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    • 专利摘要:
    High molecular weight N,N-dimethylacrylamide copolymers and terpolymers were synthesized. These polymers offer outstanding advantages as injection water viscosifiers in enhanced oil recovery processes including chemical, miscible, and steam or in processes requiring profile improvement through adsorption and/or gelation. They are very valuable in applications where high salinity is a problem since they are relatively insensitive to metal salts (such as those containing polyvalent ions, such as Ca++ and Mg++).
    公开号:SU1314958A3
    申请号:SU833595851
    申请日:1983-05-10
    公开日:1987-05-30
    发明作者:Флойд Кастнер Кеннет
    申请人:Дзе Гудйер Тайр Энд Раббер Компани (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to oil production, in particular, to methods for flooding oil deposits with thickened water.
    The purpose of the invention is to increase the recovery rate of oil by increasing the viscosity of the displacing agent. To improve the ratio of water and oil mobility, water-soluble high molecular weight polymers are usually added to the injection water used to extract oil (greater than 1,000,000. A significant increase in water viscosity can be achieved by adding certain polymers in small amounts (100 -1500 parts per ml.). Usually, two main types of polymers are used for this: polyacrylamides and polysaccharides. I use partially hydrolyzed and anionic polyacrylamides: in some cases, the cation was also used. polyacrylamides. An improvement in the mobility ratio achieved by using polyacrylamides decreases with increasing salinity and the concentration of bivalent members. Therefore, a source of light is usually needed for effective use of polyacrylamides in oil extraction (EOR). water (total soluble solids less than 10,000 ppm). The medium into which the polyacrylamide solution is injected should also be practically free of salts.
    Poly-L, K-dimethylacrylamide (poly-DMA) is a non-ionic compound and therefore insensitive to metallic salts.
    N about n and SN
    sn
    N, N-Dimethyl Acrylamide (DMA)
    + CH2- fH-
    N
    L .j
    POLY-DMA
    Due to their low molecular weight, polymers synthesized by known methods do not usually provide the high viscosity required for use in EOR. The invention provides a method for synthesizing ultrahigh molecular weight DMA copolymers (polymers containing chain compounds, repeating units derived from DMA monomer). These high molecular weight DMA copolymers are good thickeners for use in EOR. This method uses the copolymerization of monomer S, N-dimethylacrylamide (DMA) with sodium sulphate monomer styrene (SSS) or monomer N-methylol acrylamide (NMA).
    S03 Na

    sodium styrene sulfonate (SSS)
    n and sn-s-s-kg

    snrn

    thirty
    N-methylolacrylamide (NMA)

    In this polymerization can be used the system of initiation of oxidation - reduction of persulfate
    35 ammonium (sodium pyrosulfate). Copolymerization results in a polymer with a much higher molecular weight than that which can be synthesized using only 40 DMA monomer.
    The invention discloses a proposed method for recovering oil from an underground oil reservoir and involves injecting viscous water into the area of the reservoir through at least one injection well, with the result that oil flows from the specified area to collect it through at least
    at least one output well injected into the reservoir area; viscous water contains a water-soluble, chain-bonded polymer, obtained from N, N-dimethylacrylamide and at least
    least one member selected from
    a group consisting of sodium methyl acrylamide and sodium styrene sulfonate:
    The method of extracting oil from oil-bearing underground reservoirs, including
    injecting viscous water into the field area at least one injection well, resulting in oil flowing out of the area of the reservoir
    for collecting through at least one outlet well injected into the reservoir, viscous water contains a polymer in water, with a chain link formed from N, N-dimethyl acrylamide, of at least one member selected from the group containing N-methylol acrylamide and sodium styrene sulfonate, and at least one member selected from the group
    one member selected from the group consisting of sodium metabisulfite, sodium thiosulfite and sodium dithionite to the reaction solution, 5 containing water, oil, dispersing agent, N, N-dimethyl acrylamide and at least one member selected from the group consisting of N-methyl acrylamide and sodium stifolol sulfonate in quantities and under conditions sufficient to initiate polymerization an aqueous solution of the polymer, including water and a high-molecular-weight chain-bonded polymer, containing sodium 2-acrylamido -2-t5 called from , N-dimethyl acrylamide and
    tylpropanesulfonate, potassium 2-acrylamino-2-methylpropanesulfonate, ammonium 2-acrylamido-2-methylpropanesulfonate and calcium 2-acrylamido-2-methylpropanesulfonate;
    A method for synthesizing high molecular weight polymers, comprising adding a metal sulphate and at least one member selected from the group consisting of sodium metabisulfite, sodium thiosulfate and sodium dithionite to an aqueous reaction solution consisting of N, N-dimethyl- rilamide and at least one member selected from the group consisting of N-methylol acrylamide and sodium styrene sulfonate, in quantities and under conditions sufficient to initiate polymerization;
    A method for synthesizing high molecular weight polymers, comprising adding a metal persulfate and at least one member selected from the group consisting of sodium metabisulfate, sodium thiosulfate and sodium dithionite to an aqueous solution of the reaction consisting of N, N- dimethyl acryl amide, at least one member selected from the group consisting of sodium methyl acrylamide and sodium styrene sulfonate and at least one member selected from the group consisting of sodium 2-acrylamido-2-methylpropanesulfonate, potassium-2 -acrylamido-2- methylprop sulfonate, ammonium 2-acrylamido-2-methylpropanesulfonate, and calcium 2-acrylamido-2-metsh1pro
    , j The ultrahigh molecular weight DMA and SSS copolymer can be synthesized in an aqueous medium at a very wide temperature range. The loading concentration of the monomer used in the synthesis of DMA / SSS copolymers in an aqueous solution can vary widely from 2 to 50% by weight, based on the total weight of the reaction solution (monomers, water, initiators, etc.).
    pansulfonate in quantities and at
    conditions that are sufficient for the use of
    start polymerization; monomer loading concentration (total
    Method of synthesis of a polymer with a high concentration of all monomers in an aqueous
    molecular weight, which includes the addition of the reaction solution) in the range of 10% of the metal persulphate and by 20% w / w. For example, the composition of
    1A9584
    one member selected from the group consisting of sodium metabisulfite, sodium thiosulfite and sodium dithionite to the reaction solution, 5 containing water, oil, dispersing agent, N, N-dimethyl acrylamide and at least one member selected from the group consisting of N-methylol-acrylamide and sodium styrofol sulfonate in quantities and under conditions sufficient to initiate polymerization; an aqueous polymer solution comprising water and a high molecular weight chain chain polymer, with at least one member selected from the group consisting of N-metstoltol-acrylamide and styrene sodium sulfonate;
    a water soluble high molecular weight polymer with chain links, formed from K, K-dimethylacrylamide and at least one member selected from the group consisting of N-methylol acrylamide and sodium styrene sulfonate.
    H O H CH CH2-C-c4j-C-CH7.
    sh
    Metal 2-acrylamido-2-methylpropanesulfonate
    (M Na, K, NHi)
     P 0
    СНг С-С-ТЯ-С- СИ2.2. ЗОЗ СНп,
    Sa

    Calcium 2-acrylamido-2-methylpropanesulfonate.
    The super molecular weight DMA and SSS copolymer can be synthesized in an aqueous medium at a very wide temperature range. The loading concentration of monomer used in the synthesis of DMA / SSS copolymers in aqueous solution can vary from 2 to 50% by weight, based on the total weight of the reaction solution (monomers, water, initiators, etc.).
    bmno it is advisable to use
    five
    80 parts of water, 19.8 parts. WMAAO, 02 parts. SSS (monomer loading concentration 20% by weight) can be used in the polymerization in the synthesis of ultrahigh molecular weight DMA / SSS copolymers. In the DMA / SSS polymerization, the loading level of the SSS monomer varies from 0.1 to 5% by weight of the total weight of the monomers used in the reaction solution. Good results were obtained when using SSS monomer loading in the amount of 0.5-1.5 wt.% Of the total weight of all monomers. The best results were obtained using a total monomer concentration of about 20 wt.% (Total concentration of all monomers in the reaction solution) in this aqueous copolymerization.
    DMA / NMA copolymers with ultra-high molecular weight can be synthesized using a reaction solution including DMA, NMA, oxidation-reduction initiators and water. The loading concentration of the monomer DMA / bfMA used in this aqueous polymerization can vary in the range of 2-50% by weight of the total weight of the reaction solution. It is preferable to use a loading concentration of monomer in the range of 10 to 20 wt.% Of the total reaction solution. The level of NMA loading used in such a polymerization reaction can vary in the range of 0.1–5% by weight of the total amount of monomers in the reaction solution. Very good results have been obtained and it is therefore preferable to use a loading level of NMA in the range of 1-3% by weight of the total monomers. For example, a reaction solution comprising 80 parts of water, 19.4 parts of DMA and 0.6 parts of NMA leads to productive polymerization (the level of loading of NMA is equal to 3% by weight of the total weight of monomers).
    Such polymerizations, leading to ultrahigh molecular weight DMA / SSS and DMA / NMA copolymers, can be initiated using free radicals, for example, oxidation-reduction initiator systems such as metal persulfates and pyrosulfites. Potassium persulphate and ammonium persulphate have been used with great success as initiators of oxidation-reduction in conjunction with pyrosulfur14958-6
    tom rub. Various metal persulphates (for example, sodium and potassium) and ammonium persulphate (hereinafter, the term metal persulphates will include 5 ammonium persulphate) can be used as oxidation initiators - reduction when used in combination with sodium pyrosulphate, sodium thiosulphate and sodium dithionate. on three . These components of the redox initiator can be used in an amount of 0.01-0.1 h per 1UU h of monomer. Most successful for initiation
    J5 similar polymerization turned out to be an amount of ammonium persulfate, equal to 0.0375 parts per 100 parts of monomer, and sodium pyrosulfate, equal to 0.0375 parts per 100 g of monomer. You can also use some other initiation systems. For example, metal persulphate used at elevated temperatures alone can initiate the polymerization of co5 DMA polymers (copolymers DMA / SSS and DMA / NMA).
    The temperature range at which this polymerization can be carried out varies from 5 to 50 ° C. Pred0 is a respectful range of 15-25 ° C, with the best results being achieved at 20 ° C. The time required for polymerization (5 and its end), is usually 6-18 hours. This reaction time may vary depending on the types of initiators used, the polymerization temperature and concentration.
    0 It is usually desirable to remove dissolved oxygen from the aqueous solution before starting the polymerization. This can be done by passing inert gas bubbles through the solution or
     nitrogen before the polymerization begins. It may also be desirable to continue passing an inert gas or nitrogen during the initial stages of the polymerization.
    0
    Such aqueous polymerization, which results in the formation of DMA / SSS and DMA / NMA copolymers with ultra high molecular weight, leads to the formation of a water-soluble gel-like mass. This polymer should be dissolved in water and dissolved in additional water for use as a viscosity enhancer.
    when applied to EOR. These polymers should be dissolved in such an amount of water that the resulting polymer concentration leads to the desired viscosity of the injected water. It is obvious that the viscosity of the injected water increases with increasing polymer concentration. Usually preferred for use in an EOR, the viscosity (according to Brookfield) is 2-30 cP.
    When preparing these solutions, it is necessary that the shear forces do not cause molecular breaks in the polymer chains of these copolymers. In order to avoid the formation of breaks in the bonds of the molecules of the bond when dissolving these polymers, strong mixing, stirring, etc. should be avoided. The appearance of such molecular breaks, caused by shear forces, can significantly reduce the molecular weight of polymers and, therefore, its usefulness for increasing viscosity.
    DMA, may comprise 0.1-10% by weight of the total monomer loading. The number of meta-AMPS, useful in the polymerization of these three-link polymer
    5 ranges from 4 to 50% by weight of vol. monomer loading. The amount of NMA monomers required for this polymerization decreases as the level of DMA monomer used increases.
    tO is polymerizable. The concentration of qi loading of the monomer can vary with in the range of 2-50 weight. from the entire target reaction. The preferred loading concentration of monomer is
     5 is 10-20 wt.%. The optimum ratio of the various monomers involved in the polymerization of a three-stage polymer varies with temperature, the total concentration of
    0 load of monomers and the number of inits ators;
    The initiators suitable for the polymerisation of the three-stage polymer DM are the same initiators, which
    in the EOR (viscosity decreases). 25 solutions have been proposed for use.
    The incorporation of these polymers in water should last a long time. Such high molecular weight DMA copolymers are very valuable viscosity enhancers of injected water for EOR due to their permeability to salts (the viscosity of their aqueous solutions is not due to the presence of salts).
    DMA, NMA, or SSS triple polymers with metal salts of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) with ultra high molecular weight are very useful as viscosity enhancers for use in EOR. Such kind of triple polymers have very high viscosity in fresh water and retain a very high viscosity in brine. Sodium AMPS (sodium-2-acrylamido-2-methylpropanesulfonate), calcium AMPS (calcium 2-acrylamido-2-methylpropanesulfonate), potassium AMPS (potassium 2-acrylamido-2-methylpropane sulfonate), ammonium AMPS (ammonium 2-acrylamide 2-methyl propanesulfonate) proved to be very useful monomers for the synthesis of these three-unit polymers of ultrahigh molecular weight. The DMA loading level in the synthesis of such three-unit polymers can be 30-95% by weight of the total monomer loading. NMA monomer loading level used in the synthesis of these three-chain monomers
    DMA, may comprise 0.1-10% by weight of the total monomer loading. The number of meta-AMPS, useful in the polymerization of these three-stage polymers,
    varies from 4 to 50 wt.% of the total monomer loading. The amount of NMA monomers required for this polymerization decreases as the level of DMA monomer used in the polymerization increases. The loading concentration of the monomer can vary from 2-50 wt. from the entire reaction solution. The preferred loading concentration of the monomer is 10-20% by weight. The optimal ratio of the various monomers involved in the polymerization of the three-unit polymer varies with the temperature, the total loading concentration of the monomers and the amount of initiators;
    The initiators suitable for the polymerization of the three-membered polymer DMA are the same initiators which
    have been proposed for use
    five
    Q
    in the synthesis of DMA copolymers. The concentration of initiators suitable for use in the polymerization of the three-unit polymer may be 0.010-0.05 parts per 100 parts of monomer. Preferred concentration of initiators. lies in the range of 0.02-0.04 hours per 100 hours of monomer.
    The system for initiating oxidation, which is 0.0375 parts per 100 hours of ammonium persulfate monomer and 0.0375 parts per 100 hours of sodium pyrosulfate monomer, has been successfully used in this polymerization of a three-stage polymer. Usually, to initiate polymerization, an oxidation-reduction initiator is added in an amount of 0.5% by weight of an aqueous solution.
    Temperatures at which this polymerization can proceed.
    0
    five
    also
    can vary from 5 to 50 ° C. Preferred is a temperature of 15-25 ° C.
    As with the polymerization of the DMA copolymer, it is desirable to remove dissolved oxygen from the aqueous solution. This can be accomplished by passing an inert gas (nitrogen or helium) through the aqueous composition of polymerization, by using oxygen scavengers (for example, sodium dithionate), or by vacuum degassing. The preferred monomer composition used in
    the polymerization of the three-unit polymer contains, wt%: DMA AO-50; NMAO, 1-10; metal-amps 40-50. After completion of the polymerization, which usually takes 6-18 hours, its product has the form of a gel-like mass. Such aqueous polymerization reactions generally have a high yield (greater than 99%). The weight content of the chain bonds formed in the polymer from the monomer is equal to the weight content of this monomer in the loading of the monomers used in the synthesis of this polymer. The resulting material must be dissolved in an amount of water that provides the desired viscosity of the injected water used in the extraction of oil. As with DMA polymers, the formation of shear-induced molecular breaks in this three-phase polymer should be prevented. This can lead to a loss of viscosity of the injected water per unit weight using a three-stage DMA polymer. Like DMA copolymers, DMA three-stage polymers require a long time of dissolution in sprayed water, which is associated with the need to eliminate the occurrence of significant shear forces (resulting in strong shaking, stirring, etc.). The viscosity of the injected water produced can be controlled by dissolving in water the required amount of three-membered polymer DMA. The three-part polymer obtained by this polymerization has an ultra-high molecular weight and significantly increases the viscosity of fresh water. The three-membered polymer DMA is affected by saline solutions, however, it retains a high viscosity in salt water. The three-link polymers DMA, NMA, and metal-AMPS are excellent viscosity enhancers for a variety of applications used in oil recovery.
    OMA copolymers and three-unit polymers can also be synthesized by using polymerization in an oil-water dispersion. Ultra-high molecular weight polymers obtained by polymerization in an oil-water dispersion are liquid (and not gel-like.

    (ABOUT
    31495810
    | as in water polymerization). This liquid can be easily diluted further to obtain the polymer concentration required for use as injected water when extracting oil. Additional dilution is achieved almost immediately after mixing with additional water. The final properties of the copolymers and three-unit polymers of DMA obtained by polymerization in an oil-water dispersion are equivalent to the properties of the corresponding polymers obtained in aqueous polymerization 15 (they are equally high-quality viscosity increments for oil recovery). Polymerization in water-oil dispersion has a significant advantage over water polymerization, since the resulting polymers with ultra-high molecular weight can be easily and quickly dissolved (with further dilution) in the injected water.
    20
    thirty
    35
    40
    25
    Synthesis of polymers DMA / SSS, DMA / NMA and three-unit polymers DMA / SSS / metal AMPS and DMA / NMA / metal AMPS in an oil-water dispersion is carried out using the same composition of monomers, activators and the same reaction conditions as in the synthesis in water ultra high molecular weight polymers. In addition to pea-- gents involved in water polymerization, oils and a dispersing agent are also present in the oil – water dispersion. Examples of oils suitable for use include kerosene, diesel fuel, hexane, decane, pentadecan, benzene, toluene, 2, 4-dimethyl-hexane, mineral oil (liquid petrolatum) and 3-ethyloctane. This is not an exhaustive list of applicable oils. Most alkanes containing 5 or more carbon atoms can be used as well. also most aromatic hydrocarbons. 50 Alkenes should not be used because they can be involved in polymerization. Dispersing agents are non-ionic surfactants, soluble in hydrocarbons and insoluble in water. Examples of dispersing agents that can be used in polymerizations in an oily dispersion are polyesters, such as
    45
    55
    such as Igepal SO-430, manufactured by the GAF Corporation, polyglycerolins, for example, Vitconol-14, manufactured by Vitko Chemical, and polyglycerol stearates, for example, Vitkinol-18b (Vitko-Chemical), as well as mixtures of these substances.
     С9Н 9- О О-СН-гШ2-ОУз
    IGEPAL SOCHZO
    JTH dispersants (non-ionic surface substances) are added to the oil, which is used in water-oil polymerization. The oil used in this polymerization contains 2-20 wt.% Dispersing agent. The feed composition used in water-based polymerization contains 25 wt.% Of oil and dispersing agent in an amount depending on the total amount of the reaction solution. In such a polymerization process, a larger amount of oil can be used with a corresponding increase in the amount of dispersing agent, but, as a rule, this is not advantageous. Good results were obtained using a mixture containing about 25% by weight of monomers, 50% by weight of water and 25% by weight of oil. A composition containing less than 25% by weight of monomers can also be used, but this does not give good results.
    It is often desirable to use deionized water in such a composition. Oxygen dissolved in the monomers, water and oil must be removed before polymerization. This can be done by passing an inert gas or nitrogen through a mixture of monomers, water and oil. The mixture of monomers, water, and oil is mixed vigorously to form a water-in-oil emulsion. The emulsion is brought to the desired temperature (usually to ambient temperature, about 20 ° C) and initiators are added to it. Ammonium persulphate is successfully used as initiators, after which sodium pyrosulphate is added. The composition containing the initiator is stirred throughout the entire polymerization process.
    After the required time has passed, the polymerization reaction can be stopped by adding a polymerization breaker such as hydroquinone.
    five
    five
    simple methyl ether. The reaction time is 6-18 hours. The time required for the reaction depends on the terature, the concentration of initiators and the desired degree of polymerization. It is usually desirable to bring the reaction to completion (when the entire supply of monomers is exhausted). Such polymerization reactions in water-oil emulsions have a high yield (exceeding 99%). The weight content of the chain bonds formed from the monomers in the polymer is equal to the weight content of this monomer in the load of all the monomers used by the P synthesis of the polymer.
    The effectiveness of polymers to increase the amount of recoverable oil as viscosity enhancers of injected water is partly determined by their molecular weight. To efficiently use these polymers when extracting oil, it is necessary that they have a high molecular weight (1,000,000 and Phmie). Thus, the determination of molecular weight is an important element in the characterization of polymer viscosity enhancers of injected water. The laser beam scatter method can be used to determine the average molecular weight of these polymers.
    The average molecular weight can be determined analytically as follows. I
    0.3-0.5 g of copolymers of dimethylacrylamide (sodium styrene sulfonate DMA / SSS) were placed in 100 ml beakers. 75 ml of distilled water was added to each of the four menses; after a period of 6 days dissolution occurred. Then the polymer solutions in the tumors were diluted with distilled water to a volume of 100 ml. The remaining samples with different concentrations, used in the method of light scattering, were volumetrically prepared from these solutions. The specific increments of the refractive index were measured with a Bryce-Oenix differential refractometer equipped with a mercury lamp and band-pass filters with bands in the 633, 546 and 436 nm ranges. Calibration was performed on potassium chloride solutions. Small-angle scattering of the laser beam was carried out using a KMH-6 photometer Chromatic after filtering
    0
    five
    0
    five
    13131А
    Thieves filter on 1.2 microns. Scattering on all samples was measured in a ring of 6-7 ° with a diaphragm of 0.2 mm. The KHM-6 laser had a wavelength of 633 nm.
    The average molecular weight of the various DMA / SSS copolymers, determined using the procedure described, is given in Table. one.
    The copolymers differ in the weight content of sodium styrene sulfonate, in the total amount of monomers in the reaction solution used in the synthesis. Brookfield copolymer viscosity was also determined by the method described in Example 3.15.
    Table 1


    3.8
    4.4
    1760000 1830000
    --СН2.-Ш
    N СНт, | x
    where X and y are integers, indicates that the distribution of chain links formed from DMA and No. 1A in the polymer chain is random.
    NMR spectroscopy was also used to confirm
    Sho-ss o
    I

    vT
    where X, y and Z are integers.
    suggests that the distribution of chain links formed from DMA, NMA and NaAMPS in the polymer chain is random.
    14 Continuation of table 1

    5.4 f, 8
    2960000 3590000

    All DMA / SSS copolymers have a high molecular weight (in excess of 1,000,000). As can be seen from Table 1, the molecular weight increases with increasing viscosity according to Brookfield. Various DMA / SSS and DMA / NMA copolymers have been synthesized, having much more viscosity according to Brookfield than those given in this example. Their molecular weight is greater than the molecular weight indicated above.
    To confirm the presence of chain bonds in the DMA / LHMA copolymers formed from S, S-dimethylacrylamide and N-methylol acrylamide, nuclear magnetic resonance (NMR) spectroscopy was used. These chain-bonded copolymers formed from DMA and NMA can be represented by the formula
    .
     I
    ; N
    H CH20H

    40
    jy
    55

    the presence of chain bonds in three-link polymers DMA / NMA / NaAMPS, formed from N, N-dimethylacrylamide, N-methyl acrylamide and sodium-2-acrylamide-2- methyl propane sulfonate, which can be represented by the formula
    I
     SNS
    . to e.
    CH CH-iSO Na
    Samples of DMA / NMA copolymers, three-unit DMA / NMA / NaAMPS polymers used in NMR analysis, were synthesized in 10 mm JTMP sample tubes by introducing
    151314958
    a known amount of each monomese is possible on a regular basis.
    or its aqueous solution (see Table 2) into tubes, followed by diluting DjO and bringing the total weight of each solution to 2.5 g. Initiators were added to polymerize the samples. Polymerized samples were tested at a frequency of 20 MHz with a restriction applied,
    the power of the isotope C;
    unchanged H band with unbounded sequence. The sweep width was 5000 Hz, the accumulation time was 0.5 s, the pulse delay was 4.5 s, and the pulse width was 12 µs.
    Tab. 2 shows the different monomer compositions) used in
    Copies of the reaction solutions used in the synthesis of these polymers. In each of these examples, polymerization was initiated by adding 0.030 ml of a 1% aqueous solution (NHjjSjOg and 0.030 ml of a 1% aqueous solution of Na SjOj. Table 2 also shows the percentage of each monomer (relative to the content of all monomers) contained in the solution reactions .. The total amount by weight of chain bonds obtained from each monomer in the polymers is also shown in Table 2 (column 3).
    table 2
    sixteen
    The percentage of chain bonds formed from each of these monomers (as shown in column 3) is determined by NMR. As can be seen from the comparison of the percentage of this monomer in the reaction solution and the percentage of chain bonds formed from this monomer in the synthesized polymer, the weight percentage in the polymer of chain links formed from monomer is approximately equal to the weight percentage of this monomer in the reaction solution ( based on the total amount of this polymer. Such polymerization reactions usually have high yields, since all monomers in the solution polymerize into polymers. These three homopolymers were the standards are accepted and used to determine the chemical shift of the chain bonds formed from these monomers.
    DMA / SSS copolymers having chain linkages derived from N, N-dimethylacrylamide and sodium styrene sulfonate can be represented by the formula
    SNG-CH
    0.50 DMA100 DMA100 DMA40
    0.50 Na-AMPS 100 Na-AMPS 100 Na-AMPS

    100 NMA
    97.6 DMA 2.49 NMA
    100 NMA
    97.2 DMA, 2.8 NMA
    47.6 DMA
    45
    47.6 DMA, S 4,8 NMA
    47.6 Na-AMPS3.6 NMA,
    48.8 Na-AMPS-5
    where X and y are integers, and v- indicates that the distribution of chain links formed from DMA and SSS in the polymer chain is random.
    DMA / SSS /, / Na-AMPS three-link polymers having chain linkages formed from N, N-dimethyl-acylamide, sodium styrene sulfonate and sodium 2-acrylamide-2-methylpropanesulfonate can be represented by the formula
    SNG-CH
    i CH
    / about tfjz CHi
    17
    where X, y and z are integers, indicates that the distribution of chain bonds formed from DMA, SSS, Na-AMPS in the polymer chain is random.
    131495818
    Three-link polymers having chain links formed from DMA, NMA and SSS are also useful as viscosity enhancers for extracting oil and can be represented by the formula
    -CH2-CH
    BUT
    x
    CH; j DOWNLOAD
    CH2-CH
    n
    where X, y and z are integers, a- indicates that the distribution of chain links formed from DMA, NMA. and SSS in the polymer chain is random.
    where W, X, y and Z are integers, and V-indicates that the distribution of chain links formed from DMA, NMA, S & S to the polymer chain is random.
    Other METABIL-AMPS, such as K-AMPS, ha, GAMPS and Ca-AMPS, are also useful as monomers from which can be formed chain
    CH2.-CHS about
    5H
    where X, y and z are integers, the a-l indicates that the distribution of chain links formed from DMA, NMA and acrylamide is random,
    Such three-link polymers containing chain-bonded compounds formed from acrylamide are inferior to DMA / NMA copolymers, since their acylamide group can easily be hydrolyzed to form a salt-impermeable product. The greater the number of chain bonds formed from acrylamide contained in such a three-membered
    Polymers having chain links formed from DMA, NMA, SSS and Na-AMPS are also useful as viscosity enhancers during extraction and can be represented by the formula
    bonding to form polymers useful for oil extraction,
    Acrylamide was copolymerized with DMA and NMA to form a three-stage polymer useful for extracting oil. It has chain links formed from acrylamide, OHM and NMA, which can be represented by the formula:
    polymer, the more sensitive it will be to salts. In addition, it may be preferable to co-impregnate a small amount of acrylamide into EOR polymers (which results in a polymer that contains chain bonds formed from acrylamide), although they will be more sensitive to salts, Acrylamide can also be copolymerized to form trimeric DMA / SSS / acrylamnd polymers, DMA copolymers / / NMA / SSS / acrylamide, copolymers
    VML / MMA / metal-MGRZ / acrylamide and VMA / KMA / 555 / metal-AKP5 / / acrylamide copolymers, useful as viscosity enhancers of injected water during oil recovery. In the case of hydrolysis of acrylamide compounds, they will become more sensitive to salts.
    The polymerization processes described above use various monomers to form polymers containing chain links (repeating units) formed from these monomers. These chain bonds are different from the monomers from which they were formed, in that they no longer contain a carbon-carbon double bond.
    Example 1. DMA and SSS were added to deionized water to obtain a monomer concentration of 10 res.%. This solution contained 9.9% DMA and 0.1% SSS. The solution was thoroughly sprinkled with nitrogen to remove dissolved oxygen completely. 100 ml of this solution was injected into a polymerization butyl designed for 4 oz (113.2 g). When nitrogen was passed through this solution, 0.0375 hours was added to it for 100 hours, ammonium persulphate in the form of a 0.5% aqueous solution and 0.0375 hours to 100 hours of metabisul phyte sodium in the form of 0.5% water solution. This solution was well mixed, and then the polymerization was dried and left in a thermostat at 20 ° C for 18 hours. This led to the synthesis of an ultra-high molecular weight DMA and SSS copolymer having a gel-like consistency. This ultrahigh molecular weight DMA copolymer has only weak ionic properties and is therefore relatively insensitive to salt solutions. It is the best viscosity enhancer when extracting oil in cases where salt in water injection equipment usually reduces the viscosity of ionic
    polymer solutions. I
    Example 2. Preparing a 20% aqueous solution of DMA, NMA, containing 19.4% DMA and 0.6% NMA. De-ionized water was used to prepare this solution. For 20 minutes, the solution was treated with nitrogen using a porous glass tube. Ammonium persulfate (0.0375 parts per 100) and sodium metabisulfate (0.0375 parts per 100) participated
    whether in this polymerization as initiators in the form of 0.5% aqueous solutions.
    The ammonium persulfate / sodium metabisulfate initiators were added while the nitrogen was purged. A polymerization bottle with a capacity of 113.2 g was sealed, intensively stirred and kept for 18 hours in a thermostat with a temperature of 20 C.
    As a result, a DMA and NMA copolymer with ultra high molecular weight, having a thick gel consistency, was obtained. This polymer is a good viscosity enhancer for injected water when extracting oil, as it is not sensitive to saline solutions (salt does not reduce the viscosity of injected water treated with this copolymer).
    Example 3. Brookfield viscosity diluted solutions of ultrahigh molecular weight copolymers synthesized in Examples 1 and 2 were determined to determine the effectiveness of the DMA / SSS and DMA / NMA copolymers as an oil viscosity enhancer. 0.3% solution DMA / SSS copolymer (synthesized in Example 1) and a 0.3% solution of DMA / NMA copolymer (synthesized in Example 2) were prepared by diluting the gel-like mass with deionized water. Samples were shaken periodically for a week until the material completely dissolved in water. Brookfield viscosity was measured at 60 rpm on a No. 1 spinner. The procedure was repeated on a separate aliquot sample with the addition of NaCl to obtain a 3.5% aqueous solution, and then repeated on another aliquoted sample with the addition of sea salt to obtain a 5% aqueous solution of sea salt.
    The results of the experiment are presented in Table. 3
     Table3
    21131А958
    The sea salt used in this example was a synthetic composition containing, in: NaCl 77.76; MgCl 10; 88; MgS04 4.74; CaSO 3,6; KCl 2.46; KBG 0.24, CaCOj 0.34.
    As can be seen from the table. 3, the DMA and SSS copolymer was slightly affected by the brine, which caused a slight decrease in viscosity observed with the addition of salt. The decrease in viscosity in the DMA and NMA copolymer solution was not significant. Solutions of this DMA / NMA copolymer are not affected by brine; the observed slight decrease in viscosity may be more likely due to the further addition of the polymer solution than by the salt applied to polymers with ultra high molecular weight. The DMA / fJMA copolymers are the best viscosity increases of injected water under conditions of high salinity.
    Example 4 In order to show the advantages of these DMA copolymers as viscosity enhancers under high salinity conditions, they were compared with an industrial viscosity enhancer when extracting Dow Pusher 500 oil (Dow Chemical). This is a partially hydrolyzed ultra-high molecular weight polyacrylamide. A 0.3% Dow-Pusher 500 solution was prepared, to which, up to a concentration of 5%, the artificial salt composition described in the yrimer 3 was added. the solution was determined using the technology described in Reamer 3. The Dow-Pusher 500 gave a Brookfield viscosity equal to 10.1 cP. Brookfield viscosity, determined by the same concentration of copolymer DMA / NMA in the same solution of sea salt, was twice as high (see prier 3). Since in practice, salts are often present in the injected ode and underground regions where this 50 ode falls, copolymers of DMA with a high molecular weight have distinct advantages over the already known viscosity increases of water sprayed.55
    Example 5. Na-AMPS was prepared by stoichiometric addition of the AMPS powder to the NaOH solution. The pH of this flax is van 5 nd with a go amp
     About dobnym duk and in
    DMA tom los,
    20 San Dil weight and prices
     But about about Oh About 0.5
     not the last of us
    tour 35 is ny on on system 40
    vor plant poli
    Described I
    Thieves;
    0
    22
    th solution was brought to 9-10 by adding AMPS or dissolved NaOH; this solution was diluted with deionized water to a concentration of 5% by weight. This solution was kept at 5-15 ° C during the reaction and the pH of this solution was constantly above 9. AMPS was added until this indicator reached 9. It was possible.
    About add more sodium hydroxide to a pH above 9 and further addition of AMPS is possible. The products of this reaction were sodium AMPS and water.
     1.12 g of a 14.3% solution of NMA and DMA were injected into a 29.57 ml glass vial in which there were already 1.92 g of a 50% aqueous solution, Na-AMPS (prepared as described above) . This solution was then diluted to a weight of 10 g (total weight of water and monomers in solution) with deionized water, so that the monomer concentration was 20%.
    Then, nitrogen was passed through the solution for 4 minutes, while the ampoule was placed in a thermostat with a temperature of 0 ° C. 0.1 ml of a 0.5% ammonium persulfate solution was added to the ampule. Then, 0.1 ml of a 0.5% sodium metabisulfate solution was added. After the ampoule was blocked and agitated, it was placed in a thermostat with a tempera
    10 ° C at 18 o'clock. As a result of this polymerization, a three-unit DMA polymer with an ultrahigh molecular weight was obtained, with the polymerization mass having a gel-like consistency. 0
    Aliquots of the products of this polymerization were diluted to a concentration of 0.25% of salt-free water and salt solutions of various concentrations. The Brookfield viscosity of these solutions was determined using a technique
    described in example 3. I
    The effect of salt on the viscosity of three-link polymers DMA / Na-AMPS / NMA is as follows;
    Concentration
    salt, h per 1 million
    ABOUT
    1000 5000 10,000
    Brookfield Viscosity, cps
    4820.0
    295.0
    59.0
    43.0
    23
    30.0 26.5 23.3
    The salt composition used in this example consisted of 75% sodium chloride and 25% calcium chloride. The three-link polymer has ultra-high viscosity in fresh water, all
    It has a high viscosity in very saline water and is very convenient for use as a general purpose viscosity enhancer applicable in both fresh and highly saline water. It also has a high temperature stability and stability in the presence of divalent ions (in the presence of Ca ions there is no precipitate).
    Example 6. The process described in Example 5 was used to synthesize a three-stage polymer DMA, NMA and K-AMPS, but sodium hydroxide was replaced by potassium hydroxide. The Brookfield viscosity of the prepared solution was determined in the same way as described in example 3, the Brookfield viscosity, equal to 20.5 Cp, was observed at a concentration of this three-unit polymer equal to 0.25% in 10% aqueous chloride solution on three . This proves the possibility of successfully replacing Na-AMPS with K-AMPS to produce a three-stage DMA polymer useful as a viscosity enhancer for oil recovery.
    Example 7. In the process of forming a three-stage polymer DMA, NMA and ammonium-AMPS described in Example 6, aluminum hydroxide was used instead of potassium hydroxide. The Brookfield viscosity for this triple polymer was determined, as described in Example 3, in a 10% saline solution (75 parts NaCl and 25 hours CaClj and was equal to 11.0 cP. This is a very large solution viscosity with so
    Example 9. 38 g of a 33% aqueous solution of DMA in deionized water were introduced into a 236.6 ml polymerization bottle equipped with a self-sealing gasket and a teflon liner. 0.125 g SSS was added to this solution, then nitrogen was passed through the solution for 10 minutes. In a nitrogen atmosphere, 12.5 g of a 6% solution of Igepal CO-430 in a solution of hexane, previously treated with nitrogen, was added to the solution. By syringe injection into the mixture was added
    high salinity.
    Example 8.B polymerization-. 0.8 ml of a 1% aqueous solution of a first bottle with a capacity of 236.6 ml, equipped with ammonium sulfate. Then added a self-sealing gasket and a Teflon insert (Teflon - DuPont trademark), placed
    0.8 ml of a 1% aqueous solution of sodium meta bisulfate. The mixture was shaken vigorously. Polymerization process
    120 g of a 33% aqueous solution of DMA in deioni- was interrupted after 6 h by added water. 3.33 g of a 48% aqueous solution of NMA in deionized water was added to the solution and treated for 10 minutes with nitrogen. Then in
    nor 2 ml of methyl ethylhydrochino solution on. As a result of this polymerization, a liquid was obtained. Brookfield viscosity 0.25% aqueous solution
    t5
    20
    25 1495824
    the solution under nitrogen atmosphere was injected with 60 ml of a 6% solution of Igepal CO-430 (dispersing agent) in a solution of hexane (pre-treated with nitrogen). The mixture was shaken vigorously. Then, 4/4 ml of a 0.5% aqueous solution of ammonium persulfate was added to the mixture using a syringe, after which 9.4 ml of a 0.5% 10% aqueous solution of sodium metabisulfate was added. The polymerization was interrupted after 6 hours by the addition of 2 mp of a 22-N aqueous solution of methylether hydroquinone.
    The Brookfield viscosity of a 0.25Z-Horo aqueous solution of this polymer was 16 cP in a 10Z-HOM saline solution (75 parts NaCl and 25 parts CaCl1) as determined by the method described in Example 3. The product obtained as a result of this polymerization in a water-in-oil emulsion, it is liquid and can easily be diluted with water to form a homogeneous solution, unlike the thick gel-forming material obtained by water polymerizing DMA / NMA copolymers, which takes a very long time to dilute in water. It is assumed that in practice polymerization will be used in an oil-water dispersion, so Kaij: when extracting oil, it is necessary to dilute these polymers in the injected water.
    thirty
    Example 9. 38 g of a 33% aqueous solution of DMA in deionized water were introduced into a 236.6 ml polymerization bottle equipped with a self-sealing gasket and a teflon liner. 0.125 g SSS was added to this solution, then nitrogen was passed through the solution for 10 minutes. In a nitrogen atmosphere, 12.5 g of a 6% solution of Igepal CO-430 in a solution of hexane, previously treated with nitrogen, was added to the solution. By syringe injection into the mixture was added
    0.8 ml of a 1% aqueous solution of ammonium persulfate. Then added
    0.8 ml of a 1% aqueous solution of sodium meta bisulfate. The mixture was shaken vigorously. Polymerization process
    interrupted after 6 hours by adding 2 ml of methyl ethylhydroquinone solution. As a result of this polymerization, a liquid was obtained. Brookfield viscosity 0.25% aqueous solution
    25131495826
    This DMA / SSS copolymer is equal to 16 c. download into the reservoir at least through
    and was determined by the method described-one injection well of water
    Hbw in example 3.polymerized polymer, which causes
    The examples described may wide-oil flow from the bedding area.
    applied to improve the recovery of the 5c collection area, at least
    Tertiary oil, In this region, through a single production well, many methods are known for using polymers to extract oil. The proposed polymeric viscosity enhancers of injected water can be used, for example, as mobility buffers in known oil recovery methods such as chemical, mixing and steam. These polymers can also be used to not control the tank profile by selectively adsorbing and / or forming gels.
    characterized by the fact that, in order to increase the degree of oil recovery by increasing the viscosity of the displacing agent, polymer-thickened water is pumped into the formation with chain compounds formed by N, N-dimethylacrylamide and N-methylolacrylamide of the general formula
    - Sh2-CH-i-0
    CH2- (fHc "o
    权利要求:
    Claims (2)
    [1]
    1. A method for extracting oil from underground oil deposits, including
    --СНт-СН
    / fn
    where X and y are integer numbers, a-L / - indicates that the distribution of chain bonds in the polymer chain is random, with a content of 100-1500 ppm in an aqueous polymer solution.
    [2]
    2. The method of pop. 1, which differs from the fact that it is pumped into

    : H2-Sn-
    t.
    or N, N-dimethyl-acrylamide, sodium styrene sulfate and sodium 2-acrylo-1-am-2-methylpropane sulfonate or 2-acrylamido-2-methyl potassium through one production well,
    characterized by the fact that, in order to increase the degree of oil recovery by increasing the viscosity of the displacing agent, polymer-thickened water is pumped into the formation with chain compounds formed by N, N-dimethylacrylamide and N-methylolacrylamide of the general formula
     Ш2-СН-i-0
    x SI CH-j
    Jx
    CH2- (fHc "o
    N
    N
    no sdda
    or N, N-dimethyl-acrylamide and sodium styrene sulfate of the general formula
    CH-i-CH
    CHs
    sn sn I II sh sn
    sn
    80s1aa
    35 layer water, thickened with polymers, formed by L, N-dimethylacrylamide, N-methyl ol acrylic amide ohm and nat. 2-acrylamido-2-methylpropanesulfonate, or potassium 2-acrylamido-240 methylpropane sulfonate, or ammonium 2-acrylamido-2-methylpropanesulfonate, or calcium 2-acrylamido-2methylpropanesulfonato .m of general formula
    -СС-0
    H - N
    l / h
    0 ®
    Ш2.80т, and
    pansulfonate, or ammonium 2-acrylamido-2-methylpropanesulfonate, or calcium-2-acrylamido-2-methylpropanesulfonatom of the general formula.
    where X and y are integers, and a./l.-indications in the polymer chain is that the distribution of chain links is tea-like.
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    同族专利:
    公开号 | 公开日
    EP0094898B1|1986-12-03|
    JPS58218588A|1983-12-19|
    DK215783D0|1983-05-13|
    NO831672L|1983-11-15|
    CA1202147A|1986-03-18|
    US4526947A|1985-07-02|
    DE3368093D1|1987-01-15|
    NO163961C|1990-08-15|
    DK215783A|1983-11-15|
    EP0094898A3|1985-01-02|
    EP0094898A2|1983-11-23|
    NO163961B|1990-05-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2716076C2|2015-02-26|2020-03-05|Репсоль, С.А.|Polyolefin proppants with superhigh molecular weight|US3509113A|1967-08-14|1970-04-28|Hercules Inc|Preparation of acrylamide-type water-soluble polymers|
    US3617572A|1969-11-03|1971-11-02|Hercules Inc|Flocculation and settling of inorganic particles in a salt solution|
    US3679000A|1970-12-04|1972-07-25|Lubrizol Corp|Secondary oil recovery method using n-sulfohydrocarbon-substituted acrylamide polymers as viscosity increasing agents|
    US3692673A|1971-02-12|1972-09-19|Lubrizol Corp|Water-soluble sulfonate polymers as flocculants|
    JPS5414631B2|1971-09-10|1979-06-08|
    US3779917A|1971-11-26|1973-12-18|Marathon Oil Co|Oil recovery with vinyl sulfonic acid-acrylamide copolymers|
    US3727689A|1972-02-09|1973-04-17|Phillips Petroleum Co|Hydraulic fracturing|
    DE2357068C2|1973-11-15|1987-09-10|Bayer Ag, 5090 Leverkusen|Process for the production of nonwovens that are resistant to cleaning|
    GB1439248A|1973-11-22|1976-06-16|Dow Chemical Co|Process for the recovery of oil|
    US3943060A|1974-07-26|1976-03-09|Calgon Corporation|Friction reducing|
    US4057521A|1974-08-05|1977-11-08|The Dow Chemical Company|Absorbent articles made from carboxylic synthetic polyelectrolytes having copolymerized N-substituted acrylamide crosslinker|
    JPS52137482A|1976-05-14|1977-11-16|Kyoritsu Yuki Kogyo Kenkyusho:Kk|Preparation of acrylamide polymer|
    US4254249A|1978-11-17|1981-03-03|Merck & Co., Inc.|Copolymers of N,N-dimethylacrylamide and acrylamide|
    US4326970A|1978-11-17|1982-04-27|Merck & Co., Inc.|Copolymers of N,N-dimethylacrylamide and acrylamide|
    US4473689A|1979-12-26|1984-09-25|Basf Wyandotte Corporation|Process for the aqueous polymerization of acrylamide|US5080809A|1983-01-28|1992-01-14|Phillips Petroleum Company|Polymers useful in the recovery and processing of natural resources|
    US5186257A|1983-01-28|1993-02-16|Phillips Petroleum Company|Polymers useful in the recovery and processing of natural resources|
    USRE33355E|1983-10-22|1990-09-25|Mitsui Toatsu Chemicals, Incorporated|Agent for absorbing and releasing water vapor|
    EP0163404B1|1984-05-28|1990-06-27|MITSUI TOATSU CHEMICALS, Inc.|Agent for absorbing and releasing water vapor|
    JPH0533083B2|1985-02-27|1993-05-18|Mitsubishi Chem Ind|
    EP0233533B1|1986-02-18|1990-11-14|American Cyanamid Company|Mobility control reagents with superior thermal stability|
    US4963632A|1988-12-29|1990-10-16|Exxon Research And Engineering Company|Mixed micellar process for preparing hydrophobically associating polymers|
    US4983699A|1989-01-03|1991-01-08|Ppg Industries, Inc.|Silylated addition polymers with pendant ionic moieties|
    US5032455A|1989-01-03|1991-07-16|Ppg Industries, Inc.|Silyated addition polymers with pendant ionic moieties|
    DE19608911A1|1996-03-07|1997-09-11|Wacker Chemie Gmbh|Crosslinkable protective colloids|
    DE19608910A1|1996-03-07|1997-09-11|Wacker Chemie Gmbh|Water-soluble, crosslinkable copolymers|
    CN101220261B|2007-12-28|2011-07-27|中国石油集团钻井工程技术研究院|Protective agent for drilling fluids at high temperature and manufacturing technology thereof|
    US9611416B2|2010-10-25|2017-04-04|Isp Investments Llc|Salt-tolerant, thermally-stable rheology modifiers|
    WO2013162902A1|2012-04-25|2013-10-31|Isp Investments Inc|Synergistic combination of a fluid loss additive and rheology modifier|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/378,154|US4526947A|1982-05-14|1982-05-14|N,N-Dimethylacrylamide copolymer injection water viscosifier for enhanced oil recovery|
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