CN102102012A - Selective water shutoff agent for horizontal well and preparation method thereof - Google Patents
Selective water shutoff agent for horizontal well and preparation method thereof Download PDFInfo
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- CN102102012A CN102102012A CN2010106063716A CN201010606371A CN102102012A CN 102102012 A CN102102012 A CN 102102012A CN 2010106063716 A CN2010106063716 A CN 2010106063716A CN 201010606371 A CN201010606371 A CN 201010606371A CN 102102012 A CN102102012 A CN 102102012A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 238000012216 screening Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 230000035699 permeability Effects 0.000 claims description 31
- 230000003750 conditioning effect Effects 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 8
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 8
- 150000002828 nitro derivatives Chemical group 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000008398 formation water Substances 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000010276 construction Methods 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 54
- 239000011435 rock Substances 0.000 description 28
- 239000011236 particulate material Substances 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 5
- 235000020681 well water Nutrition 0.000 description 5
- 239000002349 well water Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 241000237502 Ostreidae Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention discloses a selective water shutoff agent for a horizontal well and a preparation method of the selective water shutoff agent, and belongs to the technical field of oilfield chemistry. The water shutoff agent comprises the following components in parts by weight: 6.50-7.50 parts of a polymer monomer; 4.50-5.75 parts of a surface active intermediate; 0.85-1.00 part of regulator; 85.75-88.15 parts of water. The method comprises the following steps: adding the surface active intermediate into water, adding a polymer monomer, and stirring uniformly; adding a regulator after the surface active intermediate and the polymer monomer react, and stirring for reaction; and drying the reaction product, crushing into particles, and screening to obtain the selective water shutoff agent particles for the horizontal well. The water shutoff agent provided by the invention has the advantages of strong oil and water selectivity, convenient synthesis and production, stable chemical performance, strong adaptability and simple construction process; meanwhile, the sweep efficiency of the development of the horizontal well of the high-water-content old oil field can be improved, the sweep volume is enlarged, and the oil recovery rate is improved.
Description
Technical field
The present invention relates to the oilfield chemical technology field, particularly a kind of horizontal well selective water shutoff agent and preparation method thereof.
Background technology
Along with going deep into of oil-field development, horizontal well well number constantly increases, and horizontal well development oil field comprehensive water cut raises year by year, and the high-permeability pay water outlet is serious, and the low permeability pay production potential are difficult to performance, and the effective water-plugging technique of horizontal production well is demanded development urgently.The characteristics that the selective water shut-off technology utilizes plugging agent to have different chemical properties in oil, water surrounding realize the not stifled oil of water blockoff, or the purpose of few stifled oil.Abroad the RPM of use phase permeabilities are adjusted agent more in water plugging of horizontal well, and this adjustment agent is high molecular polymer or frozen glue class; Mostly the plugging agent of domestic use is that cement, clay etc. do not have optionally inorganic plugging agent to oil, water.But, there is not a kind of selective water shutoff agent to be widely used from total service condition.Reason is as follows: the one, and selectivity is not strong, and plugging agent has been blocked water, but the output of oil has also descended simultaneously, does not have economic benefit; The 2nd, cost an arm and a leg, returns of investment are low; The 3rd, the oil reservoir chemical environment that is suitable for is too narrow.
Summary of the invention
In order to solve existing level well water plugging agent poor selectivity, to cost an arm and a leg and problem such as suitable environment narrow range, the invention provides a kind of horizontal well selective water shutoff agent, each ingredients weight parts is:
Polymer monomer, 6.50～7.50 parts;
The table active intermediate, 4.50～5.75 parts;
Conditioning agent, 0.85～1.00 part;
Water, 85.75～88.15 parts.
Further, described polymer monomer is a modified methacrylic acid methylamino ethyl ester.
Further, described table active intermediate is for using the quaternised pyridylium compound of halohydrocarbon.
Further, described conditioning agent is a nitro-compound.
Further, the suitable reservoir condition of described plugging agent is: zone permeability is less than 1 μ m
2, formation temperature less than 90 ℃, formation water salinity less than 8 * 10
4Ppm.
The present invention also provides a kind of preparation method of horizontal well selective water shutoff agent, and described method comprises:
To show active intermediate and add in the entry, add polymer monomer again, be stirred to evenly;
Treat to add conditioning agent after the reaction of described table active intermediate and polymer monomer the restir reaction;
With the reaction product oven dry, be ground into particle, screening obtains horizontal well selective water shutoff agent particle.
The condition of described table active intermediate and polymer monomer reaction is: 50 ℃ of temperature, reaction times 4-5 hour; The stirring reaction time behind the described adding conditioning agent is 1-2 hour.
Horizontal well selective water shutoff agent provided by the invention has stronger oil, water selectivity, and is synthetic convenient for production, stable chemical performance, and adaptability is strong, and construction technology is simple; Simultaneously, can also improve the sweep efficiency of high moisture maturing field horizontal well development, enlarge swept volume, improve oil recovery.
Embodiment
In order to understand the present invention in depth, the present invention is described in detail below in conjunction with specific embodiment.
The embodiment of the invention provides a kind of horizontal well selective water shutoff agent, is used for high production fluid, high aqueous horizontal well selective water shut-off, and suitable reservoir condition is: zone permeability is less than 1 μ m
2, formation temperature less than 90 ℃, formation water salinity less than 8 * 10
4Ppm.The water blockoff principle of embodiment of the invention selective water shutoff agent is based on microcosmic reservoir oil moisture road stream mechanism, enter oil reservoir as plugging agent, then form the polymer cluster of shrinking in hole central authorities, oil is from the channel flow between cluster and pore wall, cluster is dissolving gradually in oil phase, disappears at last; Enter water layer as plugging agent, then the polymer polar group is adsorbed on pore surface, and molecular chain stretches to duct central authorities, forms network structure, stops flowing of water.
The using method of horizontal well selective water shutoff agent on the oil field that the embodiment of the invention provides is as follows:
(1) fixed tubular column
Inject plugging agent with profile control pump or cementing truck from oil, cover annular space.Inject discharge capacity 3～8m
3/ h, implantation concentration are 0.5%～1.25%.Consumption is dependent on horizontal section length, is generally 1500-3000m
3, the plugging agent slug is replaced to the stratum closing well 2 days with high concentration polymer solution.
(2) moving tubing string
Trip out flow string, handle pit shaft, be lowered to water plugging string.Inject plugging agent with profile control pump or cementing truck from oil pipe, inject discharge capacity 3～8m
3/ h, implantation concentration are 0.5%～1.25%.Consumption is dependent on horizontal section length, is generally 1500-3000m
3, the plugging agent slug is replaced to the stratum closing well 2 days with high concentration polymer solution.
Below by several specific embodiments, the water plugging effect of embodiment of the invention horizontal well selective water shutoff agent once is described.Wherein, the laboratory facilities and the material of test water horizontal well selective water shutoff agent water plugging effect comprise: horizontal well control water core physical simulation experimental installation, simulated oil (kerosene), local water, baking oven, oilfield horizontal well; Local water is taken from scene, Ji Dong oil field.Each component is in weight part among the following embodiment.
Embodiment 1, east, Ji G41-P1 well water blockoff core experiment:
4.75 parts table active intermediate is added in the entry, add 6.75 parts polymer monomer again, be stirred to evenly; The conditioning agent that after reacting 4 hours under 50 ℃ of temperature, adds 0.925 part, restir reaction 1 hour; With the reaction product oven dry, be ground into the particle about 0.25mm, screening obtains horizontal well selective water shutoff agent particulate material; 0.75 part of selective water shutoff agent particulate material evenly is dissolved in 99.25 parts the local water, is made into concentration and is 0.75% selective water shut-off agent solution.In actual applications, polymer monomer can be modified methacrylic acid methylamino ethyl ester; The table active intermediate can be for using the quaternised pyridylium compound of halohydrocarbon, for example
Conditioning agent can be nitro-compound, for example
Fill and present two blocks of rock cores No. 1, No. 2, back-up sand core porosity 42%.No. 1 rock core is surveyed water phase permeability, and No. 2 rock core is surveyed permeability to oil.Two baskets respectively inject 0.2PV horizontal well selective water shut-off agent solution, put into temperature and be 75 ℃ thermostat container.Take out basket after 10 days 1, No. 2, No. 1 rock core is oppositely annotated local water, the water phase permeability when surveying water filling 1PV, 5PV, 10PV, 20PV, 50PV, 100PV respectively; No. 2 rock core is oppositely annotated simulated oil (kerosene), surveys the permeability to oil when annotating simulated oil 1PV, 5PV, 10PV, 20PV, 50PV, 100PV respectively.
Experiment is found: the permeability reduction value is 81% behind No. 1 rock core notes 10PV local water, the permeability reduction value is 53% after No. 2 rock cores notes 10PV simulated oil, illustrate that horizontal well selective water shutoff agent of the present invention has oil, water selectivity, more obvious to the water layer plugging effect than oil reservoir.
Embodiment 2, east, Ji G160-P6 well water blockoff core experiment:
5 parts table active intermediate is added in the entry, add 7 parts polymer monomer again, be stirred to evenly; The conditioning agent that after reacting 4 hours under 50 ℃ of temperature, adds 0.925 part, restir reaction 1 hour; With the reaction product oven dry, be ground into the particle about 0.25mm, screening obtains horizontal well selective water shutoff agent particulate material; 1.0 parts of selective water shutoff agent particulate materials evenly are dissolved in 99 parts the local water, are made into concentration and are 1% selective water shut-off agent solution.In actual applications, polymer monomer can be modified methacrylic acid methylamino ethyl ester; The table active intermediate can be for using the quaternised pyridylium compound of halohydrocarbon, for example
Conditioning agent can be nitro-compound, for example
Fill and present two blocks of rock cores No. 1, No. 2, back-up sand core porosity 40%.No. 1 rock core is surveyed water phase permeability, and No. 2 rock core is surveyed permeability to oil.Two baskets respectively inject 0.2PV horizontal well selective water shut-off agent solution, put into temperature and be 75 ℃ thermostat container.Take out basket after 24 hours 1, No. 2, No. 1 rock core is oppositely annotated local water, the water phase permeability when surveying water filling 1PV, 5PV, 10PV, 20PV, 50PV, 100PV respectively; No. 2 rock core is oppositely annotated simulated oil (kerosene), surveys the permeability to oil when annotating simulated oil 1PV, 5PV, 10PV, 20PV, 50PV, 100PV respectively.
Experiment is found: the permeability reduction value is 72% behind No. 1 rock core notes 10PV local water, the permeability reduction value is 5% after No. 2 rock cores notes 10PV simulated oil, illustrate that horizontal well selective water shutoff agent of the present invention has oil, water selectivity, more obvious to the water layer plugging effect than oil reservoir.
Embodiment 3, east, Ji M36-P3 well water blockoff core experiment:
5.25 parts table active intermediate is added in the entry, add 7.25 parts polymer monomer again, be stirred to evenly; The conditioning agent that after reacting 4.5 hours under 50 ℃ of temperature, adds 0.95 part, restir reaction 1 hour; With the reaction product oven dry, be ground into the particle about 0.25mm, screening obtains horizontal well selective water shutoff agent particulate material; 1.25 parts of selective water shutoff agent particulate materials evenly are dissolved in 98.75 parts the local water, are made into concentration and are 1.25% selective water shut-off agent solution.In actual applications, polymer monomer can be modified methacrylic acid methylamino ethyl ester; The table active intermediate can be for using the quaternised pyridylium compound of halohydrocarbon, for example
Conditioning agent can be nitro-compound, for example
Fill and present two blocks of rock cores No. 1, No. 2, back-up sand core porosity 36%.No. 1 rock core is surveyed water phase permeability, and No. 2 rock core is surveyed permeability to oil.Two baskets respectively inject 0.2PV horizontal well selective water shutoff agent, put into temperature and be 75 ℃ thermostat container.Take out basket after 24 hours 1, No. 2, No. 1 rock core is oppositely annotated local water, the water phase permeability when surveying water filling 1PV, 5PV, 10PV, 20PV, 50PV, 100PV respectively; No. 2 rock core is oppositely annotated simulated oil (kerosene), surveys the permeability to oil when annotating simulated oil 1PV, 5PV, 10PV, 20PV, 50PV, 100PV respectively.
Experiment is found: the permeability reduction value is 56% behind No. 1 rock core notes 10PV local water, the permeability reduction value is 15% after No. 2 rock cores notes 10PV simulated oil, illustrate that horizontal well selective water shutoff agent of the present invention has oil, water selectivity, more obvious to the water layer plugging effect than oil reservoir.
Embodiment 4, east, Ji M17-9 well water blockoff core experiment:
5.75 parts table active intermediate is added in the entry, add 7.5 parts polymer monomer again, be stirred to evenly; The conditioning agent that after reacting 5 hours under 50 ℃ of temperature, adds 1 part, restir reaction 1 hour; With the reaction product oven dry, be ground into the particle about 0.25mm, screening obtains horizontal well selective water shutoff agent particulate material; 1.5 parts of selective water shutoff agent particulate materials evenly are dissolved in 98.5 parts the local water, are made into concentration and are 1.5% selective water shut-off agent solution.In actual applications, polymer monomer can be modified methacrylic acid methylamino ethyl ester; The table active intermediate can be for using the quaternised pyridylium compound of halohydrocarbon, for example
Conditioning agent can be nitro-compound, for example
Fill and present two blocks of rock cores No. 1, No. 2, back-up sand core porosity 39%.No. 1 rock core is surveyed water phase permeability, and No. 2 rock core is surveyed permeability to oil.Two baskets respectively inject 0.2PV horizontal well selective water shut-off agent solution, put into temperature and be 75 ℃ thermostat container.Take out basket after 24 hours 1, No. 2, No. 1 rock core is oppositely annotated local water, the water phase permeability when surveying water filling 1PV, 5PV, 10PV, 20PV, 50PV, 100PV respectively; No. 2 rock core is oppositely annotated simulated oil (kerosene), surveys the permeability to oil when annotating simulated oil 1PV, 5PV, 10PV, 20PV, 50PV, 100PV respectively.
Experiment is found: the permeability reduction value is 55% behind No. 1 rock core notes 10PV local water, the permeability reduction value is 5% after No. 2 rock cores notes 10PV simulated oil, illustrate that horizontal well selective water shutoff agent of the present invention has oil, water selectivity, more obvious to the water layer plugging effect than oil reservoir.
Embodiment 5, water blockoff field experiment:
The G160-P6 well location is high shallow South Area in the Ji Dong oil field, and on January 27th, 2007 went into operation, day at initial stage 37.2 tons of production fluids, 29.6 tons of day produce oils, moisture 20.5%.113.2 tons of the plug water construction production fluids day before yesterday, 3.3 tons of day produce oils, moisture 97.1%.
4.5 parts table active intermediate is added in the entry, add 6.5 parts polymer monomer again, be stirred to evenly; The conditioning agent that after reacting 4 hours under 50 ℃ of temperature, adds 0.85 part, restir reaction 1 hour; With the reaction product oven dry, be ground into the particle about 0.25mm, screening obtains horizontal well selective water shutoff agent particulate material; 0.5 part of selective water shutoff agent particulate material evenly is dissolved in 99.5 parts the local water, is made into concentration and is 0.5% selective water shut-off agent solution.The concentration that present embodiment obtains is that 0.5% selective water shut-off agent solution is the oyster white thick liquid, and density is 1.01-1.06g/cm
3, the pH value is 7.1-7.3, viscosity is 140-150mPa.s (25 ℃).In actual applications, polymer monomer can be modified methacrylic acid methylamino ethyl ester; The table active intermediate can be for using the quaternised pyridylium compound of halohydrocarbon, for example
Conditioning agent can be nitro-compound, for example
Plug water construction process: be lowered to water plugging string after the sand washing, with 3～8m
3The discharge capacity of/h is annotated clear water 20m
3, with 3～8m
3The discharge capacity of/h is injected plugging agent 1200m
3, annotate high concentration polymer solution 10m
3, annotate a high sewage 91m
3, closing well 2 days.
Daily fluid production rate is 37 tons behind the plug water construction, and oil offtake is kept the preceding level of measure, illustrates that selective water shutoff agent has played the purpose that reduces water phase permeability; Construction back is under the constant substantially condition of liquid measure, and oil offtake increases gradually, increases to 8.9 tons/day by 0.6 ton/day, has embodied the gradual recovery of permeability to oil, the mechanism of action of coincidence selectivity plugging agent.
The horizontal well selective water shutoff agent that the embodiment of the invention provides has stronger oil, water selectivity, and is synthetic convenient for production, stable chemical performance, and adaptability is strong, and construction technology is simple; Simultaneously, can also improve the sweep efficiency of high moisture maturing field horizontal well development, enlarge swept volume, improve oil recovery.
Above-described embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is the specific embodiment of the present invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a horizontal well selective water shutoff agent is characterized in that, each ingredients weight parts is:
Polymer monomer, 6.50～7.50 parts;
The table active intermediate, 4.50～5.75 parts;
Conditioning agent, 0.85～1.00 part;
Water, 85.75～88.15 parts.
2. horizontal well selective water shutoff agent as claimed in claim 1 is characterized in that, described polymer monomer is a modified methacrylic acid methylamino ethyl ester.
3. horizontal well selective water shutoff agent as claimed in claim 1 is characterized in that, described table active intermediate is for using the quaternised pyridylium compound of halohydrocarbon.
4. horizontal well selective water shutoff agent as claimed in claim 1 is characterized in that, described conditioning agent is a nitro-compound.
5. as arbitrary described horizontal well selective water shutoff agent among the claim 1-4, it is characterized in that the reservoir condition that described plugging agent is suitable for is: zone permeability is less than 1 μ m
2, formation temperature less than 90 ℃, formation water salinity less than 8 * 10
4Ppm.
6. the preparation method of a horizontal well selective water shutoff agent is characterized in that, described method comprises:
To show active intermediate and add in the entry, add polymer monomer again, be stirred to evenly;
Treat to add conditioning agent after the reaction of described table active intermediate and polymer monomer the restir reaction;
With the reaction product oven dry, be ground into particle, screening obtains horizontal well selective water shutoff agent particle.
7. the preparation method of horizontal well selective water shutoff agent as claimed in claim 6 is characterized in that, described polymer monomer is a modified methacrylic acid methylamino ethyl ester.
8. the preparation method of horizontal well selective water shutoff agent as claimed in claim 6 is characterized in that, described table active intermediate is for using the quaternised pyridylium compound of halohydrocarbon.
9. the preparation method of horizontal well selective water shutoff agent as claimed in claim 6 is characterized in that, described conditioning agent is a nitro-compound.
10. as the preparation method of arbitrary described horizontal well selective water shutoff agent among the claim 6-9, it is characterized in that the condition of described table active intermediate and polymer monomer reaction is: 50 ℃ of temperature, reaction times 4-5 hour; The stirring reaction time behind the described adding conditioning agent is 1-2 hour.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010106063716A CN102102012A (en) | 2010-12-24 | 2010-12-24 | Selective water shutoff agent for horizontal well and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106063716A CN102102012A (en) | 2010-12-24 | 2010-12-24 | Selective water shutoff agent for horizontal well and preparation method thereof |
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| CN102102012A true CN102102012A (en) | 2011-06-22 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604607A (en) * | 2012-03-01 | 2012-07-25 | 克拉玛依市正诚有限公司 | Lipophilic rigid particle plugging agent and production method as well as using method thereof |
| CN102876305A (en) * | 2011-07-14 | 2013-01-16 | 中国石油化工股份有限公司 | Oil well water shutoff agent and oil well water shutoff method |
| CN106753299A (en) * | 2016-12-30 | 2017-05-31 | 中国石油天然气股份有限公司 | Selective water plugging agent for thin oil well and preparation method and application thereof |
| CN107057666A (en) * | 2017-05-03 | 2017-08-18 | 林林 | A kind of sand prevention integrated chemical agent of supermolecule oilwell water shutoff and preparation method thereof |
-
2010
- 2010-12-24 CN CN2010106063716A patent/CN102102012A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876305A (en) * | 2011-07-14 | 2013-01-16 | 中国石油化工股份有限公司 | Oil well water shutoff agent and oil well water shutoff method |
| CN102876305B (en) * | 2011-07-14 | 2015-03-18 | 中国石油化工股份有限公司 | Oil well water shutoff agent and oil well water shutoff method |
| CN102604607A (en) * | 2012-03-01 | 2012-07-25 | 克拉玛依市正诚有限公司 | Lipophilic rigid particle plugging agent and production method as well as using method thereof |
| CN102604607B (en) * | 2012-03-01 | 2014-03-12 | 克拉玛依市正诚有限公司 | Lipophilic rigid particle plugging agent and production method as well as using method thereof |
| CN106753299A (en) * | 2016-12-30 | 2017-05-31 | 中国石油天然气股份有限公司 | Selective water plugging agent for thin oil well and preparation method and application thereof |
| CN106753299B (en) * | 2016-12-30 | 2019-09-10 | 中国石油天然气股份有限公司 | Selective water plugging agent for thin oil well and preparation method and application thereof |
| CN107057666A (en) * | 2017-05-03 | 2017-08-18 | 林林 | A kind of sand prevention integrated chemical agent of supermolecule oilwell water shutoff and preparation method thereof |
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Application publication date: 20110622 |