CN108728063A - Composition and its preparation method and application with selective water plugging function - Google Patents
Composition and its preparation method and application with selective water plugging function Download PDFInfo
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Abstract
The present invention relates to water shutoff material field, a kind of composition and preparation method thereof with selective water plugging function is disclosed, and the composition being prepared by this method and its application.Specifically, the composition contains oil-soluble resin, primary emulsion and anionic polymer, wherein the oil-soluble resin is one or more in rosin resin, gum dammar, oil-soluble phenolic resin, Petropols, terpene resin and coumarone indene resin；The primary emulsion is selected from compound shown in compound and/or formula (II) shown in formula (I).The composition with selective water plugging function provided by the invention has the not stifled oil of good water blockoff, and has temperature-resistant anti-salt performance and flushing resistance, can be well adapted for the reservoir condition of high temperature and high salt.R1O‑SO3‑M1(Formulas I) R2‑SO3‑M2(Formula II).
Description
Technical field
The present invention relates to water shutoff material fields, and in particular, to a kind of composition with selective water plugging function and its
Preparation method, and the composition being prepared by this method and its application.
Background technology
Polymerization species water shutoff material be current large-scale application water shutoff agent, be broadly divided into polymerization species relative permeability modifier and
Polymer gel class water shutoff agent.The main distinction of the two is that relative permeability modifier is mainly long chain polymer molecules class, by polymerization
Object strand stretches in water phase, is shunk in oil phase, forms the drag interaction to water phase, reduces water phase permeability, the system
The physics of pore volume will not be caused to block, but water blockoff insufficient strength, abrasion resistance are poor.Polymer gel class water shutoff agent is borrowed
The variation for helping the lower effectively movable volume of grease effect, makes Oil/water Phase Permeability that non-uniform reduction, but the processing mode occur
Fluid swivels physics can be caused to block, Porous Media ability is caused to decline, oil-producing while oil well production water is greatly lowered
Ability also reduces, and dealing with improperly can cause Liquid output too low, makes the crude oil underproduction.Therefore it is tight to be mostly used for heterogeneous situation for the system
The profile-log of water injection of weight is handled, and is used to need such as temporarily to block up method, ring by more complicated householder method when producing well water blockoff
Empty extreme pressure method, excessively displacement method etc..Although polymerizeing species water shutoff material has good practical function, must root using process
Corresponding injection technology is formulated according to the actual conditions in each oil field, water shutoff agent is otherwise injected and does not have water plugging effect not only, can also
Aquatic products amount is set to increase, crude output declines.
The water blockoffs system such as existing oil base, water base, although having certain selectivity, not only water blockoff but also stifled oil, indoor
Logistics organizations show that the oil plugging rate of existing blocking agent is all higher than 35%, and the temperature-resistant anti-salt performance of system is also poor, promote and apply
Range is smaller.The research of solution-type selective water-plugging is the direction of high polymer material technology development, the material based on molecular level
Material microstructure understanding and synthesis modification technology will be the key that selective water-plugging research；Blocking agent is studied under oil reservoir full-scale condition
With the interaction mechanism of rock, its essence is deduced from molecular level, will be the basis of selective water-plugging research and evaluation.But
Be such water shutoff material abrasion resistance it is relatively low, service life is shorter.Therefore, for harsh reservoir condition, water blockoff material is improved
The heat-resistant salt-resistant and its flushing resistance of material are of great significance.
Currently, selective water shutoff agent and Novel technique of in-depth profile control become better and approaching perfection day by day both at home and abroad, in grinding for selective water plugging material
Studying carefully exploitation, construction technology etc. has technically had tremendous development, but as oil field development, oil-layer characteristic and environment are constantly sent out
Changing keeps the contradiction of oil reservoir development more prominent, according to selectivity using water shutoff material for a long time particularly to development late stage
The characteristic of water shutoff material summarizes the experience of oil field actual development, proposes the technology that current selective water shutoff agent must pull against at present
Problem improves the water plugging effect of selective system targetedly to research and develop new technology to adapt to special oil field.
In conclusion selective water-plugging used in oilwell water shutoff is mostly by water such as polyacrylamide and its derivatives at present
Soluble polymer generates gel in stratum or frozen glue blocks water flooding, or meets water plastic or solidification envelope with oil base blocking agent
Water blockoff alters channel, but due to its poor selectivity, also will be greatly reduced oleic permeability while water blockoff, causes stifled rear low
Liquid constrains the application of water shutoff in oil well.Therefore a kind of novel highly selective water shutoff material is developed, realizes the water blockoff of oil reservoir not
Stifled oil improves oil well productivity to ultra-high water cut stage and has great importance.
Invention content
The purpose of the invention is to overcome the existing drawbacks described above of the prior art, provide a kind of with selective water plugging
Composition of function and its preparation method and application.Composition provided by the invention with selective water plugging function is with good
Water blockoff block up oil effect, and have temperature-resistant anti-salt performance and flushing resistance, high temperature and high salt can be well adapted for
Reservoir condition.
The present inventor has found under study for action, by specific oil-soluble resin, primary emulsion and anionic polymerization
Object is used cooperatively, and can obtain New Emulsion floating type water shutoff material, which has stronger with reservoir formation rock
Affinity generates stratum duct water phase by the water shutoff material after injection pump injects at producing well in stratigraphic oil pool hole
Strong closure, and abrasion resistance is strong, and then substantially reduce water phase permeability；Also, when the water shutoff material encounters earth bore
It when the oil phase in road, can have an effect and voluntarily de-plugging with crude oil, and then reduce the influence to oleic permeability, to reach water blockoff
The effect of oil is not blocked up.In addition, the water shutoff material has insensitivity, while its softening point (90 DEG C or more) to formation water salinity
It is higher, and then the temperature-resistant anti-salt performance of the water shutoff material is enhanced, it is adapted to high temperature and high salt oil deposit condition.
Also, the present inventor further investigation revealed that, specific primary emulsion is added to anion
In the aqueous solution of type polymer, stable lotion is formed, then oil-soluble resin is prepared new through being added in above-mentioned emulsion
Type lotion floating type water shutoff material.The addition of anionic polymer makes lotion have certain viscosity, to resin particle
Sand effect is suspended and taken with preferable, extends injection stroke of the water shutoff material under stratigraphic oil pool.
Therefore, to achieve the goals above, in a first aspect, the present invention provides a kind of groups with selective water plugging function
Object is closed, the composition contains oil-soluble resin, primary emulsion and anionic polymer, wherein the oil-soluble resin is selected from
It is one or more in rosin resin, gum dammar, oil-soluble phenolic resin, Petropols, terpene resin and coumarone indene resin；
The primary emulsion is selected from compound shown in compound and/or formula (II) shown in formula (I),
R1O-SO3-M1(Formulas I),
R2-SO3-M2(Formula II),
Wherein, R1For the alkyl of C12-C18, M1For alkali or alkaline earth metal, R2For aralkyl or the alkyl of C12-C18,
M2For alkali or alkaline earth metal.
Second aspect, the present invention also provides a kind of preparation method of the composition with selective water plugging function, the systems
Preparation Method includes the following steps：
(1) anionic polymer is mixed with water, forms aqueous solution；
(2) primary emulsion is mixed with the aqueous solution, forms lotion；
(3) oil-soluble resin is mixed with the lotion；
Wherein, the oil-soluble resin is selected from rosin resin, gum dammar, oil-soluble phenolic resin, Petropols, terpenes
It is one or more in resin and coumarone indene resin；The primary emulsion is selected from shown in compound and/or formula (II) shown in formula (I)
Compound,
R1O-SO3-M1(Formulas I),
R2-SO3-M2(Formula II),
Wherein, R1For the alkyl of C12-C18, M1For alkali or alkaline earth metal, R2For aralkyl or the alkyl of C12-C18,
M2For alkali or alkaline earth metal.
The third aspect, the present invention also provides the groups with selective water plugging function being prepared by above-mentioned preparation method
Close object.
Fourth aspect, the application that the present invention also provides above-mentioned compositions in water shutoff material, especially in Water in Water Shutoff in Oil Field
Application in material.
Specific implementation mode
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In a first aspect, the present invention provides a kind of composition with selective water plugging function, it is molten that the composition contains oil
Property resin, primary emulsion and anionic polymer, wherein the oil-soluble resin be selected from rosin resin, gum dammar, oil it is molten
It is one or more in property phenolic resin, Petropols, terpene resin and coumarone indene resin；The primary emulsion is selected from formula (I)
Compound shown in shown compound and/or formula (II),
R1O-SO3-M1(Formulas I),
R2-SO3-M2(Formula II),
Wherein, R1For the alkyl (or straight chained alkyl) of C12-C18, M1For alkali or alkaline earth metal, R2For aralkyl or
The alkyl (or straight chained alkyl) of C12-C18, M2For alkali or alkaline earth metal.
Composition according to the present invention, relative to the oil-soluble resin of 100 parts by weight, the content of the primary emulsion
Content for 10-400 parts by weight, the anionic polymer is 0.5-100 parts by weight；Preferably, relative to 100 parts by weight
The oil-soluble resin, the content of the primary emulsion is 40-200 parts by weight, and the content of the anionic polymer is
1-25 parts by weight.
In composition in the present invention, there is no particular limitation in source of the present invention to the oil-soluble resin, for example,
It can be obtained by conventional commercially available means.In situations where it is preferred, in order to which the purpose of selective water plugging is better achieved, it is described
The grain size of oil-soluble resin is 3-100 μm, preferably 3-50 μm.
In situations where it is preferred, in the primary emulsion, R1For the alkyl of C12-C14, M1For alkali metal, R2For aralkyl
The alkyl of base or C12-C14, M2For alkali metal.Preferably, the primary emulsion is selected from dodecyl sodium sulfate, dodecyl sulphur
It is one or more in sour sodium and neopelex.
Composition according to the present invention, there is no particular limitation for type of the present invention to the anionic polymer, can be with
For the conventional selection of this field.In situations where it is preferred, the ion degree of the anionic polymer is 5-30%, preferably
15-25%；Viscosity average molecular weigh is 10,000,000-3,500 ten thousand, preferably 20,000,000-3,000 ten thousand.It is highly preferred that the anionic is poly-
It is partial hydrolysis type polyacrylamide and/or sulfonic acid type acrylamide to close object.In the present invention, " anionic polymer from
Sub- degree " refers to the mass percentage of anion structure unit in anionic polymer, is measured according to GB12005.6-89.
In the present compositions, there is no particular limitation in source of the present invention to the anionic polymer, example
Such as, it can be obtained by conventional commercially available means.
Composition according to the present invention, the composition can also contain assistant for emulsifying agent.The present invention is to the assistant for emulsifying agent
Type there is no particular limitation, for example, the assistant for emulsifying agent can be selected from Span 20, Span 40, Span 60, Span 80, spit
It is one or more in temperature 20, polysorbate40, polysorbate60 and Tween 80.In situations where it is preferred, relative to described in 100 parts by weight
The content of oil-soluble resin, the assistant for emulsifying agent is 0-500 parts by weight, preferably 4-420 parts by weight.
In composition in the present invention, each component in the composition can mix preservation before use, can also
It is respectively independent to preserve.In situations where it is preferred, each component in the composition is using preceding respective independent preservation.
Composition according to the present invention, the composition can also contain water.Specifically, the composition when in use may be used
To be mixed with water.In situations where it is preferred, relative to every gram of oil-soluble resin, the content of the water is 5-1000mL, preferably
8-200mL, more preferably 9-170mL.
Second aspect, the present invention also provides a kind of preparation method of the composition with selective water plugging function, the party
Method includes：Oil-soluble resin, primary emulsion and anionic polymer are mixed with water.
In the present invention, the material with selective water plugging function can be obtained by way of mixing above-mentioned each ingredient,
However its water plugging property can be further increased by mixing each ingredient in a certain order, it is therefore, preferred in one kind of the present invention
Embodiment in, the present invention also provides a kind of preparation method of the composition with selective water plugging function, the preparation sides
Method includes the following steps：
(1) anionic polymer is mixed with water, forms aqueous solution；
(2) primary emulsion is mixed with the aqueous solution, forms lotion；
(3) oil-soluble resin is mixed with the lotion；
Wherein, the oil-soluble resin is selected from rosin resin, gum dammar, oil-soluble phenolic resin, Petropols, terpenes
It is one or more in resin and coumarone indene resin；The primary emulsion is selected from shown in compound and/or formula (II) shown in formula (I)
Compound,
R1O-SO3-M1(Formulas I),
R2-SO3-M2(Formula II),
Wherein, R1For the alkyl of C12-C18, M1For alkali or alkaline earth metal, R2For aralkyl or the alkyl of C12-C18,
M2For alkali or alkaline earth metal.
Preparation in accordance with the present invention, relative to the oil-soluble resin of 100 parts by weight, the use of the primary emulsion
Amount is 10-400 parts by weight, and the dosage of the anionic polymer is 0.5-100 parts by weight；Preferably, relative to 100 weight
The dosage of the oil-soluble resin of part, the primary emulsion is 40-200 parts by weight, the dosage of the anionic polymer
For 1-25 parts by weight.In the present invention, the weight of each raw material is according to rate of charge meter.
In the preparation process in accordance with the present invention, there is no particular limitation in source of the present invention to the oil-soluble resin, for example,
It can be obtained by conventional commercially available means.In situations where it is preferred, in order to which the purpose of selective water plugging is better achieved, it is described
The grain size of oil-soluble resin is 3-100 μm, preferably 3-50 μm.
In situations where it is preferred, in the primary emulsion, R1For the alkyl of C12-C14, M1For alkali metal, R2For aralkyl
The alkyl of base or C12-C14, M2For alkali metal.Preferably, the primary emulsion is selected from dodecyl sodium sulfate, dodecyl sulphur
It is one or more in sour sodium and neopelex.
Preparation in accordance with the present invention, there is no particular limitation for type of the present invention to the anionic polymer, can
Think the conventional selection of this field.In situations where it is preferred, the ion degree of the anionic polymer is 5-30%, preferably
15-25%；Viscosity average molecular weigh is 10,000,000-3,500 ten thousand, preferably 20,000,000-3,000 ten thousand.It is highly preferred that the anionic is poly-
It is partial hydrolysis type polyacrylamide and/or sulfonic acid type acrylamide to close object.
In the preparation process in accordance with the present invention, there is no particular limitation in source of the present invention to the anionic polymer,
For example, can be obtained by conventional commercially available means.
Preparation in accordance with the present invention, the composition can also contain assistant for emulsifying agent.The present invention helps emulsification to described
There is no particular limitation for the type of agent, for example, the assistant for emulsifying agent can be selected from Span 20, Span 40, Span 60, Span 80,
It is one or more in polysorbas20, polysorbate40, polysorbate60 and Tween 80.In situations where it is preferred, the institute relative to 100 parts by weight
Oil-soluble resin is stated, the dosage of the assistant for emulsifying agent is 0-500 parts by weight, preferably 4-420 parts by weight.
In preparation method in the present invention, each component in the composition can mix preservation before use, also may be used
It is preserved with respectively independent.In situations where it is preferred, each component in the composition is using preceding respective independent preservation.
Preparation in accordance with the present invention, there is no particular limitation for dosage of the present invention to the water, as long as may finally
Form the water shutoff material of stable lotion suspension.For example, relative to every gram of oil-soluble resin, the content of the water is 5-
1000mL, preferably 8-200mL, more preferably 9-170mL.
Preparation in accordance with the present invention, in step (1), the present invention does not limit the mode of the mixing particularly
It is fixed, as long as each component in system can be made to be uniformly mixed, for example, the mixing can carry out under stirring conditions.
In situations where it is preferred, the condition of the mixing includes：Mixed temperature is 20-50 DEG C, and the rate of time 1-6h, stirring are
500-700r/min。
Preparation in accordance with the present invention, in step (2), the present invention does not limit the mode of the mixing particularly
It is fixed, as long as each component in system can be made to be uniformly mixed, for example, the mixing can carry out under stirring conditions.
In situations where it is preferred, the condition of the mixing includes：Mixed temperature is 20-50 DEG C, and the rate of time 1-3h, stirring are
500-700r/min。
Preparation in accordance with the present invention, in step (3), the present invention does not limit the mode of the mixing particularly
It is fixed, as long as each component in system can be made to be uniformly mixed, for example, the mixing can carry out under stirring conditions.
In situations where it is preferred, the condition of the mixing includes：Mixed temperature is 20-50 DEG C, time 0.5-2h, the rate of stirring
For 500-700r/min.
The third aspect, the present invention also provides what the above-mentioned preparation method by the present invention was prepared to have selective water plugging
The composition (material) of function.
Fourth aspect, the application that the present invention also provides above-mentioned compositions in water shutoff material, especially in Water in Water Shutoff in Oil Field
Application in material.
In the present invention, the environmental condition in the oil field may include：Temperature be 40-130 DEG C, preferably 70-110 DEG C,
More preferably 90-110 DEG C；Salinity is 100-200,000mg/L, preferably 10,000-100,000mg/L, more preferably 50,
000-100,000mg/L。
The present invention will be described in detail by way of examples below.
Unless stated otherwise, the reagent used in following embodiment and comparative example can be commercially available.
In the following Examples and Comparative Examples,
Oil-soluble phenolic resin is purchased from Jining Hua Kai resin Co., Ltd, the trade mark 2402；
Petropols are purchased from Jitian Chemical Co., Ltd. of Shenzhen, trade mark C5C9；
Coumarone indene resin is purchased from Shandong Xiang Zhao new materials Co., Ltd, trade mark 18#；
Partial hydrolysis type polyacrylamide is purchased from Beijing Hengju Chemical Group Co., Ltd, and trade mark KYPAM glues equal
Molecular weight is 25,000,000, ion degree 24%.
Sulfonic acid type acrylamide is purchased from gloomy (China) the flocculant Co., Ltd of love, trade mark SNF3030, viscosity average molecular weigh
It is 30,000,000, ion degree 23%.
In following embodiment and comparative example, the test method being related to is as follows：
Sealing ratiod be on core flow test device according to《Drilling fluid bridge joint plugging material Experimental Method in Laboratory》SY/
Sealing ratiod testing procedure in T5840-2007 carries out.Specifically：
The measurement of water plugging rate：Artificial core is packed into core holding unit, water saturation is first used, surveys its water phase permeability (Kw1),
Then the water shutoff agent for squeezing into 10mL, after being conserved for 24 hours at 90 DEG C, then the permeability (K after water shutoff agent is added in it with aquametryw2),
Kw2And Kw1Ratio (Kw2/Kw1) it is water plugging rate.
The measurement of oil plugging rate：Artificial core is packed into core holding unit, first with oil saturation, surveys its oleic permeability (Ko1),
Then the water shutoff agent for squeezing into 10mL after being conserved for 24 hours at 90 DEG C, then measures the permeability (K after its addition water shutoff agent with oilo2),
Ko2And Ko1(Ko2/Ko1) it is oil plugging rate.
The measurement of resistance to erosion multiple：After measuring water plugging rate, continue to inject 50 times of pore volume injecteds (PV) in rock core
Water, while recording the permeability under different PV numbers, and different PV are calculated according to the above-mentioned assay method about water plugging rate
Water plugging rate under several, the maximum PV numbers of resistance to erosion multiple injected water when being water plugging rate >=80%.Under normal conditions, it measures
Water plugging rate under 50PV numbers, the value >=80% illustrate that the material has excellent flushing resistance.
Wherein, artificial core is obtained by tamping the quartz sand of 40-60 mesh in a mold.
Embodiment 1
The present embodiment is for illustrating the composition provided by the invention with selective water plugging function.
1,0.01g partially hydrolyzed polyacrylamide (PHPA)s are weighed to be added in the water of 100mL, (600r/ is sufficiently stirred at 20 DEG C
Min) after 3h, aqueous solution is formed；
2,1g neopelexes are weighed respectively and 2.5g Spans 60 are added sequentially in above-mentioned aqueous solution, at 20 DEG C
Under be sufficiently stirred (600r/min) 1h after, form stable lotion；
3,0.6g oil-soluble phenolic resins (3-50 μm of grain size) are weighed to be added in above-mentioned emulsion, are sufficiently stirred at 20 DEG C
After (600r/min) 0.5h, the water shutoff material A1 of stable lotion suspension is formed.
After tested, under conditions of high temperature (90 DEG C) and (salinity 50,000mg/L) with high salt, water shutoff material A1's is stifled
Water rate is 94.22%, and oil plugging rate 12.52%, resistance to erosion multiple is more than 50PV.This illustrates the water blockoff that the present embodiment is prepared
Material has excellent selective shut-off rate and abrasion resistance to oil/water, and tool is especially remained under high temperature and high salt conditions
There is preferable oil/water selective shut-off rate.
Embodiment 2
The present embodiment is for illustrating the composition provided by the invention with selective water plugging function.
1,1g partially hydrolyzed polyacrylamide (PHPA)s are weighed to be added in the water of 100mL, (600r/ is sufficiently stirred at 20 DEG C
Min) after 1h, aqueous solution is formed；
2,5g dodecyl sodium sulfates are weighed respectively and 0.5g polysorbate40s are added sequentially in above-mentioned aqueous solution, at 30 DEG C
After being sufficiently stirred (600r/min) 3h, stable lotion is formed；
3,10.6g coumarone indene resins (3-50 μm of grain size) are weighed to be added in above-mentioned emulsion, are sufficiently stirred at 50 DEG C
After (600r/min) 2h, the water shutoff material A2 of stable lotion suspension is formed.
After tested, under conditions of high temperature (90 DEG C) and (salinity 80,000mg/L) with high salt, water shutoff material A2's is stifled
Water rate is 99.20%, and oil plugging rate 14.56%, resistance to erosion multiple is more than 50PV.This illustrates the water blockoff that the present embodiment is prepared
Material has excellent selective shut-off rate and abrasion resistance to oil/water, and tool is especially remained under high temperature and high salt conditions
There is preferable oil/water selective shut-off rate.
Embodiment 3
The present embodiment is for illustrating the composition provided by the invention with selective water plugging function.
1,0.25g sulfonic acid type acrylamides are weighed to be added in the water of 100mL, (600r/ is sufficiently stirred at 20 DEG C
Min) after 6h, aqueous solution is formed；
2,2g lauryl sodium sulfate is weighed respectively and 1g polysorbate60s are added sequentially in above-mentioned aqueous solution, is filled at 20 DEG C
After dividing stirring (600r/min) 1h, stable lotion is formed；
3,1g Petropols (3-50 μm of grain size) are weighed to be added in above-mentioned emulsion, (600r/ is sufficiently stirred at 20 DEG C
Min) after 1.5h, the water shutoff material A3 of stable lotion suspension is formed.
After tested, under conditions of high temperature (90 DEG C) and (salinity 100,000mg/L) with high salt, water shutoff material A3's is stifled
Water rate is 96.21%, and oil plugging rate 12.74%, resistance to erosion multiple is more than 50PV.This illustrates the water blockoff that the present embodiment is prepared
Material has excellent selective shut-off rate and abrasion resistance to oil/water, and tool is especially remained under high temperature and high salt conditions
There is preferable oil/water selective shut-off rate.
Embodiment 4
The present embodiment is for illustrating the composition provided by the invention with selective water plugging function.
1,0.2g sulfonic acid type acrylamides are weighed to be added in the water of 100mL, (600r/ is sufficiently stirred at 20 DEG C
Min) after 4h, aqueous solution is formed；
2,1.5g neopelexes are weighed respectively and 1g polysorbate60s are added sequentially in above-mentioned aqueous solution, at 30 DEG C
Under be sufficiently stirred (600r/min) 2h after, form stable lotion；
3,1.5g oil-soluble phenolic resins (3-50 μm of grain size) are weighed to be added in above-mentioned emulsion, are sufficiently stirred at 30 DEG C
After (600r/min) 1h, the water shutoff material A4 of stable lotion suspension is formed.
After tested, under conditions of high temperature (90 DEG C) and (salinity 80,000mg/L) with high salt, water shutoff material A4's is stifled
Water rate is 98.22%, and oil plugging rate 6.21%, resistance to erosion multiple is more than 50PV.This illustrates the water blockoff that the present embodiment is prepared
Material has excellent selective shut-off rate and abrasion resistance to oil/water, and tool is especially remained under high temperature and high salt conditions
There is preferable oil/water selective shut-off rate.
Embodiment 5
The present embodiment is for illustrating the composition provided by the invention with selective water plugging function.
It is carried out according to the method for embodiment 4, the difference is that polysorbate60, water shutoff material A5 is not added in step (2).
After tested, under conditions of high temperature (90 DEG C) and (salinity 80,000mg/L) with high salt, water shutoff material A5's is stifled
Water rate is 95.78%, and oil plugging rate 13.56%, resistance to erosion multiple is more than 50PV.This illustrates the water blockoff that the present embodiment is prepared
Material has excellent selective shut-off rate and abrasion resistance to oil/water, and tool is especially remained under high temperature and high salt conditions
There is preferable oil/water selective shut-off rate.
Embodiment 6
The present embodiment is for illustrating the composition provided by the invention with selective water plugging function.
It is carried out according to the method for embodiment 4, the difference is that in step (1), the addition of partially hydrolyzed polyacrylamide (PHPA)
Amount is 1.5g, obtains water shutoff material A6.
After tested, under conditions of high temperature (90 DEG C) and (salinity 80,000mg/L) with high salt, water shutoff material A6's is stifled
Water rate is 92.35%, and oil plugging rate 17.89%, resistance to erosion multiple is more than 50PV.This illustrates the water blockoff that the present embodiment is prepared
Material has preferable selective shut-off rate and abrasion resistance to oil/water.
Embodiment 7
The present embodiment is for illustrating the composition provided by the invention with selective water plugging function.
It is carried out according to the method for embodiment 4, the difference is that in step (1), the addition of partially hydrolyzed polyacrylamide (PHPA)
Amount is 0.0075g, obtains water shutoff material A7.
After tested, under conditions of high temperature (90 DEG C) and (salinity 80,000mg/L) with high salt, water shutoff material A6's is stifled
Water rate is 88.56%, and oil plugging rate 19.86%, resistance to erosion multiple is more than 50PV.This illustrates the water blockoff that the present embodiment is prepared
Material has preferable selective shut-off rate and abrasion resistance to oil/water.
Embodiment 8
The present embodiment is for illustrating the composition provided by the invention with selective water plugging function.
It is carried out according to the method for embodiment 4, the difference is that in step (2), the addition of neopelex
For 6g, water shutoff material A8 is obtained.
After tested, under conditions of high temperature (90 DEG C) and (salinity 80,000mg/L) with high salt, water shutoff material A8's is stifled
Water rate is 93.14%, and oil plugging rate 13.85%, resistance to erosion multiple is more than 50PV.This illustrates the water blockoff that the present embodiment is prepared
Material has preferable selective shut-off rate and abrasion resistance to oil/water.
Embodiment 9
The present embodiment is for illustrating the composition provided by the invention with selective water plugging function.
It is carried out according to the method for embodiment 4, the difference is that in step (1), the addition of neopelex
For 0.15g, water shutoff material A9 is obtained.
After tested, under conditions of high temperature (90 DEG C) and (salinity 80,000mg/L) with high salt, water shutoff material A6's is stifled
Water rate is 86.41%, and oil plugging rate 16.24%, resistance to erosion multiple is more than 50PV.This illustrates the water blockoff that the present embodiment is prepared
Material has preferable selective shut-off rate and abrasion resistance to oil/water.
Embodiment 10
The present embodiment is for illustrating the composition provided by the invention with selective water plugging function.
It is carried out according to the method for embodiment 4, the difference is that in step (1), uses 1.5g acrylamides/acrylic acid
Copolymer (is purchased from Shandong Rett Chemical Co., Ltd., trade mark RT200, viscosity average molecular weigh is 20,000,000, ion degree 28%)
Instead of sulfonic acid type acrylamide, water shutoff material A10 is obtained.
After tested, under conditions of high temperature (90 DEG C) and (salinity 80,000mg/L) with high salt, water shutoff material A10's is stifled
Water rate is 84.12%, and oil plugging rate 17.63%, resistance to erosion multiple is less than 50PV.This illustrates the water blockoff that the present embodiment is prepared
Material has preferable selective shut-off rate to oil/water.
Embodiment 11
The present embodiment is for illustrating the composition provided by the invention with selective water plugging function.
Weigh 0.01g partially hydrolyzed polyacrylamide (PHPA)s, 1g neopelexes, 2.5g Spans 60 and 0.6g oil-solubles
Phenolic resin (3-50 μm of grain size) is added in 100mL water, after being sufficiently stirred 4.5h at 20 DEG C, is formed stable lotion and is suspended
The water shutoff material A11 of shape.
After tested, under conditions of high temperature (90 DEG C) and (salinity 50,000mg/L) with high salt, water shutoff material A11's is stifled
Water rate is 82.36%, and oil plugging rate 20.14%, resistance to erosion multiple is less than 50PV.This illustrates the water blockoff that the present embodiment is prepared
Material has preferable selective shut-off rate to oil/water.
Comparative example 1
It is carried out according to the method for embodiment 4, the difference is that being added without lauryl sodium sulfate, obtains water shutoff material D1.
After tested, under conditions of high temperature (90 DEG C) and (salinity 80,000mg/L) with high salt, water shutoff material D1's is stifled
Water rate is 80.36%, and oil plugging rate 36.23%, resistance to erosion multiple is less than 50PV.
Comparative example 2
It is carried out according to the method for embodiment 4, the difference is that being added without sulfonic acid type acrylamide, obtains water shutoff material
D2。
After tested, under conditions of high temperature (90 DEG C) and (salinity 80,000mg/L) with high salt, water shutoff material D2's is stifled
Water rate is 78.13%, and oil plugging rate 26.82%, resistance to erosion multiple is less than 50PV.
Comparative example 3
It is carried out according to the method for embodiment 4, the difference is that in step (1), uses 0.2g nonylphenol polyoxyethylene ether
Instead of neopelex, water shutoff material D4 is obtained.
After tested, under conditions of high temperature (90 DEG C) and (salinity 80,000mg/L) with high salt, water shutoff material D4's is stifled
Water rate is 75.36%, and oil plugging rate 29.38%, resistance to erosion multiple is less than 50PV.
By above example 1-11 being compared with the result of comparative example 1-3 it is found that provided by the invention have selection
Property water blockoff function composition have the effect of the not stifled oil of good water blockoff, and there is temperature-resistant anti-salt performance and abrasion resistance
Can, the reservoir condition of high temperature and high salt can be well adapted for.In particular, by the way that embodiment 4 can relatively be seen compared with comparative example 3
Go out, the present invention selects certain types of primary emulsion, and the water blockoff that can further increase water shutoff material does not block up the effect of oil.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention
In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, belongs to
Protection scope of the present invention.
Claims (16)
1. a kind of composition with selective water plugging function, which is characterized in that the composition contains oil-soluble resin, main emulsification
Agent and anionic polymer, wherein the oil-soluble resin is selected from rosin resin, gum dammar, oil-soluble phenolic resin, stone
It is one or more in oleoresin, terpene resin and coumarone indene resin；The primary emulsion be selected from formula (I) shown in compound and/
Or compound shown in formula (II),
R1O-SO3-M1(Formulas I),
R2-SO3-M2(Formula II),
Wherein, R1For the alkyl of C12-C18, M1For alkali or alkaline earth metal, R2For aralkyl or the alkyl of C12-C18, M2For
Alkali or alkaline earth metal.
2. composition according to claim 1, wherein relative to the oil-soluble resin of 100 parts by weight, the main breast
The content of agent is 10-400 parts by weight, and the content of the anionic polymer is 0.5-100 parts by weight；
Preferably, relative to the oil-soluble resin of 100 parts by weight, the content of the primary emulsion is 40-200 parts by weight,
The content of the anionic polymer is 1-25 parts by weight.
3. composition according to claim 1 or 2, wherein the grain size of the oil-soluble resin is 3-100 μm；
Preferably, in the primary emulsion, R1For the alkyl of C12-C14, M1For alkali metal, R2For aralkyl or C12-C14
Alkyl, M2For alkali metal；
It is highly preferred that the primary emulsion is selected from dodecyl sodium sulfate, lauryl sodium sulfate and neopelex
In it is one or more.
4. composition according to claim 1 or 2, wherein the ion degree of the anionic polymer is 5-30%, excellent
It is selected as 15-25%；Viscosity average molecular weigh is 10,000,000-3,500 ten thousand, preferably 20,000,000-3,000 ten thousand；
Preferably, the anionic polymer is partial hydrolysis type polyacrylamide and/or sulfonic acid type acrylamide.
5. composition according to claim 1, wherein the composition also contains assistant for emulsifying agent；Preferably, described to help breast
The one kind or more of agent in Span 20, Span 40, Span 60, Span 80, polysorbas20, polysorbate40, polysorbate60 and Tween 80
Kind；
It is highly preferred that the oil-soluble resin relative to 100 parts by weight, the content of the assistant for emulsifying agent is 0-500 parts by weight,
Preferably 4-420 parts by weight.
6. according to the composition described in any one of claim 1-5, wherein the composition also contains water；
Preferably, relative to every gram of oil-soluble resin, the content of the water is 5-1000mL, preferably 8-200mL, more preferably
9-170mL。
7. a kind of preparation method of the composition with selective water plugging function, which is characterized in that the preparation method includes following
Step：
(1) anionic polymer is mixed with water, forms aqueous solution；
(2) primary emulsion is mixed with the aqueous solution, forms lotion；
(3) oil-soluble resin is mixed with the lotion；
Wherein, the oil-soluble resin is selected from rosin resin, gum dammar, oil-soluble phenolic resin, Petropols, terpene resin
With it is one or more in coumarone indene resin；The primary emulsion is selected from chemical combination shown in compound and/or formula (II) shown in formula (I)
Object,
R1O-SO3-M1(Formulas I),
R2-SO3-M2(Formula II),
Wherein, R1For the alkyl of C12-C18, M1For alkali or alkaline earth metal, R2For aralkyl or the alkyl of C12-C18, M2For
Alkali or alkaline earth metal.
8. preparation method according to claim 7, wherein relative to the oil-soluble resin of 100 parts by weight, the master
The dosage of emulsifier is 10-400 parts by weight, and the dosage of the anionic polymer is 0.5-100 parts by weight；
Preferably, relative to the oil-soluble resin of 100 parts by weight, the dosage of the primary emulsion is 40-200 parts by weight,
The dosage of the anionic polymer is 1-25 parts by weight.
9. preparation method according to claim 7 or 8, wherein the grain size of the oil-soluble resin is 3-100 μm；
Preferably, in the primary emulsion, R1For the alkyl of C12-C14, M1For alkali metal, R2For aralkyl or C12-C14
Alkyl, M2For alkali metal；
It is highly preferred that the primary emulsion is selected from dodecyl sodium sulfate, lauryl sodium sulfate and neopelex
In it is one or more.
10. preparation method according to claim 7 or 8, wherein the ion degree of the anionic polymer is 5-
30%, preferably 15-25%；Viscosity average molecular weigh is 10,000,000-3,500 ten thousand, preferably 20,000,000-3,000 ten thousand；
Preferably, the anionic polymer is partial hydrolysis type polyacrylamide and/or sulfonic acid type acrylamide.
11. preparation method according to claim 7, wherein in step (2), successively by primary emulsion and assistant for emulsifying agent
It is mixed with the aqueous solution, forms lotion；
Preferably, the assistant for emulsifying agent be selected from Span 20, Span 40, Span 60, Span 80, polysorbas20, polysorbate40, polysorbate60 and
It is one or more in Tween 80；
It is highly preferred that the oil-soluble resin relative to 100 parts by weight, the dosage of the assistant for emulsifying agent is 0-500 parts by weight,
Preferably 4-420 parts by weight.
12. according to the preparation method described in any one of claim 7-11, wherein relative to every gram of oil-soluble resin, institute
The dosage for stating water is 5-1000mL, preferably 8-200mL, more preferably 9-170mL.
13. the preparation method according to claim 7 or 11, wherein in step (1), the mixing is in a manner of stirring
It carries out, and the condition of the mixing includes：Mixed temperature is 20-50 DEG C, time 1-6h, and the rate of stirring is 500-
700r/min；
Preferably, in step (2), the mixing is carried out in a manner of stirring, and the condition of the mixing includes：Mixed temperature
Degree is 20-50 DEG C, time 1-3h, and the rate of stirring is 500-700r/min；
Preferably, in step (3), the mixing is carried out in a manner of stirring, and the condition of the mixing includes：Mixed temperature
Degree is 20-50 DEG C, time 0.5-2h, and the rate of stirring is 500-700r/min.
14. the group with selective water plugging function being prepared by the preparation method described in any one of claim 7-13
Close object.
15. application of the composition described in any one of claim 1-6 and 14 in water shutoff material, especially stifled in oil field
Application in water material.
16. application according to claim 15, wherein the environmental condition in the oil field includes：Temperature is 40-130 DEG C, excellent
It is selected as 70-110 DEG C, more preferably 90-110 DEG C；Salinity is 100-200,000mg/L, preferably 10,000-100,000mg/
L, more preferably 50,000-100,000mg/L.
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