CN106590570A - High salinity oil reservoir gas drive foaming agent composition and preparation method thereof - Google Patents
High salinity oil reservoir gas drive foaming agent composition and preparation method thereof Download PDFInfo
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- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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Abstract
The invention relates to a high salinity oil reservoir gas drive foaming agent composition and a preparation method thereof, and mainly solves the problems that in an existing high salinity oil reservoir gas drive oil extraction process, foaming agents have poor salt resistance, can generate precipitate after encountering divalent ions, and the formed foams have low blocking capability. The foaming agent composition provided by the invention comprises the following components by mole fraction: 1 part of a long chain polyether nitrogen-containing compound and 0.1-50 parts of a long chain diphenyl ether sulfonate surfactant, wherein the long chain polyether nitrogen-containing compound has a general molecular formula shown as formula (I), the long chain diphenyl ether sulfonate surfactant has a general molecular formula shown as formula (II), the R1 is a fatty group of C10-C26, y is a chain segment sum, R4 and R5 are any one of alkyl and substituted alkyl of C1-C5, and R6 is alkylene of C1-C4. The technical scheme well solves the problems, and can be used for high salinity oil reservoir gas drive oil extraction.
Description
Technical field
The present invention relates to a kind of high salinity 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 technique, 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 foam 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 foam used for tertiary oil recovery adopts Recompounded multielement system mostly, while comprising nonionic surfactant 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 dodecylbenzene sodium sulfonate be foaming agent, foam stabilizer by modified guanidine glue, hydroxyethyl cellulose, 12
Alcohol is constituted, and dodecylbenzene sodium sulfonate is anion surfactant, and salt tolerance is relatively low.Patent CN1093589C is disclosed
A kind of foam compsoite oil drive method, wherein using the alkali of 0.5～1.5wt%, the surfactant of 0.05～0.5wt% and
The polymer composition foaming agent combination of 0.05～0.5wt%, because system contains inorganic base, to stratum and oil well injury is brought,
The problems such as causing etching apparatus and pipeline, and inorganic base can seriously reduce the viscosity of polymer, and the viscosity for needed for reaching is only
The concentration of polymer must be greatly improved, oil recovery integrated cost is improved.
Cation foam 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 foam 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
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, micelle, the higher surface activity 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 diphenyl ether sulfonate 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 intensified oil reduction foaming agent combination and preparation method.
The content of the invention
One of the technical problem to be solved is that foam salt resistance ability present in existing gas drive oil recovery process is poor, shape
Into the little problem of foam blocking ability, there is provided a kind of new foaming agent combination.Said composition has in salinity
Will not form foam and have the advantages that resistance factor is high with ion precipitation under the stratum water condition of 0～250000mg/L.
The two of the technical problem to be solved are to provide a kind of foam combination corresponding with technical problem one is solved
The preparation method of thing.
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
Fraction meter includes a long-chain polyether nitrogen-containing compound and 0.1～50 part of long-chain diphenyl ether sulfonate surfactant；
The long-chain polyether nitrogen-containing compound, with following general molecular formula：
The long-chain diphenyl ether sulfonate surfactant, with following general molecular formula：
In formula (I), the R1For C10～C26Fat-based；Y adds sum, y=0～20 for PO segments；Z adds for EO segments
Sum, z=0～60；R4、R5For C1～C5Alkyl, replace alkyl in any one；R6For C1～C4Alkylidene；
In formula (II), the R2For C10～C26Fat-based；The 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
One kind 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、R5For C1～C5Alkyl, replace alkyl in any one；It is wherein described
The substituent group in alkyl is replaced to be the substituted radicals such as hydroxyl substituent, halogenic substituent.
In above-mentioned technical proposal, the R6Preferably it is C2H4Or C3H6。
In above-mentioned technical proposal, the preferred version of the z is more than 0, more preferably less than equal to 30, more preferably
Z=1～20.
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 and z is while preferably greater than 0.In above-mentioned technical proposal, the R2For C10～C26
Fat-based, the fat-based can be able to be saturated carbon chains containing the group such as acyl group, carbonyl, ether, hydroxyl, also may be used
To contain unsaturated carbon chains, as the preferred R2Preferred version be C12～C20Alkyl.
In above-mentioned technical proposal, the R3For H or C1～C26Fat-based, the fat-based can containing acyl group, carbonyl,
The groups such as ether, hydroxyl, can be saturated carbon chains, it is also possible to containing unsaturated carbon chains, as preferred R3Preferred version
For H or C1～C16Alkyl.
In above-mentioned technical proposal, the preferred version of the X is K+、Na+、NH4 +In at least one；Long-chain polyether is nitrogenous
Compound is preferably 1 with the mol ratio of long-chain diphenyl ether sulfonate:0.2～10.
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 tap 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)zR6Cl；
D, by R1O(CHCH3CH2O)y(CH2CH2O)zR6Cl 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 R6NR4R5With hydrogen peroxide in 60～70 DEG C of reactions, Jing after processing
To long-chain polyether nitrogen-containing compound；
(2) preparation of foaming agent combination
The desired amount of long-chain polyether nitrogen-containing compound, long-chain diphenyl ether sulfonate mix homogeneously are obtained into foaming agent combination.
The key active ingredient of foam of the present invention is long-chain diphenyl ether 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 concentrated solution with water, is directly made into the foam 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 tap 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, polymer, alkali.
Long-chain diphenyl ether sulfonate belongs to Shuangzi type from structure in the foaming agent combination of the present invention so that its salt tolerance has
Very big raising, the agent can keep clear in the mineralized water of salinity 300000mg/L；Long-chain polyether nitrogen
Compound due to simultaneous with the functional group of yin, yang both sexes, while also non-ionic fragment, it may have preferable salt tolerance；
After two kinds of components compounding, the anionicsite of long-chain diphenyl ether sulfonate and the cationic moiety of long-chain polyether quaternary ammonium salt, due to
Electrostatic attraction effect between anions and canons foam opposite charges polar group so that foam agent molecule adsorbance on the surface
Increase, so as to the diffusion that the gas with the incomparable interface arrangement density of single foam, obstruction passes through liquid film, is allowed to
It is more readily 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 salt oil
During the steam nitrogen displacement of reservoir oil of Tibetan.
The foaming agent combination of the present invention, can effectively macropore plugging, experiment finds, salinity 250000mg/L,
Under conditions of 80 DEG C, the foam resistance factor that said composition is formed achieves preferable technique effect up to 150.
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 compositionss HF-1, preparation process：
(1) long-chain polyether nitrogen-containing compound (C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2O conjunction)
Into with 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 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 funnel
85 grams of thionyl chlorides of Deca, react 10 hours after completion of dropping at 90 DEG C.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 funnel is slowly dripped in flask,
System remains alkalescence, 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 C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2100 grams are added to reflux condensation mode dress
Put, in the four-hole boiling flask of thermometer, agitator, be heated to 60 DEG C, be slowly added dropwise H2O230 grams of solution, at 70 DEG C
Reaction 5 hours, with petroleum ether extraction, vacuum drying, analyzes, in product by high performance liquid chromatography (HPLC)
C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2O content is 97.72wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 77.3 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolution；138 grams of long-chain diphenyl ether sulfonate is added thereto to again, adds enough sheets
Ground tap water is configured to the solution of 30wt% to 713 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent compositionss HF-1.
【Embodiment 2】
The preparation of compositionss HF-2, preparation process：
(1) long-chain polyether nitrogen-containing compound (C16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2
N(C2H5)(C3H7O) O) synthesis with prepare：
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 funnel
35 grams of thionyl chlorides of Deca, react 10 hours after completion of dropping at 90 DEG C.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 funnel is slowly dripped to
In flask, system remains alkalescence, 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 C16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2N(C2H5)(C3H7O) 100 grams are added to and carry
In reflux condensate device, thermometer, the four-hole boiling flask of agitator, 60 DEG C are heated to, are slowly added dropwise H2O230 grams of solution,
React 5 hours at 70 DEG C, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, product
Middle C16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2N(C2H5)(C3H7O) O content is 96.32wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 19 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolution；78.1 grams of long-chain diphenyl ether sulfonate is added thereto to again, adds enough sheets
Ground tap water is configured to the solution of 30wt% to 321 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent compositionss HF-2.
【Embodiment 3】
The preparation of compositionss HF-3, preparation process：
(1) long-chain polyether nitrogen-containing compound (C14H29OCHCH3CH2O(CH2CH2O)30CH2CH2N(C3H7O)2O conjunction)
Into with preparation：
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 funnel
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 funnel is slowly dripped in flask,
System remains alkalescence, 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 C14H29OCHCH3CH2O(CH2CH2O)30CH2CH2N(C3H7O)2100 grams are added to reflux condensation mode dress
Put, in the four-hole boiling flask of thermometer, agitator, be heated to 60 DEG C, be slowly added dropwise H2O230 grams of solution, at 70 DEG C
Reaction 5 hours, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, in product
C14H29OCHCH3CH2O(CH2CH2O)30CH2CH2N(C3H7O)2O content is 96.71wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 183 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolution；15.5 grams of long-chain diphenyl ether sulfonate is added thereto to again, adds enough sheets
Ground tap water is configured to the solution of 30wt% to 642 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent compositionss HF-3.
【Embodiment 4】
The preparation of compositionss HF-4, preparation process：
(1) long-chain polyether nitrogen-containing compound (C20H33OCHCH3CH2OCH2CH2OCH2CH2N(C3H7)(C5H11) O)
Synthesis and preparation：
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 funnel
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 funnel slowly dripped in flask,
System remains alkalescence, 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 C20H33OCHCH3CH2OCH2CH2OCH2CH2N(C3H7)(C5H11) 100 grams be added to reflux condensation mode
In device, thermometer, the four-hole boiling flask of agitator, 60 DEG C are heated to, are slowly added dropwise H2O230 grams of solution, at 70 DEG C
Lower reaction 5 hours, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, in product
C20H33OCHCH3CH2OCH2CH2OCH2CH2N(C3H7)(C5H11) O content be 97.61wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 57.7 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolution；98 grams of long-chain diphenyl ether sulfonate is added thereto to again, adds enough sheets
Ground tap water is configured to the solution of 30wt% to 514 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent compositionss HF-4.
【Embodiment 5】
The preparation of compositionss HF-5, preparation process：
(1) long-chain polyether nitrogen-containing compound (C12H25O(CHCH3CH2O)20CH2CH2OCH2CH2N(CH3)(C2H5) O)
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 funnel
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 funnel slowly drips to flask
In, system remains alkalescence, 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 C12H25O(CHCH3CH2O)20CH2CH2OCH2CH2N(CH3)(C2H5) 100 grams be added to returned cold
In solidifying device, thermometer, the four-hole boiling flask of agitator, 60 DEG C are heated to, are slowly added dropwise H2O230 grams of solution, at 70 DEG C
Lower reaction 5 hours, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, in product
C12H25O(CHCH3CH2O)20CH2CH2OCH2CH2N(CH3)(C2H5) O content be 96.97wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 154 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolution；32.5 grams of long-chain diphenyl ether sulfonate is added thereto to again, adds enough sheets
Ground tap water is configured to the solution of 30wt% to 605 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Compositionss HF-5.
【Embodiment 6】
The preparation of compositionss HF-6, preparation process：
(1) long-chain polyether nitrogen-containing compound (C12H25O(CH2CH2O)7CH2CH2N(CH3)2O 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 funnel 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 funnel 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 C12H25O(CH2CH2O)7CH2CH2N(CH3)2100 grams are added to reflux condensate device, thermometer, stir
In mixing the four-hole boiling flask of device, 60 DEG C are heated to, are slowly added dropwise H2O230 grams of solution, reacts 5 hours at 70 DEG C, uses
Petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, C in product12H25O(CH2CH2O)7CH2CH2
N(CH3)2O content is 97.32wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 60 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolution；129.6 grams of long-chain diphenyl ether sulfonate is added thereto to again, is added enough
Local tap water is configured to the solution of 30wt% to 625 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent compositionss HF-6.
【Embodiment 7】
The preparation of compositionss HF-7, preparation process：
(1) long-chain polyether nitrogen-containing compound (C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2O conjunction)
Into with 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 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 funnel
85 grams of thionyl chlorides of Deca, react 10 hours after completion of dropping at 90 DEG C.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 funnel is slowly dripped in flask,
System remains alkalescence, 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 C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2100 grams are added to reflux condensation mode dress
Put, in the four-hole boiling flask of thermometer, agitator, be heated to 60 DEG C, be slowly added dropwise H2O230 grams of solution, at 70 DEG C
Reaction 5 hours, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, in product
C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2O content is 97.32wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 7.6 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolution；353 grams of long-chain diphenyl ether sulfonate is added thereto to again, adds enough sheets
Ground tap water is configured to the solution of 30wt% to 1202 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent compositionss HF-7.
【Embodiment 8】
The preparation of compositionss HF-8, preparation process：
(1) long-chain polyether nitrogen-containing compound (C26H45O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2O conjunction)
Into with preparation：
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 funnel
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 funnel is slowly dripped in flask, body
System remains alkalescence, 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 C26H45O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2100 grams are added to reflux condensation mode dress
Put, in the four-hole boiling flask of thermometer, agitator, be heated to 60 DEG C, be slowly added dropwise H2O230 grams of solution, at 70 DEG C
Reaction 5 hours, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, in product
C26H45O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2O content is 97.12wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 97.1 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolution；115 grams of long-chain diphenyl ether sulfonate is added thereto to again, adds enough sheets
Ground tap water is configured to the solution of 30wt% to 696 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent compositionss HF-8.
【Embodiment 9】
The preparation of compositionss HF-9, preparation process：
(1) long-chain polyether nitrogen-containing compound (C10H21O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2O conjunction)
Into with preparation：
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 funnel
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 funnel is slowly dripped in flask, body
System remains alkalescence, 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 C10H21O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2100 grams are added to reflux condensation mode dress
Put, in the four-hole boiling flask of thermometer, agitator, be heated to 60 DEG C, be slowly added dropwise H2O230 grams of solution, at 70 DEG C
Reaction 5 hours, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, in product
C10H21O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2O content is 97.33wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 94 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolution；129.6 grams of long-chain diphenyl ether sulfonate is added thereto to again, is added enough
Local tap water is configured to the solution of 30wt% to 737 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product bubble
Foam agent compositionss HF-9.
【Embodiment 10】
The preparation of compositionss HF-10, preparation process：
(1) long-chain polyether nitrogen-containing compound (C14H29N(CH3)2O 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 funnel is slowly dripped in flask, and system remains alkalescence, 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 C14H29N(CH3)2During 100 grams are added to reflux condensate device, thermometer, the four-hole boiling flask of agitator,
60 DEG C are heated to, H is slowly added dropwise2O230 grams of solution, reacts 5 hours at 70 DEG C, and with petroleum ether extraction, vacuum is done
It is dry, Jing high performance liquid chromatography (HPLC) analysis, C in product14H29N(CH3)2O content is 96.69wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 26.6 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolution；129.6 grams of long-chain diphenyl ether sulfonate is added thereto to again, is added enough
Local tap water is configured to the solution of 30wt% to 518 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent compositionss HF-10.
【Embodiment 11】
Respectively prepare (1) calcium ion concentration 5000mg/L, the simulation water I of total salinity 250000mg/L, (2) calcium from
Sub- concentration 3000mg/L, the simulation water II of total salinity 100000mg/L is molten by a certain amount of foam HF-1～HF-10
Solution, is configured to the solution of 0.15wt%.
Combinations of the above thing solution is taken under the conditions of 80 DEG C, be 100 centimetres in length, a diameter of 3.8 centimetres are filled out in sand tube
Row foam blocking ability determination experiment, the resistance formed after record injection foam balance forms the ratio of resistance with water filling, 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)7CH2CH2N(CH3)2O,【It is real
Apply example 2】The C of middle synthesis16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2N(C2H5)(C3H7O) O,【Implement
Example 3】The C of middle synthesis14H29OCHCH3CH2O(CH2CH2O)30CH2CH2N(C3H7O)2O,【Embodiment 4】Middle conjunction
Into C20H33OCHCH3CH2OCH2CH2OCH2CH2N(C3H7)(C5H11) O,【Embodiment 5】Middle synthesis
C12H25O(CHCH3CH2O)20CH2CH2OCH2CH2N(CH3)(C2H5) O single dose, 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 3.
【Comparative example 2】
Use【Embodiment 1-5】In long-chain diphenyl ether 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,
The foaming agent combination foam resistance factor that simulation water I is prepared only has 26, the foaming agent combination foam resistance that simulation water II is prepared
The power factor only has 10.
【Comparative example 4】
The preparation of compositionss LF-2, preparation process：
(1) long-chain polyether nitrogen-containing compound (C12H25O(CH2CH2O)8(CHCH3CH2O)2CHCH3CH2N(CH3)2O)
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, 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 funnel
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 funnel is slowly dripped in flask,
System remains alkalescence, 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 C12H25O(CH2CH2O)8(CHCH3CH2O)2CHCH3CH2N(CH3)2100 grams are added to reflux condensation mode
In device, thermometer, the four-hole boiling flask of agitator, 60 DEG C are heated to, are slowly added dropwise H2O230 grams of solution, at 70 DEG C
Lower reaction 5 hours, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, in product
C12H25O(CH2CH2O)8(CHCH3CH2O)2CHCH3CH2N(CH3)2O content is 97.62wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 77.3 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolution；Identical long-chain diphenyl ether sulfonate in 129.6 grams of HF-1 is added thereto to again,
Enough local tap waters are added to 684 grams, the solution of 30wt% is configured to, be sufficiently stirred for 30min to be completely dissolved for
Only, foaming agent combination LF-2 is obtained final product.
Said composition is same【Embodiment 11】Carry out foaming properties test, the foaming agent combination foam resistance that simulation water I is prepared
The factor only has 10, and the foaming agent combination foam resistance factor that simulation water II is prepared only has 7.
【Comparative example 5】
Dodecylbenzene sodium sulfonate is dissolved separately in simulation water I and simulation water II, foam mass fraction is 0.5%, is mixed
Conjunction forms foam aqueous solution, and Precipitation is arranged at solution bottom.
Composition component structure in the embodiment of table 1
| Foam | R1 | y | z | R4 | R5 | R6 | R2 | R3 | m+n | a+b | L | X | I and II mol ratio |
| HF-1 | C12H25 | 3 | 7 | CH3 | CH3 | C2H4 | C16H33 | CH3 | 2.0 | 2.0 | OC2H4O | K | 1:2 |
| HF-2 | C16H33 | 10 | 20 | C2H5 | C3H7O | C2H4 | C20H41 | H | 3.0 | 3.0 | C3H6 | Na | 1:10 |
| HF-3 | C14H29 | 1 | 30 | C3H7O | C3H7O | C2H4 | C12H25 | C8H17 | 2.7 | 2.7 | CH2 | K | 1:0.2 |
| HF-4 | C20H33 | 1 | 1 | C3H7 | C5H11 | C2H4 | C12H25 | C16H33 | 4.0 | 4.0 | O | Na | 1:1 |
| HF-5 | C12H25 | 20 | 1 | C2H5 | CH3 | C2H4 | C16H33 | C2H5 | 2.3 | 2.3 | CH2 | NH4 | 1:0.5 |
| HF-6 | C12H25 | 0 | 7 | CH3 | CH3 | C2H4 | C16H33 | CH3 | 2.0 | 2.0 | O | K | 1:2 |
| HF-7 | C12H25 | 3 | 7 | CH3 | CH3 | C3H6 | C16H33 | CH3 | 2.0 | 2.0 | OC3H6O | K | 1:50 |
| HF-8 | C26H45 | 3 | 7 | CH3 | CH3 | C2H4 | C10H21 | CH3 | 2.0 | 2.0 | C2H4 | K | 1:2 |
| HF-9 | C10H21 | 3 | 7 | CH3 | CH3 | C2H4 | C16H33 | CH3 | 2.0 | 2.0 | O | K | 1:2 |
| HF-10 | C12H25 | 0 | 0 | CH3 | CH3 | C2H4 | C16H33 | CH3 | 2.0 | 2.0 | CH2 | K | 1:2 |
Sealing characteristics of the compositionss in the embodiment of table 2 in simulation water
| Foam | HF-1 | HF-2 | HF-3 | HF-4 | HF-5 | HF-6 | HF-7 | HF-8 | HF-9 | HF-10 |
| The resistance factor of simulation water I | 180 | 170 | 175 | 180 | 170 | 146 | 147 | 141 | 136 | 136 |
| The resistance factor of simulation water II | 154 | 161 | 167 | 147 | 136 | 131 | 113 | 111 | 117 | 106 |
Sealing characteristics of the compositionss in the comparative example 1 of table 3 in simulation water
Sealing characteristics of the compositionss in the comparative example 2 of table 4 in simulation water
Claims (10)
1. a kind of foaming agent combination, with molar fraction, including 1 part long-chain polyether nitrogen-containing compound and
0.1～50 part of long-chain diphenyl ether sulfonate surfactant；
Wherein, the long-chain polyether nitrogen-containing compound, with general molecular formula shown in formula (I)：
The long-chain diphenyl ether sulfonate surfactant, with following general molecular formula：
In formula (I), the R1For C10～C26Fat-based；Y adds sum, y=0～20 for PO segments；Z is EO
Segment adds sum, z=0～60；R4、R5For C1～C5Alkyl, replace alkyl in any one；R6 is
C1～C4Alkylidene；In formula (II), the R2For C10～C26Fat-based；The R3For H or C1～C26
Fat-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 the one kind in alkali metal ion, alkaline-earth metal ions or ammonium ion, and works as X
For alkali metal ion or ammonium ion when, a=n, b=m, when X be alkaline-earth metal ions when, 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 R6Preferably it is C2H4
Or C3H6。
4. foaming agent combination according to claim 1, it is characterised in that the z be more than 0 less than etc.
In 30.
5. foaming agent combination according to claim 1, it is characterised in that y=1～20.
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 diphenyl ether 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)zR6Cl；
D, by R1O(CHCH3CH2O)y(CH2CH2O)zR6Cl and NR4R5In a solvent, in reaction temperature
70～90 DEG C of reactions of degree obtain R Jing after processing1O(CHCH3CH2O)y(CH2CH2O)z R7NR4R5；
E, by R1O(CHCH3CH2O)y(CH2CH2O)z R6NR4R5React at 60～70 DEG C with hydrogen peroxide,
Long-chain polyether nitrogen-containing compound is obtained Jing after processing；
(2) preparation of foaming agent combination
The desired amount of long-chain polyether nitrogen-containing compound, long-chain diphenyl ether sulfonate mix homogeneously are obtained into foam combination
Thing.
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| US11629283B2 (en) | 2019-01-02 | 2023-04-18 | Petrochina Company Limited | N,N,N′,N′-tetradodecyl-substituted diphenyl ether sulfonate anionic Gemini surfactant and synthesis method thereof |
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