CN105086983A - Betaine-surfactant-containing fracturing fluid drag reduction agent and preparation method and application thereof - Google Patents
Betaine-surfactant-containing fracturing fluid drag reduction agent and preparation method and application thereof Download PDFInfo
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- CN105086983A CN105086983A CN201410202763.4A CN201410202763A CN105086983A CN 105086983 A CN105086983 A CN 105086983A CN 201410202763 A CN201410202763 A CN 201410202763A CN 105086983 A CN105086983 A CN 105086983A
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Abstract
The present invention relates to a betaine-surfactant-containing fracturing fluid drag reduction agent and a preparation method and application thereof, and mainly solves the problems of narrow temperature range of a clear water fracturing fluid surfactant drag reduction agent used for development of shale gas in the prior art. The betaine-surfactant-containing fracturing fluid drag reduction agent includes fatty alcohol ethoxylate two aliphatic chain hydrocarbon betaine surfactant and an anionic amphiphilic molecule; the fatty alcohol ethoxylate ethoxylate two aliphatic chain hydrocarbon betaine surfactant has the general formula shown as (I), wherein X is one substance selected from carboxylate and sulfonate, R1 is C12-C22 aliphatic chain hydrocarbon group, R2 and R3 are independently selected from C1-C4 aliphatic hydrocarbon chain groups, R4 is C1-C4 alkylene group, n = 0-10; the molar ratio of the betaine surfactant and the anionic amphiphilic molecule is 1: (0.5 to 2), and by the technical scheme, the problem can be better solved, and the method can be used for the fracturing process of shale gas development.
Description
Technical field
The present invention relates to a kind of fracturing liquid flow improver containing beet alkali surface activator and its preparation method and application.
Background technology
One of the important sources that shale gas will be 21 century fossil energy.Along with the Successful commercial of U.S.'s shale gas reservoir is developed, shale gas resource receives increasing concern.Shale gas reservoir belongs to low permeability reservoir, and the rate of permeation of its permeability ratio Clastic Rock Gas Reservoirs also will a low 2-3 order of magnitude, and fracturing reform becomes the important means of shale gas exploratory development.Current huge discharge staged fracturing of horizontal well is the Main Yield-increasing technology of shale gas exploitation, and the high-efficiency water-base flow improver preparing riverfrac treatment liquid is one of key determining the success or failure of shale gas fracturing technology.
Early 1930s, people just find that adding some solvable additive in a liquid can reduce frictional resistance.1948, B.A.Toms found the drag reduction phenomenon of high molecular polymer when turbulent flow, caused the extensive attention of region of chemistry, community of physicists, fluid force educational circles and polymer educational circles, and had applied for first flow improver patent in 1949.Polymkeric substance as flow improver all has ultra-high molecular weight, and molecular weight reaches two, 3,000,000 usually, and even more than 10,000,000.Polymer drag reducer can reach very high drag-reduction effect when consumption is very little, but is subject to violent shearing and can causes molecule chain break thus lose anti-drag function, namely usually said shear degradation.Tensio-active agent flow improver realizes drag reduction by forming micella in a fluid, and it has good anti-shear performance.Common aqueous based surfactant drag reduction system comprises: the inorganic salt solution etc. of cats product and anionic amphiphilic molecule compound system, beet alkali surface activator and anionic amphiphilic molecule compound system, anion surfactant and non-ionic amphiphilic molecule compound system and cats product.
The mechanism of action of current flow improver mainly contains that viscoelastic is said, turbulent flow suppresses to say, but all can not best explain drag reduction phenomenon.Newest research results shows that the fluid flowed in pipe radially can be divided into three parts: the laminar sub-layer pressing close to tube wall, the turbulent core of tube hub (contains most fluid, wherein liquid particle constantly occurs mutually to clash into and blending, flow forward desultorily), (its flow state shows as the transition of laminar flow to turbulent flow, and buffer zone is the place that turbulent flow is formed at first in the buffer zone being between laminar sub-layer and turbulent core.The part of laminar sub-layer near buffer zone is thin interbed, and fluid molecule occasional wherein enters buffer zone, then starts vibration, forms eddy current whirlpool, and motion acceleration is also close to turbulent core, finally enters turbulent core.Fluid molecule between thin layer enters the large energy of moment meeting loss of turbulent core from buffer zone.Flow improver can stretch in a fluid, absorbs the energy between thin layer, and the fluid molecule between interference thin layer enters turbulent core from buffer zone thus stops it form turbulent flow or weaken turbulent extent, thus reaches the effect of drag reduction.
Shale gas is mainly arranged in dark-coloured mud shale or high-carbon mud shale, to adsorb or unbound state is present in mud stone, high-carbon mud stone, shale and aleuritic texture rock class interlayer.The marine facies that many covers thickness is large, distributional stability, organic content are high of southern china and north distribution or lacustrine facies black or dark shales, all have certain Shale Gas Accumulation condition and larger resource potential.The feature that Marine Strata in China shale has " second child assorted three is high ", the epoch are old, and series of strata are many, the complex structure motion of many phases, and strength at break is large, and thermal evolution history is complicated, and ripening degree is high; The feature that terrestrial facies shale has " one new one dark two low ", the epoch are new, bury dark, ripe low, the features such as brittle mineral content is low.China's shale gas enrichment reservoir thickness is suitable with the U.S., and buried depth is larger than the U.S., and its formation temperature can reach more than 100 DEG C.Although the natural fracture tool in gas bearing shale has certain effect, the infiltration lane needed for the economic exploitation usually cannot be provided.Under most gas bearing shale all needs enforcement pressure break to make more shale scope be exposed to the pressure reduction conditions of pit shaft.In shale, around horizontal well, compact arranged hydraulically created fracture can accelerate gas extraction speed.Riverfrac treatment is most widely used general, the most successful a kind of fracturing liquid in the exploitation of current shale gas, and flow improver used mostly is the polymer-type flow improver of guanidine glue class or polyacrylamide.Because polymer drag reducer can cause certain injury to shale gas reservoir stratum, by contrast, tensio-active agent flow improver has very strong competitive power.According to the geology characteristic of Chinese shale gas reservoir, appropriate table surface-active agent flow improver should all have high drag reducing efficiency (>=70%) in wide temperature range, wider salinity scope, also should have flow improver addition little simultaneously, to prepare the surface tension of riverfrac treatment liquid little and to features such as formation at target locations injury are little.
Research show quaternary surfactant, beet alkali surface activator or oxidation amine surfactants and anionic amphiphilic molecule composite after can obtain tensio-active agent drag reduction system, but the drag reduction temperature range width of these drag reduction systems only about 30 DEG C.If hydrocarbon-bearing pool and the ground difference in temperature are comparatively large, when carrying out slick-water fracturing operations, tensio-active agent flow improver can not ensure sufficiently high drag reducing efficiency in whole flow process.In order to obtain the tensio-active agent drag reduction system in wide temperature range with drag-reduction effect, many researchists have carried out unremitting effort.US4,828,765 report three aliphatic group Soxylat A 25-7 ammonium chlorides and anionic amphiphilic molecule is composite obtains the flow improver system in wide temperature range with obvious resistance reducing performance.But because epoxy chain link is positioned at the outermost of surfactant molecule, cause drag reducing efficiency lower in comparatively large-temperature range, only on indivedual temperature spot, be greater than 70%.US7,987,866B2 report utilizes alkyl betaine tensio-active agent and must have obvious resistance reducing performance in 50 ~ 120 DEG C of temperature ranges with the anion surfactant of Soxylat A 25-7 segment is composite.Because in slick-water fracturing operations, riverfrac treatment liquid must have the drag reducing efficiency of quite high (>=70%) under normal temperature condition, so alkyl betaine tensio-active agent and the Applicable temperature scope with the anion surfactant compound system of Soxylat A 25-7 segment are clearly not applicable for slick-water fracturing operations.This patent reports a kind of fatty alcohol-polyoxyethylene ether base two aliphatic group beet alkali surface activator and the composite tensio-active agent drag reduction system of anionic amphiphilic molecule.The riverfrac treatment liquid drag reducing efficiency in the temperature range of 5 DEG C to 80 DEG C utilizing this tensio-active agent flow improver to prepare all is greater than more than 70%, there is addition few (minimum reach 0.15% (wt)) simultaneously, insensitive to preparation water salinity, the advantages such as application range of shear rate is wide, effectively can be applied to the riverfrac treatment construction of shale gas reservoir.
Summary of the invention
One of technical problem to be solved by this invention be in prior art for develop shale gas fracturing liquid in the narrower problem of tensio-active agent flow improver use temperature scope, a kind of fracturing liquid flow improver containing beet alkali surface activator is provided, this fracturing liquid flow improver comprises fatty alcohol-polyoxyethylene ether base two aliphatic group beet alkali surface activator and anionic amphiphilic molecule, solve this problem preferably, there is use temperature wide ranges, the advantage that addition is few.
Two of technical problem to be solved by this invention is to provide the preparation method of one of a kind of technical solution problem containing the fracturing liquid flow improver of beet alkali surface activator.
Three of technical problem to be solved by this invention is to provide a kind of application of the fracturing liquid flow improver containing beet alkali surface activator.
In order to one of solve the problems of the technologies described above, the technical solution used in the present invention is as follows: containing the fracturing liquid flow improver of beet alkali surface activator, comprise fatty alcohol-polyoxyethylene ether base two aliphatic group beet alkali surface activator and anionic amphiphilic molecule, described fatty alcohol-polyoxyethylene ether base two aliphatic group beet alkali surface activator is as shown in formula I:
Wherein X is selected from any one in carboxylate radical, sulfonate radical, R
1for C
12~ C
22fat chain alkylene, R
2and R
3all independently be selected from C
1~ C
4fat chain alkylene, R
4for C
1~ C
4alkylidene group, n is the adduction number of ethoxy group EO, n=0 ~ 10; The ratio of described fatty alcohol-polyoxyethylene ether base two fat chain alkylene beet alkali surface activator and anionic amphiphilic molecule take molar amount as 1:(0.5 ~ 2).
In technique scheme, R
1be preferably C
12~ C
18fat chain alkylene, be more preferably C
12~ C
18alkyl.
In technique scheme, R
2and R
3all independent preferably C
1~ C
4alkyl, R
2and R
3all more independent preferably C
1~ C
2alkyl, further R
2and R
3be preferably identical C
1~ C
2alkyl.
In technique scheme, R
4be preferably C
2~ C
3alkylidene group, be more preferably-CH
2cH
2-.
In technique scheme, the adduction number of described ethoxy group EO is preferably n=1 ~ 4.
In technique scheme, preferred version is: described anionic amphiphilic molecule is preferably negatively charged ion aromatic series amphiphile, amphiphilic molecule, at least one in the negatively charged ion aromatic series amphiphile, amphiphilic molecule more preferably as shown in formula II or formula III:
Any one wherein in Y optimization acid root, sulfonate radical, any one in the preferred hydrogen of Z, alkyl, hydroxyl, halogen.
In technique scheme, fracturing liquid flow improver containing beet alkali surface activator can be the composition that described fatty alcohol-polyoxyethylene ether base two fat chain alkylene beet alkali surface activator and anionic amphiphilic molecular mixing evenly obtain, and also can be enriched material, paste or solution that both mix with water.
In order to solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: containing the preparation method of the fracturing liquid flow improver of beet alkali surface activator, comprise the following steps:
(a) N, N '-two preparation of fat chain alkylene fatty alcohol-polyoxyethylene ether base amine
Fatty alcohol-polyoxyethylene ether and amination catalysis are added reactor and is warming up to 80 ~ 120 DEG C, after fatty alcohol-polyoxyethylene ether melting, be decompressed to vacuum tightness is 0.01 ~ 0.099MPa, stir, carry out nitrogen replacement and hydrogen exchange, be warming up to 160 ~ 240 DEG C of reducing catalysts 40 ~ 80 minutes, adjustment hydrogen pressure to 0.01 ~ 0.03MPa; With nitrogen feed 2 ~ 10 part of two fat chain alkylene amine of 0.035 ~ 0.2MPa, be warming up to 190 DEG C ~ 220 DEG C reactions 2 ~ 6 hours, being decompressed to vacuum tightness is that namely the unnecessary two fat chain alkylene amine of 0.05 ~ 0.099MPa removing obtain N, N '-two fat chain alkylene fatty alcohol-polyoxyethylene ether base amine;
The preparation of (b) fatty alcohol-polyoxyethylene ether base two fat chain alkylene trimethyl-glycine
Intermediate synthesized by step (a) is dissolved in solvent, then according to mol ratio 1:(1.0 ~ 3.0 of '-two fat chain alkylene fatty alcohol-polyoxyethylene ether base amine and carboxylating agent by N, N) quantity add carboxylating agent 90 DEG C, synthesis under normal pressure obtains described fatty alcohol-polyoxyethylene ether base two fat chain alkylene trimethyl-glycine for 5 ~ 6 hours;
C () is containing the preparation of the fracturing liquid flow improver of beet alkali surface activator
By the fatty alcohol-polyoxyethylene ether base two fat chain alkylene trimethyl-glycine that obtains in step (b) in described ratio and described anionic amphiphilic molecular mixing even, obtain the described fracturing liquid flow improver containing beet alkali surface activator.
Wherein, described beet alkali surface activator is selected from material shown in logical formula I.
In technique scheme, the time of described stirring is preferably 30 ~ 60 minutes; The number of times of described nitrogen replacement is at least one times, preferably 4 times; The number of times of hydrogen exchange is at least one times, is preferably 4 times.
In technique scheme, described amination catalysis can be well-known to those skilled in the art any one, inventive point of the present invention does not lie in this, the Cu-203 catalyzer of preferred Harshaw company.
In technique scheme, described solvent can be known by art technology people for dissolving N, the common solvent of N '-two fat chain alkylene fatty alcohol-polyoxyethylene ether base amine substance, be preferably dehydrated alcohol.
In technique scheme, described carboxylating agent can be well-known to those skilled in the art any one, inventive point of the present invention does not lie in this, preferred sodium chloroacetate.
In order to solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: containing the application of fracturing liquid flow improver in fracturing liquid of beet alkali surface activator.
In technique scheme, the temperature of described application is preferably 5 DEG C to 80 DEG C; In described fracturing liquid, in the quality of fatty alcohol-polyoxyethylene ether base two fat chain alkylene beet alkali surface activator and anionic amphiphilic molecule, the concentration containing the fracturing liquid flow improver of beet alkali surface activator is preferably 0.15% (wt) ~ 0.5% (wt).
In technique scheme, the application of the described fracturing liquid flow improver containing beet alkali surface activator, the water sources well-known to those skilled in the art such as applicable tap water, river, salt solution, Oil Field water, clear water, sewage; Be particularly useful for riverfrac treatment liquid.
Tensio-active agent flow improver use temperature scope for riverfrac treatment liquid is one of principal element affecting fracturing effect.The use temperature narrow limits of tensio-active agent flow improver may cause high temperature shale gas reservoir fracturing effect bad.The present invention proposes a kind of fracturing liquid flow improver containing beet alkali surface activator, comprise fatty alcohol-polyoxyethylene ether base two fat chain alkylene beet alkali surface activator and anionic amphiphilic molecule, there is flow improver broad application temperature range, addition is few, insensitive to preparation water salinity, the advantages such as application range of shear rate is wide, effectively can be applied to the pressing crack construction of shale gas reservoir, especially riverfrac treatment construction.
The surfactant micelle of fatty alcohol-polyoxyethylene ether base two fat chain alkylene beet alkali surface activator molecule in the present invention in the formula aqueous solution can keep vermicular texture thus ensure resistance reducing performance in very wide temperature range; Simultaneously this beet alkali surface activator has raw material and is easy to get, and synthetic route is ripe, the finished product low cost and other advantages, and according to filling a prescription, the tensio-active agent flow improver obtained is applicable to shale gas fracturing operation, especially slick-water fracturing operations.
Adopt the tensio-active agent flow improver of the present invention's preparation in water, the maximum drag reducing efficiency of more than 70% more than consumption 0.15% (wt) can be reached the temperature range of 5 DEG C to 80 DEG C, can be applicable to the slick-water fracturing operations developing shale gas.
Accompanying drawing explanation
It is the pipeline frictional resistance instrument of the resistance reducing performance of evaluation table surface-active agent flow improver shown in Fig. 1, evaluation procedure: tensio-active agent flow improver is mixed with the certain density aqueous solution (such as 2 ‰ (wt) or 5 ‰ (wt)), adds container for storing liquid.With fresh feed pump, testing liquid is pumped into measurement piping system, after being full of whole measurement pipeline, measurement piping system is isolated from the outside.The measurement pipeline diameter of common pipeline frictional resistance instrument has 1/2 cun, 3/8 cun and 1/4 cun of equidimension.Open different size successively and measure pipeline and the measuring system on it, utilize recycle pump to make solution to be measured with certain flow circulation in pipeline, the pressure drop on measurement fixed length pipeline under a series of different circular flow.Drag reducing efficiency under utilizing public formula I to calculate different circular flow, then drag reducing efficiency is mapped to the circular flow of fluid or Reynolds number, can obtain the drag reducing efficiency under specific caliber, the maximum drag reducing efficiency can chosen wherein represents the resistance reducing performance of tensio-active agent flow improver.
Be further described below by specific embodiment.
Embodiment
[embodiment 1]
The Cu-203 Study on Catalytic Amination of Alcohols catalyzer of 1000 grams of polyoxyethylene octadecanols (EO=2.1) and 100 grams of Harshaw companies is added in low pressure reaction still and is warming up to 100 DEG C, be decompressed to vacuum tightness 0.9, stir 30 minutes removing volatile components, then 4 nitrogen replacements and 4 hydrogen exchanges are carried out successively, regulation system pressure is 0.02Mpa, with nitrogen pressurization charging 1188 grams of dimethylamine of 0.5Mpa, be warming up to 220 DEG C of reactions 5 hours, be cooled to 160 DEG C, the unnecessary dimethylamine of decompression removing obtains intermediate.Intermediate is dissolved in after dehydrated alcohol is mixed with the solution of 40% and adds in reactor, then add 353 grams of sodium chloroacetates 90 DEG C, under normal pressure reaction terminate after 5 ~ 6 hours.Underpressure distillation adds 5000ml benzene, stirring and dissolving reaction product except after desolventizing dehydrated alcohol in reactor.Then add the 5000ml15%NaCl aqueous solution, to stir after 30 minutes stratification at 60 DEG C, point sub-cloud aqueous phase after profit layering.Add the 5000ml15%NaCl aqueous solution again, to stir after 30 minutes stratification at 60 DEG C, the aqueous phase of point sub-cloud after layering.Then release reaction product and obtain 1150 grams of target products after revolving steaming removing excess of solvent.
100 grams of KCl and 2 gram acrylamides and quaternary ammonium salt monomer multipolymer (JYPQ) (Shandong Lu Yue Chemical Co., Ltd.) are added stirring and dissolving in 9.885Kg tap water, then add 9.77 grams of polyoxyethylene octadecanol base dimethyl betaines and stir 4 hours, finally add to place after 5.23 grams of 2-sodium naphthalene sulfonates stir 6 hours and spend the night, the tensio-active agent dreg reducer solution that the bubble-free concentration of clear is 0.15% (wt) can be obtained.The test result of 31 DEG C, pipe friction instrument shows that the maximum drag reducing efficiency of this fluid reaches 74%.
[embodiment 2]
2 grams of JYPQ (with embodiment 1) are added stirring and dissolving in 9.985Kg tap water, then add 9.77 grams of polyoxyethylene octadecanol base (EO=2.1) dimethyl betaines and stir 4 hours, finally add to place after 5.23 grams of 2-sodium naphthalene sulfonates stir 6 hours and spend the night, the tensio-active agent dreg reducer solution that the bubble-free concentration of clear is 0.15% (wt) can be obtained.The test result of 30 DEG C, pipe friction instrument shows that the maximum drag reducing efficiency of this fluid reaches 74%.
[embodiment 3]
9.77 grams of polyoxyethylene octadecanol base (EO=2.1) dimethyl betaines are added in 9.985Kg tap water to stir and dissolve for 4 hours, then add to place after 5.23 grams of 2-sodium naphthalene sulfonates stir 6 hours and spend the night, the tensio-active agent dreg reducer solution that the bubble-free concentration of clear is 0.15% (wt) can be obtained.The test result of 32 DEG C, pipe friction instrument shows that the maximum drag reducing efficiency of this fluid reaches 73%.
[embodiment 4]
200 grams of KCl are added stirring and dissolving in 9.785Kg tap water, then add 9.77 grams of polyoxyethylene octadecanol base (EO=2.1) dimethyl betaines and stir 4 hours, finally add to place after 5.23 grams of 2-sodium naphthalene sulfonates stir 6 hours and spend the night, the tensio-active agent dreg reducer solution that the bubble-free concentration of clear is 0.15% (wt) can be obtained.The test result of 28 DEG C, pipe friction instrument shows that the maximum drag reducing efficiency of this fluid reaches 75%.
[embodiment 5]
9.28 grams of polyoxyethylene octadecanol base (EO=2.1) dimethyl betaines are added stirring 4 hours KCl and adds stirring and dissolving in 9.985Kg tap water, then add 5.72 grams of 2-sodium naphthalene sulfonates stir within 6 hours, fully dissolve after place and spend the night, the tensio-active agent dreg reducer solution that the bubble-free concentration of clear is 0.15% (wt) can be obtained.The test result of 30 DEG C, pipe friction instrument shows that the maximum drag reducing efficiency of this fluid reaches 73%.
[embodiment 6]
The Cu-203 Study on Catalytic Amination of Alcohols catalyzer of 1000 grams of hexadecanol Soxylat A 25-7s (EO=2.1) and 100 grams of Harshaw companies is added in low pressure reaction still and is warming up to 100 DEG C, be decompressed to vacuum tightness 0.9, stir 30 minutes removing volatile components, then 4 nitrogen replacements and 4 hydrogen exchanges are carried out successively, regulation system pressure is 0.02Mpa, with nitrogen pressurization charging 1287 grams of dimethylamine of 0.5Mpa, be warming up to 220 DEG C of reactions 5 hours, be cooled to 160 DEG C, the unnecessary dimethylamine of decompression removing obtains intermediate.Intermediate is dissolved in after dehydrated alcohol is mixed with the solution of 40% and adds in reactor, then add 382.5 grams of sodium chloroacetates 90 DEG C, under normal pressure reaction terminate after 5 ~ 6 hours.Underpressure distillation adds 5000ml benzene, stirring and dissolving reaction product except after desolventizing dehydrated alcohol in reactor.Then add the 5000ml15%NaCl aqueous solution, to stir after 30 minutes stratification at 60 DEG C, point sub-cloud aqueous phase after profit layering.Add the 5000ml15%NaCl aqueous solution again, to stir after 30 minutes stratification at 60 DEG C, the aqueous phase of point sub-cloud after layering.Then release reaction product and obtain 1130 grams of target products after revolving steaming removing excess of solvent.
9.54 grams of hexadecanol polyoxyethylene ether (EO=2.1) dimethyl betaines are added stirring 4 hours KCl and adds stirring and dissolving in 9.985Kg tap water, then add 5.46 grams of 2-sodium naphthalene sulfonates stir within 6 hours, fully dissolve after place and spend the night, the tensio-active agent dreg reducer solution that the bubble-free concentration of clear is 0.15% (wt) can be obtained.The test result of 25 DEG C, pipe friction instrument shows that the maximum drag reducing efficiency of this fluid reaches 74%.
[embodiment 7]
9 grams of Dodecyl Polyoxyethylene Ether base (EO=2.1) dimethyl betaines are added stirring 4 hours KCl and adds stirring and dissolving in 9.985Kg tap water, then add 6 grams of 2-sodium naphthalene sulfonates stir within 6 hours, fully dissolve after place and spend the night, the tensio-active agent dreg reducer solution that the bubble-free concentration of clear is 0.15% (wt) can be obtained.The test result of 20 DEG C, pipe friction instrument shows that the maximum drag reducing efficiency of this fluid reaches 72%.
[embodiment 8]
32.57 grams of polyoxyethylene octadecanol base (EO=2.1) dimethyl betaines are added in 9.95Kg tap water to stir and dissolve for 4 hours, then add 17.43 grams of 2-sodium naphthalene sulfonates stir within 6 hours, fully dissolve after place and spend the night, the tensio-active agent dreg reducer solution that the bubble-free concentration of clear is 0.5% (wt) can be obtained.Utilize pipe friction instrument to test the frictional resistance of this fluid 5 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C and 80 DEG C respectively, result shows that the maximum drag reducing efficiency of this fluid is all greater than 74%.
[comparative example 1]
Hexadecyldimethyl benzyl ammonium Soxylat A 25-7 (EO=2) ammonium chloride and sodium salicylate is composite tests under concentration 0.2% (wt), the condition of 22 DEG C that to obtain maximum drag reducing efficiency be 58%.
[comparative example 2]
Hexadecyldimethyl benzyl ammonium Soxylat A 25-7 (EO=2) ammonium chloride and sodium salicylate is composite tests under concentration 0.5% (wt), the condition of 55 DEG C that to obtain maximum drag reducing efficiency be 70%.
[comparative example 3]
Hexadecyldimethyl benzyl ammonium Soxylat A 25-7 (EO=2) ammonium chloride and sodium salicylate is composite tests under concentration 0.5% (wt), the condition of 65 DEG C that to obtain maximum drag reducing efficiency be 57%.
Table 1
Continued 1
Claims (10)
1., containing a fracturing liquid flow improver for beet alkali surface activator, comprise fatty alcohol-polyoxyethylene ether base two fat chain alkylene beet alkali surface activator and anionic amphiphilic molecule; Described fatty alcohol-polyoxyethylene ether base two fat chain alkylene beet alkali surface activator is as shown in logical formula I:
Wherein X is selected from any one in carboxylate radical, sulfonate radical, R
1for C
12~ C
22fat chain alkylene, R
2and R
3all independently be selected from C
1~ C
4fat chain alkylene, R
4for C
1~ C
4alkylidene group, n is the adduction number of ethoxy group EO, n=0 ~ 10; The ratio of described fatty alcohol-polyoxyethylene ether base two fat chain alkylene beet alkali surface activator and anionic amphiphilic molecule take molar amount as 1:(0.5 ~ 2).
2., according to claim 1 containing the fracturing liquid flow improver of beet alkali surface activator, it is characterized in that described anionic amphiphilic molecule is selected from negatively charged ion aromatic series amphiphile, amphiphilic molecule.
3., according to claim 2 containing the fracturing liquid flow improver of beet alkali surface activator, it is characterized in that at least one in described anionic amphiphilic molecule molecule as shown in formula II or formula III:
Wherein Y is selected from any one in carboxylate radical, sulfonate radical, Z be selected from hydrogen, alkyl, hydroxyl, halogen any one.
4., according to claim 1 containing the fracturing liquid flow improver of beet alkali surface activator, it is characterized in that described R
1for C
12~ C
18fat chain alkylene.
5., according to claim 1 containing the fracturing liquid flow improver of beet alkali surface activator, it is characterized in that described R
2and R
3all independently be selected from C
1~ C
4fat chain alkylene.
6., according to claim 1 containing the fracturing liquid flow improver of beet alkali surface activator, it is characterized in that the adduction number of described ethoxy group EO is 1 ~ 4.
7. the preparation method of the arbitrary described fracturing liquid flow improver containing beet alkali surface activator of claim 1 ~ 6, comprises the following steps:
(a) N, N '-two preparation of fat chain alkylene fatty alcohol-polyoxyethylene ether base amine
Fatty alcohol-polyoxyethylene ether and amination catalysis are added reactor and is warming up to 80 ~ 120 DEG C, after fatty alcohol-polyoxyethylene ether melting, be decompressed to vacuum tightness is 0.01 ~ 0.099MPa, stir, carry out nitrogen replacement and hydrogen exchange, be warming up to 160 ~ 240 DEG C of reducing catalysts 40 ~ 80 minutes, adjustment hydrogen pressure to 0.01 ~ 0.03MPa; With nitrogen feed 2 ~ 10 part of two fat chain alkylene amine of 0.035 ~ 0.2MPa, be warming up to 190 DEG C ~ 220 DEG C reactions 2 ~ 6 hours, being decompressed to vacuum tightness is that namely the unnecessary two fat chain alkylene amine of 0.05 ~ 0.099MPa removing obtain N, N '-two fat chain alkylene fatty alcohol-polyoxyethylene ether base amine;
The preparation of (b) fatty alcohol-polyoxyethylene ether base two fat chain alkylene trimethyl-glycine
Intermediate synthesized by step (a) is dissolved in solvent, then according to mol ratio 1:(1.0 ~ 3.0 of '-two fat chain alkylene fatty alcohol-polyoxyethylene ether base amine and carboxylating agent by N, N) quantity add carboxylating agent 90 DEG C, synthesis under normal pressure obtains described fatty alcohol-polyoxyethylene ether base two fat chain alkylene trimethyl-glycine for 5 ~ 6 hours;
C () is containing the preparation of the fracturing liquid flow improver of beet alkali surface activator
By the fatty alcohol-polyoxyethylene ether base two fat chain alkylene trimethyl-glycine that obtains in step (b) in described ratio and described anionic amphiphilic molecular mixing even, obtain the described fracturing liquid flow improver containing beet alkali surface activator.
8. the arbitrary described application of fracturing liquid flow improver in fracturing liquid containing beet alkali surface activator of claim 1 ~ 6.
9., according to claim 7 containing the application of fracturing liquid flow improver in fracturing liquid of beet alkali surface activator, it is characterized in that the temperature of described application is 5 DEG C ~ 80 DEG C.
10. according to claim 7 containing the application of fracturing liquid flow improver in fracturing liquid of beet alkali surface activator, it is characterized in that in described fracturing liquid, in the quality of fatty alcohol-polyoxyethylene ether base two fat chain alkylene beet alkali surface activator and anionic amphiphilic molecule, the concentration of the described fracturing liquid flow improver containing beet alkali surface activator is 0.15% (wt) ~ 0.5% (wt).
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106590610A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Water-based fracturing fluid drag reducer and applications thereof |
| CN109679625A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The composition and preparation method and purposes of displacement of reservoir oil Surfactant Used in Viscoelastic Fracturing Fluids |
| CN109679622A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | Composition containing polyether sulfonate surfactant and preparation method and purposes |
| CN109705835A (en) * | 2018-12-29 | 2019-05-03 | 中国石油大学(华东) | A kind of halophilic viscoelastic surfactant clean fracturing fluid and preparation method thereof |
| CN115305073A (en) * | 2022-07-14 | 2022-11-08 | 江苏海洋大学 | Gemini surfactant for preparing water reducing water from formation brine and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106590610A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Water-based fracturing fluid drag reducer and applications thereof |
| CN106590610B (en) * | 2015-10-20 | 2022-04-01 | 中国石油化工股份有限公司 | Water-based fracturing fluid drag reducer and application thereof |
| CN109679625A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The composition and preparation method and purposes of displacement of reservoir oil Surfactant Used in Viscoelastic Fracturing Fluids |
| CN109679622A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | Composition containing polyether sulfonate surfactant and preparation method and purposes |
| CN109679622B (en) * | 2017-10-19 | 2021-06-22 | 中国石油化工股份有限公司 | Polyether sulfonate-containing surfactant composition, preparation method and application |
| CN109679625B (en) * | 2017-10-19 | 2021-06-22 | 中国石油化工股份有限公司 | Composition of viscoelastic surfactant for oil displacement, preparation method and application |
| CN109705835A (en) * | 2018-12-29 | 2019-05-03 | 中国石油大学(华东) | A kind of halophilic viscoelastic surfactant clean fracturing fluid and preparation method thereof |
| CN109705835B (en) * | 2018-12-29 | 2021-05-28 | 中国石油大学(华东) | High-salt-resistant viscoelastic surfactant clean fracturing fluid and preparation method thereof |
| CN115305073A (en) * | 2022-07-14 | 2022-11-08 | 江苏海洋大学 | Gemini surfactant for preparing water reducing water from formation brine and preparation method thereof |
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| CN105086983B (en) | 2018-11-20 |
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