CN106398672A - Preparation method of water soluble phenolic resin crosslinking agent for temporary plugging steering acidizing - Google Patents
Preparation method of water soluble phenolic resin crosslinking agent for temporary plugging steering acidizing Download PDFInfo
- Publication number
- CN106398672A CN106398672A CN201610806332.8A CN201610806332A CN106398672A CN 106398672 A CN106398672 A CN 106398672A CN 201610806332 A CN201610806332 A CN 201610806332A CN 106398672 A CN106398672 A CN 106398672A
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- Prior art keywords
- preparation
- steering
- temporary plugging
- acidizing
- water soluble
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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
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a preparation method of a water soluble phenolic resin crosslinking agent for temporary plugging steering acidizing, relates to an oilfield chemical agent, and in particular, relates to a preparation method for an acidizing additive. The preparation method comprises the steps: heating phenol to melt, then adding an NaOH aqueous solution, heating to 60 DEG C, then adding formaldehyde, and carrying out a first alkali catalytic reaction under a stirring condition; and then adding an NaOH aqueous solution again, heating up to 85 DEG C, adding formaldehyde, carrying out a second alkali catalytic reaction, and thus obtaining the water soluble phenolic resin after the second alkali catalytic reaction is finished. The water soluble phenolic resin crosslinking agent prepared by the method is suitable for a chemical crosslinking temporary plugging agent depended by chemical steering in the oilfield steering acidizing technology; the chemical crosslinking temporary plugging agent prepared by the method has the advantages of bright color and good water solubility. The chemical crosslinking temporary plugging agent has the technical advantages of strong temporary plugging steering capability, good steering effect, and difficult causing of secondary damage to a reservoir stratum, and can be widely used in oilfield oil water well acidizing measures.
Description
Technical field
The present invention relates to a kind of oilfield chemistry agent, the especially preparation method of acidizing additive.
Background technology
Acidifying can release pollution and the blocking of near wellbore zone oil reservoir effectively, improves the company of pit shaft and near wellbore zone reservoir
The general character, increases oil well productivity.Minimum impedance concept is followed in the flowing of acid solution, and in acidization, acid solution preferentially enters permeability relatively
Good reservoir.In the stronger reservoir of anisotropism, most of acid solution enters middle and high permeable formation, only has small part acid solution even
Acid solution is not had to enter less permeable layer, this purpose being not only difficult to reservoir homogeneous acidification, increasing oil well productivity, can make on the contrary
The anisotropism of reservoir further enhances, and increases exploitation difficulty.Therefore, using acid solution steering technique realize homogeneous acidification reservoir,
Improve acidifying section, significant to well production increment.
According to steering mechanism, acid solution steering technique is generally divided into mechanical steering and chemistry diversion.Mechanical steering mainly includes
Packer turns to and granule turns to, and mechanical steering technology is more ripe, but complex operation, expensive, to containing many
When the reservoir in little thin layer and crack carries out turning to acidifying, the turning efficiency of acid solution is poor.Compare mechanical steering technology, chemistry diversion
Technology has the characteristics that easy construction, risk are low.Chemistry diversion technology mainly includes microgranule steering, foam turns to, polymer turns
Turn to surfactant, microgranule steering technique easily causes secondary injury to reservoir;Foam steering technique steering capability is limited,
Easily cause leak-off in hypertonic reservoir;Number of polymers is still had to remain in reservoir after the row of returning although polymer temporarily blocks up steering technique
In, but the temporary stall of polymer is to a kind of effective wide variety of acidifying steering technique of still can yet be regarded as, as long as temporarily blocking up system
Reasonably optimizing is it is possible to reduce the secondary injury to reservoir as far as possible.
According to diverting agent state in the earth formation, five classes can be divided into:Gel-type, resin type, gel-type, sedimentation type and
Dispersion type.What application was more now is containing the high molecular frozen glue of organic synthesiss or granule diverting agent.
Acidifying temporarily blocks up inorganic crosslinking agent such as potassium dichromate, aluminium citrate, various chromic salts etc. used in system to environment all
There are certain pollution, conventional organic crosslinking agent such as organic chrome cross linker, organic aluminum crosslinker, organic aldehyde cross-linking agent, organic boron
Cross-linking agent, organic zirconium crosslinker etc..Phenolic resin is exactly wide variety of a kind of organic aldehydes in polymer gel class diverting agent
Cross-linking agent, can crosslink reaction with polyacrylamide polymer molecule and form frozen glue.
Content of the invention
Mesh of the present invention is to provide a kind of temporary stall that can overcome prior art defect to acidifying water soluble phenol resin
The preparation method of cross-linking agent.
The technical scheme is that:Phenol is heated to after melting adding NaOH aqueous solution, adds after being warming up to 60 DEG C
Formaldehyde, carries out first time base catalyzed reactions under stirring condition, then add NaOH aqueous solution again, through being warming up to after 85 DEG C, plus
Enter formaldehyde and carry out second base catalyzed reactions, after second base catalyzed reactions terminates, obtain water soluble phenol resin.
The present invention, with sodium hydroxide as catalyst, passes through two step base catalysiss method synthesizing water-solubility phenolic aldehyde trees with phenol and formaldehyde
Fat, it is achieved that polynary hydroxymethylation on phenol phenyl ring, makes product possess stronger dehydration condensation ability;Be conducive to
Formaldehyde participates in the hydroxymethylation of phenol, and removing residue formaldehyde amount is much smaller than the formaldehyde amount of a step base catalysiss method product residue.
Base catalyzed reactions of the present invention are that first time base catalysiss can be real at 60 DEG C using the starting point of two-step method
Existing catalyst and the full and uniform mixing feeding intake and preliminary fusion reaction obtain half bright semi-finished product masterbatch, for second temperature raising
To at 85 DEG C, abundant base catalysiss fusion reaction lays the first stone, and through test of many times contrast, the phenolic resin that only two step method draws is handed over
Bright, good water solubility effect that connection agent just has a color.
The water soluble phenol resin cross-linking agent color prepared by the present invention is bright, and water solublity is fine.Water soluble phenol resin
Temporarily block up that system gelation time is adjustable in 4~72h for cross-linking agent, it is adjustable in 48~150h that broken glue returns row's time, gelation intensity is-
0.03MPa~-0.09MPa, 20h placed at 70 DEG C by become frozen glue, and system is dehydrated, and intensity substantially reduces, thorough beneficial to residual acid
Row is returned at bottom.
The water soluble phenol resin cross-linking agent of the inventive method preparation, is suitable for oil field and turns to chemistry diversion in Acidizing Technology
Relied on a kind of chemical crosslinking diverting agent, the chemical crosslinking diverting agent of the method preparation has that color is bright, and water solublity is special very well
Point.Have and temporarily block up steering capability by force, turning efficiency is good, and is difficult to cause secondary injury technological merit to reservoir, can be widely used for
In oil field oil water well acidizing measure.
Further, in described first time base catalyzed reactions, phenol is 1: 3 with the molar ratio of formaldehyde.
In described second base catalyzed reactions, phenol is 1: 3 with the molar ratio of formaldehyde.
Saving raw material be can ensure that using above rate of charge, and react completely, no excess raw material is remaining.
Specific embodiment
First, raw material prepares:
1st, take sodium hydroxide 0.04mol, add water, be made into the NaOH aqueous solution of 120mL, and be divided into two parts, Yi Fenwei
90mL, another is 30mL, stand-by.
2nd, weigh 18.8g(0.2mol)Phenol.
3rd, take pure formaldehyde 18g, add 27g water, make the formalin 45g that mass percent is 40%, and be divided into
Two parts, a is 36g(Wherein formaldehyde is 14.4g), another is 9g(Wherein formaldehyde is 3.6g), stand-by.
2nd, preparation technology:
By 18.8g(0.2mol)Phenol is added in there-necked flask, is heated to 50 DEG C so as to be melt into liquid, and adds
90mLNaOH aqueous solution, after continuously stirred 20min, is heated to 60 DEG C, adds 36g formalin, continuously stirred carries out
Base catalyzed reactions.
After 60min, add 30mLNaOH aqueous solution, be warming up to 85 DEG C, add 9g formalin, carry out the respectively
Secondary base catalyzed reactions 30min, 60min, 90min,(120min)Sampling, is bright brownish red, complete to the product finally giving
Entirely it is dissolved in the glue of water, i.e. cross-linking agent product.
3rd, apply:
In temporary stall is to acidifying, synergy liquid prepares required main one-tenth to the cross-linking agent products application made using the present invention
Point, described potentiation formula of liquid is:0.4% hydroxypropyl guar gum, 0.1% antibacterial, 1% potassium chloride, 0.2% cleanup additive, 1% process above
The cross-linking agent product made and 0.08% gel breaker, remaining is water, and total quality is 100%.Its effect is that synergy liquid entrance is hypertonic
Crosslinking is crosslinked under formation conditions, its viscosity is significantly increased after reservoir, thus realizing temporarily blocking up further to hypertonic reservoir,
Increase the effect turning to acidifying.
As applied on certain well, the oil that increases day by day reaches 4t/d, and yield amplification reaches 260%.
Claims (3)
1. temporary stall to acidifying with the preparation method of water soluble phenol resin cross-linking agent it is characterised in that:Phenol is heated to melting
Add NaOH aqueous solution after melting, add after being warming up to 60 DEG C and under formaldehyde, stirring condition, carry out first time base catalyzed reactions, then
Add NaOH aqueous solution again, through being warming up to after 85 DEG C, add formaldehyde to carry out second base catalyzed reactions, treat second base catalysis
After reaction terminates, obtain water soluble phenol resin.
2. preparation method according to claim 1 it is characterised in that:In described first time base catalyzed reactions, phenol with
The molar ratio of formaldehyde is 1: 3.
3. preparation method according to claim 1 and 2 it is characterised in that:In described second base catalyzed reactions, phenol
Molar ratio with formaldehyde is 1: 3.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108304609A (en) * | 2017-12-20 | 2018-07-20 | 北京石油化工学院 | A kind of judgment method of oil/gas well compact reservoir crack steering capability size |
CN109111557A (en) * | 2018-07-30 | 2019-01-01 | 兰州理工大学 | The preparation method of agent for improving oilfield recovery low solubility phenolic resin |
CN109554172A (en) * | 2017-09-26 | 2019-04-02 | 中国石油化工股份有限公司 | A kind of acid fracturing diverting agent and its application |
CN113234426A (en) * | 2021-04-30 | 2021-08-10 | 河北科技大学 | Reversible composite gel, preparation method and application |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109554172A (en) * | 2017-09-26 | 2019-04-02 | 中国石油化工股份有限公司 | A kind of acid fracturing diverting agent and its application |
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CN108304609B (en) * | 2017-12-20 | 2021-04-27 | 北京石油化工学院 | Method for judging steering capacity of tight reservoir fracture of oil and gas well |
CN109111557A (en) * | 2018-07-30 | 2019-01-01 | 兰州理工大学 | The preparation method of agent for improving oilfield recovery low solubility phenolic resin |
CN109111557B (en) * | 2018-07-30 | 2021-06-22 | 兰州理工大学 | Preparation method of low-solubility phenolic resin for improving recovery ratio of oil field |
CN113234426A (en) * | 2021-04-30 | 2021-08-10 | 河北科技大学 | Reversible composite gel, preparation method and application |
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Application publication date: 20170215 |