• 专利附录
  • 专利说明
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    • 专利摘要:
    Improved waterflooding of an oil-bearing subterranean reservoir is obtained by flooding with a water-soluble polymer obtained as a product of radiation-induced polymerization of acrylamide and/or methacrylamide and acrylic acid, methacrylic acid, and/or alkali metal salts thereof. The polymerization is preferably carried out in 10-60 percent aqueous monomer solution with gamma radiation. The mixture of monomers, before radiation, preferably contains 25-99 percent acrylamide and 75-1 percent sodium acrylate. Such polymers are useful as mobility and/or viscosity control agents. A miscible or miscible-like displacing slug can precede injection of the polymer.
    公开号:SU936822A3
    申请号:SU731967215
    申请日:1973-11-05
    公开日:1982-06-15
    发明作者:Дж.Ристэйно Альфред；В.Бристоув Вильям
    申请人:Геркулес Инк. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the development of oil deposits, preferably secondary. and tertiary development methods in which an aqueous solution, mobility and / or viscosity regulator is pumped: into an oil B formation.
    There is a method of developing an oil deposit, which consists in displacing oil from the reservoir by pumping a displacing agent into it and extracting oil to the surface by means of wells, in which a copolymer of acrylic acid and acrylamide is pumped as a displacing agent (1].
    The disadvantage of this method is the low oil recovery.
    The closest to the proposed technical essence and the achieved result is a method of developing an oil reservoir, which consists in displacing oil 20 from the reservoir by injecting an aqueous polymer solution into it through injection wells .. and extracting oil through production wells, in which chemically injected as a polymer catalyzed polymers, in particular partially hydrolyzed polyacrylamide. (2].
    The disadvantage of this method is the low oil recovery associated with incomplete coverage of the reservoir by displacement.
    The aim of the invention is to increase oil recovery by increasing the coverage of the reservoir by displacement.
    This goal is achieved by the fact that according to the method of developing an oil reservoir, which involves displacing oil from a formation by injecting an aqueous polymer solution into a Negro through injection wells and extracting oil through production wells, the polymer obtained by the reaction of acrylamide and acrylic acid with a weight ratio (60:10) - (90 /: 40) in an aqueous, alkaline medium under the influence of gamma radiation from 60 and at an intensity of 10,000 to 220,000 rad / h and a total radiation dose and a range of 1 350 to 50,000 rad.
    ‘936822
    Improvement has taken place in the regulation of mobility in the process of oil production, preferably in secondary and tertiary processes, can be achieved by using an aqueous solution of a water-soluble polymer obtained by radiation polymerization of acrylamide and acrylic acid. The polymerizable aqueous solution may contain about 10-60 wt.% Ionomer. The irradiation intensity is 25O- '1,000,000 rad / h at a dosage of 500,300,000 rad. The reaction product can be diluted with water and used directly, or the polymer can be extracted from the reaction product, dried, and then dissolved. The injection rate can be improved by using aqueous solutions of these polymers in comparison with the equivalent molecular weight of known polymers.
    A monomer is a combination of one compound selected from the group consisting of acrylamide and one compound selected from the group consisting of acrylic acid. A small amount of additional ethylenically unsaturated copolymerizable monomers can also be used.
    The monomer is preferably irradiated in an aqueous solution containing about 10-60% and preferably 1545% by weight of dissolved monomer. At a lower monomer concentration, the product is a thickened polymer solution at a concentration above 15% by weight. The product is a non-gel. At a concentration above 60% of the monomer, the product is insoluble in water; therefore, high concentrations are undesirable. Obviously, the monomer concentration limit also depends on the radiation conditions, the monomer used and the type of product that must be obtained for any particular application. The intrinsic viscosity of the polymer increases with increasing monomer concentration, reaches the point where the number of cross-linked bonds increases, while other variables remain constant.
    The aqueous monomer solution should preferably contain no more than 5 ppm. transition metal ions, for example nickel, iron, cobalt and not more than 0.5 ppm monovalent and divalent copper ions.
    The irradiation of an aqueous solution of monomer can be produced by high energy ionizing radiation. The radiation wavelength is below 3500 A and preferably below 2000 A. By their nature, the radiation can be electromagnetic or particulate, examples include irradiation with accelerated electrons, protons, neutrons, as well as x-rays and gamma rays, the latter being preferred .
    The radiation intensity is from about 1000 to 300000 rad / h, and more preferably from 5000 to 200000 rad / h. Intensity directly affects the molecular weight of the copolymer, i.e., at. Under the same conditions, low intensity tends to give higher molecular weights.
    The radiation dose is preferably 15 about 1000 rad and preferably about 1,500 rad. The maximum dose is preferably not more than 100,000 rad and more preferably not more than 50,000 rad.
    The radiation dose directly affects the characteristic viscosity and the degree of conversion of monomer to polymer. For a given radiation intensity and monomer concentration, an increase in radiation, as a rule, leads to a decrease in the intrinsic viscosity of the obtained polymer and an increase in the degree of conversion of the monomer to the polymer. The radiation dose also affects the solubility of the polymer in water, and it has been found that if the radiation dose is too high, a water-insoluble polymer can be obtained. With a preferred radiation dose, almost 100% and preferably 80-100% conversion of the monomer to the polymer can be achieved without unnecessary insolubility.
    The pH of the aqueous solution of monomer 35 is not usually a critical value, but an insoluble product may form if the value is too low. The preferred pH is 3-13 and more preferably from 8 to 11. However, the indicators can be higher and lower, but it should be noted that hydrolysis occurs at a pH of much less than 3 and much more than 11.
    While this method can be used in the preparation of polymers with character 45-terrorism viscosity from about 6 to 30 dl / g and 2. sodium chloride at 25.5 ° C, the process can be modified to obtain characteristic polymers. viscosity below 6 dl / g or higher, about 30 dl / g 50 in 2 N. sodium chloride at 25.5 ° C. Polymers with an intrinsic * viscosity below about 6 dl / g are obtained by polymerization as described above in the presence of a chain growth agent. The chain growth agent is capable of reducing the active chain size growth by 5 $ and, thus, forming full moats with a low molecular weight and lower intrinsic viscosity. In ka. 936822, any chain growth agent can be used as a chain growth agent to help reduce polymer chain growth and produce lower molecular weight and lower intrinsic viscosity j of the polymer that can be dissolved in the reaction medium. Examples of such agents include lower alkyl alcohols 1, for example methanol, ethanol and isopropanol, halogen compounds, for example trichloroacetic acid, thiosorbitols containing 2 thio groups and 4 secondary hydroxyl groups and mercaptans. The amount of chain growth agent depends on the desired degree of intrinsic viscosity, monomer concentration, and constant chain transfer of the chain transfer agent used. Upon receipt of polymers with intrinsic viscosity at! about 6-30 dl / g, the use of a chain transfer agent is not necessary, but if necessary, such polymers can be obtained in. the presence of chain transfer agents.
    In order to obtain polymers with an intrinsic viscosity higher than 30 dl / g, the polymerization reaction must be completed when 25 is less than 75%, and preferably 60% of the weight of the monomer is converted to a polymer. It was found that the intrinsic viscosity of the obtained polymer decreases with an increase in the percentage of conversion of monomer to polymer. For economic reasons, the conversion should be at least 20%.
    Variable radiation intensities, total radiation dose, and monomer concentration index are independent constants. While the polymers used can be obtained at any monomer concentration, radiation intensity and dosage as described above, any combination of concentration, dose and intensity within these limits cannot be used to obtain the polymers used in the proposed method. For example, if the polymer can be obtained at a monomer concentration of 60% by weight, the radiation dose is low to form a water-soluble polymer; when using a monomer concentration of 60 wt.%, an intensity of 250 rad / h and a dose of 300,000 rad, water-insoluble polymers are formed.
    Due to this interdependence of monomer intensity, dose and concentration, it may be necessary to apply a limited amount of experimentation to obtain a polymer with the desired intrinsic viscosity. In the table. 1 gives a characteristic of obtaining polymer samples with various indicators of viscosity, efficiency, dose, monomer concentration, degree
    In the conversion and agent of chain growth on the intrinsic viscosity of the polymer. In accordance with this, the reaction conditions for obtaining a water-soluble polymer with an intrinsic viscosity different from that of the intrinsic viscosity of the polymers of Table 1 can be determined by minor changes in the reaction conditions given in the table. 1 to obtain a polymer with an intrinsic viscosity close to the intrinsic viscosity of the polymer to be obtained. Such changes can be made taking into account the data on the effectiveness of the intensity, dose, monomer concentration, percent conversion of monomer to polymer, chain growth agent for the characteristic viscosity of the polymer. For example, a polymer with an intrinsic viscosity of about 16 dl / g can be prepared under the same reaction conditions of Example F of Table. 1, but the radiation intensity increases, the total radiation dose increases, the monomer concentration decreases, the percentage of monomer conversion increases, and / or the reaction proceeds in the presence of a chain transfer agent. Preferably, said decrease in intrinsic viscosity is achieved by increasing the radiation intensity, lowering the monomer concentration and / or using a chain growth agent.
    The product of irradiation is an aqueous solution of a water-soluble polymer, which may be in the form of a solidifying liquid or non-closing rubbery gel, depending on the concentration and intrinsic viscosity of the polymer. The viscosity of the polymer solution increases with increasing polymer concentration and intrinsic viscosity of the polymer. The resulting polymer solution’s radiation can be mixed with water and used directly or the polymer solution can be concentrated by a known method. mi or restored in a special form, for example, dry. For example, a non-curing gel can be separated and water recovered by known methods. Water can be extracted from the gel with a water-immiscible volatile organic liquid that is not affinity for the copolymer, for example methanol.
    Copolymer "> preferably compatible with formation water and rock. The polymer may contain cations, preferably monovalent, more preferably sodium.
    Polymers obtained by radiation polymerization have, as a rule, relatively low Hagens constant. This constant refers to linearity over 7 936822 leimers, where the molecular weight is constant, i.e. for two copolymers having similar molecular weights but different Haggens constant (lower Haggens constant means a more linear polymer). Polymers with a Hagens constant below 1 and preferably below 0.7 and more preferably below 0.5 are most often used in the present invention. In some cases, a mixture of polymers with low, medium, and / or high Huggins constants is appropriate to provide an improved method for developing an oil reservoir.
    Preferably, the copolymer does not clog the formation either by adsorption, or by adsorption, or by flocculation of clay in the formation, or as a result of reaction with formation waters. Linear polymers, i.e. unbranched, are particularly suitable for this purpose. If the copolymer is anionic, maximum mobility characteristics are usually achieved with minimal flocculation.
    The intrinsic viscosity of the polymer can vary from less than 1 to 60 dl / g, preferably from 5 to 35 dl / g. The permeability of the formation rock subjected to watering has a great influence on the intrinsic viscosity, but the low permeability of the rock requires, as a rule, a lower intrinsic viscosity. For example, groyanetsa, a bridge below 50 requires an intrinsic viscosity of less than 10, permeability of 200 or more requires higher intrinsic viscosities and more than 20 for high results. Indicators of characteristic viscosity measurement in a solution of 2 N. sodium chloride at 25.5 ° C. Obviously, copolymers with very high intrinsic viscosities can plug holes in the formation; this may be desirable in heterogeneous formations. However, the effectiveness of the polymer increases with an increase in intrinsic viscosity, while the degree of branching does not increase and the polymer does not clog the formation. Mixtures of polymers with different intrinsic viscosity values can also be used. If the formation has a high permeability, i.e., exceeds 1 D, the intrinsic viscosity is preferably higher than 25 dl / g.
    The polymer can be dissolved and diluted with water to the desired concentration. It is preferable to avoid the use of water containing a large number of polyvalent metal ions, which adversely affect the viscosity of the polymer solution or on the solution ! bridge in polymer water. The amount of polyvalent metal ions present in an aqueous polymer solution depends on the specifics
    IS achieve maximum avoid dissolving polyego into the formation. When you reach a volume with a gel in the form then
    VOD8 metal ions, temperature and pH of the solution, as well as from the intrinsic viscosity and anionic polymer content. As a rule, the polymer becomes less resistant to polyvalent metal ions, since the intrinsic viscosity, anionic content, and concentration of polymers increase. It is preferable to avoid the use of water containing a sufficient amount of copper and / or iron ions, due to their negative effect on the solubility of the polymer in water, etc. If a maximum viscosity is desired at a given polymer concentration, the water should preferably contain less than 500 ppm. ’’ ”Solid’ dissolved solids (TRV), that is, should be ’’ soft. ” If maximum viscosity is desired, the water should preferably contain less than 50 ppm divalent cations, for example calcium and / or magnesium. If viscosity is required, the gel should be measured and injected with the maximum polymer; at first, the gel is extruded and cut into small parts, for example, the size of the air force, and then mixed into the new solution at low shear rates. Pump characteristics and agitator speed are especially taken into account at low shear rates. In order to facilitate the solubility of the polymer, water-soluble alkali salts, i.e. salts which give a pH above 7 in water, for example, alkali metal carbonates, can be mixed with an aqueous solution. Preferred in this case is sodium carbonate. The amount of alkali salts added to the vada should be strictly controlled to avoid hydrolysis of the polymer. Other known additives may also be used.
    The polymer may be injected into the front of the dewatering formation, or an aqueous polymer solution may be supplied following an appropriate displacement fluid. To improve the injection profile, the polymer solution is supplied prior to the normal production process, for example to a displacement fluid. When the polymer is injected after the displacing fluid, preferably less than 5-70% or more wells.
    The aqueous polymer may contain various additives to impart the desired qualities to the oil production process. For example, salts, surfactants, alcohols, pH regulators, oxygen-depleting agents, corrosion inhibitors, biocides, passivators, viscosity stabilizers, stabilizers, etc. can be added to an aqueous polymer solution. Thus, it is possible to add to an aqueous polymer solution any components that are compatible with the polymer and do not adversely affect formation dehydration. A special case is the addition of a polymer to the aqueous phase of an emulsion or micellar dispersion.
    All data is given as a percentage of volume.
    Obtaining copolymers.
    'For tests using polymers obtained as a result of gamma radiation of cobalt 60, the magnitude of the radiation intensity and dosage are given in table. I. The method of producing polymer A is given below, with regard to the production of other polymers, the methods are identical except for the data in table. I.
    To 24,000 g of deionized water, 692 g of sodium hydroxide are added. After cooling the solution to 30 ° C., 1.250 g of acrylic acid are added. Then 5,000 g of acrylamide are added with stirring, and the pH is adjusted to 9.4. The resulting solution contains 75 wt.% Acrylamide (ALD) and 25 wt.% Sodium acrylate (NaA) and has a total monomer concentration of 21.4 wt.%. The solution is purged with N 2 for 20 minutes and then closed. The sample is irradiated with cobalt 60 by gamma radiation at an intensity of 18000 rad / h with a total dose of 8800 rad / h (P). The resulting product has the appearance of a gel.
    A portion of the gel is weighed and then extracted with methanol to precipitate the polymer. The polymer was dried in vacuo at 36 ° C and a pressure of 0.02 lb / in2 for 24 h to constant weight at 110 ° C Weight of dry product divided by the theoretical weight, giving 93% conversion of monomer.
    A portion of the gel dissolves in water and is extruded in the form of spaghetti, cut into particles of explosives, and then dissolves in water with stirring at low revolutions per minute to avoid significant jigging of the polymer.
    The remainder of the gel is reduced to a dry powder from the first extrusion of the gel, then dissolved in water and with the addition of methanol. The polymer precipitates from the solution. The polymer is granulated to a size of less than 20 mesh and dried in vacuum at 60 ° C.
    Characteristic viscosity is measured at 25.5 ° C in 2 N. aqueous solution of NaC1. Haggens constant is measured in a known manner.
    The monomer used in. sample C is soluble in water with a content of 9.18 wt.% methanol (table. 1).
    in the rear and high cast in you936822 10
    Example Ϊ. Dehydration. Samples taken from sandstone formations are first washed with toluene, then dried in a vacuum. Permeability is 100-200 ppm. Sandstone bars are then encapsulated in plastic with the exception of the ends. The polymers are dissolved in water containing the specified in table. 2 ppm solid. Soluble substances (TRV) and filtered through a sieve with a mesh size of 200 mesh to filter out large particles. Then injected into the sandstone samples. The initial permeability and permeability after washing is measured with water containing approximately 500 ppm. 1FB. Corresponding mobility indicators are measured after injection of the polymer solution into 10 pore objects.
    The results are shown in table. 2.
    Series 1-6 compared to series 7-8 require a higher corresponding lu mobility.
    Series 7-8 are carried out using commercial, partially hydrolyzed high molecular weight polyacrylamide. The content of anions in example 1 is about 30%, intrinsic viscosity 12.7 in 2 N. sodium chloride solution at 25.5 ° C and a Hagens constant of 0.56. The polymer 11 has an anion content of 30%, a characteristic viscosity of 15.1 in 2 N. a solution of sodium chloride at 25.5 ° C and a Hagens constant of approximately 0.26.
    Example 2. Sandstone samples with a permeability of about 500-1500 ppm are processed as in example 1. Then they are washed with an aqueous solution of 700 ppm. the specified polymer.
    The results are given in table. 3. The corresponding mobility of the polymers according to the proposed method in the front and rear of sandstone samples is equivalent to, but not polymer 111. Polymer 111 is a commercial partially hydrolyzed very high molecular weight polyacrylamide with an intrinsic viscosity of approximately 20.1 in 2 N. a solution of sodium chloride at 25.5 ° C and a Hagens constant of 0.16.
    Example 3. A series of 3 and 4 table. 3 are drawn on the graph of the corresponding mobility on the ordinate of the well volume for the front and rear of the samples. In FIG. 1 shows polymer E (series 3), where it is indicated that the corresponding mobility of the front and rear is substantially equal and constant after six volumes of wells.
    In FIG. Figure 2 shows that the corresponding mobility of polymer 111 (series 4) in the front and rear is significantly different and increases with increasing injection volume in
    And 936822 well. Permanent mobility (see Fig. 1) can be achieved after permeation is carried out. An increase in the corresponding mobility (see Fig. 2) indicates a constant reduction of mobility; this is undesirable in secondary and tertiary oil production processes.
    Example 4. The example is an illustration of the effectiveness of the proposed copolymers in oil production from highly permeable formations.
    Pipes with a diameter of 2 ”and a length of 6” are filled with white Ottawa sand (grain size 60-200 places) moistened with water. To facilitate filling with sand, the pipe undergoes vibration. The ends are closed by ceramic-metal disks, and pressure hooks are placed along the pipe. The absolute permeability of the filled tubes is 4-6 g and porosity of approximately 35%. Pipes are flooded indicated in the table. 4 oil (viscosity measured at 23 ° C) until saturated with water and then flooded with water 1.1 volumes of wells with water or 1.1 volumes of wells with an aqueous polymer solution. It is then washed with 1.1 volumes of water.
    The results are presented in table. 4.
    Additionally, the oil produced makes up the difference between the oil produced after watering and the polymer, that is, the gradually increasing flow produced during watering. Water saturation before watering is 1214% of the pore volume for 200 chemically pure oil and 10-12% for 1,120 chemically Stop oil. As indicated in the table. 4, the copolymers of the proposed method give a production of 30% more than 220 chemically pure oil compared with known polymers with the same degree more wine
    For the desired concentration, and approximately 10% of 220 chemically pure oil at half concentration.
    1,140 chemically pure oil pre-copolymers allow production at
    27% more oil than polymer 111. The mobility of the dewatering medium is achieved after injection of 1.1 pore volumes and depends on the oil saturation of the sand-filled pipe. water permeability, and hence the mobility of an aqueous dehydration medium, increases with decreasing oil saturation. The mobility ratio is determined by the mobility of the displacing fluid divided by the mobility of the displaced fluid. If the ratio is greater than 1, then mobility is unfavorable. For the production of 210-225 chemically pure oil, the copolymers of the proposed method have a beneficial effect, while 15 for polymers 11 and 111, the mobility ratio is unfavorable. However, both polymers have an unfavorable ratio when displacing 1,140 chemically pure oil, but the mobility ratio of the copolymers according to the proposed method is 50% of polymer 111 and, therefore, more efficient.
    Example 5. To compare the proposed copolymers with the known tests with samples of sandstone (diameter 1 ", length 3). Samples are first washed with toluene, then dried in vacuo. Then they are flooded with water containing about 500 ppm. TRV. About 10 pore volumes of the solution of the indicated polymer are injected at a speed of 10 and 1 ft / day, and then the samples are washed with water at a speed of 10 ft / day (the content in water is about 500 ppm TPV). The input injection and the resulting polymer concentration are analyzed to calculate polymer loss.
    The results are shown in table. 5.
    The copolymer according to the proposed method has the highest rate of mobility for the rear at approximately equal concentrations. These copolymers give the most homogeneous corresponding mobility and the rate of reduction of permeability through the sample.
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    Note: Series 1-4 and 7-8 contain 700 ppm. polymer dissolved in water containing approximately 500 ppm Series 5 contains 300 ppm. polymer dissolved in water with a TRV content of about 500 ppm Series 6 contains 700 ppm. a polymer dissolved in water with a TRV content of 18,000-20,000.
    The polymer solution was obtained by diluting the gel with water. The polymer solution obtained by diluting the powder with water.
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    权利要求:
    Claims (5)
    [1]
    I
    The invention relates to the development of oil deposits, preferably to the secondary. n tertiary development methods in which a water solution of a mobility regulator n / nln viscosity is pumped: into an oil reservoir.
    A known method of developing an oil reservoir is to displace oil from the reservoir by pumping a displacing agent into it and extracting oil to the surface through wells, in which an acrylic acid copolymer and acrylamide 1 is injected as a displacing agent.
    The disadvantage of this method is low oil recovery.
    The closest to the proposed technical essence and the achieved result is a method of developing an oil reservoir consisting in pumping out oil from a reservoir by pumping an aqueous polymer solution into it through injection wells and extracting oil through production wells, in which poly
    the measure is injected with chemically catalyzed polymers, in particular partially hydroplated polyacrylamide (2.
    The disadvantage of the known method is low oil recovery of the reservoir, due to incomplete coverage of the reservoir.
    The aim of the invention is to increase oil recovery due to the increased coverage
    10 layer displacement.
    The goal is achieved by the method of developing an oil reservoir, which involves displacing oil from the reservoir by pumping an aqueous solution
    15 of the polikur through injection wells and the extraction of oil through operational skinches, polymer is the polymer obtained by the reaction of acrylamide and acrylic acid at a weight ratio of (60:10) - (90 /: 40) in an aqueous, alkaline medium under the influence of gamma ( Co-emission with and at an intensity of from 10,000 to 220,000 rad / h and a total dose of radiation and limits from 1,350 to 50,000 rad.  Improvement of the process of controlling mobility in the process of oil extraction, preferably in secondary and tertiary processes, can be achieved with the use of an aqueous solution of a water-soluble polymer, acrylamide and acrylic acid, resulting from the radiation polymerization.  A complete aqueous solution may contain about 10-60 wt. % lifOHOMepa.  The irradiation intensity is 250-1000000 rad / hr at a dosage of 500300000 rad.  The reaction product can be diluted with water and used directly or the polymer can be extracted from the reaction product, dried and then dissolved.  The rate of injection can be increased with the use of aqueous solutions of these. polymers versus equivalent molecular weights of known polymers.  The monomer is a combination of one compound selected from the group consisting of acrylamide and one compound selected from the group consisting of acrylic acid.  A small amount of additional ethylenically unsaturated copolymerizable monomers can also be used.  Irradiation of the monomer preferably occurs in an aqueous solution containing about 10-60% and preferably 01545 wt. % dissolved monomer.  At a lower monomer concentration, the product is a thickened polymer solution at a concentration above 15 wt. % product is a non-hardened gel.  At a concentration above 60% monomer, the product is insoluble in water; thus, high concentrations are undesirable.  It is obvious that the limit of the monomer concentration also depends on the radiation conditions of the monomer used and on the type. product to be obtained for any particular use.  The intrinsic viscosity of a polymer increases with increasing monomer concentration, reaches a point where the number of cross-links increases, while other variables remain constant.  An aqueous solution of the monomer should preferably contain no more than 5 ppm of transition metal ions, such as nickel, iron, cobalt and no more than OJ5 ppm, ion monovalent and divalent copper.  Irradiation of an aqueous monomer solution can be produced by high energy ionizing radiation.  The radiation wavelength is below 3500 A and preferably below 2000 A.  Radiation in nature can be electromagnetic or macroparticles.  examples include the irradiation of accelerated electrons, photons, neutrons, as well as x-rays and gamma rays, the latter being preferred.  The emission intensity is, preferably, from 1000 to 300000 rad / h and more preferably from 5000 to 200000 rad / h.  The intensity directly affects the molecular weight of the copolymer, t.  e.  at.  under the same conditions, low intensity, as a rule, gives higher molecular weights.  The radiation dose of the premise {o is about 1000 rad, and preferably about 1,500 rad.  The maximum dosage is preferably no more than lOOOOO glad and more no less than 50,000 more glad.  The dose of radiation directly affects the intrinsic viscosity and the degree of conversion of the monomer into the polymer.  At a given intensity of radiation and concentration of the monomer, an increase in the radiation, as a rule, leads to a decrease in the characteristic viscosity of the polymer obtained and an increase in the degree of conversion of the monomer into the polymer.  The dose of radiation also affects the solubility of the polymer in water and it has been found that if the dose of radiation is too high, a water-insoluble polymer can be obtained.  With a preferred dose of radiation, almost 100% and preferably 80-1009b conversion of the monomer into the polymer can be achieved without undue insolubility.  The pH of an aqueous monomer solution is not how.  usually critical, but with too low an insoluble product may form.  The preferred pH is 3-13 n, more preferably from 8 to P.  However, the indicators can be higher and lower, but it should be noted that hydrolysis occurs at a pH much less than 3 and much more than 11.  While this method can be used in the preparation of polymers with a characteristic viscosity of about 6 to 30 dl / g in 2N.  sodium chloride at 25.5 ° C, the process can be modified to produce polymers with a characteristic viscosity of less than 6 dl / g or higher, about 30 dl / g at 2 n.  sodium chloride at 25.5 ° C.  Polymers with an intrinsic viscosity lower than 6 dp / g are prepared by carrying out polymerization, as described above, in the presence of a chain growth agent.  The chain growth agent can reduce the growth of the active potmer chains and thus form an ovoid, populations with low molecular weight and lower characteristic viscosity.  In ka5.  As a chain growth agent, any chain growth agent can be used to help reduce the growth of polymer chains and the formation of lower molecular weight and lower characteristic viscosity of the polymer that can be dissolved in the reaction medium.  Examples of such agents include lower alkyl spirits), for example, methanol, zanol, and isopropaiol.  halogeno-compounds, for example trichloroacetic acid, thiosorbitol containing 2 thio groups and 4 secondary hydroxyl groups 1X and mercaptans.  The amount of chain growth agent depends on the desired degree of intrinsic viscosity, monomer concentration and chain transfer constant of the chain transfer agent used.  In the preparation of polymers with an intrinsic viscosity of about 6-30 dl / g, the use of a chain transfer agent is not necessary, but if necessary, such polymers can be obtained in.  the presence of chain transfer agents.  To obtain polymers with a characteristic viscosity higher than 30 dl / g, the polymerization reaction must be terminated when less than 75%, and preferably 60% of the weight of the monomer is converted to the polymer.  The intrinsic viscosity of the polymer obtained was found to decrease with an increase in the percentage of conversion monomer in the polymer.  For economic reasons, conversion should be at least 20%. .  The variable radiation intensities, the total radiation dose and the concentration and monomer indices are independent constant.  While the polymers used can be obtained at any monomer concentration, radiation intensity and dosage as indicated above, any combination of co-concentration, dose and intensity within these limits cannot be used to obtain the polymers used in the proposed method.  For example, if the polymer can be obtained npw, the monomer concentration is 60 wt. The dose of radiation is low to form a water soluble polymer; when using a monomer concentration of 60 wt. %, the intensity of 250 rad / h and a dose of 300,000 glad the formation of water-insoluble polymers.  Due to this interdependence of intensity, dose, and monomer concentration, it may be necessary to apply a limited amount of experimentation to obtain a polymer with the desired intrinsic viscosity.  In tab.  Figure 1 describes the characteristics of obtaining samples of polymers with different viscosity indices, efficacy, dose, monomer concentration, degree 2 &amp; conversion and chain growth agent to characteristic viscosity of the polymer.  In accordance with these conditions of the reaction, the preparation of a water-soluble polymer with an intrinsic viscosity different from the intrinsic viscosity of the polymers is given in tab.  1, can be determined by minor changes in the reaction conditions given. in tab.   to obtain a polymer with an intrinsic viscosity close to that of the polymer to be obtained.  Such changes can be made taking into account the given data on the intensity of the effects, the dose, the monomer concentration, the percentage of monomer converted to polyme, the chain growth agent on the characteristic viscosity of the polymer.  For example, a polymer with an intrinsic viscosity of about 16 dl / g can be obtained under those CONDITIONS of the reaction of example F table.  1, but the intensity of the radiation increases, the total dose of radiation increases, the monomer concentration quenches, the percentage of monomer conversion increases, and / or the reaction takes place in the presence of a chain transfer agent.  Preferably, this reduction in intrinsic viscosity is achieved by increasing the intensity of radiation, lowering the monomer concentration and / or using a chain growth agent. The product of irradiation is an aqueous solution of a water-soluble polymer, which can be in the form of a solidifying fluid or non-blocking rubber gel concentration dependent and intrinsic: polymer viscosity.  The viscosity of the polymer solution increases with increasing polymer concentration and intrinsic viscosity of the polymer.  The resulting polymer solution can be mixed with water and used directly or the polymer solution can be concentrated by known methods or reconstituted in a special form, for example, in a dry form.  For example, a non-solid gel can be separated and the water extracted by known methods.  Water can be extras. Water from a gel is water-miscible with a volatile organic liquid that does not represent an affinity for a copolymer, such as methanol.  Compliantly compatible with formation water and rock.  The polymer may contain cations, preferably monovalent, more preferably sodium.  The polymers obtained as a result of radiation polymerization have, as a rule, relatively low Haggeis constants.  This constant refers to linearity.  lnmera, where the molecular weight is constant, t. e.  for two copolymers having similar molecular weights, but different Hagtens constants (lower Haggens constant means a more linear polymer).  Haggens constant polymers below 1 and preferably below 0.7 and more preferably below 0 are most often used in the present invention.  In some cases, a mixture of polymers with low, medium, and / or high Huggins constants is consistent with obtaining an improved method for developing a petroleum reservoir.  It is desirable that the copolymer does not plug the formation either by adsorption, or by adsorption or flocculation of the clay in the formation, or by reaction with the formation waters.  Linear polymers, tons  e.  unblown, especially suitable for this purpose.  If copoly1 ": ep is anionic, maximum mobility characteristics are usually achieved with minimal flocculation.  The intrinsic viscosity of the polymer can vary from less than 1 to 60 dl / g, preferably from 5 to 35 dl / g.  The permeability of reservoir rocks subjected to watering has a large effect on the intrinsic viscosity, but low permeability of the rock requires, as a rule, lower intrinsic viscosity.  For example, if a bridge below 50 requires an intrinsic viscosity of less than 10, a permeability of 200 gli more requires higher characteristic viscosities and more than 20 for better results.  Indicators characteristic viscosity measurement} in a solution of 2 n.  sodium chloride at 25.5 ° C.  Obviously, copolymers with very high characteristic bridges can plug holes in the reservoir, these may be desirable in heterogeneous formations.  However, the efficiency of the polymer increases with increasing intrinsic viscosity, and the degree of branching does not increase and the polymer does not clog the formation.  Mixtures of polymers with different intrinsic viscosity values can also be used.  If the formation has a high permeability, t.  e.  exceeds 1 D, characteristic viscosity preferably above 25 fv-. lr.  The polymer can be dissolved and diluted with water to the desired concentration.  It is preferable to avoid the use of water containing a large amount of polyvalent metal ions, which adversely affect the viscosity of the polymer solution or dissolve the polymer in water.  The amount of metal ionopic acid present in an aqueous solution of a polyviajjCHTHbix polymer depends on the specific metal ions, the temperature and pH of the solution, as well as on the characteristic viscosity and anion content of the polymer.  As a rule, the polymer becomes less resistant to phi- (with the polyvalent metal ion, as the intrinsic viscosity, anionic content and concentration of polymers increase.  It is preferable to avoid the use of water containing a sufficient amount of copper and / or iron ions, due to the negative effect on the solubility of the polymer in water, etc.  d.  If, at a given polymer concentration, the maximum viscosity is desired, the water should preferably contain less than 500 ppm of solid dissolved substances (TPB), t.  e.  must be soft.  If maximum viscosity is desired, water should preferably contain less than 50 ppm of divalent cations, for example calcium and / or magnesium.  If it is necessary to achieve maximum viscosity, dissolve the polymer and inject it into the formation should be avoided.  When maximum viscosity is reached with a gel in the form of a polymer, the gel is first screwed up, and then cut into small pieces, for example, the size of the VVS, and then mixed into the aqueous solution at low shear rates.  The pump characteristics and agitator speed are especially taken into account at low shear rates.  In order to facilitate the solubility of the polymer, water-soluble alkaline salts can be added to the aqueous solution, i.  e.  salts giving a pH above 7 in water, for example alkali metal carbonates.  Sodium carbonate is preferred in this case.  The amount of alkaline salts added to water must be strictly controlled in order to avoid hydrolysis of the polymer.  Other known additives may also be used.  The polymer can be injected (1) into the drainage reservoir or the aqueous solution of the polymer can be supplied following a suitable displacement fluid.  To improve the injection profile, the polymer solution is fed up to the usual extraction process, for example, to the displacing liquid.  When the polymer is injected after the effluent, preferably less than 5-70% or more wells.  Aqueous polymer pacfbop can contain different additives to impart the desired qualities to the oil production process.  For example, salts, surfactants, pies, pH regulators, oxygen-removing agents, corrosion inhibitors, biocides, passivators, viscosity stabilizers, stabilizers, etc. can be added to an aqueous polymer solution.  d.  Thus, any components that are compatible with the polymer and which have a negative effect on the dewatering of the formation can be added to the aqueous polymer solution.  A particular case is the addition of a polymer to the aqueous phase of an emulsin or micellar dispersion.  All data are percentages of volume.  Obtaining copolymers.  For the tests, polymers obtained as a result of gamma radiation from kobat 60 are used, the intensity of radiation and the dosage are given in Table.  one.  The method for producing polymer A is given below; for the preparation of other polymers, the methods are identical except for the data given in Table.  I.  To 24,000 g of deionized water are added 692 g of CcdIxyukidi and nat.  After cooling the solution to 30 ° C, 1.250 g of acrylic acid is added.  Further, 5,000 g of acrylamide is added with stirring, and the pH is adjusted to 9.4.  The resulting solution contains 75 wt. % acrylamide (AAD) and 25 wt. % sodium acrylate (NaA) and has a total monomer concentration of 21.4 wt. %  The solution is blown through Nj for 20 minutes and then closed.  The sample is subjected to nrra diacine cobalt 60 gamma radiation at an intensity of 18,000 rad / h with a total dose of 8800 rad / h (P).  The resulting product has the form of a gel.  The portion of the gel is weighed and then extracted with methanol before the polymer precipitates.  The polymer is dried under vacuum at 36 ° C and a pressure of 0.02 pounds / inch for 24 hours until a constant weight is obtained at 110 ° C.  The weight of the dry product divided by the theoretical weight gives a 93% monomer conversion.  A portion of the gel is dissolved in water and extruded in the form of spaghetti, cut to size of explosive particles, and then dissolved in water with stirring at low revolutions per minute to avoid a significant shift. polymer  The remaining gel is reduced to cjTcoro powder from the first extrusion of the gel, then dissolves in water and with the addition of methanol. the polymer falls out of solution.  The polymer is granulated to less than 20 mesh and suipgs in vacuum at 60 ° C.  Inherent viscosity is measured at 25.5 ° C in 2N.  NaC1 aqueous solution.  The Haggens constant is measured in a known manner.  Monomer used in Sample C is diluted in water with a content of 9.18 wt. % methanol (table.  one).  210 Example.  Dehydration.  Samples taken from the sandstone formation {}, first washed with toluene, then dried in a vacuum.  Permeability is 100-200 ppm.  BpycicH sandstone is then encapsulated into plastic except for the ends.  The polymers are dissolved in the water containing the table.  2 h / ths. soluble substances (TPB) and filtered through a sieve with a mesh size of 200 mesh for screening large particles.  Then injected into sandstone samples.  The initial permeability and permeability after washing is measured with water containing, for example, 500 ppm.  iPB.  The corresponding mobility indices are measured after injection of the polymer solution into 10 pore objects.  The results are shown in Table.  2  Series 1-6 as compared with series 7-8 require higher corresponding mobility in the rear and high reduction in the rear.  Series 7-8 are conducted using commercial, partially hydrolyzed high molecular weight polyacrylamide.  The content of anisnes in example 1 is about 30%, the intrinsic viscosity is 12.7 to 2 and.  sodium chloride solution at 25.5 ° C and Haggens constant 0.56.  Polymer 11 has an anion content of 30%, an intrinsic viscosity of 15, i in 2 n.  sodium chloride solution at 25.5 ° С and Haggens postsignal, trimerno, 0.26.  Example
    [2]
    2. Sandstone samples with permeability of about 500–1500 ppm are treated as in Example 1. Then they are washed with an aqueous solution of 700 ppm of the indicated polymer. The results are given in Table. 3. The corresponding polymer mobility of the proposed method in the front and rear of sandstone samples is almost equivalent, but not to polymer 111. Polymer 111 is a commercially partially hydrolyzed very high molecular weight polyacrylamide with an intrinsic viscosity of about 20.1 to 2 n. sodium chloride solution at 25 ° C and Haggens constant 0.16. Example
    [3]
    3. Seri 3 and 4 table. 3 vep4einii on the chart corresponding mobility on. ordinate volume of wells for the front and rear samples. FIG. 1 shows Polymer E (Series 3), where it is indicated that the corresponding mobility of the front and rear is substantially equal and constant after six volumes of wells. FIG. Figure 2 shows that the corresponding mobility of Polymer 1P (Series 4) in the front and rear is significantly different and increases with increasing injection volume into the well. Permanent mobility (see fig. Can be achieved after carrying out permeability. Increasing the corresponding mobility (see fig. 2) shows a permanent reduction in mobility; this is undesirable in secondary and tertiary oil production processes. Example 4. Example | illustrating the effectiveness of the proposed copolymers in the extraction of oil from highly permeable formations. Pipes with a diameter of 2 and a length of 6 are filled with white Ottawa (grain size 60-200 mesh) moistened with water. To facilitate filling with sand, the bottom pipe vibrations are broken. The ends are covered with metal ceramic discs, and pressure hooks are placed along the pipe. The absolute permeability of the filled pipes is 4-6 grams and the porosity is about 35%. The pipes are flooded with oil indicated in Table 4 (viscosity is 23). ° C) until saturated with water and then watered with either 1.1 volumes of wells with water or 1.1 volumes of wells with an aqueous solution of a sample, then 1.1 volumes of water are washed in. The results are presented in table.
    [4]
    4. Oil is additionally extracted, which is the difference between oil produced after watering and polymer, i.e. nodenenBO increasing flow produced when watering has been added to water content of 1214% of pore volume for 200 chemically pure oil and 10-12% dd 1,120 chemically shy oil. As indicated in the table. 4, the Schülimers according to the proposed method yield up to 30 more than 220 chemically pure oil compared to known polymers at the same degree of concentration, and about 10% more than 220 chemically pure oil at half the concentration. For 1,140 chemically pure petroleum, the proposed copolymers make it possible to extract 27% more oil than polymer 111. The mobility of the dehydrating medium reaches 1.1 pore volume after injection and depends on the oil pipe, the pipe filled with sand, and the water content of the dewatering feed increases with reduced oil prices. The ratio of mobility is determined by the mobility of the displacing fluid divided by the mobility of the displacing fluid. If the ratio is greater than 1, then mobility is unfavorable. For the production of 210-22S chemically pure oil, the copolymers of the proposed method have a favorable effect, whereas for polymers 11 and 111 the mobility ratio is unfavorable. However, both polymers have an unfavorable ratio when displacing 1,140 chemically pure oil, but the ratio of the mobility of the copolymers in the proposed method is 50% of a half measure of 111 and, therefore, more efficient. Example 5. For the selection of the proposed copolymers with lime, tests were carried out with sandstone samples (diametr 1, length 3.). The samples are interrupted by Viachale with toluene, then dried under vacuum. Then they are surrounded by water containing about 500 ppm. TRV. Approximately 10 volumes of pores of the solution of the nonmiepa solution are injected at a speed of 10 and 1 ft / day, and then the samples are washed with a water of 10 ft / day (the water content is approximately 500 ppm of TPB). The input injection and polymer concentrations obtained are analyzed to calculate polymer losses. The results are shown in Table.
    [5]
    5. The copolymer according to the proposed method has the highest mobility index for the rear of the rim-like concentrations. These copolymers give the most uniform corresponding mobility and the rate of permeability through the sample.
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    引用文献:
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