CN105626012A - Pressure-reducing injection-increasing agent and pressure-reducing injection-increasing method for water injection oil well - Google Patents
Pressure-reducing injection-increasing agent and pressure-reducing injection-increasing method for water injection oil well Download PDFInfo
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Abstract
The invention discloses a pressure-reducing injection-increasing agent which contains hydrophobic modified cyclodextrin. The hydrophobic modified cyclodextrin contains modified groups which contain at least one type of first modified group and at least one type of second modified group. The first modified groups are hydrophobic groups and the second modified groups are hydrophobic groups containing hydrophilic functional groups. The invention further discloses a pressure-reducing injection-increasing method for a water injection oil well. The method includes the step that the pressure-reducing injection-increasing agent is injected in the water injection oil wall according to the pressure-reducing injection-increasing agent and the pressure-reducing injection-increasing method. Due to the fact that the pressure-reducing injection-increasing agent contains the hydrophobic modified cyclodextrin, the pressure-reducing injection-increasing effect on the low-permeability reservoir water injection wall is good. The hydrophobic modified cyclodextrin used in the pressure-reducing injection-increasing agent is simple in preparation process and suitable for being produced on a large scale.
Description
Technical field
The present invention relates to a kind of increasing injection agent, the invention still further relates to a kind of water injection well increasing injection method.
Background technology
Waterflooding extraction is the main mining type of low permeability oil field. In recovery process, due to factors such as water sensitivity damage, fouling and solid phase blockings, cause that stratum pilot ability is weak, all there is the problems such as water filling injection pressure height, little, the voidage-injection imbalance of water injection rate in hypotonic oil well, thus causing water injection pressure too high, water injection rate quickly reduces, and oil well output successively decreases rapidly. Acidification is the relatively good water injection well increasing injection processing method of a kind of effect that oil field is commonly used, but acidifying is higher to construction requirement on the one hand, it is easy to causing corrosion, on the other hand, the action period is shorter.
Therefore, the increasing injection method that exploitation is new is needed badly.
CN101812289B discloses a kind of nano polysilicon granule, this granule is with silicon dioxide for core, surface bond contains hydrophobic group and helps organic compound modified dose of adsorptivity group, particle diameter is 5-60nm, containing hydrophobic group and organic compound shared weight ratio respectively 5-35% and the 1-10% in nano polysilicon particles helping adsorptivity group; Described organic compound modified dose is organo-silicon compound and/or organic acid compound, and described organo-silicon compound are the alkoxy silane of carbon chain lengths 1-20, chlorosilane or silazane; Organic acid molecule formula is the carbon chain lengths of RCOOH, R is 2-20; Described hydrophobic group is one or more in methyl, ethyl, vinyl, fluoro-alkyl; The described adsorptivity group that helps is one or more in hydroxyl, carboxyl, epoxy radicals or amido. The increasing injection of low-permeability oilfield is had certain effect by this poly-silicon grain.
Summary of the invention
It is an object of the invention to provide a kind of new increasing injection agent, this increasing injection agent is easily prepared, and has good increasing injection effect.
The present inventor finds in research process, introduces hydrophobic group and the hydrophobically modified cyclodextrin that has the hydrophobic group of hydrophilic functional group and formed has good increasing injection effect in cyclodextrin molecular structure. Complete the present invention on this basis.
According to the first aspect of the invention, the invention provides a kind of increasing injection agent, this increasing injection agent contains hydrophobically modified cyclodextrin, described hydrophobically modified cyclodextrin contains modified group, described modified group contains at least one first modified group and at least one second modified group, described first modified group is hydrophobic group, and described second modified group is the hydrophobic group containing hydrophilic functional group.
According to the second aspect of the invention, the invention provides a kind of water injection well increasing injection method, the method includes the increasing injection agent injected in water injection well according to the present invention.
Increasing injection agent according to the present invention contains hydrophobically modified cyclodextrin, LOW PERMEABILITY RESERVOIR water injection well is had good increasing injection effect, its reason may is that this cyclodextrin outer surface contains hydrophobic group and the hydrophobic group containing hydrophilic radical, not only there is good hydrophobicity, and the adsorptivity of rock is strong, it is thus possible to play good increasing injection effect.
The preparation technology of the hydrophobically modified cyclodextrin used in the increasing injection agent according to the present invention is succinct, is suitable to large-scale production.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below.
Fig. 1 is the photo of the film surface that water is formed at hydrophobically modified cyclodextrin powder prepared by the embodiment of the present invention 1.
Fig. 2 is the photo of the film surface that water is formed at hydrophobically modified cyclodextrin powder prepared by the embodiment of the present invention 2.
Fig. 3 is the photo of the film surface that water is formed at hydrophobically modified cyclodextrin powder prepared by the embodiment of the present invention 3.
Detailed description of the invention
According to the first aspect of the invention, the invention provides a kind of increasing injection agent, this increasing injection agent contains hydrophobically modified cyclodextrin, and described hydrophobically modified cyclodextrin contains modified group.
Described cyclodextrin can be common various cyclodextrin, one or more the combination in alpha-cyclodextrin, beta-schardinger dextrin-and gamma-cyclodextrin.
Described modified group contains at least one first modified group and at least one second modified group.
Described first modified group is hydrophobic group. Described first modified group can be C6-C30Alkyl, the C that is replaced by fluorine atoms6-C30Alkyl andIn one or more, R1��R2And R3It is respectively C1-C10Alkyl or the C that is replaced by fluorine atoms1-C10Alkyl. in described first modified group, described alkyl can be saturated hydrocarbyl (such as alkyl), it is also possible to for unsaturated alkyl (alkyl as containing ethylene linkage), described alkyl can be fat-based, it is also possible to for alcyl, it is also possible to for aromatic radical. in described first modified group, the instantiation of described alkyl can include but not limited to: hexyl (includes the various isomers of hexyl), heptyl (includes the various isomers of heptyl), octyl group (includes the various isomers of octyl group), nonyl (includes the various isomers of nonyl), decyl (includes the various isomers of decyl), undecyl (includes the various isomers of undecyl), dodecyl (includes the various isomers of dodecyl), myristyl (includes the various isomers of myristyl), cetyl (includes the various isomers of cetyl), octadecyl (includes the various isomers of octadecyl), eicosyl (includes the various isomers of eicosyl), tetracosyl (includes the various isomers of tetracosyl) and alkylbenzene is (namely, the phenyl that one or more hydrogen on phenyl ring are replaced by alkyl, described alkyl can be C1-C20Alkyl, it is preferred to C6-C12Alkyl) in one or more. In described first modified group, one or more hydrogen atom that " fluoro " refers in alkyl is replaced by fluorine atoms.
From the angle improving increasing injection effect further, described first modified group is preferably C8-C20Alkyl, the C that is replaced by fluorine atoms8-C20Alkyl andIn one or more, R1��R2And R3It is respectively C1-C5Alkyl or the C that is replaced by fluorine atoms1-C5Alkyl.
It is highly preferred that described first modified group is C8-C16Alkyl, by C6-C12Alkyl replace phenyl andIn one or more, R1��R2And R3It is respectively C1-C5Alkyl.
It is further preferred that described first modified group selected from n-octyl, dodecyl, nonyl phenyl andWherein, R1��R2And R3For butyl.
Described second modified group is the hydrophobic group containing hydrophilic functional group. Described hydrophilic radical can be one or more in hydroxyl, carboxyl and amino. Described amino includes-NH2With-NH-, it is preferred to-NH2��
Described second modified group can be the C replaced by hydroxyl, carboxyl and/or amino6-C30Alkyl andIn one or more, R4��R5And R6It is respectively the C replaced by hydroxyl, amino and/or carboxyl1-C10Alkyl. in described second modified group, described alkyl can be saturated hydrocarbyl (such as alkyl), it is also possible to for unsaturated alkyl (alkyl as containing ethylene linkage), described alkyl can be fat-based, it is also possible to for alcyl, it is also possible to for aromatic radical. the instantiation of the alkyl in described second modified group can include but not limited to: hexyl (includes the various isomers of hexyl), heptyl (includes the various isomers of heptyl), octyl group (includes the various isomers of octyl group), nonyl (includes the various isomers of nonyl), decyl (includes the various isomers of decyl), undecyl (includes the various isomers of undecyl), dodecyl (includes the various isomers of dodecyl), myristyl (includes the various isomers of myristyl), cetyl (includes the various isomers of cetyl), octadecyl (includes the various isomers of octadecyl), eicosyl (includes the various isomers of eicosyl) and one or more in tetracosyl (including the various isomers of tetracosyl).
From the angle improving increasing injection effect further, described second modified group is preferably the C replaced by hydroxyl, carboxyl and/or amino8-C20Alkyl (such as alkyl) andIn one or more, R4��R5And R6It is respectively the C replaced by hydroxyl, amino and/or carboxyl1-C5Alkyl.
It is highly preferred that described second modified group is the C replaced by hydroxyl and/or carboxyl10-C18Alkyl in one or more.
It is further preferred that described second modified group is-(CH2)10COOH��-(CH2)16COOH and-(CH2)18One or more in COOH.
Described modified group and described cyclodextrin pass through chemical bonds. Specifically, described modified group can by the hydrogen atom on hydroxyl at least part of in substituted cyclodextrin molecular structure or hydroxyl with cyclodextrin with chemical bonds. As the case may be, described modified group can by the hydrogen atom on the hydroxyl in direct substitution cyclodextrin molecular structure with cyclodextrin with chemical bonding; Can also by connection base with cyclodextrin with chemical bonding, one end of described connection base by the hydrogen atom on the hydroxyl in substituted cyclodextrin molecular structure with cyclodextrin with chemical bonds, the other end and described modified group are with chemical bonds, described connection base can be such as carbonyl (namely)��
Increasing injection agent according to the present invention, with the total amount of described hydrophobically modified cyclodextrin for benchmark, the content of described modified group can be 10-45 weight %, it is preferred to 15-40 weight %. From the angle improving increasing injection effect further, with the total amount of described hydrophobically modified cyclodextrin for benchmark, the content of described modified group is preferably 20-35 weight %. The content of described modified group can be determined by weight method.
Increasing injection agent according to the present invention, described first modified group and described second modified group synergism so that there is good increasing injection effect according to the increasing injection agent of the present invention. From the angle improving increasing injection effect further, the mol ratio of described first modified group and described second modified group can be 0.1-5:1, more preferably 0.2-2.5:1, more preferably 0.5-1.5:1. Mol ratio between described first modified group and described second modified group can be measured by nuclear magnetic resonance spectroscopy, it is also possible to by when preparing this hydrophobically modified cyclodextrin for forming the compound of the first modified group and the consumption for forming the compound of the second modified group is determined.
Increasing injection agent according to the present invention, described hydrophobically modified cyclodextrin can by replacing part of hydroxyl in cyclodextrin molecular structure or the hydrogen atom in the part of hydroxyl group containing the first modified group and the group containing the second modified group and obtain. In one embodiment of the invention, described hydrophobically modified cyclodextrin adopts following methods to prepare: when condensation reaction, by cyclodextrin and modifying agent, described modifying agent contains the first modifying agent and the second modifying agent, described first modifying agent and described second modifying agent each contain can with the functional group of the hydroxyl generation condensation reaction in cyclodextrin molecular structure, described first modified group is formed by described first modifying agent, and described second modified group is formed by described second modifying agent.
According to this embodiment, the concrete structure of described first modifying agent can select according to the kind of the first modified group. Specifically, described first modifying agent is R7OH��R8COOH andIn one or more, R7And R8It is respectively C6-C30Alkyl or the C that is replaced by fluorine atoms6-C30Alkyl, it is preferred to C8-C20Alkyl or the C that is replaced by fluorine atoms8-C20Alkyl, more preferably C8-C16Alkyl or by C6-C12Alkyl replace phenyl; R9��R10And R11It is respectively C1-C10Alkyl or the C that is replaced by fluorine atoms1-C10Alkyl, it is preferred to C1-C5Alkyl or the C that is replaced by fluorine atoms1-C5Alkyl, more preferably C1-C5Alkyl; R12For hydrogen or C1-C5Alkyl. Specifically, described first modifying agent is one or more in n-heptanol, n-octyl alcohol, lauric acid/dodecanoic acid, nonyl phenol and ethyoxyl three normal-butyl silane.
According to this embodiment, the concrete structure of described second modifying agent can select according to the kind of the second modified group. Specifically, described second modifying agent is HO-R13-OH��HO-R14-NH2�� HOOC-R15-NH2��HOOC-R16-COOH andIn one or more, R13��R14��R15And R16It is respectively C6-C30Alkylene (be preferably alkylidene), it is preferred to C8-C20Alkylene (be preferably alkylidene), more preferably C10-C18Alkylidene; R17��R18And R19It is respectively the C replaced by hydroxyl, amino and/or carboxyl1-C10Alkyl (be preferably alkyl), it is preferred to the C replaced by hydroxyl, amino and/or carboxyl1-C5Alkyl (be preferably alkyl); R20For hydrogen or C1-C5Alkyl. Specifically, described second modifying agent is one or more in dodecanedioic acid, octadecane diacid, Semen arachidis hypogaeae diacid and octacosanol.
According to this embodiment, the consumption of described first modifying agent and the second modifying agent can be determined according to the expection content of modified group in the hydrophobically modified cyclodextrin of final preparation. Usually, the consumption of described first modifying agent and the second modifying agent makes in the hydrophobically modified cyclodextrin of final preparation, and the content of modified group is 10-45 weight %, it is preferred to 15-40 weight %, more preferably 20-35 weight %. Specifically, described first modifying agent can be 0.5-3:1 with the mol ratio of cyclodextrin, it is preferred to 1.2-2.5:1, more preferably 1.5-2:1; The mol ratio of described second modifying agent and cyclodextrin can be 1-6:1, it is preferred to 1.2-5:1, more preferably 1.3-3.5:1. The mol ratio of the first modifying agent and the second modifying agent can be 0.1-5:1, it is preferred to 0.2-2.5:1. From the angle improving increasing injection effect further, the mol ratio of the first modifying agent and the second modifying agent is more preferably 0.5-1.5:1.
According to this embodiment, the contact of cyclodextrin and the first modifying agent and the second modifying agent carries out at least one solvent, and described solvent for can dissolve cyclodextrin, can dissolve again the liquid substance of the first modifying agent and the second modifying agent, it is possible to for C6-C12Aromatic hydrocarbon, sulfone kind solvent and amide solvent. The instantiation of described solvent can include but not limited to: one or more in benzene, toluene, dimethyl sulfoxide and N,N-dimethylformamide. The consumption of described solvent can be conventional selection. Usually, the consumption of described solvent makes the concentration of cyclodextrin be 1-25 weight %.
According to this embodiment, the contact of cyclodextrin and the first modifying agent and the second modifying agent carries out when condensation reaction, such first modifying agent and the second modifying agent can respectively with the hydroxyl generation condensation reaction in cyclodextrin molecular structure, thus introducing the first modified group and the second modified group in cyclodextrin molecular structure. The condition of described contact is to be able to ensure that the first modifying agent and the second modifying agent can be as the criterion with cyclodextrin generation condensation reaction. Preferably, described contact carries out at the temperature of 50-140 DEG C. The persistent period of described contact can select according to the temperature carrying out contacting. Usually, the persistent period of described contact can be 2-20 hour.
According to this embodiment, it is possible to the first modifying agent and the second modifying agent are contacted with cyclodextrin simultaneously; Can also first make the first modifying agent contact with cyclodextrin, then will contact the mixture and the second modifying agent that obtain. Preferably, first make the first modifying agent contact with cyclodextrin, then will contact the mixture and the second modifying agent that obtain. Described first modifying agent and cyclodextrin contact at the temperature preferably in 60-80 DEG C, and the time of contact can be 2-6 hour; First modifying agent contacts the mixture obtained with cyclodextrin and the second modifying agent contacts preferably at the temperature of 100-140 DEG C, and the time of contact can be 2-14 hour.
Contact according to this embodiment, cyclodextrin and the first modifying agent and the second modifying agent carries out preferably under the existence of at least one catalyst, so can improve reaction rate further and make haptoreaction carry out more gentle when. Described catalyst can be the material that can promote hydroxyls dehydrate condensation reaction, for instance acid. Specifically, described catalyst can be p-methyl benzenesulfonic acid and/or concentrated sulphuric acid. The consumption of described catalyst is as the criterion to be capable of catalysis, it does not have be particularly limited to. Usually, relative to 100 parts by weight of cyclodextrin, the consumption of described catalyst can be 0.5-10 weight portion.
According to this embodiment, it is possible to by removing the solvent in the mixture that contact obtains, collecting the solid obtained is described hydrophobically modified cyclodextrin. Conventional method elimination can be adopted to contact the solvent in the mixture obtained, for instance the solvent in the mixture that elimination contact obtains at reduced pressure conditions.
Increasing injection compositions according to the present invention, the contact angle of water is more than 85 �� by the thin film that described hydrophobically modified cyclodextrin is formed, and is typically in the scope of 85 ��-160 ��, it is preferable that in the scope of 90 ��-120 ��.
Increasing injection compositions according to the present invention, with the total amount of said composition for benchmark, the content of described hydrophobically modified cyclodextrin can be 2 weight ��-1 weight %.
Increasing injection compositions according to the present invention, except containing described hydrophobically modified cyclodextrin, it is also possible to containing dispersant, described hydrophobically modified cyclodextrin is scattered in described dispersant. Described dispersant can be various can by finely dispersed for hydrophobically modified cyclodextrin liquid substance. Specifically, described dispersant can be that water and/or alcohol are (such as C1-C5Alcohol), it is preferred to one or more in water, methanol and ethanol. The consumption of described dispersant can be conventional selection. Usually, with the total amount of increasing injection agent for benchmark, the content of described dispersant can be 98-99.8 weight %.
According to the second aspect of the invention, the invention provides a kind of water injection well increasing injection method, the method includes the increasing injection agent injected in water injection well according to the present invention. Described increasing injection agent and composition thereof have been carried out detailed description above, no longer describe in detail herein.
The method according to the invention, the consumption of described increasing injection agent can select according to the actual conditions of water injection well, it does not have is particularly limited to.
Describe the present invention in detail below in conjunction with embodiment, but and be not so limited the scope of the present invention.
In following example and comparative example, adopt the contact angle instrument water contact angle that model is DSA100 purchased from KRUSS instrument company of Germany.
In following example and comparative example, the condition of simulation core flooding experiment includes: adopting fill out sand tube core (long 60cm, interior diameter 10cm), permeability is about 2.5 darcies.
In following example and comparative example, weight method is adopted to determine the content of modified group in the hydrophobically modified cyclodextrin of preparation, wherein, the content of modified group=[quality of the hydrophobically modified cyclodextrin of (quality of the hydrophobically modified cyclodextrin obtained-as the quality of cyclodextrin of raw material)/obtain] �� 100%.
Preparation embodiment 1-8 is for preparing the hydrophobically modified cyclodextrin in the increasing injection agent according to the present invention.
Preparation embodiment 1
To 120mLN, dinethylformamide adds 10g beta-schardinger dextrin-(purchased from traditional Chinese medicines group chemical reagent Beijing company limited). With stirring, the temperature of mixture is increased to 80 DEG C, is subsequently adding the 2g n-octyl alcohol as the first modifying agent, be simultaneously introduced 0.4g p-methyl benzenesulfonic acid as catalyst, at 80 DEG C of stirring reaction 2h. Then, add the 5g dodecanedioic acid as the second modifying agent, and temperature is increased to 110 DEG C, continue reaction 2h at such a temperature. Finally, the mixture being obtained by reacting is carried out decompression distillation, after removing solvent, the solid matter collected is dried to constant weight in the vacuum drying oven of 60 DEG C, obtains hydrophobically modified cyclodextrin. In this hydrophobically modified cyclodextrin, the content of modified group is 30 weight %.
Adopt tabletting method that hydrophobically modified cyclodextrin is made the thin film that thickness is 450 ��m to be used for measuring contact angle, wherein, water photo on this film surface is as it is shown in figure 1, contact angle is 120 �� (as comparisons, water contact angle on the thin film formed by beta-schardinger dextrin-is 5 ��).
Preparation comparative example 1
To 120mLN, dinethylformamide adds 10g beta-schardinger dextrin-(purchased from traditional Chinese medicines group chemical reagent Beijing company limited). With stirring, the temperature of mixture is increased to 80 DEG C, is subsequently adding 7g n-octyl alcohol and 0.4g p-methyl benzenesulfonic acid, at 80 DEG C of stirring reaction 2h. The mixture being obtained by reacting is carried out decompression distillation, after removing solvent, the solid matter collected is dried to constant weight in the vacuum drying oven of 60 DEG C, obtains modified cyclodextrin. In this modified cyclodextrin, the content of modified group is 25 weight %.
Adopting the method identical with preparation embodiment 1 that modified cyclodextrin is made the thin film that thickness is 450 ��m to be used for measuring contact angle, wherein, contact angle is 150 ��.
Preparation comparative example 2
To 120mLN, dinethylformamide adds 10g beta-schardinger dextrin-(purchased from traditional Chinese medicines group chemical reagent Beijing company limited). With stirring, the temperature of mixture is increased to 110 DEG C, is subsequently adding 7g dodecanedioic acid, and temperature is increased to 110 DEG C, react 2h at such a temperature. Finally, the mixture being obtained by reacting is carried out decompression distillation, after removing solvent, the solid matter collected is dried to constant weight in the vacuum drying oven of 60 DEG C, obtains hydrophobically modified cyclodextrin. In this hydrophobically modified cyclodextrin, the content of modified group is 40 weight %.
Adopting the method identical with preparation embodiment 1 that modified cyclodextrin is made the thin film that thickness is 450 ��m to be used for measuring contact angle, wherein, contact angle is 30 ��.
Preparation embodiment 2
5g alpha-cyclodextrin (purchased from traditional Chinese medicines group chemical reagent Beijing company limited) is added in the mixed solvent (wherein, dimethyl sulfoxide is 1:1 with the volume ratio of toluene) of 200mL dimethyl sulfoxide and toluene. With stirring, the temperature of mixture is increased to 60 DEG C, is subsequently adding 0.8g as the lauric acid/dodecanoic acid of the first modifying agent and 1.2g nonyl phenol, is simultaneously introduced 0.3g concentrated sulphuric acid (concentration is 98 weight %), at 60 DEG C of stirring reaction 4h. Then, add the 5g octadecane diacid as the second modifying agent, and temperature is increased to 110 DEG C, continue reaction 6h at such a temperature. Finally, the mixture being obtained by reacting is carried out decompression distillation, after removing solvent, the solid matter collected is dried to constant weight in the vacuum drying oven of 60 DEG C, obtains hydrophobically modified cyclodextrin. In this hydrophobically modified cyclodextrin, the content of modified group is 35 weight %.
Adopt the method identical with preparation embodiment 1 that modified cyclodextrin is made the thin film that thickness is 450 ��m to be used for measuring contact angle, wherein, water photo on this film surface is as shown in Figure 2, contact angle is 105 �� (as comparisons, water contact angle on the thin film formed by alpha-cyclodextrin is 8 ��).
Preparation embodiment 3
15g gamma-cyclodextrin (purchased from traditional Chinese medicines group chemical reagent Beijing company limited) is added in the mixed solvent (wherein, DMF is 1:1 with the volume ratio of toluene) of 100mLN, dinethylformamide and toluene. With stirring, the temperature of mixture is increased to 60 DEG C, is subsequently adding the 5.5g ethyoxyl three normal-butyl silane as the first modifying agent, be simultaneously introduced 0.1g concentrated sulphuric acid (concentration is 98 weight %), at 60 DEG C of stirring reaction 4h. Then, add 4g as octacosanol as the second modifying agent of the Semen arachidis hypogaeae diacid (that is, eicosane diacid) of the second modifying agent and 1g, and temperature is increased to 120 DEG C, continue at such a temperature to react 12h. Finally, the mixture being obtained by reacting is carried out decompression distillation, after removing solvent, the solid matter collected is dried to constant weight in the vacuum drying oven of 60 DEG C, obtains hydrophobically modified cyclodextrin. In this hydrophobically modified cyclodextrin, the content of modified group is 28 weight %.
Adopt the method identical with preparation embodiment 1 that modified cyclodextrin is made the thin film that thickness is 450 ��m to be used for measuring contact angle, wherein, water photo on this film surface is as shown in Figure 3, contact angle is 95 �� (as comparisons, water contact angle on the thin film formed by gamma-cyclodextrin is 10 ��).
Preparation embodiment 4
The method identical with preparation embodiment 1 is adopted to prepare hydrophobically modified cyclodextrin, the difference is that, the consumption of n-octyl alcohol is 1g, and the consumption of dodecanedioic acid is 6g. In this hydrophobically modified cyclodextrin, the content of modified group is 32 weight %. Adopting the method identical with preparation embodiment 1 that modified cyclodextrin is made the thin film that thickness is 450 ��m to be used for measuring contact angle, wherein, contact angle is 90 ��.
Preparation embodiment 5
The method identical with preparation embodiment 2 is adopted to prepare hydrophobically modified cyclodextrin, the difference is that, the consumption of lauric acid/dodecanoic acid is 0.4g, and the consumption of nonyl phenol is 0.6g, and the consumption of octadecane diacid is 7g. In this hydrophobically modified cyclodextrin, the content of modified group is 33 weight %. Adopting the method identical with preparation embodiment 1 that modified cyclodextrin is made the thin film that thickness is 450 ��m to be used for measuring contact angle, wherein, contact angle is 108 ��.
Preparation embodiment 6
The method identical with preparation embodiment 1 is adopted to prepare hydrophobically modified cyclodextrin, the difference is that, the consumption of n-octyl alcohol is 1.2g, and the consumption of dodecanedioic acid is 3g. In this hydrophobically modified cyclodextrin, the content of modified group is 17 weight %. Adopting the method identical with preparation embodiment 1 that modified cyclodextrin is made the thin film that thickness is 450 ��m to be used for measuring contact angle, wherein, contact angle is 92 ��.
Preparation embodiment 7
The method identical with preparation embodiment 1 is adopted to prepare hydrophobically modified cyclodextrin, the difference is that, the consumption of n-octyl alcohol is 3g, and the consumption of dodecanedioic acid is 7.5g. In this hydrophobically modified cyclodextrin, the content of modified group is 40 weight %. Adopting the method identical with preparation embodiment 1 that modified cyclodextrin is made the thin film that thickness is 450 ��m to be used for measuring contact angle, wherein, contact angle is 155 ��.
Preparation embodiment 8
To 120mLN, dinethylformamide adds 10g beta-schardinger dextrin-(purchased from traditional Chinese medicines group chemical reagent Beijing company limited). With stirring, the temperature of mixture is increased to 80 DEG C, is subsequently adding 2g as the n-octyl alcohol of the first modifying agent and 5g as the dodecanedioic acid of the second modifying agent, is simultaneously introduced 0.4g p-methyl benzenesulfonic acid as catalyst, at 80 DEG C of stirring reaction 4h. Finally, the mixture being obtained by reacting is carried out decompression distillation, after removing solvent, the solid matter collected is dried to constant weight in the vacuum drying oven of 60 DEG C, obtains hydrophobically modified cyclodextrin. In this hydrophobically modified cyclodextrin, the content of modified group is 28 weight %.
Adopting the method identical with preparation embodiment 1 that modified cyclodextrin is made the thin film that thickness is 450 ��m to be used for measuring contact angle, wherein, contact angle is 85 ��.
Embodiment 1-8 is used for the present invention is described.
Hydrophobically modified cyclodextrin prepared by preparation embodiment 1-8 is dispersed in water by embodiment 1-8 respectively, form the dispersion liquid that hydrophobically modified cyclodextrin content is 2 weight ��, this dispersion liquid is simulated core flooding experiment (before injection increasing injection agent, the flow velocity of water is as shown in table 1) as increasing injection agent, determine that (after injecting increasing injection agent, flow velocity is more high at the flow velocity injecting water after increasing injection agent, show that increasing injection effect is more good), result is listed in Table 1. Wherein, embodiment 1,4 is identical with the experiment condition of 6-8 and comparative example 1-3 and 6, and embodiment 2 is identical with the experiment condition of 5 and comparative example 4, and embodiment 3 is identical with the experiment condition of comparative example 5.
Comparative example 1-5
Adopt the method identical with embodiment 1-8, modified cyclodextrin, beta-schardinger dextrin-, alpha-cyclodextrin and the gamma-cyclodextrin prepared by comparative example 1-2 are dispersed in water respectively, formation modified cyclodextrin or the dispersion liquid that cyclodextrin content is 2 weight ��, this dispersion liquid is simulated core flooding experiment as increasing injection agent, determining the flow velocity of water after injecting this increasing injection agent, result is listed in Table 1.
Comparative example 6
Adopt the method identical with embodiment 1-8, the nano polysilicon Granular composite method adopted and CN101812289B embodiment 1 is identical prepared is in water, form the dispersion liquid that nano polysilicon granule content is 2 weight ��, this dispersion liquid is simulated core flooding experiment as increasing injection agent, determining the flow velocity of water after injecting this increasing injection agent, result is listed in Table 1.
Table 1
1: hydrophobically modified cyclodextrin cannot form dispersion liquid in water
2: hydrophobically modified cyclodextrin can only be partially dispersed in water
From the results shown in Table 1, adopt the increasing injection agent of the present invention that core is processed, the flow velocity of water can be significantly improved, it was shown that according to the increasing injection agent of the present invention, there is good increasing injection effect.
Claims (14)
1. an increasing injection agent, this increasing injection agent contains hydrophobically modified cyclodextrin, described hydrophobically modified cyclodextrin contains modified group, described modified group contains at least one first modified group and at least one second modified group, described first modified group is hydrophobic group, and described second modified group is the hydrophobic group containing hydrophilic functional group.
2. increasing injection agent according to claim 1, wherein, described first modified group is C6-C30Alkyl, the C that is replaced by fluorine atoms6-C30Alkyl andIn one or more, R1��R2And R3It is respectively C1-C10Alkyl or the C that is replaced by fluorine atoms1-C10Alkyl;
Preferably, described first modified group is C8-C20Alkyl, the C that is replaced by fluorine atoms8-C20Alkyl andIn one or more, R1��R2And R3It is respectively C1-C5Alkyl or the C that is replaced by fluorine atoms1-C5Alkyl;
It is highly preferred that described first modified group is C8-C16Alkyl, by C6-C12Alkyl replace phenyl andIn one or more, R1��R2And R3It is respectively C1-C5Alkyl.
3. increasing injection agent according to claim 1, wherein, described second modified group is the C replaced by hydroxyl, carboxyl and/or amino6-C30Alkyl andIn one or more, R4��R5And R6It is respectively the C replaced by hydroxyl, amino and/or carboxyl1-C10Alkyl;
Preferably, the second modified group is the C replaced by hydroxyl, carboxyl and/or amino8-C20Alkyl andIn one or more, R4��R5And R6It is respectively the C replaced by hydroxyl, amino and/or carboxyl1-C5Alkyl;
It is highly preferred that described second modified group is the C replaced by hydroxyl and/or carboxyl10-C18Alkyl in one or more.
4. the increasing injection agent according to any one in claim 1-3, wherein, the mol ratio of described first modified group and described second modified group is 0.1-5:1.
5. the increasing injection agent according to any one in claim 1-3, wherein, with the total amount of described hydrophobically modified cyclodextrin for benchmark, the content of described modified group is 10-45 weight %.
6. the increasing injection agent according to any one in claim 1-3, wherein, described hydrophobically modified cyclodextrin adopts following methods to prepare: when condensation reaction, by cyclodextrin and modifying agent, described modifying agent contains the first modifying agent and the second modifying agent, described first modifying agent and described second modifying agent each contain can with the functional group of the hydroxyl generation condensation reaction in cyclodextrin molecular structure, described first modified group is formed by described first modifying agent, and described second modified group is formed by described second modifying agent.
7. increasing injection agent according to claim 6, wherein, described first modifying agent is R7OH��R8COOH andIn one or more, R7And R8It is respectively C6-C30Alkyl or the C that is replaced by fluorine atoms6-C30Alkyl, it is preferred to C8-C20Alkyl or the C that is replaced by fluorine atoms8-C20Alkyl, more preferably C8-C16Alkyl or by C6-C12Alkyl replace phenyl; R9��R10And R11It is respectively C1-C10Alkyl or the C that is replaced by fluorine atoms1-C10Alkyl, it is preferred to C1-C5Alkyl or the C that is replaced by fluorine atoms1-C5Alkyl, more preferably C1-C5Alkyl; R12For hydrogen or C1-C5Alkyl.
8. increasing injection agent according to claim 6, wherein, described second modifying agent is HO-R13-OH��HO-R14-NH2��HOOC-R15-NH2��HOOC-R16-COOH andIn one or more, R13��R14��R15And R16It is respectively C6-C30Alkylene, it is preferred to C8-C20Alkylene, more preferably C10-C18Alkylidene; R17��R18And R19It is respectively the C replaced by hydroxyl, amino and/or carboxyl1-C10Alkyl, it is preferred to by hydroxyl, amino and/or carboxyl replace C1-C5Alkyl; R20For hydrogen or C1-C5Alkyl.
9. increasing injection agent according to claim 6, wherein, the mol ratio of described first modifying agent and cyclodextrin is 0.5-3:1, and the mol ratio of described second modifying agent and cyclodextrin is 1-6:1.
10. increasing injection agent according to claim 6, wherein, described contact carries out at the temperature of 50-140 DEG C, and the persistent period of described contact is 2-20 hour.
11. increasing injection agent according to claim 1, wherein, with the total amount of described increasing injection agent for benchmark, the content of described hydrophobically modified cyclodextrin is 2 weight ��-1 weight %.
12. the increasing injection agent according to claim 1 or 11, wherein, described increasing injection agent is possibly together with dispersant, and with the total amount of described increasing injection agent for benchmark, the content of described dispersant is 98-99.8 weight %.
13. increasing injection agent according to claim 12, wherein, described dispersant is water and C1-C5Alcohol in one or more.
14. a water injection well increasing injection method, the method includes injecting the increasing injection agent in claim 1-13 described in any one in water injection well.
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