CN106590604A - Foaming agent composition for high temperature gas drive and preparation method thereof - Google Patents
Foaming agent composition for high temperature gas drive and preparation method thereof Download PDFInfo
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- CN106590604A CN106590604A CN201510681538.8A CN201510681538A CN106590604A CN 106590604 A CN106590604 A CN 106590604A CN 201510681538 A CN201510681538 A CN 201510681538A CN 106590604 A CN106590604 A CN 106590604A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/594—Compositions used in combination with injected gas, e.g. CO2 orcarbonated gas
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
Abstract
The invention relates to a foaming agent composition for high temperature gas drive and a preparation method thereof. The composition mainly solves the problems that the foaming agent does not have heat resistance and plugging capability of formed foam is low in the prior art. The composition comprises the following components according to mole fraction: 1 part of a long-chain polyether nitrogen containing compound and 0.1-50 parts of a long-chain diaryl sulfonate surfactant; wherein the long chain polyether nitrogen containing compound comprises a general molecular formula shown in formula (I), and the long-chain diaryl sulfonate surfactant comprises a molecular formula shown in formula (II), wherein in the formula (I), R1 is a C10-C26 fatty group; y=0-20, and z=0-60; R4, R5 and R6 are any one of C1-C5 alkyl and substituted alkyl; R7 is C1-C4 alkylene; and Y is selected from anion with electric neutrality of the molecule shown in the formula (I). The technical scheme can better solve the problems, and is used for high temperature gas drive oil extraction.
Description
Technical field
The present invention relates to a kind of be used for high-temperature oil reservoir gas drive foaming agent combination and preparation method.
Background technology
How China's main oilfield improves oil recovery factor through once with after secondary recovery coming into high water-cut stage, maximum
Limit ground exploitation remaining reserves, tertiary oil recovery technology has played very important effect in terms of oilfield stable production high yield is ensured.
In tertiary oil recovery new technology, chemical combined flooding remains one of very promising method of tool.Its mechanism of oil displacement is mainly
Polymer or glue increase the viscosity of driven water-replacing, reduce oil and water mobility ratio, alleviate channelling phenomenon, improve sweep efficiency；Live on surface
Property agent and alkali reduce oil/water interfacial tension, increase capillary number, promote crude oil be desorbed from rock and effectively dispersion, realization is to residual
Effective driving of excess oil, so as to improve recovery ratio.But the polymer heat and salt resistance in chemical combined flooding always perplexs high
A difficult problem for warm high salinity reservoirs application.
In order to improve the ability of closure high permeability zone, people have found that foam has than polymer or glue more through substantial amounts of research
Entrance well simultaneously reduces the infiltrative ability of high permeability zone.By adding foaming agent and gas mixing, in the form of aerated fluid
Displacement is carried out, high permeability zone can be selectively blocked, fluid entry profile is adjusted, increases sweep efficiency.However, even so,
Foam flooding is less in mining site large-scale application, and the unstability of foam system is the basic reason that its application is restricted.
At present foaming agent used for tertiary oil recovery adopts Recompounded multielement system mostly, while comprising nonionic surface active agent and ion
Type surfactant.In order to strengthen the stability of single foam, alkali, alcohol, polymer, alkanol acyl are generally additionally added in formula
The auxiliary agents such as amine form strengthening foam.It is used for low-permeability oil deposit carbon dioxide foaming as patent CN101619210A provides one kind
Stabilizer, the agent from neopelex be foaming agent, foam stabilizer by modified guanidine glue, hydroxyethyl cellulose, 12
Alcohol is constituted, and the addition of polymer causes the temperature tolerance of system to be greatly lowered.Patent CN1093589C discloses a kind of foam
Combination flooding method, wherein using the poly- of the alkali of 0.5～1.5wt%, the surfactant of 0.05～0.5wt% and 0.05～0.5wt%
Compound constitutes foaming agent combination, because system contains inorganic base, to stratum and oil well injury is brought, and causes etching apparatus and pipe
The problems such as road, and inorganic base can seriously reduce the viscosity of polymer, and the viscosity for needed for reaching is had to greatly improve polymer
Concentration, make oil recovery integrated cost improve.Under normal circumstances, alkanolamide surfactant is good foam stabilizer,
Liquid viscosity can be increased, strengthen foaming properties, this foam stabilizer will be applied in some commodity, such as《Detergents and cosmetic
Product science》2009 (04), CN200910234823.X, US 854048 etc. mentions alkanolamide class surfactant and is added to
In the dilute aqueous solution of anion surfactant, viscosity increase, foam stability strengthens.Although this kind of foam stabilizer will not be over the ground
Layer is damaged, but in the case of a high temperature foam stabilizing effect is not obvious, and salinity increases alkanolamide dissolubility and reduces.
Cation foaming agent easily adsorbs or produces precipitation because of it by stratum, is generally not used for tertiary oil recovery.Due to zwitterion bubble
Its aqueous solution easily forms precipitation when the close equal proportion of foam agent mixes, so as to cause zwitterion foaming agent mixed system not only to exist
Become incompatibility using in, and correlation theory research is also more delayed.Research discovery in recent years, zwitterion surface
The activating agent mixed system aqueous solution has many anomalous properties, such as because cationic and anionic surfactant is existed in aqueous
Interaction between strong electrostatic interaction and hydrophobic carbon chain, promotes the different charged surfactants of two kinds of bands interionic
Associate, micella, the higher surface-active of the single surfactant of producing ratio are readily formed in the solution.Additionally, negative and positive from
Sub- Surfactants mixed system can obviously reduce absorption loss of the cationic surfactant on rock core, so as to can significantly drop
The inherent shortcoming of low cationic surfactant.
For this purpose, one aspect of the present invention absorbs has used for reference forefathers with regard to anions and canons Surfactants mixed system result of study,
On the other hand traditional anion surfactant is replaced using the long-chain diaryl sulfosalt surfactant of Shuangzi type, it is long
Chain polyethers nitrogen-containing compound replaces traditional long chain quaternary, easily precipitates when overcoming cationic anionic surfactant combination
The shortcomings of, invent the foam anti-channeling composition for gas drive.
The content of the invention
One of the technical problem to be solved is that the stickiness fingering that exists during existing high temperature gas drive, has channeling are asked
Topic, there is provided a kind of new foaming agent combination for high temperature gas drive, said composition forms foam with gas, with resistance because
The high advantage of son.The two of the technical problem to be solved be to provide it is a kind of with solve that technical problem one is corresponding is used for
The preparation method of high temperature gas drive foaming agent combination.
To solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of foaming agent combination, with mole
Number meter includes 1 part of long-chain polyether nitrogen-containing compound and 0.1～50 part of long-chain diaryl sulfosalt surfactant；
Wherein, the long-chain polyether nitrogen-containing compound, with general molecular formula shown in formula (I)：
The long-chain diaryl sulfosalt surfactant, with general molecular formula shown in formula (II)：
In formula (I), the R1For C10～C26Fat-based；Y=0～20, z=0～60；R4、R5、R6For C1～C5Alkyl,
Replace any one in alkyl；R7For C1～C4Alkylidene；Y is in electroneutral the moon selected from molecule shown in formula (I) is made
Ion；J is the valence state of Y, and 1/j is the quantity of Y；In formula (II), the R2For C10～C26Fat-based；It is described
R3For H or C1～C26Fat-based；N, m are 0～3 integer or decimal and n+m>1；L is O, S ,-(CH2)1-3-、
-OC2H4O-、-OC3H6One kind in O-；X is at least one in alkali metal ion, alkaline-earth metal ions or ammonium ion,
And when X is alkali metal ion or ammonium ion, a=n, b=m, when X is alkaline-earth metal ions, a=n/2, b=m/2.
In above-mentioned technical proposal, the R1For C10～C26Fat-based, can be containing acyl group, carbonyl, ether, hydroxyl etc.
Group, can be saturated carbon chains, it is also possible to containing unsaturated carbon chains, as preferred R1Preferred version be C10～C20Alkane
Base, alkylbenzene.
In above-mentioned technical proposal, the R4、R5、R6For C1～C5Alkyl, replace alkyl in any one；Wherein
Substituent in the replacement alkyl can be the substituted radicals such as hydroxyl substituent, halogenic substituent.
In above-mentioned technical proposal, the R7Preferably C2H4Or C3H6。
In above-mentioned technical proposal, the preferred version of the z is to be less than or equal to 30 more than 0, further preferably greater than 0.
In above-mentioned technical proposal, the preferred version of the y is more preferably y=1～20 more than 0.
In above-mentioned technical proposal, the Y has no particular/special requirement, and can be selected from arbitrarily makes molecule shown in formula (I) be in electroneutral
Anion, for example but do not limit selected from halide ion, sulfate ion, sulfurous acid with ion, acetic acid with ion, poly- the moon
Ion etc.；Wherein preferably, Y is preferably halide ion, more preferably in chlorion or bromide ion extremely
Few one kind.
In above-mentioned technical proposal, the R2For C10～C26Fat-based, can be containing acyl group, carbonyl, ether, hydroxyl etc.
Group, can be saturated carbon chains, it is also possible to containing unsaturated carbon chains, as the preferred R2Preferred version be C12～C20
Alkyl.
In above-mentioned technical proposal, the R3For H or C1～C26Fat-based, acyl group, carbonyl, ether, hydroxyl can be contained
The groups such as base, can be saturated carbon chains, it is also possible to containing unsaturated carbon chains, as preferred R3Preferred version be H or C1～C16
Alkyl.
In above-mentioned technical proposal, the preferred version of the X is K+、Na+、NH4 +In at least one；The long-chain polyether
Nitrogen-containing compound is preferably 1 with the mol ratio of long-chain diaryl sulfonate:0.2～10.
In above-mentioned technical proposal, the y and z is while preferably greater than 0.
Foaming agent combination in the present invention does not have particular/special requirement when preparing to water, can be deionized water, can also be
Water containing inorganic mineral, and the water for containing inorganic mineral can be running water, oil field stratum water or oilfield injection water.
To solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of preparation side of foaming agent combination
Method, comprises the following steps：
(1) synthesis of long-chain polyether nitrogen-containing compound
A, in the presence of base catalyst, R1OH obtains R with aequum propylene oxide reaction1O(CHCH3CH2O)yH；
B, in the presence of base catalyst, R1O(CHCH3CH2O)yH is obtained with aequum reacting ethylene oxide
R1O(CHCH3CH2O)y(CH2CH2O)z+1H；
C, by R1O(CHCH3CH2O)y(CH2CH2O)z+1H reacts Jing after processing with thionyl chloride and obtains
R1O(CHCH3CH2O)y(CH2CH2O)zR7Cl；
D, by R1O(CHCH3CH2O)y(CH2CH2O)z R7Cl and NR4R5In a solvent, in 70～90 DEG C of reaction temperature
Reaction obtains R Jing after processing1O(CHCH3CH2O)y(CH2CH2O)z R7NR4R5；
E, by R1O(CHCH3CH2O)y(CH2CH2O)z R7NR4R5With YR6In a solvent at base catalyst reaction Jing
The long-chain polyether nitrogen-containing compound is obtained after reason；
(2) preparation of foaming agent combination
The desired amount of long-chain polyether nitrogen-containing compound, long-chain diaryl sulfonate are well mixed and obtain the foaming agent combination.
The key active ingredient of foaming agent of the present invention is long-chain diaryl sulfonate and long-chain polyether nitrogen-containing compound, this area skill
Art personnel know, for the ease of transport and store or onsite application etc. from the aspect of, various supply forms can be adopted, for example
Water-free solid-state form, or aqueous solid-state form, or aqueous cream form, or aqueous solution form；It is water-soluble
Liquid form includes being made into the form of concentrate with water, is directly made into the foaming agent form of live displacement of reservoir oil desired concn；Wherein, it is right
Water does not have particular/special requirement, can be deionized water, can also be the water containing inorganic mineral, and the water for containing inorganic mineral can
Being running water, oil field stratum water or oilfield injection water.
Foaming agent combination of the present invention has good compatibility, can also contain other inorganic agents commonly used in the art, such as table
The oil recovery auxiliary agent such as face activating agent, alkali.
The present invention for high temperature gas drive foaming agent combination, by nitrogenous using long-chain diaryl sulfonate and long-chain polyether
Two kinds of component compoundings of compound, achieve the effect of preferable Synergistic so that on the surface adsorbance increases foam agent molecule
Greatly, so as to the diffusion that the gas with the incomparable interface arrangement density of single foaming agent, obstruction passes through liquid film, it is allowed to more
Easily formed and stable foam.And two kinds of components all do not contain the easy group for hydrolyzing so that it can apply to high temperature gas drive
During.In addition, to carbon dioxide foaming, due to the little interfacial tension of carbon dioxide/water termination so that surfactant is arrived
The driving force of Interfacial Adsorption is weaker, and the adsorbance of surfactant to interface is less, the oxygen atom of oxygen propyl group and oxygen ethyl group
There is the interaction of Lewis soda acids and the carbon atom of carbon dioxide between, enhance the solvation of hydrophobic chain, Ke Yiqi
To adsorbance is increased, interfacial tension is reduced, and then strengthen the stability of the foam formed containing carbon dioxide.
The present invention for high temperature gas drive foaming agent combination, can effectively macropore plugging, experiment finds, in mineralising
Degree 50000mg/L, under conditions of 200 DEG C, gas drive is carried out after water drive, 0.3pV gases are broken through, using the combination
Thing forms foam injection 1.0pV, and gas is broken through, and resistance factor achieves preferable technique effect up to 100.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
In order to be better understood from the present invention, present disclosure, but present disclosure are expanded on further with reference to embodiments
It is not limited solely to the following examples.
【Embodiment 1】
The preparation of composition HF-1, preparation process：
(1) long-chain polyether nitrogen-containing compound (C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2 N(CH3)2C3H7Cl)
Synthesis with prepare：
186.0 grams of dodecanols, 5.6 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, it is heated to 80～
When 90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, then with nitrogen displacement 3～4 times, system is reacted
Temperature is adjusted to 150 DEG C and is slowly passed through 179.9 grams of expoxy propane, and control pressure≤0.60MPa is cooled to 90 DEG C, is removed in vacuum
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 360.0 grams of oxirane, control pressure≤0.60MPa by low-boiling-point substance, continuation.
After reaction terminates, neutralization, dehydration, obtain C after cooling12H25O(CHCH3CH2O)3(CH2CH2O)8H, yield 98.8wt%.
339 grams are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
C12H25O(CHCH3CH2O)3(CH2CH2O)8H and 57 gram of pyridine, is heated to 70 DEG C under stirring, slow with dropping funel
85 grams of thionyl chlorides are added dropwise, are reacted 10 hours at 90 DEG C after completion of dropping.After reaction terminates, reactant stood, cooled down
Layering, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, in obtaining after drying
Between product C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2Cl, yield is 88%.
By C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2143 grams of Cl is added and is carried reflux condensate device, temperature
In degree meter, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (CH3)2Solution dropping funel is slowly dripped in flask,
System remains alkalescent, stratification after reacting 10 hours.By the saturated common salt washing after the vacuum distillation of upper strata with heat
Wash 5-6 time, obtain desired intermediate C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2, yield
For 83%.
By 739 grams of C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2 N(CH3)2Throw with 80 grams of chloro-propanes
In entering the pressure reactor equipped with agitating device, in the case where KOH makees catalysts conditions, react under 0.2～0.3MPa pressure
4h, Jing high performance liquid chromatography (HPLC) is analyzed, C in product12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2
N(CH3)2C3H7Cl contents are 96.62wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 84.6 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；138 grams of long-chain diaryl sulfonate is added thereto to again, adds enough sheets
Ground running water is configured to the solution of 30wt% to 720 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent composition HF-1.
【Embodiment 2】
The preparation of composition HF-2, preparation process：
(1) long-chain polyether nitrogen-containing compound (C16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2
N(C2H5)(C3H7O)CH3Br synthesis) and preparation：
121 grams of hexadecanols, 3 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, 80～90 are heated to
DEG C when, open vacuum system, be dehydrated under a high vacuum 1 hour, then with nitrogen displacement 3～4 times, by system reaction temperature
Degree is adjusted to 150 DEG C and is slowly passed through 300 grams of expoxy propane, and control pressure≤0.60MPa is cooled to 90 DEG C, low boiling is removed in vacuum
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 500.0 grams of oxirane, control pressure≤0.60MPa by thing, continuation.Instead
After should terminating, neutralization, dehydration, obtain C after cooling16H33O(CHCH3CH2O)10(CH2CH2O)21H, yield 98.6wt%.
131 grams are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
C16H33O(CHCH3CH2O)10(CH2CH2O)21H and 20 gram of pyridine, is heated to 70 DEG C under stirring, slow with dropping funel
35 grams of thionyl chlorides are added dropwise, are reacted 10 hours at 90 DEG C after completion of dropping.After reaction terminates, reactant stood, cooled down
Layering, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, in obtaining after drying
Between product C16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2Cl, yield is 86.6%.
By C16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2135 grams of Cl is added and is carried reflux condensate device, temperature
In degree meter, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (C2H5)(C3H6OH) solution dropping funel is slowly dripped to
In flask, system remains alkalescent, stratification after reacting 10 hours.The saturation of heat will be used after the vacuum distillation of upper strata
Brine It 5-6 time, obtains desired intermediate C16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2
N(C2H5)(C3H7O), yield is 83.3%.
By 900 grams of C16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2 N(C2H5)(C3H7O) with 53 grams of bromos
In ethane pressure reactor of the input equipped with agitating device, in the case where KOH makees catalysts conditions, in 0.2～0.3MPa pressure
Lower reaction 4h, Jing high performance liquid chromatography (HPLC) analysis, in product
C16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2 N(C2H5)(C3H7O)CH3Br contents are 96.72wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 20.8 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；78.1 grams of long-chain diaryl sulfonate is added thereto to again, adds enough sheets
Ground running water is configured to the solution of 30wt% to 325 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent composition HF-2.
【Embodiment 3】
The preparation of composition HF-3, preparation process：
(1) long-chain polyether nitrogen-containing compound (C14H29OCHCH3CH2O(CH2CH2O)30CH2CH2N(C3H7O)2C5H11Br)
Synthesis with prepare：
107.0 grams of tetradecanols, 3.0 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, it is heated to 80～
When 90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, then with nitrogen displacement 3～4 times, system is reacted
Temperature is adjusted to 150 DEG C and is slowly passed through 60 grams of expoxy propane, and control pressure≤0.60MPa is cooled to 90 DEG C, low boiling is removed in vacuum
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 700.0 grams of oxirane, control pressure≤0.60MPa by thing, continuation.Instead
After should terminating, neutralization, dehydration, obtain C after cooling14H29OCHCH3CH2O(CH2CH2O)31H, yield 98.7wt%.
327 grams are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
C14H29OCHCH3CH2O(CH2CH2O)31H and 20 gram of pyridine, is heated to 70 DEG C under stirring, slowly dripped with dropping funel
Plus 35 grams of thionyl chlorides, react 10 hours at 90 DEG C after completion of dropping.After reaction terminates, reactant is stood, cooling divides
Layer, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, after drying centre is obtained
Product C14H29OCHCH3CH2O(CH2CH2O)30CH2CH2Cl, yield is 87%.
By C14H29OCHCH3CH2O(CH2CH2O)30CH2CH2165 grams of Cl is added and is carried reflux condensate device, temperature
In meter, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (C3H6OH)2Solution dropping funel is slowly dripped in flask,
System remains alkalescent, stratification after reacting 10 hours.By the saturated common salt washing after the vacuum distillation of upper strata with heat
Wash 5-6 time, obtain desired intermediate C14H29OCHCH3CH2O(CH2CH2O)30CH2CH2N(C3H7O)2, yield
For 83.3%.
By 900 grams of C14H29OCHCH3CH2O(CH2CH2O)30CH2CH2N(C3H7O)2With 80 grams of bromo pentane inputs
In pressure reactor equipped with agitating device, in the case where KOH makees catalysts conditions, 4h is reacted under 0.2～0.3MPa pressure,
Jing high performance liquid chromatography (HPLC) is analyzed, in product
C14H29OCHCH3CH2O(CH2CH2O)30CH2CH2N(C3H7O)2C5H11Br contents are 96.77wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 196 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；15.5 grams of long-chain diaryl sulfonate is added thereto to again, adds enough sheets
Ground running water is configured to the solution of 30wt% to 685 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent composition HF-3.
【Embodiment 4】
The preparation of composition HF-4, preparation process：
(1) long-chain polyether nitrogen-containing compound (C20H33OCHCH3CH2OCH2CH2OCH2CH2N(C3H7)(C5H11)CH3Cl)
Synthesis with prepare：
145.0 grams of myristyl phenol, 2.0 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, is heated to
When 80～90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, then with nitrogen displacement 3～4 times, by system
Reaction temperature is adjusted to 150 DEG C and is slowly passed through 60 grams of expoxy propane, and control pressure≤0.60MPa is cooled to 90 DEG C, and vacuum is removed
Low-boiling-point substance, continuation is gone system reaction temperature to be adjusted to into 150 DEG C and is slowly passed through 90.0 grams of oxirane, control pressure≤0.60MPa.
After reaction terminates, neutralization, dehydration, obtain C after cooling20H33OCHCH3CH2O(CH2CH2O)2H, yield 99.6wt%.
218 grams are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
C20H33OCHCH3CH2O(CH2CH2O)2H and 20 gram of pyridine, is heated to 70 DEG C under stirring, be slowly added dropwise with dropping funel
35 grams of thionyl chlorides, react 10 hours after completion of dropping at 90 DEG C.After reaction terminates, reactant is stood, cooling is layered,
Upper strata is neutralized to into neutrality with sodium hydroxide solution, with saturated common salt water washing 5-6 time of heat, after drying intermediate product is obtained
C20H33OCHCH3CH2O CH2CH2OCH2CH2Cl, yield is 87.1%.
By C20H33OCHCH3CH2OCH2CH2OCH2CH296 grams of Cl add with reflux condensate device, thermometer,
In the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (C3H7)(C5H11) solution dropping funel slowly dripped in flask,
System remains alkalescent, stratification after reacting 10 hours.By the saturated common salt washing after the vacuum distillation of upper strata with heat
Wash 5-6 time, obtain desired intermediate C20H33OCHCH3CH2OCH2CH2OCH2CH2N(C3H7)(C5H11), yield
For 83.7%.
By 547 grams of C20H33OCHCH3CH2OCH2CH2OCH2CH2N(C3H7)(C5H11) throw with 51 grams of chloromethanes
In entering the pressure reactor equipped with agitating device, in the case where KOH makees catalysts conditions, react under 0.2～0.3MPa pressure
4h, Jing high performance liquid chromatography (HPLC) is analyzed, in product
C20H33OCHCH3CH2OCH2CH2OCH2CH2N(C3H7)(C5H11)CH3Cl contents are 98.67wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 61 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；98 grams of long-chain diaryl sulfonate is added thereto to again, adds enough sheets
Ground running water is configured to the solution of 30wt% to 526 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent composition HF-4.
【Embodiment 5】
The preparation of composition HF-5, preparation process：
(1) long-chain polyether nitrogen-containing compound (C12H25O(CHCH3CH2O)20CH2CH2OCH2CH2
N(CH3)(C2H5)C4H9Cl synthesis) and preparation：
93.0 grams of dodecanols, 5.6 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, it is heated to 80～
When 90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, then with nitrogen displacement 3～4 times, system is reacted
Temperature is adjusted to 150 DEG C and is slowly passed through 600 grams of expoxy propane, and control pressure≤0.60MPa is cooled to 90 DEG C, is removed in vacuum
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 90 grams of oxirane, control pressure≤0.60MPa by low-boiling-point substance, continuation.
After reaction terminates, neutralization, dehydration, obtain C after cooling12H25O(CHCH3CH2O)20(CH2CH2O)2H, yield 98.6wt%.
287 grams are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
C12H25O(CHCH3CH2O)20(CH2CH2O)2H and 30 gram of pyridine, is heated to 70 DEG C under stirring, slowly dripped with dropping funel
Plus 35 grams of thionyl chlorides, react 10 hours at 90 DEG C after completion of dropping.After reaction terminates, reactant is stood, cooling divides
Layer, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, after drying centre is obtained
Product C12H25O(CHCH3CH2O)20CH2CH2OCH2CH2Cl, yield is 88%.
By C12H25O(CHCH3CH2O)20CH2CH2OCH2CH2146 grams of Cl is added and is carried reflux condensate device, temperature
In meter, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (CH3)(C2H5) solution dropping funel slowly drips to flask
In, system remains alkalescent, stratification after reacting 10 hours.The saturated common salt of heat will be used after the vacuum distillation of upper strata
Water washing 5-6 time, obtains desired intermediate C12H25O(CHCH3CH2O)20CH2CH2OCH2CH2N(CH3)(C2H5),
Yield is 83.3%.
By 740 grams of C12H25O(CHCH3CH2O)20CH2CH2OCH2CH2 N(CH3)(C2H5) and 70 grams of butyl bromides
It is anti-under 0.2～0.3MPa pressure in the case where KOH makees catalysts conditions in pressure reactor of the input equipped with agitating device
Answer 4h, Jing high performance liquid chromatography (HPLC) analysis, C in product12H25O(CHCH3CH2O)20CH2CH2OCH2CH2
N(CH3)(C2H5)C4H9Cl contents are 97.61wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 165 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；32.5 grams of long-chain diaryl sulfonate is added thereto to again, adds enough sheets
Ground running water is configured to the solution of 30wt% to 646 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foaming agent
Composition HF-5.
【Embodiment 6】
The preparation of composition HF-6, preparation process：
(1) long-chain polyether nitrogen-containing compound (C12H25O(CH2CH2O)7CH2CH2 N(CH3)2C3H7Cl synthesis) and preparation：
186.0 grams of dodecanols, 5.6 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, it is heated to 80～
When 90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, then with nitrogen displacement 3～4 times, system is reacted
Temperature is adjusted to 150 DEG C and is slowly passed through 360.0 grams of oxirane, control pressure≤0.60MPa, after reaction terminates, after cooling in
With, dehydration, obtain C12H25O(CH2CH2O)8H, yield 99.3wt%.
269 grams are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
C12H25O(CH2CH2O)8H and 57 gram of pyridine, is heated to 70 DEG C under stirring, with dropping funel 85 grams of thionyl are slowly added dropwise
Chlorine, reacts 10 hours after completion of dropping at 90 DEG C.After reaction terminates, reactant is stood, cooling is layered, and uses hydroxide
Upper strata is neutralized to neutrality by sodium solution, with saturated common salt water washing 5-6 time of heat, after drying intermediate product C is obtained12H25O
(CH2CH2O)7CH2CH2Cl, yield is 88.3%.
By C12H25O(CH2CH2O)7CH2CH2115 grams of Cl add with reflux condensate device, thermometer, the four of agitator
In mouth flask, 77 DEG C are heated to, by N (CH3)2Solution dropping funel is slowly dripped in flask, and system remains weak base
Property, stratification after reacting 10 hours.After the vacuum distillation of upper strata with saturated common salt water washing 5-6 time of heat, mesh will be obtained
Mark intermediate product C12H25O(CH2CH2O)7CH2CH2N(CH3)2, yield is 83.8%.
By 564 grams of C12H25O(CH2CH2O)7CH2CH2 N(CH3)2Agitating device is housed with 80 grams of chloro-propane inputs
Pressure reactor in, in the case where KOH makees catalysts conditions, 4h, Jing efficient liquid phases are reacted under 0.2～0.3MPa pressure
Chromatogram (HPLC) is analyzed, C in product12H25O(CH2CH2O)7CH2CH2 N(CH3)2C3H7Cl contents are 96.76wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 66.4 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；129.6 grams of long-chain diaryl sulfonate is added thereto to again, is added enough
Local running water is configured to the solution of 30wt% to 646 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent composition HF-6.
【Embodiment 7】
The preparation of composition HF-7, preparation process：
(1) long-chain polyether nitrogen-containing compound (C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2 N(CH3)2C3H7Cl)
Synthesis with prepare：
186.0 grams of dodecanols, 5.6 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, it is heated to 80～
When 90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, then with nitrogen displacement 3～4 times, system is reacted
Temperature is adjusted to 150 DEG C and is slowly passed through 179.9 grams of expoxy propane, and control pressure≤0.60MPa is cooled to 90 DEG C, is removed in vacuum
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 360.0 grams of oxirane, control pressure≤0.60MPa by low-boiling-point substance, continuation.
After reaction terminates, neutralization, dehydration, obtain C after cooling12H25O(CHCH3CH2O)3(CH2CH2O)8H, yield 98.8wt%.
339 grams are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
C12H25O(CHCH3CH2O)3(CH2CH2O)8H and 57 gram of pyridine, is heated to 70 DEG C under stirring, slow with dropping funel
85 grams of thionyl chlorides are added dropwise, are reacted 10 hours at 90 DEG C after completion of dropping.After reaction terminates, reactant stood, cooled down
Layering, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, in obtaining after drying
Between product C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2Cl, yield is 88%.
By C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2143 grams of Cl is added and is carried reflux condensate device, temperature
In degree meter, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (CH3)2Solution dropping funel is slowly dripped in flask,
System remains alkalescent, stratification after reacting 10 hours.By the saturated common salt washing after the vacuum distillation of upper strata with heat
Wash 5-6 time, obtain desired intermediate C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2, yield
For 83%.
By 739 grams of C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2 N(CH3)2Throw with 80 grams of chloro-propanes
In entering the pressure reactor equipped with agitating device, in the case where KOH makees catalysts conditions, react under 0.2～0.3MPa pressure
4h, Jing high performance liquid chromatography (HPLC) is analyzed, C in product12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2
N(CH3)2C3H7Cl contents are 96.62wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 4.3 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；162 grams of long-chain diaryl sulfonate is added thereto to again, adds enough sheets
Ground running water is configured to the solution of 30wt% to 553 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent composition HF-7.
【Embodiment 8】
The preparation of composition HF-8, preparation process：
(1) long-chain polyether nitrogen-containing compound (C26H45O(CHCH3CH2O)3(CH2CH2O)7CH2CH2 N(CH3)2C3H7Cl)
Synthesis with prepare：
373.0 grams of eicosyl phenol, 5.6 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, is heated to
When 80～90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, then with nitrogen displacement 3～4 times, by system
Reaction temperature is adjusted to 150 DEG C and is slowly passed through 179.9 grams of expoxy propane, and control pressure≤0.60MPa is cooled to 90 DEG C, vacuum
Low-boiling-point substance is removed, system reaction temperature is adjusted to 150 DEG C and is slowly passed through 360.0 grams of oxirane, control pressure by continuation
≤0.60MPa.After reaction terminates, neutralization, dehydration, obtain C after cooling26H45O(CHCH3CH2O)3(CH2CH2O)8H,
Yield 98.6wt%.
437 grams are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
C26H45O(CHCH3CH2O)3(CH2CH2O)8H and 57 gram of pyridine, is heated to 70 DEG C under stirring, slowly dripped with dropping funel
Plus 85 grams of thionyl chlorides, react 10 hours at 90 DEG C after completion of dropping.After reaction terminates, reactant is stood, cooling divides
Layer, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, after drying centre is obtained
Product C26H45O(CHCH3CH2O)3(CH2CH2O)7CH2CH2Cl, yield is 87.8%.
By C26H45O(CHCH3CH2O)3(CH2CH2O)7CH2CH2183 grams of Cl is added and is carried reflux condensate device, temperature
In meter, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (CH3)2Solution dropping funel is slowly dripped in flask, body
System remains alkalescent, stratification after reacting 10 hours.The saturated common salt water washing of heat will be used after the vacuum distillation of upper strata
5-6 time, obtain desired intermediate C26H45O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2, yield is
83%.
By 928 grams of C26H45O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2With 80 grams of chloro-propane inputs
In pressure reactor equipped with agitating device, in the case where KOH makees catalysts conditions, 4h is reacted under 0.2～0.3MPa pressure,
Jing high performance liquid chromatography (HPLC) is analyzed, C in product26H45O(CHCH3CH2O)3(CH2CH2O)7CH2CH2
N(CH3)2C3H7Cl contents are 96.77wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 103.9 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；115 grams of long-chain diaryl sulfonate is added thereto to again, adds enough sheets
Ground running water is configured to the solution of 30wt% to 717 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent composition HF-8.
【Embodiment 9】
The preparation of composition HF-9, preparation process：
(1) long-chain polyether nitrogen-containing compound (C10H21O(CHCH3CH2O)3(CH2CH2O)7CH2CH2 N(CH3)2C3H7Cl)
Synthesis with prepare：
172.0 grams of decane alcohol, 5.6 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, it is heated to 80～
When 90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, then with nitrogen displacement 3～4 times, system is reacted
Temperature is adjusted to 150 DEG C and is slowly passed through 179.9 grams of expoxy propane, and control pressure≤0.60MPa is cooled to 90 DEG C, is removed in vacuum
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 360.0 grams of oxirane, control pressure≤0.60MPa by low-boiling-point substance, continuation.
After reaction terminates, neutralization, dehydration, obtain C after cooling10H21O(CHCH3CH2O)3(CH2CH2O)8H, yield 98.7wt%.
325 grams are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
C10H21O(CHCH3CH2O)3(CH2CH2O)8H and 57 gram of pyridine, is heated to 70 DEG C under stirring, slowly dripped with dropping funel
Plus 85 grams of thionyl chlorides, react 10 hours at 90 DEG C after completion of dropping.After reaction terminates, reactant is stood, cooling divides
Layer, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, after drying centre is obtained
Product C10H21O(CHCH3CH2O)3(CH2CH2O)7CH2CH2Cl, yield is 88.1%.
By C10H21O(CHCH3CH2O)3(CH2CH2O)7CH2CH2137 grams of Cl is added and is carried reflux condensate device, temperature
In meter, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (CH3)2Solution dropping funel is slowly dripped in flask, body
System remains alkalescent, stratification after reacting 10 hours.The saturated common salt water washing of heat will be used after the vacuum distillation of upper strata
5-6 time, obtain desired intermediate C10H21O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2, yield is
83.7%.
By 739 grams of C10H21O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2With 80 grams of chloro-propane inputs
In pressure reactor equipped with agitating device, in the case where KOH makees catalysts conditions, 4h is reacted under 0.2～0.3MPa pressure,
Jing high performance liquid chromatography (HPLC) is analyzed, C in product10H21O(CHCH3CH2O)3(CH2CH2O)7CH2CH2
N(CH3)2C3H7Cl contents are 96.78wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 101 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；129.6 grams of long-chain diaryl sulfonate is added thereto to again, is added enough
Local running water is configured to the solution of 30wt% to 758 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product bubble
Foam agent composition HF-9.
【Embodiment 10】
The preparation of composition HF-10, preparation process：
(1) long-chain polyether nitrogen-containing compound (C14H29N(CH3)2C3H7Cl synthesis) and preparation：
By C14H29143 grams of Cl is added with reflux condensate device, thermometer, the four-hole boiling flask of agitator, is heated to 77 DEG C,
By N (CH3)2Solution dropping funel is slowly dripped in flask, and system remains alkalescent, and reaction stands after 10 hours
Layering.After the vacuum distillation of upper strata with saturated common salt water washing 5-6 time of heat, desired intermediate C will be obtained14H29N(CH3)2,
Yield is 88.7%.
By 739 grams of C14H29N(CH3)2In the 80 grams of chloro-propane pressure reactors of input equipped with agitating device,
KOH makees under catalysts conditions, and 4h is reacted under 0.2～0.3MPa pressure, and Jing high performance liquid chromatography (HPLC) is analyzed,
C in product14H29N(CH3)2C3H7Cl contents are 98.67wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 32.4 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；129.6 grams of long-chain diaryl sulfonate is added thereto to again, is added enough
Local running water is configured to the solution of 30wt% to 539 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product bubble
Foam agent composition HF-10.
【Embodiment 11】
The simulation water of salinity 50000mg/L is prepared, by a certain amount of foaming agent HF-1～HF-10 dissolvings, 0.15 is configured to
The solution of wt%.
Combinations of the above thing solution is taken respectively under the conditions of 60 and 300 DEG C, be 100 centimetres in length, a diameter of 3.8 centimetres are filled out
Foam blocking ability determination experiment is carried out in sand tube, the pressure reduction formed after record injection 1.0pV foams forms pressure reduction with water filling
Ratio, as resistance factor, the results are shown in Table shown in 2.
【Comparative example 1】
Use【Embodiment 1】The C of middle synthesis12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2 N(CH3)2C3H7Cl,
【Embodiment 2】The C of middle synthesis16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2
N(C2H5)(C3H7O)C2H5Br,【Embodiment 3】Middle synthesis
C14H29OCHCH3CH2O(CH2CH2O)30CH2CH2N(C3H7O)2C5H11Br,【Embodiment 4】Middle synthesis
C20H33OCHCH3CH2OCH2CH2OCH2CH2N(C3H7)(C5H11)CH3Cl,【Embodiment 5】Middle synthesis
C12H25O(CHCH3CH2O)20CH2CH2OCH2CH2N(CH3)(C2H5)C4H9The single dose of Cl, is added without subsequent component system
It is standby into foaming agent combination, together【Embodiment 11】Foaming properties test is carried out, be the results are shown in Table shown in 3.
【Comparative example 2】
Use【Embodiment 1-5】In long-chain diaryl sulfonate, be added without subsequent component and be prepared into foaming agent combination,
Together【Embodiment 11】Foaming properties test is carried out, be the results are shown in Table shown in 4.
【Comparative example 3】
Together【Embodiment 1】, difference is successively not reacted step by step with expoxy propane and oxirane,
But both are mixed into the reaction of later stepping row.179.9 grams of expoxy propane and 360.0 grams of rings are slowly passed through at 140～150 DEG C
Oxidative ethane mixture, control pressure≤0.60MPa, remaining is identical, obtains long-chain polyether nitrogen-containing compound, and together【Embodiment
1】The foaming agent combination LF-1 of corresponding proportion is prepared into, together【Embodiment 11】Foaming properties determination test result is carried out,
As a result 60 DEG C of resistance factors only have 37,300 DEG C of resistance factors there was only 10.
【Comparative example 4】
The preparation of composition LF-2, preparation process：
(1) long-chain polyether nitrogen-containing compound (C12H25O(CH2CH2O)8(CHCH3CH2O)2CHCH3CH2 N(CH3)2C3H7Cl)
Synthesis with prepare：
186.0 grams of dodecanols, 5.6 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, it is heated to 80～
When 90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, then with nitrogen displacement 3～4 times, system is reacted
Temperature is adjusted to 150 DEG C and is slowly passed through 360.0 grams of oxirane, and control pressure≤0.60MPa is cooled to 90 DEG C, is removed in vacuum
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 179.9 grams of expoxy propane, control pressure≤0.60MPa by low-boiling-point substance, continuation.
After reaction terminates, neutralization, dehydration, obtain C after cooling12H25O(CH2CH2O)8(CHCH3CH2O)3H, yield 98.8wt%.
339 grams are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
C12H25O(CH2CH2O)8(CHCH3CH2O)3H and 57 gram of pyridine, is heated to 70 DEG C under stirring, slowly dripped with dropping funel
Plus 85 grams of thionyl chlorides, react 10 hours at 90 DEG C after completion of dropping.After reaction terminates, reactant is stood, cooling divides
Layer, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, after drying centre is obtained
Product C12H25O(CH2CH2O)8(CHCH3CH2O)2CHCH3CH2Cl, yield is 88%.
By C12H25O(CH2CH2O)8(CHCH3CH2O)2CHCH3CH2143 grams of Cl is added and is carried reflux condensate device, temperature
In degree meter, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (CH3)2Solution dropping funel is slowly dripped in flask,
System remains alkalescent, stratification after reacting 10 hours.By the saturated common salt washing after the vacuum distillation of upper strata with heat
Wash 5-6 time, obtain desired intermediate C12H25O(CH2CH2O)8(CHCH3CH2O)2CHCH3CH2N(CH3)2, receive
Rate is 83%.
By 739 grams of C12H25O(CH2CH2O)8(CHCH3CH2O)2CHCH3CH2N(CH3)2With 80 grams of chloro-propanes
It is anti-under 0.2～0.3MPa pressure in the case where KOH makees catalysts conditions in pressure reactor of the input equipped with agitating device
Answer 4h, Jing high performance liquid chromatography (HPLC) analysis, in product
C12H25O(CH2CH2O)8(CHCH3CH2O)2CHCH3CH2N(CH3)2C3H7Cl contents are 96.67wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 84.6 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；Identical long-chain diaryl sulfonate in 129.6 grams of HF-1 is added thereto to again,
Enough local running water are added to 705 grams, the solution of 30wt% is configured to, 30min is sufficiently stirred for being completely dissolved
Till, obtain final product foaming agent combination LF-2.
Said composition is same【Embodiment 11】Foaming properties test is carried out, as a result 60 DEG C of resistance factors only have 30,300 DEG C of resistances
The factor only has 11.
【Comparative example 5】
It it is 100 centimetres in length under the conditions of 60 DEG C, a diameter of 3.8 centimetres, permeability is filled out in sand tube for 1000mD's
Carbon dioxide displacement is carried out after water drive, carbon dioxide injection 0.3pV is shown in gas.
Composition component structure in the embodiment of table 1
Sealing characteristics of the composition in the embodiment of table 2 in simulation water
Sealing characteristics of the composition in the comparative example 1 of table 3 in simulation water
Sealing characteristics of the composition in the comparative example 2 of table 4 in simulation water
Claims (10)
1. a kind of foaming agent combination, long-chain polyether nitrogen-containing compound in terms of molfraction including 1 part and
0.1～50 part of long-chain diaryl sulfosalt surfactant；
Wherein, the long-chain polyether nitrogen-containing compound, with general molecular formula shown in formula (I)：
The long-chain diaryl sulfosalt surfactant, with general molecular formula shown in formula (II)：
In formula (I), the R1For C10～C26Fat-based；Y=0～20, z=0～60；R4、R5、R6For C1～C5
Alkyl, replace alkyl in any one；R7For C1～C4Alkylidene；Y is selected to be made shown in formula (I)
Molecule is in electroneutral anion；J is the valence state of Y, and 1/j is the quantity of Y；In formula (II), the R2
For C10～C26Fat-based；The R3For H or C1～C26Fat-based；N, m be 0～3 integer or
Decimal and n+m>1；L is O, S ,-(CH2)1-3-、-OC2H4O-、-OC3H6One kind in O-；X is
At least one in alkali metal ion, alkaline-earth metal ions or ammonium ion, and when X is alkali metal ion or ammonium
During ion, a=n, b=m, when X is alkaline-earth metal ions, a=n/2, b=m/2.
2. foaming agent combination according to claim 1, it is characterised in that the R1For C10～C20Alkane
Base, alkylbenzene.
3. foaming agent combination according to claim 1, it is characterised in that the R7Preferably C2H4Or
C3H6。
4. foaming agent combination according to claim 1, it is characterised in that the z is more than 0.
5. foaming agent combination according to claim 1, it is characterised in that the y is more than 0.
6. foaming agent combination according to claim 1, it is characterised in that the R2For C12～C20Alkane
Any one in base.
7. foaming agent combination according to claim 1, it is characterised in that the R3For H or C1～C16
Alkyl in any one.
8. foaming agent combination according to claim 1, it is characterised in that the X is K+、Na+、NH4 +
In at least one.
9. foaming agent combination according to claim 1, it is characterised in that the nitrogenous chemical combination of the long-chain polyether
Thing is 1 with the mol ratio of long-chain diaryl sulfonate:0.2～10.
10. the preparation method of foaming agent combination described in claim 1, comprises the following steps：
(1) synthesis of long-chain polyether nitrogen-containing compound
A, in the presence of base catalyst, R1OH obtains R with aequum propylene oxide reaction1O
(CHCH3CH2O)yH；
B, in the presence of base catalyst, R1O(CHCH3CH2O)yH is obtained with aequum reacting ethylene oxide
R1O(CHCH3CH2O)y(CH2CH2O)z+1H；
C, by R1O(CHCH3CH2O)y(CH2CH2O)z+1H reacts Jing after processing with thionyl chloride and obtains
R1O(CHCH3CH2O)y(CH2CH2O)zR7Cl；
D, by R1O(CHCH3CH2O)y(CH2CH2O)z R7Cl and NR4R5In a solvent, in reaction temperature
70～90 DEG C of reactions obtain R Jing after processing1O(CHCH3CH2O)y(CH2CH2O)z R7NR4R5；
E, by R1O(CHCH3CH2O)y(CH2CH2O)z R7NR4R5With YR6In a solvent in base catalyst
Reaction obtains the long-chain polyether nitrogen-containing compound Jing after processing；
(2) preparation of foaming agent combination
The desired amount of long-chain polyether nitrogen-containing compound, long-chain diaryl sulfonate are well mixed and obtain described bubble
Foam agent composition.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573917A (en) * | 2017-10-18 | 2018-01-12 | 中国石油化工股份有限公司 | Solid foam water discharge agent composition and its preparation method and application |
| CN107603581A (en) * | 2017-10-18 | 2018-01-19 | 中国石油化工股份有限公司 | Efficient foam water discharge agent composition and its preparation method and application |
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| CN107603581A (en) * | 2017-10-18 | 2018-01-19 | 中国石油化工股份有限公司 | Efficient foam water discharge agent composition and its preparation method and application |
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