CN104109518B - Displacement composition for low-permeability oil deposit and preparation method thereof - Google Patents
Displacement composition for low-permeability oil deposit and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of displacement composition for low-permeability oil deposit and preparation method thereof, mainly solves the polymer in existing combination flooding and is used to easily cause formation blockage in low-permeability oil deposit oil displacement process, injects the problem of difficult.The present invention is by using a kind of Long carbon chain beet alkali surface activator and mineral salt compositions, wherein any one of Long carbon chain beet alkali surface activator in long-chain carboxylic acid's glycine betaine, sulphonic acid betaine, carbochain C14~C40Alkyl or alkenyl, inorganic salts CaCl2、MgCl2, NaCl, NaHCO3In any one or composition, the mass ratio of long-chain beet alkali surface activator and inorganic salts is 1:（1~100）Technical scheme while profit ultralow interfacial tension is formed, there is increasing injection, the advantages of system is simple, preferably solve the problem, available in low-permeability oil deposit enhanced oil recovery process.
Description
Technical field
The present invention relates to a kind of displacement composition for low-permeability oil deposit and preparation method thereof.
Background technology
China land major part main force oil field enters the tail period stage, and water content and oil field produced degree are increasingly
Height, under these circumstances, employ and to have developed low-permeability oil deposit extremely urgent.Because low-permeability oil deposit is in the prevalence of pore throat
The characteristics of tiny, non-darcy flow and high startup pressure, surface molecular power and capillary force action are strong, only exist larger
Liquid could flow during displacement pressure.Therefore, increasing injection is to improve the vital factor of these oil recoveries.
The flooding method applied in current oil extraction can be divided into four major classes:First, heating power drives, including steam drives, burnt
Oil reservoir etc.；Second, mixed phase drives, including CO2Mixed phase, hydrocarbon mixed phase and other inert gas mixed phases drive；Third, chemical flooding；Fourth, micro- life
Thing is recovered the oil, including biopolymer, MICROBIAL SURFACTANT are driven.Wherein, chemical flooding is extremely important and big in intensified oil reduction
Technology that scale is implemented, including polymer flooding, surfactant flooding, caustic waterflooding etc. and polymer, alkali, surfactant
Multiple combinations technology.
The effect of chemical flooding is the result of physical action and chemical action, and what physical action referred to displacing fluid involves effect,
And chemical action refers to the microcosmic oil drive effect of displacing fluid.The core of chemical action is to reduce the interface of displacing fluid and crude oil
Power.Surfactant is due to having oleophylic concurrently（It is hydrophobic）With it is hydrophilic（Oleophobic）Property, when surfactant is dissolved in water, molecule is main
It is distributed on oil-water interfaces, oil water interfacial tension can be significantly reduced.The reduction of oil water interfacial tension means surfactant
System can overcome the cohesive force between crude oil, and larger oil droplet is dispersed into small oil droplet, so as to improve passing through when crude oil flows through pore throat
Rate.Physical action realizes that the polymer of HMW can improve the viscosity of injection liquid by polymer, improves profit
The mobility ratio of phase, and then improve sweep efficiency.Chemical combined flooding can give full play to the synergy of various chemical reagent, significantly
Degree improves oil displacement efficiency.But chemical combined flooding oil displacement system be present, the polymer in chemical flooding due to molecule compared with
Greatly, it is easy to block duct, cause injection difficult, it is difficult to be applied successfully in low-permeability oil deposit.Therefore, development of low-permeability oil reservoir
It is a great problem, the average recovery ratio that Sinopec has developed low-permeability oil deposit unit is 22.2%, than foreign same type oil reservoir
Average recovery ratio low 4.1%.
At present, development of low-permeability oil reservoir situation generally use several method is improved：First, physical mechanical method, i.e. Encryption Well
Net, and/or bulk fracture treatment and pit shaft lift technique etc.；Second, gas drive, by realizing mixed phase or non-mixed phase in stratum
Mother oil displacement come out, strata pressure, with the presence or absence of conditions such as cracks bring very big influence to tar productivity；Third, chemical displacement system
The middle polymer for adding low molecule amount, molecular weight are usual<5000000.Such as in document《Oilfield chemistry》Mentioned in 2008, vol25
A kind of sulfobetaines with aromatic ring can form ultralow interfacial tension, the polyacrylamide with low molecule amount with crude oil
（4800000）Compounding, using artificial core, rock core mean permeability is 29 ~ 46mD, surfactant 1000mg/L, polymer
During 400mg/L, recovery ratio 10% is improved, surfactant 1000mg/L, is arrived though recovery ratio can be improved during polymer 800mg/L
16%, but inject difficult.
Recently, viscoelastic surfactant because its molecular weight it is small, viscosity is very low under high shear, under low sheraing viscosity rise,
The easy row of returning, the features such as will not being damaged to stratum, gradually causes the concern of oilfielder.Such as patent CN101182411A
A kind of displacement composition for the vermiculate glues that anion surfactant is formed is mentioned, with the electrolyte containing sodium ion in alkalescence
Under the conditions of induction enuatrol be made, recovery ratio can be improved to a certain extent.There is no polymer in said composition, can apply
In low permeability pay oil displacement process, document《China University Of Petroleum Beijing's journal》2009, vol33 use oleic acid glycine betaine in 2%HCl
Highly viscous fluid, etc. can be formed in the aqueous solution.But contain inorganic base or acid in above-mentioned composition, injured to chronostratigraphic zone,
And the viscoelastic composition of report is only focused in its aggregate structure in aqueous, it is impossible to while formed with crude oil super
Low interfacial tension.
Therefore, the present invention provides a kind of displacement of reservoir oil combination of the alkali-free of Long carbon chain beet alkali surface activator and inorganic salts composition
Thing, body phase is set to possess high viscosity by the self assembly of control surface activating agent, while surfactant has high boundary in itself
Face activity, so as to improve the recovery ratio of low-permeability oil deposit.
The content of the invention
One of technical problems to be solved by the invention are that the polymer in existing chemical combined flooding is used for low-permeability oil deposit
Formation blockage is easily caused in oil displacement process, injects the problem of difficult, there is provided for the displacement composition of low-permeability oil deposit, the drive
The advantages of fluid composition has increasing injection while profit ultralow interfacial tension is formed, and system is simple.
The two of the technical problems to be solved by the invention are to provide a kind of with solving one of the technical problem corresponding displacement of reservoir oil
The preparation method of composition.
The three of the technical problems to be solved by the invention are to provide a kind of displacement of reservoir oil corresponding with one of above-mentioned technical problem
Method.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：The displacement of reservoir oil for low-permeability oil deposit
Composition, including Long carbon chain beet alkali surface activator, inorganic salts, described Long carbon chain beet alkali surface activator are selected from long-chain
Any one in carboxylic acid betaine salt, sulphonate betaine, inorganic salts are selected from CaCl2、MgCl2、NaCl、NaHCO3In extremely
Few one kind；
Long-chain carboxylic acid's betaine salt general molecular formula is：
Long-chain sulfonate betaine salt general molecular formula is：
The R is C14~C40Alkyl, any one in alkenyl, the R ' is C1~C5Alkylidene, R ' ' is C1~C5
Alkylidene, any one in hydroxyl substituted alkylene, the matter of the long-chain beet alkali surface activator and the inorganic salts
Amount is than being 1:(1~100).
R described in above-mentioned technical proposal is preferably C16~C30Between alkyl or alkenyl.Live on the long-chain glycine betaine surface
Property agent and the inorganic salts mass ratio be preferably 1:(2~50).
The present composition can be supplied in solid form, can be supplied with paste or solution form.When with solid or
When cream form is supplied, those skilled in the art will know that being used for the displacement of reservoir oil after being dissolved with water.
In order to which field application is convenient, the present composition preferably includes water.Now in more preferably described displacement composition with
The ratio between displacement composition and water described in weight meter are (0.55 ~ 16):100.
For the two of above-mentioned technical problem, technical scheme is as follows：The displacement of reservoir oil group for low-permeability oil deposit
The preparation method of compound, comprises the following steps：
a）Aliphatic acid or its ester and required amidation reagent are added into reactor, reacted 8 ~ 20 hours in 140 ~ 170 DEG C；
Sulfonated reagent or carboxylating reagent are then added, continues reaction 3 ~ 10 hours in 75 ~ 95 DEG C, obtains alkyl betaine；According to starting
Raw material meter, aliphatic acid or its ester：Amidation reagent：The mol ratio of sulfonated reagent or carboxylating reagent is 1:（1~3）:（1~3）；
B) the obtained beet alkali surface activator of inorganic salts and step a is dissolved in the water well mixed, obtained required
Composition.
Amidation reagent general molecular formula described in above-mentioned technical proposal is preferably, wherein R ' is C1~
C5Alkylidene, described sulfonated reagent general molecular formula is preferably, described carboxylating reagent general molecular formula is excellent
Elect as, R ' ' is preferably C1~C5Alkylidene, any one in hydroxyl substituted alkylene.
In order to solve the above-mentioned technical problem three, technical scheme is as follows：A kind of displacement of reservoir oil side of low-permeability oil deposit
Method, including the displacement composition injection low-permeability oil deposit of the solution form is subjected to the displacement of reservoir oil.
The permeability of low-permeability oil deposit described in above-mentioned technical proposal is preferably 1 ~ 40mD, more preferably 2 ~ 30mD.
The polymer of macromolecular is not contained in the displacement composition of the present invention, is formed by surfactant and inorganic salts
Small molecule aggregation carrys out the viscosity of regulation composition, and the purpose of increasing injection, Er Qiebiao are reached while sweep efficiency is improved
Face activating agent can reduce oil, water interfacial tension simultaneously, so as to effectively overcome the cohesive force between crude oil, be advantageous to the stream of crude oil
Go out, and then greatly improve oil displacement efficiency.
Using the displacement composition of the present invention in low-permeability oil deposit enhanced oil recovery process, have interfacial activity high：Live on surface
Property agent composition dosage be 0.01 ~ 0.5% under the conditions of can form 10 with Henan underground crude oil-3~10-4MN/m ultralow interface
Tension force；Permeability is used to fill out sand tube model for 30 millidarcies, injection pressure only has the 80% of water injection pressure, on the basis of water drive
On can continue improve recovery ratio 12%.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
By 9- octadecenoic acids and N, N- dimethyl -1,4- butanediamine according to mol ratio 1:In 1.5 input reactors, in
8h is stirred at 165 DEG C, rear 165 DEG C of oil pumps, which vacuumize, removes unreacted N, N- dimethyl-Putriscine, is surveyed through liquid chromatogram
It is 99.0wt% to determine octadecylene acid amides butanediamine content.Rubbed again into above-mentioned system according to 9- octadecenoic acids and 4- chloro-butyric acid sodium
You are than being 1:1.5 add 4- chloro-butyric acid sodium, and with 85 DEG C of reaction 6h, after reaction terminates, it is unreacted to wash removing with absolute ethyl alcohol
4- chloro-butyric acid sodium, after solvent is evaporated off, obtain octadecylene acid amides butyrobetaine, content 97.0wt%.
By octadecylene acid amides butyrobetaine and NaCl according to mass ratio 1:10 mixing composition displacement compositions, the displacement of reservoir oil group
Compound is with water according to mass ratio 5.5:100 is well mixed, when determining 25 DEG C with Malvern dynamic light scattering particle instrument Nano ZS90
Its micella size formed, it the results are shown in Table 1.
At 75 DEG C, determine octadecylene acid amides butyrobetaine, NaCl and water with TX-500C rotating interfacial tensimeters and form
Composition and Henan crude oil between oil water interfacial tension, the results are shown in Table 1.
It it is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is carries out oil displacement test on the rock core of 20 bold and unconstrained darcies, temperature
Spend for 75 DEG C, first with water drive to aqueous 98wt%, metaideophone 0.3pv（Rock pore volume）Octadecylene acid amides butyrobetaine,
With after the composition of water composition, being driven to aqueous 100wt%, composition drives injection pressure and injects pressure ratio with water drive and carry NaCl
High oil recovery factor the results are shown in Table 1.
【Embodiment 2】
By 12- tetracosenoic acids and N, N- dimethyl -1,2- ethylenediamines according to mol ratio 1:In 3 input reactors, in
10h is stirred at 160 DEG C, rear 165 DEG C of oil pumps, which vacuumize, removes unreacted N, N- dimethyl -1,2- ethylenediamines, through liquid chromatogram
It is 98.9wt% to determine two tetradecene acid amides ethylenediamine contents.Again into above-mentioned system according to 12- tetracosenoic acids and 2- chloroethenes
Base sodium sulfonate mol ratio is 1:3 add 2- chloroethyl sodium sulfonates, with 80 DEG C of reaction 10h, after reaction terminates, are washed with absolute ethyl alcohol
Unreacted 2- chloroethyls sodium sulfonate is removed, after solvent is evaporated off, obtains two tetradecene acid amides ethyl glycine betaines, content is
97.1wt%。
By two tetradecene acid amides ethyl glycine betaines and CaCl2According to mass ratio 1:5 mixing composition displacement compositions, the displacement of reservoir oil
Composition is with water according to mass ratio 3:100 is well mixed, when determining 25 DEG C with Malvern dynamic light scattering particle instrument Nano ZS90
Its micella size formed, it the results are shown in Table 1.
At 75 DEG C, two tetradecene acid amides ethyl glycine betaines, CaCl are determined with TX-500C rotating interfacial tensimeters2With water
Oil water interfacial tension between the composition and Henan crude oil of composition, the results are shown in Table 1.
It it is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is carries out oil displacement test on the rock core of 10 bold and unconstrained darcies, temperature
Spend for 75 DEG C, first with water drive to aqueous 98wt%, metaideophone 0.3pv（Rock pore volume）Two tetradecene acid amides ethyl glycine betaines,
CaCl2After the composition of water composition, aqueous 100wt% is driven to, composition drives injection pressure and injects pressure ratio with water drive and carry
High oil recovery factor the results are shown in Table 1.
【Embodiment 3】
By 7,15- lumequeic acids and N, N-dimethyl -1,2- ethylenediamine is according to mol ratio 1:In 2 input reactors, in
20h is stirred at 170 DEG C, rear 165 DEG C of oil pumps, which vacuumize, removes unreacted N, N-dimethyl -1,2- ethylenediamine, through liquid chromatogram
It is 99.0wt% to determine 30 acrylamide ethylenediamine contents.Again into above-mentioned system according to 7,15- lumequeic acids and chloromethane sulfonic acid
Sodium mol ratio is 1:1.5 add chloromethane sodium sulfonate, and with 95 DEG C of reaction 3h, after reaction terminates, it is not anti-to wash removing with absolute ethyl alcohol
The chloromethane sodium sulfonate answered, after solvent is evaporated off, obtain 30 acrylamide ethyl glycine betaines, content 97.3wt%.
By 30 acrylamide ethyl glycine betaines and NaHCO3According to mass ratio 1:2 mixing composition displacement compositions, the displacement of reservoir oil
Composition is with water according to mass ratio 0.55:100 is well mixed, and 25 are determined with Malvern dynamic light scattering particle instrument Nano ZS90
DEG C when its formed micella size, the results are shown in Table 1.
At 75 DEG C, 30 acrylamide ethyl glycine betaines, NaHCO are determined with TX-500C rotating interfacial tensimeters3With water group
Into composition and Henan crude oil between oil water interfacial tension, the results are shown in Table 1.
It it is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is carries out oil displacement test on the rock core of 30 bold and unconstrained darcies, temperature
Spend for 75 DEG C, first with water drive to aqueous 98wt%, metaideophone 0.3pv（Rock pore volume）30 acrylamide ethyl glycine betaines,
NaHCO3After the composition of water composition, be driven to aqueous 100wt%, composition drive injection pressure and water drive injection pressure ratio and
Improve oil recovery factor and the results are shown in Table 1.
【Embodiment 4】
By cetyl carboxylate methyl ester and N, N- dimethyl -1,5- pentanediamines according to mol ratio 1:In 1.5 input reactors,
20h is stirred at 140 DEG C, rear 175 DEG C of oil pumps, which vacuumize, removes unreacted N, N- dimethyl -1,5- pentanediamines, through liquid phase color
Spectrum measure hexadecyl amide pentanediamine content is 99.2wt%.Again into above-mentioned system according to cetyl carboxylate methyl ester and 4-
Chloro-3-hydroxyl sodium butyrate mol ratio is 1:1 adds 4- chloro-3-hydroxyl sodium butyrates, with 80 DEG C of reaction 10h, reacts after terminating, with nothing
Water-ethanol washing removes unreacted 4- chloro-3-hydroxyls sodium butyrate, after solvent is evaporated off, obtains hexadecyl amide amyl group beet
Alkali, content 97.0wt%.
By hexadecyl amide amyl group glycine betaine and MgCl2According to mass ratio 1:50 mixing composition displacement compositions, the drive
Fluid composition is with water according to mass ratio 2.5:100 is well mixed, and 25 are determined with Malvern dynamic light scattering particle instrument Nano ZS90
DEG C when its formed micella size, the results are shown in Table 1.
At 75 DEG C, hexadecyl amide amyl group glycine betaine, MgCl are determined with TX-500C rotating interfacial tensimeters2With water
Oil water interfacial tension between the composition and Henan crude oil of composition, the results are shown in Table 1.
It it is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is to carry out oil displacement test, temperature on the rock core of 2 bold and unconstrained darcies
For 75 DEG C, first with water drive to aqueous 98wt%, metaideophone 0.3pv（Rock pore volume）Hexadecyl amide amyl group glycine betaine,
MgCl2After the composition of water composition, aqueous 100wt% is driven to, composition drives injection pressure and injects pressure ratio with water drive and carry
High oil recovery factor the results are shown in Table 1.
【Embodiment 5】
By 5,10- eicosenoic acids and N, N- dimethyl -1,3- propane diamine according to mol ratio 1:In 1 input reactor, in
20h is stirred at 165 DEG C, rear 165 DEG C of oil pumps, which vacuumize, removes unreacted N, N- dimethyl -1,3- propane diamine, through liquid chromatogram
It is 98.9wt% to determine icosa alkene acid amides propane diamine content.Again into above-mentioned system according to 5,10- eicosenoic acids and sodium chloroacetate
Mol ratio is 1:1.5 add sodium chloroacetate, and with 90 DEG C of reaction 3h, after reaction terminates, it is unreacted to wash removing with absolute ethyl alcohol
Sodium chloroacetate, after solvent is evaporated off, obtain icosa alkene amido propyl betaine, content 97.6wt%.
By icosa alkene amido propyl betaine, NaCl, CaCl2According to mass ratio 1:27:3 mixing composition displacement compositions,
The displacement composition is with water according to mass ratio 16:100 is well mixed, is surveyed with Malvern dynamic light scattering particle instrument Nano ZS90
The micella size that it is formed when fixed 25 DEG C, the results are shown in Table 1.
At 75 DEG C, icosa alkene amido propyl betaine, NaCl, CaCl are determined with TX-500C rotating interfacial tensimeters2With
Oil water interfacial tension between the composition and Henan crude oil of water composition, the results are shown in Table 1.
It it is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is carries out oil displacement test on the rock core of 15 bold and unconstrained darcies, temperature
Spend for 75 DEG C, first with water drive to aqueous 98wt%, metaideophone 0.3pv（Rock pore volume）Icosa alkene amido propyl betaine,
NaCl、CaCl2After the composition of water composition, aqueous 100wt% is driven to, composition drives injection pressure and water drive injection pressure ratio
Value and raising oil recovery factor the results are shown in Table 1.
【Embodiment 6】
By octadecyl carboxylate methyl ester and N, N-dimethyl methyl diamines is according to mol ratio 1:In 1.5 input reactors, in
20h is stirred at 140 DEG C, rear 160 DEG C of oil pumps, which vacuumize, removes unreacted N, N-dimethyl methyl diamines, through liquid chromatogram measuring
Octadecyl amide methanediamine content is 99.0wt%.Again into above-mentioned system according to octadecyl carboxylate methyl ester and chloro- 2 hydroxyls of 3-
Base propanesulfonate mol ratio is 1:3 add 3- chloro-2-hydroxypropanesulfonacid acid sodium salts, with 80 DEG C of reaction 10h, react after terminating, with anhydrous second
Alcohol washing removes unreacted 3- chloro-2-hydroxypropanesulfonacid acid sodium salts, after solvent is evaporated off, obtains octadecyl amide methyl betaine, contains
Measure as 97.1wt%.
By octadecyl amide methyl betaine, MgCl2、CaCl2According to mass ratio 1:1.5:1.5 mixing composition displacement of reservoir oil groups
Compound, the displacement composition is with water according to mass ratio 1:100 is well mixed, with Malvern dynamic light scattering particle instrument Nano
The micella size that it is formed when ZS90 determines 25 DEG C, the results are shown in Table 1.
At 75 DEG C, octadecyl amide methyl betaine, MgCl are determined with TX-500C rotating interfacial tensimeters2、CaCl2
Oil water interfacial tension between the composition and Henan crude oil of water composition, the results are shown in Table 1.
It it is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is carries out oil displacement test on the rock core of 10 bold and unconstrained darcies, temperature
Spend for 75 DEG C, first with water drive to aqueous 98wt%, metaideophone 0.3pv（Rock pore volume）Octadecyl amide methyl betaine,
MgCl2、CaCl2After the composition of composition, be driven to aqueous 100wt%, composition drive injection pressure and water drive injection pressure ratio and
Improve oil recovery factor and the results are shown in Table 1.
【Embodiment 7】
By pentadecyl carboxylate methyl ester and N, N- dimethyl -1,5- pentanediamines according to mol ratio 1:In 1.5 input reactors,
20h is stirred at 140 DEG C, rear 175 DEG C of oil pumps, which vacuumize, removes unreacted N, N- dimethyl -1,5- pentanediamines, through liquid phase color
Spectrum measure pentadecyl acid amides pentanediamine content is 99.0wt%.Again into above-mentioned system according to pentadecyl carboxylate methyl ester and 6-
Chlorine sodium n-caproate mol ratio is 1:2 add 6- chlorine sodium n-caproates, and with 80 DEG C of reaction 10h, after reaction terminates, removing is washed with absolute ethyl alcohol
Unreacted 6- chlorine sodium n-caproate, after solvent is evaporated off, obtain pentadecyl acid amides amyl group glycine betaine, content 97.1wt%.
By pentadecyl acid amides amyl group glycine betaine and NaCl according to mass ratio 1:100 mixing composition displacement compositions, the drive
Fluid composition is with water according to mass ratio 16:100 is well mixed, and 25 are determined with Malvern dynamic light scattering particle instrument Nano ZS90
DEG C when its formed micella size, the results are shown in Table 1.
At 75 DEG C, pentadecyl acid amides amyl group glycine betaine, NaCl and water group are determined with TX-500C rotating interfacial tensimeters
Into composition and Henan crude oil between oil water interfacial tension, the results are shown in Table 1.
It it is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is carries out oil displacement test on the rock core of 20 bold and unconstrained darcies, temperature
Spend for 75 DEG C, first with water drive to aqueous 98wt%, metaideophone 0.3pv（Rock pore volume）Pentadecyl acid amides amyl group glycine betaine,
With after the composition of water composition, being driven to aqueous 100wt%, composition drives injection pressure and injects pressure ratio with water drive and carry NaCl
High oil recovery factor the results are shown in Table 1.
【Embodiment 8】
By the carbon enoic acids of 10,20,30- 40 and N, N- dimethyl -1,4- butanediamine according to mol ratio 1:1.5 input reactors
In, 8h is stirred at 165 DEG C, rear 165 DEG C of oil pumps, which vacuumize, removes unreacted N, N- dimethyl-Putriscine, through liquid phase
The acrylamide butanediamine content of chromatographic determination 40 is 98.9wt%.Again into above-mentioned system according to the carbon enoic acids of 10,20,30- 40 with
4- chloro-butyric acid sodium mol ratio is 1:1.5 add 4- chloro-butyric acid sodium, with 85 DEG C of reaction 6h, after reaction terminates, are washed with absolute ethyl alcohol
Unreacted 4- chloro-butyric acids sodium is removed, after solvent is evaporated off, obtains 40 acrylamide butyrobetaines, content 97.1wt%.
By 40 acrylamide butyrobetaines and NaCl according to mass ratio 1:10 mixing composition displacement compositions, the displacement of reservoir oil group
Compound is with water according to mass ratio 5.5:100 is well mixed, when determining 25 DEG C with Malvern dynamic light scattering particle instrument Nano ZS90
Its micella size formed, it the results are shown in Table 1.
At 75 DEG C, determine 40 acrylamide butyrobetaines, NaCl and water with TX-500C rotating interfacial tensimeters and form
Composition and Henan crude oil between oil water interfacial tension, the results are shown in Table 1.
It it is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is carries out oil displacement test on the rock core of 20 bold and unconstrained darcies, temperature
Spend for 75 DEG C, first with water drive to aqueous 98wt%, metaideophone 0.3pv（Rock pore volume）40 acrylamide butyrobetaines,
With after the composition of water composition, being driven to aqueous 100wt%, composition drives injection pressure and injects pressure ratio with water drive and carry NaCl
High oil recovery factor the results are shown in Table 1.
【Embodiment 9】
By 9- octadecenoic acids and N, N- dimethyl -1,4- butanediamine according to mol ratio 1:In 1.5 input reactors, in
8h is stirred at 165 DEG C, rear 165 DEG C of oil pumps, which vacuumize, removes unreacted N, N- dimethyl-Putriscine, is surveyed through liquid chromatogram
It is 99.0wt% to determine octadecylene acid amides butanediamine content.Again into above-mentioned system according to 9- octadecenoic acids and the sodium sulfonate of 5- chlorine penta
Mol ratio is 1:1.5 add the sodium sulfonate of 5- chlorine penta, and with 85 DEG C of reaction 6h, after reaction terminates, it is not anti-to wash removing with absolute ethyl alcohol
The sodium sulfonate of 5- chlorine penta answered, after solvent is evaporated off, obtain octadecylene acid amides butyrobetaine, content 97.0wt%.
By octadecylene acid amides butyrobetaine and NaCl according to mass ratio 1:1 mixing composition displacement composition, the displacement of reservoir oil group
Compound is with water according to mass ratio 1:100 is well mixed, when determining 25 DEG C with Malvern dynamic light scattering particle instrument Nano ZS90 its
The micella size of formation, the results are shown in Table 1.
At 75 DEG C, determine octadecylene acid amides butyrobetaine, NaCl and water with TX-500C rotating interfacial tensimeters and form
Composition and Henan crude oil between oil water interfacial tension, the results are shown in Table 1.
It it is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is carries out oil displacement test on the rock core of 20 bold and unconstrained darcies, temperature
Spend for 75 DEG C, first with water drive to aqueous 98wt%, metaideophone 0.3pv（Rock pore volume）Octadecylene acid amides butyrobetaine,
With after the composition of water composition, being driven to aqueous 100wt%, composition drives injection pressure and injects pressure ratio with water drive and carry NaCl
High oil recovery factor the results are shown in Table 1.
【Comparative example 1】
By tridecyl carboxylate methyl ester and N, N- dimethyl -1,4- butanediamine according to mol ratio 1:In 1.5 input reactors,
8h is stirred at 165 DEG C, rear 165 DEG C of oil pumps, which vacuumize, removes unreacted N, N- dimethyl-Putriscine, through liquid chromatogram
It is 99.0wt% to determine tridecyl acid amides butanediamine content.Again into above-mentioned system according to tridecyl carboxylic acid and 4- chloro-butyric acids
Sodium mol ratio is 1:1.5 add 4- chloro-butyric acid sodium, and with 85 DEG C of reaction 6h, after reaction terminates, it is not anti-to wash removing with absolute ethyl alcohol
The 4- chloro-butyric acid sodium answered, after solvent is evaporated off, obtain tridecyl acid amides butyrobetaine, content 97.0wt%.
By tridecyl acid amides butyrobetaine and NaCl according to mass ratio 1:10 mixing composition displacement compositions, the displacement of reservoir oil
Composition is with water according to mass ratio 5.5:100 is well mixed, and 25 DEG C are determined with Malvern dynamic light scattering particle instrument Nano ZS90
When its formed micella size, the results are shown in Table 1.
At 75 DEG C, tridecyl acid amides butyrobetaine, NaCl and water group are determined with TX-500C rotating interfacial tensimeters
Into composition and Henan crude oil between oil water interfacial tension, the results are shown in Table 1.
It it is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is carries out oil displacement test on the rock core of 20 bold and unconstrained darcies, temperature
Spend for 75 DEG C, first with water drive to aqueous 98wt%, metaideophone 0.3pv（Rock pore volume）Tridecyl acid amides butyrobetaine,
With after the composition of water composition, being driven to aqueous 100wt%, composition drives injection pressure and injects pressure ratio with water drive and carry NaCl
High oil recovery factor the results are shown in Table 1.
【Comparative example 2】
By 9- octadecenoic acids and N, N- dimethyl -1,4- butanediamine according to mol ratio 1:In 1.5 input reactors, in
8h is stirred at 165 DEG C, rear 165 DEG C of oil pumps, which vacuumize, removes unreacted N, N- dimethyl-Putriscine, is surveyed through liquid chromatogram
It is 99.0wt% to determine octadecylene acid amides butanediamine content.Rubbed again into above-mentioned system according to 9- octadecenoic acids and 4- chloro-butyric acid sodium
You are than being 1:1.5 add 4- chloro-butyric acid sodium, and with 85 DEG C of reaction 6h, after reaction terminates, it is unreacted to wash removing with absolute ethyl alcohol
4- chloro-butyric acid sodium, after solvent is evaporated off, obtain octadecylene acid amides butyrobetaine, content 97.0wt%.
By octadecylene acid amides butyrobetaine and water according to mass ratio 0.5:100 is well mixed.
At 75 DEG C, the group of octadecylene acid amides butyrobetaine and water composition is determined with TX-500C rotating interfacial tensimeters
Oil water interfacial tension between compound and Henan crude oil, the results are shown in Table 1.
It it is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is carries out oil displacement test on the rock core of 20 bold and unconstrained darcies, temperature
Spend for 75 DEG C, first with water drive to aqueous 98wt%, metaideophone 0.3pv（Rock pore volume）Octadecylene acid amides butyrobetaine with
After the composition of water composition, aqueous 100wt% is driven to, composition drives injection pressure and injects pressure ratio with water drive and improve crude oil
Recovery ratio the results are shown in Table 1.
【Comparative example 3】
By dodecyl carboxylic acid glycine betaine, the polyacrylamide of molecular weight 4800000, NaCl according to mass ratio 1:0.5:10
Mixing composition displacement of reservoir oil composition, by the displacement of reservoir oil composition and water according to mass ratio 1.15:100 mixing.
At 75 DEG C, with TX-500C rotating interfacial tensimeters determine empgen BB, molecular weight 4800000 it is poly-
Oil water interfacial tension between the composition and Henan crude oil of acrylamide, NaCl and water composition, the results are shown in Table 1.
It it is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is carries out oil displacement test on the rock core of 20 bold and unconstrained darcies, temperature
Spend for 75 DEG C, first with water drive to aqueous 98wt%, metaideophone 0.3pv（Rock pore volume）Empgen BB, molecular weight
After the composition of 4800000 polyacrylamide, NaCl and water composition, be driven to aqueous 100wt%, composition drive injection pressure with
Water drive, which injects pressure ratio and improves oil recovery factor, the results are shown in Table 1.
Table 1（It is continued）The aggregate size of composition formation in embodiment and comparative example,
And with Henan crude oil interfacial tension, injection pressure ratio and recovery ratio result
Table 1（It is continuous）The aggregate size of composition formation in embodiment and comparative example,
And with Henan crude oil interfacial tension, injection pressure ratio and recovery ratio result
Claims (8)
1. for the displacement composition of low-permeability oil deposit, it is made up of Long carbon chain beet alkali surface activator, inorganic salts, water, it is described
Long carbon chain beet alkali surface activator be long-chain carboxylic acid's betaine salt, inorganic salts are selected from CaCl2、MgCl2、NaCl、NaHCO3In
At least one；
Long-chain carboxylic acid's betaine salt general molecular formula is：
The R is C14~C40Alkyl, any one in alkenyl, the R ' is C1~C5Alkylidene, R " is C1~C5Asia
Any one in alkyl, hydroxyl substituted alkylene, the quality of the Long carbon chain beet alkali surface activator and the inorganic salts
Than for 1:(1~100).
2. it is used for the displacement composition of low-permeability oil deposit according to claim 1, it is characterised in that described R is C16~C30It
Between alkyl or alkenyl.
3. it is used for the displacement composition of low-permeability oil deposit according to claim 1, it is characterised in that the Long carbon chain glycine betaine
The mass ratio of surfactant and the inorganic salts is 1:(2~50).
4. the displacement composition according to any one of claims 1 to 3, it is characterised in that with weight in the displacement composition
The ratio between dosage sum and water of Long carbon chain beet alkali surface activator described in gauge and inorganic salts are (0.55~16):100.
5. it is used for the preparation method of the displacement composition of low-permeability oil deposit according to any one of Claims 1 to 4, including with
Lower step：
A) aliphatic acid or its ester and required amidation reagent are added into reactor, reacted 8~20 hours in 140~170 DEG C；And
After add carboxylating reagent, continue reaction 3~10 hours in 75~95 DEG C, obtain long-chain carboxylic acid's betaine salt described in logical formula (I)；
According to initiation material meter, aliphatic acid or its ester：Amidation reagent：The mol ratio of carboxylating reagent is 1:(1~3):(1~3)；
B) the obtained glycine betaine of inorganic salts and step a is dissolved in the water well mixed, obtains described displacement composition；
Described amidation reagent general molecular formula isWherein R ' is C1~C5Alkylidene, described carboxylation
Reagent molecule formula is that Cl-R " COONa, R " are C1~C5Alkylidene, any one in hydroxyl substituted alkylene.
6. a kind of flooding method of low-permeability oil deposit, including displacement composition injection any one of Claims 1 to 4 is low
Permeate oil reservoir and carry out the displacement of reservoir oil.
7. the flooding method of low-permeability oil deposit according to claim 6, it is characterised in that the permeability of the low-permeability oil deposit
For 1~40mD.
8. the flooding method of low-permeability oil deposit according to claim 7, it is characterised in that the permeability of the low-permeability oil deposit
For 2~30mD.
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| CN106631912A (en) * | 2015-10-29 | 2017-05-10 | 中国石油天然气股份有限公司 | Hydroxyl sulfobetaine surfactant and preparation method and application thereof |
| US11028315B2 (en) | 2016-04-08 | 2021-06-08 | Rhodia Operations | Zwitterionic surfactants suitable for enhanced oil recovery |
| CN107916101A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | Alkali-free, which sticks, plays surfactant and preparation method and applications |
| CN107916099B (en) * | 2016-10-08 | 2020-08-07 | 中国石油化工股份有限公司 | Alkali-free viscoelastic surfactant composition and preparation method and application thereof |
| CN107916096B (en) * | 2016-10-08 | 2023-04-07 | 中国石油化工股份有限公司 | Viscoelastic surfactant composition for oil displacement and preparation method and application thereof |
| CN107916098A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | Displacement of reservoir oil Surfactant Used in Viscoelastic Fracturing Fluids composition and its preparation method and application |
| CN107916097B (en) * | 2016-10-08 | 2020-08-07 | 中国石油化工股份有限公司 | Viscoelastic betaine surfactant composition for oil displacement |
| CN107916100A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | Viscoelasticity beet alkali surface activator and its preparation method and application |
| CN109681170B (en) * | 2017-10-18 | 2021-05-28 | 中国石油化工股份有限公司 | Method for discharging liquid and gas production by adopting pH value response foam drainage agent |
| US20210380867A1 (en) * | 2020-06-08 | 2021-12-09 | Saudi Arabian Oil Company | Methods and compositions for downhole diversion of well treatment fluid |
| US12071838B2 (en) | 2022-10-07 | 2024-08-27 | Saudi Arabian Oil Company | Viscoelastic surfactants for acid diversion in downhole operations |
| US11959017B1 (en) | 2022-10-07 | 2024-04-16 | Saudi Arabian Oil Company | Methods and materials for wellbore fluid diversion using visco-elastic surfactants |
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