CN106590610A - Water-based fracturing fluid drag reducer and applications thereof - Google Patents
Water-based fracturing fluid drag reducer and applications thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/28—Friction or drag reducing additives
Abstract
The present invention relates to a novel water-based fracturing fluid drag reducer composition and applications of the composition as a fracturing fluid drag reducer. A purpose of the present invention is to mainly solves the problems of low resistance reduction rate and low tolerance to hard water of the surfactant drag reducer in the prior art. The technical scheme of the present invention comprises that the novel water-based fracturing fluid drag reducer composition comprises an amphoteric surfactant represented by a formula (I) and a long chain fatty acid salt, wherein the long chain fatty acid salt is at least one selected from a formula (II), a formula (III) and a formula (IV), and a weight ratio of the cationic surfactant to the long chain fatty acid salt is 50:1-1:50. With the technical scheme of the present invention, the problems in the prior art are well solved. The novel water-based fracturing fluid drag reducer composition of the present invention can be used for the shale gas fracturing mining process. The formula (I), the formula R4COOM (II), the R4SO3M formula (III) and the R4SO4M Formula (IV) are defined in the specification.
Description
Technical field
The present invention relates to a kind of aqueous fracturing fluid drag reducer and its preparation method and application.
Background technology
Shale gas reservoir generally belongs to super low-porosity and low-permeability reservoir, the permeability of permeability ratio Clastic Rock Gas Reservoirs will also the low 2-3 order of magnitude, for such gas reservoir, fracturing reform is the important means of exploration and development.Increasing application has been obtained suitable for the fracturing technique for exploiting hypotonic, low hole unconventional reservoir shale gas reservoir exploitation.However, injection water is hindered by the shear stress that flows in pipeline and lithosphere, fluid displacement can be substantially reduced.Effectively reducing the frictional resistance of liquid can reduce the demand to equipment, and construction cost is reduced to a certain extent.Therefore, in order to lower frictional resistance, drag reduction agent addition agent is generally needed to be added in slippery water fracturing fluid.
Earliest water-based drag reducer is polymer, but solution polymer product viscosity itself is big, and polymer content is low, and dissolution time is long, unstable chemcial property, therefore to transport and greatly constant using bringing.It is crucial that, polymer drag reducer polymer drag reducing agent is generally linear molecule, and molecular weight is more than 500,000, but in the presence of the factors such as Strong shear power, high temperature, backbone will be destroyed, and cannot repair.Surfactant drag reducer therefore, it is possible to form vermiculate glues causes extensive concern.And surfactant can effectively reduce injection fluid and contact angle and surface tension between reservoir fluid, rock, the capillary force that drag reduction water flows in shale reservoir is reduced, and then improve fracturing effect.
Surfactant vermiculate glues (are less than 10 under low Reynolds number4) be present in aqueous solution in a kind of disorderly arranged mode, flowing shearing is not almost acted on.(it is more than 10 under high Reynolds number4), aligning for micelle result in obviously drag-reduction effect.And (it is more than 10 under higher Reynolds number5), shearing force destroys vermiculate glues, and drag-reduction effect is quickly reduced.The Reynolds number scope that surfactant system has obvious drag-reduction effect depends on several factors, such as：Total concentration, proportioning, surfactant hydrophobic chain length etc..
Lot of documents shows that cationic surfactant and organic salt mixed system easily form vermiculate glues.Some of them system effectively applies to (U.S. Patent number in the heat exchange applications of pipeline：4705860, title, quaternary ammonium salts and their use as drag reduction agents), but most of cationic surfactant/organic salt system, such as cetyl trimethylammonium bromide/sodium salicylate system is easy from vermiculate glues englobement micelle under high Reynolds number, lose resistance reducing performance, and the easy Precipitation in high contents of calcium and magnesium water environment system.There is preferable resistance reducing performance under in order to obtain high Reynolds number, and the surfactant drag reduction agent prescription with higher hard water tolerance, we have searched out the compositionss of new amphoteric surfactant and hard soap.We have found that the surfactant formula of the type can effectively lift the tolerance to hard water, obtain good drag-reduction effect.
The content of the invention
One of the technical problem to be solved is that surfactant drag reducer resistance-reducing yield present in prior art is low, the problem low to hard water tolerance, there is provided a kind of new aqueous fracturing fluid drag reducer, the drag reducer is used to having the advantages that in aqueous fracturing fluid that resistance-reducing yield to be high, hard water resistance tolerance is strong.
The two of the technical problem to be solved are application of one of above-mentioned technical problem aqueous fracturing fluid drag reducer in fracturing fluid.
In order to solve one of above-mentioned technical problem, technical scheme is as follows：Aqueous fracturing fluid drag reducing agent composition, including the amphoteric surfactant and hard soap described in formula (I)；At least one of the hard soap in the soap shown in formula (II), formula (III) or formula (IV)；Wherein, R is the group of the saturation containing 8～24 carbon atoms or unsaturated aliphatic base or acyl group, R1And R2It is independently selected from the alkyl of 1～4 carbon atom or the hydroxyalkyl of 2～4 carbon atoms, R3It is the alkylidene of 1～6 carbon atom；
Wherein, the amphoteric surfactant and the weight ratio of the hard soap are 1:(0.02～50)；At least one of the hard soap in fat carboxylate, Fatty sulphonates or fat sulphate.
In above-mentioned technical proposal, R1And R2It is preferred that methyl, ethyl or propyl group.
In above-mentioned technical proposal, R3It is preferred that the alkylidene of 2～3 carbon atoms.
In above-mentioned technical proposal, R preferred aliphatic series group or R5NHC3H6-, wherein R5It is acyl group.
At least one in soap in above-mentioned technical proposal, shown in the preferred formula (II) of the hard soap, formula (III) or formula (IV)；
R4COOM formulas (II)；R4SO3M formulas (III)；R4SO4M formulas (IV)；
Wherein, R4Preferably comprise the saturation or unsaturated aliphatic base of 8～24 carbon atoms, M independent preferably H, alkali metal or NH4；
In above-mentioned technical proposal, the hard soap preferably comprises the saturation of 12～22 carbon atoms or unsaturated aliphatic base.
In above-mentioned technical proposal, optimum technical scheme is：Aqueous fracturing fluid drag reducer, including the amphoteric surfactant and the hard soap described in formula (I)；At least one of the hard soap in the soap shown in formula (II), formula (III) or formula (IV)；Wherein, R is the saturation containing 8～24 carbon atoms or unsaturated aliphatic base, the more preferably aliphatic group of 12～22 carbon atoms, the alkyl or alkylene of more preferably 12～24 carbon atoms；R1And R2It is independently selected from the alkyl of 1～4 carbon atom or the hydroxyalkyl of 2～4 carbon atoms, R3It is the alkylidene of 1～6 carbon atom, the more preferably alkylidene of 2～3 carbon atoms；R4It is the saturation containing 8～24 carbon atoms or unsaturated aliphatic base, the alkyl or alkylene of the saturation or unsaturated aliphatic hydrocarbyl moiety of more preferably 12～22 carbon atoms, more preferably 12～22 carbon atoms；M is selected from H, alkali metal or NH4.Now highest drag reducing efficiency can maintain more than 65%, and the salinity that can tolerate water is 11786ppmw.
In above-mentioned technical proposal, as preferred scheme：It is preferred that at least two in the amphoteric surfactant described in formula (I) compound with the one kind in the fat carboxylate, Fatty sulphonates or fat sulphate, preferable synergism can be played, its drag-reduction effect is substantially better than a kind of effect of the compounding in a kind of and the fat carboxylate, Fatty sulphonates or the fat sulphate in the amphoteric surfactant described in formula (I).
In above-mentioned technical proposal, as preferred scheme：It is preferred that at least two compoundings in a kind of and the fat carboxylate, Fatty sulphonates or the fat sulphate in the amphoteric surfactant described in formula (I), preferable synergism can also be played, its drag-reduction effect is also significantly better than a kind of effect of the compounding in a kind of and the fat carboxylate, Fatty sulphonates or the fat sulphate in the amphoteric surfactant described in formula (I).
In above-mentioned technical proposal, the aqueous fracturing fluid drag reducer can also include water, wherein the mass-volume concentration of the amphoteric surfactant and hard soap is preferably 0.1～10kg/m3。
The fracturing fluid drag reducer of the present invention can be supplied in solid form respectively for ease of accumulating, and scene is respectively added to used in fracturing fluid；Can also supply in solid mixture form after first mix homogeneously, scene is added to used in fracturing fluid；For ease of onsite application can also aqueous solution form supply.The present composition can also include other components commonly used in the art, such as clay stabilizer, antibacterial, antisludging agent, pH adjusting agent, anti-fluid loss agents, demulsifier etc..
When the present invention is using aqueous solution form, can be in the form of concentrated solution, dilute when deployed, or be preferably directly made into the concentration of onsite application, the concentration preferably amphoteric surfactant of onsite application and hard soap amount to the 0.1～10kg/m for accounting for the fracturing fluid3。
In order to solve the two of above-mentioned technical problem, technical scheme is as follows：Application of the aqueous fracturing fluid drag reducer in fracturing fluid any one of one of above-mentioned technical problem technical scheme.
In above-mentioned technical proposal, preferred version is：The fracturing fluid is preferably aqueous fracturing fluid；The use temperature of the application is preferably 5～120 DEG C；The concentration that the amphoteric surfactant and hard soap are amounted in fracturing fluid is preferably 0.1～10kg/m3, the preferably above-mentioned hard soap of the hard soap.
The fracturing fluid drag reducer of the present invention is used in fracturing fluid, and the water quality of fracturing fluid is not specially required, and can make the water quality well-known to those skilled in the art such as deionized water, clear water, river, sewage, salinity water, stratum water.
The assay method of the resistance-reducing yield of the present composition is as follows：
The drag reducing efficiency of fracturing fluid drag reducer carries out test and obtains using flowing loop friction drag test system.Experiment test group water solution is in the stainless pipe that a length of 3 meters of internal diameters are 1/2 inch as the pressure reduction of change in flow changes.Carry out turbulent flow drag reduction flowing research when, measure turbulent flow drag reduction flowing Fanning friction factor with the result of variations of Reynolds number after, by comparing the size for obtaining drag reducing efficiency with the Fanning friction factor of the water under identical Reynolds number.Drag reducing efficiency DR formula are as follows, obtained by pressure difference data：
In formula：Δ P is the drag reducer fluid for preparing by testing pressure reduction during pipeline, KPa；
ΔPsBe clear water by test pipeline when pressure reduction, KPa.
Reynolds number Re is defined by the parameter of streaming flow：
μ is solvent viscosity, and ρ is the density of fluid, and Q is fluid flow, and D is internal diameter of the pipeline, therefore Reynolds number is proportional with flow.The data for finally giving are the relation curve between drag reducing efficiency DR and Reynolds number.
The drag reducing efficiency that drag reducing efficiency size when fixed Reynolds number Re is 20000 is the aqueous fracturing fluid drag reducer is taken in the present invention.
The key problem in technology of the present invention is to define a kind of new fracturing fluid drag reduction agent prescription, combined using amphoteric surfactant and long-chain fat salt, it is prepared for efficient fracturing fluid drag reducer, fracturing fluid is used for using the aqueous fracturing fluid drag reducer of the present invention, especially in aqueous fracturing fluid, using 5～120 DEG C of temperature, 0.1～10kg/m of concentration3Under conditions of, resistance-reducing yield can tolerate that the salinity of water, higher than 10000ppmw, obtains preferable technique effect up to 80%.
Below by specification drawings and specific embodiments, the present invention is described in detail.
Description of the drawings
Fig. 1 is the graph of relation between drag reducing efficiency DR and Reynolds number.
Specific embodiment
Following examples are 11786ppmw from the salinity of water, and wherein calcium ion is 72.6ppmw, magnesium ion 2.5ppmw, sodium ion 4019.5ppmw, chloride ion 4332.5ppmw.
【Comparative example 1】
The quality such as N- empgen BBs and disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is compounded, and is dissolved in hard water and the friction reducer aqueous solution of 2000ppmw, the drag reducing efficiency tested under different temperatures, without drag reducing efficiency is obtained.
【Comparative example 2】
The quality such as oleamide base glycine betaine and enuatrol is compounded, and is dissolved in hard water and the friction reducer aqueous solution of 1000ppmw is obtained, without drag reducing efficiency.
【Comparative example 3】
The quality such as cetyl trimethylammonium bromide and sodium salicylate is compounded, and is dissolved in deionized water and the friction reducer aqueous solution of 2000ppmw is obtained, and is precipitated at a temperature of 15 DEG C.Drag reducing efficiency under test different temperatures, highest drag reducing efficiency can be maintained at 65%.Temperature applicable range is 20～60 DEG C.
【Comparative example 4】
The quality such as cetyl trimethylammonium bromide and sodium salicylate is compounded, and is dissolved in hard water and the friction reducer aqueous solution of 1000ppmw, Precipitation is obtained.
【Embodiment 1】
The quality such as N- empgen BBs and sodium stearate is compounded, and in being added to hard water, the aqueous solution of 1000ppmw is obtained, and the drag reducing efficiency tested under different temperatures, highest drag reducing efficiency can be maintained at 60%.Temperature applicable range is 30～100 DEG C.
【Embodiment 2】
The quality such as N- empgen BBs and enuatrol is compounded, and in being added to hard water, the aqueous solution of 1000ppmw is obtained, and the drag reducing efficiency tested under different temperatures, highest drag reducing efficiency can be maintained at 70%, as shown in Figure 1.Temperature applicable range is 5～100 DEG C.
【Embodiment 3】
The quality such as N- empgen BBs and erucic acid sodium is compounded, and in being added to hard water, the aqueous solution of 1000ppmw is obtained, and the drag reducing efficiency tested under different temperatures, highest drag reducing efficiency can be maintained at 70%.Temperature applicable range is 5～120 DEG C.
【Embodiment 4】
The quality such as N- empgen BBs and sodium palmitate is compounded, and in being added to hard water, the aqueous solution of 1000ppmw is obtained, and the drag reducing efficiency tested under different temperatures, highest drag reducing efficiency can be maintained at 65%.Temperature applicable range is 20～90 DEG C.
【Embodiment 5】
The quality such as N- empgen BBs and sodium laurate is compounded, and in being added to hard water, the aqueous solution of 1000ppmw is obtained, and the drag reducing efficiency tested under different temperatures, highest drag reducing efficiency can be maintained at 65%.Temperature applicable range is 5～60 DEG C.
【Embodiment 6】
The quality such as N- empgen BBs and dodecyl sodium sulfate is compounded, and in being added to hard water, the aqueous solution of 1000ppmw is obtained, and the drag reducing efficiency tested under different temperatures, highest drag reducing efficiency can be maintained at 50%.Temperature applicable range is 5～50 DEG C.
【Embodiment 7】
The quality such as N- empgen BBs and sodium lauryl sulphate is compounded, and in being added to hard water, the aqueous solution of 1000ppmw is obtained, and the drag reducing efficiency tested under different temperatures, highest drag reducing efficiency can be maintained at 50%.Temperature applicable range is 5～50 DEG C.
【Embodiment 8】
The quality such as N- myristyl betaines and enuatrol is compounded, and in being added to hard water, the aqueous solution of 1000ppmw is obtained, and the drag reducing efficiency tested under different temperatures, highest drag reducing efficiency can be maintained at 50%.Temperature applicable range is 10～100 DEG C.
【Embodiment 9】
The quality such as N- cetyl betaines and enuatrol is compounded, and in being added to hard water, the aqueous solution of 1000ppmw is obtained, and the drag reducing efficiency tested under different temperatures, highest drag reducing efficiency can be maintained at 50%.Temperature applicable range is 10～110 DEG C.
【Embodiment 10】
The quality such as N- cetyl betaines and Sodium docosanoate is compounded, and in being added to hard water, the aqueous solution of 1000ppmw is obtained, and the drag reducing efficiency tested under different temperatures, highest drag reducing efficiency can be maintained at 50%.Temperature applicable range is 65～110 DEG C.
【Embodiment 11】
N- cetyl betaines, N- empgen BBs are according to mol ratio 1：1 is mixed to get glycine betaine complex, then by the quality such as glycine betaine complex and enuatrol compounding, in being added to hard water, the aqueous solution of 1000ppmw is obtained, and the drag reducing efficiency tested under different temperatures, highest drag reducing efficiency can be maintained at 80%.Temperature applicable range is 5～110 DEG C.(there is preferable synergism, effect is significant is better than embodiment 2,9)
【Embodiment 12】
Sodium docosanoate, enuatrol are according to mol ratio 1：1 is mixed to get compound fat hydrochlorate, then by the quality such as compound fat hydrochlorate and N- cetyl betaines compounding, in being added to hard water, the aqueous solution of 1000ppmw is obtained, and the drag reducing efficiency tested under different temperatures, highest drag reducing efficiency can be maintained at 76%.Temperature applicable range is 10～110 DEG C.(there is preferable synergism, effect is significant is better than embodiment 9,10)
It was found by the inventors of the present invention that the chain length and degree of unsaturation of hard soap of the present invention directly affect applicable temperature range, chain length is longer, and applicable temperature upper limit is higher, and degree of unsaturation is bigger, limits at applicable temperature lower.This can also from embodiment 1 to 5 on year-on-year basis in intuitively find out.Present inventor have further discovered that, in beet alkali surface activator and soap mixed system, when glycine betaine is amido betaine, drag-reduction effect is very poor.
Table 1
Claims (9)
1. the amphoteric surfactant and hard soap described in a kind of aqueous fracturing fluid drag reducer, including formula (I)；Wherein, R is the group of the saturation containing 8～24 carbon atoms or unsaturated aliphatic base or acyl group, R1、R2It is independently selected from the alkyl of 1～4 carbon atom or the hydroxyalkyl of 2～4 carbon atoms, R3It is the alkylidene of 1～6 carbon atom；
Wherein, the amphoteric surfactant and the weight ratio of the hard soap are 1:(0.02～50)；At least one of the hard soap in fat carboxylate, Fatty sulphonates, fat sulphate.
2. aqueous fracturing fluid drag reducer according to claim 1, is characterized in that at least one of the hard soap in the soap shown in formula (II), formula (III) or formula (IV)；
R4COOM formulas (II)；R4SO3M formulas (III)；R4SO4M formulas (IV)；
Wherein, R4It is the saturation containing 8～24 carbon atoms or unsaturated aliphatic base, M is independently selected from H, alkali metal or NH4。
3. aqueous fracturing fluid drag reducer according to claim 1, is characterized in that R1And R2It is methyl, ethyl or propyl group.
4. aqueous fracturing fluid drag reducer according to claim 1, is characterized in that R3It is methylene.
5. aqueous fracturing fluid drag reducer according to claim 1, is characterized in that R is aliphatic group or R5NHC3H6-, wherein R5It is acyl group.
6. aqueous fracturing fluid drag reducer according to claim 1, is characterized in that R in the hard soap4It is the saturation containing 12～22 carbon atoms or unsaturated aliphatic base.
7. application of the aqueous fracturing fluid drag reducer in fracturing fluid any one of claim 1 to 6.
8. the application according to the aqueous fracturing fluid drag reducer described in claim 7 in fracturing fluid, is characterized in that the fracturing fluid includes water, wherein the concentration that the amphoteric surfactant and hard soap total account for the fracturing fluid is 0.1～10kg/m3。
9. application of the aqueous fracturing fluid drag reducer according to claim 7 in fracturing fluid, the temperature that it is characterized in that the application is 5～120 DEG C.
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| CN1177974A (en) * | 1995-03-09 | 1998-04-01 | 阿克佐诺贝尔公司 | Use of a betaine surfactant together with an anionic surfactant as a drag-reducing agent |
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