CN105131921A - Anti-salt anti-high-temperature high-intensity gel blocking agent - Google Patents
Anti-salt anti-high-temperature high-intensity gel blocking agent Download PDFInfo
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- CN105131921A CN105131921A CN201510563658.8A CN201510563658A CN105131921A CN 105131921 A CN105131921 A CN 105131921A CN 201510563658 A CN201510563658 A CN 201510563658A CN 105131921 A CN105131921 A CN 105131921A
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- resisting high
- temperature
- salt
- crosslinked gel
- aqua
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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
- 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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- 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
- C09K8/5045—Compositions based on water or polar solvents containing inorganic compounds
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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
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention relates to an anti-salt anti-high-temperature high-intensity gel blocking agent. The gel blocking agent contains, by weight, 20-25 parts of sulfonated modified micromolecule biopolymers, 2.5-4 parts of micromolecule acrylamide and sodium methallyl sulfonate copolymers, 1.3-3 parts of cross-linking agents, and 0.5-1.5 parts of a pH regulator. The cross-linking agents are phenolic resin compounds, and are prepared from phenolic compounds and aldehyde compounds or compounds which can generate aldehydes. The sulfonated modified micromolecule biopolymers are prepared from plant extract products after sodium sulfite sulfonation. The pH regulator is one of ammonium chloride, formic acid, oxalic acid and citric acid. The gelling intensity of the gel blocking agent is 4*10<4>-10*10<4> mPa*S and the gelling time is 4-6h when the temperature is 120 DEG C and the salinity is 20*10<4>mg/l. The gel blocking agent is suitable for bottom water sandstone oil reservoir horizontal wells, the blocking rate to tahe first region Triassic natural cores is 96.4% and the acidifying removal rate is 98%.
Description
Technical field
The present invention relates to oil-gas field development technical field, be specifically related to a kind of salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua for end water Sandstone Water horizontal well.
Background technology
System in Tahe Oilfield 1,9 district Triassic system petroclastic rock oil reservoir is that end water grows oil reservoir, reservoir buried depth 4400 ~ 4700 meters, formation temperature 110 ~ 120 DEG C, and reservoir pressure coefficient 1.02 ~ 1.1 is normal temps, pressure system; Formation water salinity is high, is about 20 × 10
4about mg/l, calcium ions and magnesium ions content is high, is about 1 × 10
4about mg/l.1,9 district's Triassic system petroclastic rock oil reservoirs are ooze stratum in mesopore, end water thickness is large, generally be greater than 50m, end water energy is sufficient, and core intersection is little, be generally less than 30m, this oil reservoir many employings horizontal well casing pipe well cementation perforation completion and the exploitation of horizontal well sieve tube completion, only have a small amount of straight well casing cementing perforation completion for this reason.
Along with the carrying out of exploitation, horizontal well is water breakthrough progressively, and the moisture rapid water of production fluid raises even water logging, and oil offtake declines fast, have impact on the development effectiveness of this oil reservoir in serious.Early stage takes middle matter oil in water emulsion+calcium carbonate superfine powder (sodium carbonate) water blockoff, obtain good effect, but along with the enforcement of this technology many rounds water blockoff, effect of increasing production is deteriorated gradually, carry out the high strength plugging agent Study and Development meeting the requirement of oil reservoir water blockoff for this reason.
The subject matter that water sandstone oil reservoir water plugging of horizontal well technology at the bottom of the degree of Triassic deep layer high temperature height ore deposit, current similar system in Tahe Oilfield 1,9 district exists is:
(1) early stage middle matter oil in water emulsion+calcium carbonate superfine powder (sodium carbonate) plugging agent solid phase particle of taking, can injection poor, only form nearly pit shaft shutoff, weak effect;
(2) main plugging agent calcium carbonate superfine powder (sodium carbonate) solid phase particle is easily along with producing extraction gradually, and validity period is short;
(3) commonly use gel plugging agent at present, intensity is low, and shear Adsorption Effect by stratum large, the effective shut-off capacity in deep is poor.
Need research one to meet high-temperature stratum requirement for this reason, there is good anti-salt property (20 × 10
4mg/l), can injection efficiency good, shearing the factor such as absorption by stratum affects little, has the high strength plugging agent formula system of the effective shut-off capacity in good deep.
Summary of the invention
For the problem of deep layer high temperature, high ore deposit degree horizontal well with bottom water reservoir Development and Production feature, the plugging agent plugging strength deficiency used both at home and abroad at present, the effective shut-off capacity difference in deep, the invention provides a kind of salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua, improve shut-off capacity and the plugging effect of blocking agent formation.
Specifically, the present invention is achieved through the following technical solutions:
A kind of salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua, with parts by weight, this salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua contains:
Sulfonation modifying small molecules biological polymer 20 ~ 25 parts,
Small molecules acrylamide and methylpropene sodium sulfonate multipolymer 2.5 ~ 4 parts,
Linking agent 1.3 ~ 3 parts, and
PH adjusting agent 0.5 ~ 1.5 part;
Wherein, described linking agent is phenolic resin compound.
Aforesaid salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua, described sulfonation modifying small molecules biological polymer is that pulp concentrating liquid is made through S-WAT sulfonation.
Wherein, described small molecules acrylamide and methylpropene sodium sulfonate multipolymer are that the acrylamide of 3:1 and methylpropene sodium sulfonate obtain by mol ratio, and the molecular weight of preferred small molecules acrylamide and methylpropene sodium sulfonate multipolymer is 600 × 10
4~ 800 × 10
4.
Wherein, the compound that described phenolic resin compound maybe can produce aldehyde by phenolic compound and aldehyde compound is that 1:6 is obtained by reacting with mol ratio.
Wherein, described phenolic compound is the one in phenol, Resorcinol or Resorcinol.
Wherein, described aldehyde compound maybe can produce the compound of aldehyde is one in formaldehyde, glutaraldehyde, paraformaldehyde, hexamethylenetetramine or urea.
Wherein, described pH adjusting agent is weak organic acid or mineral acid, the one in preferred ammonium chloride, formic acid, oxalic acid, citric acid.
Wherein, described salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua is that base fluid is prepared with water, and described water is clear water or salinity is 2 × 10
4the oilfield injection water of mg/L.
The present invention with a kind of sulfonation modifying small molecules biological polymer and small molecules acrylamide and methylpropene sodium sulfonate multipolymer for thickening material, resol class material is linking agent, weak organic acid or mineral acid are PH conditioning agent, homogeneous aqueous solution is made in configuration, under being heated to formation temperature conditions, leave standstill plastic, obtain a kind of salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua, be applicable to the high temperature of similar system in Tahe Oilfield 1,9 district Triassic Bottom water energy abundance, the sandstone oil reservoir horizontal well of high salinity, temperature be 120 DEG C, salinity is 20 × 10
4during mg/l, gelling strength is 4 × 10
4~ 10 × 10
4mPa ﹒ S, gelation time is 4 ~ 6 hours; Being applied to end Shuitu enters in the plug water construction of watered-out well, and be 96.4% to Tahe 1 district Triassic system natural core sealing ratiod, acidifying releasing rate is 98%.
Embodiment
Salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua of the present invention, thickening material adopts two micromolecular polymkeric substance, and in stratum filtration process, shear Adsorption Effect by stratum little, plugging strength is large, effective.
In order to fully understand object of the present invention, feature and effect, by following embodiment, the present invention is elaborated.
The invention provides a kind of salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua, with parts by weight, this salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua contains: sulfonation modifying small molecules biological polymer 4 ~ 5 parts, small molecules acrylamide and methylpropene sodium sulfonate multipolymer 0.5 ~ 0.8 part, linking agent 0.3 ~ 0.6 part, and pH adjusting agent 0.1 ~ 0.3 part; Described linking agent is phenolic resin compound.
Wherein, described sulfonation modifying small molecules biological polymer makes through S-WAT sulfonation with pulp concentrating liquid, the pulp concentrating liquid in described pulp concentrating liquid preferred acid system commercial paper process.
Described small molecules acrylamide and methylpropene sodium sulfonate multipolymer are acrylamide and the methylpropene sodium sulfonate of 3:1 by mol ratio, with ammonium persulphate-S-WAT redox initiation system, obtained by Solution Free Radical copolymerization, the molecular weight of preferred small molecules acrylamide and methylpropene sodium sulfonate multipolymer is 600 × 10
4~ 800 × 10
4.
Sulfonation modifying small molecules biological polymer and small molecules acrylamide and methylpropene sodium sulfonate multipolymer are the thickening material of plugging agent system, by above synergistic effect therebetween, intensity and anti-salt, the anticalcium magnesium ability of crosslinked gel plugging aqua of the present invention can be improved.
The compound that described phenolic resin compound maybe can produce aldehyde by phenolic compound and aldehyde compound is 1:6 with mol ratio, reacts and obtain for 2.5 hours at 110 DEG C.Described phenolic compound is the one in phenol, Resorcinol or Resorcinol, and the compound that described aldehyde compound maybe can produce aldehyde is the one in formaldehyde, glutaraldehyde, paraformaldehyde, hexamethylenetetramine or urea.
Phenolic resin compound, as linking agent, can make polymer molecule be cross-linked to form spacial framework.
Described pH adjusting agent is weak organic acid or mineral acid, the one in preferred ammonium chloride, formic acid, oxalic acid, citric acid, and the pH value of crosslinked gel plugging aqua of the present invention is adjusted to 3.5 ~ 6.2.
PH adjusting agent regulates the acid or alkali environment of linking agent, meets cross-linking agents condition.
This salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua is that base fluid is prepared with water, and described water is clear water, low mineralization tap water or highly mineralized formation brines, and preferred salinity is 2 × 10
4mg/L, calcium ions and magnesium ions content are 1 × 10
4the local water of mg/L.
Preferably, when base fluid is 500ml, this salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua contains: sulfonation modifying small molecules biological polymer 4 ~ 5g, small molecules acrylamide and methylpropene sodium sulfonate multipolymer 0.5 ~ 0.8g, linking agent 0.3 ~ 0.6g, and pH adjusting agent 0.1 ~ 0.3g.
A kind of salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua of the present invention, is applicable to end water Sandstone Water horizontal well, temperature be 120 DEG C, salinity is 20 × 10
4during mg/l, gelling strength is 4 × 10
4~ 10 × 10
4mPa ﹒ S, gelation time is 4 ~ 6 hours.
A kind of salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua of the present invention is 96.4% to Tahe 1 district Triassic system natural core sealing ratiod, and acidifying releasing rate is 98%.
Below, enumerate embodiment and the present invention is further described, but the present invention is not limited to following embodiment.
Raw material used in embodiment, except special envoy illustrates, is all buy the raw material from conventional commercial.
The preparation method of sulfonation modifying small molecules biological polymer is: in pulping liquor, add the milk of lime that weight percent is 15%, at 97 DEG C, heat 45min; By calcifying solution standing sedimentation, throw out leaches, add after washing weight percent be 50% the vitriol oil carry out sulfonation reaction; Material, through filtering, removes calcium sulfate; Filtrate concentrates, and crystallisation by cooling obtains sulfonation modifying small molecules biological polymer.
The preparation method of small molecules acrylamide and methylpropene sodium sulfonate multipolymer is: to take mol ratio as the acrylamide of 3:1 and methylpropene sodium sulfonate preparation mass concentration be 35% solution (dosing water is the pure water of resins exchange process), be heated to 45 DEG C in a kettle. and keep stable, the nitrogen purging 30min of 98% is greater than with content, add the ammonium persulphate-S-WAT initiator system of 0.04% ~ 0.08%, by Solution Free Radical copolymerization, then by extruding, granulation, drying, the technique such as pulverizing obtains.The molecular weight of gained small molecules acrylamide and methylpropene sodium sulfonate multipolymer is 600 × 10
4~ 800 × 10
4.
The preparation method of resol: add 100kg pure water in a kettle., be heated to 95 DEG C, add Resorcinol 16kg and dissolve, then add hexamethylenetetramine 42kg and urea 58kg respectively, at 110 DEG C, react 150min, then through extruding, drying, the technique such as pulverizing obtains resol.
Embodiment 1 prepares crosslinked gel plugging water sample 1#
Take sulfonation modifying small molecules biological polymer 20g, small molecules acrylamide and methylpropene sodium sulfonate multipolymer 2.5g, phenolic resin crosslinking agent 1.5g and pH adjusting agent 1g, under 1000r/min high-speed stirring condition, join in 500ml clear water successively, stir 10min, be mixed with uniform solution, swelling 60min, then stir 10min, obtain crosslinked gel plugging water sample 1#.
Embodiment 2 prepares crosslinked gel plugging water sample 2#
Take sulfonation modifying small molecules biological polymer 25g, small molecules acrylamide and methylpropene sodium sulfonate multipolymer 4g, phenolic resin crosslinking agent 3g and pH adjusting agent 1.5g, under 1000r/min high-speed stirring condition, (salinity is 20 × 10 to join 500ml tower one local water successively
4mg/l, calcium ions and magnesium ions content is 1 × 10
4mg/l), in, stir 10min, be mixed with uniform solution, swelling 60min, then stir 10min, obtain crosslinked gel plugging water sample 2#.
Embodiment 3 measures gelling strength and the gelation time of the crosslinked gel plugging aqua of embodiment 1 and 2
Gelling strength and gelation time measuring method as follows:
The Gelling Water-plugging agent solution 100ml of Example 1 and embodiment 2 adds sealing in cillin bottle (100ml) respectively, and the baking oven putting into 120 DEG C heats plastic and timing, within every 1 hour, observes plastic situation.When the quick retrogradation of plugging agent, every 20min HAKKERS150 high temperature rheometer, at shearing rate 1.5s
-1lower mensuration gel strength.Time when gel strength reaches maximum is gelation time, and the intensity when gel strength is stablized is gel strength.Concrete measurement result is as shown in table 1.
Table 1
| Crosslinked gel plugging aqua | Gelling strength (mPa ﹒ S) | Gelation time (min) |
| Embodiment 1 | 56840 | 283 |
| Embodiment 2 | 93617 | 245 |
The highly mineralized formation brines that preparation crosslinked gel plugging water sample 2# dosing adopts is salinity is 2 × 10
4mg/L, calcium ions and magnesium ions content are 1 × 10
4the local water of mg/L, gelling strength reaches 93617mPa ﹒ S, has good anti-salt property.The present embodiment adopts highly mineralized formation brines dosing, the intensity that the crosslinked gel plugging aqua obtained is still higher.
Embodiment 4 by the crosslinked gel plugging aqua sample application of embodiment 1 in Tahe 1 district Triassic system TK105H well (maintain secrecy test)
The Gelling Water-plugging agent solution 200ml of Example 1 carries out plug water construction in TK105H well, well temperature is 120 DEG C, rock core is natural core 2PV, record construction oil pressure and be increased to 24MPa by 3MPa, casing pressure is increased to 20MPa by 0, water ratio is down to 86% by 95.0%, illustrates and achieves good water blockoff correctional effect; Measuring reservoir core plugging rate is 96.4%, and acidifying releasing rate is 98%.
To the above-mentioned explanation of the disclosed embodiments, those skilled in the art are realized or uses the present invention.To be apparent for a person skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (8)
1. a salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua, with parts by weight, this salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua contains:
Sulfonation modifying small molecules biological polymer 20 ~ 25 parts,
Small molecules acrylamide and methylpropene sodium sulfonate multipolymer 2.5 ~ 4 parts,
Linking agent 1.3 ~ 3 parts, and
PH adjusting agent 0.5 ~ 1.5 part;
Wherein, described linking agent is phenolic resin compound.
2. salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua according to claim 1, is characterized in that, described sulfonation modifying small molecules biological polymer is that pulp concentrating liquid is made through S-WAT sulfonation.
3. salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua according to claim 1 and 2, it is characterized in that, described small molecules acrylamide and methylpropene sodium sulfonate multipolymer are that the acrylamide of 3:1 and methylpropene sodium sulfonate obtain by mol ratio, and the molecular weight of preferred small molecules acrylamide and methylpropene sodium sulfonate multipolymer is 600 × 10
4~ 800 × 10
4.
4. the salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua according to any one of claims 1 to 3, is characterized in that, the compound that described phenolic resin compound maybe can produce aldehyde by phenolic compound and aldehyde compound is that 1:6 is obtained by reacting with mol ratio.
5. the salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua according to any one of Claims 1 to 4, it is characterized in that, described phenolic compound is the one in phenol, Resorcinol or Resorcinol.
6. the salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua according to any one of Claims 1 to 5, is characterized in that, the compound that described aldehyde compound maybe can produce aldehyde is the one in formaldehyde, glutaraldehyde, paraformaldehyde, hexamethylenetetramine or urea.
7. the salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua according to any one of claim 1 ~ 6, it is characterized in that, described pH adjusting agent is weak organic acid or mineral acid, the one in preferred ammonium chloride, formic acid, oxalic acid, citric acid.
8. the salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua according to any one of claim 1 ~ 7, is characterized in that, described salt-resisting high-temperature-resisting high strength crosslinked gel plugging aqua is that base fluid is prepared with water, and described water is clear water or salinity is 2 × 10
4the oilfield injection water of mg/L.
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Cited By (4)
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| CN105622856A (en) * | 2016-04-01 | 2016-06-01 | 中国石油化工股份有限公司 | Preparation process of positioning channeling blocking agent |
| CN106916578A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | A kind of high temperature resistant Weak Gels type profile control agent and preparation method thereof |
| CN109280542A (en) * | 2017-07-20 | 2019-01-29 | 中国石油天然气股份有限公司 | A kind of high temperature resistant frozen glue sealing agent and its preparation method and application |
| CN112175595A (en) * | 2019-07-02 | 2021-01-05 | 中石化南京化工研究院有限公司 | Temperature-resistant and salt-resistant profile control water shutoff agent |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916578A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | A kind of high temperature resistant Weak Gels type profile control agent and preparation method thereof |
| CN105622856A (en) * | 2016-04-01 | 2016-06-01 | 中国石油化工股份有限公司 | Preparation process of positioning channeling blocking agent |
| CN105622856B (en) * | 2016-04-01 | 2018-01-30 | 中国石油化工股份有限公司 | A kind of preparation technology for positioning envelope and altering agent |
| CN109280542A (en) * | 2017-07-20 | 2019-01-29 | 中国石油天然气股份有限公司 | A kind of high temperature resistant frozen glue sealing agent and its preparation method and application |
| CN109280542B (en) * | 2017-07-20 | 2021-04-30 | 中国石油天然气股份有限公司 | High-temperature-resistant gel plugging agent and preparation method and application thereof |
| CN112175595A (en) * | 2019-07-02 | 2021-01-05 | 中石化南京化工研究院有限公司 | Temperature-resistant and salt-resistant profile control water shutoff agent |
| CN112175595B (en) * | 2019-07-02 | 2022-12-27 | 中石化南京化工研究院有限公司 | Temperature-resistant and salt-resistant profile control water shutoff agent |
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|---|---|
| CN105131921B (en) | 2018-03-23 |
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