CN106928957B - A kind of foam fracturing structural type polymer foam stabilizer and preparation method thereof - Google Patents
A kind of foam fracturing structural type polymer foam stabilizer and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
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Abstract
The present invention provides a kind of foam fracturing structural type polymer foam stabilizer and preparation method thereof.The foam stabilizer is characterized in that, blistering rate >=600% of the aqueous solution containing foam stabilizer described in 0.3wt%, half-life period >=12h.The preparation method comprises the following steps: deionized water, solubilizer, the water-soluble monomer containing vinyl group, structural type monomer, Anionic surface-active monomer, anionic surfactant, redox system initiator, azo-initiator being carried out multistage cause and polymerize, it is warming up to 80~95 DEG C of insulation reactions 8~for 24 hours, make molecular weight 200~4,000,000 of obtained polymer to get the foam stabilizer.Foam stabilizer of the invention has excellent foam stability energy, efficient frothing capacity, excellent solubilized synergistic effect and heatproof resistant to shearing, and prop-carrying capacity is strong, at low cost, strong operability.
Description
Technical field
The invention belongs to polymeric additives and oil recovery chemicals technical field, and in particular to a kind of foam fracturing structure
Type polymer foam stabilizer and preparation method thereof.
Background technique
Foam is the multiphase dispersion that gas is scattered in liquid.Gas is dispersed phase, and liquid is decentralized medium.Preparation
During foam, bubble in liquid formed easily on liquid level under the action of density contrast the liquid film that is constituted with a small amount of liquid every
Open bubble coalescence object --- the foam of gas.Aerated fluid is the bubble dispersion of gas composition, has high surface certainly
It is thermodynamic unstable system by energy, so foam can decay, reason generally believes two aspects: liquid in foam
It is precipitated and gas penetration Liquid film diffusion.Foam is complete in drilling well profile control, oil recovery gas production, fracture acidizing, drilling well with its unique performance
It is more and more applied in the fields such as well, such as foam flooding, foam drilling, foamed cement well cementation, foam acidizing, foam punching
Husky well-flushing, foam fracturing, foam gas production, steam drive foam profile control, foam-polymer combination flooding etc., be it is at low cost, there is development
The method of future.Although foam has many important applications, there is a fatal weakness, be exactly it is unstable, certain need to be taken
A little measures change condition, and the stability of reinforced foam system is to meet application requirement.
Foam fracturing, which refers to, is added foaming agent on the basis of conventional fracturing fluid, such as nitrogen or carbon dioxide gas, shape
At foam to composition with gas phase be interior phase, liquid phase for the low damage fracture liquid system of foreign minister fracturing process.Foam fracturing fluid
Belong to more complicated non-newtonian liquid, its property, flow behavior and feature is controlled by many variable factors.Gas bubble
Foam quality is mostly 50%~70%, is energization system when foam quality is less than 52%, is typically used as conventional post-fracturing liquid in hot pursuit,
To help the row of returning of raffinate after pressing；When bubble quality is greater than 52%, interior phase bubble particles are small, and stability is good, long half time, distribution
Uniformly, bubble contacts with each other with bubble when flowing, interferes with each other, and keeps its viscosity big, and prop-carrying capacity is strong, can be used for fracturing fluid.
Foam fracturing fluid just takes the lead in being applied early in the 1970s in the U.S., and just there is larger hair in nineteen eighty-two later
Exhibition.Foam fracturing fluid research can substantially be divided into four-stage: first generation foam fracturing fluid used in the seventies, mainly by salt
Water, acids, methanol, crude oil, nitrogen and foaming agent are formulated, and due to foam stability difference and the service life is short, and it is dense to take sand
Degree only has 120~240Kg/m3, construct on a small scale so being only applicable to shallow well；Second generation foam fracturing fluid used in the eighties
It is made of salt water, foaming agent, polymer (natural plant gum), foam stabilizer and nitrogen or carbon dioxide, its foam stability is generally, partly
The phase decline compared with short, viscosity is big, takes sand concentration and is generally 480~600Kg/m3, scale is smaller, applies suitable for all kinds of conventional oil well pressure breaks
Work；The third generation foam fracturing fluid of the nineties is by salt water, foaming agent, guanidine glue and its derivative, crosslinking agent, nitrogen or carbon dioxide
Composition, since it is to use crosslinked gel body as foam stabilizer, so being affected by soda acid, by the shadow of crosslinking power and stability
It rings obviously, therefore stability is general, 600Kg/m can be greater than by taking sand concentration3, it is able to satisfy biggish scope of construction item；After the nineties
Four generation foam fracturing fluids are similar compared with the third generation in composition but larger, and guanidine glue class foam stabilizer heatproof resistant to shearing is stablized
Property and prop-carrying capacity can not preferably meet, and to the performance of foam stabilizer, more stringent requirements are proposed.
With the exploitation of the unconventional oil and gas reservoir such as low pressure, hypotonic, water sensitivity in recent years, pressure break is as increasing yield and injection technology
It is widely applied on oil field；Wherein, foam fracturing fluid is got the attention as a kind of low damage fracture liquid system,
Compared to conventional water-based fracturing, gas and foaming agent are added usually in guanidine glue crosslinked fracturing fluid, due to the addition of gas, bubble
Foam fracturing fluid is smaller compared to conventional aqueous fracturing fluid density, and fluid pressure is low, and foam stores centainly under condition of formation pressure
Energy, these reasons enable after pressing crack construction the fracturing fluid row of returning rapidly；And the addition of foam reduces liquid phase, reduces
Stratum leak-off, to reduce core damage, these are of great significance for the oil-gas storages such as exploitation low pressure, hypotonic.
Foaming agent used in foam fracturing fluid be surfactant, can be divided into anion foaming agent, Cationic Latherin agent,
Nonionic foaming agent and amphoteric ion foaming agent etc..In general, anion foaming agent has compared with low surface tension, such as carboxylate
Class, Sulfates, Sulfonates and sulfosuccinate salt etc., good foam property, dosage is few, but stability is poor.For into
One step improves the frothing capacity of anion foaming agent, generally also needs to be used in compounding with cationic surfactant, but need to examine
Consider the compatibility of the two.
Foam stabilizer is mainly common thickening agent in aqueous fracturing fluid.It is insoluble that this foam stabilizer requires lower water
Property, stronger thickening capabilities, use carboxymethyl guanidine glue or carboxy-methyl hydroxy propyl guanidine glue as foam stabilizer more both at home and abroad.But guanidine glue
Class thickening agent is affected by acid-base property, and gel structure is unstable after crosslinking, and performance difference is very big, therefore foam stability is poor, right
Execution conditions are more demanding.
The starting foam volume of foaming agent is an important factor for determining foaming agent frothing capacity and practical application is sieved in the middle
Select the important indicator of foaming agent.The foam stability (half-life period) of foam stabilizer be also in practical application it is in need of consideration it is important because
Element.Under normal circumstances, it needs that foaming agent and foam stabilizer are added simultaneously, it should be in view of blistering when determining the use concentration of the two
Property and stability, it is also necessary to consider operability and economy.Cost is not only increased using foaming agent and foam stabilizer, also needs to examine
Consider the influence that the interaction of the two may cause, practical operation is complex and cumbersome.
Summary of the invention
It is an object of the present invention to provide a kind of foam fracturing structural type polymer foam stabilizers.
Another object of the present invention is to provide a kind of preparation method of above-mentioned foam stabilizer.
To achieve the above object, as one aspect of the present invention, it is poly- that the present invention provides a kind of foam fracturing structural type
Close object foam stabilizer, the foam stabilizer have the feature that the aqueous solution containing 0.3% foam stabilizer blistering rate >=600%,
Half-life period >=12h, the percentage are mass percent.
The foam stabilizer is obtained by following raw material components through multi-step polymerization: by mass percentage, deionized water 48~
67%, solubilizer 3~5%, the water-soluble monomer 25~35% containing vinyl group, structural type monomer 2~4%, anion table
Face activated monomer 2~5%, anionic surfactant 1~3%, redox system initiator 0.1~0.5%, azo draw
Send out agent 0.1~0.5%.
Wherein, it is short to preferably include the anion surface active that mass ratio is 1:4~4:1 for the Anionic surface-active monomer
Carbochain monomer and anion surface active Long carbon chain monomer.
The redox system initiator preferably includes the oxidant and reducing agent that mass ratio is 1:1.
The N- Long carbon chain alkyl acrylamide that the preferred carbon chain lengths of structural type monomer are 8~18.
The anion surface active short carbon chain monomer is preferably Sodium Allyl Sulfonate or vinyl sodium benzosulfonate.
The 2- propionamido- Long carbon chain alkyl that the preferred carbon chain lengths of anion surface active Long carbon chain monomer are 8~18
Sodium sulfonate.
As another aspect of the present invention, the present invention also provides a kind of preparation methods of aforementioned foam stabilizer comprising
Following steps: by deionized water, solubilizer, the water-soluble monomer containing vinyl group, structural type monomer, anion surface active
Monomer, anionic surfactant, redox system initiator, azo-initiator carry out multistage cause and polymerize, and are warming up to
80~95 DEG C of insulation reactions 8~for 24 hours, make molecular weight 200~4,000,000 of obtained polymer to get the foam stabilizer；
Wherein, by mass percentage, deionized water 48~67%, solubilizer 3~5%, contain the water-soluble of vinyl group
Property monomer 25~35%, structural type monomer 2~4%, Anionic surface-active monomer 2~5%, anionic surfactant 1~
3%, redox system initiator 0.1~0.5%, azo-initiator 0.1~0.5%.
Wherein it is preferred to which the Anionic surface-active monomer includes that the anionic surface that mass ratio is 1:4~4:1 is living
Property short carbon chain monomer and anion surface active Long carbon chain monomer.
Preferably, the redox system initiator includes the oxidant and reducing agent that mass ratio is 1:1.
Preferably, the structural type monomer is the N- Long carbon chain alkyl acrylamide that carbon chain lengths are 8~18；The N- long
Alkyl chain length acrylamide is by the Long carbon chain alkylamine and acrylic acid catalytic polymerization in a solvent that are 8~18 by carbon chain lengths
And it obtains.
Preferably, the azo-initiator is nitrogen bis-isobutyronitrile, azobisisoheptonitrile, two isobutyl imidazoline salt of azo
Hydrochlorate or azo-bis-isobutyrate hydrochloride.
Preferably, it is any one of 8~18 higher aliphatic or two or more that the solubilizer, which is carbon chain lengths,
Combination.
Preferably, the water-soluble monomer containing vinyl group is to contain acrylamide, acrylic acid, metering system
Any two or more combinations in the water-soluble monomer of acid, sodium acrylate and acrylic acid.
Preferably, the anionic surfactant is Long carbon chain sodium alkyl sulfonate, the carbochain that carbon chain lengths are 8~18
Length is 8~18 Long carbon chain sodium alkyl benzene sulfonate and carbon chain lengths are any one of 8~18 Long carbon chain sodium alkyl sulfates
Or two or more combinations.
Preferably, the preparation method further includes post-processing step: will after reaction resulting polymer be granulated,
Dry, crushing and packaging.
Wherein, as further preferred, the Long carbon chain alkylamine for being 8~18 for carbon chain lengths and acrylic acid are in solvent
The step of middle catalytic polymerization includes:
It is kept for 10~30 DEG C of temperature in the kettle, 45.5~51.9% toluene solvant is added in a kettle, is then added 38
~42% carbon chain lengths are that 8~18 Long carbon chain alkylamine is stirred to dissolution, add 10~12% acrylic acid and 0.1~
0.5% catalyst p-methyl benzenesulfonic acid sodium is stirred to dissolution, 85~95 DEG C is warming up to after closed reactor, separation reaction generates
Water, react 20 at 85~95 DEG C later~for 24 hours, then be cooled to up to no distillate in 80~90 DEG C of 8~12h of vacuum distillation
The faint yellow oily solid obtained in a kettle after room temperature is N- Long carbon chain alkyl acrylamide, wherein the percentage
Than the mass percent for referring both to account for hybrid reaction system gross mass.
As further preferred, the oxidant in the redox system initiator be sodium peroxydisulfate, potassium peroxydisulfate or
Ammonium persulfate, reducing agent are sodium hydrogensulfite or sodium sulfite.
As further preferred, the anion surface active short carbon chain monomer is Sodium Allyl Sulfonate or to vinyl benzene
Sodium sulfonate.
As further preferred, the anion surface active Long carbon chain monomer is the 2- propionyl that carbon chain lengths are 8~18
Amido Long carbon chain sodium alkyl sulfonate；The 2- propionamido- Long carbon chain sodium alkyl sulfonate is by being 8~18 by carbon chain lengths
Long carbon chain alkyl alkene is obtained with acrylonitrile compolymer.
More specifically, the step of Long carbon chain alkyl alkene and acrylonitrile compolymer for being 8~18 by carbon chain lengths includes: to protect
Hold 0~5 DEG C of temperature in the kettle, sequentially add in a kettle 44~48% carbon chain lengths be 8~18 Long carbon chain alkyl alkene and
12~14% acrylonitrile, is stirred to dissolving each other, and 28~30% oleum is then added dropwise, reacts 1~2h later, then be warming up to
20~30 DEG C, the reaction was continued 16~20h, 8~16% sodium hydroxide is added later, then reacts 4~8h and separates in reaction
Water is cooled to room temperature, and obtained white solid is 2- propionamido- Long carbon chain sodium alkyl sulfonate, wherein the percentage
Refer both to account for the mass percent of hybrid reaction system gross mass.Preferably, after reaction obtains the white solid, also to it
It is filtered, washs and dries, the washing is preferably successively washed with acrylonitrile and acetone, and the preferred vacuum of drying is dry
It is dry；0.5~1h is preferably added dropwise in the oleum.
Preferably, preparation method of the foam fracturing with structural type polymer foam stabilizer, specifically includes as follows
Step: it is kept for 10~30 DEG C of temperature in the kettle, sequentially adds deionized water in a kettle by composition of raw materials amount, solubilizer, contains
The water-soluble monomer of vinyl group, N- Long carbon chain alkyl acrylamide, Sodium Allyl Sulfonate or vinyl sodium benzosulfonate, 2- third
Amide groups Long carbon chain sodium alkyl sulfonate, anionic surfactant, stirring to dissolution；Redox system initiator is added later
And azo-initiator carries out multistage initiation；80~95 DEG C of insulation reactions 8~for 24 hours are warming up to, obtained polymer is made
Molecular weight is 200~4,000,000 to get the foam stabilizer.
As another aspect of the invention, the present invention also provides a kind of use of foam fracturing made from aforementioned preparation process
Structural type polymer foam stabilizer.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
1, excellent foam stability energy: after foam stabilizer dissolution of the invention, the structural type group on polymer molecular chain passes through
Association, such as hydrogen bond, Van der Waals force maintain liquid film to stablize, have delayed liquid film drain and gas diffusion, with excellent steady
Steep effect.
2, efficient frothing capacity: foam stabilizer of the invention has excellent foaming effect simultaneously.After foam stabilizer dissolution, gather
The anionic surfactant component closed in object is dissolved in the water, and mutually assists with the anion surface active group of polymer molecule
Same-action, the significant surface tension for reducing water, therefore there is efficient foaming effect.
3, solubilized synergy: the addition of higher aliphatic is for the surface-active base in anionic surfactant and polymer
Group has solubilization, by being alternatively arranged with surfactant group, reduces the repulsive force between surface active groups, makes table
Face tension further decreases, and further improves foaming effect；The stable alignment of surfactant group also enhances foam
Stability, therefore foam stabilizing effect is also strengthened.
4, heatproof resistant to shearing, prop-carrying capacity are strong: after foam stabilizer dissolution of the invention, the structural type base on polymer molecular chain
Group, by association, forms stable tridimensional network, while the anion surface active group on strand is increased
The influence of solvent and stable alignment, keep spacial framework more stable, have stronger prop-carrying capacity, heatproof resistant to shearing effect is excellent
It is different.
5, inexpensive, strong operability: foam stabilizer of the invention solves traditional handicraft while using foaming agent and foam stabilizing
The problem of agent higher cost, and the influence that may cause without considering the interaction of the two, therefore cost is greatly reduced, and
Improve operability.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this hair
It is bright to be described in further detail.
Like that the research staff of general polymerization Science and Technology Ltd. by research accumulation for many years, polymerize in heat and salinity tolerance in Beijing
Object clean fracturing fluid thickener (patent No.: ZL201110223102.6) and multiple association type polymeric cleaners fracturing fluid thickener
The Molecular Design and indoor synthesis of APCF (patent No.: ZL201310172795.X), pilot scale research, product in large-scale production
Experience abundant is tired out.The fracturing fluid stable structure of preparation, performance are stablized, and have heat and salinity tolerance shear resistant good, good fluidity,
Frictional resistance is small, and cleaning is suitable for high-salinity brine and seawater-based fracturing fluid without residue, fragile glue and the row of returning and other effects, adapts to 15
~240 DEG C of super-wide temperature range, it is each in Jilin Oil Field, Daqing oil field, Shengli Oil Field and the external U.S., Canadian oil field etc.
A oil field is on probation, promote and large-scale application is more than 1000 mouthfuls of wells.
Traditional foam fracturing foam stabilizer, mostly using guanidine glue or modified guanidine glue (carboxymethyl guanidine glue or carboxy-methyl hydroxy propyl
Guanidine glue etc.) it is used as foam stabilizer.But guanidine glue class thickening agent is affected by acid-base property, the Gel Properties difference formed after crosslinking is very
Greatly, therefore foam stability is poor, more demanding to execution conditions.The research and development technology personnel of the application are by gathering artificial synthesized
It closes species foam stabilizer and carries out technological improvement and innovation, be prepared for a kind of foam fracturing structural type polymer foam stabilizer, with
Guanidine glue and its derivative species foam stabilizer are substituted, is solved the problems, such as present on its stability and heatproof resistant to shearing.The foam stabilizer foam stabilizing
It has excellent performance, and with the features such as efficient foaming effect, temperature and shearing sustainability is excellent, and prop-carrying capacity is strong.
Specifically, in preparation method, by into polymer molecular chain simultaneously introduce contain but be not limited to as acrylamide,
The water-soluble monomer that two or more of acrylic acid, methacrylic acid, sodium acrylate, potassium acrylate etc. contain vinyl group participates in
Copolymerization；N- Long carbon chain alkyl acrylamide is introduced as structures alone；Introduce anion surface active short carbon chain monomer allyl
Sodium sulfonate or vinyl sodium benzosulfonate are as comonomer；It is long to introduce anion surface active Long carbon chain monomer 2- propionamido-
Alkyl chain length sodium sulfonate (carbon chain lengths 8~18) is used as comonomer；Introducing Long carbon chain sodium alkyl sulfonate (carbon chain lengths 8~
18), one in Long carbon chain sodium alkyl benzene sulfonate (carbon chain lengths 8~18) or Long carbon chain sodium alkyl sulfate (carbon chain lengths 8~18)
Kind or any two or more anionic surfactant participate in micellar copolymerization；It introduces higher aliphatic (carbon chain lengths 8~18)
One of or any two or more be used as solubilizer.Simultaneously using polymerization in multistage initiation and kettle, through copolyreaction, one is obtained
Kind foam fracturing structural type polymer foam stabilizer.
The preparation method of above-mentioned foam stabilizer provided by the invention, includes the following steps:
By deionized water, solubilizer, the water-soluble monomer containing vinyl group, structural type monomer, anion surface active
Monomer, anionic surfactant, redox system initiator, azo-initiator carry out multistage cause and polymerize, and are warming up to
80~95 DEG C of insulation reactions 8~for 24 hours, make molecular weight 200~4,000,000 of obtained polymer to get the foam stabilizer；
Wherein, by mass percentage, deionized water 48~67%, solubilizer 3~5%, contain the water-soluble of vinyl group
Property monomer 25~35%, structural type monomer 2~4%, Anionic surface-active monomer 2~5%, anionic surfactant 1~
3%, redox system initiator 0.1~0.5%, azo-initiator 0.1~0.5%.
Its technical evaluation index are as follows: blistering rate >=600% of the aqueous solution containing 0.3% foam stabilizer, half-life period >=
12h, the percentage are mass percent.
Evaluation method are as follows: using Waring Blender method evaluation foaming characteristic and foam stability energy.When experiment, 100mL is matched
The 0.3% foam stabilizer aqueous solution made pours into Waring blender, after stirring 1min under 9000r/min revolving speed, immediately will
Foam pours into 1000mL graduated cylinder, reads foaming volume ml, the ratio with 100mL is blistering rate, while recording bubble
The time used is the half-life period of foam when foam volume damper half.
Embodiment 1
The preparation and performance test of foam fracturing structural type polymer foam stabilizer 1:
1,10 DEG C of temperature in the kettle are kept, toluene 74.85g is added in monomer reaction kettle, adds octadecylamine 57g and stirs
It mixes to dissolution, adds acrylic acid 18g and p-methyl benzenesulfonic acid sodium 0.15g is stirred to dissolution.85 are warming up to after closed reactor
DEG C, the water generated by the closed separation reaction of separator, reaction for 24 hours, then in 80 DEG C of vacuum distillation 12h up to no distillate,
The faint yellow oily solid obtained in a kettle after being cooled to room temperature is N- octadecyl acrylamide.
2,2 DEG C of temperature in the kettle are kept, octyl alkene 66g and acrylonitrile 18g are sequentially added in monomer reaction kettle, stirring is extremely
It dissolves each other, then oleum 42g is added dropwise, 1h is added dropwise, then react 2h.20 DEG C are warming up to, the reaction was continued 20h, then 50% hydrogen-oxygen is added dropwise
Change sodium solution 48g, while by the water in the closed separation reaction of separator, reacting 8h.20 DEG C are cooled to, white is obtained by filtration
Solid, then acrylonitrile and acetone washing are successively used, vacuum drying, obtained white powder is 2- propionamido- octyl sulfonic acid
Sodium.
3,20 DEG C of temperature in the kettle are kept, sequentially adds deionized water 100g, n-octyl alcohol 10g, propylene in stirring polymeric kettle
Amide 40g, sodium acrylate 30g, N- octadecyl acrylamide 4g, Sodium Allyl Sulfonate 2g, 2- propionamido- octyl sulfonic acid
Sodium 8g, octyl sodium sulfonate 6g, stirring add ammonium persulfate 0.5g and sodium sulfite 0.5g to dissolving；Add azo two
Isobutyronitrile 0.2g；It is warming up to 95 DEG C of insulation reaction 8h.
4, after step 3 reaction being terminated the cooling of obtained blob of viscose, through granulation, drying, crushing, fine powdered foam pressure is obtained
It splits with structural type polymer foam stabilizer 1.
Product foam fracturing structural type polymer foam stabilizer 1 in the present embodiment is powdered, test result are as follows:
0.3wt% foam fracturing structural type polymer foam stabilizer aqueous solution blistering rate 750%；Half-life period 15h.
Embodiment 2
The preparation and performance test of foam fracturing structural type polymer foam stabilizer 2:
1, keep 30 DEG C of temperature in the kettle, in monomer reaction kettle be added toluene 95g, add octyl amine 84g stir to
Dissolution, adds acrylic acid 20g and p-methyl benzenesulfonic acid sodium 1g is stirred to dissolution.It is warming up to 95 DEG C after closed reactor, passes through
The water that the closed separation reaction of separator generates, reacts 20h, then be cooled to room up to no distillate in 90 DEG C of vacuum distillation 8h
The faint yellow oily solid obtained in a kettle after temperature is N- octyl acrylamide.
2,5 DEG C of temperature in the kettle are kept, octadecyl alkene 96g and acrylonitrile 28g are sequentially added in monomer reaction kettle, is stirred
To dissolving each other, then oleum 60g is added dropwise, 0.5h is added dropwise, then react 1h.30 DEG C are warming up to, the reaction was continued 16h, then it is added dropwise 50%
Sodium hydroxide solution 32g, while by the water in the closed separation reaction of separator, react 4h.10 DEG C are cooled to, is obtained by filtration
White solid, then acrylonitrile and acetone washing are successively used, vacuum drying, obtained white powder is 2- propionamido- octadecane
Base sodium sulfonate.
3,30 DEG C of temperature in the kettle are kept, sequentially adds deionized water 195g, octadecyl alcolol 15g, propylene in stirring polymeric kettle
Sour sodium 40g, methacrylic acid 20g, potassium acrylate 15g, N- octyl acrylamide 12g, vinyl sodium benzosulfonate 4.8g, 2-
Propionamido- sodium stearyl sulfonate 1.2g, sodium stearyl sulfate 3g, stirring to dissolve, add sodium peroxydisulfate 0.15g and
Sodium hydrogensulfite 0.15g；Add two isobutyl imidazoline hydrochloride 1.5g of azo；It is warming up to 80 DEG C of insulation reactions for 24 hours.
4, after step 3 reaction being terminated the cooling of obtained blob of viscose, through granulation, drying, crushing, fine powdered foam pressure is obtained
It splits with structural type polymer foam stabilizer 2.
Product foam fracturing structural type polymer foam stabilizer 2 in the present embodiment is powdered, test result are as follows:
0.3wt% foam fracturing structural type polymer foam stabilizer aqueous solution blistering rate 820%；Half-life period 13.5h.
Embodiment 3
The preparation and performance test of foam fracturing structural type polymer foam stabilizer 3:
1,20 DEG C of temperature in the kettle are kept, toluene 48.7g is added in monomer reaction kettle, adds lauryl amine 40g and stirs
It mixes to dissolution, adds acrylic acid 11g and p-methyl benzenesulfonic acid sodium 0.3g is stirred to dissolution.90 are warming up to after closed reactor
DEG C, the water generated by the closed separation reaction of separator reacts 22h, then in 85 DEG C of vacuum distillation 10h up to no distillate,
The faint yellow oily solid obtained in a kettle after being cooled to room temperature is N- dodecylacrylamide.
2,2 DEG C of temperature in the kettle are kept, dodecyl alkene 46g and acrylonitrile 13g are sequentially added in monomer reaction kettle, is stirred
To dissolving each other, then oleum 29g is added dropwise, 0.8h is added dropwise, then react 1.5h.25 DEG C are warming up to, the reaction was continued 18h, then be added dropwise
50% sodium hydroxide solution 24g, while by the water in the closed separation reaction of separator, react 6h.15 DEG C are cooled to, filtering
White solid is obtained, then successively uses acrylonitrile and acetone washing, vacuum drying, obtained white powder is 2- propionamido- ten
Dialkyl sulfonates.
3,20 DEG C of temperature in the kettle are kept, sequentially adds deionized water 57g, lauryl alcohol 2g, hexadecanol in stirring polymeric kettle
2g, acrylamide 20g, sodium acrylate 5g, potassium acrylate 5g, N- dodecylacrylamide 3g, Sodium Allyl Sulfonate 2g, 2- third
Amide groups dodecyl sodium sulfate 2g, dodecyl sodium sulfate 1g, cetyl benzenesulfonic acid sodium 1g, stirring are added to dissolving
Potassium peroxydisulfate 0.15g and sodium sulfite 0.15g；Add azo-bis-isobutyrate hydrochloride 0.3g；It is warming up to 90 DEG C of insulation reactions
16h。
4, after step 3 reaction being terminated the cooling of obtained blob of viscose, through granulation, drying, crushing, fine powdered foam pressure is obtained
It splits with structural type polymer foam stabilizer 3.
Product foam fracturing structural type polymer foam stabilizer 3 in the present embodiment is powdered, test result are as follows:
0.3wt% foam fracturing structural type polymer foam stabilizer aqueous solution blistering rate 850%；Half-life period 14.5h.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention
Within the scope of.
Claims (10)
1. a kind of foam fracturing preparation method of structural type polymer foam stabilizer, which comprises the following steps:
By deionized water, solubilizer, the water-soluble monomer containing vinyl group, structural type monomer, Anionic surface-active monomer,
Anionic surfactant, redox system initiator and azo-initiator carry out it is multistage cause polymerization, be warming up to 80~
95 DEG C of insulation reactions 8~for 24 hours, make molecular weight 200~4,000,000 of obtained polymer to get the foam stabilizer；
Wherein, by mass percentage, above-mentioned raw materials match are as follows: deionized water 48~67%, contains ethylene at solubilizer 3~5%
Water-soluble monomer 25~35%, structural type monomer 2~4%, the Anionic surface-active monomer 2~5%, anionic surface of group
Activating agent 1~3%, redox system initiator 0.1~0.5%, azo-initiator 0.1~0.5%；
Wherein, it is any one of 8~18 higher aliphatic or two or more combinations that the solubilizer, which is carbon chain lengths,；
The water-soluble monomer containing vinyl group is to contain acrylamide, acrylic acid, methacrylic acid, sodium acrylate and third
Any two or more combinations in the water-soluble monomer of olefin(e) acid potassium；
The structural type monomer is the N- Long carbon chain alkyl acrylamide that carbon chain lengths are 8~18；
The Anionic surface-active monomer includes the anion surface active short carbon chain monomer and yin that mass ratio is 1: 4~4: 1
Ion surface active Long carbon chain monomer；
The anionic surfactant is that Long carbon chain sodium alkyl sulfonate, the carbon chain lengths that carbon chain lengths are 8~18 are 8~18
Long carbon chain sodium alkyl benzene sulfonate and carbon chain lengths are at least one of 8~18 Long carbon chain sodium alkyl sulfates；
The anion surface active short carbon chain monomer is Sodium Allyl Sulfonate or vinyl sodium benzosulfonate；
The anion surface active Long carbon chain monomer is the 2- propionamido- Long carbon chain alkyl sulfonic acid that carbon chain lengths are 8~18
Sodium.
2. preparation method according to claim 1, which is characterized in that
The redox system initiator includes the oxidant and reducing agent that mass ratio is 1: 1；And/or
The N- Long carbon chain alkyl acrylamide be by by carbon chain lengths be 8~18 Long carbon chain alkylamine and acrylic acid molten
Catalytic polymerization in agent and obtain；And/or the azo-initiator is that nitrogen bis-isobutyronitrile, azobisisoheptonitrile, azo two are different
Butamisole quinoline hydrochloride or azo-bis-isobutyrate hydrochloride.
3. preparation method according to claim 2, which is characterized in that
It is described by carbon chain lengths be 8~18 Long carbon chain alkylamine and acrylic acid in a solvent catalytic polymerization the step of include:
Keep 10~30 DEG C of temperature in the kettle, in a kettle be added 45.5~51.9% toluene solvant, then be added 38~
42% carbon chain lengths are that 8~18 Long carbon chain alkylamine is stirred to dissolution, add 10~12% acrylic acid and 0.1~
0.5% catalyst p-methyl benzenesulfonic acid sodium is stirred to dissolution, 85~95 DEG C is warming up to after closed reactor, separation reaction generates
Water, react 20 at 85~95 DEG C later~for 24 hours, then be cooled to up to no distillate in 80~90 DEG C of 8~12h of vacuum distillation
The faint yellow oily solid obtained in a kettle after room temperature is N- Long carbon chain alkyl acrylamide, wherein the percentage
Than the mass percent for referring both to account for hybrid reaction system gross mass.
4. preparation method according to claim 2, which is characterized in that the oxidant in the redox system initiator
For sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate, reducing agent is sodium hydrogensulfite or sodium sulfite；And/or
The 2- acrylamido Long carbon chain sodium alkyl sulfonate be by by carbon chain lengths be 8~18 Long carbon chain alkyl alkene and third
The copolymerization of alkene nitrile obtains.
5. the preparation method according to claim 4, which is characterized in that the Long carbon chain alkane for being 8~18 by carbon chain lengths
The step of base alkene and acrylonitrile compolymer includes: to be kept for 0~5 DEG C of temperature in the kettle, sequentially adds 44~48% carbon in a kettle
Chain length is 8~18 Long carbon chain alkyl alkene and 12~14% acrylonitrile, is stirred to dissolving each other, and 28~30% hair is then added dropwise
Cigarette sulfuric acid reacts 1~2h later, then is warming up to 20~30 DEG C, the reaction was continued 16~20h, and 8~16% hydroxide is added later
Sodium, then react 4~8h and separate the water in reaction, it is cooled to room temperature, obtained white solid is the long carbon of 2- acrylamido
Sodium alkanesulfonate, wherein the percentage refers both to account for the mass percent of hybrid reaction system gross mass.
6. preparation method according to claim 5, which is characterized in that also right after reaction obtains the white solid
It is filtered, washs and dries；And/or
0.5~1h is added dropwise in the oleum.
7. preparation method according to claim 6, which is characterized in that the washing is successively to be carried out with acrylonitrile and acetone
Washing, the drying are vacuum drying.
8. preparation method according to claim 1, which is characterized in that it includes the following steps:
It is kept for 10~30 DEG C of temperature in the kettle, sequentially adds deionized water in a kettle by composition of raw materials amount, solubilizer, contains second
The water-soluble monomer of alkenyl group, N- Long carbon chain alkyl acrylamide, Sodium Allyl Sulfonate or vinyl sodium benzosulfonate, 2- propylene
Amide groups Long carbon chain sodium alkyl sulfonate, anionic surfactant, stirring to dissolution；Redox system initiator is added later
And azo-initiator carries out multistage initiation；80~95 DEG C of insulation reactions 8~for 24 hours are warming up to, obtained polymer is made
Molecular weight is 200~4,000,000 to get the foam stabilizer.
9. preparation method according to claim 1, which is characterized in that the preparation method further includes post-processing step: will
Resulting polymer is granulated, is dried, is crushed and is packed after reaction.
10. the foam fracturing structural type polymer that preparation method described in any one is prepared according to claim 1~9
Foam stabilizer.
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| CN112266780B (en) * | 2020-10-13 | 2022-12-20 | 宁波锋成先进能源材料研究院有限公司 | Modified nano foam stabilizer and preparation method and application thereof |
| CN115386040A (en) * | 2021-05-25 | 2022-11-25 | 中国石油天然气股份有限公司 | High-salinity-resistant foam stabilizer and preparation method thereof |
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| US20070148101A1 (en) * | 2005-12-28 | 2007-06-28 | Marcia Snyder | Foamable alcoholic composition |
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| CN102652011A (en) * | 2009-12-10 | 2012-08-29 | 诺伊堡皮肤护理两合公司 | Emulsifier-free, polymer-stabilized foam formulations |
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