CN109422817A - A kind of micron-level crosslinked spherex and its preparation method and application - Google Patents
A kind of micron-level crosslinked spherex and its preparation method and application Download PDFInfo
- Publication number
- CN109422817A CN109422817A CN201710720848.5A CN201710720848A CN109422817A CN 109422817 A CN109422817 A CN 109422817A CN 201710720848 A CN201710720848 A CN 201710720848A CN 109422817 A CN109422817 A CN 109422817A
- Authority
- CN
- China
- Prior art keywords
- parts
- spherex
- sodium
- starch
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/003—Crosslinking of starch
-
- 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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
-
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/514—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
-
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
Abstract
The invention discloses a kind of micron-level crosslinked spherex and its preparation method and application, the raw material of the spherex includes following component: 100 parts of deionized waters, 1~20 part of starch, 10~50 parts of triethanolamines, 0.105~14.6 part of epoxychloropropane, 200~1000 parts of alkane derivatives, 8~250 parts of emulsifiers, 0.05~10 part of zwitterionic surfactant, 0.5~200 part of inorganic salt solution, 200~1000 parts of organic solvent.The partial size of the spherex is 0.1~500 μm.Spherex prepared by the present invention has the polydispersion feature of uniform particle sizes' distribution.
Description
Technical field
The invention belongs to Microspheres Technique fields, and in particular to a kind of spherex and its preparation method and application.
Background technique
It is more to be primarily used to solution barefoot interval for drilling fluid oil-gas Layer drilling technology (abbreviation temporary shielding method ,barrier building temporary seal incores)
It is the problem of pressure series of strata stratum protection oil-gas Layer, i.e., unfavorable using two damaged during drilling oil-gas Layer to oil-gas Layer
Factor (pressure difference and mud solid phase particle) is translated into the favorable factor of protection oil-gas Layer, reaches and reduces drilling fluid, cement
The purpose of slurry, pressure difference and soaking time to formation damage.
The basic conception of drilling fluid oil-gas Layer drilling technology is drilling fluid column pressure when opening using oil-gas Layer is drilled
The pressure difference formed between power and oil gas stressor layer forces and consolidating for type and size is artificially added in drilling fluid in a very short period of time
Body particle enters oil-gas Layer pore throat, near the borehole wall quickly, shallow-layer, effectively form a blocking strips, prevent drilling fluid from continuing
Oil-gas Layer is invaded, damage of the drilling fluid to oil-gas Layer is reduced.Its thickness must be significantly smaller than perforating depth, to go into operation in complete well
When, pass through perforation de-plugging.After the completion of drilling well, if barefoot completion, blocking strips can be eliminated by measures such as acidifications, restore oil-gas Layer
Permeability originally guarantees that oil/gas well has preferable yield.
Microballoon class compound is a kind of diverting agent of reservoir protection more common at present, and wherein spherex also receives
Extensive research.The prior art is more to the research of the spherex of monodisperse or polydispersion, patent CN201010546156.1 and
CN201410236878.5 describes the preparation method of two kinds of monodisperse spherexes.CN201510151917.6 describes one kind
The preparation method of nanoscale polydispersion spherex.CN201510175382.6 provides a kind of tool granular gradient performance polymer
The preparation method of microballoon.For equally distributed polydispersion spherex almost without report.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of spherex and its preparation method and application, the starch
The advantages that microballoon has equally distributed polydispersity, and microballoon hardness is high, low in cost.
First aspect present invention provides a kind of spherex, and based on parts by weight, the raw material of the spherex includes such as
Lower component: 100 parts of deionized waters, 1~20 part of starch, 10~50 parts of triethanolamines, 0.105~14.6 part of epoxychloropropane, 200
~1000 parts of alkane derivatives, 8~250 parts of emulsifiers, 0.05~10 part of zwitterionic surfactant, 0.5~200 part of nothing
Machine salting liquid, wherein inorganic salts solute accounts for 0.025~50 part, 200~1000 parts of organic solvent.
In above-mentioned spherex, based on parts by weight, the raw material of the amphoteric ion spherex includes following component:
100 parts of deionized waters, 5~15 parts of starch, 20~40 parts of triethanolamines, 1.04~7.8 parts of epoxychloropropane, 300~500 parts of alkane
Hydrocarbon compound, 30~100 parts of emulsifiers, 1~6 part of zwitterionic surfactant, 50~150 parts of inorganic salt solutions, wherein
Inorganic salts solute accounts for 0.5~30 part, 300~500 parts of organic solvent.
In above-mentioned spherex, the size tunable range of the spherex is 0.1~500 μm, the spherex grain
In partial size integrated distribution section, (wherein, partial size integrated distribution section is defined as removing outside both ends partial size boundary diameter, partial size point
The continuum of cloth proportion >=90%, from the point of view of grain size distribution, partial size integrated distribution section is exactly that particle diameter distribution is in
The region of near linear distribution, does not include the region with obvious inflection point at both ends) the interior polydispersity being evenly distributed, it is described
Particle diameter distribution in partial size integrated distribution section, which has the feature that, is divided into n section for partial size integrated distribution section, each
The microballoon accounting in section are as follows:, wherein n is the integer greater than 1.
In above-mentioned spherex, the starch is green starch, tapioca, sweet potato starch, starch from sweet potato, potato
One or more of starch, wheat starch, water caltrop starch, Rhizoma Nelumbinis starch, cornstarch, preferably cornstarch and/or potato
Starch.
In above-mentioned spherex, its structure of the zwitterionic surfactant is as follows:,
Wherein: integer of the n between 2-6, preferably n are 3 or 4；R is the carbochain of carbon number 1-18, and preferably R is the carbochain of carbon number 12-18.
The carbochain is saturated carbon chains, can be linear chain or branched chain.Substituted hydroxyl, amino or carboxylic can be contained by (removing end group carbon) in carbochain
Base is only on the same carbon monosubstituted.The zwitterionic surfactant is specifically as follows dimethyl dodecyl base sulphur third
Base ammonium salt, dimethyl hexadecyl base sulfoethyl ammonium salt, dimethyl stearyl sulphur butyl ammonium salt, dimethyl (3- hydroxydodecanoic
Base) sulfopropyl ammonium salt, one or more of dimethyl (6- amino myristyl) sulfoethyl ammonium salt.
In above-mentioned spherex, the alkane derivative is saturated alkane, can be alkane and/or cycloalkane,
The alkane, cycloalkane can be halogenated alkane, be specifically as follows n-hexane, normal heptane, normal octane, decane, positive 12
Alkane, isohexane, isoheptane, isooctane, different ten alkane, Permethyl 99A, pentamethylene, hexamethylene, cycloheptane, cyclooctane, chloroform,
One of chloropentane, chlorohexane, chloro-octane, chlorododecane are a variety of.
In above-mentioned spherex, the emulsifier can be anionic surfactant, specially detergent alkylate
One or more of sodium sulfonate, cetyl benzenesulfonic acid sodium, sodium dodecyl benzene sulfonate, cetyl phenyl-hydrogen-sulfate sodium；It can also
Think nonionic surface active agent, specially Span20, Span40, Span60, Span80, Tween20, Tween40,
One or more of Tween60, Tween80.
In above-mentioned spherex, the inorganic salts be soluble inorganic salt, the inorganic salts be sodium salt, sylvite, ammonium salt,
One of calcium salt, magnesium salts are a variety of, when the inorganic salts are sodium salt, specially sodium chloride, sodium bromide, sodium sulphate, sulfurous
One of sour sodium, sodium carbonate, sodium bicarbonate, sodium nitrate, sodium phosphate, dibastic sodium phosphate, sodium metasilicate are a variety of；When the inorganic salts
When for sylvite, specially potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, saleratus, potassium nitrate, potassium phosphate, phosphorus
Potassium hydrogen phthalate, potassium silicate it is one or more；When the inorganic salts be ammonium salt when, specially ammonium chloride, ammonium bromide, ammonium nitrate one
Kind is a variety of；When the inorganic salts are calcium salt, specially calcium chloride or calcium bromide；When the inorganic salts are magnesium salts, specifically
For magnesium chloride, magnesium bromide, magnesium sulfate, magnesium nitrate it is one or more.
In above-mentioned spherex, the organic solvent be dehydrated alcohol, n-butyl alcohol, ethyl acetate, butyl acetate, acetone,
One or more of dimethylbenzene, n-hexane, carbon tetrachloride, ethyl acetate and/or dehydrated alcohol.
Second aspect of the present invention provides a kind of preparation method of above-mentioned spherex, and the preparation method includes in following
Hold:
(1) it weighs a certain amount of starch to be added to the water, a certain amount of triethanolamine is then added, mixed at 20~80 DEG C equal
It is even, it adds epoxychloropropane and is reacted；
(2) zwitterionic surfactant is added in the feed liquid obtained to step (1), is uniformly mixed, obtains water phase A；
(3) a certain amount of alkane derivative is weighed, emulsifier is then added, is uniformly mixed to after being completely dissolved and obtains oily phase B；
(4) under the conditions of 30~60 DEG C, the water phase A that step (2) the obtains and oily phase B that step (3) obtains is uniformly mixed, then
Inorganic salt solution and epoxychloropropane are slowly at the uniform velocity added into mixed liquor, is finished to inorganic salt solution and epoxychloropropane addition
The reaction was continued afterwards, is demulsified after the reaction was completed and removes upper oil phase, obtains microballoon after then washed, dry.
In the method for the present invention, based on parts by weight, the deionized water, starch, triethanolamine, epoxychloropropane, alkane
Class compound, emulsifier, zwitterionic surfactant, inorganic salt solution, solvent dosage be respectively as follows: 100 parts of deionized waters,
1~20 part of starch, 10~50 parts of triethanolamines, 0.105~14.6 part of epoxychloropropane, 200~1000 parts of alkane derivatives,
8~250 parts of emulsifiers, 0.05~10 part of zwitterionic surfactant, 0.5~200 part of inorganic salt solution, wherein inorganic salts are molten
Matter accounts for 0.025~50 part, 200~1000 parts of organic solvent；Preferably 100 parts of deionized waters, 5~15 parts of starch, 20~40 parts
Triethanolamine, 1.04~7.8 parts of epoxychloropropane, 300~500 parts of alkane derivatives, 30~100 parts of emulsifiers, 1~6 part
Zwitterionic surfactant, 50~150 parts of inorganic salt solutions, wherein inorganic salts solute accounts for 0.5~30 part, organic solvent 300
~500 parts.
In the method for the present invention, starch as described in step (1) is green starch, tapioca, sweet potato starch, sweet potato shallow lake
One or more of powder, potato starch, wheat starch, water caltrop starch, Rhizoma Nelumbinis starch, cornstarch, preferably cornstarch and/
Or potato starch.
In the method for the present invention, reaction temperature described in step (1) is 30~60 DEG C；Reaction time is 0.5~4h, preferably
1~3h.
In the method for the present invention, the reaction time is 0.5~4h, preferably 1~3h in step (1).
In the method for the present invention, its structure of zwitterionic surfactant described in step (2) is as follows:,
Wherein: integer of the n between 2-6, preferably n are 3 or 4；R is the carbochain of carbon number 1-18, and preferably R is the carbochain of carbon number 12-18.
The carbochain is saturated carbon chains, can be linear chain or branched chain.Substituted hydroxyl, amino or carboxylic can be contained by (removing end group carbon) in carbochain
Base is only on the same carbon monosubstituted.The zwitterionic surfactant is specifically as follows dimethyl dodecyl base sulphur third
Base ammonium salt, dimethyl hexadecyl base sulfoethyl ammonium salt, dimethyl stearyl sulphur butyl ammonium salt, dimethyl (3- hydroxydodecanoic
Base) sulfopropyl ammonium salt, one or more of dimethyl (6- amino myristyl) sulfoethyl ammonium salt.
In the method for the present invention, alkane derivative described in step (3) be saturated alkane, can be alkane and/or
Cycloalkane, the alkane, cycloalkane can be halogenated alkane, be specifically as follows n-hexane, normal heptane, normal octane, decane,
N-dodecane, isohexane, isoheptane, isooctane, different ten alkane, Permethyl 99A, pentamethylene, hexamethylene, cycloheptane, cyclooctane, three
One of chloromethanes, chloropentane, chlorohexane, chloro-octane, chlorododecane are a variety of.
In the method for the present invention, emulsifier described in step (3) can be anionic surfactant, specially 12
One of sodium alkyl benzene sulfonate, cetyl benzenesulfonic acid sodium, sodium dodecyl benzene sulfonate, cetyl phenyl-hydrogen-sulfate sodium are several
Kind；May be nonionic surface active agent, specially Span20, Span40, Span60, Span80, Tween20,
One or more of Tween40, Tween60, Tween80.
In the method for the present invention, inorganic salts described in step (4) be soluble inorganic salt, the inorganic salts be sodium salt, sylvite,
One of ammonium salt, calcium salt, magnesium salts are a variety of, when the inorganic salts be sodium salt when, specially sodium chloride, sodium bromide, sodium sulphate,
One of sodium sulfite, sodium carbonate, sodium bicarbonate, sodium nitrate, sodium phosphate, dibastic sodium phosphate, sodium metasilicate are a variety of；When the nothing
When machine salt is sylvite, specially potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, saleratus, potassium nitrate, phosphoric acid
Potassium, potassium hydrogen phosphate, potassium silicate it is one or more；When the inorganic salts are ammonium salt, specially ammonium chloride, ammonium bromide, nitric acid
Ammonium it is one or more；When the inorganic salts are calcium salt, specially calcium chloride or calcium bromide；When the inorganic salts are magnesium salts
When, specially magnesium chloride, magnesium bromide, magnesium sulfate, magnesium nitrate it is one or more.
In the method for the present invention, being slowly at the uniform velocity added described in step (4) can use this field is existing arbitrarily can be real
The mode of solvent is now at the uniform velocity added, mode is such as added dropwise.
In the method for the present invention, demulsification can be arbitrarily may be implemented using this field is existing in demulsification described in step (4)
Mode, such as mechanical stirring or addition organic solvent are demulsified, it is preferred to use organic solvent is added and is demulsified.Step (4)
Described in washing be with organic solvent washing, the washing operation is technology contents well known to those skilled in the art.This hair
In bright method, demulsification described in step (4) and washing process are carried out using identical or different organic solvent, it is preferred to use identical
Organic solvent.The organic solvent be dehydrated alcohol, n-butyl alcohol, ethyl acetate, butyl acetate, acetone, dimethylbenzene, just oneself
One or more of alkane, carbon tetrachloride, ethyl acetate and/or dehydrated alcohol.
In the method for the present invention, described in step (4) it is dry for dry 10 at 50~100 DEG C~for 24 hours.
Third aspect present invention additionally provides application of the above-mentioned spherex in reservoir protection diverting agent.Spherex
As one of drilling fluid system component, the temporarily stifled effect of shielding is played.It can be played under the dosage of 0.5~5wt% good
Effect.The drilling fluid that microballoon is added has good shut-off capacity, can effectively block hole or microfissure, forms fine and close mud
Cake prevents filtrate from largely penetrating into stratum, reduces filter loss.
Compared with prior art, spherex of the present invention and preparation method thereof has the advantages that
1, spherex of the present invention is the microballoon for the polydispersity being distributed with uniform particle sizes, the list with prior art preparation
Disperse different with polydispersion spherex.When spherex in reservoir protection diverting agent field in application, due to geologic structure
Multifarious, reservoir porosity span is big, if only being difficult to meet the requirement of broad spectrum activity by the microballoon of single dispersing particle diameter, uses effect
Fruit is unable to satisfy industrial requirements.In addition, normal distribution is presented in existing polydispersion microballoon, the effective range of partial size is narrow, effect
It is obvious limited.The equally distributed polydispersion spherex that this technology provides can solve these problems very well, i.e., in any grain
In diameter section, microballoon accounting is suitable, and microspheres amount is high, temporarily blocks up significant effect, can satisfy the requirement of broad spectrum activity.
2, in spherex preparation method of the present invention, by the collective effect of triethanolamine and epoxychloropropane, especially
It is the mode of operation that epoxychloropropane is separately added into two steps, so that the structure of linear fraction and branched fraction in starch is big
It is small quite, there is similar molecular dimension, guarantee that the microballoon of preparation is more easily-controllable, particle diameter distribution has uniformity.Then rear
The starch in face is cross-linked into during microballoon, by using zwitterionic surfactant, and inorganic salts is slowly at the uniform velocity added simultaneously
And epoxychloropropane so that linear change is presented in the spherex particle size of preparation, and then is made under their collective effect
The standby polydispersion spherex for obtaining uniform particle sizes' distribution.
Specific embodiment
Spherex of the present invention and its preparation method and application is described further below by specific embodiment,
But it is not construed as limiting the invention.
Spherex partial size described in the embodiment of the present invention is measured by 3000 Particle Size Analyzer of Malvern, test side
Method is wet process measurement.
Meaning shown in particle size range (a μm-b μm) in following all examples and comparative example is a≤D < b.
Material ratio appeared in following all examples and comparative example is the mass parts ratio of material.
Embodiment 1
It weighs 10 parts of cornstarch to be added in 100 parts of deionized waters, adds 10 parts of triethanolamines, sufficiently dissolved at 80 DEG C.
Then 0.005 part of epoxychloropropane is added, reacts 3h after mixing.1 part of dimethyl dodecyl base sulfopropyl ammonium salt is added, it is sufficiently mixed
It closes, gained feed liquid is water phase A.800 parts of hexamethylenes separately are taken, 250 parts of emulsifiers (Span80:Tween60=3:2) are added, it is high
Speed stirring makes it completely dissolved, and gained feed liquid is oily phase B.A is poured slowly into B at 50 DEG C, 50 parts of NaCl is weighed and prepares
It is slowly added dropwise in mixed phase at 200 parts of inorganic salt solutions, and under equality of temperature with 7.5 parts of epoxychloropropane, is at the uniform velocity added dropwise simultaneously
Time 5h, the reaction was continued 2h after being added dropwise.Then stop reaction, mixed phase is added by organic solvent of 200 parts of dehydrated alcohols
It is demulsified, filters off upper oil phase, separately wash microballoon with 600 parts of dehydrated alcohols, finally freeze-day with constant temperature is to obtain the final product white for 24 hours at 50 DEG C
The powdered microballoon of color.The partial size integrated distribution section of the spherex is 20~220 μm, and (97.2% partial size is in this section
It is interior), the particle diameter distribution in partial size integrated distribution section has the feature that (20 μm -70 μm): 22.7%；(70 μm -120
μm): 25.9%；(120 μm -170 μm): 27.2%；(170 μm -220 μm): 24.2%.
Embodiment 2
It weighs 5 parts of potato starch to be added in 100ml deionized water, adds 15 parts of triethanolamines, sufficiently dissolved at 20 DEG C.
Then 0.04 part of epoxychloropropane is added, reacts 2h after mixing.0.05 part of dimethyl hexadecyl base sulfoethyl ammonium salt is added, sufficiently
Mixing, gained feed liquid is water phase A.1000 parts of normal octanes separately are taken, 30 parts of emulsifier (Span60:Tween80=2:3 mass are added
Portion rate), high-speed stirred makes it completely dissolved, and gained feed liquid is oily phase B.A is poured slowly into B at 60 DEG C, weighs 0.5
Part CaCl240 parts of inorganic salt solutions are configured to, and are added dropwise in starch solution simultaneously under equality of temperature with 1 part of epoxychloropropane, it is even
Fast time for adding 8h, the reaction was continued 2h after being added dropwise.Stop reaction later, is added using 500 parts of n-butyl alcohols as organic solvent mixed
Conjunction is mutually demulsified, and filters off upper oil phase, separately washs microballoons with 500 parts of n-butyl alcohols, and finally freeze-day with constant temperature 20h at 60 DEG C to obtain the final product
White powder microballoon.The partial size integrated distribution section of the spherex is 75~375 μm, and (96.4% partial size is in this area
In), the particle diameter distribution in partial size integrated distribution section has the feature that (75 μm -150 μm): 22.5%；(150 μ
M-225 μm): 27.5%；(225 μm -300 μm): 25.2%；(300 μm -375 μm): 24.8%.
Embodiment 3
It weighs 20 portions of tapiocas to be added in 100 parts of deionized waters, adds 50 parts of triethanolamines, sufficiently dissolved at 40 DEG C.
Then 0.6 part of epoxychloropropane is added, reacts 1.5h after mixing.10 parts of dimethyl stearyl sulphur butyl ammonium salts are added, sufficiently
Mixing, gained feed liquid is water phase A.500 parts of chloropentanes separately are taken, 100 parts of emulsifiers (Span60:Tween60=2:1) are added,
High-speed stirred makes it completely dissolved, and gained feed liquid is oily phase B.A is poured slowly into B at 40 DEG C, weighs 20 parts of MgCl2Match
150 parts of inorganic salt solutions are made, and are added dropwise in starch solution simultaneously under equality of temperature with 14 parts of epoxychloropropane, when being at the uniform velocity added dropwise
Between 10h.The reaction was continued after being added dropwise 2h, stops reaction later, using 200 parts of ethyl acetate be organic solvent addition mixed phase into
It goes and is demulsified, filter off upper oil phase, separately wash microballoons with 300 parts of ethyl acetate, finally freeze-day with constant temperature 14h is to obtain the final product white at 90 DEG C
Powdered microballoon.The partial size integrated distribution section of the spherex is 50~350 μm, and (95.5% partial size is in this section
It is interior), the particle diameter distribution in partial size integrated distribution section has the feature that (50 μm -110 μm): 18.4%；(110 μm-
170 μm): 19.8%；(170 μm -230 μm): 19.8%；(230 μm -290 μm): 21.2%；(290 μm -330 μm): 20.8%.
Embodiment 4
It weighs 15 parts of green starch to be added in 100ml deionized water, adds 40 parts of triethanolamines, sufficiently dissolved at 60 DEG C.
Then 0.3 part of epoxychloropropane is added, reacts 1h after mixing.6 parts of dimethyl (3- hydroxydodecyl) sulfopropyl ammonium salt is added,
It is sufficiently mixed, gained feed liquid is water phase A.It separately takes 300 parts of alkane compounds (hexamethylene: chloroform=2:1), is added 80 parts
Emulsifier (Span80:Tween80=3:1), high-speed stirred makes it completely dissolved, and gained feed liquid is oily phase B.By A at 30 DEG C
It is poured slowly into B, weighs 30 parts of K2SO450 parts of inorganic salt solutions are configured to, and are dripped simultaneously under equality of temperature with 11 parts of epoxychloropropane
It is added in starch solution, at the uniform velocity time for adding 7h, the reaction was continued 2h after being added dropwise.Stop reaction, later with 200 parts of acetic acid fourths
Ester is that organic solvent addition mixed phase is demulsified, and filters off upper oil phase, separately washs microballoons with 100 parts of butyl acetates, finally exist
Freeze-day with constant temperature 10h is at 100 DEG C up to white powder microballoon.The partial size integrated distribution section of the spherex is 150~570
μm (96.9% partial size is in this section), the particle diameter distribution in partial size integrated distribution section have the feature that (150
μm -210 μm): 13.1%；(210 μm -270 μm): 13.2%；(270 μm -330 μm): 15.2%；(330 μm -390 μm): 13.8%；
(390 μm -450 μm): 14.7%；(450 μm -510 μm): 14.4%；(510 μm -570 μm): 15.6%.
Embodiment 5
It weighs 1 part of sweet potato starch to be added in 100 parts of deionized waters, adds 20 parts of triethanolamines, sufficiently dissolved at 50 DEG C.So
0.03 part of epoxychloropropane is added afterwards, reacts 2.5h after mixing.0.05 part of dimethyl (6- amino myristyl) sulfoethyl is added
Ammonium salt is sufficiently mixed, and gained feed liquid is water phase A.It separately takes 200 parts of alkane compounds (normal heptane: hexamethylene=1:1), is added 8
Part emulsifier (neopelex), high-speed stirred makes it completely dissolved, and gained feed liquid is oily phase B.By A at 55 DEG C
It is poured slowly into B, 0.025 part of KCl is weighed and is configured to 0.5 part of KCl solution, and dripped simultaneously under equality of temperature with 0.1 part of epoxychloropropane
It is added in starch solution, at the uniform velocity time for adding 9h.The reaction was continued after being added dropwise 2h.Stop reaction, later with 75 parts of acetic acid fourths
Ester is that organic solvent addition mixed phase is demulsified, and filters off upper oil phase, separately washs microballoons with 125 parts of butyl acetates, finally exist
Freeze-day with constant temperature 18h is at 70 DEG C up to white powder microballoon.The partial size integrated distribution section of the spherex is 0.1~7.6 μ
The partial size of m(93.8% is in this section), the particle diameter distribution in partial size integrated distribution section has the feature that (0.1 μ
M -1.6 μm): 18.5%；(1.6 μm -3.1 μm): 19.9%；(3.1 μm -4.6 μm): 21.5%；(4.6 μm -6.1 μm): 21.4%；
(6.1 μm -7.6 μm): 18.7%.
Conventional surfactants are used only in comparative example 1()
Weigh 10 parts of cornstarch to be added in 100 parts of deionized waters, sufficiently be dissolved at 80 DEG C, be cooled to later 50 DEG C it is spare.
1 part of lauryl sodium sulfate is added, is sufficiently mixed, gained feed liquid is water phase A.800 parts of hexamethylenes separately are taken, 250 parts of creams are added
Agent (Span80:Tween60=3:2), high-speed stirred makes it completely dissolved, and gained feed liquid is oily phase B.A is delayed at 50 DEG C
Slowly B is poured into, and 7.5 parts of epoxychloropropane is added in mixed phase under equality of temperature, reaction stops reaction after carrying out 7h, with 200 parts
Dehydrated alcohol is that organic solvent addition mixed phase is demulsified, and filters off upper oil phase, separately washs microballoons with 600 parts of dehydrated alcohols,
Finally at 50 DEG C freeze-day with constant temperature for 24 hours up to white powder microballoon.The partial size integrated distribution section of the spherex is 50
~350 μm (94.7% partial size is in this section), the particle diameter distribution in partial size integrated distribution section has following special
Sign: (50 μm -150 μm): 12.3%；(150 μm -250 μm): 73.5%；(250 μm -350 μm): 14.2%.
Salt is added dropwise in the micro- crosslinking of comparative example 2()
It weighs 10 parts of cornstarch to be added in 100 parts of deionized waters, sufficiently be dissolved at 80 DEG C.0.005 part of epoxy chloropropionate is added
Alkane reacts 3h after mixing, 1 part of dimethyl dodecyl base sulfopropyl ammonium salt is added later, is sufficiently mixed, gained feed liquid is water phase
A.800 parts of hexamethylenes separately are taken, 250 parts of emulsifiers (Span80:Tween60=3:2) are added, high-speed stirred makes it completely dissolved,
Gained feed liquid is oily phase B.A is poured slowly into B at 50 DEG C, 50 parts of NaCl is weighed and is configured to 200 parts of inorganic salt solutions, and
It is added dropwise in mixed phase simultaneously under equality of temperature with 7.5 parts of epoxychloropropane, at the uniform velocity time for adding 5h, the reaction was continued after being added dropwise
2h.Later stop reaction, using 200 parts of dehydrated alcohols be organic solvent be added mixed phase be demulsified, elimination upper oil phase, separately with
600 parts of dehydrated alcohols wash microballoons, finally at 50 DEG C freeze-day with constant temperature for 24 hours up to white powder microballoon.The spherex
Partial size integrated distribution section be 1~200 μm (92.9% partial size is in this section), in partial size integrated distribution section
Particle diameter distribution have the feature that (1 μm -50 μm): 31.4%；(50 μm -100 μm): 19.1%；(100 μm -150 μm):
30.3%；(150 μm -200 μm): 19.2%.
Comparative example 3(triethanolamine, micro- crosslinking)
It weighs 10 parts of cornstarch to be added in 100 parts of deionized waters, adds 10 parts of triethanolamines, sufficiently dissolved at 80 DEG C.
Then 0.005 part of epoxychloropropane is added, reacts 3h after mixing.1 part of dimethyl dodecyl base sulfopropyl ammonium salt is added, it is sufficiently mixed
It closes, gained feed liquid is water phase A.800 parts of hexamethylenes separately are taken, 250 parts of emulsifiers (Span80:Tween60=3:2) are added, it is high
Speed stirring makes it completely dissolved, and gained feed liquid is oily phase B.A is poured slowly into B at 50 DEG C, and by 7.5 parts of rings under equality of temperature
Oxygen chloropropane is added in mixed phase, and reaction stops reaction after carrying out 7h, and mixed phase is added by organic solvent of 200 parts of dehydrated alcohols
It is demulsified, filters off upper oil phase, separately wash microballoon with 600 parts of dehydrated alcohols, finally freeze-day with constant temperature is to obtain the final product white for 24 hours at 50 DEG C
The powdered microballoon of color.The partial size integrated distribution section of the spherex is 10~210 μm, and (96.6% partial size is in this section
It is interior), the particle diameter distribution in partial size integrated distribution section has the feature that (10 μm -60 μm): 32.2%；(60 μm of -110 μ
M): 17.2%；(110 μm -160 μm): 21.7%；(160 μm -210 μm): 28.9%.
Salt is added dropwise in comparative example 4(triethanolamine)
It weighs 10 parts of cornstarch to be added in 100 parts of deionized waters, adds 10 parts of triethanolamines, sufficiently dissolved at 80 DEG C,
Be cooled to later 50 DEG C it is spare.1 part of dimethyl dodecyl base sulfopropyl ammonium salt is added, is sufficiently mixed, gained feed liquid is water phase
A.800 parts of hexamethylenes separately are taken, 250 parts of emulsifiers (Span80:Tween60=3:2) are added, high-speed stirred makes it completely dissolved,
Gained feed liquid is oily phase B.A is poured slowly into B at 50 DEG C, 50 parts of NaCl is weighed and is configured to 200 parts of inorganic salt solutions, and
It is added dropwise in mixed phase simultaneously under equality of temperature with 7.5 parts of epoxychloropropane, at the uniform velocity time for adding 5h, the reaction was continued after being added dropwise
2h.Later stop reaction, using 200 parts of dehydrated alcohols be organic solvent be added mixed phase be demulsified, elimination upper oil phase, separately with
600 parts of dehydrated alcohols wash microballoons, finally at 50 DEG C freeze-day with constant temperature for 24 hours up to white powder microballoon.The spherex
Partial size integrated distribution section be 10~210 μm (93.1% partial size is in this section), in partial size integrated distribution section
Particle diameter distribution have the feature that (10 μm -60 μm): 6.5%；(60 μm -110 μm): 38.7%；(110 μm -160 μm):
41.1%；(160 μm -210 μm): 3.9%.
Applicating evaluating of the micron-level crosslinked spherex as diverting agent -- casting bed blocks experiment, chooses embodiment and compares
The sample of example preparation is evaluated.Laboratory apparatus: drilling fluid sand bed filtration instrument, blender, baking oven.Experimental material: 860 Jing Jing of building
Starch (density 1.19g/cm3), embodiment sample, comparative example and 20-40 mesh sand sample.
Experimental procedure:
1, with slurry: to starch+3% embodiment sample or comparative example by formula well.
2, it makes casting bed: being added to 350cm in cylinder with 20-40 mesh sand3Place, shakes up；
3, the experiment slurry (400mL-500mL) prepared is added, is fixed on instrument stan the simultaneously good lower channel of sealing；
4, it opens bleed pressure and is adjusted to 0.69mPa, open simultaneously lower switch, measure mud filtrate invasion sand during half an hour
The case where bed.
Experimental result:
Filter loss FL after being formulated 30min is added1, basicly stable after mud filtrate invasion casting bed depth D.After forming stable mud cake,
Drilling fluid is poured out in pressure release, and filter loss FL of the clear water to the position 400mL, after (0.69mPa) measurement 30min that pressurizes is added2, experiment knot
Fruit is shown in Table 1:
1 experimental result of table
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Filter loss FL1/ml | 0 | 0 | 0 | 0 | 0 | 2 | 0 | 3 | 0 |
| Depth D/cm3 | 125 | 185 | 160 | 210 | 220 | 350 | 305 | 315 | 350 |
| Filter loss FL2/ml | 0 | 0 | 0 | 0 | 0 | 55 | 14 | 25 | 58 |
By the above results it is found that clear water is under 0.69mPa pressure, and 30min is without leak-off when using the sample of embodiment 1-5
Amount, illustrates that plugging effect is good, and when using the sample of comparative example 1-4, clear water is under 0.69mPa pressure, and 30min filter loss is most
It can reach 58ml greatly, illustrate that effect is bad.
Claims (33)
1. a kind of spherex, based on parts by weight, the raw material of the spherex include following component: 100 parts of deionized waters,
1~20 part of starch, 10~50 parts of triethanolamines, 0.105~14.6 part of epoxychloropropane, 200~1000 parts of alkane derivatives,
8~250 parts of emulsifiers, 0.05~10 part of zwitterionic surfactant, 0.5~200 part of inorganic salt solution, wherein inorganic salts are molten
Matter accounts for 0.025~50 part, 200~1000 parts of organic solvent.
2. spherex described in accordance with the claim 1, wherein based on parts by weight, the original of the amphoteric ion spherex
Material includes following component: 100 parts of deionized waters, 5~15 parts of starch, 20~40 parts of triethanolamines, 1.04~7.8 parts of epoxy chloropropionates
Alkane, 300~500 parts of alkane derivatives, 30~100 parts of emulsifiers, 1~6 part of zwitterionic surfactant, 50~150 parts
Inorganic salt solution, wherein inorganic salts solute accounts for 0.5~30 part, 300~500 parts of organic solvent.
3. spherex according to claim 1 or 2, wherein the size tunable range of the spherex be 0.1~
500μm。
4. spherex described in accordance with the claim 1, wherein the spherex partial size is in partial size integrated distribution section
Equally distributed polydispersity, the particle diameter distribution in partial size integrated distribution section, which has the feature that, concentrates partial size point
Cloth section is divided into n section, the microballoon accounting in each section are as follows:, wherein n is the integer greater than 1.
5. spherex according to claim 1 or 2, wherein the starch is green starch, tapioca, sweet potato
One or more of starch, starch from sweet potato, potato starch, wheat starch, water caltrop starch, Rhizoma Nelumbinis starch, cornstarch, preferably
Cornstarch and/or potato starch.
6. spherex according to claim 1 or 2, wherein its structure of the zwitterionic surfactant is as follows:, in which: integer of the n between 2-6, preferably n are 3 or 4；R is the carbochain of carbon number 1-18, excellent
Selecting R is the carbochain of carbon number 12-18, and it is linear chain or branched chain that the carbochain, which is saturated carbon chains,.
7. spherex according to claim 5, wherein the zwitterionic surfactant carbochain is except on end group carbon
It is monosubstituted on the same carbon containing substituted hydroxyl, amino or carboxyl.
8. spherex according to claim 1 or 2, wherein the zwitterionic surfactant is dimethyl ten
Dialkyl group sulfopropyl ammonium salt, dimethyl hexadecyl base sulfoethyl ammonium salt, dimethyl stearyl sulphur butyl ammonium salt, dimethyl (3-
Hydroxydodecyl) sulfopropyl ammonium salt, one or more of dimethyl (6- amino myristyl) sulfoethyl ammonium salt.
9. spherex according to claim 1 or 2, wherein the alkane derivative is saturated alkane, such as alkane
Hydrocarbon and/or cycloalkane.
10. spherex according to claim 9, wherein the alkane, cycloalkane are halogenated alkanes.
11. spherex according to claim 1 or 2, wherein the emulsifier is n-hexane, normal heptane, just pungent
Alkane, decane, n-dodecane, isohexane, isoheptane, isooctane, different ten alkane, Permethyl 99A, pentamethylene, hexamethylene, cycloheptane,
One of cyclooctane, chloroform, chloropentane, chlorohexane, chloro-octane, chlorododecane are a variety of.
12. spherex according to claim 1 or 2, wherein the emulsifier be anionic surfactant or
Nonionic surface active agent.
13. spherex according to claim 12, wherein the emulsifier is neopelex, 16
Sodium alkyl benzene sulfonate, sodium dodecyl benzene sulfonate, cetyl phenyl-hydrogen-sulfate sodium, Span20, Span40, Span60, Span80,
One or more of Tween20, Tween40, Tween60, Tween80.
14. spherex according to claim 1 or 2, wherein the inorganic salts are soluble inorganic salt, the nothing
Machine salt is one of sodium salt, sylvite, ammonium salt, calcium salt, magnesium salts or a variety of, when the inorganic salts are sodium salt, specially chlorination
Sodium, sodium bromide, sodium sulphate, sodium sulfite, sodium carbonate, sodium bicarbonate, sodium nitrate, sodium phosphate, dibastic sodium phosphate, one in sodium metasilicate
Kind is a variety of；When the inorganic salts are sylvite, specially potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, carbonic acid
Hydrogen potassium, potassium nitrate, potassium phosphate, potassium hydrogen phosphate, potassium silicate it is one or more；When the inorganic salts are ammonium salt, specially chlorine
Change ammonium, ammonium bromide, ammonium nitrate it is one or more；When the inorganic salts are calcium salt, specially calcium chloride or calcium bromide；Work as institute
State inorganic salts be magnesium salts when, specially magnesium chloride, magnesium bromide, magnesium sulfate, magnesium nitrate it is one or more.
15. spherex described in accordance with the claim 1, wherein the organic solvent is dehydrated alcohol, n-butyl alcohol, acetic acid second
One or more of ester, butyl acetate, acetone, dimethylbenzene, n-hexane, carbon tetrachloride, ethyl acetate and/or anhydrous second
Alcohol.
16. a kind of preparation method of spherex, the preparation method includes following content:
(1) it weighs a certain amount of starch to be added to the water, a certain amount of triethanolamine is then added, mixed at 20~80 DEG C equal
It is even, it adds epoxychloropropane and is reacted；
(2) zwitterionic surfactant is added in the feed liquid obtained to step (1), is uniformly mixed, obtains water phase A；
(3) a certain amount of alkane derivative is weighed, emulsifier is then added, is uniformly mixed to after being completely dissolved and obtains oily phase B；
(4) under the conditions of 30~60 DEG C, the water phase A that step (2) the obtains and oily phase B that step (3) obtains is uniformly mixed, then
Inorganic salt solution and epoxychloropropane are slowly at the uniform velocity added into mixed liquor, is finished to inorganic salt solution and epoxychloropropane addition
The reaction was continued afterwards, is demulsified after the reaction was completed and removes upper oil phase, obtains microballoon after then washed, dry.
17. preparation method according to claim 16, wherein based on parts by weight, the deionized water, starch, three second
The dosage of hydramine, epoxychloropropane, alkane derivative, emulsifier, zwitterionic surfactant, inorganic salt solution, solvent
Be respectively as follows: 100 parts of deionized waters, 1~20 part of starch, 10~50 parts of triethanolamines, 0.105~14.6 epoxychloropropane, 200~
1000 parts of alkane derivatives, 8~250 parts of emulsifiers, 0.05~10 part of zwitterionic surfactant, 0.5~200 part it is inorganic
Salting liquid, wherein inorganic salts solute accounts for 0.025~50 part, 200~1000 parts of organic solvent；Preferably 100 parts of deionized waters, 5
~15 parts of starch, 20~40 parts of triethanolamines, 1.04~7.8 parts of epoxychloropropane, 300~500 parts of alkane derivatives, 30~
100 parts of emulsifiers, 1~6 part of zwitterionic surfactant, 50~150 parts of inorganic salt solutions, wherein inorganic salts solute accounts for 0.5
~30 parts, 300~500 parts of organic solvent.
18. preparation method according to claim 16, wherein starch as described in step (1) is green starch, para arrowroot
One of powder, sweet potato starch, starch from sweet potato, potato starch, wheat starch, water caltrop starch, Rhizoma Nelumbinis starch, cornstarch are several
Kind, preferably cornstarch and/or potato starch.
19. preparation method according to claim 16, wherein reaction temperature described in step (1) is 30~60 DEG C；Reaction
Time is 0.5~4h, preferably 1~3h.
20. preparation method according to claim 16, wherein its structure of the zwitterionic surfactant is as follows:, in which: integer of the n between 2-6, preferably n are 3 or 4；R is the carbochain of carbon number 1-18, excellent
Selecting R is the carbochain of carbon number 12-18, and it is linear chain or branched chain that the carbochain, which is saturated carbon chains,.
21. preparation method according to claim 20, wherein the zwitterionic surfactant carbochain removes end group carbon
On containing substituted hydroxyl, amino or carboxyl, be monosubstituted on the same carbon.
22. preparation method according to claim 16, wherein the zwitterionic surfactant is dimethyl 12
Alkyl sulfopropyl ammonium salt, dimethyl hexadecyl base sulfoethyl ammonium salt, dimethyl stearyl sulphur butyl ammonium salt, dimethyl (3- hydroxyl
Base dodecyl) sulfopropyl ammonium salt, one or more of dimethyl (6- amino myristyl) sulfoethyl ammonium salt.
23. preparation method according to claim 16, wherein the alkane derivative is saturated alkane, such as alkane
Hydrocarbon and/or cycloalkane.
24. according to the preparation method described in claim 23, wherein the alkane, cycloalkane are halogenated alkanes.
25. preparation method according to claim 16, wherein alkane derivative described in step (3) be n-hexane,
Normal heptane, normal octane, decane, n-dodecane, isohexane, isoheptane, isooctane, different ten alkane, Permethyl 99A, pentamethylene, ring
One of hexane, cycloheptane, cyclooctane, chloroform, chloropentane, chlorohexane, chloro-octane, chlorododecane are a variety of.
26. preparation method according to claim 16, wherein emulsifier described in step (3) is anionic surface
Activating agent or nonionic surfactant.
27. preparation method according to claim 16, wherein emulsifier described in step (3) is detergent alkylate sulphur
Sour sodium, cetyl benzenesulfonic acid sodium, sodium dodecyl benzene sulfonate, cetyl phenyl-hydrogen-sulfate sodium, Span20, Span40, Span60,
One or more of Span80, Tween20, Tween40, Tween60, Tween80.
28. preparation method according to claim 16, wherein inorganic salts described in step (4) are soluble inorganic salt, institute
State inorganic salts for one of sodium salt, sylvite, ammonium salt, calcium salt, magnesium salts or a variety of, when the inorganic salts are sodium salt, specially
Sodium chloride, sodium bromide, sodium sulphate, sodium sulfite, sodium carbonate, sodium bicarbonate, sodium nitrate, sodium phosphate, dibastic sodium phosphate, in sodium metasilicate
It is one or more；When the inorganic salts be sylvite when, specially potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate,
Saleratus, potassium nitrate, potassium phosphate, potassium hydrogen phosphate, potassium silicate it is one or more；When the inorganic salts are ammonium salt, specifically
For ammonium chloride, ammonium bromide, ammonium nitrate it is one or more；When the inorganic salts are calcium salt, specially calcium chloride or calcium bromide；
When the inorganic salts be magnesium salts when, specially magnesium chloride, magnesium bromide, magnesium sulfate, magnesium nitrate it is one or more.
29. preparation method according to claim 16, wherein demulsification described in step (4) is using mechanical stirring or adds
Enter organic solvent to be demulsified, it is preferred to use organic solvent is added and is demulsified；Washing described in step (4) is with organic molten
Agent washing.
30. according to the preparation method described in claim 29, wherein demulsification described in step (4) and washing process are using identical
Or different organic solvents carries out, it is preferred to use identical organic solvent.
31. according to the preparation method described in claim 29, wherein the organic solvent is dehydrated alcohol, n-butyl alcohol, acetic acid second
One or more of ester, butyl acetate, acetone, dimethylbenzene, n-hexane, carbon tetrachloride, ethyl acetate and/or anhydrous second
Alcohol.
32. preparation method according to claim 16, wherein dry described in step (4) is dry at 50~100 DEG C
10~for 24 hours.
33. application of the spherex of any of claims 1 or 2 in reservoir protection diverting agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710720848.5A CN109422817B (en) | 2017-08-22 | 2017-08-22 | Micron-sized crosslinked starch microspheres and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710720848.5A CN109422817B (en) | 2017-08-22 | 2017-08-22 | Micron-sized crosslinked starch microspheres and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109422817A true CN109422817A (en) | 2019-03-05 |
| CN109422817B CN109422817B (en) | 2020-11-06 |
Family
ID=65499116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710720848.5A Active CN109422817B (en) | 2017-08-22 | 2017-08-22 | Micron-sized crosslinked starch microspheres and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109422817B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110482545A (en) * | 2019-09-04 | 2019-11-22 | 中国科学院山西煤炭化学研究所 | A kind of preparation method and its usage of high-crosslinking-degree starch |
| CN114437677A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Drilling fluid and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1756780A (en) * | 2002-12-30 | 2006-04-05 | 巴斯福股份公司 | Ampholytic copolymer and use thereof |
| CN101255333A (en) * | 2008-04-21 | 2008-09-03 | 北京中科日升科技有限公司 | Anti-temperature starch composition for drilling liquid and preparation method thereof |
| US20100230169A1 (en) * | 2009-03-12 | 2010-09-16 | Daniel Guy Pomerleau | Compositions and methods for inhibiting lost circulation during well operations |
| CN103861566A (en) * | 2014-03-22 | 2014-06-18 | 广东工业大学 | Preparation method of efficiently-adsorptive modified starch microspheres and application of modified starch microspheres |
| CN104004134A (en) * | 2014-05-30 | 2014-08-27 | 西华大学 | Preparation method of grain size controllable monodisperse nano starch microspheres |
| CN104624129A (en) * | 2015-01-08 | 2015-05-20 | 华南理工大学 | Preparation method of starch nanometer microspheres based on ionic liquid-type surfactant microemulsion system |
| CN104785179A (en) * | 2015-04-01 | 2015-07-22 | 中国科学院化学研究所 | Preparation method for starch nanospheres |
| CN106543992A (en) * | 2016-09-30 | 2017-03-29 | 成都西油华巍科技有限公司 | A kind of polymer for drilling fluid microsphere sealing agent and preparation method thereof |
-
2017
- 2017-08-22 CN CN201710720848.5A patent/CN109422817B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1756780A (en) * | 2002-12-30 | 2006-04-05 | 巴斯福股份公司 | Ampholytic copolymer and use thereof |
| CN101255333A (en) * | 2008-04-21 | 2008-09-03 | 北京中科日升科技有限公司 | Anti-temperature starch composition for drilling liquid and preparation method thereof |
| US20100230169A1 (en) * | 2009-03-12 | 2010-09-16 | Daniel Guy Pomerleau | Compositions and methods for inhibiting lost circulation during well operations |
| CN103861566A (en) * | 2014-03-22 | 2014-06-18 | 广东工业大学 | Preparation method of efficiently-adsorptive modified starch microspheres and application of modified starch microspheres |
| CN104004134A (en) * | 2014-05-30 | 2014-08-27 | 西华大学 | Preparation method of grain size controllable monodisperse nano starch microspheres |
| CN104624129A (en) * | 2015-01-08 | 2015-05-20 | 华南理工大学 | Preparation method of starch nanometer microspheres based on ionic liquid-type surfactant microemulsion system |
| CN104785179A (en) * | 2015-04-01 | 2015-07-22 | 中国科学院化学研究所 | Preparation method for starch nanospheres |
| CN106543992A (en) * | 2016-09-30 | 2017-03-29 | 成都西油华巍科技有限公司 | A kind of polymer for drilling fluid microsphere sealing agent and preparation method thereof |
Non-Patent Citations (8)
| Title |
|---|
| YATI YANG等: ""Preparation, Characterization and Adsorption Performance of a Novel Anionic Starch Microsphere"", 《MOLECULES》 * |
| 中国洗涤用品工业协会编: "《中国洗涤用品企业大全》", 31 January 2002, 中国轻工业出版社 * |
| 刘亚伟: "《淀粉生产及其深加工技术》", 31 July 2001, 中国轻工业出版社 * |
| 单洁 等: ""耐温抗盐改性淀粉钻井液降滤失剂的合成及性能研究"", 《油田化学》 * |
| 李仲谨 等: ""两步交联法制备淀粉微球的研究"", 《食品科技》 * |
| 杨焘: "" 钻井液用耐高温改性淀粉的合成与应用研究"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 王基铭 等: "《石油化工技术进展》", 30 April 2002, 中国石化出版社 * |
| 王正远: "《化工产品购销手册》", 28 February 2002, 中国物资出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110482545A (en) * | 2019-09-04 | 2019-11-22 | 中国科学院山西煤炭化学研究所 | A kind of preparation method and its usage of high-crosslinking-degree starch |
| CN110482545B (en) * | 2019-09-04 | 2023-01-03 | 中国科学院山西煤炭化学研究所 | Preparation method and application of high-crosslinking-degree starch |
| CN114437677A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Drilling fluid and preparation method and application thereof |
| CN114437677B (en) * | 2020-10-30 | 2023-03-14 | 中国石油化工股份有限公司 | Drilling fluid and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109422817B (en) | 2020-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109423264A (en) | A kind of spherex and its preparation method and application | |
| Kazman et al. | Effect of low levels of exchangeable sodium and applied phosphogypsum on the infiltration rate of various soils 1 | |
| Gong et al. | Effect of wettability alteration on enhanced heavy oil recovery by alkaline flooding | |
| DE60105443T2 (en) | STUNNED BOHRLOCHZEMENSCHLÄMME | |
| CN109422817A (en) | A kind of micron-level crosslinked spherex and its preparation method and application | |
| CN109422886A (en) | A kind of anion doped spherex material and its preparation method and application | |
| CN104388064A (en) | Calcium chloride-containing water-based drilling fluid | |
| CN108102622A (en) | A kind of drilling fluid agent and preparation method thereof | |
| Alibrahim | Cloud point extraction of polycyclic aromatic hydrocarbons in aqueous solution with nonionic surfactants | |
| CN109420469A (en) | A kind of cation doping spherex material and its preparation method and application | |
| Xie et al. | Effect of self-diverting acid viscosity and the chemical structure of coal under different acid environment | |
| CN106854391A (en) | A kind of ardealite base inner wall putty powder and preparation method thereof | |
| US20120285691A1 (en) | Permeability modification and water shut off composition and process | |
| CN109423265A (en) | A kind of anti-salt temperature-resistant spherex and its preparation method and application | |
| CN106520109B (en) | A kind of preparation method of modified by nano particles clean fracturing fluid | |
| CN108714410A (en) | A kind of bentonite drier and preparation method thereof | |
| CN105295858A (en) | Tackifier for oil-based drilling fluid | |
| Edelstein et al. | Water salinity and sodicity effects on soil structure and hydraulic properties | |
| Xue et al. | Effect of process parameters and agglomeration mechanisms on NPK compound fertiliser | |
| CN109422852B (en) | Micron-sized starch microsphere and preparation method and application thereof | |
| CN105733534A (en) | Water-plugging gel cement slurry and preparation method thereof | |
| CN106179108A (en) | Heterogeneous foam system of magnetic response type and preparation method thereof | |
| CN109422887A (en) | A kind of anionic starch microballoon and its preparation method and application | |
| CN109423266A (en) | A kind of amphoteric ion spherex and its preparation method and application | |
| CN108070364A (en) | A kind of water-base drilling fluid potent shale control agent aqua, pulvis and preparation method thereof and inhibitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230830 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TR01 | Transfer of patent right |