CN1008442B - Process for manufacturing inverse microlatices of hydrosoluble copolymers - Google Patents
Process for manufacturing inverse microlatices of hydrosoluble copolymersInfo
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- CN1008442B CN1008442B CN 85104912 CN85104912A CN1008442B CN 1008442 B CN1008442 B CN 1008442B CN 85104912 CN85104912 CN 85104912 CN 85104912 A CN85104912 A CN 85104912A CN 1008442 B CN1008442 B CN 1008442B
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Abstract
The present invention relates to a novel method for preparing reversible micro latex of water soluble copolymers through copolymerization in reversible micro emulsion, wherein the reversible micro emulsion is prepared by mixing a water phase containing water soluble monomers to be copolymerized, an organic phase and a non-ionic surface active agent or a non-ionic surface active agent mixture, and the hydrophile-lipophile balance value of the non-ionic surface active agent or the mixture is from 8 to 9. The obtained micro latex can be diluted by water to form a thickening liquid which can be used for improving the extraction of hydrocarbons from oil strata and particularly used in a method for enhancing the quantity of petroleum extraction or preventing water from flowing into a production well.
Description
The present invention relates in reversible microemulsion, the interpolymerization by at least two kinds of water-soluble vinyl monomers prepares the method for reversible fine latex and the reversible fine latex that makes with this method.
The present invention also is the application that is used for improving the viscous water solution of hydrocarbon recovery about these reversible latex in preparation.
Energy dilemma has caused developing various exploration methods, is present in the oil of the maximum in oil field with extraction.In the whole bag of tricks of being considered, one of them is a technology of reservoir sweep, and this technology is to inject salt solution to flow out from the blowhole of adsorbing it to order about oil.Yet the difference between oil and the water aspect mobile greatly reduces the effect of this method.As everyone knows, come the multiviscosisty injection water to improve this technology with polyacrylamide, acrylic amide-acrylic sodium salt copolymer or these water-soluble polymerss of polyose as partial hydrolysis.
On the other hand, have been found that the aqueous solution with the polymkeric substance multiviscosisty injects oil well, gather simultaneously water and oil fully limit the generation of water, but do not change the produced quantity of oil.Yet under the actual condition of using on the oil field, the use of water-soluble polymers usually is a thorny operation.In fact, the processing of this powder of polyacrylamide, storage and dissolving also some problem can occur, particularly because such powder moisture absorption gas forms the agglomerates structure, as want spended time is then wanted in its dissolving.
In view of this reason, the new method of some control water-soluble polymerss has been proposed, particularly handle with reversible latex, have all advantages relevant in general with liquid treatment.In this respect, United States Patent (USP) 3,284,393,3,624,019,3,826,771,4,022,731, disclosed German patent application DE-A-2,554,082 and English Patent 2,030,578 very valuable.
From the disclosed data of these application documents, this tensio-active agent usually is to be selected from the low nonionogenic tenside of hydrophile-lipophile balance value (HLB) so that a kind of water-in-oil emulsion to be provided, and this nonionogenic tenside generally is made up of pure monoesters of oleic acid sorb (sugar) or the pure monoesters of stearic acid sorb (sugar).On the other hand, also report some hydrophile-lipophile balance value higher surface activity agent, also be easy to form water-in-oil emulsion (French Patent 2,245,671).
Yet the reversible latex that makes according to art methods has different shortcomings, particularly its unstable, this unstable causes very strong sedimentation trend, but also cause when they are soluble in the aqueous phase, promptly settled inverse process needs strong and careful shearing.
Recently, the suggestion of the reversible fine latex of the water-soluble polymers that stability in use is improved has put forward (french patent application 2,524,895), and it is by positively charged ion or anion surfactant preparation.
Now found a kind of novel method for preparing reversible fine latex, this fine latex prepares with a certain proportion of nonionogenic tenside, and it can make the content of multipolymer increase.Reversible fine latex by the prepared water solubility copolymer of the present invention is stable and transparent.In view of will be formed for improving the thickening fluid that oilfield exploitation is used with such fine latex, this just seems especially important.
And the fine latex for preparing by method of the present invention has it from the reversible advantage.
The method that the present invention prepares reversible fine latex is generally limited by the following step;
(a), preparation water-in-oil-type microemulsion (stable and transparent), its method is to mix following material:
(ⅰ) with (ⅱ) the Acrylic Acid Monomer aqueous solution of copolymerization;
(ⅱ) contain a kind of oil phase of hydrocarbon liquid at least;
(ⅲ) at least in the presence of a kind of nonionogenic tenside, the scope of the hydrophile-lipophile balance value of its non-ionic surface active be 8-11(when using surfactant mixtures, its hydrophile-lipophile balance value will be paid attention to.）
(b), the reversible microemulsion that makes of (a) step is remained under the polymerizing condition, until polymerization fully and till generating stable, transparent, the reversible fine latex of high-molecular weight (what is called transparent also mean translucent).
We remember that emulsion is a kind of biphase, muddy and unsettled medium.Under agitation observe particle, no matter be dispersed in the water or or be dispersed in that its granular size mean value is micron-sized in the oil, distribution range is very wide.When making the emulsion polymerization, this polymer dispersed is in big emulsion droplet (the about 1-10 micron of diameter) and little emulsifying agent micelle (the about 5-10 millimicron of diameter).
Also can form microemulsion by two kinds of immiscible each other liquid and tensio-active agent, but opposite with above-mentioned milk sap, need not to be provided with energy, this mixture that each composition forms is a stable on a kind of transparent or semitransparent thermodynamics.
In the prescription of the reversible microemulsion that preparation fine latex of the present invention is used, liquid phase contains two kinds of water soluble propene's acid mono at least: be acrylamide and/or Methacrylamide on the one hand; On the other hand, be the another kind of Acrylic Acid Monomer that is selected from vinylformic acid, methacrylic acid and these sour an alkali metal salts at least.In the Acrylic Acid Monomer mixture, by weight, the content range of second kind of Acrylic Acid Monomer is between 15-60%, and quantity is in the scope of 20-45% mostly.
In order to obtain the reversible microemulsion, usually need to adopt some special conditionss, its significant parameter is as follows: the character of the hydrophile-lipophile balance value of surfactant concentrations, tensio-active agent or surfactant mixture, temperature, organic phase and the composition of water.
By weight, the monomer content of this water is generally 20-80%, and that usual employing is 30-70%.
In general, the pH value scope of monomer solution is 8-13, and favourable scope then is 9-11.
The selection of organic phase has remarkably influenced for obtaining the required minimum surface surfactant concentration of microemulsion.This class organic phase can be made up of the mixture of hydrocarbon or hydro carbons, in order to make reversible microemulsion a cheap prescription (lower surfactant concentration) is arranged, and optimum organic phase is isoparaffin or its mixture.
The weight ratio of water and organic phase (hydrocarbon) should be high as much as possible, obtains the high fine latex of a multipolymer content like this after interpolymerization is finished.In fact this ratio range for example is 0.5-3/1; The ratio of usually choosing is near 2/1.
Should select one or more tensio-active agents from such angle, that be exactly its hydrophile-lipophile balance value (HLB) scope be 8-10.In fact, if exceed this scope, or can not obtain reversible microemulsion, perhaps need a large amount of tensio-active agents, this is that an economic means institute is unallowed.In addition, in the hydrophile-lipophile balance value scope of determining like this, surfactant content must be enough to obtain reversible microemulsion.Surfactant concentration is too low, and resulting reversible latex is similar to the milk sap of prior art, and this is not a content of the present invention.
In the hydrophile-lipophile balance value scope, the ratio of surfactant concentrations in each composition of littleization liquid preferably be higher than the following institute that establishes an equation that determines by experiment be similar to the value Y(that stipulates by weight % count):
Y＝5.8X
2-110X+534
Wherein X is the hydrophile-lipophile balance value of tensio-active agent or surfactant mixture.
The accompanying drawing simple declaration
What accompanying drawing was represented is a curve, the relation of this curve representation surfactant concentration and HLB value (hydrophile-lipophile balance value).On figure, show preferable range of the present invention with hachure.
As for the upper limit of surfactant concentration, from considering economically, preferably with its concentration limit at below 25% of each composition weight of reversible micro emulsion.
In view of in the presence of non-ionic surface active agent, reversible microemulsion, must carefully be controlled for the temperature of mixture when the reversible microemulsion of preparation the sensitiveness of temperature. When the concentration of surfactant approaches when obtaining the required least concentration of reversible micro emulsion, the impact of this temperature is bigger.
In order to reduce the content of required surfactant, temperature to reversible emulsion stability Impact is restricted to minimum limit, should carry out under such temperature as far as possible when the preparation reversible emulsion, and this temperature will be close to the selected value of copolymerisation as far as possible.
The water soluble propene's acid monomers that is present in the above-mentioned reversible micro emulsion is to carry out polymerization by photochemical action or heat effect: this method is formed by photochemical initiation copolymerisation (for example ultraviolet ray irradiation) or by means of free radical generating agent heat initiation copolymerisation, its free radical generating agent is hydrophobic such as azodiisobutyronitrile, or hydrophilic as crossing (two) potassium sulfate.
During with photochemical initiation, copolymerisation is carried out very fast, for example in minutes quantitatively carries out, and causes generating stable and transparent fine latex, and its micelle radius is 20-40 millimicron magnitude, and micelle radius distribution narrow range.
Can measure the particle size of the gel that is scattered in the reversible fine latex of the present invention with the quasi-elastic light scattering method. The light source of light scattering device is made up of the spectrum physics argon ion laser that operates under 488 millimicrons, derive the time correlation function of scattering strength with the digital correlation Functional Analysis instrument in 72 roads, the intensity related data is processed with accumulative, has obtained the average attenuation rate＜Γ of variance V and correlation function-1, V can measure this attenuation rate and distribute amplitude, and its value can be drawn by following formula:
V＝（<Γ>
2<Γ
2>）/<Γ>
2
Wherein,＜Γ2It is the second distribution moments number.
For low polydispersity copolymer solution, variance V(first approximation) relevant with polydispersity index, the molecular number of the weight/mean molecule quantity of polydispersity index MW/Mn(mean molecule quantity) represent with following relational expression:
MW/Mn＝1+4V
Prepared molecular weight of copolymer depends on the temperature of copolymerisation to a great extent. For the reversible fine latex that specify to be used for improves oil extraction, when hope obtained the very high polymer of molecular weight, preferred temperature should be less than about or approximate 30 ℃.
Method of the present invention provides a kind of stable, transparent reversible fine latex, the content height of its water solubility copolymer (being the 20-35 % by weight). Preparation is reversible in the presence of non-ionic surface active agent Fine latex and opposite in order to the reversible micro emulsion for preparing fine latex has significant stability to temperature.
The reversible fine latex that makes by method of the present invention can be used in a lot of aspects, particularly can be used in the production technique of oil: the inflow of sealing is prevented during solidifying, prepare drilling mud, oil mining in raising the recovery of hydrocarbons rate, ground, and is used as completion fluid or fracturing fluid.
In general, the method that improves oil recovery with aqueous solutions of polymers comprises: inject said solution to the oil field through an Injection Well at least, this solution circulates in the stratum, reclaims by the hydro carbons of displacement with a producing well at least.
Improve the method for recovery ratio and the difference that the above-mentioned method for the preparation of WO emulsion does not have essence with reversible fine latex of the present invention. The reversible fine latex of the present invention's research is from reversible. Generally need not add additional surfactants and be beneficial to this conversion, be exactly like this in said method. These fine latexes are for example in use after water dilution, with respect to regard to the resulting water weight, press 50-5000ppm with regard to copolymer, preferably dilute in the ratio of 100-2000ppm. The experiment in laboratory has shown the efficient of used reversible fine latex.
The method that prevents water inflow producing well comprises, by the present invention reversible fine latex being dissolved in the water and the aqueous solutions of polymers that is prepared into inject will be processed the intra-field producing well of part in, polymer is adsorbed on the formation wall all around of Injection Well to a great extent, then when this well recovers the oil again, oil and/or gas optionally pass treatment region, and the water that passes through has then reduced.
Except these purposes, the water-soluble polymer that is prepared into micro emulsion also can be used as:
The solid coagulant of-separate out suspended in liquid
Flotation assistant and draining assistant that-preparation paper pulp is used, or
The flocculant that-processing water is used
Reversible fine latex by method preparation of the present invention also can be used in the assembling of glass fibre, on the tanning industry or in the paint field.
Embodiment
The following examples are used for illustrating the present invention, in any case but can not think to limit its scope, provide embodiment 1,10 and 14-17 with method relatively, but these several embodiment do not constitute content of the present invention.
Embodiment 1(comparative example)
In stirring down, mix following three kinds of raw materials: 77.8g SOLTROL 220(rostone wax oil, initial distillation point is 244 ℃, 287 ℃ of sink nodes), contain the mixture 25g of polyoxyethylene sorbitol six oleic acid esters (ATLAS G 1086) 21.4g and oleic acid sorbitan sesquialter ester (ARLACEL 83) 3.6g, its HLB value (hydrophile-lipophile balance value) is 9.25.61.3g acrylamide, 20.7g glacial acrylic acid be dissolved in by 42.2 gram distilled water restrain the 50%(weight with 23.0) in the mixture formed of sodium hydroxide solution, this solution is added in the mixture of oil/surfactant.The amount of tensio-active agent (by weight) is equivalent to 10% of whole compositions.At room temperature, after 1 hour, gained milk sap (muddy, shakiness) is heated to 40 ℃, adds therein and be equivalent to have 6.5 * 10 in every mole of monomer with nitrogen purge
-4The mole t-butylperoxy pivarate was kept between temperature 40-50 ℃ about 1 hour.
The latex that makes like this is muddy, carries out decant at duration of storage.
Embodiment 2
Repeat embodiment 1, but used surfactant mixtures is 63.5g, by weight, then is equivalent to 22% of whole compositions, opposite with embodiment 1, resulting mixture is clear thorough single-phase (microemulsion), is still after interpolymerization so.Precipitate with acetone, then use acetone more in succession, methyl alcohol washs, and what make is the multipolymer of acrylic amide-acrylic sodium, and (multipolymer 400ppm, NaCl500ppm) viscosity in is 1.30mm at the aqueous solution to record it under 30 ℃
2/ S.
Embodiment 3
Repeat embodiment 1, but make organic solvent with isoparaffin fraction (ISOPAR M) and tensio-active agent (36.6g) mixture, the first distillation point of this isoparaffin is 207 ℃, and the distillation point is 254 ℃ eventually; The weight of such tensio-active agent being is equivalent to 14% of whole composition weight, and the mixture of gained is one clear thorough single-phase.
After the copolymerization, the single-phase mixture that is obtained (fine latex) contains acrylic amide-acrylic sodium multipolymer 35.3%(by weight).Record under 30 ℃ and contain said multipolymer 400ppm, the viscosity in aqueous solution of NaCl5000ppm is 1.4mm
2/ S.
Embodiment 4
Contain vinylformic acid 38.25g, acrylamide 89.25g and be neutralized to sodium hydroxide pH value near 10 the aqueous solution in, add ISOPAR M(isoparaffin fraction) 255g and the 90g surfactant mixture (its HLB is 9.3) formed by NOFABLE SO-992 12.6g and polyoxyethylene sorbitol six oleic acid ester 77.4g.By weight, this amount of tensio-active agent is equivalent to 15% of whole compositions.In 2 hours the gained single-phase mixture of heating, add Diisopropyl azodicarboxylate 0.21g the degassing 1 hour and under 60 ℃, the usefulness quasi-elastic light scattering method that obtains records about 25 millimicrons of its micelle radius fine latex (variance is 3%), stable and transparent.
Precipitate in acetone, then use acetone, methanol wash in succession, what obtain (the full conversion) is the multipolymer of acrylic amide-acrylic sodium, and recording its viscosity in the aqueous solution of multipolymer that is containing 400ppm under 30 ℃ and 5000 ppm NaCl is 1.5mm
2/ S.
Embodiment 5
Repeat embodiment 4, but do not add Diisopropyl azodicarboxylate, carry out copolymerization under uviolizing (5 minutes), temperature maintenance is at 20 ℃.Along with whole conversions, what obtain then is the acrylic amide-acrylic sodium multipolymer, with the aqueous solution that contains this multipolymer 400ppm, sodium-chlor 5000ppm, is 3.15mm 30 ℃ of viscosity of measuring its multipolymer down
2/ S.On the other hand, the multipolymer that makes being dissolved in the water that contains NaCl 20g/l, is that zero-sum finds that according to shearing rate the interior viscosity of said multipolymer equals 3250cc/g according to measuring and being extrapolated to concentration.Used viscometer is the LS30 viscometer of CONTRAVES company during mensuration.
Embodiment 6
Condition with embodiment 4 prepares reversible microemulsion, changes in two kinds of tensio-active agents every kind ratio, measure under each situation, after polymerization, for to obtain to stablize, the minimum quantity of the transparent required tensio-active agent of reversible fine latex.
It the results are shown in the following table
The table I
For obtaining required minimum of stable and transparent reversible fine latex
HLB
Surfactant concentration (% by weight)
8.5 18
9 14
9.5 12
10.2 16
Embodiment 7
Contain 60g vinylformic acid, add ISPAR M(200g in the 400g aqueous solution of 140g acrylamide and a certain amount of sodium hydroxide) and embodiment 5 in surfactant mixture (92g), amount of sodium hydroxide is enough to make its pH value to remain near 10 in this solution, and this amount of tensio-active agent is equivalent to 13.3% of whole composition weight.Carry out under the identical condition that this interpolymerization is narrated in embodiment 5, what make is stable, a transparent fine latex, and its micelle radius is measured through the quasi-elastic light scattering method and is about 40 millimicrons, and its variance is 5%.By weight, this reversible fine latex contains acrylic amide-acrylic sodium multipolymer 31.6%, contains sodium acrylate 35.9%(weight in this multipolymer).
The interior viscosity of the said polymer is that 3520cc/g(is in NaCl 20g/l solution).
Embodiment 8
In the aqueous solution that contains vinylformic acid 40g, acrylamide 160g and a certain amount of sodium hydroxide, add the surfactant mixture 106g among ISOPAR M 200g and the embodiment 4, it is 9 that amount of sodium hydroxide wherein is enough to keep said water-soluble pH value.This amount of surfactant mixture is equivalent to 15% of whole composition weight.Its interpolymerization is carried out under the condition identical with embodiment 5, and what make is a single-phase mixture, by weight, contains acrylic amide-acrylic sodium multipolymer 30.1% in this mixture, contains sodium acrylate 24.6% in this multipolymer.
Under 30 ℃, NaCl(5g/l) exist down, the viscosity in aqueous solution that contains said multipolymer 400ppm after measured is 2.7mm
2/ S.
Embodiment 9
Repeat embodiment 8, but will replace not changing under other the condition of ISOPAR M with trimethylammonium-pentane, what obtain be the reversible fine latex of its feature similar embodiment 8.
Embodiment 10(comparative example)
Repeat embodiment 8, but replace other condition of different chain alkane solvents (ISO-PAR M) not change with aromatics solution (toluene), even add the tensio-active agent (by weight, 31%) of high-content, also can not the reversible microemulsion of acquisition.
Embodiment 11
In the 400g aqueous solution that contains vinylformic acid 60g, acrylamide 140g (its pH value is adjusted to 10 with sodium hydroxide), add ISOPAR M 200g and contain sorbitan trioleate (montane 85) 11%(weight) and oxyethyl group dehydration sorbose trioleate (Montanox 85) 89%(weight) the mixture 115g of these two kinds of tensio-active agents compositions, wherein the HLB of surfactant mixture is 10, and the amount of tensio-active agent is equivalent to 16% of whole composition weight.
Carry out copolymerization under the same terms of embodiment 5 narrations, what obtain is a single-phase mixture, by weight, contains acrylic amide-acrylic sodium multipolymer 30.5%, and containing sodium acrylate in this multipolymer is 35.9%(weight).
The interior viscosity of the said polymer is that 3200cc/g(is in the NaCl of the 20g/l aqueous solution).
Embodiment 12
In containing the 400 gram aqueous solution (regulating its pH value to 9 with sodium hydroxide) of acrylamide 170g, vinylformic acid 30g, add the surfactant mixture 115g of ISOPAR M 200g and embodiment 11.By weight, the amount of tensio-active agent is equivalent to 16% of whole compositions.
The copolymerization of carrying out under the condition identical with embodiment 5, what obtain is a single-phase mixture.By weight, this mixture contains acrylic amide-acrylic sodium multipolymer 29.3%, and this multipolymer contains sodium acrylate 18.7%.
Embodiment 13
In the 400g aqueous solution that contains vinylformic acid 50g, acrylamide 150g, add 200gISOPAR M and 100 gram polyoxyethylene sorbitol oleic acid ester (ATLAS G 1087; HLB=9.2), add the pH to 10 that sodium hydroxide is regulated this aqueous solution.By weight, 14.3% of the quite whole compositions of the polyoxyethylene sorbitol oleic acid ester of adding.
Make the reversible microemulsion copolymerization that obtains like this under the condition that embodiment 5 is narrated, product is stable, and transparent reversible fine latex by weight, wherein contains acrylic amide-acrylic sodium multipolymer 30.7%, contains sodium acrylate 30.3% in this multipolymer.
Embodiment 14(comparative example)
Except the ratio that changes two kinds of tensio-active agents is 7.6 to obtain HLB, repeat example 7, being impossible obtain any reversible microemulsion under such condition, also is like this even improve the consumption (by weight, being higher than 31%) of tensio-active agent.
Embodiment 15(comparative example)
When utilizing the method for embodiment 7, its surfactant mixture replaces with NONYL PHENOL ETHOXYLATED, this NONYL PHENOL ETHOXYLATED of per molecule contains 8 oxyethane repeating units, its HLB is 12.3, other conditions do not change, under such condition, also can not obtain any reversible microemulsion even improve the consumption (by weight, being higher than 35%) of tensio-active agent.
Embodiment 16-22
In the 255g aqueous solution that contains vinylformic acid 44g, acrylamide 82g (regulating pH value near 10 with sodium hydroxide), the surfactant mixture that adds 255gISOPAR M and the used HLB value of front embodiment and be 9.3 different amounts (by weight.Dehydration sorbose sesquioleate 14%, Sorbitol Powder six oleic acid esters 86% of polyethoxylated), the amount of its surfactant mixture is listed in the following table II.With the degassing of gained mixture, heated 45 minutes down at 45 ℃ in order to make monomer copolymerization.
So obtained a series of reversible latex like this, by weight, the concentration of its final copolymer is the 22-25% of whole compositions.Sodium acrylate weight ratio in multipolymer is 42%.Its final latex is measured its latex particle hydrodynamic radius R with its optical transmission value of turbidimetry for Determination, the accurate elasticity diffusion method of using up
HWith the stability of having evaluated latex, in the II that is listed in the table below.
The table II
Surfactant concentration light transmission R
H
Embodiment stability
(weight %) be (millimicron) (%)
16
*8.2 1.1＞more than 89 hours
17
*11.0 1.2＞60 back sedimentations
18 13.4 82 37 18-22's
19 15.5 82 35 samples in addition
20 18.0 85 27.5 some months afterwards all
21 20.2 88 25 is stable
22 21.1 91 24
*Comparative example
Table is found out on the contrary with the result of embodiment 16 and 17 thus, is stable from embodiment 18 to 22 fine latexes that obtained, and high light transmission and little particle radius are arranged.
With corresponding HLB value, shown in the drawings with the curve that the concentration value of tensio-active agent or surfactant mixture is done, the zone of stablizing reversible fine latex that this curve is pointed out to obtain and can obtain approximate limit between the stable reversible fine latex zone, the hachure scope on this figure is a preferable range of the present invention.
Embodiment 23 to 25
100g ISOPAR M and surfactant mixture (HLB=9.3) 53g same with front embodiment are added in the aqueous solution of 200g, and this aqueous solution contains vinylformic acid 30g, acrylamide 70g, is 9 with sodium hydroxide with its pH value that neutralizes.
Add the 0.15g Diisopropyl azodicarboxylate in the single-phase mixture of gained, outgas, insulation is 5 hours under the temperature different with the embodiment that is studied.What obtain all is stable and transparent reversible fine latex, and this interpolymerization is completely.
In acetone, precipitate, then wash separation of acrylamide-sodium acrylate copolymer in succession with acetone, methyl alcohol.Under 30 ℃, in the aqueous solution that contains 1000ppm multipolymer, 5000ppm sodium-chlor, measure its viscosity, its viscosity number is looked the temperature of its interpolymerization and different:
Embodiment 23 T °=60 ℃ of viscosity: 2.4mm
2/ S
Embodiment 24 T °=40 ℃ of viscosity: 4.9mm
2/ S
Embodiment 25 T °=25 ℃ of viscosity: 7.4mm
2/ S
Embodiment 26
Injectability test in porous medium
In glass infuser, pack into ENTRAIGUES EN 38, measure the sand that its particle size range is 28-50 μ m through granulometry, so just, made porous medium, the characteristic of the porous medium of Huo Deing is as follows like this: L=60mm, φ=20mm, Vp=8.6cc, k=2.04D, the penetration degree that φ=45%(K=represents with darcy for water; φ=porosity).The reversible fine latex that obtains among the embodiment 7 is dispersed in the oil field uses.Its total salinity near in the salt solution of 39/l with the preparation acrylic amide-acrylic sodium copolymer solution (1000ppm), when measuring with the LS30 viscosity determinator, the flow curve of said copolymer solution show the relative viscosity value have on to the shearing rate curve platform exist (when shearing rate is zero, relative viscosity η
Ro=20, when temperature is 30 ℃).
Then, with perfusion type piston pump, (q=1.5cc/h) injects this polymers soln under weighing apparatus constant speed rate; End at the porous medium that polymers soln is arranged is measured the pressure-losses, and this pressure-losses is used and represented by the ratio of the initial value that obtains of oil-field brine.Determined the degree of mobilization ratio like this, it is stabilized in 21.6 numerical value under experiment condition.In addition, observe also that to measure the stable phase of polymer concentration between stabilization that degree of mobilization reduces and the filler entrance and exit according to viscosimetry corresponding.On the one hand degree of mobilization is reduced value and platform viscosity ratio, no polymkeric substance loss between the entrance and exit of porous medium on the other hand, this shows: it is gratifying that selected porous medium is gone into ability to the suction of fine latex dispersion liquid, and the trace of particularly not observing obstruction resembles.
Inject the oil field again when using salt solution behind injection of polymer solution, the reduction value that records rate of permeation is 2.36, and this shows have the polymer layer that is adsorbed on the porous medium wall.This behavior is the characteristics of high-molecular weight acrylic amide-acrylic sodium multipolymer just.
On the other hand, the lasting fact that reduces of the rate of permeation of water may make people think over and use reversible fine latex of the present invention to flow into recovery well to prevent water, and this sets forth as the following examples.
Embodiment 27
Prepare porous medium (L=20Cm with the method for getting the Vosges sandstone rock core that contains 10% clay approximately; φ=5Cm).This Vosges sandstone is to seawater (total salinity ≈ 37g/l), and the rate of permeation of oil-field water (total salinity ≈ 8g/l) is respectively 0.478D and 0.467D.Porosity is 18%.
With the fine latex of embodiment 13, respectively contain the solution of active copolymer 500ppm respectively with seawater and oil-field water preparation, be dispersed in the relative viscosity that the said fine latex in two kinds of water is obtained in the Newtonian region, be respectively η
Ro=5.1(oil-field water) and η
Ro=3.1(seawater), the ratio of two viscosity is 1.65.
This and the French Patent 2325797(U.S. same Patent 4095651 of authorizing this application people) pointed consistent, wherein about preventing that water from flowing into recovery well, be with the constant speed rate q=3Cm that weighs fine latex solution (Cp=500ppm)
3/ h(r=2.1 second
-1) be injected at (t=30 ℃) in the seawater.At the about 5P ' of fine latex injection of solution V(PV=micropore volume) after, intermittently injection of polymer by the inlet face injection seawater of the sand of coring, is will be determined at polymkeric substance to introduce front and back penetration of sea water rate R on the one hand
KReduction, on the other hand in order to derive the thickness of adsorption layer thus, calculation formula:
R wherein
ρBe defined as average pore radius, equal
。
The value that obtains is as follows: R
K=1.80, δ=0.62 μ m.
Via the exit face of the sand of coring, oppositely inject oil-field water, with the generation of simulation, obtained the new numerical value of permeability reduction and adsorbent layer thickness: R so respectively in oily WIH
K=2.92, δ=0.90 micron.The ratio of adsorbent layer thickness is 1.61 when using oil-field water and seawater respectively.This number and 1.65 ten minutes are approaching, and 1.65 are illustrated in the ratio of said two kinds of underwater platform viscosity.This shows, has introduced multipolymer under such condition, promptly introduces multipolymer when the absorption bed thickness changes with the same same ratio with viscosity.Like this, effusive soft water has reduced from the oil field, so reduced the ratio (WOR) of effusive water and oil.
Claims (12)
1, a kind of production is stable, and the method for reversible latex is characterized in that adopting following step:
(a) mix:
-contain at least a Acrylic Acid Monomer (i) of acrylamide and Methacrylamide and the another kind of at least Acrylic Acid Monomer aqueous solution (ii) that is selected from an alkali metal salt of vinylformic acid, methacrylic acid and said acid of being selected from, concentration is 20-80% (by weight) in the said aqueous solution
-contain a kind of oil phase of hydrocarbon liquid at least, the weight ratio of this aqueous solution and this oil phase be 0.5/1 to 3/1 and
The nonionogenic tenside or the non-ionic surfactant mixture of-its HLB value from 8 to 11, it should equal the y value (representing with weight percentage) that provides by following relational expression at least with respect to whole ratios that exists about composition, so that form a kind of reversible microemulsion
y=5.8X
2-110X+534
Wherein X is the HLB of said tensio-active agent or surfactant mixture, and
The reversible microemulsion that obtains in (a) step is under the copolymerization conditions.
2,, it is characterized in that said Acrylic Acid Monomer (ⅱ) is a sodium acrylate according to the method for claim 1.
3,, it is characterized in that by weight the amount of said Acrylic Acid Monomer (ⅱ) is an Acrylic Acid Monomer, the 15-60% of mixture according to the method for claim 1.
4,, it is characterized in that by weight the amount of said sodium acrylate is the 15-60% of Acrylic Acid Monomer mixture according to the method for claim 2.
5, according to the method for claim 3, the amount that it is characterized in that said Acrylic Acid Monomer (ⅱ) is the 20-45% of Acrylic Acid Monomer mixture weight.
6, the method according to claim 4 is characterized in that the amount of said sodium acrylate is the 20-45% of propylene monomer mixture weight.
7,, it is characterized in that the pH of the said aqueous solution in (a) step is 8-13 according to the method for the claim of one of claim 1-6.
8, according to the method for the claim of one of claim 1-6, it is characterized in that the oil phase in its (a) step contains a kind of isoparaffin at least.
9,, it is characterized in that monomer solution in (a) step and the weight ratio between the oil phase are about 2/1 according to the method for the claim of one of claim 1-6.
10,, it is characterized in that the tensio-active agent in (a) step or the ratio of surfactant mixture mostly are 25% of the whole composition weight of said reversible microemulsion most according to the method for the claim of one of claim 1-6.
11, according to the method for the claim of one of claim 1-6, it is characterized in that the polymerization in (b) step is in the presence of the free radical reaction initiator, make it to carry out with heating method.
12,, it is characterized in that the polymerization in (b) step is caused by uviolizing according to the method for the claim of one of claim 1-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85104912 CN1008442B (en) | 1984-06-07 | 1985-06-27 | Process for manufacturing inverse microlatices of hydrosoluble copolymers |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8408906A FR2565623B1 (en) | 1984-06-07 | 1984-06-07 | USE OF HIGH REVERSE MICROLATEX IN WATER-SOLUBLE COPOLYMERS FOR IMPROVING HYDROCARBON PRODUCTION |
| CN 85104912 CN1008442B (en) | 1984-06-07 | 1985-06-27 | Process for manufacturing inverse microlatices of hydrosoluble copolymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85104912A CN85104912A (en) | 1987-01-14 |
| CN1008442B true CN1008442B (en) | 1990-06-20 |
Family
ID=25741814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85104912 Expired CN1008442B (en) | 1984-06-07 | 1985-06-27 | Process for manufacturing inverse microlatices of hydrosoluble copolymers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1008442B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100384896C (en) * | 2006-04-29 | 2008-04-30 | 沈阳化工学院 | Process for preparing acrylic amide-acrylic sodium polymer nano particle micro emulsion |
| CN102432747B (en) * | 2010-09-29 | 2014-10-22 | 中国石油化工股份有限公司 | Amine lactone type amphoteric high polymer emulsion as well as preparation method and application thereof |
| MX364227B (en) * | 2012-11-14 | 2019-04-17 | Basf Se | Process for tertiary mineral oil production. |
| EP3294829A4 (en) * | 2015-05-13 | 2019-01-09 | Ecolab USA Inc. | Invertible water-in-oil latices and methods of use |
-
1985
- 1985-06-27 CN CN 85104912 patent/CN1008442B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85104912A (en) | 1987-01-14 |
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