CN104672374A - Controllable dispersion method of nano-micron structural intermediate micro-particles and composite material prepared by nano-micron structural intermediate micro-particles - Google Patents
Controllable dispersion method of nano-micron structural intermediate micro-particles and composite material prepared by nano-micron structural intermediate micro-particles Download PDFInfo
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Abstract
The invention disclosed a controllable dispersion method of nano-micron structural intermediate micro-particles; with adopting of a layered structure material and through purification extraction, intercalation reaction and separation processes, the nano-micron structural intermediate having the particle size of 1-50 [mu]m, having crystal layer-to-layer hollows, having the controllable interlamellar spacing of 1-4 nm, having controllable dispersion in water, alcohol and common solvents and having long-term preservation characteristics in a usual environment is obtained. Relative to the monomer, 0.5-10.0 parts by mass of the nano-micron intermediate, 10.0-30.0 parts by mass of a polymer monomer, 0.01-1.0 part by mass of an oxidant, 0.01-1.0 part by mass of a reducing agent, and 3.0-15.0 parts by mass of an auxiliary agent are adopted for forming a suspension, the suspension is mixed together with a sodium hydroxide solution having the pH value adjusted to 7.5-11.5, a polymerization reaction is induced to generate a polymer nano composite material having a 30-70 nm dispersed phase and having the advantages of uniform dispersion, high-temperature resistance and easy dissolving, then the polymer nano composite material is made into a nano composite working fluid used for protection of oil-gas bed pore passage permeability, seepage and diversion and oil-gas substantial increase, and economic and social significance of nanotechnology energy innovation application is generated.
Description
Field belonging to the present invention
The technology of the present invention belongs to field of compound material, relate to a kind of high molecule nano composite material, in particular to a kind of inorganic controlled dispersing method of a micrometer structure intermediate and the high molecule nano composite material prepared thus and nano combined working fluid product received, be applied to hydrocarbon zone exploitation engineering, improve the flow conductivity and production efficiency of hydrocarbon zone.
The background of prior art
The nano effect that nano material and nano composite material and widespread use thereof produce, in the pole broad range of applications of military project, building, electronics, geology, resource and sun power and new forms of energy, the important criterion of sci-tech competitive power and sustainable economic development between country and crucial mainstay are become.
Utilize various nano composite material to produce efficiently useful nano effect, must adopt the effective dispersion technology making nano unit be scattered in other external phase medium evenly, in order, this is the key obtaining high performance composite.The nano-powder particle of prior art, itself, containing a lot of fracture, unsatisfied chemical bond and surface charge, has high surfactivity, and this is also that nano-powder particle easily produces the basic reason of reuniting and reducing performance in other medium.In fact, the uniform, controllable dispersion technology of nano unit, nano material, similarity is had with the dispersion technology of existing micro-powder, but greatest differences is had, main manifestations is nano unit, nano material at few addition and under affecting about external phase medium any quality event hardly, increase substantially composite system performance.
Existing high-activity nano powder granule is scattered in solvent, solution and melt, produces surface adsorption, electric charge and electrically changes and reduce activity, causes system flocculation, coagulation or reunion and performance significantly to reduce.These problems long-term ubiquity in existing all nano materials and matrix material preparation process of nano-particle material, significantly reduce nano effect and seriously hinder its widespread use, it is very urgent for creating efficiently controlled nano-dispersed technology thus.
The nano-powder particle of prior art development and coacervate thereof, even if be placed in dry air or encloses container, also should not preserve for a long time, this is because oxygen, nitrogen oxide, carbon dioxide and detrimental impurity in the inevitable absorbed air of high-activity nano powder or Toxic, not only make nano powder surface inactivation, also produce toxic.
When prior art utilizes nano particle to manufacture high molecule nano composite material, adopt the leading treatment process of nano powder surface, at nano powder surface grafting, covering function molecular radical, utilize this functional group and consistency and the strong interaction for the treatment of dispersed polymer, make nanoparticulate dispersed in macromolecule matrix.The degree of this nanoparticulate dispersed adopts dispersion parameter to characterize, and dispersity represents with the inverse of the mean diameter of dispersion particle or length (see Ke Yangchuan, application of polymer-inorganic nanocomposite, Beijing: chemical industry press, 2003):
D＝1/a (1)
In formula, D is particle dispersion, and a is mean diameter or the length of particle, is generally the statistical average value of size measured by particle, is namely a statistical parameter.
According to the statistical calculation method of formula (1), when adopting conventional particle surface treatment technology that nano particle accumulation body is scattered in macromolecule matrix, the multiple distribution patterns structure that nano particle progressively forms nanoparticle independence through dispersion process or is coupled to each other.The nano-particles size of this pattern compares with original nanometer accumulation body, will become large or diminish, the change of nano-dispersed form that Here it is, and this dispersing morphology characterizes with following statistical method:
D
r＝1/a
r(2)
In formula, D
radd up Particle Phase to dispersity, a
rthe Average equivalent diameter of particle or the ratio of length and its original size, i.e. a
r=a/a
0(a is mean diameter or the length of particle, is generally the statistical average value of size measured by particle, is namely a statistical parameter a
0be the original size of particle, be the size before dispersion).
According to the dispersity that formula (2) statistical parameter characterizes, by the form of reflection nanoparticulate dispersed, especially nano particle is through disperseing the multiple distribution patterns form progressively forming nanoparticle independence or be coupled to each other.During according to formula (2) statistical computation dispersion parameter, D
r> 1, shows the true dispersion process of nanometer occurs; D
r< 1, show nanometer standard or false dispersion process occur, nanoclusters collecting process will occur in other words, and this need measure nano-dispersed form by prior art, concrete analysis dispersion or reunion degree D
r=1, show ideal dispersion process occurs.
All nano-dispersed degree can be characterized according to the statistical method according to formula (1) or formula (2).According to formula (2) statistical method, when nano-dispersed is D
rduring>=1 situation, the dispersing morphology of regulation and control nanoparticle or nano unit, as connected node, stacked system or array pattern, the novel material system of formulating remarkable nano effect can be designed, if the dispersing morphology of regulation and control in high molecule nano composite material, can produce the high performance polymer nano composite material of remarkable nano effect.High (nearly 2.7 hundred million tons of the world's macromolecular material annual production of macromolecular material output, nearly 100,000,000 tons of China's macromolecular material ultimate production of 2011), it has very strong processibility, functional and widespread use, macromolecular material over-all properties is improved, for solving a complex hydrocarbon resource exploitation difficult problem with nano-dispersed.
Usually, inorganic nano disperses and assembling in macromolecular material melt, solvent, can obtain nano composite material, but nanophase high surface and easy agglomeration causes high molecule nano composite material unstable properties.Prior art adopts phyllosilicate nano to prepare polyester, nylon and polyolefine high molecule nano composite material mutually, all produces 1 ~ 3% coacervate, directly affects the macromolecular material transparency and surface-functional.
The typical lamellar silicate that prior art adopts has periodically lamella crystal structure, flag layer crystal body structure if you would be taken off and comprise 2 layers of coated 1 layer of alumina octahedral structure of silicon-oxy tetrahedron, the sheet interlayer spacing of this lamella crystal molecular structure and lamellar spacing are all about 1nm, and the space of sheet interlayer exists positively charged ion and aquation rete thereof.This layered silicate such as montmorillonite is raw material, produces permutoid reaction, and expands sheet interlayer spacing, make monomer enter the sheet sheaf space of expansion with organic cation and its interlayer cation, and the intercalation configuration forming intercalation synthesis body is shown in accompanying drawing 1.
But, insert layered silicate as the intercalation synthesis body formed between montmorillonite layer with intercalator molecule, when disperseing in macromolecular material, still produce uneven, the coacervate of dispersion and disperse uppity problem.
Existing hydrocarbon resources is mainly positioned at the complicated reservoirs of deep layer, ultra-deep layer, the feature of complex oil and gas reservoir is crack, hole duct with coexist or common ecological complex way exist, the exploitation of complex hydrocarbon layer be normal to produce perviousness and flow conductivity decline and output and seriously to successively decrease problem, and this comes from the reservoir borehole well instability of oil-gas mining engineering, the blocking of fluid duct and damages.The crack of existing complex hydrocarbon layer and hole duct are normal distribution and the orientation complexity features of hundreds of nanometer ~ tens micron-scale, and this duct produces strong stress sensitivity under work fluid column immense pressure (30 ~ 300MPa).For the feature of complicated reservoirs, nanometer and the multiple dimensioned material system of micron are used for the drilling completion engineering of oil and gas reservoir by prior art, by analyzing rock core duct characteristic, set up hydrocarbon zone crack and hole pore distribution function model, as shown in formula (3).
In formula, μ is crack, aperture position parameter, and σ is scale parameter.
The crack of this Normal Distribution or the frequency distribution of hole variable parameter are determined completely by μ, σ.Based on rock core crack, derivation flaw size h ' model is.
In formula, σ
efor putting on the effective stress in duct, crack, ε is fracture faces mark dimension, and a, b are rock core constant.
Prior art, based on complex oil and gas reservoir duct theoretical basis, utilizes complicated reservoirs crack and hole duct stress sensitivity and permeates seepage flow sexual intercourse, sets up the multiple dimensioned matrix material of nano-micrometer and reservoir pore action model is:
(1) statistics size r and nano-micrometer scantling R in duct keeps certain matching relationship
R＝r/3～r/4 (5)
(2) nano-micrometer material has controlled visco-elasticity, and regulation and control duct, stratum is wetting to be regulated and controled macromolecular material visco-elasticity with flow conductivity nano-micrometer material and disperses in rock duct to assemble effect with migration.
(3) nano-micrometer material produces absorption exchangeability, and the regulation and control shutoff of duct, stratum and perviousness nano-micrometer material produce in duct, stratum and adsorb, exchange and seal-off effect, regulate and control duct perviousness.
Therefore, nano-micrometer material produces nano combined drilling fluid, well finishing liquid, can effectively control oil/gas drilling Completion Operations; Nano-composite gel viscoelastic body, super-hydrophobic, the super oleophobic surface effect in controllable hydrocarbon zone duct, improves decreasing water cut and increasing oil efficiency; Nanophase stabilized emulsion system, can suppress formation rock clay dispersibility; Nano combined controlled degradation system, produces stifled and self-degradation temporarily, improves oil gas flow conductivity in oil gas duct.
Prior art sets up core permeability, activity and kapillary invasion depth characterizing method.Characterize heterogeneous suspensoid changes duct rate of permeation process in duct, stratum generation perviousness, see formula (6).
In formula, σ
ebe effective stress, K is core permeability, and a, b are rock core constants.
With heterogeneous composite material regulation and control formation rock activity and stratum clay aquation, characterize it forms " detention layer " resisting fluid scouring stability at the nearly borehole wall, see formula (7).
τ
aquation=k Tln (a
water/ a
rock) (7)
In formula, T is absolute temperature, a
waterdrilling liquid water activity, a
rockbe rock, the borehole wall or clay activity, k is constant.
Characterize heterogeneous composite material regulation and control fluid in the kapillary invasion depth of formation rock, see formula (8).
h＝Kσcosθ/R (8)
In formula, σ is surface tension, and θ is wetting angle, and R is capillary radius; θ >=90, h≤0.
Available hydrocarbon resource production technique mainly adopts the auxiliary agents such as macromolecule tackifer, nano-calcium carbonate and initial state layered silicate.Macromolecular material produces thickening, visco-elasticity and shear resistant; inorganic nano produces infiltration, shutoff effect mutually; inorganic nano better disperses at polymer or solvent medium; form nano-micrometer composite suspension liquid, emulsion, gel and membrane-forming agent utilisation technology, achieve tangible results in reservoir protection, stabilizing borehole technique and function controllability.But the exploitation of existing complex oil and gas reservoir is in deep regional and high temperature, the extreme complex environment of ultra-high voltage, hole-size elongation, borehole well instability or cave in and gas channel cutout problem ubiquity.Macromolecule tackifer described in employing, nano-calcium carbonate and high molecule nano composite material, address these problems poor effect, is difficult to solve nano-micrometer hole and duct, crack seepage flow and a rate of permeation frequent variations difficult problem.
The macromolecular material of prior art, nano material and matrix material thereof are used for the exploitation of complex hydrocarbon layer.But, high molecule nano composite material is in synthesis or application process, easy generation nano-dispersed instability and nanometer agglomeration, make this kind of material in reservoir shutoff and select in flow conductivity application, moistened surface and heatproof poor stability, high pressure volatility and degradation property problem often occur, and can accelerate Oil/gas Well production rate decline in the application.
Inorganic non-metallic ore resources involved by current material technology particularly layered silicate mineral reserve is very abundant, only China's laminar silicic acid salt mine just reaches over one hundred kind (wherein, only montmorillonite can developed ore reserve super hundreds billion of ton far away, prospective reserves exceedance trillion tons).The layer silicate of prior art, the inorganic nano material precursor needed for obtaining through process for separating and purifying, optimizes its sheet interlayer and attracts with repulsive force fluctuation characteristic and be coupled with hydrogen bond action, its interlamellar spacing of controllable (d
001) and dispersed.Layer silicate interlamellar spacing regulation process model such as accompanying drawing 2 is illustrated, in interlamellar spacing regulation process, interlamellar spacing changes the inductive phase from laminated silicate interlayer effect, successively through state I (d
001>=2nm be intercalated molecule insert state), state I I (d
001>=4nm is the state that monomer or activator enter between enlargement layer) and state I II (d
001>=6nm is the stripping state completely of full plies).
Design optimization nano-micrometer intermediate layer spacing is between state I and II, and controllable lamella dispersion state and degree of scatter, form the multiple dimensioned ergasia of nano-micrometer of nanometer and micron disperse phase and self-assembly.Thus, by high polymer molten and solvent dispersion, set up nano composite material and nano combined working fluid and oil-gas mining engineer applied technology thereof.
For the problem of prior art, need especially to carry out inorganic materials structure design, the multi-functional controlled morphologies of initiative nano-dispersed and micron packaging assembly, make that nano unit, nanophase are controlled is scattered in Conventional solvents, macromolecule matrix or hydrocarbon zone duct equably, form multi-functional, feature of environmental protection nano composite material and nano combined working fluid system.This technological invention is imitated flow conductivity gas channel to structure complex hydrocarbon floor height, is improved oil-gas mining and yield-increasing efficiency, has ubiquity meaning.
Object of the present invention
The invention provides that preparation is a kind of collects the nano-micrometer scaffold intermediate microparticle material and controlled dispersion technology thereof that metrical scale and micron scale structures be integrated, it is characterized in that by processing or high molecular polymerization condition, make nano-micrometer scaffold intermediate particulate produce even, controlled dispersion at Conventional solvents, solution and melt, form nano composite material.
The nano-micrometer material shape of nano-micrometer scaffold intermediate particulate material morphologies provided by the invention and prior art, has essential difference, as shown in Figure 3.Existing micron particle material technology, obtains the nano-micrometre mixed system of part nanodispersed phase, i.e. nano-micrometer material system, dispersity D by multiple dispersing technology
r> 1.
Nano-micrometer scaffold intermediate microparticle material provided by the invention, feature adopts micro-meter scale starting material, the nanostructure of hollow out is produced in microparticles, and integral particle material still keeps micro-meter scale, the nanostructure of this hollow out and micron particle yardstick coexist in one, form nano-micrometer scaffold intermediate structural system.
The nano-micrometer scaffold intermediate microparticle material that the present invention proposes, feature is controlled dispersion or decomposition in medium, produces nano unit disperses and micro-meter scale is assembled nano material or nano composite material.
The starting material of described nano-micrometer scaffold intermediate particulate are natural layer silicate mineral, as montmorillonite, kaolin, attapulgite, sepiolite, wollastonite, chlorite, stratiform silicon-dioxide, their arbitrary symbiosis or mixed systems.
Described layered silicate starting material, feature adopts organic cation to carry out cation-intercalated permutoid reaction at its interlayer, the monomer content of regulation and control interlamellar spacing and interlayer space.
The described nano-micrometer scaffold intermediate particulate containing monomer, feature has copolymerization activity.
Described nano-micrometer scaffold intermediate particulate, is characterized in that being made up of following nanometer and micrometer structure:
Grain diameter 1 ~ 50 μm
Crystalline structure interlamellar spacing 1 ~ 4nm
Particulate whiteness 60.0 ~ 90.0
Described layer silicate raw material, adopts natural layer silicate ore deposit, is prepared from through industrial separation, purifying and extraction process.Cation exchange capacity is greater than the layered silicate raw material of 70mmol/g lower than 500ppm to adopt iron level, is (10 ~ 30): 1, at 80 DEG C of thermostatic water-circulator baths and 400rmin according to raw material and quality ratio
-1continuously stirring 30min forms suspension, after standing 2.5 hours, get the organic intercalation agent being equivalent to this layered silicate raw materials quality part 10.0 ~ 15.0 to be dissolved in suitable quantity of water and to make solution, this solution is added in described laminar silicic acid salt suspensioning liquid, carry out ion exchange reaction and form intercalation suspension in 6 ~ 24 hours under 80 DEG C with nitrogen atmosphere, the upper strata of intercalation suspension is separated, suction filtration and the AgNO that cleans to 0.1mol/L
3fail to detect Cl
-exist.Repeatedly optimize this sepn process and last handling process, the interlamellar spacing detecting products therefrom, at 1.0 ~ 4.0nm, is nano-micrometer scaffold intermediate.Finally, by the nano-micrometer scaffold intermediate sample of separated and collected 80 DEG C of vacuum-dryings 24 hours, through pulverizing, sieving and sorting process makes nano-micrometer intermediate microparticle, this particulate powder detects through Electronic Speculum has 1 ~ 4nm interlamellar spacing structure and 1 ~ 50 μm of micron packaging assembly, deposits and keep high reactivity in usual environment long-term stability;
Described nano-micrometer scaffold intermediate particulate, by relative to high polymer monomer mass parts 0.5 ~ 10.0, by conventional solution, solvent dispersion or polymerization methods, forms nanocomposite system;
Described nano-micrometer scaffold intermediate material, feature is controlled dispersion in solvent dispersion or solution in-situ polymerization technique, forms nano combined suspension and nano composite material.
Described nano-micrometer scaffold intermediate particulate, it is characterized in that forming controlled dispersed multiphase system at the high polymer monomer aqueous solution, Organic Alcohol solution, this heterogeneous system synthesizes high molecule nano composite material through home position polymerization reaction.
It is composed as follows that described polymerization reaction system presses mass fraction:
Described polymerization reaction system adopts monomer solution radical initiation reaction, synthesis high molecule nano composite material process is: the monomer solution of 15.0 ~ 25.0 mass percentage concentration, oxygenant and the reductive agent of 0.01 ~ 0.50 is relative to monomer mass part, suspension is mixed into mass parts 0.5 ~ 10.0 nano-micrometer intermediate, the auxiliary agent of 3.0 ~ 15.0 mass parts is added to this suspension, add appropriate sodium hydroxide solution again, regulate reaction suspension pH value 7.5 ~ 11.5, control this reaction initiation temperature 5 ~ 15 DEG C of low temperature polymerizations after 30 ~ 90 minutes, reaction rises to higher temperature, reaction 1 hour is continued through azo-initiator, gained pyroreaction slurries are proceeded in temperature control adiabatic polymerisation device, letting nitrogen in and deoxidizing 20min, then azo initiator is added every 3min, logical nitrogen is stopped after making polymerization system viscosity reach threshold value, reaction colloid product insulation slaking 2 ~ 3 hours, hydrolysis reactor put into by colloid, add the mixing of appropriate hydrolytic reagent and carry out high-temperature hydrolysis, the molecular weight of prepared colloid product, solids content detects by standard GB12005.2-89 and GB12005.1-89, products distribution is measured by Electronic Speculum, obtaining disperse phase mean sizes is 30nm ~ 70nm,
Described high polymer monomer is acrylamide, vinylformic acid or their the two comonomers mixed any, and the mass percentage concentration of monomer solution is 15.0 ~ 25.0.
Described laminar silicic acid salt mine raw material is montmorillonite, kaolin, attapulgite, sepiolite, wollastonite, chlorite, stratiform silicon-dioxide, their arbitrary symbiosis or mixed systems.
Described layered silicate and water are (10 ~ 30) in mass ratio: 1 anabolic reaction suspension.
Described nano-micrometer scaffold intermediate adopts organic intercalation agent reaction preparation, described organic intercalation agent is, 12 carbon chain aliphatic amine, 16 carbon chain aliphatic amine, 18 carbon chain aliphatic amine, cetyl trimethylammonium bromide (CTAB), Cetyltrimethylammonium bromide, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride (CTAC), they are the two mixture arbitrarily, or they and protonic acid be 1: 1 composition formed in molar ratio, described organic intercalation agent is relative to layered silicate quality part 5.0 ~ 15.0, the intercalator formed and layered silicate reactive suspension anabolic reaction system.
Described nano-micrometer scaffold intermediate particulate, it is the powder particle product obtained through filtration, collection process that is dry and that pulverize from the suspension of laminar silicic acid reactant salt, can be stored in drying, sealing or low temperature environment for a long time, preservation period is greater than 1 year and keeps reactive behavior.
Described nano-micrometer scaffold intermediate particulate, with it relative to monomer mass part 0.5 ~ 10.0, reacts with monomer in situ polymerization, forms controlled surface pattern, wetting and durothermic polyacrylamide nano matrix material.
Described auxiliary agent is urea, disodium ethylene diamine tetraacetate complexing agent, glycerol or their any the two compositions, and auxiliary agent is 3.0 ~ 15.0 relative to monomer mass part;
Described oxygenant is ammonium persulfate, Sodium Persulfate, Diisopropyl azodicarboxylate or hydrogen peroxide, is 0.01 ~ 0.50 relative to monomer mass part; Described reductive agent is S-WAT or iron protochloride, and reductive agent is 0.01 ~ 0.50 relative to monomer mass part, and reductive agent and oxygenant are according to mass parts 1: 1 compound use.
Described nano-micrometer scaffold intermediate particulate, high molecule nano composite material is synthesized: described high molecule nano composite material is as auxiliary agent by free radical reaction method and home position polymerization reaction technique, add drilling fluid, the well finishing liquid base slurry by international API standard preparation by mass parts 0.1 ~ 0.5, make the nano combined Drilling and completion fluids system for complex hydrocarbon layer.
Described nano-micrometer scaffold intermediate particulate, high molecule nano composite material is synthesized by free radical reaction method and home position polymerization reaction technique, described high molecule nano composite material as auxiliary agent, for the preparation of the multi-phase emulsion of the stability of resisting high-concentration salts solution and resistance to more than 70 DEG C hot environments, drilling fluid or completion fluid system.
Described nano-micrometer scaffold intermediate particulate and high polymer monomer home position polymerization reaction synthesize high molecule nano composite material, control nano-dispersed, nucleation, assembling and complex effect, overcome the deficiency of existing nano-dispersed technology.
Described a kind of nano-micrometer scaffold intermediate particulate, for the synthesis of suspension, high molecular nanometer combined drilling liquid or well finishing liquid, for regulating and controlling oil-gas mining engineering seepage channel and flow conductivity.
Described a kind of nano-micrometer scaffold intermediate particulate, for the preparation of high molecular nanometer combined drilling liquid or well finishing liquid, for reservoir protection and the maintenance reservoir permeability of oil-gas mining engineering.
Described nano-micrometer scaffold intermediate particulate, is cross-linked to form 300 ~ 500nm gel product, for the leak stopping of hydrocarbon zone duct and flow conductivity regulation and control by the high molecule nano composite material of its synthesis with conventional industrial cross-linking agent solution.
Described nano-micrometer scaffold intermediate particulate, forms product emulsion by its particulate or by the high molecule nano composite material of its synthesis, can reduce lubricating coefficient, for the lubrication drag reduction of hydrocarbon zone drilling well, Well Completion Engineering of Oil Reservoirs.
Described nano-micrometer scaffold intermediate particulate; by its particulate or and by its synthesis high molecule nano composite material emulsion system; stable emulsion characteristic is produced in multi phase interface dispersion; this product emulsion for suppressing hydrocarbon zone duct to be expanded, reducing rock expansion rate, for suppressing drilling well, the rock expansion of completion and stabilized hydrocarbon layer.
The nano combined suspension of described nano-micrometer scaffold intermediate, nano-composite emulsion or its high molecular nanometer composite cooling liquid, produce with oil and gas reservoir duct and mate coupling, and the infiltration of protection duct is with flow conductivity.
Described nano combined working fluid, by solution nano-dispersed and assembling approach, regulation and control suspensoid emulsification, stable, wetting, film forming and intercept multi-functional, produce the infiltration of protection reservoir, water conservancy diversion and improve oil and gas production effect.
Described nano-micrometer scaffold intermediate particulate, by relative to high polymer monomer mass parts 0.5 ~ 10.0, by melt extruding or injection molding mode, being scattered in organic crystal polymer, obtaining high molecule nano composite material.
Fig. 1 is that intercalator molecule inserts montmorillonite lamella and enlargement layer spacing and the procedure chart that monomer is inserted.
Fig. 2 is laminate structure intermediate layer spacing d
001-interlaminar action power relational model schematic diagram.
Fig. 3 is the nano-micrometer intermediate of this project proposition and the form of nano-micrometer material.
The invention process method
The inorganic intermediate feed of embodiment 1-3 natural layered silicate mineral synthesis nano-micrometer adopts layered silicate as montmorillonite raw ore, detect its whiteness > 60%, smectite content > 70%, cation exchange capacity > 50mmol/g, be defined as raw ore raw material.Through water flotation separation, sedimentation, cation exchange reaction, polishing purification and aftertreatment technology, prepare montmorillonite starting material; Select class gel mineral as attapulgite or sepiolite be raw ore material time, carry out raw material with whiteness and mineral content examination criteria preferred.Choose the solids mixing particle of 100g calcium ions laminar silicic acid salt mine as Ca-montmorillonite and 1 ~ 10g sodium carbonate, by solid: water=1: (10 ~ 30) mass ratio, make layered silicate sodium carbonate suspension, cation exchange reaction is carried out, containing the easy expanded polystyrene veneer layered silicate montmorillonite raw material of sodium ion between productive zone at 70 ~ 85 DEG C.The homogeneity that this reaction process is combined multiple source layer silicate mineral with acidification technique forms, in table 1.
Embodiment 4-7 synthesizes layered silicate slurries that nano-micrometer structure intercalation intermediate formed through sodium and acidification reaction technique and organic ammonium salt reacts, and contains the intercalation intermediate of ammonium ion, react and see formula (9) between productive zone.
MMT-Ca+Na
2CO
3→MMT-Na+(R-NH
4 +)→R-NH
4 +-MMT (9)
According to proton number and amine functional group mol ratio 1: 1, the mixing acid of sour phosphorus and sulfuric acid mass ratio 0.92 and organic amine are reacted and generates quaternary ammonium salt product, as the intercalator of intercalation; Layered silicate and water in mass ratio 1: (10 ~ 30) make aqeous suspension, aqeous suspension and quaternary ammonium salt solution by pure amount than 100: (10 ~ 20) mix, and sodium hydroxide regulates water solution system pH value to be that 7 ~ 9 reaction conditionss carry out cation exchange reaction.The layered silicate slurries of refining intercalation, make its cation exchange capacity (CEC) reach 0.9 ~ 1.0mmol/g, adopt industrial drying process to produce the nano-micrometer scaffold intermediate particulate product that CEC is up to standard, interlamellar spacing is controlled, as table 2.
Embodiment 8-11 synthesizes nano-micrometer structure intercalation intermediate and presses proton number and ammonium functional group mol ratio 1: 1, is acidifying quaternary ammonium salt by protonic acid phosphoric acid and Octadecylamine hybrid reaction; Layered silicate and quality are than 1: (10 ~ 30) make aqeous suspension, aqeous suspension and acidifying quaternary ammonium salt solution by pure amount than 100: (10 ~ 20) mix, sodium hydrate regulator solution pH value be 7 ~ 9 and temperature of reaction 70 ~ 85 DEG C of conditions carry out cation exchange reaction 6 hours, preferred intercalation reaction product, layered silicate cation exchange capacity is made to reach 0.9 ~ 1.0mmol/g, obtain the nano-micrometer scaffold intermediate of embodiment 8, in table 3.Equally, with cetyl trimethylammonium bromide (CTAB) intercalator and phosphoric acid 1: 1 hybrid reaction in molar ratio, 6 hours are reacted again with intercalating layered silicates, the system temperature of reaction of making progressively is increased to 70 ~ 85 DEG C, regulation and control laminated silicate interlayer distance, through centrifugal or press spray dry production stratiform silicate powder particulate product, in this technique, adopt A1
2o
3(Mg, Na, Ca)
n.xSiO
2.yH
2the layered silicate of O (n=0 ~ 2) composition, obtains the nano-micrometer scaffold intermediate of embodiment 9 and 10 respectively, adopts SiO
2.Ti2O
3.nH
2the layered silicate of O composition obtains the nano-micrometer scaffold intermediate of embodiment 11, in table 3.
Embodiment 12 is synthesized nano-micrometer scaffold intermediate and is adopted montmorillonite (MMT) and magnesium oxide/alumina composite salt to make compound MMT nano-micrometer intermediate by 1: 1 mass ratio, with MMT (CEC=1.0mmol/g), palmityl trimethyl ammonium chloride and thanomin are by 1: 2 mass ratio composition compound swelling agent, this compound swelling agent and compound MMT nano-micrometer intermediate, intercalation is carried out in the liquid phase that 2-acrylamide-2-methylpro panesulfonic acid (AMPS) and acrylamide form, reaction conditions is with embodiment 8-11, be obtained by reacting the compound nano-micrometer intermediate that organises.Calculate the compound nano-micrometer structure montmorillonite intermediate layer spacing that organises and expand 1.42nm to from the 1.18nm of raw material.This compound MMT nano-micrometer intermediate is " comonomer " and acrylamide monomer, through emulsion free-radical mechanism and load with ammonium persulfate initiator initiated polymerization, 5 ~ 70 DEG C of temperature polymerizations reactions 1 ~ 5 hour, synthesis polyacrylamide nano matrix material, obtains polyacrylamide nano matrix material through aftertreatment.
Embodiment 13 ~ 20 is synthesized polyacrylamide nano-micrometer matrix material and is adopted free-atom aqueous solution Reactive Synthesis polyacrylamide nano matrix material.The monomer of 25.0% mass concentration, nano-micrometer scaffold intermediate relative to the ammonium persulfate oxygenant of monomer mass part 0.10 and S-WAT reductive agent, mass parts 0.5 ~ 4.0, composition mixing suspension.3.0 ~ 15.0 mass parts solubility promoter urea and complexing agent disodium ethylene diamine tetraacetate is added to this suspension, and a small amount of sodium hydroxide solution stirs, regulate suspension pH value about 10.5, control reaction initiation temperature 5 ~ 15 DEG C and low temperature polymerization 30 ~ 90 minutes, then reaction heat up continue under high temperature azo-initiator reaction 1 hour pyroreaction slurries, proceed to letting nitrogen in and deoxidizing 20min in temperature control adiabatic polymerisation device, then add every 3min and load with Diisopropyl azodicarboxylate initiator, polymerization system viscosity stops logical nitrogen after reaching threshold value, after terminating to reaction, colloid insulation slaking 2 ~ 3 hours.Take out colloid and put into hydrolysis reactor, add appropriate hydrolytic reagent and mix temperature adjustment hydrolysis reaction.Gained colloid product relative molecular mass, solid content etc., reference standard GB12005.2-89 polyacrylamide determination of solid content method; System viscosity is measured, intrinsic viscosity calculation formula: [η]=[2 (η with reference to GB12005.1-89
r-1-ln η
r)]
1/2/ ms and relative molecular mass M=1.563 × [η]
1.515× 10
5(wherein, s is solid content, and m is sample quality.Relative viscosity η=t/t
0), with Ubbelohde viscometer one point method working sample intrinsic viscosity, correct inorganic phase content; With reference to GB12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method working sample degree of hydrolysis, calculation formula:
In formula: HD is degree of hydrolysis, %; C is hydrochloric acid standard solution concentration, mol/L; V is the milliliter number that sample solution consumes hydrochloric acid standard solution, mL; M is sample mass, g; S is sample solid content, %; 23 is differences of sodium acrylate and acrylamide chain link quality; 71 is acrylamide chain link quality suitable with 1.00mL hydrochloric acid standard solution [c (HCl)=1.000mol/L].(10) measure and calculation embodiment 12 ~ 20 sample degree of hydrolysis is 10 ~ 30% with the formula, and reaction parameter and product property are in table 4.
Embodiment 21 ~ 25 is synthesized polymer nano-micrometer scaffold intermediate matrix material and is adopted free-atom aqueous solution initiation reaction technique, oxygenant and reductant concentration relative to monomer mass part be 0.10, the nano-micrometer scaffold intermediate mass parts of embodiment 12 is the polymerizing condition of 0.5 ~ 2.5 (relative to monomer) and similar embodiment 12, synthesis polyacrylamide nano matrix material, control the release of azo initiator massfraction and substep feed postition and reaction heat, obtain the polyacrylamide nano composite products of different viscosity, in table 5.
Embodiment 26-30 synthesizes nano-micrometer plural gel and strength characteristics and utilizes low-concentration polyacrylamide nano composite material and cross-linking agent solution and intermolecular with weak cross linked gel characteristic in molecule, employing molecular weight 8.51 × 10
6, degree of hydrolysis 30.8% and solid content 90.5% polyacrylamide nano composite powder, add 2000mL sodium chloride brine and be stirred to and dissolve completely, be made into 8000mg/L polymer mother liquor, room temperature places 24h.Get polymer mother liquor and pour another sesame seed cake into, add the commercial organic chrome cross linker solution of SC-1 type, stablizer thiocarbamide, be made into desired concn cross-linking system with sodium chloride brine dilution.Finally, adopt 0.5mol/L sodium hydroxide solution regulation system pH value 8.0 ~ 9.0, obtain even Weak Gels solution, load sealed glass tube, be placed in 80 DEG C of thermostat containers, analyze when gel-strength is substantially unchanged and determine Weak Gels intensity.Equally, the solution of polyacrylamide nano matrix material concentration 3000mg/L, crosslinker concentration 900mg/L, NaCl concentration 5000mg/L and stablizer thiourea concentration 200mg/L, regulate pH=7 ~ 8.5, preparation 300 ~ 500nm disperse phase Weak Gels, 30 ~ 100 DEG C of gel-strengths are raised to F and G from C and G.
Polyacrylamide high molecular nanometer plural gel, for high temperature and high salt oil deposit deep temporary blocking and shutoff.By shutoff particle size-rock pore size matching relationship, with polyacrylamide nano-micrometer composite particles for plugging agent, form visco-elasticity, distortion and the multiple dimensioned suspension of wettability, to inject under rock duct, the shutoff of detect aperture road junction and work fluid column immense pressure particles deform with to duct deep migration, detect salinity to affect plastic situation, temporary shielding blocking composition and Sealing Conditions is determined, in table 6 according to reservoir core plugging test.
Embodiment 31-32 nano-micrometer matrix material suppresses hydrocarbon zone mud shale dispersiveness synthesis polyacrylamide nano matrix material auxiliary agent, and molecular weight is 8.51 × 10
6, degree of hydrolysis 30.8%, solid content 90.5%, is made into 1.0% concentration of aqueous solution, and according to existing solution inhibition testing regulation, detect 2 hours and 16 hours turgiditys in rock core fragment solution, Calculation Estimation system inhibition, in table 7.
Comparative example 3 repression of swelling is by prior art (Ke Y C, Wu T B, Wang Y. Preparation of core-shell structured particles and their nucleation in PET:I.Preparation of monodisperse SiO
2/ PS core-shell composite particles.Petroleum Science, 2005,2 (1): 70-75) synthesis of nano SiO
2, prepare 0.6% inhibition working fluid, then according to existing solution inhibition testing regulation, detect it to the inhibition of rock core fragment 2 hours and 16 hours, in table 7.
It is reagent that comparative example 4 repression of swelling removes ionized water, invades bubble rock core fragment, detect the rate of expansion of 2 hours and 16 hours, in table 7 according to existing inhibition testing regulation in water.
Embodiment 32-34 synthesizes nano-micrometer composite emulsifying liquid and adopts industrial Sp-80 emulsifying agent and calcium stearate to form emulsifier composition in proportion, and said composition and hydrotalcite nano-micrometer scaffold intermediate make nano-composite emulsion.Synthesize 4.0% calcium-base bentonite aqeous suspension magma, add 4.0% nano-composite emulsion successively, 6.0% white oil and emulsifier composition 163 thereof or anionic and OP-10 emulsifier composition, mechanically mixing even embodiment 32 product; Synthesize 4.0% calcium-base bentonite aqeous suspension magma, add 4.0% nano-composite emulsion successively, 3.0% polymeric alcohol lubricant, machinery
Mix to obtain embodiment 33 product; Synthesize 4.0% calcium-base bentonite aqeous suspension magma, add 4.0% nano-composite emulsion successively, 6.0% white oil and emulsifier composition 163 thereof or anionic and OP-10 emulsifier composition and 3.0% polymeric alcohol lubricant, mechanically mixing is even obtains embodiment 34 product, oilness is compared in detection, in table 8.
Comparative example 5 ~ 7 oilness drilling fluid synthesizes 4.0% calcium-base bentonite aqeous suspension magma, adds 0.2% caustic soda, 0.3% polyacrylamide, 2.0% high-temperature resisting and salt-resisting anti-collapse dehydration agent (KFT), 0.15% xanthan gum (XC), 1.5% low Poison sulfonated gilsonite borehole wall stabilizer (ZX-8), 22.0% weighting agent BaSO successively
4, 6.0% white oil and emulsifier composition 163 thereof or anionic and OP-10 emulsifier composition, and 3.0% polymeric alcohol lubricant, composition well site drilling fluid system.The drilling fluid that 3% emulsified olefin makes comparative example 5 is added in the drilling fluid of well site; Add 3.0% emulsified olefin and 3.0% polymeric alcohol lubricant at well site drilling fluid, make the drilling fluid of comparative example 6; Add 3.0% emulsified olefin and 3.0% polymeric alcohol lubricant at well site drilling fluid, the drilling fluid of composition comparative example 7, in table 8.
The shutoff of embodiment 35 ~ 39 polyacrylamide nano-micrometer matrix material gelatin membrane protection reservoir characteristics synthesis technique and embodiment 13-25 similar.Optimize molecular weight >=8,000,000/mol polyacrylamide nano-micrometer matrix material hydrolysis temperature, time and crosslinking reaction condition, regulation and control degree of hydrolysis 15 ~ 30%, 0.1 ~ 0.5wt.% nano composite material and 4.0% bentonite suspension base is adopted to starch compound, prepare nano combined drilling fluid, well finishing liquid, measure this nano combined working fluid at hydrocarbon zone rock core deposition film forming and isolation plugging effect, evaluate its suspension, filtrate reducing and maintenance reservoir permeability.Test nano-micrometer combined drilling liquid and well finishing liquid, the permeability resume figure level that the reservoir pore of creeping at straight well, horizontal well and orientation well is protected, in table 9.
Comparative example 8-11 evaluates the damage of drilling fluid and completion fluid oil reservoir indoor evaluation method of reservoir protection Property comparison example 8 conventionally standard SY/T5306-2003; Comparative example 9 is I & M company intelligence starch degradation enzyme systems; Comparative example 10 is Shengli Oil Field polyacrylamide compound of calcium carbonate systems; Comparative example 11 is Shengli Oil Field PAC calcium carbonate compound systems.
Embodiment 40 receives-and microfacies intermediate deposits character and deposits in air by the nano-micrometer intermediate powder particulate of preparation; take out after the shelf-time is greater than 1 year and be scattered in xylene solution and melt polyethylene terephthalate polymer (limiting viscosity 0.65 ~ 0.70) material matrix; adopt existing laser light scattering techniques and Electron Microscopy to detect this two kinds of dispersity respectively, evaluate the particulate activated characteristic of nano-micrometer intermediate powder.
Comparative example 12-13 nano material deposits character conventionally (Ke Yangchuan, Pieter Stroeve, Polymer layered silicate and silica nanocomposites, Elsevier, Armsterdam, 2005,5) synthesize grain diameter 30 ~ 50nm silicon-dioxide, 30 ~ 50nm titanium dioxide, measure them respectively at oil phase dimethylbenzene suspension and the dispersion stabilization at polyester fondant, evaluate and deposit activity.
Table 1
Annotation: adopt common commercial whiteness instrument to measure powder whiteness, following table all adopts this whiteness instrument to measure whiteness.
Table 2
Annotation: phosphoric acid or sulfuric acid and organic amine mass ratio n (HA)/n (OA)=0.92 join intercalant solution; X-ray measuring diffraction peak, the various interlamellar spacing d of Bragg Equation for Calculating
001: 2dsin θ=n λ.
Table 3
Table 4
Annotation: inorganic mesophase spherule content is and accounts for monomer mass mark; Intermediate is compound nano-micrometer montmorillonite intermediate slurries respectively, and their 1: 1 mixing nano-micrometer intermediates.
Table 5
Annotation, reaction conditions: monomer mass mark 25wt%, oxygenant, reduction dosage are 0.08wt% relative to monomer, and azo initiator consumption is 0.05wt%, polymerization initiating temperature 15 DEG C, pH value 10.5; Wen Feng, refers to polymerization reaction heat peak-peak.
Table 6
Annotation: gel-strength progressively increases from C, F, G, H.
Table 7
Annotation: base slurry is 6% In Xiazijie Region, xinjiang wilkinite water suspension: quantitatively characterizing material system inhibition, adopts swell increment and rate of expansion parameter.Swell increment=(expansion height after sample immersion-originally height); Rate of expansion=(swell increment/originally height).
Table 8
Annotation: adopt the fast viscometer determining rheological parameter of NDZ six; Extreme boundary lubrication instrument is adopted to measure lubricating coefficient
Table 9
Annotation: JHMD High Temperature High Pressure the dynamic damage evaluates instrument experiment condition: pollute time 125min, pressure reduction 3.5MPa, rate of permeation test confined pressure 3.0MPa, pollutes confined pressure 6.0MPa; Core perm-plug method: 14.2 ~ 204.2 × 10
-3μm
2; Survey the permeability to oil difference Δ K that core pollutes front and back.
Table 10
Claims (15)
1. a dispersing method for nano-micrometer scaffold intermediate particulate, is characterized in that adopting layer silicate raw material, and synthesis has nanocrystalline structure and the microparticles structured material of following composition:
Grain diameter 1 ~ 50 μm
Crystalline structure interlamellar spacing 1 ~ 4nm
Particle whiteness 60.0 ~ 90.0
Described layer silicate raw material, adopts natural layer silicate ore deposit, is prepared from through industrial separation, purifying and extraction process.Cation exchange capacity is greater than the layered silicate raw material of 70mmol/g lower than 500ppm to adopt iron level, is (10 ~ 30): 1, at 80 DEG C of thermostatic water-circulator baths and 400rmin according to raw material and quality ratio
-1continuously stirring 30min forms suspension, after standing 2.5 hours, get the organic intercalation agent being equivalent to this layered silicate raw materials quality part 10.0 ~ 15.0 to be dissolved in suitable quantity of water and to make solution, this solution is added in described laminar silicic acid salt suspensioning liquid, carry out ion exchange reaction and form intercalation suspension in 6 ~ 24 hours under 80 DEG C with nitrogen atmosphere, the upper strata of intercalation suspension is separated, suction filtration and the AgN0 that cleans to 0.1mol/L
3fail to detect Cl
-exist.Repeatedly optimize this sepn process and last handling process, the interlamellar spacing detecting products therefrom, at 1.0 ~ 4.0nm, is nano-micrometer scaffold intermediate.Finally, by the nano-micrometer scaffold intermediate sample of separated and collected 80 DEG C of vacuum-dryings 24 hours, through pulverizing, sieving and sorting process makes nano-micrometer intermediate microparticle, this particulate powder detects through Electronic Speculum has 1 ~ 4nm interlamellar spacing structure and 1 ~ 50 μm of micron packaging assembly, deposits and keep high reactivity in usual environment long-term stability;
Described nano-micrometer scaffold intermediate particulate, by relative to high polymer monomer mass parts 0.5 ~ 10.0, by conventional solution, solvent dispersion or polymerization methods, forms nanocomposite system;
Described nano-micrometer scaffold intermediate particulate, it is characterized in that forming controlled dispersed multiphase system at the high polymer monomer aqueous solution, Organic Alcohol solution, this heterogeneous system synthesizes high molecule nano composite material through home position polymerization reaction, and it is composed as follows that described polymerization reaction system presses mass fraction:
Described polymerization reaction system is by free radical reaction synthesis high molecule nano composite material, process is: the monomer solution of 15.0 ~ 25.0 mass percentage concentration, oxygenant and the reductive agent of 0.01 ~ 0.50 is relative to monomer mass part, suspension is mixed into mass parts 0.5 ~ 10.0 nano-micrometer intermediate, the auxiliary agent of 3.0 ~ 15.0 mass parts is added to this suspension, add appropriate sodium hydroxide solution again, regulate reaction suspension pH value 7.5 ~ 11.5, control this reaction initiation temperature 5 ~ 15 DEG C of low temperature polymerizations after 30 ~ 90 minutes, reaction rises to higher temperature, reaction 1 hour is continued through azo-initiator, gained pyroreaction slurries are proceeded in temperature control adiabatic polymerisation device, letting nitrogen in and deoxidizing 20min, then azo initiator is added every 3min, logical nitrogen is stopped after making polymerization system viscosity reach threshold value, reaction colloid product insulation slaking 2 ~ 3 hours, hydrolysis reactor put into by colloid, add the mixing of appropriate hydrolytic reagent and carry out high-temperature hydrolysis, the molecular weight of prepared colloid product, solids content detects by standard GB12005.2-89 and GB12005.1-89, products distribution is measured by Electronic Speculum, obtaining disperse phase mean sizes is 30nm ~ 70nm,
Described nano-micrometer scaffold intermediate particulate, by relative to high polymer monomer mass parts 0.5 ~ 10.0, by melt extruding or injection molding mode, being scattered in organic crystal polymer, obtaining high molecule nano composite material.
2. as claim 1, the dispersing method of described a kind of nano-micrometer scaffold intermediate particulate, adopt layered silicate pit wood material to be montmorillonite, kaolin, attapulgite, sepiolite, wollastonite, chlorite, stratiform silicon-dioxide, their arbitrary symbiosis or mixed systems, described layered silicate and water are (30 ~ 10) in mass ratio: 1.
3. as claim 1, the dispersing method of described a kind of nano-micrometer scaffold intermediate particulate, feature adopts organic intercalation agent to be 12 carbon chain aliphatic amine, 16 carbon chain aliphatic amine, 18 carbon chain aliphatic amine, cetyl trimethylammonium bromide (CTAB), Cetyltrimethylammonium bromide, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride (CTAC), they are the two mixture arbitrarily, or they and protonic acid be 1: 1 composition formed in molar ratio, described organic intercalation agent is relative to layered silicate quality part 5.0 ~ 15.0, composition intercalation system.
4. as claim 1 or 3, the dispersing method of described a kind of nano-micrometer scaffold intermediate particulate, to it is characterized in that from reaction suspension after filtration, dry and disintegrating process obtains nano-micrometer scaffold intermediate particulate product, be greater than 1 year in drying, sealing or low temperature environment preservation period, and keep reactive behavior.
5. as claim 1 or 5, the dispersing method of described a kind of nano-micrometer scaffold intermediate particulate, it is characterized in that described high polymer monomer is acrylamide, vinylformic acid or their the two comonomers mixed any, monomer mass percentage concentration 15.0 ~ 25.0.
6. as claim 1, the dispersing method of described a kind of nano-micrometer scaffold intermediate particulate, it is characterized in that reacting relative to the nano-micrometer scaffold intermediate of monomer mass part 0.5 ~ 10.0 and monomer in situ polymerization, form surface topography and wettability is controlled and durothermic polyacrylamide nano matrix material.
7. as claim 1, the dispersing method of described a kind of nano-micrometer scaffold intermediate particulate, it is characterized in that auxiliary agent is urea, disodium ethylene diamine tetraacetate complexing agent, glycerol or their any the two compositions, auxiliary agent is 3.0 ~ 15.0 relative to monomer mass part.
8. as claim 1, the dispersing method of described a kind of nano-micrometer scaffold intermediate particulate, it is characterized in that oxygenant is ammonium persulfate, Sodium Persulfate, Diisopropyl azodicarboxylate or hydrogen peroxide, oxygenant is 0.01 ~ 0.50 relative to monomer mass part; Described reductive agent is S-WAT or iron protochloride, and reductive agent is 0.01 ~ 0.50 relative to monomer mass part, and reductive agent and oxygenant are according to mass parts 1: 1 compound use.
9. as claim 1, the dispersing method of described a kind of nano-micrometer scaffold intermediate particulate, it is characterized in that synthesized high molecule nano composite material is as auxiliary agent, drilling fluid, the well finishing liquid base slurry by international API standard preparation is added, for the preparation of nano combined Drilling and completion fluids system by mass parts 0.1 ~ 0.5.
10. as claim 1, the dispersing method of described a kind of nano-micrometer scaffold intermediate particulate, it is characterized in that synthesized high molecule nano composite material is as auxiliary agent, for the preparation of the multi-phase emulsion of salt tolerant and resistance to more than 70 DEG C high-temperature stabilities, drilling fluid or completion fluid system.
11. as claim 1; the dispersing method of described a kind of nano-micrometer scaffold intermediate particulate; it is characterized in that the nano combined drilling fluid that employing nano-micrometer scaffold intermediate particulate or high molecule nano composite material are made or well finishing liquid; for complex oil and gas reservoir exploitation engineering; the regulation and control seepage flow of fluid channel and flow conductivity, makes its permeability resume figure be greater than 90%.
12. as claim 1; the dispersing method of described a kind of nano-micrometer scaffold intermediate particulate; it is characterized in that the nano combined drilling fluid that employing nano-micrometer scaffold intermediate particulate or high molecule nano composite material are made or well finishing liquid; for oil and gas reservoir protection and maintenance reservoir hypertonicity, reservoir permeability recovery value is made to be greater than 90%.
13. as claim 1, the dispersing method of described a kind of nano-micrometer scaffold intermediate particulate, it is characterized in that high molecule nano composite material and universal industrial linking agent react formation 300 ~ 500nm gel product through solution crosslinking, for oil and gas reservoir duct leak stopping and regulation and control duct flow conductivity.
14. as claim 1; the dispersing method of described a kind of nano-micrometer scaffold intermediate particulate; it is characterized in that the lubricating coefficient of the nano-composite emulsion product of nano-micrometer scaffold intermediate particulate or its high molecule nano composite material is lower than 0.07, be applied to hydrocarbon zone drilling well, Well Completion Engineering of Oil Reservoirs produces lubrication drag reduction effect.
15. as claim 1; the dispersing method of described a kind of nano-micrometer scaffold intermediate particulate; it is characterized in that nano-micrometer scaffold intermediate particulate or its polymer nanocomposites form the product of controllable expansion; be applied to and suppress rock expansion to make its rate of expansion be less than 7.0%, produce and suppress hydrocarbon zone drilling completion rock expansion and stabilizing effect.
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