CN107868379A - Profile control RPP acid amides microballoon and preparation method thereof - Google Patents
Profile control RPP acid amides microballoon and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of polyacrylamide polymer gel micro-ball of synthesis, mainly solving the technical problems that existing polypropylene amides gel micro-ball expansion rate does not possess the problem of slow swollen feature, the present invention is by using polyacrylamide polymer gel micro-ball, including following construction unit：Acrylamide construction unit, anionic monomer construction unit or cationic monomer construction unit, non-ionic monomer construction unit, crosslinking agent construction unit and modified cellulose construction unit；Wherein, the acrylamide construction unit, anionic monomer construction unit or cationic monomer construction unit, non-ionic monomer construction unit form polymer backbone conformation, the crosslinking agent construction unit forms cross-linked structure with main polymer chain, the modified cellulose construction unit and the mutually interspersed technical scheme for forming network structure of cross-linked structure, preferably solve the problem, go for existing traditional profile control and water plugging technique.
Description
Technical field
The present invention relates to a kind of polyacrylamide polymer gel particle of synthesis, is specifically related to a kind of micron to milli
The polyacrylamide composite gel microballoon of meter ruler cun, can be used in tertiary oil recovery as profile-controlling and plugging agent.
Background technology
Oil is described as " industrial blood ", is one of most important energy of modern industry, but China's oil is external
Interdependency remains high, and is highly detrimental to the long-term energy strategic security of country.The oil field in China is mainly continental deposit oil field,
Anisotropism is serious, and each elephant has been enter into tertiary phase, in early stage oil recovery process substantial amounts of water filling etc. cause oil reservoir
Water content is high, and anisotropism is serious, easily causes injection liquid and scurries into producing well from high permeability formation, reduces oil displacement efficiency etc..Crosslinking is poly-
Compound adjustment liquid stream trend, is played an important role due to that can block high permeability zone in terms of profile control and water plugging.
The machine of high aquifer formation can be effectively blocked with machinery trapping using absorption of the polyacrylamide in porous media
Reason Needham was proposed at first in 1974, has triggered on this basis the gel particle of water-absorbing resin class being used for chemistry tune
Cut open a series of researchs of water blockoff.Studies have shown that gel particle is strong to anisotropism, and moisture content is high, and the oil field deep of macropore is adjusted
Preferable effect is cutd open.Due to having certain deformability after gel particle water swelling, can pass through under certain pressure difference
Displacement enters stratum depths, in stratum depths because strata pressure gradually reduces, expands swell after particle constantly water suction, stagnant
Stay in and macropore is blocked in duct, and then adjust in-place permeability, play a part of deep rock tunneling.
Gel particle has advantages below：1st, gel is formed in synthesizing, cross-linked stable, avoids underground crosslinked system to ore deposit
The shortcomings that hiding condition responsive, adaptability is extensive.2nd, the gel after expanding has certain deformability, can be under certain pressure difference
Deformation passes through duct, into oil deposit deep part.3rd, cross-linked network imparts the preferable heat endurance of gel particle.4th, using technique letter
It is single, it can be used cooperatively with other techniques.
But further improved with the demand of oil field development, inherit the gel particle of conventional water absorbent resins plurality of advantages
Also occur many problems during profile control and water plugging.In the requirement of depth profile control, injecting the initial stage on stratum needs gel
Grain shut-off capacity is weaker, can deform and pass through in duct, and just needs it to play a part of closure after entering stratum depths,
And the degraded with gel network under the conditions of mineral reserve, the shut-off capacity of gel particle gradually fail.Depth profile control requirement
One kind can slowly expand, and even early stage expands smaller, the increased ability of late expansion multiple, and traditional water-absorbing resin class is coagulated
Glue particle is then that expansion early stage is more rapid, and late expansion is slow, does not possess slow swollen this feature, therefore is unfavorable for depth tune
Cut open.
Cellulose is the maximum natural polymer of nature yield, cheap.Simultaneously because ring-type in cellulosic molecule
The presence of structure makes its strand have stronger rigidity, also causes the gel network that with the addition of cellulose to have stronger elasticity,
While it is recognised that, can be progressively under the conditions of acidity, alkalescence, heat, oxygen etc. are a variety of as the cellulose of polysaccharide
Degraded.Therefore, cellulose can be as a kind of one of means of regulation and control gel long-term behaviour.
The content of the invention
One of technical problems to be solved by the invention are that solve existing polypropylene amides gel micro-ball expansion rate not have
Standby the problem of delaying swollen feature.A kind of polyacrylamide polymer gel micro-ball is provided, by introducing cellulose in polyacrylamide
Dual interpenetrating networks are formed in amine gel and ensure intensity in expansion polymer gel microsphere at initial stage, while by cellulose in water
In degraded failure realize gel micro-ball late expansion accelerate effect.
The two of the technical problems to be solved by the invention be to provide it is a kind of solve in one of technical problem polyacrylamide-
The synthesis preparation method of cellulose gel microballoon, using inverse suspension polymerization, azeotropic water removing obtains polyacrylamide-cellulose gel
The dry powder of glue microballoon.
One of to solve the above problems, the technical solution adopted by the present invention is as follows：A kind of polyacrylamide polymer coagulates
Glue microballoon, including following construction unit：Acrylamide construction unit, anionic monomer construction unit or cationic monomer structure list
Member, non-ionic monomer construction unit, crosslinking agent construction unit and modified cellulose construction unit；Wherein, the acrylamide knot
Structure unit, anionic monomer construction unit or cationic monomer construction unit, non-ionic monomer construction unit form polymerization owner
Chain structure, the crosslinking agent construction unit form cross-linked structure with main polymer chain, and the modified cellulose construction unit is with handing over
Connection structure is mutually interspersed to form network structure.
In above-mentioned technical proposal, the polyacrylamide polymer gel micro-ball, count in parts by weight, preferably by comprising
The reaction system of following components react to obtain：
(1) 30-60 parts acrylamide；
(2) 1-50 parts cationic monomer or anionic monomer；
(3) 1-20 parts non-ionic monomer；
(4) 1-5 parts modified cellulose；
(5) 0.01-0.2 parts crosslinking agent.
In above-mentioned technical proposal, described anionic monomer preferably be selected from acrylic acid, methacrylic acid, sodium vinyl sulfonate,
To at least one of vinylbenzenesulfonic acid, ALS, 2- acrylamide-2-methylpro panesulfonic acid sodium；It is described sun from
Sub- monomer preferably be selected from MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, 2- acrylamido -2- trimethoxysilyl propyl methacrylates ammonium chloride,
In dimethyl ethyl allyl ammonium chloride, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac at least
It is a kind of.
In above-mentioned technical proposal, described non-ionic monomer preferably is selected from Methacrylamide, DMAA, diethyl
Base acrylamide, NMA, dimethylaminoethyl methacrylate, vinyl pyrrolidone, tert-butyl group acryloyl
At least one of amine, N-isopropylacrylamide.
In above-mentioned technical proposal, described crosslinking agent preferably is selected from, to vinyl benzene, N, N '-methylene-bisacrylamide, gathering
At least one of ethylene glycol diacrylate, N, N '-penylene BMI, pentaerythritol triacrylate.
Modified cellulose described in above-mentioned technical proposal preferably is selected from hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl
At least one of cellulose, hydroxypropyl methyl cellulose.
In above-mentioned technical proposal, described reaction system further preferably includes：
(6) 0.0001-0.0005 composite initiators；
(7) 30-80 parts deionized water；
(8) 100-200 parts oil solvent；
(9) 2-15 parts emulsifying agent；
(10) 0.01~0.3 parts of disodium ethylene diamine tetraacetate.
In above-mentioned technical proposal, described emulsifying agent preferably is selected from sorbitan ester shown in formula (I), shown in formula (II)
At least one of APES shown in AEO, formula (III)：
In formula, a+b+c+d is equal to 20,40,60,80；R1、R2It is independently selected from C1-C16Straight or branched alkyl,
E, f is respectively and independently selected between 5-80.
In above-mentioned technical proposal, described oil solvent is selected from least one of aliphatic hydrocarbon, mineral oil or vegetable oil；It is described
Aliphatic hydrocarbon be selected from n-hexane, hexamethylene, heptane, at least one of octane.Described mineral oil be selected from white oil (3#, 5#,
7#, 11#, 15#, 18#), diesel oil, kerosene, at least one of atoleine.Described vegetable oil is selected from peanut oil, soya-bean oil, Asia
At least one of sesame oil, castor oil, rape seed oil, olive oil.
In above-mentioned technical proposal, by accounting for based on the percentage of reaction system weight, described composite initiator preferably include with
Lower component：
(a) 0.001~0.3% persulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide；
(b) 0.001~0.3% sulphite, acid sulphite, thiosulfate；
(c) 0.001~0.5% tetramethylethylenediamine, dimethyl-ethylenediamine or ethylenediamine
(d) 0.002~0.3% azo compound.
In above-mentioned technical proposal, described azo compound preferably is selected from azodiisobutyronitrile, AMBN, azo
Two different heptonitriles, azo-bis-iso-dimethyl, azo diisobutyl amidine hydrochloride, 2,2 '-azo [2- (2- imidazoline -2- bases)
Propane] dihydrochloride, the own nitrile of azo two (2,5- dimethyl -6- carboxyls), at least one in 4,4 '-azo two (4- cyanopentanoic acids)
Kind.
For solve the above problems two, the technical solution adopted by the present invention is as follows：A kind of polyacrylamide polymer coagulates
The preparation method of glue microballoon, comprises the following steps：
1) by the desired amount of acrylamide monomer, the moon or cationic monomer, non-ionic monomer, modified cellulose, crosslinking agent
It is soluble in water respectively, it is well mixed, adjusts pH value=7-12, be configured to the aqueous solution；
2) emulsifying agent is added in oil phase and be uniformly dissolved, added in reactor；
3) under 300-500r/min stir speed (S.S.), the aqueous solution is added in reactor, with the oil phase dissolved with emulsifying agent
Mix, lead to inert gas deoxygenation, water-bath temperature control is at 20-35 DEG C；
4) different component in composite initiator is each configured to the aqueous solution, be then added dropwise in reactor, speed is added dropwise
Degree is not more than 1ml/min, persistently leads to inert gas and stirs；
5) first reacted under 20-35 DEG C DEG C of water-bath, then again warming-in-water to 50-60 DEG C reaction；
6) reaction product is distilled under agitation, azeotropic water removing；
7) reaction product after water removal is removed into degreaser, is washed out, dries, obtained described polyacrylamide and birds of the same feather flock together
Compound gel micro-ball.
The present invention's is crucial in the cellulose chain by introducing rigid molecule in the gel micro-ball of polyacrylamide, shape
Into a kind of natural polymer cellulose and synthesis high polymer polyacrylamide IPN dual-network, the increase of network density will suppress
The expansion rate at initial stage of gel micro-ball, with the extension of Bulking Time, meta-alkalescence of the cellulose in high temperature, high salt and practical application
Under environment, degraded aggravation, gel network is released, and expansion accelerates, and occurs delaying swollen phenomenon.
Using technical scheme, obtained polyacrylamide polymer gel micro-ball is swollen after expansion one week
Swollen multiple is only 9.2 times, expansion one month after expansion multiple be 21.7 times, and Bulking Time be up to March after, expansion still after
It is continuous, have and significantly delay swollen performance, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
By 40 parts of acrylamides, 4 parts of 2- acrylamide-2-methylpro panesulfonic acid sodium, 2 parts of N-tert-butyl acrylamides, 2 parts of hydroxyls
Methylcellulose, 0.05 part of crosslinking agent, 0.02 part of disodium ethylene diamine tetraacetate, which is dissolved in 60 parts of water, is configured to the aqueous solution.By 5 parts
Emulsifying agent, which is dissolved in hexamethylene, is configured to oil-phase solution.Oil-phase solution is added in reactor, stir speed (S.S.) 500r/min, will be anti-
Answer the system aqueous solution to add in reactor, lead to inert gas shielding, 30 DEG C of bath temperature.After persistently stirring 30min, draw compound
Hair system is added dropwise in reactor respectively,.After sustained response 2 hours, bath temperature is warming up to 55 DEG C, reacted 1 hour.
Transfer reaction system to be mounted with stirring, water knockout drum and condensation reflux unit three-necked bottle in, the azeotropic at 80 DEG C
Water removal, after the volume of water obtained by water knockout drum is more than 80% of water volume in system, stop distillation, take out reactant, vacuum is taken out
Filter, dried after being washed twice respectively with hexamethylene and ethanol and obtain polymer gel microsphere.
By the gained sample dispersion of embodiment 1 in hexamethylene, stir 1 hour, its particle diameter is determined after ultrasonic 10min, as
The initial particle of microballoon.It is scattered under the gained sample of embodiment 1 is stirred in the simulated formation water of 30000mg/L salinities, in
Different time is expanded respectively at 80 DEG C, and it is as shown in table 1 to determine its expansion multiple.
As 1# show the gained sample of embodiment 1 at 80 DEG C in table 1, aging different time in 30000mg/L salt solution
Expansion multiple, it can be seen that after expansion one week, expansion multiple is only 9.2 times, and expansion multiple is 21.7 after expanding one month
Times, and after Bulking Time is up to March, expansion is still continuing.With polyacrylamide network gel microballoon simple in comparative example 1
Compared after 1 week close to maximum swelling multiple, have and significantly delay swollen performance.
【Embodiment 2】
By 40 parts of acrylamides, 4 parts of 2- acrylamide-2-methylpro panesulfonic acid sodium, 2 parts of N-tert-butyl acrylamides, 2 parts of hydroxyls
Ethyl cellulose, 0.05 part of crosslinking agent, 0.02 part of disodium ethylene diamine tetraacetate, which is dissolved in 60 parts of water, is configured to the aqueous solution.By 5 parts
Emulsifying agent, which is dissolved in hexamethylene, is configured to oil-phase solution.Oil-phase solution is added in reactor, stir speed (S.S.) 500r/min, will be anti-
Answer the system aqueous solution to add in reactor, lead to inert gas shielding, 30 DEG C of bath temperature.After persistently stirring 30min, draw compound
Hair system is added dropwise in reactor respectively,.After sustained response 2 hours, bath temperature is warming up to 55 DEG C, reacted 1 hour.
Transfer reaction system to be mounted with stirring, water knockout drum and condensation reflux unit three-necked bottle in, the azeotropic at 80 DEG C
Water removal, after the volume of water obtained by water knockout drum is more than 80% of water volume in system, stop distillation, take out reactant, vacuum is taken out
Filter, is dried for standby after being washed twice respectively with hexamethylene and ethanol.
By the gained sample dispersion of embodiment 2 in hexamethylene, stir 1 hour, its particle diameter is determined after ultrasonic 10min, as
The initial particle of microballoon.It is scattered under the gained sample of embodiment 2 is stirred in the simulated formation water of 30000mg/L salinities, in
Different time is expanded respectively at 80 DEG C, and it is as shown in table 1 to determine its expansion multiple.
As 2# show the gained sample of embodiment 2 at 80 DEG C in table 1, aging different time in 30000mg/L salt solution
Expansion multiple, it can be seen that after expansion one week, expansion multiple is only 9.4 times, and expansion multiple is 23.6 after expanding one month
Times, and after Bulking Time is up to March, expansion is still continuing.With polyacrylamide network gel microballoon simple in comparative example 1
Compared after 1 week close to maximum swelling multiple, have and significantly delay swollen performance.
【Embodiment 3】
By 40 parts of acrylamides, 4 parts of 2- acrylamide-2-methylpro panesulfonic acid sodium, 2 parts of N-tert-butyl acrylamides, 2 parts of hydroxyls
Propyl methocel, 0.05 part of crosslinking agent, 0.02 part of disodium ethylene diamine tetraacetate, which is dissolved in 60 parts of water, is configured to the aqueous solution.Will
5 parts of emulsifying agents are dissolved in hexamethylene and are configured to oil-phase solution.Oil-phase solution is added in reactor, stir speed (S.S.) 500r/min,
The reaction system aqueous solution is added in reactor, leads to inert gas shielding, 30 DEG C of bath temperature., will be multiple after persistently stirring 30min
Initiation system is closed to be added dropwise in reactor respectively.After sustained response 2 hours, bath temperature is warming up to 55 DEG C, reacted 1 hour.
Transfer reaction system to be mounted with stirring, water knockout drum and condensation reflux unit three-necked bottle in, the azeotropic at 80 DEG C
Water removal, after the volume of water obtained by water knockout drum is more than 80% of water volume in system, stop distillation, take out reactant, vacuum is taken out
Filter, is dried for standby after being washed twice respectively with hexamethylene and ethanol.
By the gained sample dispersion of embodiment 3 in hexamethylene, stir 1 hour, its particle diameter is determined after ultrasonic 10min, as
The initial particle of microballoon.It is scattered under the gained sample of embodiment 3 is stirred in the simulated formation water of 30000mg/L salinities, in
Different time is expanded respectively at 80 DEG C, and it is as shown in table 1 to determine its expansion multiple.
As 3# show the gained sample of embodiment 3 at 80 DEG C in table 1, aging different time in 30000mg/L salt solution
Expansion multiple, it can be seen that after expansion one week, expansion multiple is only 8.8 times, and expansion multiple is 22.4 after expanding one month
Times, and after Bulking Time is up to March, expansion is still continuing.With polyacrylamide network gel microballoon simple in comparative example 1
Compared after 1 week close to maximum swelling multiple, have and significantly delay swollen performance.Simultaneously because the modification employed in embodiment 3
Cellulose is hydroxypropyl methyl cellulose, and stability is slightly good compared to the cellulose employed in Examples 1 and 2, therefore can see
Go out, the expansion multiple after one week is minimum, and it is the most obvious to delay swollen phenomenon.
【Embodiment 4】
By 40 parts of acrylamides, 4 parts of 2- acrylamide-2-methylpro panesulfonic acid sodium, 2 parts of N-tert-butyl acrylamides, 2 parts of carboxylics
Methylcellulose, 0.05 part of crosslinking agent, 0.02 part of disodium ethylene diamine tetraacetate, which is dissolved in 60 parts of water, is configured to the aqueous solution.By 5 parts
Emulsifying agent, which is dissolved in hexamethylene, is configured to oil-phase solution.Oil-phase solution is added in reactor, stir speed (S.S.) 500r/min, will be anti-
Answer the system aqueous solution to add in reactor, lead to inert gas shielding, 30 DEG C of bath temperature.After persistently stirring 30min, draw compound
Hair system is added dropwise in reactor respectively.After sustained response 2 hours, bath temperature is warming up to 55 DEG C, reacted 1 hour.
Transfer reaction system to be mounted with stirring, water knockout drum and condensation reflux unit three-necked bottle in, the azeotropic at 80 DEG C
Water removal, after the volume of water obtained by water knockout drum is more than 80% of water volume in system, stop distillation, take out reactant, vacuum is taken out
Filter, is dried for standby after being washed twice respectively with hexamethylene and ethanol.
By the gained sample dispersion of embodiment 4 in hexamethylene, stir 1 hour, its particle diameter is determined after ultrasonic 10min, as
The initial particle of microballoon.It is scattered under the gained sample of embodiment 4 is stirred in the simulated formation water of 30000mg/L salinities, in
Different time is expanded respectively at 80 DEG C, and it is as shown in table 1 to determine its expansion multiple.
As 4# show the gained sample of embodiment 4 at 80 DEG C in table 1, aging different time in 30000mg/L salt solution
Expansion multiple, it can be seen that after expansion one week, expansion multiple is only 17 times, and expansion multiple is 24.8 times after expanding one month,
And after Bulking Time is up to March, expansion is still continuing.With polyacrylamide network gel microballoon simple in comparative example 11
Compared after week close to maximum swelling multiple, have and significantly delay swollen performance.But it can also be seen that due to selected in embodiment 4
Modified cellulose it is best for hydrophilicity, degraded in water also fast compared with cellulose selected by preceding embodiment, therefore embodiment 4
The expansion multiple at initial stage of gained sample is most fast, but compared to without for the comparative example for adding modified cellulose, is still had
Significantly delay swollen phenomenon.
【Comparative example 1】
By 40 parts of acrylamides, 4 parts of 2- acrylamide-2-methylpro panesulfonic acid sodium, 2 parts of N-tert-butyl acrylamides, 0.05
Part crosslinking agent, 0.02 part of disodium ethylene diamine tetraacetate, which is dissolved in 60 parts of water, is configured to the aqueous solution.5 parts of emulsifying agents are dissolved in hexamethylene
In be configured to oil-phase solution.Oil-phase solution is added in reactor, stir speed (S.S.) 500r/min, the reaction system aqueous solution added
In reactor, lead to inert gas shielding, 30 DEG C of bath temperature.After persistently stirring 30min, composite initiation system is added dropwise to respectively
In reactor, rate of addition is controlled in 0.2-1ml/min.After sustained response 2 hours, bath temperature is warming up to 55 DEG C, reaction 1
Hour.
Transfer reaction system to be mounted with stirring, water knockout drum and condensation reflux unit three-necked bottle in, the azeotropic at 80 DEG C
Water removal, after the volume of water obtained by water knockout drum is more than 80% of water volume in system, stop distillation, take out reactant, vacuum is taken out
Filter, is dried for standby after being washed twice respectively with hexamethylene and ethanol.
By the gained sample dispersion of comparative example 1 in hexamethylene, stir 1 hour, its particle diameter is determined after ultrasonic 10min, as
The initial particle of microballoon.It is scattered under the gained sample of comparative example 1 is stirred in the simulated formation water of 30000mg/L salinities, in
Different time is expanded respectively at 80 DEG C, and it is as shown in table 1 to determine its expansion multiple.
As 5# show the gained sample of comparative example 1 at 80 DEG C in table 1, aging different time in 30000mg/L salt solution
Expansion multiple, it can be seen that expansion multiple has just reached 25.2 times after one day, and i.e. convergence balance is swollen after one week for expansion
Swollen multiple, increased unobvious after one week to three months expansion multiples, and particle diameter caused by a small amount of aquation degraded has occurred in the later stage subtracts
Small phenomenon.Initial stage, expansion multiple was too fast, unslow swollen ability.
【Comparative example 2】
By 40 parts of acrylamides, 6 parts of 2- acrylamide-2-methylpro panesulfonic acid sodium, 2 parts of hydroxymethyl celluloses, 0.05 part
Crosslinking agent, 0.02 part of disodium ethylene diamine tetraacetate, which is dissolved in 60 parts of water, is configured to the aqueous solution.5 parts of emulsifying agents are dissolved in hexamethylene
It is configured to oil-phase solution.Oil-phase solution is added in reactor, stir speed (S.S.) 500r/min, the reaction system aqueous solution added anti-
Answer in kettle, lead to inert gas shielding, 30 DEG C of bath temperature.After persistently stirring 30min, composite initiation system is added dropwise to respectively anti-
Answer in kettle,.After sustained response 2 hours, bath temperature is warming up to 55 DEG C, reacted 1 hour.
Transfer reaction system to be mounted with stirring, water knockout drum and condensation reflux unit three-necked bottle in, the azeotropic at 80 DEG C
Water removal, after the volume of water obtained by water knockout drum is more than 80% of water volume in system, stop distillation, take out reactant, vacuum is taken out
Filter, dried after being washed twice respectively with hexamethylene and ethanol and obtain polymer gel microsphere.
By the gained sample dispersion of comparative example 2 in hexamethylene, stir 1 hour, its particle diameter is determined after ultrasonic 10min, as
The initial particle of microballoon.It is scattered under the gained sample of comparative example 2 is stirred in the simulated formation water of 30000mg/L salinities, in
Different time is expanded respectively at 80 DEG C, and it is as shown in table 1 to determine its expansion multiple.
As 6# show the gained sample of comparative example 2 at 80 DEG C in table 1, aging different time in 30000mg/L salt solution
Expansion multiple, it can be seen that after non-ionic monomer is substituted with ion monomer completely, the enhancing of gel network hydrophilicity, initial stage
Expansion is very fast, expands and is occurring mainly in first day, late expansion unobvious, does not delay swollen phenomenon, while further hydration is very fast,
Expansion multiple reduces.
【Comparative example 3】
By 40 parts of acrylamides, 6 parts of N-tert-butyl acrylamides, 2 parts of hydroxymethyl celluloses, 0.05 part of crosslinking agent, 0.02 part
Disodium ethylene diamine tetraacetate, which is dissolved in 60 parts of water, is configured to the aqueous solution.5 parts of emulsifying agents are dissolved in hexamethylene to be configured to oil phase molten
Liquid.Oil-phase solution is added in reactor, stir speed (S.S.) 500r/min, the reaction system aqueous solution is added in reactor, led to lazy
Property gas shield, 30 DEG C of bath temperature.After persistently stirring 30min, composite initiation system is added dropwise in reactor respectively,.Hold
After continuous reaction 2 hours, bath temperature is warming up to 55 DEG C, reacted 1 hour.
Transfer reaction system to be mounted with stirring, water knockout drum and condensation reflux unit three-necked bottle in, the azeotropic at 80 DEG C
Water removal, after the volume of water obtained by water knockout drum is more than 80% of water volume in system, stop distillation, take out reactant, vacuum is taken out
Filter, dried after being washed twice respectively with hexamethylene and ethanol and obtain polymer gel microsphere.
By the gained sample dispersion of comparative example 3 in hexamethylene, stir 1 hour, its particle diameter is determined after ultrasonic 10min, as
The initial particle of microballoon.It is scattered under the gained sample of comparative example 3 is stirred in the simulated formation water of 30000mg/L salinities, in
Different time is expanded respectively at 80 DEG C, and it is as shown in table 1 to determine its expansion multiple.
As 7# show the gained sample of comparative example 3 at 80 DEG C in table 1, aging different time in 30000mg/L salt solution
Expansion multiple, it can be seen that after ion monomer is substituted with non-ionic monomer completely, gel network hydrophilicity significantly drops
Low, ion concentration difference, which reduces, inside and outside gel network causes the expansion multiple of final gel particle relatively low, and expansion multiple is still after 90 days
Be so minimum, and gel is without significantly delaying swollen phenomenon, main expansion multiple appears in expansion initial stage, the change of late expansion multiple
Change little.
The embodiment of table 1 and comparative sample capabilities list
Claims (10)
1. a kind of polyacrylamide polymer gel micro-ball, including following construction unit：Acrylamide construction unit, anion
Monomeric building blocks or cationic monomer construction unit, non-ionic monomer construction unit, crosslinking agent construction unit and modified fibre
Plain construction unit；Wherein, the acrylamide construction unit, anionic monomer construction unit or cationic monomer construction unit,
Non-ionic monomer construction unit forms polymer backbone conformation, and the crosslinking agent construction unit forms crosslinking knot with main polymer chain
Structure, the modified cellulose construction unit mutually interts with cross-linked structure forms network structure.
2. polyacrylamide polymer gel micro-ball according to claim 1, it is characterised in that the polyacrylamide
Birds of the same feather flock together compound gel micro-ball, count in parts by weight, the reaction system of the following components included by wherein synthesizing formula reacts to obtain：
(1) 30-60 parts acrylamide；
(2) 1-50 parts cationic monomer or anionic monomer；
(3) 1-20 parts non-ionic monomer；
(4) 1-5 parts modified cellulose；
(5) 0.01-0.2 parts crosslinking agent.
3. polyacrylamide polymer gel micro-ball according to claim 1 or 2, it is characterised in that described anion
Monomer be selected from acrylic acid, methacrylic acid, sodium vinyl sulfonate, to vinylbenzenesulfonic acid, ALS, 2- acrylamides
At least one of base -2- methyl propane sulfonic acid sodium；Described cationic monomer is selected from methylacryoyloxyethyl trimethyl ammonia chloride
Ammonium, 2- acrylamido -2- trimethoxysilyl propyl methacrylates ammonium chloride, dimethyl ethyl allyl ammonium chloride, dimethyl diallyl
At least one of ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac；Described non-ionic monomer be selected from Methacrylamide,
DMAA, acrylamide, NMA, dimethylaminoethyl methacrylate, vinylpyridine
At least one of pyrrolidone.
4. polyacrylamide polymer gel micro-ball according to claim 1 or 2, it is characterised in that described crosslinking agent
Selected to vinyl benzene, N, N '-methylene-bisacrylamide, polyethyleneglycol diacrylate, N, a N '-penylene bismaleimide
At least one of amine, pentaerythritol triacrylate.
5. polyacrylamide polymer gel micro-ball according to claim 1 or 2, it is characterised in that described is modified fine
Dimension element is selected from least one of hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose.
6. polyacrylamide polymer gel micro-ball according to claim 2, it is characterised in that described reaction system
Also include：
(6) 0.0001-0.0005 composite initiators；
(7) 30-80 parts deionized water；
(8) 100-200 parts oil solvent；
(9) 2-15 parts emulsifying agent；
(10) 0.01~0.3 parts of disodium ethylene diamine tetraacetate.
7. polyacrylamide polymer gel micro-ball according to claim 6, it is characterised in that described emulsifying agent choosing
From the sorbitan ester shown in formula (I), the AEO shown in formula (II), the alkyl phenol polyoxy shown in formula (III)
At least one of vinethene：
In formula, a+b+c+d is equal to 20,40,60 or 80；R1、R2It is independently selected from C1-C16Straight or branched alkyl；E=5
~80, f=5-80.
8. polyacrylamide polymer gel micro-ball according to claim 6, it is characterised in that described compound initiation
Agent includes following components：
(a) 0.001~0.3% persulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide；
(b) 0.001~0.3% sulphite, acid sulphite, thiosulfate；
(c) 0.001~0.5% tetramethylethylenediamine, dimethyl-ethylenediamine or ethylenediamine
(d) 0.002~0.3% azo compound.
9. polyacrylamide polymer gel micro-ball according to claim 8, it is characterised in that described azo
Compound is selected from azodiisobutyronitrile, AMBN, ABVN, azo-bis-iso-dimethyl, the isobutyl of azo two
Base amidine hydrochloride, 2,2 '-azo [2- (2- imidazoline -2- bases) propane] dihydrochloride, azo two (2,5- dimethyl -6- carboxyls)
At least one of own nitrile, 4,4 '-azo two (4- cyanopentanoic acids).
10. a kind of preparation method of any described polyacrylamide polymer gel micro-ball of claim 1~9, including with
Lower step：
1) the desired amount of acrylamide monomer, the moon or cationic monomer, non-ionic monomer, modified cellulose, crosslinking agent are distinguished
It is soluble in water, it is well mixed, adjusts pH value=7-12, be configured to the aqueous solution；
2) emulsifying agent is added in oil phase and be uniformly dissolved, added in reactor；
3) under 300-500r/min stir speed (S.S.), the aqueous solution is added in reactor, mixed with the oil phase dissolved with emulsifying agent
Stirring, lead to inert gas deoxygenation, water-bath temperature control is at 20-35 DEG C；
4) different component in composite initiator is each configured to the aqueous solution, be then added dropwise in reactor, rate of addition is not
More than 1ml/min, persistently lead to inert gas and stir；
5) first reacted under 20-35 DEG C DEG C of water-bath, then again warming-in-water to 50-60 DEG C reaction；
6) reaction product is distilled under agitation, azeotropic water removing；
7) reaction product after water removal is removed into degreaser, is washed out, dries, obtain described polyacrylamide polymer
Gel micro-ball.
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| CN110724508A (en) * | 2018-07-16 | 2020-01-24 | 长江大学 | Fiber composite gel particle bridging agent for fractured reservoir and preparation method thereof |
| CN111909672A (en) * | 2020-08-10 | 2020-11-10 | 山东达源环保工程有限公司 | Preparation method of carboxymethyl cellulose modified profile control water shutoff agent |
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