-45 ℃.
In the step, a three-necked flask is firstly put into a super constant temperature water bath, then a stirrer, a reflux condenser and a thermometer are arranged on the three-necked flask, and then 100 parts by mass of phenol is added and heated to 40-45 ℃ to obtain the phenol in a molten state.
The volume of the three-necked flask is set and changed as needed, and for example, the volume of the three-necked flask is 500mL or 1000mL.
Step 2: sodium hydroxide solution was added to the three-necked flask and stirred well.
In the step, 15-32 parts by mass of sodium hydroxide solution is added into a three-necked flask containing phenol in a molten state, and the mixture is stirred uniformly.
Wherein, the sodium hydroxide solution can be prepared by distilled water or deionized water. In the embodiment of the present application, this is not particularly limited.
Step 3: dividing the formaldehyde solution into a first mass part of formaldehyde solution and a second mass part of formaldehyde solution according to the mass ratio of 7:3, adding the first mass part of formaldehyde solution into a three-neck flask within 30min, heating to 76 ℃, reacting for 30min, and cooling to 50 ℃.
In the step, 215-260 parts by weight of formaldehyde solution with the mass concentration of 37% are divided into two parts according to the mass concentration of 7:3, the formaldehyde solution with more parts by weight is slowly added into the three-neck flask within 30min, then the three-neck flask is heated to 76 ℃ by a super constant temperature water bath, stirred and reacted for 30min, and then the temperature is reduced to 50 ℃.
Step 4: adding barium hydroxide solution into the three-necked flask, adding a second mass part of formaldehyde solution, heating to 82-86 ℃, and reacting for 1.5-2 h under the stirring condition.
Adding 4-10 parts by weight of barium hydroxide solution into a three-necked flask, wherein the total weight part of the barium hydroxide and the sodium hydroxide is 1-2% of the weight part of phenol, the weight part of the sodium hydroxide is 75-80% of the total weight part, and the weight part of the barium hydroxide is 20-25% of the total weight part. The barium hydroxide solution can be prepared by distilled water or deionized water. In the embodiment of the present application, this is not particularly limited.
Then adding the residual formaldehyde solution in parts by weight, heating to 82-86 ℃, and reacting for 1.5-2 h at constant temperature under the stirring condition.
In the embodiment of the application, a two-step catalytic method composite alkali synthesis process with sodium hydroxide as a main component and barium hydroxide as an auxiliary component is adopted, the reaction temperature is 76-86 ℃, and the reaction time is 2.5-3 h.
Step 5: cooling to room temperature, adding the mutual solvent and the polyhydroxy phenol, and stirring uniformly to obtain the phenolic resin cross-linking agent.
In the step, polyhydroxy phenol and 16-32 parts by weight of mutual solvent are added and stirred uniformly to obtain the water-soluble phenolic resin crosslinking agent.
The preparation method of the phenolic resin cross-linking agent provided by the embodiment of the application synthesizes the water-soluble phenolic resin by using a two-step synthesis method through double-catalyst composite catalysis of sodium hydroxide and barium hydroxide, and simultaneously controls the synthesis temperature to be 76-86 ℃ and the total reaction time to be 2.5-3 hours, and adds the mutual solvent and the polyhydroxy phenol in the synthesis process through controlling the preparation raw material proportion, so that the synthesized water-soluble phenolic resin has long storage time and is not easy to self-polymerize, thereby prolonging the field storage time of the phenolic resin cross-linking agent.
In addition, the phenolic resin cross-linking agent provided by the embodiment of the application has the advantage that the phenolic resin cross-linking agent and polyacrylamide are subjected to cross-linking reaction at low temperature by adding the polyhydroxy phenol with higher reactivity than phenol, so that the field application range of the phenolic resin cross-linking agent is enlarged.
In addition, it was found by experiment that: the phenolic resin cross-linking agent still has good water solubility and cross-linking reaction activity with polyacrylamide after being stored for 180 days at normal temperature, and can be cross-linked with the polyacrylamide to form the movable gel profile control agent at the temperature of 30-120 ℃, so that the field application range of the water-soluble phenolic resin is effectively widened.
The technical scheme of the application will be described in detail through specific examples.
In the following specific examples, the operations involved were performed under conventional conditions or conditions recommended by the manufacturer, without specifying the conditions. The raw materials used are not specified by the manufacturer and the specification are all conventional products which can be obtained by commercial purchase.
Example 1
1. The preparation raw materials of the phenolic resin cross-linking agent comprise:
phenol: 50g
Formaldehyde with mass concentration of 37 percent: 130g
Sodium hydroxide solution with mass concentration of 5 percent: 15g
Barium hydroxide solution with mass concentration of 5 percent: 5g
Ethylene glycol: 10g
2. The preparation method of the phenolic resin cross-linking agent comprises the following steps:
1. putting a 500ml three-neck flask into a super constant temperature water bath, and arranging a stirrer, a reflux condenser and a thermometer on the flask; 50g of phenol was charged into the flask, and the flask was heated to 40 to 45℃to be in a molten state.
2. 15g of 5% sodium hydroxide solution was added and stirred well.
3. 130g of formaldehyde solution with the mass concentration of 37% is divided into 91g and 39g, 91g of formaldehyde solution with the mass concentration of 37% is slowly added into a three-necked flask within 30min, a constant-temperature water bath is heated to 76 ℃, and the mixture is stirred and reacted for 30min, and the temperature is reduced to 50 ℃.
4. 5g of 5% barium hydroxide solution is added, and meanwhile, the rest 39g of formaldehyde solution with the mass concentration of 37% is added, the temperature is raised to 84-86 ℃, and the reaction is carried out for 1.5-2 h at constant temperature under the stirring condition.
5. Cooling to room temperature, adding 10g of ethylene glycol, and stirring uniformly to obtain the phenolic resin cross-linking agent.
Example 2
1. The preparation raw materials of the phenolic resin cross-linking agent comprise:
phenol: 50g
Formaldehyde with mass concentration of 37 percent: 110g
Sodium hydroxide solution with mass concentration of 5 percent: 10g
Barium hydroxide solution with mass concentration of 5 percent: 3g
Ethylene glycol: 10g
2. The preparation method of the phenolic resin cross-linking agent comprises the following steps:
1. putting a 500ml three-neck flask into a super constant temperature water bath, and arranging a stirrer, a reflux condenser and a thermometer on the flask; 50g of phenol was charged into the flask, and the flask was heated to 40 to 45℃to be in a molten state.
2. 10g of 5% sodium hydroxide solution was added and stirred well.
3. 110g of formaldehyde solution with the mass concentration of 37% is divided into 77g and 33g, 77g of formaldehyde solution with the mass concentration of 37% is slowly added into a three-necked flask within 30min, a constant-temperature water bath is heated to 76 ℃, stirring and reaction are carried out for 30min, and the temperature is reduced to 50 ℃.
4. 3g of 5% barium hydroxide solution is added, and the rest 33g of formaldehyde solution with the mass concentration of 37% is added, the temperature is raised to 84-86 ℃, and the reaction is carried out for 1.5-2 h at constant temperature under the stirring condition.
5. Cooling to room temperature, adding 10g of ethylene glycol, and stirring uniformly to obtain the phenolic resin cross-linking agent.
Example 3
1. The preparation raw materials of the phenolic resin cross-linking agent comprise:
phenol: 50g
Formaldehyde with mass concentration of 37 percent: 130g
Sodium hydroxide solution with mass concentration of 5 percent: 15g
Barium hydroxide solution with mass concentration of 5 percent: 4g
Ethylene glycol: 5g
Tertiary butanol: 5g
Resorcinol: 4g
2. The preparation method of the phenolic resin cross-linking agent comprises the following steps:
1. putting a 500ml three-neck flask into a super constant temperature water bath, and arranging a stirrer, a reflux condenser and a thermometer on the flask; 50g of phenol was charged into the flask, and the flask was heated to 40 to 45℃to be in a molten state.
2. 15g of 5% sodium hydroxide solution was added and stirred well.
3. 130g of formaldehyde solution with the mass concentration of 37% is divided into 91g and 39g, 91g of formaldehyde solution with the mass concentration of 37% is slowly added into a three-necked flask within 30min, a constant-temperature water bath is heated to 76 ℃, and the mixture is stirred and reacted for 30min, and the temperature is reduced to 50 ℃.
4. 54g of 5% barium hydroxide solution is added, and meanwhile, the rest 39g of formaldehyde solution with the mass concentration of 37% is added, the temperature is raised to 84-86 ℃, and the reaction is carried out for 1.5-2 h at constant temperature under the stirring condition.
5. Cooling to room temperature, adding 5g of ethylene glycol, 5g of tertiary butanol and 4g of resorcinol, and uniformly stirring to obtain the phenolic resin cross-linking agent.
Example 4
1. The preparation raw materials of the phenolic resin cross-linking agent comprise:
phenol: 100g of
Formaldehyde with mass concentration of 37 percent: 230g
Sodium hydroxide solution with mass concentration of 5 percent: 25g
Barium hydroxide solution with mass concentration of 5 percent: 6g
Ethylene glycol: 15g
Tertiary butanol: 15g
Hydroquinone: 6g
2. The preparation method of the phenolic resin cross-linking agent comprises the following steps:
1. putting a 500ml three-neck flask into a super constant temperature water bath, and arranging a stirrer, a reflux condenser and a thermometer on the flask; the flask was charged with 100g of phenol and heated to 40 to 45℃to bring it into a molten state.
2. 25g of 5% sodium hydroxide solution was added and stirred well.
3. 230g of formaldehyde solution with the mass concentration of 37% is divided into 161g and 69g, 161g of formaldehyde solution with the mass concentration of 37% is slowly added into a three-necked flask within 30min, a constant-temperature water bath is heated to 76 ℃, and the mixture is stirred and reacted for 30min, and the temperature is reduced to 50 ℃.
4.6 g of 5% barium hydroxide solution is added, and the rest 69g of formaldehyde solution with the mass concentration of 37% is added, the temperature is raised to 84-86 ℃, and the reaction is carried out for 1.5-2 h at constant temperature under the stirring condition.
5. Cooling to room temperature, adding 15g of ethylene glycol, 15g of tertiary butanol and 6g of hydroquinone, and uniformly stirring to obtain the phenolic resin cross-linking agent.
Comparative example 1
Resorcinol is not included in the preparation raw materials of this comparative example, and the remaining components and masses are the same as in example 3, and are not described here again.
Application example 1
The appearance of the phenolic resin cross-linking agent provided in the example 1 is observed, and the movable gel profile control agent obtained after the cross-linking reaction with polyacrylamide at 90 ℃ is tested, and test data are respectively shown in table 1 and table 2.
The movable gel profile control agent obtained by the cross-linking reaction of the phenolic resin cross-linking agent provided in the example 3 and polyacrylamide at 38 ℃ is tested, and test data can be seen in table 3.
The movable gel profile control agent obtained by the crosslinking reaction of the phenolic resin crosslinking agent provided in example 4 and polyacrylamide at 120 ℃ is tested, and test data can be shown in table 4.
Table 1 example provides appearance observations of phenolic resin crosslinkers
Table 2 test data for phenolic resin crosslinker provided in example 1 at 90 c
TABLE 3 test data for the phenolic resin crosslinkers provided in example 3 at 38℃
Table 4 example 4 provides experimental data for phenolic resin crosslinkers at 120 c
As can be seen from table 1: the newly prepared phenolic resin cross-linking agent is red dilute solution and can be mutually dissolved with water. After 180 days at room temperature, the solution is still a red dilute solution and is miscible with water. The phenolic resin crosslinking agent can be stored for a long time and has good water solubility.
From table 2 it can be seen that: when the concentration of the polyacrylamide is 1000mg/L, the viscosity of the movable gel profile control agent synthesized by adopting the newly synthesized phenolic resin cross-linking agent and the polyacrylamide is 1365MP.s, and the viscosity of the movable gel profile control agent synthesized by adopting the phenolic resin cross-linking agent and the polyacrylamide after being placed for 180 days at room temperature is 1360MP.s, and the viscosity of the two is similar. When the concentration of the polyacrylamide is 1500mg/L, the viscosity of the movable gel profile control agent synthesized by adopting the newly synthesized phenolic resin cross-linking agent and the polyacrylamide is 2136mP.s, and the viscosity of the movable gel profile control agent synthesized by adopting the phenolic resin cross-linking agent and the polyacrylamide after being placed for 180 days at room temperature is 2143mP.s, wherein the two viscosities are similar. From this, it can be seen that the water-soluble phenolic resin crosslinking agent synthesized in example 1 has better long-term stability and can be stored for a longer period of time.
In the concentration range of 1000 to 1500mg/L of polyacrylamide, the viscosity of the movable gel profile control agent obtained by the reaction of the phenolic resin crosslinking agent provided in example 2 with polyacrylamide is similar to that of the movable gel profile control agent synthesized by the phenolic resin crosslinking agent and polyacrylamide after 180 days of standing at room temperature, and thus, it can be explained that: the water-soluble phenolic resin cross-linking agent synthesized by the embodiment of the application has better long-term stability and can be stored for a longer time.
As can be seen from table 3: because resorcinol is added into the phenolic resin cross-linking agent provided in the embodiment 3, the phenolic resin cross-linking agent and polyacrylamide can undergo a cross-linking reaction at 38 ℃, namely, the phenolic resin cross-linking agent and the polyacrylamide can undergo a cross-linking reaction at a low temperature, so that the phenolic resin cross-linking agent can be applied to the movable gel profile control agent profile control of a low-temperature oil reservoir.
The phenolic resin crosslinking agent synthesized by resorcinol is not added, namely the phenolic resin crosslinking agent provided in the comparative example 1 does not undergo a crosslinking reaction with polyacrylamide at 38 ℃. From this, it is found that the addition of resorcinol is advantageous in promoting the crosslinking reaction of the phenolic resin crosslinking agent with polyacrylamide at low temperatures.
As can be seen from table 4: the concentration of polyacrylamide is 1200mg/L, the concentration of phenolic resin crosslinking agent is 1500mg/L, the viscosity of the synthesized movable gel profile control agent is 1253mP.s, the gel viscosity after 30 days is 1086mP.s, and the gel viscosity is not changed greatly. The concentration of polyacrylamide is 1500mg/L, the concentration of phenolic resin crosslinking agent is 2000mg/L, the viscosity of the synthesized movable gel profile control agent is 1832MP.s, the gel viscosity after 30 days is 1612MP.s, and the gel viscosity is not changed greatly. Therefore, the movable gel profile control agent formed by crosslinking the phenolic resin crosslinking agent and the polyacrylamide provided by the embodiment of the application has good stability at a high temperature of 120 ℃.
Wherein the viscosity of the movable gel profile control agent is 7.34S- 1 Measured at normal temperature.
It should be noted that, in order to make the phenolic resin crosslinking agents provided in examples 1 and 2 have wide adaptability, if the phenolic resin crosslinking agents provided in examples 1 and 2 are applied to reservoirs below 75 ℃, resorcinol with a concentration of 30 to 80mg/L may be directly added after polyacrylamide and the phenolic resin crosslinking agent provided in examples 1 or 2 are added directly in preparing the mobile gel, so that the phenolic resin crosslinking agents provided in examples 1 and 2 can be applied to low-temperature reservoirs. If the phenolic resin crosslinking agents provided in the examples 1 and 2 are applied to high-temperature oil reservoirs at 100-120 ℃, the movable gel can be directly prepared, and after the polyacrylamide and the phenolic resin crosslinking agent in the examples 1 or 2 are added, hydroquinone with the concentration of 50-100 mg/L is directly added, so that the stability of the movable gel in the high-temperature oil reservoirs is improved.
In the embodiment of the application, resorcinol or hydroquinone can be added in the preparation of the phenolic resin cross-linking agent, and then the resorcinol or hydroquinone is subjected to cross-linking reaction with polyacrylamide to obtain the movable gel. Alternatively, resorcinol or hydroquinone may be not added to obtain a phenolic resin crosslinking agent, and then resorcinol or hydroquinone may be added to obtain a mobile gel when the phenolic resin crosslinking agent is applied in situ (when the phenolic resin crosslinking agent and polyacrylamide undergo a crosslinking reaction), thereby improving the application of the mobile gel in low-temperature oil reservoirs or improving the stability of the mobile gel in high-temperature oil reservoirs. In field applications, any manner may be selected, and is not particularly limited herein.
Application example 2
The application example mainly carries out gel deep profile control and flooding on 4 water injection wells with broken blocks of the North China sandstone oilfield path 36 through the phenolic resin crosslinking agent provided in the example 1.
The movable gel profile control agent comprises: 1000-1500 mg/L polyacrylamide and 1500mg/L phenolic resin cross-linking agent. After the movable gel profile control agent is used for profile control, daily oil production of an oil well is increased from 5.2t to 17.1t, and daily oil increase is 11.9t. The comprehensive water content is reduced from 94.6% to 85.8%, and the reduction is 8.8%. The accumulated oil increment reaches 6483t, and the effective period is more than 2 years.
Therefore, the movable gel profile control agent synthesized by the phenolic resin crosslinking agent and the polyacrylamide can realize better profile control and oil increasing effects.
The foregoing description is only for the convenience of those skilled in the art to understand the technical solution of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (7)
1. The phenolic resin cross-linking agent is characterized by comprising the following raw materials in parts by weight:
100 parts by weight of phenol, 215-260 parts by weight of formaldehyde solution, 15-32 parts by weight of sodium hydroxide solution, 4-10 parts by weight of barium hydroxide solution, 16-32 parts by weight of mutual solvent and polyhydroxy phenol;
the polyhydric phenol comprises resorcinol, and the mutual solvent comprises at least one of ethylene glycol and tertiary butanol;
the preparation method of the phenolic resin cross-linking agent comprises the following steps:
according to the mass parts of the components, placing a three-necked flask into a constant-temperature water bath, adding the phenol into the three-necked flask, and heating to 40-45 ℃;
adding the sodium hydroxide solution into the three-necked flask, and uniformly stirring;
dividing the formaldehyde solution into a first mass part of formaldehyde solution and a second mass part of formaldehyde solution according to the mass ratio of 7:3, adding the first mass part of formaldehyde solution into the three-neck flask within 30min, heating to 76 ℃, reacting for 30min, and cooling to 50 ℃;
adding the barium hydroxide solution into the three-neck flask, adding the second mass part of formaldehyde solution, heating to 82-86 ℃, and reacting for 1.5-2 h under the stirring condition;
cooling to room temperature, adding the mutual solvent and the polyhydroxy phenol, and stirring uniformly to obtain the phenolic resin crosslinking agent.
2. The phenolic resin cross-linking agent of claim 1, wherein the polyhydric phenol comprises hydroquinone.
3. The phenolic resin cross-linking agent of claim 1, wherein the mass fraction of the polyhydroxy phenol is no more than 8.
4. Phenolic resin cross-linking agent according to claim 1, characterized in that the mass concentration of sodium hydroxide in the sodium hydroxide solution is 5%.
5. The phenolic resin cross-linking agent of claim 1, wherein the mass concentration of barium hydroxide in the barium hydroxide solution is 5%.
6. The phenolic resin cross-linking agent of claim 1, wherein the total mass fraction of sodium hydroxide in the sodium hydroxide solution and barium hydroxide in the barium hydroxide solution is 1% -2% of the phenol mass fraction.
7. The phenolic resin cross-linking agent according to claim 6, wherein the mass fraction of sodium hydroxide is 75% -80% of the total mass fraction of sodium hydroxide and barium hydroxide, and the mass fraction of barium hydroxide is 20% -25% of the total mass fraction of sodium hydroxide and barium hydroxide.
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