CN104788595B - A kind of polyacrylamide nano composite and its preparation method and application - Google Patents
A kind of polyacrylamide nano composite and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of polyacrylamide nano composite and its preparation method and application.The present invention synthesizes polyacrylamide nano composite using polyacrylamide with nano inorganic phase in-situ polymerization, the nano inorganic is mutually after using nonionic surface active agent to intercalation modifying laminar silicic acid salt treatment, add the reaction of the hydrotalcite slurry containing magnalium and obtain, specific steps：It is oxygen-free environment in maintenance reaction kettle, nano inorganic phase and cosolvent, complexing agent, oxidant, reducing agent, auxiliary agent is added into acrylamide aqueous solution system, react to form polyacrylamide nano composite by polymerizeing intercalation synthesis.The characteristic that there is the composite nanoparticle to be uniformly dispersed, molecular weight is higher, have the nano effect that reservoir is efficiently protected in high-temperature resisting and salt-resisting and oil field concurrently, and preparation method can be used for industrializing.
Description
Technical field
The present invention relates to a kind of polyacrylamide nano composite and its preparation method and application, belong to high polymer material
Production technical field.
Background technology
Acrylamide copolymer is the general designation of methacrylamide homopolymer and acrylamide monomer and other monomer copolymers,
Industrially, the polymer containing more than 50% acrylamide monomer, referred to as polyacrylamide.Study at present it is more mainly
The several methods such as aqueous solution polymerization, inverse emulsion polymerization and conversed phase micro emulsion copolymerization.Polyacrylamide is tertiary oil recovery field
One of wide variety of high molecular weight water soluble polymer, it is widely used in the fields such as sewage disposal, papermaking and petroleum drilling and mining.
The high molecular weight polyacrylamide (PAM) used in existing petroleum drilling and mining technology has with partially hydrolyzed polyacrylamide (PHPA)
There are easy shear degradation, heatproof and salt-resistance difference.Polyacrylamide and its derivative are water soluble polymer, are made into
There is the property that bigger than surface, adsorption capacity is strong, cohesion is big and specific surface respond etc. is unique after nanoparticle,
Made polyacrylamide nano composite, the combination property such as its heatproof, anti-shearing, antipollution are improved.
It is compound that patent application 201310132122.1 (open CN104109525A) discloses a kind of polyacrylamide nano
The preparation method of fracturing fluid, after intercalation group is mixed with nitrate with phyllosilicate by using organic long-chain intercalator
Into nano inorganic phase, after the inorganic phase is prepared with polyacrylamide amine monomers through in-situ polymerization recombination reaction, gained is compound
Material has high temperature resistant, anti-shearing etc. characteristic.
But agglomeration traits of the inorganic nanoparticles in complex hydrocarbon exploits application process, to building complex hydrocarbon floor height
Imitate flow conductivity gas channel to have limited, reduce oil-gas mining efficiency.Therefore solves polyacrylamide nano composite
Microscopic pattern scattering problem is also of universal significance.Above-mentioned prior art is related to polyacrylamide nano composite fracturing fluid
Application performance improves, but and the unresolved reunion scattering problem of inorganic nano-particle in the polymer, also have no related at present
Report.
The content of the invention
It is an object of the invention to provide a kind of method for preparing polyacrylamide nano composite and thus obtained
Polyacrylamide nano composite, solving prior art polyacrylamide materials high temperature resistance, salt-resistance difference and into production
While the problems such as cumbersome, the reunion scattering problem of nanoparticle in the polymer is also solved.
The invention provides a kind of preparation method of polyacrylamide nano composite, comprise the following steps：
A. by acrylamide monomer and pure water by weight 1:The ratio mixing of (2.5-3.5), based on the acrylamide
The quality of monomer adds 0.3-0.6% cosolvent, 0.2-0.3% complexing agent and 0.2-0.3% auxiliary agent, controls frequency
30-35Hz stirs more than 20min, turns into acrylamide reaction system；
B. aforesaid propylene acid amides pH value of reaction system 9-10 is adjusted, the quality based on the acrylamide monomer adds 0.5-
1.5% nano inorganic phase, stirs as reactant mixed system；
C. above-mentioned reactant mixed system is transferred to polymeric kettle, under oxygen-free environment, based on the acrylamide monomer
Quality add 0.8-1.0% oxidant and 0.8-1.0% reducing agent, it is aggregated reaction generation polymeric reaction product, instead
When temperature of reaction system no longer raises during answering, insulation maintains 3-5h, produces polymeric reaction product；
D. above-mentioned polymeric reaction product through being granulated, dry be the polyacrylamide nano composite；
Wherein, the preparation process of the nano inorganic phase includes：
E. phyllosilicate and water are pressed into mass parts 1:(10-20) is mixed in a kettle, maintains stirring 20-30min, shape
Into swelling system；
F. the quality based on layered silicate, above-mentioned swelling body is tied up at 70-80 DEG C to the intercalation for adding 1-10%
Agent, stirring reaction 10-12h under 30-35Hz, afterwards the quality based on layered silicate add 1-2% nonionic table
Face activating agent, continue to react 4-6h, obtain intercalation system；
G. the volume based on above-mentioned intercalation system, the 20-30% hydrotalcite slurry containing magnalium is added, in 60-65
DEG C reaction 3-5h, obtain the nano inorganic phase；
H. the hydrotalcite slurry containing magnalium is to use water-soluble magnesium salt and aluminium salt and 2- acrylamido -2- methyl
The mixture of propane sulfonic acid obtains through co-precipitation in the basic conditions.
The method according to the invention, polyacrylamide is synthesized with nano inorganic phase in-situ polymerization using polyacrylamide
Nano composite material, and the nano inorganic for introducing polymerization reaction system is mutually to inserting by using nonionic surface active agent
The modified phyllosilicate of layer is handled and obtained.In specific embodiments of the present invention, intercalator used can be sun from
Sub- surfactant, intercalation obtain intercalation modifying phyllosilicate slurries after terminating, added into the phyllosilicate slurries non-
Ionic surfactant is handled intercalated layered system, can prevent the phyllosilicate slurries and the hydrotalcite slurry containing magnalium
Reunite, so as to lift the dispersion effect of obtained nano inorganic phase.Research finds, the laminar silicic acid obtained according to the inventive method
Salt intercalation piece interlamellar spacing can reach 2-4nm, and the average grain diameter of gained nano inorganic multiphase aggregate can be 0.9-1.5 μm, adopt
It is compound that with the aggregated intercalation synthesis of crystal type acrylamide monomer the polyacrylamide nano to be formed is reacted with the nano inorganic phase
Material, nano inorganic is mutually achievable dispersed in polyacrylamide matrix, so as to strengthen organic phase-inorganic phase interaction
Effect, i.e., known nano effect, the polyacrylamide nano composite high temperature resistance increase of gained can be made, solved existing
The problem of reunion of technology nanoparticle in the polymer is scattered and reduces polymer high temperature resistance.Further research shows,
The polyacrylamide nano composite prepared according to the inventive method is more beneficial for nanoparticle during practical application in industry
The redisperse of aggregate in the polymer, so that polyacrylamide nano composite of the present invention and preparation method thereof can
Realize industrial applications.
The method according to the invention, when polymerisation generates polymeric reaction product, reaction system has a temperature-rise period,
Be raised to system temperature after the temperature of top maintain it is stable (that is, system temperature no longer raise substantially and maintain one it is basicly stable
Temperature range), in concrete operations it is observed that：Oxidizing and Reducing Agents is added to after reaction system through after a while
System temperature can be begun to ramp up, and no longer be risen after system temperature is raised to certain top temperature, now be needed real to reaction system
Isothermal holding is applied, to prevent system temperature from reducing so as to be more conducive to complete polymerisation.The time that reaction system starts to warm up with
And the maximum temperature (peak temperature) that can reach understands according to the difference of reaction system all differences, for example, in room temperature or slightly below
(20 DEG C or so or 5-15 DEG C) operates in the environment of room temperature, and generally reaction system can start to warm up after 50-70min,
Accessible top temperature is 80-90 DEG C, when observing that temperature tops out, or observes temperature in a relatively-stationary area
Between fluctuate (such as ± 5 DEG C), you can think to have reached peak temperature, can start to be incubated to continue to react.
The method according to the invention, polymerisation requirement of the present invention are implemented in oxygen-free environment, can pass through elder generation
Inert gas is introduced into polymeric kettle and forms oxygen-free environment, it is in practical operation to use nitrogen more, for example, can first maintain to be passed through nitrogen
Gas 20-30min, to remove the air in polymeric kettle, in a particular embodiment, the nitrogen gas purity used is 98.99-
99.999%th, pressure 0.50-0.55MPa, flow 40-50m3/h。
The method according to the invention, the acrylamide monomer can be crystal type monomer.
Phyllosilicate used in the present invention can be the conventional silicate with layered crystal structure and sheet crystal formation
Class mineral, in a particular embodiment, layered silicate can be montmorillonite, clay, hydrotalcite, kaolin, concave convex rod
Stone, sepiolite, wollastonite, chlorite, stratiform silica etc. or their mixed system.
In embodiment of the present invention, the cosolvent can be urea or polyethylene glycol etc., and the complexing agent can be
Disodium ethylene diamine tetraacetate or tetrasodium ethylenediamine tetraacetate etc., the auxiliary agent can be ammoniacal liquor, sodium chloride, ammonium chloride etc..
In embodiment of the present invention, the oxidant can be ammonium persulfate, potassium peroxydisulfate, potassium sulfite, azo two
Isobutyronitrile or hydrogen peroxide etc., the reducing agent can be sodium sulfite, sodium hydrogensulfite, frerrous chloride or oxalic acid etc..
The method according to the invention, intercalator used can select conventional cationic surface in intercalation system
Activating agent, such as cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride or monoethanolamine etc., the nonionic table
Face activating agent can be selected from Span series, Tween series, the surfactant of OP series, such as span-80, Tween60, OP-
10 etc..
The method according to the invention, when preparing the hydrotalcite slurry containing magnalium, such as magnesium nitrate, nitric acid can be used
The water-soluble magnesium salts such as aluminium and aluminium salt, and 2- acrylamide-2-methylpro panesulfonic acids, realize that co-precipitation is anti-in the basic conditions
Should, such as the conventional alkaline reagent such as sodium hydroxide, sodium acid carbonate, potassium hydroxide can be used.In further embodiment,
When preparing the hydrotalcite slurry containing magnalium, magnesium nitrate is with aluminum nitrate with mol ratio=2:1 is dissolved in distilled water, sodium hydroxide and 2- third
Acrylamide base -2- methyl propane sulfonic acids (AMPS) are with mol ratio=1:1 is dissolved in distilled water, after the two is well mixed at room temperature,
React to obtain the required hydrotalcite slurry containing magnalium through coprecipitation.
A kind of polyacrylamide nano composite of the present invention, is prepared according to any of the above-described method.
Polyacrylamide nano composite of the present invention can be applied to prepare sewage disposal, papermaking or petroleum drilling and mining
Deng the inorganic agent in field.
In embodiment of the present invention, the polyacrylamide nano composite can be used for preparing oil-gas mining pressure break
Liquid.
A kind of polyacrylamide nano composite of the present invention, before testing its performance, Ke Yixian
Handled using following steps：The polymeric reaction product is first extruded into stripping and slicing from polymeric kettle, through thick granulation, is carefully granulated
To 4-6mm polyacrylamide nano composite material granulars, after the particle drying, crushing, storage is to be tested, be embodied
In scheme, through 60 mesh sieves, packaging and storage, the drying temperature are controlled as 76-81 DEG C again after the composite material granular crushes, and
There can be ± 2 DEG C of fluctuation.
A kind of polyacrylamide nano composite material and preparation method thereof provided by the invention can be used for industrializing, and nanoparticle exists
Be uniformly dispersed in polyacrylamide matrix, and material molecule amount is higher, water-soluble and Efficient Adhesive Promotion is good, have concurrently high temperature resistance, salt resistance,
The overall characteristics such as anti-shearing, antipollution, it can be applied to prepare the inorganic agent in the fields such as sewage disposal, papermaking or petroleum drilling and mining, example
Such as it is used to prepare oil-gas mining fracturing fluid, the high-temperature oil gas that is particularly suitable for use in exploits the preparation of fracturing fluid, such as high temperature resistance 130-200
DEG C fracturing fluid.
Brief description of the drawings
Fig. 1-3 is the nano inorganic phase grain size distribution prepared by 1-3 of the embodiment of the present invention.
Fig. 4 is the zata potential diagrams of the poly- propionamide nano composite material prepared by the embodiment of the present invention 5.
Fig. 5 is real for the salt-resistance of the polyacrylamide nano composite prepared by 4-6 of the embodiment of the present invention and comparative example
Test figure.
Fig. 6 is the shear resistant of present example example 4-6 and the polyacrylamide nano composite prepared by comparative example
Lab diagram.
Embodiment
Technical scheme is further elaborated below by way of specific embodiment, but the present invention is not limited to these
Embodiment.
The preparation of embodiment 1-3 nano inorganic phases
A. phyllosilicate and water are pressed into mass parts 1:15 are mixed in a kettle, stir 20-30min at room temperature,
Form swelling system；
B. above-mentioned gained swelling system is warming up to 80 DEG C, quality based on layered silicate adds 10%, 8%,
6% cetyl trimethylammonium bromide, setting stirring unit frequency 30Hz, reacts 12h；
C. the quality based on layered silicate, 2% span-80, reaction are added into above-mentioned gained reaction system
4h；
D. coprecipitation is used, by technical grade magnesium nitrate, aluminum nitrate with mol ratio 2:1 is dissolved in distilled water, sodium hydroxide, 2-
Acrylamide-2-methylpro panesulfonic acid (AMPS) is with mol ratio 1:1 is dissolved in distilled water, is well mixed at room temperature, reaction obtains
Hydrotalcite slurry containing magnalium；
E. the hydrotalcite slurry added into the reaction system obtained by above-mentioned steps c in step d, 65 DEG C of reactions of design temperature
4h, then system is cooled to 30 DEG C or so or room temperature obtains nano inorganic phase.
The grain size distribution of nano inorganic phase as shown in Figure 1 to Figure 3, can be seen by Fig. 1-3 obtained by different dosage intercalators
Go out, prepared nano inorganic phase grain size distribution meets standardized normal distribution, is calculated according to statistics, corresponding in Fig. 1-3
In the average diameter of aggregation particulate that intercalator dosage is 10%, 8%, 6% be respectively 995.6nm, 1111nm, 1448nm.
The preparation of the polyacrylamide nano composite of embodiment 4
A. by crystal type acrylamide monomer and pure water by weight 1:2.5 ratio mixes in modulation kettle, based on institute
The quality for stating acrylamide monomer adds 0.6% urea, 0.2% disodium ethylene diamine tetraacetate and 0.2% ammoniacal liquor, stirring
25min, frequency 30Hz；
B. it is 9.5 or so above-mentioned reaction system to be adjusted into pH value, and the quality based on the acrylamide monomer adds 0.5%
Above-described embodiment 2 nano inorganic phase, stir 15min；
C. above-mentioned gained mixed system is transferred to polymeric kettle, is passed through the nitrogen 25min that purity is 99.999%, pressure is
0.50-0.55MPa, flow 45-50m3/ h, to remove the air in reactor, the quality based on the acrylamide monomer
0.8% ammonium persulfate and 0.8% sodium sulfite is added, polymerization generation polymeric reaction product, system initial temperature is 15 DEG C
Left and right, ammonium persulfate and sodium sulfite start to warm up after adding through 55min or so, reaction system, when system temperature is no longer lasting
Rise, and it is stable at 80 ± 5 DEG C, system implementation is incubated and maintains 3h, produces polymeric reaction product；
D. above-mentioned gained polymeric reaction product is extruded into stripping and slicing from polymeric kettle, obtains 4-6mm through thick granulation, thin granulation and gather
Acrylamide nanocomposite particles, after by gained particle through turn round percolation machine be dried into vibration drying bed, control
76 ± 2 DEG C of temperature；
E. above-mentioned gained polyacrylamide nano composite material granular is crushed, packed after crossing 60 mesh sieves into storehouse.
Each method for testing performance of polyacrylamide nano composite prepared by the present embodiment is specific as follows：
With reference to GB12005.1-89, concentration is used to make solvent for the 1.0mol/L NaCl aqueous solution, at 30 ± 0.1 DEG C,
The inherent viscosity of composite is determined with one point method using Ubbelohde viscometer, is further calculated by Mark-Houwink equations
Go out the relative molecular mass of composite；
The composite of a certain fixed weight is taken, it is dissolved in distilled water at room temperature, is fully determined wherein not after dissolving
The weight of molten thing produces the content of insoluble matter in composite；
Composite is toasted into 24h, and material before and after measure baking respectively in the constant temperature oven for set fixed temperature
The inherent viscosity of material, if inherent viscosity is more than or equal to 6dl/g after baking, illustrate the tolerance temperature that the temperature is composite
Degree, produce the temperature resistance of composite；
The API fluid loss characteristics of composite is determined using the method for dynamic filtration, i.e. take the composite wood of a certain fixed weight
Material, is dissolved in distilled water at room temperature by it, and the accumulative filter loss that press filtration is committed a breach of etiquette in measure nano composite material 30min in is i.e.
Obtain the API fluid loss characteristics of composite；
The front and rear permeability of rock core pollution is surveyed using the multi-functional core experiment instrument of DYQ-1 types, core permeability is calculated
Recovery value, and then evaluate reservoir protection effect；
Using the apparent viscosity of HTHP rheometer (viscosimeter) or six fast rotary viscosity design determining composites with cutting
The variation relation for cutting the time produces the shear resistant of material；
After composite is dissolved in into the sodium chloride solution of various concentrations, then using HTHP rheometer (viscosimeter) or six
The apparent viscosity of fast rotary viscosity design determining composite produces the salt-resistance of material with the variation relation of sodium chloride concentration.
Properties of product testing result is listed in table 1.
The preparation of the polyacrylamide nano composite of embodiment 5
A. by crystal type acrylamide monomer and pure water by weight 1:2.5 ratio mixes in modulation kettle, based on institute
The quality for stating acrylamide monomer adds 0.6% urea, 0.2% disodium ethylene diamine tetraacetate and 0.2% ammoniacal liquor, stirring
25min, frequency 30Hz；
B. it is 10 or so above-mentioned reaction system to be adjusted into pH value, and the quality based on the acrylamide monomer adds 1.0%
Above-described embodiment 2 in nano inorganic phase, stir 15min；
C. above-mentioned gained mixed system is transferred to polymeric kettle, is passed through the nitrogen 25min that purity is 99.999%, pressure is
0.50-0.55MPa, flow 45-50m3/ h, to remove the air in reactor, the quality based on the acrylamide monomer
0.8% ammonium persulfate and 0.8% sodium sulfite is added, polymerization generation polymeric reaction product, system initial temperature is 15 DEG C
Left and right, ammonium persulfate and sodium sulfite start to warm up after adding through 50min or so, reaction system, when system temperature is no longer lasting
Rise, and it is stable at 80 ± 5 DEG C, system implementation is incubated and maintains 3h, produces polymeric reaction product；
D. above-mentioned gained polymeric reaction product is extruded into stripping and slicing from polymeric kettle, obtains 4-6mm through thick granulation, thin granulation and gather
Acrylamide nanocomposite particles, after by gained particle through turn round percolation machine be dried into vibration drying bed, control
78 ± 2 DEG C of temperature；
E. above-mentioned gained polyacrylamide nano composite material granular is crushed, packed after crossing 60 mesh sieves into storehouse.
The zata potentiometric properties of the polyacrylamide nano composite of the present embodiment are measured using zata potentiometers, remaining
Each performance measurement method is the same as embodiment 4.
Properties of product testing result is listed in table 1.
The zata potential diagrams of product are as shown in figure 4, product is anion-polyacrylamide nano composite material, by figure
Data show that nanocomposite colloid solution system is stable, are uniformly dispersed.
The preparation of the polyacrylamide nano composite of embodiment 6
A. by crystal type acrylamide monomer and pure water by weight 1:2.5 ratio mixes in modulation kettle, based on institute
The quality for stating acrylamide monomer adds 0.5% urea, 0.2% disodium ethylene diamine tetraacetate and 0.2% ammoniacal liquor, stirring
25min, frequency 30Hz；
B. it is 9 or so above-mentioned reaction system to be adjusted into pH value, and the quality based on the acrylamide monomer adds 1.5%
Nano inorganic phase in embodiment 2, stir 15min；
C. above-mentioned gained mixed system is transferred to polymeric kettle, is passed through the nitrogen 25min that purity is 99.999%, pressure is
0.50-0.55MPa, flow 45-50m3/ h, to remove the air in reactor, the quality based on the acrylamide monomer
0.8% ammonium persulfate and 0.8% sodium sulfite is added, polymerization generation polymeric reaction product, system initial temperature is 15 DEG C
Left and right, ammonium persulfate and sodium sulfite start to warm up after adding through 50min or so, reaction system, when system temperature is no longer lasting
Rise, and it is stable at 80 ± 5 DEG C, system implementation is incubated and maintains 3h, produces polymeric reaction product；
D. above-mentioned gained polymeric reaction product is extruded into stripping and slicing from polymeric kettle, obtains 4-6mm through thick granulation, thin granulation and gather
Acrylamide nanocomposite particles, after by gained particle through turn round percolation machine be dried into vibration drying bed, control
80 ± 2 DEG C of temperature；
E. above-mentioned gained polyacrylamide nano composite material granular is crushed, packed after crossing 60 mesh sieves into storehouse.
Each performance measurement method of polyacrylamide nano composite is the same as embodiment 4 obtained by the present embodiment.
Properties of product testing result is listed in table 1.
The preparation of comparative example polyacrylamide
A. by crystal type acrylamide monomer and pure water by weight 1:2.5 ratio mixes in modulation kettle, and adds matter
Urea, 0.2% disodium ethylene diamine tetraacetate and 0.2% ammoniacal liquor that part is 0.5% are measured, stirs 25min, frequency 30Hz；
B. above-mentioned gained mixed system is transferred to polymeric kettle, is passed through the nitrogen 25min that purity is 99.999%, pressure is
0.50-0.55MPa, flow 45-50m3/ h, to remove the air in reactor, add the persulfuric acid that mass parts are 0.8%
Ammonium, the sodium sulfite that mass parts are 0.8% is added, polymerization generation polyacrylamide, system initial temperature is 15 DEG C or so, over cure
Sour ammonium and sodium sulfite start to warm up after adding through 70min or so, reaction system, when system temperature no longer persistently raises, and it is steady
80 ± 5 DEG C are scheduled on, system implementation is incubated and maintains 3h, produces polyacrylamide；
C. above-mentioned gained polyacrylamide is extruded into stripping and slicing from polymeric kettle, 4-6mm poly- third is obtained through thick granulation, thin be granulated
Acrylamide particle, after by gained particle through turn round percolation machine be dried into vibration drying bed, control 78 ± 2 DEG C of temperature；
E. above-mentioned gained polyacrylamide particle is crushed, packed after crossing 60 mesh sieves into storehouse.
Each performance measurement method of polyacrylamide is the same as embodiment 4 obtained by the present embodiment.
Properties of product testing result is listed in table 1.
Table 1
The salt resistance property and anti-shearing property of embodiment 4-6 and the polyacrylamide nano composite prepared by comparative example
Respectively as shown in Figure 5 and Figure 6.Comparing embodiment 4-6 and comparative example data, understood with reference to Fig. 5, Fig. 6, it is produced according to the present invention
Polyacrylamide nano composite there is higher molecular weight, the higher explanation Efficient Adhesive Promotion of inherent viscosity is more preferable, water-soluble
The lower explanation of thing content is water-soluble more preferable, and the reduction of API dehydration values and the rise of core permeability recovery value illustrate in oil field
The characteristic of protection reservoir more preferably, and has high temperature resistant, salt-resistance and shear resistant concurrently.
The preparation of the polyacrylamide nano composite fracturing fluid of embodiment 7~9
Add pure water 400mL respectively in three 1000mL beakers, produced by the invention poly- third is slowly added under mechanical agitation
Acrylamide nano composite material 1.6g, 2.0g, 2.4g, being sufficiently agitated until product, all dissolving is complete, and regulation system pH is 4-
5, add crosslinking agent zirconium oxychloride 0.80g, clay inhibitor potassium chloride 1.0g, bactericide TTAB
0.4g, cleanup additive OP-100.80g, stir and polyacrylamide nano composite fracturing fluid is just made.Determined with six fast viscosimeters
Its results of property is as listed in table 2.
0.80g gel breaker ammonium persulfates are added into above-mentioned polyacrylamide nano composite fracturing fluid, are broken under the conditions of 90 DEG C
Glue processing 8h after, breaking glue solution is centrifuged, dry weigh after residue obtained amount be respectively 50mg/L, 56mg/L, 60mg/L, thus may be used
See that residue is seldom, is not easily blocked and splits after the polyacrylamide nano composite fracturing liquid rubber-breaking being prepared using the present invention
Seam.
According to oil and gas industry standard SY/T5107-2005《Aqueous fracturing fluid method of evaluating performance》Evaluate high-temperature high-pressure
Fluidity energy is split, is 170s in shear rate-1With under continuous shear stress, detection fracturing fluid apparent viscosity is considered as in more than 50mPas
Meet fracturing engineering requirement.Polyacrylamide nano composite pressure visible according to the data of table 2, being prepared using the present invention
Splitting liquid has the characteristic that apparent viscosity is high, anti-shearing, flow conductivity gas channel is imitated to structure complex hydrocarbon floor height, raising oil gas is opened
Adopt and had significant practical applications with yield-increasing efficiency tool, be applicable to industrial production.
Table 2
Note：θ in table600、θ300、θ200、θ100、θ6、θ3Respectively six fast viscosimeters 600 turns, 300 turns, 200 turns, 100
Turn, 6 turns, the reading under 3 turns, AV is apparent viscosity, and PV is plastic viscosity, wherein AV=0.5 × θ600, PV=θ600-θ300。
Claims (9)
1. a kind of preparation method of polyacrylamide nano composite, comprises the following steps：
By acrylamide monomer and pure water by weight 1:The ratio mixing of (2.5-3.5), based on the acrylamide monomer
Quality adds 0.3-0.6% cosolvent, 0.2-0.3% complexing agent and 0.2-0.3% auxiliary agent, the 30-35Hz stirrings of control frequency
More than 20min, turn into acrylamide reaction system；
Aforesaid propylene acid amides pH value of reaction system 9-10 is adjusted, the quality based on the acrylamide monomer adds 0.5-1.5%
Nano inorganic phase, stir as reactant mixed system；
Above-mentioned reactant mixed system is transferred to polymeric kettle, under oxygen-free environment, the quality based on the acrylamide monomer
Add 0.8-1.0% oxidant and 0.8-1.0% reducing agent, initiated polymerization generation polymeric reaction product, course of reaction
In reach 80-90 DEG C when the temperature of reaction system, temperature of reaction system no longer raises, and insulation maintains 3-5h, produces required poly-
Close reaction product；
Above-mentioned polymeric reaction product is through being granulated, the dry as polyacrylamide nano composite；
Wherein, the preparation process of the nano inorganic phase includes：
Phyllosilicate and water are pressed into mass parts 1:(10-20) is mixed in a kettle, is maintained stirring 20-30min, is formed swelling
System；
Based on the quality of layered silicate, above-mentioned swelling body is tied up at 70-80 DEG C to the intercalator for adding 1-10%, 30-
Stirring reaction 10-12h under 35Hz, afterwards the quality addition 1-2% based on layered silicate non-ionic surfactant
Agent, continue to react 4-6h, obtain intercalation system；
Based on the volume of above-mentioned intercalation system, the 20-30% hydrotalcite slurry containing magnalium is added, is reacted in 60-65 DEG C
3-5h, obtain the nano inorganic phase；
The aggregation of described nano inorganic phase, there is the redisperse characteristic in other matrixes;
The hydrotalcite slurry containing magnalium is to use water-soluble magnesium salt and aluminium salt and 2- acrylamide-2-methylpro panesulfonic acids
Mixture obtained in the basic conditions through co-precipitation；
The acrylamide monomer is crystal type monomer；
In the intercalation system, intercalating layered silicates piece interlamellar spacing is 2-4nm, and the aggregation of the nano inorganic phase
Average grain diameter be 0.9-1.5 microns.
2. the preparation method of polyacrylamide nano composite according to claim 1, wherein, layered silicate
For montmorillonite, hydrotalcite, kaolin, attapulgite, sepiolite, wollastonite, chlorite, stratiform silica or theirs is mixed
Zoarium system.
3. the preparation method of polyacrylamide nano composite according to claim 1, wherein, the cosolvent is urine
Element or polyethylene glycol, the complexing agent are disodium ethylene diamine tetraacetate or tetrasodium ethylenediamine tetraacetate, and the auxiliary agent is ammoniacal liquor, chlorine
Change sodium or ammonium chloride.
4. the preparation method of polyacrylamide nano composite according to claim 1, wherein, the oxidant was
Ammonium sulfate, potassium peroxydisulfate, azodiisobutyronitrile or hydrogen peroxide, the reducing agent are sodium sulfite, sodium hydrogensulfite, chlorination
Ferrous or oxalic acid.
5. the preparation method of polyacrylamide nano composite according to claim 1, wherein, for forming described insert
The intercalator of layer reaction system, selected from cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride or monoethanolamine,
The nonionic surface active agent is selected from Span series, Tween series or OP series of surfactants.
6. the preparation method of polyacrylamide nano composite according to claim 1, wherein, the water containing magnalium
In the preparation of talcum slurries, the mol ratio 2 of the water-soluble magnesium salt and aluminium salt:1,2- acrylamide-2-methylpro panesulfonic acid with
The mol ratio 1 of alkaline reagent:1.
7. a kind of polyacrylamide nano composite, it is prepared according to any one of claim 1-6 methods described.
8. the polyacrylamide nano composite described in claim 7 is applied to prepare sewage disposal, papermaking, petroleum drilling and mining neck
The inorganic agent in domain.
9. application according to claim 8, wherein, the polyacrylamide nano composite is used for oil-gas mining pressure break
The preparation of liquid.
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| WO2017220391A1 (en) * | 2016-06-23 | 2017-12-28 | Basf Se | Process of fracturing subterranean formations |
| CN106590599B (en) * | 2016-11-18 | 2019-07-23 | 中国石油大学(北京) | A kind of nano combined nucleocapsid particles oil displacement agent and its preparation method and application |
| CN106669592B (en) * | 2016-12-07 | 2019-10-11 | 常州大学 | The preparation method of iron nickel load nanometer calper calcium peroxide for micro-polluted water treatment |
| CN106977651B (en) * | 2017-03-17 | 2019-10-25 | 中国海洋石油集团有限公司 | Polymer/compound fluid loss agent of intercalation montmorillonite and its preparation method and application |
| CN107513128B (en) * | 2017-07-28 | 2020-04-28 | 河南工业大学 | Polyacrylamide/aluminum tripolyphosphate nanocomposite and preparation method thereof |
| CN107418552A (en) * | 2017-08-14 | 2017-12-01 | 中国石油天然气股份有限公司 | A kind of water-swellable nano material and the water-control oil-increasing fracturing process based on this |
| CN110684152B (en) * | 2018-07-05 | 2021-01-05 | 中国石油大学(北京) | Nano composite plugging agent and preparation method and application thereof |
| CN111073198B (en) * | 2019-12-26 | 2021-04-16 | 中国石油大学(北京) | Copolymerization nanocomposite and preparation method and application thereof |
| CN112538127A (en) * | 2020-11-05 | 2021-03-23 | 宁波锋成先进能源材料研究院有限公司 | Polyacrylamide nano composite material and preparation method and application thereof |
| CN115637143A (en) * | 2021-07-20 | 2023-01-24 | 中国石油天然气集团有限公司 | Multifunctional emulsion slick water concentration system and preparation method thereof |
| CN115196733B (en) * | 2022-07-20 | 2023-10-31 | 克拉玛依新科澳石油天然气技术股份有限公司 | Oilfield sewage treatment medicament and preparation method thereof |
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