CN106946743B - A kind of gemini cationic surfactant and preparation method thereof and fracturing fluid - Google Patents
A kind of gemini cationic surfactant and preparation method thereof and fracturing fluid Download PDFInfo
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- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
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Abstract
The present invention provides a kind of gemini cationic surfactants, have Formulas I structure: in Formulas I, R is the alkyl that carbon atom number is 10~30, and n is 11~17；M is 2~6；X is O or N；Y is halogen.Compared with prior art, the present invention passes through cleverly Molecular Design, it is combined together self-degradation, spontaneous airway dysfunction are innovative, provide it is a kind of and meanwhile have inorganic salts dosage it is low, can self-degradation, from the fracturing fluid of the superior performances such as anger, product is hydrophilic small molecules and lipophilic molecules after this fracturing fluid degradation, it is harmless to stratum, thus need not the row of returning.The present invention also provides a kind of preparation method of gemini cationic surfactant and fracturing fluids.
Description
Technical field
The present invention relates to hydraulic fracturing technology field more particularly to a kind of gemini cationic surfactant and its preparation sides
Method and fracturing fluid.
Background technique
The surfactant type fracturing fluid of domestic application receives its industrial applications due to having the following problems at present
Limitation: it first is that the electrostatic repulsion forces between single-stranded surfactant head are bigger, need to be added a large amount of salt to shield, matches
It is bigger to set salt amount needed for fracturing fluid；Second is that at present surfactant carbon chain lengths it is shorter, the fracturing fluid configured it is resistance to
Warm ability is poor, general≤60 DEG C；Third is that more for domestic old filed, reservoir pressure coefficient reduces obvious, fracturing fluid recovery (backflow)
Difficulty is easy to cause secondary injury to reservoir, while returning drain and being also easy to bring serious problem of environmental pollution.
In view of the above problems, patent CN103756662 discloses a kind of multi-functional not row's of returning surfactant fracturing fluid.It should
Invention design has synthesized a kind of Gemini surface active of bis- oleyldimethylammonium chloride compositions of hexa-methylene α-and ω-, point
Containing there are two hydrophilic, lipophilic group in son, by the covalent bond structure of cis-double bonds by the ion of two surfactant molecules
Head base connects, and the electrical charge rejection between ion head base is effectively prevented to act on, and a small amount of inorganic salts only need to be added can
The intermeshing network structure of vermiculate glues is formed it into, solid-carrying performance is excellent, and experiment shows that this kind of fracturing fluid is not necessarily to the row of returning,
It is also smaller to the damage on stratum.It is the degradable list containing ester bond or amido bond that patent US7704926, which discloses a kind of main component,
The fracturing fluid of chain cationic surfactant.The invention is by introducing and can break in common single-stranded cationic surfactant molecule
The ester bond or amido bond split allows to issue raw degradation in certain pH environment and temperature condition, loses surface-active.To
It avoids after surfactant molecule encounters crude oil in fracturing process, forms emulsion particle, subsequent oil displacement process is caused not
Benefit influences.
In addition, the processing of de-plugging energization is carried out to oil well using self generating gas system in oil extraction in oil field technology, it can be effectively
Improve stratum permeability, increase stratum energy, adjustment stratigraphic section and improve fracturing fluid recovery (backflow) rate, reaches and improve oil production
Target.Certainly angry technology common at present is the compound system that one or two kinds of chemical components and multiple additives are formed,
After injecting stratum, angry system reaction is made to generate a large amount of CO under catalyst or certain stratum temperature action2Or alkaline gas,
Increase stratum energy, reduce oil water interfacial tension, reduce viscosity of crude, promotes fracturing fluid recovery (backflow).Patent US4178993 is disclosed
It is a kind of to react the technical solution for generating a large amount of nitrogen and carrying out de-plugging energization at a certain temperature using sodium nitrite and ammonium chloride.
Patent CN101671553A is using sodium nitrite and foaming agent as A agent, ammonium chloride, ethylenediamine tetra-acetic acid, acidic materials catalyst
It is made with foam stabilizer as B agent spherical, A agent and B agent mix under formation conditions and generate gas and release heat, reach energization
Purpose.However gas producing agent and acid solution cannot all mix these methods on the ground in the construction process, need using isolation
Liquid, the injection of multistage plug, complicated construction technique.
Synthesis apparently, do not report while having the pressure of low inorganic salts dosage, self-degradation and spontaneous airway dysfunction by the prior art
Liquid is split, to meet the use demand in market.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of gemini cationic surfactants and preparation method thereof and pressure
Split liquid, the present invention provide fracturing fluid made from gemini cationic surfactant have simultaneously low inorganic salts dosage, self-degradation and
Spontaneous airway dysfunction.
The present invention provides a kind of gemini cationic surfactants, have Formulas I structure:
In Formulas I, R is the alkyl that carbon source subnumber is 10~30, and n is 11~17；M is 2~6；X is O or N；Y is halogen.
The present invention provides a kind of preparation methods of gemini cationic surfactant described in above-mentioned technical proposal, including
Following steps:
(1) 1 structural compounds of formula and bis- (trichloromethyl) carbonic esters are reacted, obtains 2 structural compounds of formula；
(2) 2 structural compounds of formula are reacted with 3 structural compounds of formula, obtains 4 structural compounds of formula；
(3) 4 structural compounds of formula are reacted with 5 structural compounds of formula, obtains the Shuangzi cationic surface of Formulas I structure
Activating agent；
Wherein, the R in formula 1, formula 2, formula 4 and Formulas I is the alkyl that carbon atom number is 10~30；
X in formula 3, formula 4 and Formulas I is O or N, and n is 11~17；
It is halogen that m in formula 5 and Formulas I, which is 2~6, Y,.
Preferably, the temperature reacted in the step (1) is 35~150 DEG C, and the time of reaction is 0.5~10 hour.
Preferably, the reaction in the step (2) carries out in the presence of a catalyst.
The present invention provides a kind of fracturing fluids, including gemini cationic surfactant described in above-mentioned technical proposal.
Preferably, the fracturing fluid includes:
Gemini cationic surfactant described in above-mentioned technical proposal；
Crosslinking agent；
Water.
Preferably, the crosslinking agent is selected from potassium chloride, ammonium chloride, sodium chloride, potassium bromide, ammonium bromide, sodium bromide or bigcatkin willow
Sour sodium.
Preferably, mass content of the gemini cationic surfactant in fracturing fluid is 0.5~3%.
Preferably, mass content of the crosslinking agent in fracturing fluid is 0.5~3%.
Preferably, the fracturing fluid further includes pH adjusting agent.
Compared with prior art, the present invention is innovative by self-degradation, spontaneous airway dysfunction by cleverly Molecular Design
Be combined together, provide it is a kind of and meanwhile have inorganic salts dosage it is low, can self-degradation, from the pressure break of the superior performances such as anger
Liquid, product is hydrophilic small molecules and lipophilic molecules after the degradation of this fracturing fluid, harmless to stratum, thus need not the row of returning.This
The key component of fracturing fluid is the gemini cationic surfactant containing a kind of special construction in invention:
This surfactant can be self-assembly of vermiculate glues in aqueous solution and further occurrence tangles to be formed
Reticular structure, to achieve the purpose that increasing stick to meet the needs of fracturing fluid takes sand.Surfactant self assembly in aqueous solution
Behavior is mainly determined that hydrophobic tail is longer by the structure of its hydrophobic tail and hydrophilic head base, and the repulsion between hydrophilic head base is made
With smaller, be more conducive to assembling and form vermiculate glues, but dissolubility is deteriorated simultaneously.Single-stranded surfactant in the prior art
Molecule causes it to be more likely to be self-assembly of globular micelle in aqueous solution because of the electrical charge rejection effect between hydrophilic head base,
It thus needs to be added a large amount of inorganic salts to shield the charge of hydrophilic head base, its self assembly pattern is promoted to be changed by globular micelle
Vermiculate glues.And the surfactant molecule with longer hydrophobic carbochain is because that raw material is difficult to obtain is with high costs, and dissolves
Property is very poor to be difficult to practical application.The gemini cationic surfactant that the present invention uses joined chemistry between hydrophilic head base
Key can form hydrogen bond between hydrophilic head base simultaneously because using carbamate bond structure, common chemically and physically
Reduce the repulsive interaction between hydrophilic head base under effect, thus the dosage of inorganic salts can be greatly reduced, and further increase
Its increasing stick effect.
Cationic surfactant fracturing fluid is also easy to adsorb in rock surface in the prior art, makes originally in hydrophilic
Rock surface becomes hydrophobic and formation damage and broken glue is caused to be not thorough, if while also continuing being deposited in reservoir after pressure break
In, it can be plucked out of together with crude oil in subsequent oil recovery process and cause emulsification of crude oil problem, thus must the row of returning.In the present invention
Surfactant molecule can at suitable pH with the urethane bond for connecting hydrophobic chain and hydrophilic head base under the action of temperature
With fracture, so that surfactant molecular degradation is at electrically charged polar micromolecules and nonpolar hydrophobic carbochain.And it had been broken
It can produce gas in journey, achieve the purpose that energization, polar micromolecules product can be adsorbed on rock surface, do not changing rock profit
Clay stabilizer is served as while moist, hydrophobic carbochain, which can be dissolved directly into crude oil, to be produced together without causing crude oil newborn
Change, thus will not both damage stratum will not interfere subsequent oil recovery process, while broken glue is also more complete, is not required to the row of returning.
Therefore, gemini cationic surfactant provided by the invention is prepared fracturing fluid while there is inorganic salts use
Amount is few, can self-degradation and from angry function, sand carrying effect is good, without the row of returning.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the structural schematic diagram of gemini cationic surfactant provided by the invention；
Fig. 2 is that viscosity changes with time sample 1 at different temperatures in table 1；
Fig. 3 is that viscosity changes with time sample 1 at different temperatures in table 2；
Fig. 4 is that viscosity changes with time sample 1 at different temperatures in table 3；
Fig. 5 is that the obtained fracturing fluid of embodiment 7 degrade after different time under 90 DEG C of condition of different pH in 25 DEG C of tests
Viscosity variation；
Fig. 6 is that the obtained fracturing fluid of embodiment 8 degrade after different time under 90 DEG C of condition of different pH in 25 DEG C of tests
Viscosity variation；
Fig. 7 is that the obtained fracturing fluid of embodiment 9 degrade after different time under 90 DEG C of condition of different pH in 25 DEG C of tests
Viscosity variation.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The present invention provides a kind of gemini cationic surfactants, have Formulas I structure:
In Formulas I, R is the alkyl that carbon atom number is 10~30, preferably carbon atom number be 14~18 straight chained alkyl, it is more excellent
It is selected as-C16H33Or-C18H37；
N is 11~17, preferably 12~16, more preferably 13~15；
M is 2~6, preferably 2~4；
X is O or N；
Y is halogen, preferably Cl or Br.
Fig. 1 is the structural schematic diagram of gemini cationic surfactant provided by the invention, including the drop connecting with ion
Solve group, the spacer group between ion.
The present invention provides a kind of preparation methods of gemini cationic surfactant described in above-mentioned technical proposal, including
Following steps:
(1) 1 structural compounds of formula and bis- (trichloromethyl) carbonic esters are reacted, obtains 2 structural compounds of formula；
(2) 2 structural compounds of formula are reacted with 3 structural compounds of formula, obtains 4 structural compounds of formula；
(3) 4 structural compounds of formula are reacted with 5 structural compounds of formula, obtains the Shuangzi cationic surface of Formulas I structure
Activating agent；
Wherein, the R in formula 1, formula 2, formula 4 and Formulas I is the alkyl that carbon atom number is 10~30；
X in formula 3, formula 4 and Formulas I is O or N, and n is 11~17；
It is halogen that m in formula 5 and Formulas I, which is 2~6, Y,.
In the present invention, the R in formula 1, formula 2, formula 4 and Formulas I is consistent with R described in above-mentioned technical proposal；Formula 3, formula 4 and Formulas I
In X and n it is consistent with X described in above-mentioned technical proposal and n；M and Y mono- described in m and Y and above-mentioned technical proposal in formula 5 and Formulas I
It causes；Details are not described herein.
In the present invention, the compound solution of 1 structure of formula is preferably added drop-wise to bis- (trichloromethyl) carbon in the step (1)
In acid esters (BTC) solution, the dropping temperature is preferably 0~5 DEG C.In the present invention, the 1 structural compounds solution of formula and double
Solvent in (trichloromethyl) carbonic ester (BTC) solution is preferably homogeneous solvent, preferably toluene, dimethylbenzene or chlorobenzene.At this
In invention, the reaction in the step (1) preferably carries out under stirring conditions.In the present invention, reaction in the step (1)
Temperature be preferably 35~150 DEG C, more preferably 50~120 DEG C, most preferably 80~100 DEG C.In the present invention, the step
(1) time reacted in is preferably 0.5~10 hour, more preferably 1~8 hour, most preferably 3~6 hours.
In the present invention, it is described after the reaction was completed, preferably by obtained reaction product lead to nitrogen to remove hydrogen chloride gas
After recycle organic solvent, obtain 2 structural compounds of formula.In the present invention, the method for recycling organic solvent is preferably distilled.
In the present invention, the reaction temperature in the step (2) is preferably 20~30 DEG C；Reaction time is preferably 6~18
Hour, more preferably 10~14 hours.In the present invention, the reaction in the step (2) preferably in the presence of a catalyst into
Row, the catalyst is preferably dibutyltin dilaurate.In the present invention, the reaction in the step (2) is preferably in height
Temperature is lower to be carried out, and the temperature of the high temperature is preferably 35~45 DEG C.Reaction in step (2) of the present invention is in catalyst and hot conditions
Lower progress can accelerate reaction speed.
In the present invention, the temperature reacted in the step (3) is preferably 50~100 DEG C, and more preferably 60~80 DEG C；Instead
The time answered is preferably 48~72 hours.In the present invention, the reaction in the step (3) preferably under stirring conditions into
Row.In the present invention, the step (3) preferably obtained reaction product is distilled off after the reaction was completed therein organic molten
Agent obtains the compound of Formulas I structure.
In the present invention, the molar ratio of 1 structural compounds of formula and bis- (trichloromethyl) carbonic esters is preferably 1:(0.3
~0.4), more preferably 1:0.35；The molar ratio of 3 structural compounds of 2 structural compounds of formula and formula is preferably 1:(0.8~1.2),
More preferably 1:1；The molar ratio of 5 structural compounds of 4 structural compounds of formula and formula is preferably 1:(0.3~0.7), more preferably 1:
0.5.The present invention is to 1 structural compounds of formula, bis- (trichloromethyl) carbonic esters, 5 structural compounds of 3 structural compounds of formula and formula
Source there is no special limitation, method well known to those skilled in the art synthesis can be used, can also be bought and be obtained by market.
The present invention provides a kind of fracturing fluids, including gemini cationic surfactant described in above-mentioned technical proposal.?
In the present invention, the fracturing fluid preferably includes gemini cationic surfactant；Crosslinking agent；Water.In the present invention, the Shuangzi
Cationic surfactant is gemini cationic surfactant described in above-mentioned technical proposal, and details are not described herein.In this hair
In bright, mass content of the gemini cationic surfactant in fracturing fluid is preferably 0.5~3%, more preferably 1~
2.5%, most preferably 1.5~2%.In the present invention, the crosslinking agent is preferably selected from potassium chloride, ammonium chloride, sodium chloride, bromination
Potassium, ammonium bromide, sodium bromide or sodium salicylate, more preferably ammonium chloride.In the present invention, matter of the crosslinking agent in fracturing fluid
Measuring content is preferably 0.5~3%, and more preferably 1~2.5%, most preferably 1.5~2%.In the present invention, the water is preferred
For deionized water.It is also preferable to include pH adjusting agent in fracturing fluid provided by the invention, the reservoir according to applied by fracturing fluid
Condition (pH value, temperature of reservoir itself etc.) selection addition pH adjusting agent itself.In the present invention, the pH adjusting agent makes
The pH value of fracturing fluid is in the range of 6.8~8.5.The present invention can adjust its degradation speed by adjusting the pH value of fracturing fluid.?
In the present invention, the pH adjusting agent is preferably alkali compounds, such as sodium hydroxide, potassium hydroxide, triethylamine or sodium bicarbonate,
In view of the dissolution equilibrium of carbon dioxide is preferably sodium bicarbonate.In the present invention, the pH value of the fracturing fluid be preferably 6.5~
8.5。
The present invention does not have special limitation to the preparation method of the fracturing fluid, using pressure well known to those skilled in the art
Prepared by the preparation method for splitting liquid, can such as be prepared by the following method:
By gemini cationic surfactant, crosslinking agent and water stirring and dissolving, fracturing fluid is obtained.PH value is added if necessary
Regulator.
Fracturing fluid provided by the invention may be used as well and wellfracturing, and required inorganic salts dosage is few, and increasing stick effect is good；
And may occur from degrading at the formation temperature, unchanged layer wetability, to stratum fanout free region, without the row of returning；Simultaneously with drop
The releasable carbon dioxide gas of solution preocess supplements stratum energy.
Raw material used in following embodiment of the present invention and equipment are commercial goods, limited using the resistance to lucky reagent of Town in Shanghai
Octadecylamine, the N of company's production, N- dimethylethanolamine；Bis- (three chloromethanes of Sinopharm Chemical Reagent Co., Ltd.'s production
Base) carbonic ester, glycol dibromide, ammonium chloride, dibutyltin dilaurate, acetone, methylene chloride.
Four-hole boiling flask, two mouth flask and the single-necked flask produced using Beijing Xin Weier glass apparatus Co., Ltd is used
The EUROSTAR type magnetic heating stirrer of German IKA company production is heated and is stirred, using TAAR-G2 produced in USA
Type Multifunctional flow measurer can be carried out test to the viscosity and degradability of fracturing fluid.
Embodiment 1C18- urethane bond-dimethyl amine (surfactant 1) synthesis
C18- urethane bond-dimethyl amine synthesis synthetic route is as follows:
Bis- (three are added in the four-hole boiling flask that mechanical agitator, thermometer, constant pressure funnel, reflux condensing tube are housed
Chloromethyl) carbonic ester 29.7g (0.1mol) and methylene chloride (70mL), stirring is opened, is cooled to 0~5 DEG C.Octadecylamine (is closed
At (1) compound in route) (methylene chloride (90mL) solution of 0.3mol is through constant pressure funnel with the left side 1.5mL/min by 80.7g
Right speed instills in reaction system, after being added dropwise, is stirred at room temperature after 0.5h and is warming up to 50 DEG C of back flow reaction 5h again.Instead
It should terminate, lead to nitrogen and remove hydrogen chloride gas, steam product octadecylisocyanate after vacuum distillation recycling methylene chloride and (close
At (2) compound 69.4g, yield 78.2% in route).
Octadecylisocyanate 29.5g (0.1mol) is added in single-necked flask, N, N- dimethylethanolamine 8.9g
(0.1mol), dibutyltin dilaurate 1mL, methylene chloride 100mL open magnetic agitation, react at room temperature 8h.Reaction terminates
Afterwards, reaction solution is washed with 100mL, isolates organic phase, methylene chloride is removed in vacuum after anhydrous sodium sulfate is dry and obtains product 18
Alkylamino formic acid dimethylaminoethanol ester ((3) compound in synthetic route) (36.2g, yield 94.3%).
Equipped with reflux condensing tube two mouth flask in be added 18 carbamic acid dimethylaminoethanol esters (38.4g,
0.1mol), 1,2- Bromofume (11.3g, 0.06mol), acetone 80mL open magnetic agitation, and temperature rising reflux reacts 36h,
Filtering, obtains solid white powder shape dication surfactant products ((4) compound in synthetic route) (38.2g, yield
80%).
Nucleus magnetic hydrogen spectrum detection, detection are carried out to the dication surfactant products that the embodiment of the present invention 1 is prepared
As a result it is1H-NMR(500MHz,Chloroform-d)δ5.34(s,1H),4.52(s,2H),3.68(s,2H),3.52(s,
2H), 3.14 (d, 8H), 1.61 (s, 2H), 1.26 (m, 31H), 0.89 (s, 3H), dication surfactant have following knot
Structure:
Embodiment 2C16- urethane bond-dimethyl amine (surfactant 2) synthesis
Synthetic route is similar to Example 1, compound (1) octadecylamine in synthetic route is replaced with cetylamine, specifically
Synthesis mode are as follows:
Bis- (three are added in the four-hole boiling flask that mechanical agitator, thermometer, constant pressure funnel, reflux condensing tube are housed
Chloromethyl) carbonic ester 29.7g (0.1mol) and methylene chloride (70mL), stirring is opened, is cooled to 0~5 DEG C.By cetylamine
Methylene chloride (90mL) solution of 72.5g (0.3mol) instills reaction through constant pressure funnel with the speed of 1.5mL/min or so
In system, after being added dropwise, it is stirred at room temperature after 0.5h and is warming up to 50 DEG C of back flow reaction 5h again.Reaction terminates, and logical nitrogen removes
De-chlorine hydride gas, vacuum distillation steam product hexadecyl isocyanate (65g, yield 81%) after recycling methylene chloride.
Hexadecyl isocyanate 26.7g (0.1mol) is added in single-necked flask, N, N- dimethylethanolamine 8.9g
(0.1mol), dibutyltin dilaurate 1mL, methylene chloride 100mL open magnetic agitation, react at room temperature 8h.Reaction terminates
Afterwards, reaction solution is washed with 100mL, isolates organic phase, methylene chloride is removed in vacuum after anhydrous sodium sulfate is dry and obtains product 16
Alkylamino formic acid dimethylaminoethanol ester (34.8g, yield 97.6%).
Equipped with reflux condensing tube two mouth flask in be added hexadecane carbamic acid dimethylaminoethanol ester (35.7g,
0.1mol), 1,2- Bromofume (11.3g, 0.06mol), acetone 80mL open magnetic agitation, and temperature rising reflux reacts 36h,
Filtering, obtains solid white powder shape dication surfactant products (36.5g, yield 81%).
Detected according to the method in embodiment 1, testing result is, double sun that the embodiment of the present invention 2 is prepared from
Sub- surfactant has a structure that
Embodiment 3C18- urethane bond-dimethyl hydroxyl propylamine (surfactant 3) synthesis
Synthetic route is similar to Example 1,1, the 2- Bromofume in embodiment 1 is replaced with epoxychloropropane, specifically
Synthesis mode are as follows:
Bis- (three are added in the four-hole boiling flask that mechanical agitator, thermometer, constant pressure funnel, reflux condensing tube are housed
Chloromethyl) carbonic ester 29.7g (0.1mol) and methylene chloride (70mL), stirring is opened, is cooled to 0~5 DEG C.By octadecylamine
Methylene chloride (90mL) solution of 80.7g (0.3mol) instills reaction through constant pressure funnel with the speed of 1.5mL/min or so
In system, after being added dropwise, it is stirred at room temperature after 0.5h and is warming up to 50 DEG C of back flow reaction 5h again.Reaction terminates, and logical nitrogen removes
De-chlorine hydride gas, vacuum distillation steam product octadecylisocyanate (69.4g, yield after recycling methylene chloride
78.2%).
Octadecylisocyanate 29.5g (0.1mol) is added in single-necked flask, N, N- dimethylethanolamine 8.9g
(0.1mol), dibutyltin dilaurate 1mL, methylene chloride 100mL open magnetic agitation, react at room temperature 8h.Reaction terminates
Afterwards, reaction solution is washed with 100mL, isolates organic phase, methylene chloride is removed in vacuum after anhydrous sodium sulfate is dry and obtains product 18
Alkylamino formic acid dimethylaminoethanol ester (36.2g, yield 94.3%).
Equipped with reflux condensing tube two mouth flask in be added 18 carbamic acid dimethylaminoethanol esters (38.4g,
0.1mol), epoxychloropropane (5.6g, 0.06mol), acetone 80mL open magnetic agitation, and temperature rising reflux reacts 36h, mistake
Filter, obtains solid white powder shape dication surfactant products (36.2g, yield 78%).
It is detected according to method described in embodiment 1, testing result is dication prepared by the embodiment of the present invention 3
Surfactant has a structure that
Embodiment 4
The dication surfactant that embodiment 1 is prepared is dissolved in deionized water, is added after being completely dissolved
Ammonium chloride and sodium salicylate, are prepared fracturing fluid.
Surfactant, the mass content of ammonium chloride and sodium salicylate and obtained pressure break liquid status are as shown in table 1.Table
The state of 1 fracturing fluid obtained for the embodiment of the present invention 4.
The state for the fracturing fluid that 1 embodiment of the present invention 4 of table obtains
Fig. 2 is that viscosity changes with time sample 1 at different temperatures in table 1, under fixed shear frequency, with temperature
Increase, fracturing fluid viscosity decline, but in a short time (1h) keep stablize, even and if under the high temperature conditions (110 DEG C), viscosity
Also up to 28mPas, meet oil gas field requirement.
By table 2 and Fig. 2 it is found that sodium salicylate, which is added, can effectively improve the Krafft's point of surfactant solution, make it
Temperature tolerance improves, but can reduce its solubility, thus is more suitable for temperature reservoirs.
Embodiment 5
It is identical as the method that embodiment 4 prepares fracturing fluid, dication surfactant prepared by embodiment 1 is replaced with
Dication surfactant prepared by embodiment 2.
Surfactant, the mass content of ammonium chloride and sodium salicylate and obtained pressure break liquid status are as shown in table 2.Table
The state of 2 fracturing fluids obtained for the embodiment of the present invention 5.
The state for the fracturing fluid that 2 embodiment of the present invention 5 of table obtains
Fig. 3 is that viscosity changes with time sample 1 at different temperatures in table 2, under fixed shear frequency, with temperature
Increase, fracturing fluid viscosity decline, but in a short time (1h) keep stablize, even and if under the high temperature conditions (110 DEG C), viscosity
Also up to 31mPas, meet oil gas field requirement.
By table 2 and Fig. 3 it is found that sodium salicylate, which is added, can effectively improve the Krafft's point of surfactant solution, make it
Temperature tolerance improves, but can reduce its solubility, thus is more suitable for temperature reservoirs.
Embodiment 6
It is identical as the method that embodiment 4 prepares fracturing fluid, dication surfactant prepared by embodiment 1 is replaced with
Dication surfactant prepared by embodiment 3.
Surfactant, the mass content of ammonium chloride and sodium salicylate and obtained pressure break liquid status are as shown in table 3.Table
The state of 3 fracturing fluids obtained for the embodiment of the present invention 6.
The state for the fracturing fluid that 3 embodiment of the present invention 6 of table obtains
Fig. 4 is that viscosity changes with time sample 1 at different temperatures in table 3, under fixed shear frequency, with temperature
Increase, fracturing fluid viscosity decline, but in a short time (1h) keep stablize, even and if under the high temperature conditions (110 DEG C), viscosity
Also up to 25mPas, meet oil gas field requirement.
By table 3 and Fig. 4 it is found that sodium salicylate, which is added, can effectively improve the Krafft's point of surfactant solution, make it
Temperature tolerance improves, but can reduce its solubility, thus is more suitable for temperature reservoirs.
Embodiment 7
Dication surfactant, ammonium chloride and the water mixing that embodiment 1 is prepared, obtain fracturing fluid, double sun
Content of the ionic surface active agent in fracturing fluid is 2.0wt%, and content of the ammonium chloride in fracturing fluid is 1.0wt%.
By the way that the sodium bicarbonate regulation system pH value of different content is added into fracturing fluid, Fig. 5 shows that embodiment 7 obtains
Fracturing fluid degraded after different time under 90 DEG C of condition of different pH in the 25 DEG C of viscosity tested variations.When can be seen that one section
Between after the viscosity of fracturing fluid system be reduced to about 7mPas, chemical equation from 160mPas or so are as follows:
The one releasable two molecules carbon dioxide gas of molecule dication surfactant, other products are respectively oil-soluble
Octadecylamine and soluble small molecular quaternary ammonium salt, do not emulsify, on water-oil separating without influence.
Embodiment 8
Dication surfactant, ammonium chloride and the water mixing that embodiment 2 is prepared, obtain fracturing fluid, double sun
Content of the ionic surface active agent in fracturing fluid is 3.0wt%, and content of the ammonium chloride in fracturing fluid is 1.0wt%.
By the way that the sodium bicarbonate regulation system pH value of different content is added into fracturing fluid, Fig. 6 shows that embodiment 8 obtains
Fracturing fluid degraded after different time under 90 DEG C of condition of different pH in the 25 DEG C of viscosity tested variations.When can be seen that one section
Between after the viscosity of fracturing fluid system be reduced to about 8mPas, chemical equation from 100mPas or so are as follows:
The one releasable two molecules carbon dioxide gas of molecule dication surfactant, other products are respectively oil-soluble
Cetylamine and soluble small molecular quaternary ammonium salt, do not emulsify, on water-oil separating without influence.
Embodiment 9
Dication surfactant, ammonium chloride and the water mixing that embodiment 3 is prepared, obtain fracturing fluid, double sun
Content of the ionic surface active agent in fracturing fluid is 2.5wt%, and content of the ammonium chloride in fracturing fluid is 1.0wt%.
By the way that the sodium bicarbonate regulation system pH value of different content is added into fracturing fluid, Fig. 7 shows that embodiment 9 obtains
Fracturing fluid degraded after different time under 90 DEG C of condition of different pH in the 25 DEG C of viscosity tested variations.When can be seen that one section
Between after the viscosity of fracturing fluid system be reduced to about 3mPas, chemical equation from 90mPas or so are as follows:
The one releasable two molecules carbon dioxide gas of molecule dication surfactant, other products are respectively oil-soluble
Octadecylamine and soluble small molecular quaternary ammonium salt, do not emulsify, on water-oil separating without influence.
Embodiment 10
Using high temperature high pressure device test simulation reagent strata condition, pressure, temperature are studied to fracturing fluid amount of coalbed methane generated, anger
The influence of speed.Pressure break formula of liquid is embodiment 1 the dication surfactant, ammonium chloride and the water that are prepared, double sun from
Sub- surfactant content in fracturing fluid is 2.0wt%, and ammonium chloride content in fracturing fluid is 1.0wt%, and bicarbonate is added
It is 7.5 that sodium, which adjusts solution ph,.It is changed with time rule by work station real-time detection reaction system pressure, is counted by PV=nRT
The amount of the gas generated is calculated, testing result is as shown in table 4, and table 4 is the fracturing fluid anger performance inspection that the embodiment of the present invention 10 obtains
Survey result.(wherein blank pressure increase refers to isometric water by pressure increase caused by thermal evaporation, and experimental pressure increase is
Gross pressure caused by gas produced by water evaporation and surfactant are thermally decomposed in finger fracturing fluid changes, and angry pressure increase refers to reality
It tests pressurization and subtracts blank pressurization)
The fracturing fluid anger performance test results that 4 embodiment of the present invention 10 of table obtains
As shown in Table 4, normal temperature and pressure, prediction 1L fracturing fluid anger volume are 10.4L.
Embodiment 11
Using high temperature high pressure device test simulation reagent strata condition, pressure, temperature are studied to fracturing fluid amount of coalbed methane generated, anger
The influence of speed.Pressure break formula of liquid is embodiment 2 the dication surfactant, ammonium chloride and the water that are prepared, double sun from
Sub- surfactant content in fracturing fluid is 3.0wt%, and ammonium chloride content in fracturing fluid is 1.0wt%, and bicarbonate is added
It is 7.5 that sodium, which adjusts solution ph,.It is changed with time rule by work station real-time detection reaction system pressure, is counted by PV=nRT
The amount of the gas generated is calculated, testing result is as shown in table 5, and table 5 is the fracturing fluid anger performance inspection that the embodiment of the present invention 11 obtains
Survey result.
The fracturing fluid anger performance test results that 5 embodiment of the present invention 11 of table obtains
As shown in Table 5, normal temperature and pressure, prediction 1L fracturing fluid anger volume are 16.6L.
Embodiment 12
Using high temperature high pressure device test simulation reagent strata condition, pressure, temperature are studied to fracturing fluid amount of coalbed methane generated, anger
The influence of speed.Pressure break formula of liquid is embodiment 3 the dication surfactant, ammonium chloride and the water that are prepared, double sun from
Sub- surfactant content in fracturing fluid is 2.5wt%, and ammonium chloride content in fracturing fluid is 1.0wt%, and bicarbonate is added
It is 7.5 that sodium, which adjusts solution ph,.It is changed with time rule by work station real-time detection reaction system pressure, is counted by PV=nRT
The amount of the gas generated is calculated, testing result is as shown in table 6, and table 6 is the fracturing fluid anger performance inspection that the embodiment of the present invention 12 obtains
Survey result.
The fracturing fluid anger performance test results that 6 embodiment of the present invention 12 of table obtains
As shown in Table 6, normal temperature and pressure, prediction 1L fracturing fluid anger volume are 13.0L.
As seen from the above embodiment, the present invention provides a kind of gemini cationic surfactants, have Formulas I structure: Formulas I
In, R is the alkyl that carbon atom number is 10~30, and n is 11~17；M is 2~6；X is O or N；Y is halogen.With prior art phase
Than, the present invention by cleverly Molecular Design, by self-degradation, spontaneous airway dysfunction is innovative is combined together, and provides
It is a kind of at the same have inorganic salts dosage it is low, can self-degradation, from the fracturing fluid of the superior performances such as anger, produced after this fracturing fluid degradation
Object is hydrophilic small molecules and lipophilic molecules, harmless to stratum, thus need not the row of returning.
Claims (7)
1. a kind of fracturing fluid, comprising:
Gemini cationic surfactant；
Crosslinking agent；
Water；
PH adjusting agent；
The gemini cationic surfactant, has a structure in which
2. fracturing fluid according to claim 1, which is characterized in that the preparation side of the gemini cationic surfactant
Method, comprising the following steps:
(1) octadecylamine and bis- (trichloromethyl) carbonic esters are reacted, obtains octadecylisocyanate；
(2) by octadecylisocyanate and N, N- dimethylethanolamine is reacted, and obtains octadecane carbamic acid diformazan ammonia
Base ethyl alcohol ester；
(3) by octadecane carbamic acid dimethylaminoethanol ester and 1,2- Bromofume is reacted, and obtains the double of formula
Sub- cationic surfactant:
Or
(1) cetylamine and bis- (trichloromethyl) carbonic esters are reacted, obtains hexadecyl isocyanate；
(2) by hexadecyl isocyanate and N, N- dimethylethanolamine is reacted, and obtains hexadecane carbamic acid diformazan ammonia
Base ethyl alcohol ester；
(3) by hexadecane carbamic acid dimethylaminoethanol ester and 1,2- Bromofume is reacted, and obtains the double of formula
Sub- cationic surfactant:
Or
(1) octadecylamine and bis- (trichloromethyl) carbonic esters are reacted, obtains octadecylisocyanate；
(2) by octadecylisocyanate and N, N- dimethylethanolamine is reacted, and obtains octadecane carbamic acid diformazan ammonia
Base ethyl alcohol ester；
(3) octadecane carbamic acid dimethylaminoethanol ester is reacted with epoxychloropropane, obtains the Shuangzi of formula
Cationic surfactant:
3. fracturing fluid according to claim 2, which is characterized in that the temperature reacted in the step (1) is 35~150
DEG C, the time of reaction is 0.5~10 hour.
4. fracturing fluid according to claim 2, which is characterized in that the presence of reaction in the step (2) in catalyst
Lower progress.
5. fracturing fluid according to claim 1, which is characterized in that the crosslinking agent is selected from potassium chloride, ammonium chloride, chlorination
Sodium, potassium bromide, ammonium bromide, sodium bromide or sodium salicylate.
6. fracturing fluid according to claim 1, which is characterized in that the gemini cationic surfactant is in fracturing fluid
Mass content be 0.5~3%.
7. fracturing fluid according to claim 1, which is characterized in that mass content of the crosslinking agent in fracturing fluid be
0.5~3%.
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| CN108179007A (en) * | 2017-12-08 | 2018-06-19 | 成都劳恩普斯科技有限公司 | A kind of water-base drilling fluid double type shale control agent aqua, pulvis and preparation method thereof and inhibitor |
| CN108690595B (en) * | 2018-03-23 | 2021-02-26 | 捷贝通石油技术集团股份有限公司 | Method for increasing energy and improving recovery ratio of self-generated foam of oil and gas well |
| EP3844112A1 (en) | 2018-08-29 | 2021-07-07 | Ecolab USA Inc. | Use of multiple charged cationic compounds derived from primary amines or polyamines for microbial fouling control in a water system |
| EP3843871A1 (en) | 2018-08-29 | 2021-07-07 | Ecolab USA Inc. | Multiple charged ionic compounds derived from polyamines and compositions thereof and use thereof as reverse emulsion breakers in oil and gas operations |
| US11084974B2 (en) | 2018-08-29 | 2021-08-10 | Championx Usa Inc. | Use of multiple charged cationic compounds derived from polyamines for clay stabilization in oil and gas operations |
| WO2020047181A1 (en) | 2018-08-29 | 2020-03-05 | Ecolab Usa Inc. | Use of multiple charged ionic compounds derived from polyamines for waste water clarification |
| AU2019332961B2 (en) | 2018-08-29 | 2022-04-07 | Ecolab Usa Inc. | Multiple charged ionic compounds derived from polyamines and compositions thereof and methods of preparation thereof |
| CN109536155A (en) * | 2018-12-19 | 2019-03-29 | 西南石油大学 | Salt-resistant type Shuangzi cationic viscoelastic surfactants and preparation method thereof and salt tolerance clean fracturing fluid |
| WO2020160081A1 (en) | 2019-01-29 | 2020-08-06 | Ecolab Usa Inc. | Use of cationic sugar-based compounds for microbial fouling control in a water system |
| US11359291B2 (en) | 2019-04-16 | 2022-06-14 | Ecolab Usa Inc. | Use of multiple charged cationic compounds derived from polyamines and compositions thereof for corrosion inhibition in a water system |
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