CN109423265B - Salt-resistant and temperature-resistant starch microsphere as well as preparation method and application thereof - Google Patents
Salt-resistant and temperature-resistant starch microsphere as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a salt-resistant and temperature-resistant starch microsphere as well as a preparation method and application thereof, wherein the starch microsphere comprises the following raw materials: the starch microsphere comprises the following raw materials: 100 parts of deionized water, 1-20 parts of starch, 10-55 parts of triethanolamine, 0.105-14.6 parts of epoxy chloropropane, 0.1-20 parts of zwitterionic monomer, 0.001-0.2 part of initiator, 0.05-10 parts of zwitterionic surfactant, 200-750 parts of alkane compound, 10-250 parts of emulsifier, 0.5-200 parts of inorganic salt solution and 200-750 parts of organic solvent.
Description
Technical Field
The invention belongs to the technical field of microspheres, and particularly relates to a starch microsphere as well as a preparation method and application thereof.
Background
The shielding temporary plugging protection oil-gas layer drilling technology (shielding temporary plugging technology for short) is mainly used for solving the problem that a multi-pressure layer system stratum of an open hole well section protects an oil-gas layer, namely two adverse factors (pressure difference and drilling fluid solid-phase particles) which damage the oil-gas layer in the process of drilling into the oil-gas layer are utilized to convert the adverse factors into the advantageous factors for protecting the oil-gas layer, and the purpose of reducing the damage of the drilling fluid, cement paste, the pressure difference and the bubble invasion time to the oil-gas layer is achieved.
The basic idea of the shielding temporary plugging protection oil-gas reservoir drilling technology is that when an oil-gas reservoir is drilled, the pressure difference formed between the pressure of a drilling fluid liquid column and the pressure of the oil-gas reservoir forces solid particles of types and sizes artificially added in the drilling fluid to enter the pore throat of the oil-gas reservoir in a very short time, a plugging zone is quickly, shallowly and effectively formed near a well wall, the drilling fluid is prevented from continuously invading the oil-gas reservoir, and the damage of the drilling fluid to the oil-gas reservoir is reduced. Its thickness must be much less than the perforation depth in order to unblock through the perforations when the completion is put into production. After drilling is completed, if the open hole is completed, the blocking zone can be eliminated by means of acidification and the like, so that the original permeability of an oil-gas layer is recovered, and the oil-gas well is ensured to have better yield.
The microsphere compound is a more common temporary plugging agent for protecting oil and gas reservoirs at present, wherein the starch microsphere is also widely researched. The prior art has more researches on monodisperse or polydisperse starch microspheres, and patents CN201010546156.1 and CN201410236878.5 describe two preparation methods of monodisperse starch microspheres. CN201510151917.6 describes a preparation method of nano-scale polydisperse starch microspheres. CN201510175382.6 provides a method for preparing polymer microspheres with particle size gradient characteristics. There are few reports on uniformly distributed polydisperse starch microspheres.
In addition, in the application of starch microspheres, the prior patent is focused on the application of the starch microspheres in the aspects of drug carriers, food, medical treatment and the like. For example, patents CN 201510009941.6 and US 20130071479A1 both report the application potential of the prepared starch microspheres in the aspects of drug loading and delivery; EP 2506859B1 prepared starch microspheres with good swelling properties and low toxicity and applied to hemostasis treatment. The application of the starch microspheres in high-temperature, especially high-salt environments is not deeply explored in the current patent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a salt-resistant and temperature-resistant starch microsphere as well as a preparation method and application thereof.
The first aspect of the invention provides a starch microsphere, which comprises the following raw materials in parts by weight: 100 parts of deionized water, 1-20 parts of starch, 10-55 parts of triethanolamine, 0.105-14.6 parts of epoxy chloropropane, 0.1-20 parts of zwitterionic monomer, 0.001-0.2 part of initiator, 0.05-10 parts of zwitterionic surfactant, 200-750 parts of alkane compound, 10-250 parts of emulsifier and 0.5-200 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.025-50 parts and the organic solvent accounts for 200-750 parts.
In the starch microspheres, the zwitterionic starch microspheres comprise the following raw materials in parts by weight: 100 parts of deionized water, 5-15 parts of starch, 20-35 parts of triethanolamine, 1.04-7.8 parts of epoxy chloropropane, 5-15 parts of zwitterionic monomer, 0.02-0.1 part of initiator, 1-5 parts of zwitterionic surfactant, 250-450 parts of alkane compound, 30-100 parts of emulsifier and 50-150 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.5-30 parts and the organic solvent accounts for 250-450 parts.
In the starch microspheres, the controllable range of the particle size of the starch microspheres is 0.1-500 μm, the particle size of the starch microspheres is uniformly distributed in a particle size concentrated distribution interval (wherein the particle size concentrated distribution interval is defined as a continuous interval in which the proportion of the particle size distribution is greater than or equal to 90% except for the particle size boundaries at two ends, and the particle size concentrated distribution interval is an area in which the particle size distribution is approximately linearly distributed and does not include areas with obvious inflection points at two ends), and the particle size distribution in the particle size concentrated distribution interval has the following characteristics: evenly dividing the particle size concentrated distribution interval into n intervals, wherein the ratio of the microspheres in each interval is as follows:
wherein n is an integer greater than 1.
In the starch microspheres, the starch is one or more of mung bean starch, cassava starch, sweet potato starch, wheat starch, water caltrop starch, lotus root starch and corn starch, and preferably corn starch and/or potato starch.
In the starch microspheres, the starch is one or more of mung bean starch, cassava starch, sweet potato starch, wheat starch, water caltrop starch, lotus root starch and corn starch, and preferably corn starch and/or potato starch.
In the starch microsphere, the zwitterionic monomer can be one or more of DMAPS (methacryloyloxyethyl-N, N-dimethyl propane sulfonate), DAPS (N, N-dimethyl allyl amine propane sulfonate), VPPS (4-vinylpyridine propane sulfonate), MAPS (N-methyl diallyl propane sulfonate) and MABS (N-methyl diallyl butane sulfonate).
In the starch microsphere, the initiator can be one or more of potassium persulfate, sodium persulfate and ammonium persulfate.
In the starch microsphere, the structure of the zwitterionic surfactant is as follows:
wherein: n is an integer between 2 and 6, preferably n is 3 or 4; r is a carbon chain having 1 to 18 carbon atoms, preferably 12 to 18 carbon atoms. The carbon chain is a saturated carbon chain and can be a straight chain or a branched chain. The carbon chain (excluding the terminal carbon) may contain substituted hydroxyl, amino or carboxyl groups, and the same carbon may be monosubstituted. The zwitterionic surfactant can be one or more of dimethyl dodecyl sulfopropyl ammonium salt, dimethyl hexadecyl sulfoethyl ammonium salt, dimethyl octadecyl sulfobutyl ammonium salt, dimethyl (3-hydroxyl dodecyl) sulfopropyl ammonium salt and dimethyl (6-amino tetradecyl) sulfoethyl ammonium salt.
In the starch microspheres, the alkane compound is saturated alkane, and may be alkane and/or cycloalkane, and the alkane and cycloalkane may be halogenated alkane, and specifically may be one or more of n-hexane, n-heptane, n-octane, n-decane, n-dodecane, isohexane, isoheptane, isooctane, isodecane, isododecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, trichloromethane, chloropentane, chlorohexane, chlorooctane, and chlorododecane.
In the starch microspheres, the emulsifier can be an anionic surfactant, specifically one or more of sodium dodecyl benzene sulfonate, sodium hexadecylbenzene sulfonate, sodium dodecyl benzene sulfate and sodium hexadecylbenzene sulfate; the surfactant can also be nonionic surfactant, and specifically comprises one or more of Span20, Span40, Span60, Span80, Tween20, Tween40, Tween60 and Tween 80.
In the starch microspheres, the inorganic salt is a soluble inorganic salt, the inorganic salt is one or more of sodium salt, potassium salt, ammonium salt, calcium salt and magnesium salt, and when the inorganic salt is sodium salt, the inorganic salt is specifically one or more of sodium chloride, sodium bromide, sodium sulfate, sodium sulfite, sodium carbonate, sodium bicarbonate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate and sodium silicate; when the inorganic salt is potassium salt, the inorganic salt is one or more of potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, potassium bicarbonate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate and potassium silicate; when the inorganic salt is ammonium salt, the inorganic salt is one or more of ammonium chloride, ammonium bromide and ammonium nitrate; when the inorganic salt is a calcium salt, it is specifically calcium chloride or calcium bromide; when the inorganic salt is a magnesium salt, the inorganic salt is specifically one or more of magnesium chloride, magnesium bromide, magnesium sulfate and magnesium nitrate.
In the starch microspheres, the organic solvent is one or more of absolute ethyl alcohol, 1-butanol, ethyl acetate, butyl acetate, acetone, xylene, n-hexane and carbon tetrachloride, and ethyl acetate and/or absolute ethyl alcohol are preferred.
The second aspect of the present invention provides a preparation method of the above starch microsphere, which comprises the following steps:
(1) weighing a certain amount of starch, adding the starch into water, adding a certain amount of triethanolamine, uniformly mixing at 20-80 ℃, and adding epoxy chloropropane for reaction;
(2) adding a zwitterionic monomer into the feed liquid obtained in the step (1), fully dissolving and mixing, and then adding an initiator for reaction;
(3) adding a zwitterionic surfactant into the feed liquid obtained in the step (2), and uniformly mixing to obtain a water phase A;
(4) weighing a certain amount of alkane compounds, adding an emulsifier, and uniformly mixing until the alkane compounds are completely dissolved to obtain an oil phase B;
(5) and (3) uniformly mixing the water phase A obtained in the step (3) and the oil phase B obtained in the step (4) at the temperature of 30-60 ℃, slowly and uniformly adding an inorganic salt solution and epoxy chloropropane into the mixed solution, continuing to react after the inorganic salt solution and the epoxy chloropropane are added, demulsifying and removing the upper oil phase after the reaction is finished, and washing and drying to obtain the microsphere.
In the method, the amounts of the deionized water, the starch, the triethanolamine, the epichlorohydrin, the zwitterionic monomer, the initiator, the zwitterionic surfactant, the alkane compound, the emulsifier, the inorganic salt solution and the organic solvent are respectively as follows: 100 parts of deionized water, 1-20 parts of starch, 10-55 parts of triethanolamine, 0.105-14.6 parts of epoxy chloropropane, 0.1-20 parts of zwitterionic monomer, 0.001-0.2 part of initiator, 200-750 parts of alkane compound, 10-250 parts of emulsifier, 0.05-10 parts of zwitterionic surfactant and 0.5-200 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.025-50 parts and the organic solvent accounts for 200-750 parts; preferably 100 parts of deionized water, 5-15 parts of starch, 20-35 parts of triethanolamine, 1.04-7.8 parts of epoxy chloropropane, 5-15 parts of zwitterionic monomer, 0.02-0.1 part of initiator, 250-450 parts of alkane compound, 30-100 parts of emulsifier, 1-5 parts of zwitterionic surfactant and 50-150 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.5-30 parts and the solvent accounts for 250-450 parts.
In the method, the starch in the step (1) is one or more of mung bean starch, cassava starch, sweet potato starch, wheat starch, water chestnut starch, lotus root starch and corn starch, and preferably corn starch and/or potato starch.
In the method, the reaction temperature in the step (1) is 30-60 ℃; the reaction time is 0.5-4 h, preferably 1-3 h.
In the method, the reaction temperature in the step (2) is 60-80 ℃, and the reaction time is 3-6 h.
In the method of the present invention, the zwitterionic monomer in step (2) may be one or more of DMAPS (methacryloyloxyethyl-N, N-dimethylpropanesulfonate), DAPS (N, N-dimethylallylamine propanesulfonate), VPPS (4-vinylpyridine propanesulfonate), MAPS (N-methyldiallylpropyl propanesulfonate), and MABS (N-methyldiallylbutylsulfonate).
In the method of the present invention, the initiator in step (2) may be one or more of potassium persulfate, sodium persulfate, and ammonium persulfate.
In the method of the present invention, step (3) isThe structure of the zwitterionic surfactant is as follows:
wherein: n is an integer between 2 and 6, preferably n is 3 or 4; r is a carbon chain having 1 to 18 carbon atoms, preferably 12 to 18 carbon atoms. The carbon chain is a saturated carbon chain and can be a straight chain or a branched chain. The carbon chain (excluding the terminal carbon) may contain substituted hydroxyl, amino or carboxyl groups, and the same carbon may be monosubstituted. The zwitterionic surfactant can be one or more of dimethyl dodecyl sulfopropyl ammonium salt, dimethyl hexadecyl sulfoethyl ammonium salt, dimethyl octadecyl sulfobutyl ammonium salt, dimethyl (3-hydroxyl dodecyl) sulfopropyl ammonium salt and dimethyl (6-amino tetradecyl) sulfoethyl ammonium salt.
In the method of the present invention, the alkane compound in step (4) is a saturated alkane, and may be an alkane and/or a cycloalkane, and the alkane and cycloalkane may be a halogenated alkane, and specifically may be one or more of n-hexane, n-heptane, n-octane, n-decane, n-dodecane, isohexane, isoheptane, isooctane, isodecane, isododecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, trichloromethane, chloropentane, chlorohexane, chlorooctane, and chlorododecane.
In the method of the invention, the emulsifier in the step (4) can be an anionic surfactant, specifically one or more of sodium dodecyl benzene sulfonate, sodium hexadecylbenzene sulfonate, sodium dodecyl benzene sulfate and sodium hexadecylbenzene sulfate; the surfactant can also be nonionic surfactant, and specifically comprises one or more of Span20, Span40, Span60, Span80, Tween20, Tween40, Tween60 and Tween 80.
In the method, the inorganic salt in the step (5) is soluble inorganic salt, the inorganic salt is one or more of sodium salt, potassium salt, ammonium salt, calcium salt and magnesium salt, and when the inorganic salt is sodium salt, the inorganic salt is specifically one or more of sodium chloride, sodium bromide, sodium sulfate, sodium sulfite, sodium carbonate, sodium bicarbonate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate and sodium silicate; when the inorganic salt is potassium salt, the inorganic salt is one or more of potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, potassium bicarbonate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate and potassium silicate; when the inorganic salt is ammonium salt, the inorganic salt is one or more of ammonium chloride, ammonium bromide and ammonium nitrate; when the inorganic salt is a calcium salt, it is specifically calcium chloride or calcium bromide; when the inorganic salt is a magnesium salt, the inorganic salt is specifically one or more of magnesium chloride, magnesium bromide, magnesium sulfate and magnesium nitrate.
In the method of the present invention, the slow and uniform adding in step (5) may be any method capable of realizing uniform solvent adding in the field, such as a dropwise adding method.
In the method of the present invention, the demulsification in step (5) may be performed by any means available in the art, such as mechanical stirring or adding an organic solvent, preferably by adding an organic solvent. The washing described in step (5) is washing with an organic solvent, the washing operation being well known to the person skilled in the art. In the method of the present invention, the demulsification and washing processes in the step (5) are performed by using the same or different organic solvents, and preferably by using the same organic solvent. The organic solvent is one or more of absolute ethyl alcohol, 1-butanol, ethyl acetate, butyl acetate, acetone, xylene, n-hexane and carbon tetrachloride, and ethyl acetate and/or absolute ethyl alcohol are/is preferred.
In the method, the drying in the step (5) is carried out for 12-24 hours at the temperature of 55-95 ℃.
The third aspect of the invention also provides application of the starch microspheres in a temporary plugging agent for protecting an oil-gas reservoir. The starch microspheres are used as a component in a drilling fluid system to play a role in shielding and temporary plugging. The addition amount of 0.5-5 wt% can achieve good effect. The drilling fluid added with the microspheres has good plugging capability, can effectively plug pores or microcracks to form compact mud cakes, prevents a large amount of filtrate from permeating into a stratum, and reduces the filtration loss.
Compared with the prior art, the starch microsphere and the preparation method thereof have the following advantages:
1. the starch microspheres of the invention are polydisperse microspheres with uniformly distributed particle sizes, which are different from monodisperse and polydisperse starch microspheres prepared by the prior art. When the starch microspheres are applied to the field of temporary plugging agents for protecting oil and gas reservoirs, due to the fact that geological structures are different, the porosity span of the reservoirs is large, and if the microspheres with monodisperse particle sizes are used, the requirement on broad spectrum is difficult to meet, and the using effect cannot meet the industrial requirement. In addition, the existing polydisperse microspheres are normally distributed, the effective range of the particle size is narrow, and the effect is obviously limited. The uniformly distributed polydisperse starch microspheres provided by the technology can well solve the problems, namely, in any particle size interval, the microspheres have equivalent proportion, high microsphere content and obvious temporary plugging effect, and can meet the requirement of broad spectrum.
2. In the preparation method of the starch microspheres, the structures of the straight chain part and the branched chain part in the starch are equivalent in size and have similar molecular sizes by the combined action of the triethanolamine and the epoxy chloropropane, particularly the operation mode of respectively adding the epoxy chloropropane in two steps, so that the prepared microspheres are easier to control, and the particle size distribution is uniform. Then in the process of crosslinking starch into microspheres later, by using a zwitterionic surfactant and simultaneously slowly adding inorganic salt and epoxy chloropropane at a constant speed, under the combined action of the zwitterionic surfactant and the inorganic salt and the epoxy chloropropane, the particle size of the prepared starch microspheres is linearly changed, and then the poly-dispersed starch microspheres with uniformly distributed particle sizes are prepared.
3. The starch microspheres are prepared by adopting an inverse emulsion polymerization method, and starch monomers are uniformly suspended in a continuous phase under the action of mechanical stirring and a zwitterionic surfactant to complete polymerization. The reaction process has the advantages of low material viscosity and easy heat transfer and control of the reaction, and pure and uniform micron-sized microsphere products can be obtained only by simple separation, cleaning and drying after polymerization, thereby being beneficial to the amplification production and industrial application of the technology.
4. In the preparation method of the zwitterionic starch microspheres, due to the addition of the zwitterionic monomer, the salt resistance, temperature resistance and other properties of the microspheres are remarkably improved.
Detailed Description
The starch microspheres of the present invention, and the method and use of the starch microspheres are further described by the following specific examples, which should not be construed as limiting the invention.
The particle size of the starch microsphere is measured by a Malvern 3000 particle size analyzer, and the measuring method is wet measurement.
The particle size range (a μm-b μm) in all the examples and comparative examples below means a.ltoreq.D < b.
The ratios of materials presented in all the following examples and comparative examples are mass parts ratios of materials.
Example 1
Weighing 5 parts of potato starch, adding the potato starch into 100 parts of deionized water, adding 20 parts of triethanolamine, and fully dissolving at room temperature. Then 0.04 part of epoxy chloropropane is added, and the mixture is mixed and reacted for 2 hours. 3.5 parts of MAPS were weighed into the starch solution and mixed thoroughly. 0.06 part of ammonium persulfate was added at 70 ℃ and reacted for 4 hours. Adding 3 parts of dimethyl hexadecyl sulfoethyl ammonium salt, and fully mixing to obtain a feed liquid, namely the water phase A. And adding 30 parts of emulsifier (Span 40: Tween60=2: 3) into 250 parts of n-octane, and stirring at high speed to completely dissolve the n-octane to obtain a feed liquid, namely the oil phase B. Slowly pouring A into B at 60 ℃, and weighing 0.5 part of CaCl2Preparing 20 parts of inorganic salt solution, simultaneously dripping the inorganic salt solution and 1 part of epichlorohydrin into the starch solution at the same temperature, dripping the solution at a constant speed for 8 hours, and continuously reacting for 2 hours after the dripping is finished. And then stopping the reaction, adding 100 parts of carbon tetrachloride as an organic solvent into the mixed phase for demulsification, filtering an upper oil phase, washing the microspheres with 150 parts of carbon tetrachloride, and finally drying at the constant temperature of 55 ℃ for 24 hours to obtain white powdery microspheres. The particle size concentrated distribution interval of the starch microspheres is 15-175 microns (95.1% of particle sizes are in the interval), and the particle size distribution in the particle size concentrated distribution interval has the following characteristics: (15 μm-55 μm): 22.6 percent; (55 μm-95 μm): 27.2 percent; (95 μm-135 μm): 26.5 percent; (135 μm-175 μm): 23.7 percent.
Example 2
Weighing 10 parts of wheat starch, adding into 100 parts of deionized water, adding 10 parts of triethanolamine, and fully dissolving at 80 ℃. Then 0.3 part of epichlorohydrin is added, and the mixture is mixed and reacted for 3 hours. 5 parts of DMAPS are weighed and added into the starch solution, and the mixture is fully dissolved and mixed. 0.02 part of potassium persulfate was added thereto at 60 ℃ and reacted for 6 hours. Adding 1 part of dimethyl dodecyl sulfopropyl ammonium salt, and fully mixing to obtain a feed liquid, namely the water phase A. And adding 250 parts of emulsifier (Span 40: Tween40=2: 1) into 750 parts of cyclohexane, and stirring at high speed to completely dissolve the cyclohexane, wherein the obtained feed liquid is the oil phase B. Slowly pouring the A into the B at 50 ℃, weighing 50 parts of NaCl to prepare 200 parts of inorganic salt solution, simultaneously dripping the inorganic salt solution and 0.3 part of epichlorohydrin into the mixed phase at the same temperature, dripping the solution at a constant speed for 5 hours, and continuously reacting for 2 hours after the dripping is finished. And then stopping the reaction, adding 300 parts of normal hexane as an organic solvent into the mixed phase for demulsification, filtering out an upper oil phase, washing the microspheres by 450 parts of normal hexane, and finally drying at the constant temperature of 95 ℃ for 12 hours to obtain white powdery microspheres. The starch microspheres have a particle size concentration distribution interval of 120-380 μm (94.5% of particle size is in the interval), and the particle size distribution in the particle size concentration distribution interval has the following characteristics: (120 μm-185 μm): 22.9 percent; (185 μm-250 μm): 26.5 percent; (250 μm-315 μm): 27.4 percent; (315 μm-380 μm): 23.2 percent.
Example 3
20 parts of mung bean starch is weighed and added into 100 parts of deionized water, and 55 parts of triethanolamine is added and fully dissolved at 40 ℃. Then 0.6 part of epoxy chloropropane is added, and the mixture is mixed and reacted for 1 hour. 15 parts of DAPS are weighed out and added to the starch solution, and the mixture is fully dissolved and mixed. 0.2 part of sodium persulfate was added thereto at 80 ℃ and reacted for 3 hours. And adding 10 parts of dimethyl octadecyl butyl ammonium salt, and fully mixing to obtain a feed liquid, namely the water phase A. And adding 100 parts of emulsifier (Span 60: Tween40=3: 1) into 450 ml of n-octane, and stirring at high speed to completely dissolve the n-octane to obtain a feed liquid, namely the oil phase B. Slowly pouring A into B at 40 ℃, and weighing 30 parts of MgCl2Preparing 150 parts of inorganic salt solution, simultaneously dripping 14 parts of epichlorohydrin into the starch solution at the same temperature, dripping at constant speed for 10 hours, and continuously reacting for 2 hours after dripping is finished. Then stopping the reaction, adding 200 parts of dimethylbenzene as an organic solvent into the mixed phase for demulsification, filtering out an upper oil phase,and washing the microspheres with 250 parts of xylene, and finally drying at constant temperature of 85 ℃ for 14.5 hours to obtain white powdery microspheres. The starch microspheres have a particle size concentration distribution interval of 50-325 mu m (96.7% of particle size is in the interval), and the particle size distribution in the particle size concentration distribution interval has the following characteristics: (50 μm-105 μm): 22.0 percent; (105 μm-160 μm): 18.7 percent; (160 μm-215 μm): 21.6 percent; (215 μm-270 μm): 18.9 percent; (270 μm-325 μm): 18.8 percent.
Example 4
15 parts of corn starch are weighed and added into 100 parts of deionized water, and 35 parts of triethanolamine is added and fully dissolved at 60 ℃. Then 0.5 part of epoxy chloropropane is added, and the mixture is reacted for 1.5 hours after being mixed. 20 parts of VPPS are weighed and added into the starch solution, and fully dissolved and mixed. 0.1 part of an initiator (potassium persulfate: sodium persulfate =1: 1) was added at 75 ℃ and reacted for 5 hours. Adding 5 parts of dimethyl (3-hydroxy dodecyl) sulfopropyl ammonium salt, and fully mixing to obtain a feed liquid, namely the water phase A. And adding 80 parts of emulsifier (Span 60: Tween60=3: 1) into 400 parts of chloropentane, and stirring at high speed to completely dissolve the chloropentane to obtain a feed liquid, namely the oil phase B. Slowly pouring A into B at 30 ℃, and weighing 22.5 parts of K2SO4Preparing 50 parts of inorganic salt solution, simultaneously dripping 10 parts of epichlorohydrin into the starch solution at the same temperature, dripping at constant speed for 7 hours, and continuously reacting for 2 hours after dripping. And then stopping the reaction, adding 130 parts of acetone as an organic solvent into the mixed phase for demulsification, filtering out an upper oil phase, washing the microspheres with 270 parts of acetone, and finally drying at the constant temperature of 68 ℃ for 21 hours to obtain white powdery microspheres. The particle size concentrated distribution range of the starch microspheres is 150-465 μm (97.3% of particle sizes are in the range), and the particle size distribution in the particle size concentrated distribution range has the following characteristics: 150 μm to 195 μm): 12.9 percent; (195 μm-240 μm): 15.1 percent; (240 μm-285 μm): 14.4 percent; (285 μm-330 μm): 13.9 percent; (330 μm-375 μm): 13.3 percent; (375 μm-420 μm): 15.1 percent; (420 μm-465 μm): 15.3 percent.
Example 5
Weighing 1 part of sweet potato starch, adding into 100 parts of deionized water, adding 17.5 parts of triethanolamine, and fully dissolving at 50 ℃. Then add0.005 part of epoxy chloropropane is added, and the mixture is reacted for 2.75 hours after being mixed. 0.1 part of monomer (MAPS: VPPS =1: 1) was weighed into the starch solution, and mixed well. 0.001 part of ammonium persulfate was added at 65 ℃ and reacted for 4.5 hours. 0.05 part of dimethyl (6-aminotetradecyl) sulfoethyl ammonium salt is added, and the obtained feed liquid is the water phase A after full mixing. And adding 10 parts of emulsifier (Span 80) into 200 ml of alkane compound (cyclohexane: trichloromethane =3: 2), and stirring at high speed to completely dissolve the alkane compound, wherein the obtained feed liquid is the oil phase B. Slowly pouring A into B at 55 deg.C, and weighing 0.025 parts of inorganic salt (CaCl)2KCl =3:2 parts by mass) to prepare 0.5 part of inorganic salt solution, dripping the inorganic salt solution and 0.1 part of epichlorohydrin into the starch solution at the same temperature, dripping the solution at a constant speed for 9 hours, and continuing to react for 2 hours after the dripping is finished. And then stopping the reaction, adding 45 parts of butyl acetate serving as an organic solvent into the mixed phase for demulsification, filtering out an upper oil phase, washing the microspheres by 155 parts of butyl acetate, and finally drying at the constant temperature of 72 ℃ for 20 hours to obtain white powdery microspheres. The starch microspheres have a particle size concentration distribution interval of 0.1-18 μm (95.5% of particle size is in the interval), and the particle size distribution in the particle size concentration distribution interval has the following characteristics: (0.1 μm-3 μm): 16.5 percent; (3 μm-6 μm): 18.1 percent; (6 μm-9 μm): 15.2 percent; (9 μm-12 μm): 15.5 percent; (12 μm-15 μm): 17.4 percent; (15 μm-18 μm): 17.3 percent.
Example 6
7.5 parts of starch (corn: sweet potato =2: 1) was weighed into 100 parts of deionized water, and 12.5 parts of triethanolamine was added thereto, followed by sufficient dissolution at 72 ℃. Then 0.25 part of epoxy chloropropane is added, and the mixture is reacted for 1.75 hours after being mixed. 12.5 parts of monomer (DMAPS: MAPS =4: 1) are weighed into the starch solution and mixed thoroughly. 0.08 part of an initiator (potassium persulfate: ammonium persulfate =1: 1) was added at 68 ℃ and reacted for 5.5 hours. 6.4 parts of dimethyl dodecyl sulfobutyl ammonium salt is added, and the obtained feed liquid is the water phase A after full mixing. And adding 70 parts of emulsifier (sodium dodecyl benzene sulfonate) into 350ml of alkane compound (n-heptane: n-octane =3: 4), and stirring at high speed to completely dissolve the alkane compound, wherein the obtained feed liquid is the oil phase B. Slowly pouring A into B at 57 ℃, and weighing 8 parts of CaCl2Adding into 80ml water to prepare CaCl2And dripping the solution and 3.5 parts of epichlorohydrin into the starch solution at the same temperature, dripping at a constant speed for 4.5 hours, and continuously reacting for 2 hours after finishing dripping. And then stopping the reaction, adding 125 parts of ethyl acetate serving as an organic solvent into the mixed phase for demulsification, filtering out an upper oil phase, washing the microspheres by 225 parts of ethyl acetate, and finally drying at the constant temperature of 90 ℃ for 13.5 hours to obtain white powdery microspheres. The concentrated particle size distribution interval of the starch microspheres is 80-280 microns (94.9% of particle sizes are in the interval), and the particle size distribution in the concentrated particle size distribution interval has the following characteristics: (80 μm-120 μm): 18.7 percent; (120 μm-160 μm): 21.6 percent; (160 μm-200 μm): 21.1 percent; (200 μm-240 μm): 18.9 percent; (240 μm-280 μm): 19.7 percent.
Example 7
14 parts of starch (potato: mung bean =1: 1) are weighed out and added to 100 parts of water, and then 20 parts of triethanolamine are added and dissolved sufficiently at 65 ℃. Then 0.3 part of epoxy chloropropane is added, and the mixture is reacted for 1.2 hours after being mixed. 8 parts of monomer (DAPS: VVPS =1: 1) were weighed into the starch solution, and thoroughly dissolved and mixed. 0.18 part of sodium persulfate was added thereto at 80 ℃ and reacted for 3.5 hours. 6.6 parts of dimethyl hydroxyl hexadecyl sulfopropyl ammonium salt is added, and the obtained feed liquid is the water phase A after full mixing. 560 parts of alkane compound (n-octane: cyclohexane =4: 3) is taken, 80 parts of emulsifier (sodium hexadecyl benzene sulfonate) is added, and the mixture is stirred at high speed to be completely dissolved, so that the obtained feed liquid is the oil phase B. Slowly pouring A into B at 45 ℃, and weighing 20 parts of KNO3160 parts of inorganic salt solution is prepared, and is simultaneously dripped into the starch solution with 9.6 parts of epichlorohydrin at the same temperature, and the dripping time is 6 hours at uniform speed. After the dropwise addition, the reaction was continued for 2 hours. And then stopping the reaction, adding 200 parts of 1-butanol serving as an organic solvent into the mixed phase for demulsification, filtering out an upper oil phase, washing the microspheres with 360 parts of 1-butanol, and finally drying at the constant temperature of 80 ℃ for 16 hours to obtain white powdery microspheres. The starch microspheres have a particle size concentration distribution interval of 35-245 mu m (96.2% of particle sizes are in the interval), and the particle size distribution in the particle size concentration distribution interval has the following characteristics: (35 μm-70 μm): 16.2 percent; (70 μm-105 μm): 15.7 percent; (105 μm-140 μm): 17.9 percent; (140 μm-175 μm): 17.5 percent;（175μm-210μm）：17.0%；（210μm-245μm）：15.7%。
example 8
3.5 parts of corn starch are weighed into 100 parts of water, 12 parts of triethanolamine are added, and the mixture is fully dissolved at 45 ℃. Then 0.09 part of epoxy chloropropane is added, and the mixture is mixed and reacted for 2.25 hours. 1.5 parts DMAPS was weighed into the starch solution and mixed well. 0.015 part (sodium persulfate: ammonium persulfate =2: 1) was added at 67.5 ℃ and reacted for 5.25 hours. 4.5 parts of dimethyldodecylsulfopropyl ammonium salt is added, and the obtained feed liquid is the water phase A after full mixing. And adding 40 parts of emulsifier (sodium dodecyl benzene sulfonate: sodium dodecyl benzene sulfate =3: 1) into 250 parts of alkane compound (n-heptane: cyclohexane =1: 4), and stirring at high speed to completely dissolve the mixture, wherein the obtained feed liquid is the oil phase B. Slowly pouring A into B at 40 ℃, and weighing 4 parts of Na2CO3Preparing 67.5 parts of inorganic salt solution, simultaneously dripping 1.5 parts of epichlorohydrin into the starch solution at the same temperature, dripping at a constant speed for 6 hours, and continuously reacting for 2 hours after finishing dripping. And then stopping the reaction, adding 75 parts of absolute ethyl alcohol as an organic solvent into the mixed phase for demulsification, filtering out an upper oil phase, washing the microspheres by 175 parts of absolute ethyl alcohol, and finally drying at the constant temperature of 77 ℃ for 18 hours to obtain white powdery microspheres. The concentrated particle size distribution interval of the starch microspheres is 1-19 microns (92.8% of particle sizes are in the interval), and the particle size distribution in the concentrated particle size distribution interval has the following characteristics: (1 μm-4 μm): 16.6 percent; (4 μm-7 μm): 16.3 percent; (7 μm-10 μm): 17.2 percent; (10 μm-13 μm): 15.1 percent; (13 μm-16 μm): 17.4 percent; (16 μm-19 μm): 17.4 percent.
Comparative example 1 (use of conventional surfactant only)
5 parts of potato starch are weighed into 100 parts of deionized water and fully dissolved for 30min at room temperature. 3.5 parts of MAPS were weighed into the starch solution and mixed thoroughly. 0.06 part of ammonium persulfate was added at 70 ℃ and reacted for 4 hours. Adding 3 parts of sodium dodecyl sulfate, and fully mixing to obtain a feed liquid, namely the water phase A. And adding 30 parts of emulsifier (Span 40: Tween60=2: 3) into 250 parts of n-octane, and stirring at high speed to completely dissolve the n-octane to obtain a feed liquid, namely the oil phase B. Slowly pouring the A into the B at 60 ℃, adding 1 part of epoxy chloropropane into the mixed phase at the same temperature, reacting for 10h, and stopping the reaction. Adding 100 parts of carbon tetrachloride as an organic solvent into the mixed phase for demulsification, filtering an upper oil phase, washing the microspheres with 150 parts of carbon tetrachloride, and finally drying at the constant temperature of 55 ℃ for 24 hours to obtain white powdery microspheres. The starch microspheres have a particle size concentration distribution interval of 75-300 microns (92.2% of particle sizes are in the interval), and the particle size distribution in the particle size concentration distribution interval has the following characteristics: (75 μm-150 μm): 19.4 percent; (150 μm-225 μm): 59.8 percent; (225 μm-300 μm): 20.8 percent.
COMPARATIVE EXAMPLE 2 (Triethanolamine, D-SALT)
Weighing 5 parts of potato starch, adding the potato starch into 100 parts of deionized water, adding 20 parts of triethanolamine, and fully dissolving for 30min at room temperature. 3.5 parts of MAPS were weighed into the starch solution and mixed thoroughly. 0.06 part of ammonium persulfate was added at 70 ℃ and reacted for 4 hours. Adding 3 parts of dimethyl hexadecyl sulfoethyl ammonium salt, and fully mixing to obtain a feed liquid, namely the water phase A. And adding 30 parts of emulsifier (Span 40: Tween60=2: 3) into 250 parts of n-octane, and stirring at high speed to completely dissolve the n-octane to obtain a feed liquid, namely the oil phase B. Slowly pouring A into B at 60 ℃, and weighing 0.5 part of CaCl2Preparing 20 parts of inorganic salt solution, simultaneously dropwise adding the inorganic salt solution and 1 part of epoxy chloropropane into the mixed phase at the same temperature, uniformly dropwise adding for 8 hours, and continuously reacting for 2 hours after dropwise adding. And then stopping the reaction, adding 100 parts of carbon tetrachloride as an organic solvent into the mixed phase for demulsification, filtering an upper oil phase, washing the microspheres with 150 parts of carbon tetrachloride, and finally drying at the constant temperature of 55 ℃ for 24 hours to obtain white powdery microspheres. The starch microspheres have a particle size concentration distribution interval of 30-250 micrometers (91.9% of particle sizes are in the interval), and the particle size distribution in the particle size concentration distribution interval has the following characteristics: (30 μm-85 μm): 22.1 percent; (85 μm-140 μm): 27.5 percent; (140 μm-195 μm): 18.2 percent; (195 μm-250 μm): 32.2 percent.
Comparative example 3 (Triethanolamine, micro-crosslinking)
Weighing 5 parts of potato starch, adding the potato starch into 100 parts of deionized water, adding 20 parts of triethanolamine, and fully dissolving for 30min at room temperature. Then 0.04 part of epoxy chloropropane is added, and the mixture is mixed and reacted for 2 hours. 3.5 parts of MAPS were weighed into the starch solution and mixed thoroughly. 0.06 part of ammonium persulfate was added at 70 ℃ and reacted for 4 hours. Adding 3 parts of dimethyl hexadecyl sulfoethyl ammonium salt, and fully mixing to obtain a feed liquid, namely the water phase A. And adding 30 parts of emulsifier (Span 40: Tween60=2: 3) into 250 parts of n-octane, and stirring at high speed to completely dissolve the n-octane to obtain a feed liquid, namely the oil phase B. Slowly pouring the A into the B at 60 ℃, adding 1 part of epoxy chloropropane into the mixed phase at the same temperature, reacting for 10h, and stopping the reaction. Adding 100 parts of carbon tetrachloride as an organic solvent into the mixed phase for demulsification, filtering an upper oil phase, washing the microspheres with 150 parts of carbon tetrachloride, and finally drying at the constant temperature of 55 ℃ for 24 hours to obtain white powdery microspheres. The starch microspheres have a particle size concentration distribution interval of 10-150 microns (94.8% of particle sizes are in the interval), and the particle size distribution in the particle size concentration distribution interval has the following characteristics: (10 μm-45 μm): 19.6 percent; (45 μm-80 μm): 21.2 percent; (80 μm-115 μm): 27.5 percent; (115 μm-150 μm): 31.7 percent.
Comparative example 4 (micro-crosslinking, dropwise addition of salt)
5 parts of potato starch are weighed into 100 parts of deionized water and fully dissolved for 30min at room temperature. Then 0.04 part of epoxy chloropropane is added, and the mixture is mixed and reacted for 2 hours. 3.5 parts of MAPS were weighed into the starch solution and mixed thoroughly. 0.06 part of ammonium persulfate was added at 70 ℃ and reacted for 4 hours. Adding 3 parts of dimethyl hexadecyl sulfoethyl ammonium salt, and fully mixing to obtain a feed liquid, namely the water phase A. And adding 30 parts of emulsifier (Span 40: Tween60=2: 3) into 250 parts of n-octane, and stirring at high speed to completely dissolve the n-octane to obtain a feed liquid, namely the oil phase B. Slowly pouring A into B at 60 ℃, and weighing 0.5 part of CaCl2Preparing 20 parts of inorganic salt solution, simultaneously dripping the inorganic salt solution and 1 part of epichlorohydrin into the starch solution at the same temperature, dripping the solution at a constant speed for 8 hours, and continuously reacting for 2 hours after the dripping is finished. And then stopping the reaction, adding 100 parts of carbon tetrachloride as an organic solvent into the mixed phase for demulsification, filtering an upper oil phase, washing the microspheres with 150 parts of carbon tetrachloride, and finally drying at the constant temperature of 55 ℃ for 24 hours to obtain white powdery microspheres. The particle size concentrated distribution range of the starch microspheres is 15 to215 μm (93.0% of the particle size in this interval), the particle size distribution in the particle size distribution interval being characterized by: (15 μm-65 μm): 37.2 percent; (65 μm-115 μm): 19.7 percent; (115 μm-165 μm): 21.1 percent; (165 μm-215 μm): 22 percent.
Evaluation of application of starch microspheres containing zwitterionic monomers as temporary plugging agents- -sand bed plugging experiments, samples prepared in examples and comparative examples were selected for evaluation. An experimental instrument: a drilling fluid sand bed filtration loss instrument, a stirrer and an oven. Experimental materials: log 860 well slurry (density 1.19 g/cm)3) Examples, comparative examples and 20-40 mesh sand samples.
The experimental steps are as follows:
1. slurry preparation: formulated slurry +3% of example sample or comparative sample.
2. Manufacturing a sand bed: adding 20-40 mesh sand into the cylinder by 350cm3Shaking up;
3. adding prepared experimental slurry (400-500 mL), fixing on an instrument frame and sealing an upper channel and a lower channel;
4. and opening an air source, adjusting the pressure to 0.69mPa, simultaneously opening an upper switch and a lower switch, and measuring the condition that the drilling fluid invades the sand bed in the half-hour process.
The experimental results are as follows:
the filtrate loss FL is 30min after the formula is added1And the drilling fluid is basically stable after invading the sand bed to the depth D. After a stable mud cake is formed, the pressure is released, the drilling fluid is poured out, clear water is added to the position of 400mL, and the filtration loss FL after 30min of pressurization (0.69 mPa) measurement is carried out2The experimental results are shown in table 1:
TABLE 1 results of the experiment
| Sample (I) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Filtration loss FL1/ml | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 5 | 3 | 0 | 0 |
| Depth D/cm3 | 175 | 185 | 160 | 175 | 215 | 170 | 190 | 205 | 350 | 350 | 325 | 310 |
| Filtration loss FL2/ml | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 65 | 53 | 42 | 33 |
The experimental results are as follows:
from the above results, it can be seen that the clear water shows good plugging effect without filtration loss at 0.69mPa pressure for 30min when the samples of examples 1-5 are used, while the clear water shows poor plugging effect with filtration loss of 65ml at 0.69mPa pressure for 30min when the samples of comparative examples 1-4 are used.
Claims (50)
1. The starch microsphere comprises the following raw materials in parts by weight: 100 parts of deionized water, 1-20 parts of starch, 10-55 parts of triethanolamine, 0.105-14.6 parts of epoxy chloropropane, 0.1-20 parts of zwitterionic monomer, 0.001-0.2 part of initiator, 0.05-10 parts of zwitterionic surfactant, 200-750 parts of alkane compound, 10-250 parts of emulsifier and 0.5-200 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.025-50 parts and the organic solvent accounts for 200-750 parts; the preparation method of the starch microspheres comprises the following steps:
(1) weighing starch, adding the starch into water, adding triethanolamine, uniformly mixing at 20-80 ℃, and adding epoxy chloropropane for micro-crosslinking reaction;
(2) adding a zwitterionic monomer into a starch solution, fully dissolving and mixing, adding an initiator, and reacting for 3-6 h at 60-80 ℃;
(3) adding a zwitterionic surfactant into the feed liquid obtained in the step (2), and uniformly mixing to obtain a water phase A;
(4) weighing alkane compounds, adding an emulsifier, and uniformly mixing until the alkane compounds are completely dissolved to obtain an oil phase B;
(5) and (3) uniformly mixing the water phase A obtained in the step (3) and the oil phase B obtained in the step (4) at the temperature of 30-60 ℃, slowly and uniformly adding an inorganic salt solution and epoxy chloropropane into the mixed solution, continuing to react after the inorganic salt solution and the epoxy chloropropane are added, demulsifying and removing the upper oil phase after the reaction is finished, washing with a solvent, and drying to obtain the microsphere.
2. The starch microsphere according to claim 1, wherein the zwitterionic starch microsphere comprises the following raw materials in parts by weight: 100 parts of deionized water, 5-15 parts of starch, 20-35 parts of triethanolamine, 1.04-7.8 parts of epoxy chloropropane, 5-15 parts of zwitterionic monomer, 0.02-0.1 part of initiator, 1-5 parts of zwitterionic surfactant, 250-450 parts of alkane compound, 30-100 parts of emulsifier and 50-150 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.5-30 parts and the organic solvent accounts for 250-450 parts.
3. The starch microspheres according to claim 1, wherein the particle size of the starch microspheres is controllable within a range of 0.1-500 μm.
4. The starch microspheres of claim 1, wherein said starch microspheres have a uniform polydispersity of particle size distribution within a concentrated distribution interval, said concentrated distribution interval characterized by a particle size distribution of: evenly dividing the particle size concentrated distribution interval into n intervals, wherein the ratio of the microspheres in each interval is as follows:
wherein n is an integer greater than 1.
5. The starch microsphere according to claim 1, wherein the starch is one or more of mung bean starch, tapioca starch, sweet potato starch, wheat starch, water chestnut starch, lotus root starch and corn starch.
6. The starch microspheres of claim 1, wherein said starch is corn starch and/or potato starch.
7. The starch microspheres of claim 1, wherein said zwitterionic monomer is one or more of methacryloyloxyethyl-N, N-dimethylpropanesulfonate, N-dimethylallylamine propanesulfonate, 4-vinylpyridine propanesulfonate, N-methyldiallylpropane propanesulfonate, N-methyldiallylbutylsulfonate.
8. The starch microspheres of claim 1, wherein said initiator is one or two of potassium persulfate, sodium persulfate, and ammonium persulfate.
9. The starch microspheres of claim 1, wherein said zwitterionic surfactant has the following structure:
wherein: n is an integer between 2 and 6, R is a carbon chain with the carbon number of 1 to 18, and the carbon chain is a saturated carbon chain and is a straight chain or a branched chain.
10. The starch microspheres of claim 1, wherein said zwitterionic surfactant has the following structure:
wherein: n is 3 or 4; r is a carbon chain with 12-18 carbon atoms, and the carbon chain is a saturated carbon chain and is a straight chain or a branched chain.
11. The starch microspheres of claim 9, wherein said zwitterionic surfactant has a substituted hydroxyl, amino or carboxyl group on the carbon chain except for the terminal carbon, and is monosubstituted on the same carbon.
12. The starch microsphere according to claim 1, wherein the zwitterionic surfactant is one or more of dimethyldodecylsulfopropyl ammonium salt, dimethylhexadecylsulfoethyl ammonium salt, dimethyloctadecylsulfonylammonium salt, dimethyl (3-hydroxydodecyl) sulfopropyl ammonium salt and dimethyl (6-aminotetradecyl) sulfoethyl ammonium salt.
13. The starch microspheres of claim 1, wherein said alkane compound is a saturated alkane.
14. The starch microspheres of claim 1, wherein said alkane compounds are alkanes and/or cycloalkanes.
15. The starch microspheres of claim 14 wherein said alkane, cycloalkane is a haloalkane.
16. The starch microspheres of claim 1, wherein the alkane compound is one or more of n-hexane, n-heptane, n-octane, n-decane, n-dodecane, isohexane, isoheptane, isooctane, isodecane, isododecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, chloroform, chloropentane, chlorohexane, chlorooctane, and chlorododecane.
17. The starch microspheres of claim 1, wherein said emulsifier is an anionic surfactant or a nonionic surfactant.
18. The starch microsphere according to claim 1, wherein the emulsifier is one or more of sodium dodecyl benzene sulfonate, sodium hexadecylbenzene sulfonate, sodium dodecyl benzene sulfate, sodium hexadecylbenzene sulfate, Span20, Span40, Span60, Span80, Tween20, Tween40, Tween60 and Tween 80.
19. The starch microspheres of claim 1 wherein the inorganic salt is a soluble inorganic salt.
20. The starch microspheres of claim 1, wherein the inorganic salt is one or more of sodium salt, potassium salt, ammonium salt, calcium salt, magnesium salt, and when the inorganic salt is sodium salt, one or more of sodium chloride, sodium bromide, sodium sulfate, sodium sulfite, sodium carbonate, sodium bicarbonate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate, and sodium silicate; when the inorganic salt is potassium salt, the inorganic salt is one or more of potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, potassium bicarbonate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate and potassium silicate; when the inorganic salt is ammonium salt, the inorganic salt is one or more of ammonium chloride, ammonium bromide and ammonium nitrate; when the inorganic salt is a calcium salt, calcium chloride or calcium bromide; when the inorganic salt is a magnesium salt, the inorganic salt is one or more of magnesium chloride, magnesium bromide, magnesium sulfate and magnesium nitrate.
21. The starch microsphere according to claim 1, wherein the organic solvent is any one of absolute ethanol, 1-butanol, ethyl acetate, butyl acetate, acetone, xylene, n-hexane and carbon tetrachloride.
22. A method for preparing starch microspheres according to any one of claims 1 to 21, comprising the steps of:
(1) weighing starch, adding the starch into water, adding triethanolamine, uniformly mixing at 20-80 ℃, and adding epoxy chloropropane for micro-crosslinking reaction;
(2) adding a zwitterionic monomer into a starch solution, fully dissolving and mixing, adding an initiator, and reacting for 3-6 h at 60-80 ℃;
(3) adding a zwitterionic surfactant into the feed liquid obtained in the step (2), and uniformly mixing to obtain a water phase A;
(4) weighing alkane compounds, adding an emulsifier, and uniformly mixing until the alkane compounds are completely dissolved to obtain an oil phase B;
(5) and (3) uniformly mixing the water phase A obtained in the step (3) and the oil phase B obtained in the step (4) at the temperature of 30-60 ℃, slowly and uniformly adding an inorganic salt solution and epoxy chloropropane into the mixed solution, continuing to react after the inorganic salt solution and the epoxy chloropropane are added, demulsifying and removing the upper oil phase after the reaction is finished, washing with a solvent, and drying to obtain the microsphere.
23. The preparation method of claim 22, wherein the raw materials of the starch microspheres comprise deionized water, starch, triethanolamine, epichlorohydrin, zwitterionic monomer, initiator, zwitterionic surfactant, alkane compound, emulsifier, inorganic salt solution and organic solvent in parts by weight: 100 parts of deionized water, 1-20 parts of starch, 10-55 parts of triethanolamine, 0.105-14.6 parts of epoxy chloropropane, 0.1-20 parts of zwitterionic monomer, 0.001-0.2 part of initiator, 0.05-10 parts of zwitterionic surfactant, 200-750 parts of alkane compound, 10-250 parts of emulsifier, 0.5-200 parts of inorganic salt solution and 200-750 parts of organic solvent.
24. The preparation method according to claim 22 or 23, wherein the raw materials of the starch microspheres comprise deionized water, starch, triethanolamine, epichlorohydrin, a zwitterionic monomer, an initiator, a zwitterionic surfactant, an alkane compound, an emulsifier, an inorganic salt solution and an organic solvent in parts by weight: 100 parts of deionized water, 5-15 parts of starch, 20-35 parts of triethanolamine, 1.04-7.8 parts of epoxy chloropropane, 5-15 parts of zwitterionic monomer, 0.02-0.1 part of initiator, 1-5 parts of zwitterionic surfactant, 250-450 parts of alkane compound, 30-100 parts of emulsifier and 50-150 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.5-30 parts and the organic solvent accounts for 250-450 parts.
25. The preparation method according to claim 22, wherein the starch in step (1) is one or more of mung bean starch, tapioca starch, sweet potato starch, wheat starch, water chestnut starch, lotus root starch and corn starch.
26. The method according to claim 22 or 25, wherein the starch in the step (1) is corn starch and/or potato starch.
27. The method according to claim 22, wherein the reaction temperature in the step (1) is 30 to 60 ℃; the reaction time is 0.5-4 h.
28. The production process according to claim 22 or 27, wherein the reaction temperature in the step (1) is 30 to 60 ℃; the reaction time is 1-3 h.
29. The method according to claim 22, wherein the zwitterionic monomer in step (2) is one or more of methacryloyloxyethyl-N, N-dimethylpropanesulfonate, N-dimethylallylamine propanesulfonate, 4-vinylpyridine propanesulfonate, N-methyldiallylpropane propanesulfonate, and N-methyldiallylbutylsulfonate.
30. The process according to claim 22, wherein the initiator in the step (2) is any one or two of potassium persulfate, sodium persulfate and ammonium persulfate.
31. The method of claim 22 wherein said zwitterionic surfactant has the structure:
wherein: n is an integer between 2 and 6, R is a carbon chain with the carbon number of 1 to 18, and the carbon chain is a saturated carbon chain and is a straight chain or a branched chain.
32. The method of claim 22 wherein said zwitterionic surfactant has the structure:
wherein: n is 3 or 4; r is a carbon chain with 12-18 carbon atoms, and the carbon chain is a saturated carbon chain and is a straight chain or a branched chain.
33. The method according to claim 31 or 32, wherein the zwitterionic surfactant contains a hydroxyl, amino or carboxyl group substituted on the carbon chain except for the terminal group, and the same carbon is monosubstituted.
34. The method according to any one of claims 22, 31 and 32, wherein the zwitterionic surfactant is one or more of dimethyldodecylsulfopropyl ammonium salt, dimethylhexadecylsulfoethyl ammonium salt, dimethyloctadecylsulfonyl ammonium salt, dimethyl (3-hydroxydodecyl) sulfopropyl ammonium salt and dimethyl (6-aminotetradecyl) sulfoethyl ammonium salt.
35. The process according to claim 22, wherein the alkane compound in the step (4) is a saturated alkane.
36. The production process according to claim 22 or 35, wherein the alkane compound in the step (4) is an alkane and/or a cycloalkane.
37. The method according to claim 36, wherein the alkane or cycloalkane is a halogenated alkane.
38. The process according to claim 22 or 35, wherein the alkane compound in the step (4) is one or more selected from n-hexane, n-heptane, n-octane, n-decane, n-dodecane, isohexane, isoheptane, isooctane, isodecane, isododecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, trichloromethane, chloropentane, chlorohexane, chlorooctane and chlorododecane.
39. The method according to claim 22, wherein the emulsifier in the step (4) is an anionic surfactant or a nonionic surfactant.
40. The method according to claim 22 or 39, wherein the emulsifier in step (4) is one or more selected from sodium dodecylbenzene sulfonate, sodium hexadecylbenzene sulfonate, sodium dodecylbenzene sulfate, sodium hexadecylbenzene sulfate, Span20, Span40, Span60, Span80, Tween20, Tween40, Tween60 and Tween 80.
41. The method according to claim 22, wherein the inorganic salt in the step (5) is a soluble inorganic salt.
42. The method according to claim 22 or 41, wherein the inorganic salt in the step (5) is one or more of sodium salt, potassium salt, ammonium salt, calcium salt and magnesium salt, and when the inorganic salt is sodium salt, one or more of sodium chloride, sodium bromide, sodium sulfate, sodium sulfite, sodium carbonate, sodium bicarbonate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate and sodium silicate; when the inorganic salt is potassium salt, the inorganic salt is one or more of potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, potassium bicarbonate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate and potassium silicate; when the inorganic salt is ammonium salt, the inorganic salt is one or more of ammonium chloride, ammonium bromide and ammonium nitrate; when the inorganic salt is a calcium salt, calcium chloride or calcium bromide; when the inorganic salt is a magnesium salt, the inorganic salt is one or more of magnesium chloride, magnesium bromide, magnesium sulfate and magnesium nitrate.
43. The method of claim 22, wherein the demulsification in the step (5) is performed by mechanical stirring or by adding an organic solvent, and the washing in the step (5) is performed by washing with an organic solvent.
44. The production method according to claim 22 or 43, wherein the demulsification in the step (5) is performed by adding an organic solvent.
45. The method of claim 44, wherein the demulsifying and washing processes in step (5) are performed using the same or different organic solvents.
46. The production method according to claim 43 or 45, wherein the demulsification and washing processes in the step (5) are performed using the same organic solvent.
47. The method according to claim 43, wherein the organic solvent is one or more selected from the group consisting of absolute ethanol, 1-butanol, ethyl acetate, butyl acetate, acetone, xylene, n-hexane, and carbon tetrachloride.
48. The production method according to claim 43 or 47, wherein the organic solvent is ethyl acetate and/or absolute ethanol.
49. The method according to claim 22, wherein the drying in the step (5) is performed at 55 to 95 ℃ for 12 to 24 hours.
50. Use of starch microspheres according to any one of claims 1 to 21 in a temporary plugging agent for hydrocarbon reservoir protection.
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| CN201710720849.XA CN109423265B (en) | 2017-08-22 | 2017-08-22 | Salt-resistant and temperature-resistant starch microsphere as well as preparation method and application thereof |
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