CN105626012B - A kind of increasing injection agent and a kind of water injection well increasing injection method - Google Patents
A kind of increasing injection agent and a kind of water injection well increasing injection method Download PDFInfo
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Abstract
The invention discloses a kind of increasing injection agent, contain hydrophobically modified cyclodextrin, the hydrophobically modified cyclodextrin contains modified group, the modified group contains at least one first modified group and at least one second modified group, first modified group is hydrophobic grouping, and second modified group is the hydrophobic grouping containing hydrophilic functional group.The invention also discloses a kind of water injection well increasing injection method, this method includes that increasing injection agent according to the present invention is injected into water injection well.Increasing injection agent according to the present invention contains hydrophobically modified cyclodextrin, has good increasing injection effect to LOW PERMEABILITY RESERVOIR water injection well.The preparation process of hydrophobically modified cyclodextrin used in increasing injection agent according to the present invention is succinct, is suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of increasing injection agent, and the invention further relates to a kind of water injection well increasing injection methods.
Background technique
Waterflooding extraction is the main mining method of low permeability oil field.In recovery process, due to water sensitivity damage, fouling and
The factors such as solid phase blocking, cause stratum pilot ability weak, and hypotonic oil well is in the presence of water filling injection pressure is high, water injection rate is small, note is adopted
The problems such as uneven, to cause water injection pressure excessively high, water injection rate is quickly reduced, and oil well output successively decreases rapidly.Acidification is
A kind of relatively good water injection well increasing injection processing method of effect that oil field generallys use, but be acidified on the one hand to construction requirement
It is higher, it is be easy to cause corrosion, on the other hand, the action period is shorter.
Therefore, it needs to develop new increasing injection method.
CN101812289B discloses a kind of nano polysilicon particle, and using silica as core, surface bond contains the particle
It hydrophobic group and helps organic compound modified dose, partial size 5-60nm of adsorptivity group, containing hydrophobic group and helps absorption
The organic compound of property group shared weight ratio in nano polysilicon particles is respectively 5-35% and 1-10%；Described organises
Closing object dressing agent is organo-silicon compound and/or organic acid compound, and the organo-silicon compound are carbon chain lengths 1-20's
Alkoxy silane, chlorosilane or silazane；Organic acid molecule formula is RCOOH, and the carbon chain lengths of R are 2-20；The hydrophobicity
Group is one or more of methyl, ethyl, vinyl, fluoro-alkyl；It is described help adsorptivity group be hydroxyl, carboxyl,
One or more of epoxy group or amido.The poly- silicon particle has the effect of the increasing injection of low-permeability oilfield certain.
Summary of the invention
The purpose of the present invention is to provide a kind of new increasing injection agent, and the increasing injection agent is easily prepared, and has
Good increasing injection effect.
The present inventor has found in the course of the research, and hydrophobic grouping is introduced in cyclodextrin molecular structure and is had
The hydrophobic grouping of hydrophilic functional group and the hydrophobically modified cyclodextrin that is formed has good increasing injection effect.On this basis
Complete the present invention.
According to the first aspect of the invention, the present invention provides a kind of increasing injection agent, which contains thin
Water modified cyclodextrin, the hydrophobically modified cyclodextrin contain modified group, and it is modified that the modified group contains at least one first
Group and at least one second modified group, first modified group are hydrophobic grouping, second modified group be containing
The hydrophobic grouping of hydrophilic functional group.
According to the second aspect of the invention, the present invention provides a kind of water injection well increasing injection method, this method packets
It includes and injects increasing injection agent according to the present invention into water injection well.
Increasing injection agent according to the present invention contains hydrophobically modified cyclodextrin, has drop well to LOW PERMEABILITY RESERVOIR water injection well
Augmented injection effect is pressed, reason may is that hydrophobic grouping and the hydrophobic group containing hydrophilic radical are contained in the cyclodextrin outer surface
Group not only has preferable hydrophobicity, but also to the strong adsorption of rock, so as to play preferable increasing injection effect.
The preparation process of hydrophobically modified cyclodextrin used in increasing injection agent according to the present invention is succinct, is suitable for extensive
Production.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is the photo for the film surface that water is formed in hydrophobically modified cyclodextrin powder prepared by the embodiment of the present invention 1.
Fig. 2 is the photo for the film surface that water is formed in hydrophobically modified cyclodextrin powder prepared by the embodiment of the present invention 2.
Fig. 3 is the photo for the film surface that water is formed in hydrophobically modified cyclodextrin powder prepared by the embodiment of the present invention 3.
Specific embodiment
According to the first aspect of the invention, the present invention provides a kind of increasing injection agent, which contains thin
Water modified cyclodextrin, the hydrophobically modified cyclodextrin contain modified group.
The cyclodextrin can be common various cyclodextrin, such as one in alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin
Kind or two or more combinations.
The modified group contains at least one first modified group and at least one second modified group.
First modified group is hydrophobic grouping.First modified group can be C6-C30Alkyl, by fluorine atom
Substituted C6-C30Alkyl andOne or more of, R1、R2And R3Respectively C1-C10Alkyl or
The C being replaced by fluorine atoms1-C10Alkyl.In first modified group, the alkyl can be saturated hydrocarbyl (such as alkyl),
May be unsaturated alkyl (such as containing the alkyl of ethylene linkage)；The alkyl can be fat-based, or alcyl, it can be with
For aromatic radical.In first modified group, the specific example of the alkyl be can include but is not limited to: hexyl (including hexyl
Various isomers), heptyl (the various isomers including heptyl), octyl (the various isomers including octyl), nonyl (including
The various isomers of nonyl), decyl (the various isomers including decyl), undecyl (the various isomeries including undecyl
Body), dodecyl (the various isomers including dodecyl), myristyl (the various isomers including myristyl), ten
Six alkyl (the various isomers including cetyl), octadecyl (the various isomers including octadecyl), eicosyl
(the various isomers including eicosyl), tetracosyl (the various isomers including tetracosyl) and alkylbenzene
(that is, one or more hydrogen on phenyl ring are by alkyl-substituted phenyl, the alkyl can be C1-C20Alkyl, preferably C6-
C12Alkyl) one or more of.In first modified group, " fluoro " refer to one or two of alkyl with
Upper hydrogen atom is replaced by fluorine atoms.
From the angle for further increasing increasing injection effect, first modified group is preferably C8-C20Alkyl,
The C being replaced by fluorine atoms8-C20Alkyl andOne or more of, R1、R2And R3Respectively C1-C5's
Alkyl or the C being replaced by fluorine atoms1-C5Alkyl.
It is highly preferred that first modified group is C8-C16Alkyl, by C6-C12Alkyl-substituted phenyl andOne or more of, R1、R2And R3Respectively C1-C5Alkyl.
It is further preferred that first modified group be selected from n-octyl, dodecyl, nonyl phenyl and
Wherein, R1、R2And R3For butyl.
Second modified group is the hydrophobic grouping containing hydrophilic functional group.The hydrophilic radical can be hydroxyl
One or more of base, carboxyl and amino.The amino includes-NH2With-NH-, preferably-NH2。
Second modified group can be the C replaced by hydroxyl, carboxyl and/or amino6-C30Alkyl andOne or more of, R4、R5And R6The C respectively replaced by hydroxyl, amino and/or carboxyl1-C10Hydrocarbon
Base.In second modified group, the alkyl can be saturated hydrocarbyl (such as alkyl), or unsaturated alkyl (such as contains
The alkyl of ethylene linkage)；The alkyl can be fat-based, or alcyl can also be aromatic radical.Described second modified base
The specific example of alkyl in group can include but is not limited to: hexyl (the various isomers including hexyl), heptyl (including heptyl
Various isomers), octyl (the various isomers including octyl), nonyl (the various isomers including nonyl), decyl (including
The various isomers of decyl), undecyl (the various isomers including undecyl), dodecyl is (including dodecyl
Various isomers), myristyl (the various isomers including myristyl), cetyl it is (various different including cetyl
Structure body), octadecyl (the various isomers including octadecyl), eicosyl (the various isomers including eicosyl) and
One or more of tetracosyl (the various isomers including tetracosyl).
From the angle for further increasing increasing injection effect, second modified group is preferably by hydroxyl, carboxyl
And/or the C that amino replaces8-C20Alkyl (such as alkyl) andOne or more of, R4、R5And R6Respectively
From the C to be replaced by hydroxyl, amino and/or carboxyl1-C5Alkyl.
It is highly preferred that second modified group is the C replaced by hydroxyl and/or carboxyl10-C18One of alkyl
Or it is two or more.
It is further preferred that second modified group is-(CH2)10COOH、-(CH2)16COOH and-(CH2)18In COOH
One or more.
The modified group and the cyclodextrin pass through chemical bonds.Specifically, the modified group can be by taking
For the hydrogen atom in cyclodextrin molecular structure at least partly on hydroxyl or hydroxyl and and cyclodextrin with chemical bonds.According to tool
Body situation, the modified group can pass through the hydrogen atom and cyclodextrin on the hydroxyl in direct substituted cyclodextrin molecular structure
With chemical bonding；Can also be by linker and cyclodextrin with chemical bonding, one end of the linker passes through substitution
The hydrogen atom on hydroxyl in cyclodextrin molecular structure and and cyclodextrin with chemical bonds, the other end and the modified group with
Chemical bonds, the linker for example can for carbonyl (that is,)。
Increasing injection agent according to the present invention, on the basis of the total amount of the hydrophobically modified cyclodextrin, the modified group
Content can be 10-45 weight %, preferably 15-40 weight %.From the angle for further increasing increasing injection effect,
On the basis of the total amount of the hydrophobically modified cyclodextrin, the content of the modified group is preferably 20-35 weight %.The modification
The content of group can be determined by weight method.
Increasing injection agent according to the present invention, first modified group and second modified group act synergistically, and make
Obtaining increasing injection agent according to the present invention has good increasing injection effect.From the angle for further increasing increasing injection effect
It sets out, the molar ratio of first modified group and second modified group can be 0.1-5:1, more preferably 0.2-2.5:
1, more preferably 0.5-1.5:1.Molar ratio between first modified group and second modified group can pass through core
Magnetic resonance spectroscopy measurement, be used to form when can also be by preparing the hydrophobically modified cyclodextrin compound of the first modified group with
And it is used to form the dosage determination of the compound of the second modified group.
Increasing injection agent according to the present invention, the hydrophobically modified cyclodextrin can be by will be in the middle part of cyclodextrin molecular structures
Divide the hydrogen atom group containing the first modified group and the group containing the second modified group in hydroxyl or part of hydroxyl
Replace and obtains.In one embodiment of the invention, the hydrophobically modified cyclodextrin is prepared using following methods:
Under the conditions of condensation reaction, by cyclodextrin and modifying agent, the modifying agent contains the first modifying agent and the second modifying agent, described
First modifying agent and second modifying agent respectively contain the official that condensation reaction can occur with the hydroxyl in cyclodextrin molecular structure
It can roll into a ball, first modified group is formed by first modifying agent, and second modified group is by the described second modified dosage form
At.
According to the embodiment, the specific structure of first modifying agent can be carried out according to the type of the first modified group
Selection.Specifically, first modifying agent is R7OH、R8COOH andOne or more of, R7And R8Respectively
From for C6-C30Alkyl or the C that is replaced by fluorine atoms6-C30Alkyl, preferably C8-C20Alkyl or be replaced by fluorine atoms
C8-C20Alkyl, more preferably C8-C16Alkyl or by C6-C12Alkyl-substituted phenyl；R9、R10And R11Respectively
C1-C10Alkyl or the C that is replaced by fluorine atoms1-C10Alkyl, preferably C1-C5Alkyl or be replaced by fluorine atoms
C1-C5Alkyl, more preferably C1-C5Alkyl；R12For hydrogen or C1-C5Alkyl.Specifically, first modifying agent is positive heptan
One or more of alcohol, n-octyl alcohol, three normal-butyl silane of lauric acid/dodecanoic acid, nonyl phenol and ethyoxyl.
According to the embodiment, the specific structure of second modifying agent can be carried out according to the type of the second modified group
Selection.Specifically, second modifying agent is HO-R13-OH、HO-R14-NH2、HOOC-R15-NH2、HOOC-R16- COOH andOne or more of, R13、R14、R15And R16Respectively C6-C30Alkylene (preferably alkylidene),
Preferably C8-C20Alkylene (preferably alkylidene), more preferably C10-C18Alkylidene；R17、R18And R19Respectively by hydroxyl
The C that base, amino and/or carboxyl replace1-C10Alkyl (preferably alkyl), preferably replaced by hydroxyl, amino and/or carboxyl
C1-C5Alkyl (preferably alkyl)；R20For hydrogen or C1-C5Alkyl.Specifically, second modifying agent is dodecane two
One or more of acid, octadecane diacid, peanut diacid and octacosanol.
According to the embodiment, the dosage of first modifying agent and the second modifying agent can be hydrophobic according to what is finally prepared
In modified cyclodextrin depending on the expection content of modified group.Generally, the dosage of first modifying agent and the second modifying agent makes
In the hydrophobically modified cyclodextrin that finally prepare, the content of modified group is 10-45 weight %, preferably 15-40 weight %, more
Preferably 20-35 weight %.Specifically, the molar ratio of first modifying agent and cyclodextrin can be 0.5-3:1, preferably
1.2-2.5:1 more preferably 1.5-2:1；The molar ratio of second modifying agent and cyclodextrin can be 1-6:1, preferably
1.2-5:1 more preferably 1.3-3.5:1.The molar ratio of first modifying agent and the second modifying agent can be 0.1-5:1, preferably
0.2-2.5:1.From the angle for further increasing increasing injection effect, the molar ratio of the first modifying agent and the second modifying agent is more
Preferably 0.5-1.5:1.
According to the embodiment, cyclodextrin and the contact of the first modifying agent and the second modifying agent at least one solvent into
Row, the solvent can be for that can dissolve cyclodextrin and dissolve the liquid substance of the first modifying agent and the second modifying agent, can be with
For C6-C12Aromatic hydrocarbon, sulfone class solvent and amide solvent.The specific example of the solvent can include but is not limited to: benzene, first
One or more of benzene, dimethyl sulfoxide and N,N-dimethylformamide.The dosage of the solvent can be conventional choosing
It selects.Generally, the dosage of the solvent makes the concentration of cyclodextrin be 1-25 weight %.
According to the embodiment, cyclodextrin and the contact of the first modifying agent and the second modifying agent under the conditions of condensation reaction into
With the hydroxyl in cyclodextrin molecular structure condensation reaction can occur for row, such first modifying agent and the second modifying agent respectively, from
And the first modified group and the second modified group are introduced in cyclodextrin molecular structure.The condition of the contact is can ensure
Modified dose and the second modifying agent can occur subject to condensation reaction with cyclodextrin.Preferably, temperature of the contact at 50-140 DEG C
Degree is lower to carry out.The duration of the contact can be selected according to the temperature contacted.Generally, the contact is held
The continuous time can be 2-20 hours.
According to the embodiment, the first modifying agent and the second modifying agent can be contacted with cyclodextrin simultaneously；It can also be first
Contact the first modifying agent with cyclodextrin, the mixture and the second modifying agent for then obtaining contact.Preferably, first make
Modified dose contacts with cyclodextrin, the mixture and the second modifying agent for then obtaining contact.First modifying agent with
Cyclodextrin preferably 60-80 DEG C at a temperature of contacted, time of contact can be 2-6 hours；First modifying agent and ring are pasted
The essence obtained mixture of contact and the second modifying agent preferably 100-140 DEG C at a temperature of contacted, time of contact can be with
It is 2-14 hours.
According to the embodiment, cyclodextrin is preferably catalyzed at least one with the contact of the first modifying agent and the second modifying agent
It is carried out in the presence of agent, reaction rate can be further increased in this way and carries out haptoreaction under conditions of more mild.
The catalyst can be that can promote the substance of hydroxyls dehydrate condensation reaction, such as acid.Specifically, the catalyst can be
P-methyl benzenesulfonic acid and/or the concentrated sulfuric acid.The dosage of the catalyst, which is subject to, can be realized catalysis, be not particularly limited.One
As, relative to 100 parts by weight of cyclodextrin, the dosage of the catalyst can be 0.5-10 parts by weight.
It, can be by removing the solvent in the mixture that contact obtains according to the embodiment, the solid collected is
The hydrophobically modified cyclodextrin.Can be using the solvent in the mixture that conventional method removing contact obtains, such as depressurizing item
The solvent in mixture that removing contact obtains under part.
Increasing injection composition according to the present invention, the film that the hydrophobically modified cyclodextrin is formed are to the contact angle of water
85 ° or more, generally in the range of 85 ° -160 °, preferably in the range of 90 ° -120 °.
Increasing injection composition according to the present invention, on the basis of the total amount of the composition, the hydrophobically modified cyclodextrin
Content can be 2 weight, ‰ -1 weight %.
Increasing injection composition according to the present invention can also contain dispersion in addition to containing the hydrophobically modified cyclodextrin
Agent, the hydrophobically modified cyclodextrin are scattered in the dispersing agent.The dispersing agent can for it is various can be by hydrophobically modified ring
The finely dispersed liquid substance of dextrin.Specifically, the dispersing agent can be water and/or alcohol (such as C1-C5Alcohol), preferably water,
One or more of methanol and ethyl alcohol.The dosage of the dispersing agent can be conventional selection.Generally, with increasing injection
On the basis of the total amount of agent, the content of the dispersing agent can be 98-99.8 weight %.
According to the second aspect of the invention, the present invention provides a kind of water injection well increasing injection method, this method packets
It includes and injects increasing injection agent according to the present invention into water injection well.The increasing injection agent and its composition have been carried out above
Detailed description, and will not be described here in detail.
According to the method for the present invention, the dosage of the increasing injection agent can be selected according to the actual conditions of water injection well
It selects, is not particularly limited.
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
In following embodiment and comparative example, using the contact angle of the model DSA100 purchased from KRUSS instrument company, Germany
Analyzer water contact angle.
In following embodiment and comparative example, the condition of simulation core flooding experiment includes: (long using fill out sand tube core
60cm, interior diameter 10cm), permeability is about 2.5 darcies.
In following embodiment and comparative example, determine that modified group contains in the hydrophobically modified cyclodextrin of preparation using weight method
Amount, wherein the content of modified group=[(matter of the quality-of obtained hydrophobically modified cyclodextrin as the cyclodextrin of raw material
Amount)/obtained the quality of hydrophobically modified cyclodextrin] × 100%.
Preparation embodiment 1-8 is used to prepare the hydrophobically modified cyclodextrin in increasing injection agent according to the present invention.
Prepare embodiment 1
10g beta-cyclodextrin is added into 120mL N,N-dimethylformamide (to be had purchased from Chinese medicines group chemical reagent Beijing
Limit company).With stirring, the temperature of mixture is increased to 80 DEG C, n-octyl alcohol of the 2g as the first modifying agent is then added, together
When be added 0.4g p-methyl benzenesulfonic acid as catalyst, be stirred to react 2h at 80 DEG C.Then, ten of 5g as the second modifying agent are added
Two docosandioic acids, and raise the temperature to 110 DEG C, the reaction was continued at such a temperature 2h.Finally, the mixture that reaction is obtained carries out
Vacuum distillation after removing solvent, the solid matter being collected into is dried in 60 DEG C of vacuum drying oven to constant weight, hydrophobic change is obtained
Property cyclodextrin.In the hydrophobically modified cyclodextrin, the content of modified group is 30 weight %.
Hydrophobically modified cyclodextrin is made using tabletting method and is used to measure contact angle with a thickness of 450 μm of film, wherein
Photo of the water on the film surface as shown in Figure 1, contact angle be 120 ° (as control, water formed by beta-cyclodextrin it is thin
Contact angle on film is 5 °).
Prepare comparative example 1
10g beta-cyclodextrin is added into 120mL N,N-dimethylformamide (to be had purchased from Chinese medicines group chemical reagent Beijing
Limit company).With stirring, the temperature of mixture is increased to 80 DEG C, 7g n-octyl alcohol and 0.4g p-methyl benzenesulfonic acid is then added,
80 DEG C are stirred to react 2h.The mixture that reaction obtains is evaporated under reduced pressure, after removing solvent, the solid matter being collected into is existed
It dries in 60 DEG C of vacuum drying oven to constant weight, obtains modified cyclodextrin.In the modified cyclodextrin, the content of modified group is 25 weights
Measure %.
Modified cyclodextrin is made using method identical with preparation embodiment 1 and is used to measure with a thickness of 450 μm of film
Contact angle, wherein contact angle is 150 °.
Prepare comparative example 2
10g beta-cyclodextrin is added into 120mL N,N-dimethylformamide (to be had purchased from Chinese medicines group chemical reagent Beijing
Limit company).With stirring, the temperature of mixture is increased to 110 DEG C, 7g dodecanedioic acid is then added, and temperature is increased
To 110 DEG C, 2h is reacted at such a temperature.Finally, the mixture that reaction obtains is evaporated under reduced pressure, after removing solvent, will receive
The solid matter collected is dried in 60 DEG C of vacuum drying oven to constant weight, and hydrophobically modified cyclodextrin is obtained.Hydrophobically modified ring paste
In essence, the content of modified group is 40 weight %.
Modified cyclodextrin is made using method identical with preparation embodiment 1 and is used to measure with a thickness of 450 μm of film
Contact angle, wherein contact angle is 30 °.
Prepare embodiment 2
To the mixed solvent of 200mL dimethyl sulfoxide and toluene (wherein, the volume ratio of dimethyl sulfoxide and toluene is 1:1)
Middle addition 5g alpha-cyclodextrin (being purchased from Chinese medicines group chemical reagent Beijing Co., Ltd).With stirring, by the temperature liter of mixture
Up to 60 DEG C, lauric acid/dodecanoic acid and 1.2g nonyl phenol of the 0.8g as the first modifying agent is then added, while it is (dense that the 0.3g concentrated sulfuric acid is added
Degree is 98 weight %), 4h is stirred to react at 60 DEG C.Then, it is added octadecane diacid of the 5g as the second modifying agent, and by temperature
110 DEG C are increased to, the reaction was continued at such a temperature 6h.Finally, the mixture that reaction obtains is evaporated under reduced pressure, solvent is removed
Afterwards, the solid matter being collected into is dried in 60 DEG C of vacuum drying oven to constant weight, obtains hydrophobically modified cyclodextrin.This is hydrophobic to change
Property cyclodextrin in, the content of modified group is 35 weight %.
Modified cyclodextrin is made using method identical with preparation embodiment 1 and is used to measure with a thickness of 450 μm of film
Contact angle, wherein (as control, water is by α-ring as shown in Fig. 2, contact angle is 105 ° for photo of the water on the film surface
The contact angle on film that dextrin is formed is 8 °).
Prepare embodiment 3
To mixed solvent (wherein, n,N-Dimethylformamide and the toluene of 100mL n,N-Dimethylformamide and toluene
Volume ratio be 1:1) in addition 15g gamma-cyclodextrin (be purchased from Chinese medicines group chemical reagent Beijing Co., Ltd).Adjoint stirring,
The temperature of mixture is increased to 60 DEG C, ethyoxyl three normal-butyl silane of the 5.5g as the first modifying agent is then added, simultaneously
The 0.1g concentrated sulfuric acid (concentration is 98 weight %) is added, is stirred to react 4h at 60 DEG C.Then, flower of the 4g as the second modifying agent is added
The octacosanol of raw diacid (that is, eicosane diacid) and 1g as the second modifying agent, and 120 DEG C are raised the temperature to, at this
At a temperature of the reaction was continued 12h.Finally, the mixture that reaction obtains is evaporated under reduced pressure, after removing solvent, consolidate what is be collected into
Body substance is dried in 60 DEG C of vacuum drying oven to constant weight, and hydrophobically modified cyclodextrin is obtained.It is modified in the hydrophobically modified cyclodextrin
The content of group is 28 weight %.
Modified cyclodextrin is made using method identical with preparation embodiment 1 and is used to measure with a thickness of 450 μm of film
Contact angle, wherein (as control, water is by γ-ring as shown in figure 3, contact angle is 95 ° for photo of the water on the film surface
The contact angle on film that dextrin is formed is 10 °).
Prepare embodiment 4
Hydrophobically modified cyclodextrin is prepared using method identical with preparation embodiment 1, unlike, the dosage of n-octyl alcohol is
1g, the dosage of dodecanedioic acid are 6g.In the hydrophobically modified cyclodextrin, the content of modified group is 32 weight %.Using with system
Modified cyclodextrin is made the standby identical method of embodiment 1 is used to measure contact angle with a thickness of 450 μm of film, wherein contact
Angle is 90 °.
Prepare embodiment 5
Hydrophobically modified cyclodextrin is prepared using method identical with preparation embodiment 2, unlike, the dosage of lauric acid/dodecanoic acid is
0.4g, the dosage of nonyl phenol are 0.6g, and the dosage of octadecane diacid is 7g.In the hydrophobically modified cyclodextrin, modified group contains
Amount is 33 weight %.Modified cyclodextrin is made using method identical with preparation embodiment 1 and is used for a thickness of 450 μm of film
Measure contact angle, wherein contact angle is 108 °.
Prepare embodiment 6
Hydrophobically modified cyclodextrin is prepared using method identical with preparation embodiment 1, unlike, the dosage of n-octyl alcohol is
1.2g, the dosage of dodecanedioic acid are 3g.In the hydrophobically modified cyclodextrin, the content of modified group is 17 weight %.Using with
Modified cyclodextrin is made the preparation identical method of embodiment 1 is used to measure contact angle with a thickness of 450 μm of film, wherein connects
Feeler is 92 °.
Prepare embodiment 7
Hydrophobically modified cyclodextrin is prepared using method identical with preparation embodiment 1, unlike, the dosage of n-octyl alcohol is
3g, the dosage of dodecanedioic acid are 7.5g.In the hydrophobically modified cyclodextrin, the content of modified group is 40 weight %.Using with
Modified cyclodextrin is made the preparation identical method of embodiment 1 is used to measure contact angle with a thickness of 450 μm of film, wherein connects
Feeler is 155 °.
Prepare embodiment 8
10g beta-cyclodextrin is added into 120mL N,N-dimethylformamide (to be had purchased from Chinese medicines group chemical reagent Beijing
Limit company).With stirring, the temperature of mixture is increased to 80 DEG C, then be added 2g as the first modifying agent n-octyl alcohol with
And dodecanedioic acid of the 5g as the second modifying agent, while 0.4g p-methyl benzenesulfonic acid is added as catalyst, it is stirred at 80 DEG C anti-
Answer 4h.Finally, the mixture that reaction obtains is evaporated under reduced pressure, after removing solvent, by the solid matter being collected at 60 DEG C
Vacuum drying oven in dry to constant weight, obtain hydrophobically modified cyclodextrin.In the hydrophobically modified cyclodextrin, the content of modified group is
28 weight %.
Modified cyclodextrin is made using method identical with preparation embodiment 1 and is used to measure with a thickness of 450 μm of film
Contact angle, wherein contact angle is 85 °.
Embodiment 1-8 is for illustrating the present invention.
The hydrophobically modified cyclodextrin for preparing embodiment 1-8 preparation is dispersed in water respectively in embodiment 1-8, is formed hydrophobic
Modified cyclodextrin content is the dispersion liquid of 2 weight ‰, carries out simulation core flooding experiment for the dispersion liquid as increasing injection agent
(flow velocity of water is as shown in table 1 before injection increasing injection agent) determines flow velocity (the injection decompression increasing of the water after injecting increasing injection agent
Flow velocity is higher after injecting, shows that increasing injection effect is better), as a result listed in table 1.Wherein, 1,4 and 6-8 of embodiment and
The experiment condition of comparative example 1-3 and 6 is identical, and the experiment condition of embodiment 2 and 5 and comparative example 4 is identical, embodiment 3 and comparison
The experiment condition of example 5 is identical.
Comparative example 1-5
Using method identical with embodiment 1-8, modified cyclodextrin prepared by comparative example 1-2, beta-cyclodextrin, α-ring paste
Essence and gamma-cyclodextrin are dispersed in water respectively, form modified cyclodextrin or cyclodextrin content is the dispersion liquid of 2 weight ‰, will
The dispersion liquid carries out simulation core flooding experiment as increasing injection agent, determines the flow velocity of the water after injecting the increasing injection agent,
As a result it is listed in table 1.
Comparative example 6
It, will be using method identical with CN101812289B embodiment 1 preparation using method identical with embodiment 1-8
Nano polysilicon particle is dispersed in water, and the dispersion liquid that nano polysilicon granule content is 2 weight ‰ is formed, using the dispersion liquid as drop
Pressure injection agent carries out simulation core flooding experiment, determines the flow velocity of the water after injecting the increasing injection agent, as a result arranges in table 1
Out.
Table 1
1: hydrophobically modified cyclodextrin can not form dispersion liquid in water
2: hydrophobically modified cyclodextrin can only be partially dispersed in water
From the results shown in Table 1, core is handled using increasing injection agent of the invention, water can be significantly improved
Flow velocity, show increasing injection agent according to the present invention have good increasing injection effect.
Claims (14)
1. a kind of increasing injection agent, which contains hydrophobically modified cyclodextrin and dispersing agent, the hydrophobically modified ring paste
Essence contains modified group, and the modified group contains at least one first modified group and at least one second modified group, institute
The molar ratio for stating the first modified group and second modified group is 0.1-5:1, with the total amount of the hydrophobically modified cyclodextrin
On the basis of, the content of the modified group is 10-45 weight %,
First modified group is hydrophobic grouping, is C8-C16Alkyl, by C6-C12Alkyl-substituted phenyl andOne or more of, R1、R2And R3Respectively C1-C5Alkyl；
Second modified group is the hydrophobic grouping containing hydrophilic functional group, for the C replaced by hydroxyl and/or carboxyl10-C18
One or more of alkyl.
2. increasing injection agent according to claim 1, wherein first modified group is selected from n-octyl, decyl, 12
Alkyl, nonyl phenyl andWherein, R1、R2And R3For butyl.
3. increasing injection agent according to claim 1, wherein the second modified group is-(CH2)10COOH、-(CH2)16COOH and-(CH2)18One or more of COOH.
4. increasing injection agent described in any one of -3 according to claim 1, wherein first modified group and described the
The molar ratio of two modified groups is 0.5-1.5:1.
5. increasing injection agent described in any one of -3 according to claim 1, wherein with the total of the hydrophobically modified cyclodextrin
On the basis of amount, the content of the modified group is 20-35 weight %.
6. increasing injection agent according to claim 1, wherein the hydrophobically modified cyclodextrin is prepared using following methods
: under the conditions of condensation reaction, by cyclodextrin and modifying agent, the modifying agent contains the first modifying agent and second and is modified
Agent, first modifying agent and second modifying agent, which respectively contain, condensation to occur with the hydroxyl in cyclodextrin molecular structure instead
The functional group answered, first modified group are formed by first modifying agent, and second modified group is changed by described second
Property dosage form at,
First modifying agent is R7OH、R8COOH andOne or more of, R7And R8Respectively C8-C16
Alkyl or by C6-C12Alkyl-substituted phenyl；R9、R10And R11Respectively C1-C5Alkyl；R12For hydrogen or C1-C5Alkane
Base,
Second modifying agent is HO-R13-OH、HO-R14-NH2、HOOC-R15-NH2、HOOC-R16- COOH andIn
One or more, R13、R14、R15And R16Respectively C10-C18Alkylidene；R17、R18And R19Respectively by hydroxyl, ammonia
The C that base and/or carboxyl replace1-C5Alkyl,
The molar ratio of first modifying agent and cyclodextrin is 0.5-3:1, and the molar ratio of second modifying agent and cyclodextrin is
1-6:1.
7. increasing injection agent according to claim 6, wherein first modifying agent is n-heptanol, n-octyl alcohol, 12
One or more of acid, three normal-butyl silane of nonyl phenol and ethyoxyl.
8. increasing injection agent according to claim 6, wherein second modifying agent is dodecanedioic acid, octadecane two
One or more of acid, peanut diacid and octacosanol.
9. increasing injection agent according to claim 6, wherein the molar ratio of first modifying agent and cyclodextrin is 1.5-
The molar ratio of 2:1, second modifying agent and cyclodextrin is 1.3-3.5:1.
10. increasing injection agent according to claim 6, wherein it is described contact 50-140 DEG C at a temperature of carry out, it is described
The duration of contact is 2-20 hours.
11. increasing injection agent according to claim 1, wherein described to dredge on the basis of the total amount of the increasing injection agent
The content of water modified cyclodextrin is 2 weight, ‰ -1 weight %.
12. according to claim 1 or increasing injection agent described in 11, wherein on the basis of the total amount of the increasing injection agent, institute
The content for stating dispersing agent is 98-99.8 weight %.
13. increasing injection agent according to claim 1, wherein the dispersing agent is water and C1-C5One of alcohol or
It is two or more.
14. a kind of water injection well increasing injection method, this method includes being injected in claim 1-13 into water injection well arbitrarily
Increasing injection agent described in one.
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