CN107652962B - A kind of novel oilfield polymer flooding profile control agent - Google Patents
A kind of novel oilfield polymer flooding profile control agent Download PDFInfo
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- CN107652962B CN107652962B CN201710904804.8A CN201710904804A CN107652962B CN 107652962 B CN107652962 B CN 107652962B CN 201710904804 A CN201710904804 A CN 201710904804A CN 107652962 B CN107652962 B CN 107652962B
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- microballoon
- phenolic resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
Abstract
The invention discloses a kind of novel oilfield polymer flooding profile control agents.The oilfield polymer flooding profile control agent is acrylamide/phenolic resin microspheres, it is prepared according to the method included the following steps: preparing the aqueous solution of acrylamide, phenolic resin, initiator and crosslinking agent as water phase, into the water phase be added the oily phase containing emulsifier, it is reacted to obtain the final product.The addition of phenolic resin significantly improves the heat resistance of AM/PF microballoon, can satisfy the deep profile correction needs of high-temperature oil reservoir completely.The heatproof time of microballoon shortens with the growth in PF reaction time, directly proportional to oil-water ratio and crosslinking ratio, is influenced by monomer ratio (PF/AM) smaller.The entire heatproof process of AM/PF microballoon is analyzed using scanning electron microscope and infrared spectroscopy, inferred according to result: AM/PF microballoon is first happens is that the degradation of microsphere surface more small protrusion containing acrylamide, followed by polyacrylamide strand and phenolic resin are all degraded, remaining substance is the higher reticular structure of phenolic resin content after heatproof.
Description
Technical field
The present invention relates to a kind of oilfield polymer flooding profile control agents, and in particular to acrylamide/phenolic resin microspheres are in conduct
Application in the profile control agent of oilfield polymer flooding.
Background technique
Most of existing oil field in China has entered mid-later development phase.Oil field is totally in recoverable reserves recovery percent of reserves
High, the aqueous " three high " stage high, residual recoverable reserves rate of oil production is high.The average recovery ratio of China's developed field at this stage
About 30%, the reservoir conditions in these oil fields are relatively mild, and the temperature and formation water salinity of oil reservoir are lower, reservoir
Heterogeneity it is preferable, the water drive and subsequent chemistry in these oil fields, which are driven, improves recovery ratio significant effect.It is existing statistics indicate that I
The petroleum average recovery ratio of state's developed field is every to promote 1 percentage point, just will increase about 200,000,000 tons of recoverable reserves, is equivalent to mesh
The 1 year petroleum total output in preceding China.Therefore, the technical measures that recovery efficiency technique is oilfield stable production, volume increase are improved.
From the point of view of the current situation for improving recovery efficiency technique, polymer flooding is still without other effective substitute technologies at present,
And with the continuous development of technique of polymer flooding itself, and the good result that scene obtains, following a period of time interpolymer
Drive is still to improve the dominant technology of recovery ratio.But apply the reservoir temperature, formation water salinity and reservoir of polymer flooding non-
Homogenieity is relatively milder, is not suitable with the requirement of high temperature, high salinity reservoir.However as deepening continuously for exploitation, reservoir media is got over
Come more severe, some high temperature, high salinity reservoir and the serious oil reservoir of heterogeneity, as North China Oilfield, northwest oil field, Shengli Oil Field,
The high temperature and high salt oil deposit that Zhongyuan Oil Field, Tarim Oilfield etc. have some crude oil reserves very rich, since reservoir environment compares
Badly, chemical oil displacement agent used in existing raising recovery efficiency technique can not adapt to high temperature, requirement with high salt, so that these are oily
The waterflood recovery efficiency factor of hiding is relatively low, and there are also the spaces further promoted.The formation temperature in these oil fields is up to 110~150 DEG C, mine
Change degree is also up to 11 × 104~26 × 104Mg/L, and reservoir heterogeneity is serious, implements under formation condition severe so poly-
It closes object and drives raising recovery efficiency technique, there is also many problems.Therefore, exploitation is to high temperature (110~150 DEG C) reservoir media adaptability
The preferable recovery efficiency technique that improves seems very urgent.
Polymer microballoon is the novel profile control agent to grow up in recent years, compared with existing polymer flooding, polymerization
Object microballoon has that synthesis is simple, product cut size is controllable, meets constancy of volume after oil, can expand in water, but not dissolve
The advantages that, microballoon realizes deep profile controlling after entering oil reservoir injection water layer after can slowly absorbing water, sweep efficiency is improved, to mention
High recovery rate.The heat-resistant salt-resistant of polymer microballoon is substantially better than HPAM simultaneously, can be stabilized 3 at a temperature of 100 DEG C
Month.But the heat resistance of these existing polymer microballoons is also difficult to meet high temperature, the application of high heterogeneous reservoir is wanted
It asks.Therefore, the preparation good polymer microspheres of high temperature resistance have weight for the raising recovery ratio of high temperature, high salinity reservoir
The realistic meaning wanted.
Summary of the invention
The object of the present invention is to provide a kind of novel oilfield polymer flooding profile control agents, by introducing water soluble phenol resin
(PF) with acrylamide (AM) copolymerization the good acrylamide/phenolic resin microspheres of heat resistance have been prepared (AM/PF is micro-
Ball), the addition of phenolic resin significantly improves the heat resistance and swelling behavior of microballoon, it can be used in oil field deep profile control,
Improve oil recovery rate.
Acrylamide/phenolic resin microspheres provided by the invention can be as the profile control agent of oilfield polymer flooding.
Acrylamide/the phenolic resin microspheres can be prepared according to the method included the following steps:
The aqueous solution of acrylamide, phenolic resin, initiator and crosslinking agent is prepared as water phase, is added in Xiang Suoshu water phase
Oily phase containing emulsifier, it is reacted up to the acrylamide/phenolic resin microspheres.
Specifically, the temperature of the reaction is 65~75 DEG C, and concretely 70 DEG C, the time is 4 hours；
The mass fraction of emulsifier described in the oil phase is 3~8%.
Specifically, the mass ratio of the acrylamide and the phenolic resin is 1:1~2, concretely 1:1.5.
Specifically, the mass fraction of crosslinking agent described in the aqueous solution is 0~1%, but is not zero；
The crosslinking agent can be N,N methylene bis acrylamide, diacrylate or divinylbenzene.
In above-mentioned preparation method, the initiator can be potassium peroxydisulfate, ammonium persulfate or azo diisobutyl amidine hydrochloric acid
Salt.
Specifically, the oil is mutually 1.5~3.0:1 with the volume ratio of the water phase.
Specifically, before the water phase is added, the method also includes being mutually passed through nitrogen to the oil under agitation
The step of gas drive oxygen；
Before the reaction, the method also includes the steps for the emulsion emulsifiers for being mutually mixed to get the oil with the water phase
Suddenly.
Specifically, the synthesis condition of the phenolic resin is as follows:
The molar ratio of phenol and formaldehyde is 1:4；
Reaction temperature is 75 DEG C；
Reaction time is 3h.
The phenolic resin obtained under above-mentioned synthesis condition is further copolymerized the heat resistance of obtained AM/PF microballoon
It is more excellent.
Acrylamide/phenolic resin microspheres that the above method of the present invention is prepared, granular size between 10~30 μm,
Monodispersity is relatively good, and AM/PF microsphere surface equably adheres to the bead of many protrusions, these beads are likely to be balling-up
The more oligomer containing acrylamide is combined together to form after be combineding with each other with microballoon in late phase reaction drop.
The swelling multiple of acrylamide/phenolic resin microspheres of the present invention in water is 5~100, and the partial size after swelling is 50
~400 μm；The swelling process of AM/PF microballoon is slower, and 140 DEG C take around 10d or so and could be swollen completely, can be used in
Polymer flooding progress deep profile controlling (and the swelling time of general acrylamide microballoon is shorter, 1d or so will swell to maximum
Value, generally no longer changes when the time continues growing).
It is tested through heatproof, the heatproof process of AM/PF microballoon of the present invention is a process from outside to inside, after microspheres swell
Surface becomes smooth, illustrates it is that the small protrusion on surface is degraded first, has the phenolic resin of sub-fraction also with generation
Degradation, the spherical structure of microballoon is destroyed completely after heatproof, and polyacrylamide Partial digestion is complete, only remaining phenolic aldehyde
The reticular structure of resin.The variation of absorption peak is into one in substance infrared spectrum after microsphere powder, swelling 30d and heatproof
Step has determined the heatproof mechanism of AM/PF microballoon.
Heatproof experiment shows that the addition of phenolic resin significantly improves the heat resistance of AM/PF microballoon, as can at 120 DEG C
Lower heatproof 180d, heatproof also can achieve 150d at 140 DEG C, can satisfy the deep profile correction needs of high-temperature oil reservoir completely.Microballoon
The heatproof time shorten with the growth in PF reaction time, it is directly proportional to oil-water ratio and crosslinking ratio, by monomer ratio (PF/AM)
It influences smaller.The entire heatproof process of AM/PF microballoon is analyzed using scanning electron microscope and infrared spectroscopy, is carried out according to result
Infer: AM/PF microballoon is first happens is that the degradation of microsphere surface more small protrusion containing acrylamide, followed by polyacrylamide
Amine molecule chain and phenolic resin are all degraded, and remaining substance is the higher netted knot of phenolic resin content after heatproof
Structure.To sum up, acrylamide/phenolic resin microspheres of the present invention can be used in the deep profile controlling in oil field.
Detailed description of the invention
Fig. 1 is the metamorphic process of water soluble phenol resin prepared by the embodiment of the present invention 1.
Fig. 2 is the sample powder of the water soluble phenol resin of the preparation of the embodiment of the present invention 1 after precipitation.
Fig. 3 is the infrared spectrogram of Phenolic resin powder prepared by the embodiment of the present invention 1.
Fig. 4 is the scanning electron microscopic picture of 16 AM/PF microsphere samples prepared by the embodiment of the present invention 2.
Fig. 5 is the scanning electron microscopic picture of the AM/PF microballoon of optimization formula in the embodiment of the present invention 2.
Fig. 6 is the infrared spectrogram of acrylamide microballoon.
Fig. 7 is the infrared spectrogram of AM/PF microballoon prepared by the embodiment of the present invention 2.
Fig. 8 is the microscope of the AM/PF microballoon dry powder prepared when the reactive modified phenolic resin time is 3h in the embodiment of the present invention 2
Photo.
Fig. 9 is the scanning electricity of the AM/PF microballoon dry powder prepared when the reactive modified phenolic resin time is 3h in the embodiment of the present invention 2
Mirror photo.
Figure 10 is the grain size distribution of AM/PF microballoon dry powder prepared by the embodiment of the present invention 2.
Figure 11 is the graph of relation between the obtained AM/PF microballoon dry powder dry (MV) of the embodiment of the present invention 2 and crosslinking ratio.
Figure 12 is the relation curve between the obtained AM/PF microballoon dry powder dry (MV) of the embodiment of the present invention 2 and monomer ratio
Figure.
Figure 13 is the graph of relation between the obtained AM/PF microballoon dry powder dry (MV) of the embodiment of the present invention 2 and oil-water ratio.
Figure 14 is 140 DEG C of the AM/PF microballoon swellings prepared when the reactive modified phenolic resin time is 3h in the embodiment of the present invention 2
Microscope photo after 10d.
Figure 15 is comparison diagram before and after AM/PF microspheres swell prepared by the embodiment of the present invention 2.
Figure 16 is the curve graph between AM/PF microspherulite diameter (MV) distribution prepared of the embodiment of the present invention 2 and swelling time.
Figure 17 is the TG curve graph of different crosslinking agent type microballoons prepared by the embodiment of the present invention 2.
Figure 18 is the DSC curve figure of different crosslinking agent type microballoons prepared by the embodiment of the present invention 2.
The TG curve graph of AM/PF microballoon when Figure 19 is different monomers proportion in the embodiment of the present invention 2.
The TG curve graph of AM/PF microballoon when Figure 20 is different oil-water ratios in the embodiment of the present invention 2.
The TG curve graph of AM/PF microballoon when Figure 21 is different crosslinking ratios in the embodiment of the present invention 2.
Figure 22 is the AM/PF microspheres solution heatproof process photo of the preparation of the embodiment of the present invention 2 (when different reactive modified phenolic resins
Between).
Figure 23 is microspheres solution microscope photo (the different phenolic aldehyde after AM/PF microspheres swell prepared by the embodiment of the present invention 2
The resin reaction time).
Figure 24 is microspheres solution microscope photo (the different phenolic aldehyde after AM/PF microballoon heatproof prepared by the embodiment of the present invention 2
The resin reaction time).
Figure 25 is AM/PF microspheres solution heatproof process photo prepared by the embodiment of the present invention 2.
Figure 26 is the microspheres solution microscope photo (different monomers after AM/PF microspheres swell prepared by the embodiment of the present invention 2
Proportion).
Figure 27 is the microspheres solution microscope photo (different monomers after AM/PF microballoon heatproof prepared by the embodiment of the present invention 2
Proportion).
Figure 28 is AM/PF microspheres solution heatproof process photo (different crosslinking ratios) prepared by the embodiment of the present invention 2.
Figure 29 is microspheres solution microscope photo (the difference crosslinking after AM/PF microspheres swell prepared by the embodiment of the present invention 2
Than).
Figure 30 is microspheres solution microscope photo (the difference crosslinking after AM/PF microballoon heatproof prepared by the embodiment of the present invention 2
Than).
Figure 31 is AM/PF microspheres solution heatproof process photo (different oil-water ratios) prepared by the embodiment of the present invention 2.
Figure 32 is microspheres solution microscope photo (the different greases after AM/PF microspheres swell prepared by the embodiment of the present invention 2
Than).
Figure 33 is microspheres solution microscope photo (the different greases after AM/PF microballoon heatproof prepared by the embodiment of the present invention 2
Than).
Figure 34 is the stereoscan photograph of AM/PF microballoon dry powder prepared by the embodiment of the present invention 2.
Figure 35 is the stereoscan photograph after AM/PF microballoon dry powder heatproof 10d prepared by the embodiment of the present invention 2.
Figure 36 is the stereoscan photograph after AM/PF microballoon dry powder heatproof prepared by the embodiment of the present invention 2.
Figure 37 is the infrared spectrogram of AM/PF microsphere powder prepared by the embodiment of the present invention 2.
Figure 38 is the infrared spectrogram after AM/PF microspheres swell 30d prepared by the embodiment of the present invention 2.
Figure 39 is heatproof degradation process signal of the AM/PF microballoon of the preparation of the embodiment of the present invention 2 in 140 DEG C of aqueous solutions
Figure.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
The preparation of embodiment 1, water soluble phenol resin
Phenol carries out closed melting at 50 DEG C, and preparing mass fraction with the deionized water for having removed oxygen is 20% hydrogen
Sodium hydroxide solution is spare, and the phenol for weighing certain mass molten condition is added in 250mL flask, the lower 50 DEG C of drives oxygen of stirring
20min is operated, prepared sodium hydroxide solution is then added dropwise according to a certain percentage as catalyst, the reaction was continued
Temperature is finally increased to 75 DEG C by 20min, weighs certain mass according to the reaction ratio (molar ratio 1:4) of phenol and formaldehyde
Formalin (37~38%) be added dropwise with constant pressure funnel, it is small to continue logical nitrogen reaction 3 after formaldehyde is added dropwise
When, obtain final product.Reaction liquid tap water is deposited in after cooling spare in 5 DEG C of refrigerator.
The pot-life of phenolic resin: water soluble phenol resin is subjected to observation of taking pictures daily, as a result as shown in Figure 1.By
Figure it is found that the color of phenol resin solution gradually becomes orange from faint yellow, eventually become it is darker orange red, this be because
Even if refrigerating in refrigerator for newly synthesized water soluble phenol resin, still can continue that polycondensation occurs with the extension of resting period
Reaction, and always having unreacted phenol can be by the dioxygen oxidation in air, and generation synthesizes totally unfavorable polymerization inhibitor to microballoon
Agent 1,4-benzoquinone can judge the degree of metamorphism of phenolic resin by the variation of color.Pass through experiment and the synthesis of subsequent microballoon
Experiment discovery water soluble phenol resin can only keep one week superperformance, and the needs that will go bad after one week recombine.
It needs to remove a large amount of aqueous solvent before characterizing phenolic resin product, be obtained using isopropanol as precipitating reagent
Sample powder as shown in Fig. 2, by figure it can be found that the water soluble phenol resin powder that synthesize present it is faint yellow, and without drive
The reason of product of oxygen operation should be the powder of pink, generate this difference is to have accomplished in the synthesis process of resin sternly
Lattice drive oxygen, eliminate competitive reaction-oxidation reaction of reactant phenol, are conducive to subsequent microballoon synthesis.In addition the tree obtained
Rouge powder dispersibility is preferable, and there is no being sticked together, this also illustrates that it is to compare reason that precipitating is carried out using isopropanol
The method thought.
The infrared spectrum characterization of phenolic resin: phenol formaldehyde ratio 1:4, the Phenolic resin powder that the reaction time is 3h are carried out infrared
Spectrum analysis, as a result as shown in Figure 3.From the figure 3, it may be seen that 3353cm-1Place is the hydroxyl stretching vibration absworption peak of association.2969cm-1
And 2883cm-1Place is the symmetric and unsymmetric stretching vibration peak of methylene.1606cm-1Place is the C=C vibration absorption peak of phenyl ring.
It is-CO-the stretching vibration absworption peak on hydroxymethylphenol at 1219.1025cm-1Place is that the C-O stretching vibration of methylol absorbs
Peak.1150cm-1The C-C stretching vibration absworption peak of place's connection phenyl ring and methylol.882cm-1、796cm-1、756cm-1Place is respectively
The four of phenyl ring replace, three replace, two replace absorption peak.It is possible thereby to judge that hydroxymethylation has occurred on phenyl ring really, and
Three there are significant proportion replace and tetra substitution product, this illustrates that the water soluble phenol resin of synthesis has more methylol can be with
Amide groups in acrylamide generates crosslinked action, better performances.
The preparation of embodiment 2, AM/PF microballoon
It weighs a small amount of emulsifier Span80 to be placed in 250mL round-bottomed flask, a certain amount of white oil is added, so that emulsifier
Mass fraction 4%, 50 DEG C of stirred in water bath 30min are until clear obtains oily phase；By AM, PF, KPS and MBA (N, N-
Methylene-bisacrylamide) it is dissolved in suitable quantity of water according to a certain percentage；Prepared oil is mutually placed in water-bath, is connected
Good reaction unit, is stirred with the revolving speed of 250r/min, and logical nitrogen flooding oxygen 30min, then adjusts the temperature of water-bath to 25
DEG C, after it is oily mutually cool down after, water phase dropwise is added dropwise with constant pressure funnel, after water phase is added, be maintained at low temperature continue it is newborn
Change 30min.Bath temperature is transferred to 70 DEG C after lotion is uniform, reaction temperature is kept to react 4h.It is after reaction terminates, product is anti-
It answers lotion to be demulsified with the dehydrated alcohol of 10 times of volumes, filters, after being repeated several times, by product in 40 DEG C of vacuum oven
It places 24 hours, finally obtains the AM/PF polymer microballoon of rice white.
1 factor level table of table-inverse suspension method
The reaction temperature of fixed microballoon synthesis is determined as 70 DEG C, stirring rate 250r/min, reaction time total 4h, further
It probes into the reaction time of water soluble phenol resin and synthesizes influence of the monomer ratio to microballoon heat resistance required for microballoon, because
This uses L16(42) orthogonal arrage carries out the horizontal orthogonal test of two factor four, table 1 is factor-water-glass of orthogonal test.
1, microballoon preparation influence factor and formulation optimization
(1) determination of quadrature factor
1. the reactive modified phenolic resin time
The reaction time of phenolic resin is especially pronounced on the influence of the heat resistance of AM/PF microballoon, this illustrates phenolic resin
Reaction time has directly influenced the molecular structure and the degree of polymerization of resin, so that the microballoon of synthesis be made to generate on composition and structure
Difference.If previous experiments find the reaction time too short too high levels that will lead to free phenol in phenolic resin, and in microballoon
The phenol moieties that dissociate in synthesis process are oxidized to 1,4-benzoquinone, and the inhibition of 1,4-benzoquinone can inhibit initiation reaction, to cannot get mesh
Mark product；The reaction time of resin, the too long rigidity that will lead to the microspheres product finally synthesized was excessive, although can guarantee microballoon
Temperature tolerance, but microballoon elasticity it is poor with swelling behavior, the requirement of indepth plugging is not achieved.Therefore, guaranteeing temperature tolerance
On the basis of swellability, the reaction time of resin is selected as: 3h, 4h, 5h, 6h.
2. the monomer ratio of microballoon
Monomer composition is the key that copolymerization microsphere, it is desirable to which successfully the function admirable of synthesis microballoon and product, monomer are matched
Than must mainly adjust the ratio of phenolic resin and acrylamide monomer in a reasonable range, in this experiment.By
A large amount of experiment is groped and is continually improved, the results showed that content of the phenolic resin in microballoon will lead to microballoon most very little
Whole heat resistance does not reach requirement；The content of phenolic resin is too big, and certain shadow on the one hand can be generated to emulsion intercalation method
It rings, the 1,4-benzoquinone in another aspect phenolic resin can inhibit the initiation of reaction, cause finally obtained product yield not high.It is comprehensive
PF:AM (quality) is chosen after consideration are as follows: 6:12,8:12,10:12 and 12:12.
(2) orthogonal experiment data interpretation of result
According to L12(42) orthogonal design table has been respectively synthesized 16 kinds of AM/PF heatproof microballoons, 16 microsphere samples are swept
Electronic Speculum observation is retouched, as a result as shown in Figure 4.
The micromorphology for the microsphere sample being formulated to 16 is analyzed and is given a mark, and sample of the balling ratio less than 50% is lower than
5 points, the more low then score of balling ratio is lower；Balling ratio be more than 50% sample score be greater than 5 points, the more good then score of balling-up effect more
It is high.For the sample that balling ratio is not much different, according to property uniform in size judged, microspherulite diameter distribution more concentrate score more
Height, best synthesizing formula obtain 10 points, and not balling-up obtains 0 point；It is united again to heatproof number of days of 16 groups of samples in 140 DEG C
Meter.Final Orthogonal experiment results are as shown in table 2.
2 orthogonal experiments of table
Note 1) A be resin reaction time/h；2) B is monomer ratio/PF:AM
Factor each in orthogonal experiment and the horizontal heatproof number of days to microballoon are calculated weighted average (k) and very poor (R), knot
Fruit is as shown in table 3.Influence of the bigger explanation of R value to evaluation index is bigger.By data analysis in table it is found that each factor is resistance to microballoon
The size order that warm nature can influence are as follows: the monomer ratio of the reaction time > microballoon of phenolic resin.This is because the reaction time is straight
The molecular structure for influencing phenolic resin is connect, to change the reaction mechanism of phenolic resin and acrylamide, the reaction time is longer
The molecular structure of phenolic resin is more complicated, the degree of polymerization is bigger, the amide groups in methylol and acrylamide in possible resin
Polymerization reaction does not have the smaller Shi Rongyi of molecular weight, it is also possible to because when phenolic resin molecular weight is larger, in entire microballoon
Distribution will be inhomogenous, to affect the heat resistance of entire microballoon, show as the greatest differences of heatproof number of days.Phenolic aldehyde tree
The monomer ratio of rouge and acrylamide difference only changes content of the phenolic resin in microballoon, not to the structure of microballoon
Too much influence, so being only greater than monomer ratio using heatproof number of days as the influence of reactive modified phenolic resin time when factor of evaluation.
3 orthogonal experiment data analysis of table-heat resistance
Note 1) A be resin reaction time/h；2) B is monomer ratio/PF:AM
4 orthogonal experiment data analysis of table-micromorphology
Note 1) A be resin reaction time/h；2) B is monomer ratio/PF:AM
Each factor and the horizontal micromorphology to microballoon calculate weighted average (k) and very poor (R) in orthogonal experiment, as a result
As shown in table 4.Influence of the bigger explanation of R value to inspection target is bigger.In table data analysis as can be seen that using micromorphology as
The influence in the reaction time of phenolic resin is larger than the monomer ratio of microballoon when investigation factor.This be primarily due to microballoon at
Ball effect is mainly influenced by emulsion intercalation method, and the balling ratio of the more good then microballoon of emulsion intercalation method is higher in reaction process.Phenol
The time is longer in the synthesis process for urea formaldehyde, and the degree of polymerization distribution of phenolic resin is wider, enters in aqueous phase droplets when forming lotion
Phenolic resin bulk of molecule it is inhomogenous, and during balling-up, the only moderate part phenolic resin of the degree of polymerization
Can just participate in reacting, thus phenolic resin reaction time it is too long when will generate synthesis microballoon balling ratio is low and microspherulite diameter
Distribution it is wider.Influence of the monomer ratio of microballoon to the micromorphology of microballoon is relatively small, illustrates that other conditions are all conducive to
When synthetic reaction, each reaction monomers ratio, which changes, generally will not influence globulation, but can have an optimal monomer and match
Than.
According to the comprehensive analysis of two evaluation indexes, finally the optimization formula of determining AM/PF microballoon is as shown in table 5.Its
70 DEG C, sustained response 4h of middle microballoon synthesis temperature, emulsifier is the 4% of oily phase.
5 inverse suspension method of table prepares microballoon optimization formula
Constantly amplify the pattern until single microballoon visible in detail, knot using microballoon of the scanning electron microscope to optimization formula
Fruit is as shown in Figure 5.It can be found that the granular size of AM/PF microballoon is between 10~30 μm, monodispersity is relatively good for observation, and
AM/PF microsphere surface equably adheres to the bead of many protrusions, these beads, which are likely to be in balling-up late phase reaction drop, to be contained
What the more oligomer of acrylamide was combined together to form after be combineding with each other with microballoon.
2, the infrared spectrum analysis of AM/PF microballoon
Acrylamide microballoon (preparation method is identical as AM/PF microballoon) and AM/PF microsphere powder are subjected to infrared spectroscopy point
Analysis, as a result as shown in Figures 6 and 7.
As seen from Figure 6, sample is in 3407 and 3190cm-1There are the characteristic absorption peak of amide groups, 1658cm at place-1's
Carbonyl absorption peak, there are also-CH2Each absorption peak etc..This illustrates that acrylamide microsphere sample is by acrylamide monomer homopolymerization
Synthesis.Comparing Fig. 7 can be seen that on the infrared spectrum of AM/PF microsphere sample in addition to the feature with acrylamide microballoon is inhaled
It receives other than peak, the absorption peak of phenolic resin also obviously occurs, the carbon skeleton absorption peak (1611cm including phenyl ring-1、1542cm-1、 1489cm-1、1450cm-1) and phenyl ring 1,2,4 replace characteristic peak (879cm-1).The experimental results showed that phenolic resin
The synthesis process for taking part in AM/PF microballoon is phenolic resin and acrylamide copolymerization as a result, this also illustrates cause AM/PF
Microballoon and difference of the acrylamide microballoon in performance, mainly introduce the result of phenolic resin in the synthesis of microballoon.
3, the pattern of AM/PF microballoon, size and swelling behavior
Using optical microscopy, scanning electron microscope and laser particle analyzer to the form, particle diameter distribution and swelling of microballoon
Performance is analyzed；The influence of crosslinking ratio, monomer ratio and oil-water ratio to AM/PF microballoon dry powder partial size is investigated, and is had studied molten
The influence that the swollen time is distributed AM/PF microspherulite diameter, it was demonstrated that AM/PF microballoon prepared by the present invention can be as the profile control in oil field
Agent.
The form and size of 3.1 microballoon dry powder are observed
(1) the micro- sem observation of AM/PF microballoon dry powder
Four groups of microspheres product further progresss observation to reactive modified phenolic resin time 3h, first with microscopic four
The appearance and size of group microballoon, as shown in figure 8, monomer ratio (PF/AM) is respectively as follows: Fig. 8 a) 6:12；Fig. 8 b) 8:12；Fig. 8 c)
10:12；Fig. 8 d) 12:12.As seen from the figure, microballoon dry powder is spherical, and particle diameter distribution is than more uniform, substantially between 10~30 μm,
Monodispersity is preferable.
(2) scanning electron microscopic observation
For the micromorphology of more intuitive observation microballoon dry powder, scanning electron microscope will be carried out after four kinds of microsphere powder sample preparations
Observation, as shown in figure 9, monomer ratio (PF/AM) is respectively as follows: Fig. 9 a) 6:12；Fig. 9 b) 8:12；Fig. 9 c) 10:12；Fig. 9 d)
12:12.As seen from the figure, the global shape of four kinds of microballoon dry powder is still spherical, but there is the small of many protrusions on the surface of ball again
Microballoon, i.e. the surface of ball be not it is smooth, the surface texture of this protrusion can not observe under an optical microscope, this
The difference for being AM/PF microballoon and acrylamide microballoon on microcosmic, the surface of acrylamide microballoon be it is smooth, do not have
Similar small protrusion, this may be related with the heat resistance of AM/PF microballoon.Scanning electron microscope observation finds the partial size of microballoon also substantially
It is distributed between 10~30 μm, it is consistent with microscopical observed result.
(3) particle diameter distribution of microballoon dry powder
After meeting water due to microballoon water swelling, institute can occur for the particle diameter distribution that can detecte sample using laser particle analyzer
With the circulation that selects mutually for dehydrated alcohol.Measurement result such as Figure 10 and table 6.What experiment detected is the microballoon dry powder of optimization formula
(reactive modified phenolic resin time 3h, monomer ratio AM/PF=8:12).The particle diameter distribution width of the microballoon dry powder known to map analysis
It is more than ten microns to 90 microns, 30 μm of mean particle size or so.
6 AM/PF microballoon dry powder particle diameter distribution of table
3.2 influence of each preparation factor to microballoon dry powder partial size
(1) influence of the crosslinking ratio to AM/PF microballoon dry powder partial size
The crosslinking ratio for changing AM/PF microballoon on the basis of optimization formula is prepared for serial microballoon, and crosslinking ratio is respectively
0%, 0.1%, 0.25%, 0.5%, 0.75%, 1%.Granularmetric analysis is carried out to the microballoon of different crosslinking ratios respectively, as a result
As shown in figure 11.
As seen from the figure, in certain research range, the dry powder partial size of microballoon is as the variation of crosslinking ratio is presented certain
Regularity, i.e. crosslinking ratio are continuously increased, and ever-reduced trend is presented in the variation of partial size, this illustrates that the ratio of crosslinking agent improves
Afterwards, the crosslinking points of microballoon in the synthesis process just become more, then the internal structure of entire microballoon will be more close, macroscopically
When showing as other conditions and not changing, microspherulite diameter reduces.
(2) influence of the monomer ratio to AM/PF microballoon dry powder partial size
In order to further study the influence factor of AM/PF microballoon dry powder partial size, keeps other conditions constant, only change AM/
The monomer ratio (AM:PF) of PF microballoon, taking AM:PF is respectively 12:12,12:10,12:8,12:6,12:4, utilizes laser particle size
Analyzer measures the change of size of each proportion, as shown in figure 12.
As seen from the figure, as the numerical value of AM:PF is bigger, in certain numberical range, the dry powder grain of AM/PF microballoon
Diameter is in the trend totally risen.This is because phenolic resin acts as the work of a part of crosslinking agent in the synthesis process of microballoon
With phenolic resin ratio shared in the composition of microballoon is smaller, then the amide groups in the methylol and acrylamide in resin
The cross-linking reaction of generation is reduced, and the composition density of microballoon reduces, and shows as that phenolic resin is fewer, the dry powder partial size of AM/PF microballoon
It is bigger.
(3) influence of the oil-water ratio to AM/PF microballoon dry powder partial size
Fix that its dependent variable is constant, the variation and the relationship of the dry powder partial size of AM/PF microballoon, oil-water ratio for probing into oil-water ratio take
Value is 1.5,2.0,2.5,3.0.Experimental result is as shown in figure 13.By figure it can be concluded that, with the continuous increase of oily Phase Proportion,
The dry powder partial size of AM/PF microballoon is first to increase, and is in then ever-reduced trend, in general, oil-water ratio becomes larger, AM/PF
The dry powder partial size of microballoon is steadily decreasing, this is because the particle size of microballoon has directly with degree of scatter of the water phase in oily phase
Relationship, while oil-water ratio increases, in the emulsion system that entirely reacts, the reduction that the content of water phase will be opposite, and this
The relative amount of emulsifier Span-80 is to maintain constant in the process, so that water phase will more disperse in oily phase,
Aggregation probability between the droplet of reaction reduces, and the partial size of the AM/PF microballoon after end reaction becomes smaller.
Pattern and size after 3.3 AM/PF microspheres swells
(1) micro- sem observation after AM/PF microspheres swell
In order to further progress observation reactive modified phenolic resin time 3h four groups of AM/PF microspheres products swelling after pattern and
The powder of four set products is configured to the microspheres solution of 2000mg/L by size, takes suitable microspheres solution to be added to 50mL with dropper
Ampoule bottle in, sealed, be placed in 140 DEG C of baking oven with alcohol blast burner after ampoule bottle is vacuumized, by ampoule after 5 days
Bottle takes out, and takes suitable microballoon to be observed from bottle with optical microscopy, swelling result such as Figure 14 institute of four groups of microspheres products
Show, wherein monomer ratio (PF/AM) is respectively as follows: Figure 14 a) 6:12；Figure 14 b) 8:12；Figure 14 c) 10:12；Figure 14 d) 12:12.
AM/PF microspheres swell is still the spherical shape of comparison rule later it can be seen from picture, and the monomer studied with front is matched
The influence for comparing AM/PF microballoon dry powder partial size is similar, and partial size is also the increase with the relative amount of phenolic resin after swelling
Partial size presents the trend of reduction.It can be seen that the particle diameter distribution of each group of AM/PF microballoon after swelling is not to concentrate very much, size
It is distributed between 50~400 μm.
(2) the ampoule bottle observation of AM/PF microballoon
For the swelling behavior of more macroscopical observation AM/PF microballoon, the microspheres solution of 2000mg/L is moved on into ampoule bottle
In, it is then placed in 140 DEG C of baking oven and observes Swelling, respectively to the height for not being swollen and being swollen solid in complete ampoule bottle
Degree is measured and is taken pictures, as a result as shown in figure 15.By swelling front and back photo it can be seen from be swollen before height be about
0.2cm, and the height after being swollen can achieve about 6.85cm, swelling multiple macroscopically is 34.25, this explanation, and AM/PF is micro-
Ball has excellent swelling behavior, can satisfy the needs of deep profile controlling.
Influence of 3.4 swelling times to AM/PF microspherulite diameter
The AM/PF microspheres solution for being 2000mg/L by mass concentration, places different time at 140 DEG C in ampoule bottle, makes
Particle diameter distribution detection is carried out with AM/PF microballoon of the laser particle size analyzer to different swelling times, as a result as shown in figure 16.Experiment
What is measured respectively be AM/PF microballoon dry powder, swelling time is respectively 0d, 5d, 10d and 15d.
As seen from Figure 16, with the increase of swelling time, the particle diameter distribution of microballoon is from lesser range to biggish
Range is mobile, and the partial size of AM/PF microballoon dry powder is mainly distributed between 20~40 μm, and partial size is mainly distributed on 100 after placing 15d
Between~400 μm, the particle diameter distribution of the AM/PF microballoon of swelling time 0d, 5d, 10d and 15d is between the two ranges.
This illustrates that the swelling process of the swelling process and acrylamide microballoon of AM/PF microballoon is different, general acrylamide microballoon
Swelling time is shorter, and 1d or so will swell to maximum value, generally no longer changes when the time continues growing, and AM/PF microballoon
Swelling process then need about more than ten days, be the process being slowly swollen, can satisfy the stratum profile control of more deepening portion.
4, the heat resistance of AM/PF microballoon and heatproof mechanism study
The heat resistance of AM/PF microballoon is studied, different formulations microballoon is observed in terms of both macro and micro two
High temperature degradation process, further analyzes the heat resistance of AM/PF microballoon using thermogravimetric test, while utilizing scanning electron microscope and infrared
Spectroscopic analysis methods study the heatproof mechanism of AM/PF microballoon.
The temperature tolerance experiment of AM/PF microballoon carries out as steps described below:
(1) the AM/PF microspheres solution for preparing mass concentration 2000mg/L, the ampoule bottle of 50mL is transferred to dedicated dropper
In.
(2) heat resistance due to AM/PF microballoon to be investigated at 140 DEG C, so must assure that ampoule bottle in sealing
It is preceding to be in vacuum state, ampoule bottle is connected on vacuum plant with rubber tube first, vacuum pump is opened, stops taking out after 60min
Vacuumizing finally seals rubber tube, and ampoule bottle is removed from vacuum plant.
(3) ampoule bottle removed, lights alcolhol burner, and to sealing after ampoule bottle preheating, when sealing takes care.
(4) finally the ampoule bottle for sealing mouth is put into and is mixed up in the baking oven of temperature in advance, later every 1d by ampoule bottle
It takes out, observation takes pictures and with the variation of micro- sem observation microballoon difference heatproof number of days after solution is cooling, to the last microscope
Under be barely perceivable complete microballoon and think that microballoon has been degraded completely, record the time of degradation to evaluate AM/PF microballoon
Heat resistance.
4.1 AM/PF microballoon TG-DSC experimental results
(1) influence of phenolic resin and N,N methylene bis acrylamide to AM/PF microballoon heat resistance
TG-DSC curve is done to AM/PF microballoon, the AM/PF microballoon that crosslinking ratio is 0%, AM microballoon dry powder, as a result such as Figure 17
With shown in Figure 18.Figure 17 is the TG figure of three kinds of microballoons, it is found that it is apparent poor the weight-loss curve of AM/PF microballoon and AM microballoon exist
The rate of different, especially between 250~350 DEG C curve, acrylamide microballoon weightlessness is much larger than phenolic resin microspheres, from figure
It can also significantly see that AM microballoon has an apparent endothermic peak on 18 DSC curve, this illustrates not containing in micro-sphere structure
Heat resistance is poor when phenolic resin, and the phenomenon of rupture of polyacrylamide strand will occur in lower temperature.350~
In 450 DEG C of temperature ranges, by a relatively large margin and faster weightlessness is all had occurred in three classes microballoon, and DSC curve is in corresponding temperature
Also occur three endothermic peaks in section, illustrate that at this time not only polyacrylamide strand is broken, the phenolic aldehyde in microballoon
Fracture also takes place in resin structure.There is also obvious poor after 300 DEG C for the AM/PF microballoon that AM/PF microballoon and crosslinking ratio are 0%
It is different, at identical temperature the residual mass rate of AM/PF microballoon always greater than crosslinking ratio be 0% the case where, when temperature reaches 680 DEG C
Afterwards, finally remaining quality rate is 35.14%, 30.56%, 23% respectively (i.e. AM/PF microballoon > crosslinking ratio is three kinds of microballoons
0% AM/PF microballoon > AM microballoon).This is the result shows that AM/PF polymer microballoon has very greatly in terms of heat resistance compared with AM microballoon
Advantage, phenolic resin and N in AM/PF micro-sphere structure, N- methylene-bisacrylamide crosslinking agent simultaneously in use, microballoon it is resistance to
Temp effect is best.
(2) influence of the monomer ratio to AM/PF microballoon TG result
The different AM/PF microballoon dry powder of monomer ratio is done into thermogravimetric analysis respectively, experimental result is as shown in figure 19, has in figure
The TG curve graph of the microballoon of four kinds of different ratios (PF:AM).There is no apparent poor before 370 DEG C for observation four curves of discovery
Different, after temperature is greater than 370 DEG C, monomer ratio is that the sample heat resistance of PF:AM=12:12 is better than the other three sample
Product, this is because with the increase of phenolic resin content, the rigidity reinforced of ball, thus resin content is high after microballoon degradation completely
The remaining quality of microballoon it is higher, so having preferably heat resistance.
(3) influence of the oil-water ratio to AM/PF microballoon TG result
The PF:AM microballoon dry powder sample of different oil-water ratios is done into thermogravimetric test, as a result as shown in figure 20.It can be seen by figure
Out, oil-water ratio has large effect to the heat resistance of PF:AM microballoon, constantly reduces with oil-water ratio, the heat loss of three kinds of microballoons
It is sequentially increased, in 100~300 DEG C of temperature, the heat loss rate of three microsphere samples is all smaller, and heat resistance is all preferable, heat
Loss is all within 15%.After difference appears in 350 DEG C, oil-water ratio is with heat loss rate at anti-in this temperature range
Than, and finally remaining quality rate is directly proportional to oil-water ratio for microballoon, it is biggish that this illustrates that oil-water ratio has the heat resistance of microballoon
It influences, this may be because the size of oil-water ratio will affect the stability of emulsion in microballoon synthesis process, the bigger lotion of oil-water ratio
More stable, then the mixing of phenolic resin and acrylamide monomer is more uniform in the structure of the microballoon synthesized, and heat resistance is better.
(4) influence of the crosslinking ratio to AM/PF microballoon TG result
The microballoon dry powder of different crosslinking ratios is done into thermogravimetric analysis experiment, as shown in figure 21.As seen from the figure, crosslinking ratio 0%
The TG curve of microsphere sample and the curve of other five kinds of samples have very big difference, joined the heat loss of the microballoon of crosslinking agent
The sample to be 0% much smaller than crosslinking ratio, this illustrates that crosslinking agent has a great impact to the heat resistance of microballoon, N, N- methylene
Bisacrylamide needs just to can guarantee the heat resistance of microballoon with phenolic resin collective effect, but the AM/PF of different crosslinking ratios is micro-
Difference is not apparent between ball thermogravimetric curve.
The heat resistance of 4.2AM/PF microballoon
(1) influence of the reactive modified phenolic resin time to AM/PF microballoon heat resistance
For the heatproof advantage for further studying optimization formula, other conditions unanimously only study the reaction time pair of phenolic resin
The influence of AM/PF microballoon heat resistance is transferred to the ampoule bottle that capacity is 50mL after being configured to the microspheres solution of 2000mg/L
In, ampoule bottle vacuumizes, and is sealed with alcohol blast burner, is respectively put into ampoule bottle in 120 DEG C and 140 DEG C of baking oven, daily later
It is observed.Reactive modified phenolic resin time asynchronous AM/PF microballoon heatproof number of days at 120 DEG C and 140 DEG C, as shown in table 7.
Data in analytical table it is found that the optimization formula heatproof advantage of AM/PF microballoon clearly.The heatproof time can reach at 140 DEG C
It to 150d, and is even more that can be fully able to meet the use condition of high-temperature oil reservoir with heatproof 180d at 120 DEG C.
The heatproof number of days of 7 microballoon of table
In order to observe the asynchronous AM/PF microballoon heatproof process of reactive modified phenolic resin time at 140 DEG C on the whole, from heatproof
Start to have carried out observation of taking pictures to microspheres swell and the process of degradation, as a result as shown in figure 22, the reaction time point of phenolic resin
Not are as follows: Figure 22 a) 3h；Figure 22 b) 4h；Figure 22 c) 5h；Figure 22 d) 6h.As seen from the figure, four groups of microballoons are common that: resistance to
The stage that temperature starts, AM/PF microballoon are initially to be deposited in very thin one layer in ampoule bottle bottom, and color is rice white, places number of days
When increase, the liquid level of swelling is constantly increased, and solution has certain viscosity when color also becomes yellow and shakes bottle body, works as rising
Solvent swelling state can keep a period of time when to maximum value, and the height being swollen when signs of degradation takes place is begun to decline, and
Color starts to shoal, and the viscosity of solution becomes smaller, and when degrading to the end, solution becomes nearly transparent or AM/PF microballoon height
Degree has decreased to the height no longer changed.But the heatproof process of the microballoon of optimization formula is again different: optimization formula is micro- first
The swelling process of ball is slowly more, and completely, the time secondly kept after microspheres swell is especially long and without going out for 10d or so swelling
The situation that existing microballoon suspends, even if microballoon still maintains certain swelling liquid level when finally end to heatproof.The above phenomenon
Illustrate that the AM/PF microballoon of optimization formula has stable high temperature resistance, effect is substantially better than other 3 groups of products.
Above-mentioned experiment is the observation to AM/PF microballoon macroscopic view heatproof process, due to the microstate of microballoon after finally degrading
Might not be identical, so the microspheres solution after heatproof is taken out, it is molten to the AM/PF microballoon after dyeing with optical microscopy
Liquid is observed, and the picture after being just swollen with microballoon compares, and as a result as shown in figure 23 and figure 24, Figure 23 is microspheres swell
The reaction time of picture afterwards, phenolic resin is respectively as follows: Figure 23 a) 3h；Figure 23 b) 4h；Figure 23 c) 5h；Figure 23 d) 6h, Tu24Shi
The reaction time of picture after heatproof, phenolic resin is respectively as follows: Figure 24 a) 3h；Figure 24 b) 4h；Figure 24 c) 5h；Figure 24 d)
6h.The experimental results showed that AM/PF microballoon has changed a lot before and after degradation, become irregular by regular spherical shape
Shape, and macroscopically judge the microballoon degraded, it is microcosmic on be to be very different, Figure 24 can see, phenolic resin
Very regular ball is still had after reacting the AM/PF microballoon heatproof of 6h, other three groups of experimental results, which remain on to exist, not to be had
It degrades complete microballoon, only the dyeing effect of some balls is obvious without before, this illustrates the heatproof number of days macroscopically observed
It is not very accurately, some samples still have the performance of heatproof.
(2) influence of the monomer ratio to AM/PF microballoon heat resistance
Influence by the analysis reactive modified phenolic resin time to AM/PF microballoon heat resistance, it is determined that phenolic resin 3h's
Optimum reacting time then carries out four groups of microballoons (PF:AM=6:12,8:12,10:12,12:12) for only changing monomer ratio
The experiment of aqueous solution heatproof prepares the AM/PF microspheres solution that four groups of mass concentrations are 2000mg/L, is packed into ampoule bottle, vacuumizes envelope
It is put into 120 DEG C and 140 DEG C of baking oven after mouthful, is observed and taken pictures daily, the results are shown in Table 8.From the data in the table,
The heat resistance of four groups of AM/PF microspheres products all shows more excellent, and the three of PF:AM=6:12,8:12,10:12,12:12
Heatproof number of days has all reached 100d or more at 120 DEG C of set product, under 140 DEG C of high temperature in addition to one group of sample of PF:AM=6:12, separately
Outer three groups of heatproof time can also reach 100d or more, and two groups of PF:AM=8:12,12:12 of heatproof advantage is significant, also with it is above-mentioned
Thermogravimetric test result matches, and the heatproof number of days of optimization formula sample is even more to have reached 150d, can be adapted for the oil reservoir of high temperature
Condition, although there are conclusive effect, phenolic aldehyde in the reaction time of this explanation phenolic resin to the heat resistance of AM/PF microballoon
There is also an optimum values for the ratio of resin and acrylamide.
The heatproof number of days of 8 microballoon of table
To the heatproof process of four groups of AM/PF microspheres products of different ratio at 140 DEG C, since heatproof, microspheres swell
Terminate to have carried out take pictures observation, as a result as shown in figure 25, PF:AM: Figure 25 a to microballoon heatproof) 6:12；Figure 25 b) 8:12；Figure
25c) 10:12；Figure 25 d) 12:12.As seen from the figure, as soon as the swelling process of group microballoon of PF:AM=6:12 is most fast, 5d or so
Be swollen completely, and after being swollen solution color than shallower, be substantially translucent state in the heatproof later period, when 50d is micro-
The boundary heading line off color of ball and water is more transparent, is hardly visible with the presence of particle, only seldom floccule is suspended in molten
In liquid.Two groups of microballoons of PF:AM=8:12 and 10:12 macroscopically have apparent difference, the first precipitating of microballoon compared with one group of 6:12
Density is bigger and color is also deep, and swelling time line of demarcation of microballoon and water all during 10d or so, heatproof is compared always
More apparent, last degradation is the process that microballoon liquid level gradually decreases.One group of microballoon of PF:AM=12:12 is on swelling time
Time of three groups than other will be longer, and the height of swelling is relatively low, illustrates the swelling of the higher microballoon of the content of phenolic resin
Performance is poorer.
The AM/PF microballoon for taking four groups of different monomers to match carries out the observation of optical microscopy after swelling and at the end of heatproof,
As a result as shown in figures 26 and 27.(PF:AM are as follows: Figure 26 a) 6:12 as seen from Figure 26；Figure 26 b) 8:12；Figure 26 c) 10:12；
Figure 26 d) 12:12), being swollen four groups of later AM/PF microballoons is all in appearance the spherical shape of comparison rule, but but deposits in size
In very big difference, as the ratio of phenolic resin in microballoon constantly increases, reduced trend is presented in the partial size after microspheres swell, this
Also the influence result with monomer ratio in front of 3.2 to dry powder partial size is identical, this is because the polyacrylamide in swelling process
It plays a major role, phenolic resin is then that the bigger substance of rigidity is not susceptible to be swollen, and AM/PF microballoon is just combined with acryloyl
The swellability of amine and the heat resistance of phenolic resin, while meeting the resistance to requirement mildly blocked.By Figure 27 (PF:AM are as follows: Figure 27 a)
6:12；Figure 27 b) 8:12；Figure 27 c) 10:12；Figure 27 d) 12:12) as can be seen that heatproof after four groups of microballoon microscopes under
The presence of complete spherical has not almost been observed, one group of PF:AM=6:12 can only see some irregular tablets, this
It is consistent with the observed result of macroscopic view, it has degraded completely, two groups of microballoons of PF:AM=10:12 and 12:12 have also almost been degraded
Entirely, but the optimization formula of PF:AM=8:12 still has the no complete microballoon of degrading in part after heatproof in solution,
This AM/PF microballoon for also sufficiently demonstrating best monomer ratio has biggish heatproof advantage.
(3) influence of the crosslinking ratio to AM/PF microballoon heat resistance
The experiment of further progress single factors on the basis of optimization formula investigates crosslinking ratio to AM/PF microballoon heatproof
The research of performance changes N in AM/PF microballoon synthesis process, and the ratio of N'- methylene-bisacrylamide is prepared for serial crosslinking
The AM/PF microballoon of ratio, crosslinking ratio are respectively 0%, 0.1%, 0.25%, 0.5%, 0.75%, 1%, by different crosslinking ratios
AM/PF microballoon prepares the solution that mass concentration is 2000mg/L, is encased in the ampoule bottle of 50ml, ampoule bottle is vacuumized
Operation, alcolhol burner sealing after be respectively put into 120 DEG C and 140 DEG C of baking oven, carry out subsequent observation later, to heatproof process into
The heatproof time of each crosslinking ratio AM/PF microballoon is taken pictures and recorded to row, and the results are shown in Table 9.The crosslinking ratio pair it can be seen from table
The influence of the heat resistance of AM/PF microballoon is particularly significant, under the conditions of 120 DEG C and 140 DEG C, when being crosslinked smaller, and crosslinking ratio
The heatproof time for increasing microballoon also increases as, and after crosslinking ratio reaches 0.5%, is further added by the heatproof day of crosslinking ratio AM/PF microballoon
Number is slightly decreased, the results showed that three groups of samples of crosslinking ratio 0.5%, 0.75%, 1% can be well adapted for 120 DEG C of high temperature
The deep profile correction requirement of oil reservoir.And for 140 DEG C of harsh reservoir condition, only best crosslinking ratio (0.5%) AM/PF's is micro-
The heat resistance of ball is just able to satisfy.
The heatproof number of days of 9 microballoon of table
In order to record six groups of AM/PF microballoons that crosslinking ratio is respectively 0%, 0.1%, 0.25%, 0.5%, 0.75%, 1%
Heatproof process at 140 DEG C carries out observation of taking pictures to macrostate of the AM/PF microballoon in ampoule bottle, until in ampoule bottle
Microballoon be degraded to height no longer decline when complete observation, as a result as shown in figure 28.As seen from the figure, crosslinking agent is not added
One group of AM/PF microballoon has apparent difference with other five groups, from 1d is placed until the aqueous solution of degradation microballoon is semi-transparent always
There is not the line of demarcation of microballoon and water in bright state, this is showed also ten clearly demarcated in thermogravimetric test result figure in 4.1
It is aobvious, illustrate that the addition of crosslinking agent has a great impact to AM/PF microballoon.Five group microballoons of the crosslinking ratio from 0.1% to 1%
Heatproof process is substantially consistent, is all that first then swelling is kept a period of time in the swollen state, it is straight that last microballoon starts degradation
To microballoon height no longer decline heatproof experiment terminate.
In order to further study influence of the crosslinking ratio to AM/PF microballoon, using microscope to each crosslinking ratio AM/PF microballoon
Solvent swelling state and degradation state are observed, as a result such as Figure 29 (crosslinking ratio is respectively Figure 29 a) 0%；Figure 29 b) 0.1%；Figure
29c) 0.25%；Figure 29 d) 0.5%；Figure 29 e) 0.75%；Figure 29 f) 1%) and Figure 30 (crosslinking ratio be respectively Figure 29 a) 0%；Figure
29b) 0.1%；Figure 29 c) 0.25%；Figure 29 d) 0.5%；Figure 29 e) 0.75%；Figure 29 f) 1%).After observation discovery microspheres swell
All be more regular spherical shape, be especially not added one group of crosslinking agent can still be maintained spherical state after swelling, this with
The acrylamide microballoon that crosslinking agent is not added is entirely different, and acrylamide microballoon when being not added crosslinking agent is after being dissolved in water under microscope
Any substance is not observed, illustrate to be dissolved in the state that cannot keep spherical after water again immediately but has directly been extended into macromolecule
Chain, even if but it is still regular spherical shape in high temperature aqueous solution that the AM/PF microballoon of crosslinking agent, which is not added, but heatproof number of days compared with
Short, this illustrates that phenolic resin is strictly to play the role of crosslinking agent, but cannot replace handing over again during microballoon preparation
Connection agent is individually worked, and AM/PF microballoon could reach best in heat resistance when only crosslinking agent and phenolic resin are all added
Effect.From Figure 29 it can also be seen that as crosslinking ratio is increasing, partial size after microspheres swell reduces, this also with before 3.2 in
Conclusion be consistent.The state of microballoon after degradation and observation macroscopically also have difference, and the result of Figure 30 illustrates, macroscopically
Think to have degraded under complete sample microscope still it can be seen that having a large amount of microballoon, such as crosslinking ratio is 0.75% and 1%
Two groups of samples obviously there is no degrade completely there are also continue heatproof ability, in general, the more big then AM/PF of crosslinking ratio is micro-
The ability that ball keeps spherical in degradation process is stronger, and the heatproof time for macroscopically showing as microballoon is longer, experimental result explanation
Crosslinking ratio is bigger, and the heat resistance of AM/PF microballoon is usually better.
(4) influence of the oil-water ratio to AM/PF microballoon heat resistance
Influence of the single factors oil-water ratio to AM/PF microballoon heat resistance is investigated, on the basis that original oil-water ratio is 2.5
Upper two set products for being respectively synthesized oil-water ratio again and being 1.5 and 2.0, it is 2000mg/L's that three set products, which are configured to mass fraction,
AM/PF microspheres solution is injected in ampoule bottle, is respectively put into after sealing in 120 DEG C and 140 DEG C of baking oven, is observed daily, when
Microballoon in ampoule bottle is degraded to the heatproof number of days that microballoon is recorded when being no longer changed, and the results are shown in Table 10.Experimental result
Show that the heatproof number of days of the bigger AM/PF microballoon of oil-water ratio is more, this is consistent with the thermogravimetric test result in 4.1, wherein working as oil
100d or more cannot be reached at 120 DEG C and 140 DEG C when water ratio takes 1.5, resistance to temp effect is bad, and oil-water ratio is 2.0 and 2.5
The resistance to temp effects of two groups of samples obviously make moderate progress, 100d or more is attained by 120 DEG C and 140 DEG C, if for resistance to
Warm time requirement be not it is too high, consider from the cost of synthesis, oil-water ratio be 2.0 sample can satisfy requirement completely.
The heatproof number of days of 10 microballoon of table
Observation of taking pictures is carried out in 140 DEG C of heatproof process to the AM/PF microballoon of three groups of difference oil-water ratios, as a result such as Figure 31
Shown, oil-water ratio is respectively: Figure 31 a) 1.5；Figure 31 b) 2.0；Figure 31 c) 2.5.The AM/PF of three groups of oil-water ratios as seen from the figure
The heatproof process of microballoon is roughly the same, but oil-water ratio be 1.5 AM/PF microspheres product swelling rate obviously than other two groups
Fast, when 2d, has been swollen completely substantially.The heat resistance for two groups of microballoons that oil-water ratio is 2.0 and 2.5 is relatively good, wherein oil
Water still maintains highest swelling liquid level in 60d than 2.0, and one group of oil-water ratio 2.5 is also able to maintain highest in 100d
Swelling liquid level, illustrate that oil-water ratio has a great impact really to heat resistance.
Observation to the solvent swelling state and degradation state progress optical microscopy of three groups of microballoons, as a result such as Figure 32 (oil-water ratio
It is respectively: Figure 32 a) 1.5；Figure 32 b) 2.0；Figure 32 c) 2.5) and Figure 33 shown in (oil-water ratio is respectively: Figure 32 a) 1.5；Figure 32 b)
2.0；Figure 32 c) 2.5).Three set products all keep good spherical shape after swelling, and dispersibility is all relatively good.As seen from Figure 33
The form of three groups of microballoons after degradation is substantially similar, is all that dyeing effect is deteriorated, the boundary of microballoon becomes very fuzzy, is no longer
Very regular spherical shape illustrates that the dye radical on phase microballoon after degradation is substantially degraded completely, but there are still heatproof at
Divide and does not degrade.
4.3 AM/PF microballoon heatproof processes are probed into
In order to more intuitively observe the heatproof degradation process of AM/PF microballoon, scanning electron microscope is done to microballoon dry powder first, so
Scanning electron microscopic observation will be carried out after the microspheres solution drying after swelling afterwards, takes the residue of ampoule bottle bottom dry after heatproof
It is also scanned the observation of Electronic Speculum afterwards, three groups of experimental results are respectively as shown in Figure 34, Figure 35 and Figure 36.
As seen from Figure 34, the AM/PF microballoon dry powder of preparation uniformly adheres to many beads, and gradually amplification is single
Find that these small microballoons are not the simple surface for being sticked to big ball after a microballoon, but with entire ball be it is integrated, also
It is to form the surface of protrusion in the later period of microballoon synthesis, this is not observed under an optical microscope.By AM/PF microballoon heatproof
10d carries out microscopical observation after dry again, and the shape of microballoon has occurred that variation, by Figure 35 it is observed that after swelling
AM/PF microballoon be unconventional whole spherical shape, although being not observed after single microballoon is gradually amplified under similar dry powder
Apparent small protrusion, but still it can be found that the short grained presence of microsphere surface, this explanation are resistance in AM/PF microballoon after examining
What is degraded first during temperature is exactly the small protrusion in this part, and it is small that these protrusions are likely to be the AM that the reaction later period individually causes
Ball, these beads are finally closed with the big chou of AM/PF, since the content of phenolic resin in small protrusion is seldom, so high temperature declines
Solution is very fast.Figure 36 be AM/PF microballoon heatproof after substance electromicroscopic photograph, without the ball of microballoon after heatproof
Shape structure, only remaining reticular structure, this illustrates that the original structure of microballoon after degradation is destroyed completely, not the molecular chain degradation of heatproof
It has been dissolved into solution at small molecule fragment, remaining reticular structure may be the higher strand of phenolic resin content.
So speculating that the heatproof process of AM/PF microballoon substantially may be: being the degradation of the raised substance of microsphere surface, Zhi Housui first
The extension microballoon of time be gradually swollen, the polyacrylamide strand inside microballoon starts to degrade, last polyacrylamide drop
Solution completes the phenolic resin reticular structure of only remaining most heatproof.
It is the heatproof process for the AM/PF microballoon that scanning electron microscopic observation arrives above, in order to further prove to heatproof mechanism
Speculate, respectively to AM/PF microsphere powder, is swollen the microballoon of 30d and the substance after heatproof carries out infrared spectrum analysis, as a result
As shown in Figure 37 and Figure 38.Three groups of infrared results compare, and the infrared spectrogram of microsphere powder illustrates AM/PF microballoon while having
There is the characteristic peak of acrylamide to have the characteristic absorption peak of phenolic resin again.Infrared analysis is carried out again after being swollen 30d, is as a result shown
Show compared with pulverulence, the absorption peak of phenolic resin still has, but the absorption peak partial disappearance of acrylamide carbonyl, says
Polyacrylamide strand in bright AM/PF microballoon has occurred that degradation.Finally the substance after heatproof is carried out red
The absorption peak of outer analysis, acrylamide almost disappears, and the carbon skeleton absorption peak of the only phenyl ring in phenolic resin is very bright
Aobvious, this later period polyacrylamide that illustrates to degrade is close to degradable, and Partial digestion, scanning electron microscope sight also has occurred in phenolic resin
Most of final network structure observed all should be phenolic resin.The result of infrared analysis and the result one of scanning electron microscope
It causes, to the supposition of AM/PF microballoon degradation process before further demonstrating.
By the analysis of scanning electron microscope and infrared spectroscopy, heatproof degradation process of the AM/PF microballoon in 140 DEG C of aqueous solutions is big
It causes as shown in figure 39.It is that the small protrusion degradation of microsphere surface becomes smaller first, small protrusion continues degradation until completely disappearing, at this time later
The swelling of AM/PF microballoon has also reached maximum value, and the polyacrylamide strand inside microballoon is decomposed later, polypropylene
The spherical structure of AM/PF microballoon starts to be destroyed after amide degradation to a certain extent, and the spherical structure of last microballoon is broken completely
It is bad, the higher reticular structure of phenolic resin content is only left in the final stage of heatproof, solution.
Claims (1)
1. application of the acrylamide/phenolic resin microspheres in the profile control agent as oilfield polymer flooding；
Acrylamide/the phenolic resin microspheres are prepared according to the method included the following steps:
The aqueous solution of acrylamide, phenolic resin, initiator and crosslinking agent is prepared as water phase, to the oily Xiang Zhongjia containing emulsifier
Enter the water phase, it is reacted up to the acrylamide/phenolic resin microspheres；
The temperature of the reaction is 65 ~ 75 DEG C, and the time is 4 hours；
The mass fraction of emulsifier described in the oil phase is 3 ~ 8%；
The mass ratio of the acrylamide and the phenolic resin is 1:1 ~ 2；
The mass fraction of crosslinking agent described in the aqueous solution is 0 ~ 1%, but is not zero；
The oil is mutually 2.0 ~ 2.5:1 with the volume ratio of the water phase；
Before the water phase is added, the method also includes being mutually passed through the step of nitrogen flooding oxygen to the oil under agitation
Suddenly；
Before the reaction, the method also includes the step of by the oily emulsion emulsifiers being mutually mixed to get with the water phase；
The synthesis condition of the phenolic resin is as follows:
The molar ratio of phenol and formaldehyde is 1:4；
Reaction temperature is 75 DEG C；
Reaction time is 3h.
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| CN112480325B (en) * | 2020-12-02 | 2022-05-27 | 辽宁石油化工大学 | Phenolic resin-acrylamide composite microsphere and preparation method and application thereof |
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| CN102070757A (en) * | 2010-12-20 | 2011-05-25 | 中国石油大学(北京) | Preparation method of water-dispersed phenolic resin |
| CN106089168A (en) * | 2016-06-27 | 2016-11-09 | 烟台智本知识产权运营管理有限公司 | A kind of method of medium to high permeable oil reservoir integral profile control |
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| CN102070757A (en) * | 2010-12-20 | 2011-05-25 | 中国石油大学(北京) | Preparation method of water-dispersed phenolic resin |
| CN106089168A (en) * | 2016-06-27 | 2016-11-09 | 烟台智本知识产权运营管理有限公司 | A kind of method of medium to high permeable oil reservoir integral profile control |
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