• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:

    公开号:SU1237089A3
    申请号:SU823455493
    申请日:1982-06-01
    公开日:1986-06-07
    发明作者:Энгельхардт Фридрих；Шмитц Херманн；Гульден Вальтер；Хакс Эрг
    申请人:Касселла Аг, (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for extracting oil from oil fields by pumping aqueous solutions of copolymers into a formation.
    The aim of the invention is to increase the efficiency of the method due to the high resistance to electrolytes and thermal stability.
    The copolymers consist of a statistical distribution of 5–60 wt.% Of the residues of the formula (), 2–40 wt.%, Of the residues of the formula (i) and 38–93 wt.% Of the residues of the formula (1P) or their hydrolysis products. ,
    The copolymers of the proposed method are still partially substituted. As a detergent, each water-soluble base can be used, the strength of which is sufficient for reaction with hydrolyzable groups. However, NaOH, KOH, NHj OR neutral, or acidic salts of alkali metals (in particular sodium or potassium salts) and ammonium salts of carbonic, boric or phosphoric acids are preferred. The scrubbing agent is added either to the monomer solution already, or mixed with the polymer. Percolation is carried out during exothermic polymerization or by heating at the end of polymerization.
    The copolymers thus obtained can be directly dissolved in water after mechanical grinding with suitable apparatuses and applied.
    However, they can also be slashed after the water has been removed by the known processes of drying in a solid form and can be dissolved in water only when they are used.
    The following abbreviations are given in the examples and tables: AM acrylamide; K is vinyl-M-methylacetamide BHMAj N-vinylpirrolidone VILI; 2-acrylamido-2-methylpropanesulfonic acid A1ShK; Vinylacetamide BA; Vinylformamide HF; sodium a-vinyl sulfonate
    The following bases are used to neutralize the formulations: NoOH Aj KOI B; Yak B; dimethyl- | B-oxnethylamine G.
    The catalysts used are ammonium disulfate peroxide PDA; dibutylaminium chloride TWO,
    PRI me R 1. In a polymerization flask with a capacity of 2 l, equipped with
    crY1P} soy flat grinding, with a stirrer, thermometer, and gas flow tube, is dissolved in 560 ml of deionized HGr and neutralized with KOH. Then, 160 g of AM, 42.8 g and 10 g of N-vinyl-N-methyl acetamide are added and, while stirring and injecting nitrogen at 20–21 ° C, dissolve for 15 minutes, 4 g of a 0% dibutylammonium chloride solution are added. nitrogen is added with stirring, nitrogen is added over 15 minutes, 120 mg of PDA dissolved in 8 g of water is added, and by passing nitrogen, the mixture is stirred for an additional 3 minutes at increased rotational speeds. Passing Nj is completed and the gas tube and stirrer are removed. After an induction period (approximately 45 minutes), polymerization begins, the internal temperature is reduced to 67 seconds and the solution turns into a gel of a stable form.
    Then the polymer is heated for another 2 hours to BO. Measured with a Brookfield viscometer with a shear gradient of D 7,, 3 viscosity is at 20 ° C: d 42.5 MPa-s in a 0.05% aqueous solution of 3.5 ° (j ;, 18.7 mPa-s in a 0.2% aqueous solution with a salt content of 130 g of NaCE and 1 l.
    ten
    The known copolymers exhibit measured under the same viscosity conditions g up to 80% below the indicated viscosity g up to 60%. below.
    Etc. and meper 2, In a polymerization flask with a capacity of 2 liters, equipped with a flat grinder, a stir bag, a thermometer, and a gas-inlet tube, add 23 g to the solution (and OH to 560 g of deionized water; and passing nitrogen in portions of 120 g of AMIIK, then 76 g of AM and 4 g of VIMA. Stir for about 15 minutes, add 4 g of 10% aqueous solution of dibutylammonig: chlorine 5, pass nitrogen with further stirring for 1 5 minutes, then add 120 mg of PSA dissolved in 8 g of water, and by passing nitrogen, mix for another 3 minutes at above: Numbers of revolutions. Transmission W,: Finish and remove the gas feed tube and stirrer. After the induction
    a period (about 30 minutes) begins to polymerize, with the internal temperature rising to 58 seconds and
    the solution is converted to form.
    The following viscosities are obtained (measurement temperature 20 s), mPa-s: d 38.2: 7 7.2.
    Tests for applicability: resistance to shear,
    When testing the suitability of the proposed copolymer for use in tertiary oil production, shear resistance is, along with solubility free from residues, an important pre-selection criterion.
    For a shear resistance test, 500 ppm is dissolved. copolymer (the amount used based on the content of the active principle) in fresh water with a hardness of 3.5 (German degrees of hardness), i.e. 35 mg CaO / l. After this, the first measurement of viscosity (A) is carried out at room temperature. Then, for some time, the solution is stirred with a fast-rotating mixer and the viscosity is measured again. Quotient of both viscosity coefficients
    the factor (shear) is a measure of the loadability of the shear forces of the washing medium under the indicated experimental conditions. The following factors have been established for the selection of copolymers (Table ():
    Copolymer example)
    37 41 43 47 54
    (by factor (shift)
    0.68 0.64 0.73 0.63 0.72
    Data for the remaining copolymers are in the same order of magnitude. Standard copolymers of acrylamide and acrylic acid give, under the same experimental conditions, data for a factor (shift) from 0.55 to 0.40 and below. Viscosity measurement is carried out with a viscometer.
    Injectable. Dp injecting the washing medium through the zone for injection into the field and for the impeccable washing process inside the molds
    The solution requires a solution free from solids and swelling particles.
    Dp determination of the injectability of copolymer solutions Glass tubes filled with sand are washed for 24 hours at room temperature with a certain constant volume flow. In this case, the pressure of the washing medium is determined before entering I into the industrial tube after 1 h (P) and day (Pr)
    ./R,
    The factor (injectable) P is a measure of the injectability of the washing medium under the indicated conditions. Solutions of 1000 ppm are used for these experiments. copolymer in seawater, consisting of 130 g of MaCP and 10 g of CaCt per I l. The following factors have been established for the choice of copolymer:
    five
    Copolymer example)
    one
    2
    37
    41
    43
    47
    54
    (by
    Factor (injectable)
    1.12 1, 10 1.07 1.09 1.05 1.00 1.04
    Solutions with high percentages of gel particles, which sometimes occur with conventional acrylamide / acrylate polymers, show data of 1.9 or more and lead to clogging of the sandy pad.
    Viscosity The main criterion for the economics of a washing agent additive is its viscosity height in a given, often saline, medium of the deposit and the wash water at an appropriate temperature of the deposit. When using acrylamide-containing polymers, their viscosity is determined by the presence of divalent cations (in particular calcium and magnesium ions).
    The following viscosity coefficients are determined in a viscometer. Brook fie Ed at a shear gradient of D of 7.3 s for water containing 2000 ppm. copolymer, salt solutions (l30 g of NaCE and 10 g of SASEG per I l).
    (by
    Viscosity, mPa s
    6.3
    7.7 5.4 6.0 5.3 3.3 4.9
    Standard copolymers show significantly lower data under the same conditions.
    Thermal stability Another important criterion for the evaluation of polymers for tertiary mining is the long-term stability of the solutions under thermal loading. At the same time, the viscosity of the washings should not significantly decrease and they will not tend to coagulate. Aqueous solutions containing 2000 ppm of copolymer, 130 g of NaCg and 10 g of CASE are stored for testing thermal stability at a different temperature. Samples are taken at certain time intervals, cooled to room temperature, and then the viscosity is measured. Measured viscosity coefficients relate to data obtained prior to storage. Thus, 100% means full preservation.
    As follows from the data of Table 2, the proposed copolymers in the form of aqueous salt solutions show good or even very good stability.
    The solutions remain clear and transparent with the exception of the solution with the copolymer of Example 4, which shows weak turbidity. Standard copolymers of porosity under the same test conditions have a much stronger decrease in viscosity and are prone to precipitation due to water leakage,
    Mobility, Occurring de-oiling while washing oil-containing porous ropi№ix and sandy layers with the use of water-soluble polymers is investigated by laboratory experiments. Conducted during these tests, the washings are carried out in sand washing tubs.
    packing, which are filled with degassed oil of this field, i.e. dead butter. The industrial equipment consists of a tanker for storing various flushing; red; an automatic self-recording manometer; a pump for supplying an industrial medium; a proming pipe; and an automatic collector for trapping zlyuates,
    By means of a pump, pumped medium with constant volume is pumped (gmngm 1consumption from reservoirs to a sandy packing saturated with oil and heated to. In parallel with the passing blind experience, synthetic reservoir water is additionally included) the passage through the sandy packing is separately lumped and determined by volume. Comparison of crawled quantities of oil in a collection of industrial experiments with the various copolymers offered in 1: Accuracy of additives to the means of washing with and without a polymeric additive, ds indicates an increase in the amount of extractables (of crude oil using P1; 1 delayed compounds.
    The main industrial media spool: it is saline water, containing 130 g of aCg and
    0 g CaCe2 per I liter, which is used either with these additives or without them. A partial hydrolyzate of Example 2 is used as a comparative prodigrate, and a copolymer example as the proposed product.
    By adding 0.002-0.5% of the proposed copolymer to liquids for tertiary oil production, it is possible to flush more than 90% of oil from oil-bearing rock, even high-viscous oil, which is found, for example, in Venezuela. Thus, with a further increase in the amount of additives, a significant increase in the amount of oil, since it is impossible to flush out more than 100% of the oil. A further increase in the amount of additives leads to an increase in the cost of the leaching process without a corresponding, and its recovery from oil production (Table 5).
    When freshly prepared polymer solutions are used for comparative products A and B, total deoiling is formed in 85 and 82%, respectively.
    71237089
    When stored for 8 days, when the products of comparative products are used in a method, the degree of deoiling is reduced dO; 61% to 62% remains, while in perception.
    eight
    according to the proposed degree of deoiling, practically without measurement
    237089
    10 Continuation of table 1
    eleven
    Prine In examples I, 20 and 51 "place VIMA xpolieucut VF, examples
    13, 14, 31, 53 and 62 - VA, in example 69 - -ChgwnnileI et lformamnd, in example 70 - lgvimylacetamide, in example 71 - nilg1111 ctc-acetamide, in example 72 - cumndiginignnnnlngntnetl-propnonic acid, in example 73 - gammid- Sgvinil-proyionovoy kisloty.
    table 2
    Comparative0,002
    Offered0,002
    Comparative 0.02
    Suggested 0.2
    1237089
    12 Continuation of table 1
    Continuation of table 2
    Table 3
    Africa
    Also
    eleven
    Venezuela
    13
    Editor H, Gunko
    Compiler and Lopakova
    Tehred O. Sopko Proofreader V. Sinitska
    Order 3102/60 Circulation 548 Subscription
    VNIIPI USSR State Committee
    for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
    Production and printing company, Uzhgorod, st. Project, 4
    123708914
    Continued t blo.Z
    Table 4
    权利要求:
    Claims (2)
    [1]
    1. METHOD OF OIL PRODUCTION by injection into the reservoir of water containing additives, characterized in that, in order to increase the efficiency of the method due to its high resistance to electrolytes and thermostability * *, 0.002-0.5% is used as an additive a water-soluble copolymer, which in a static distribution consists of 5-60 wt.% residues of the General formula
    -CH g -CH '© ©
    X,, p from 2-40 wt.% Residues of the General formula
    -sn-sni
    N - R
    I>
    СО - (11) from 38-93 wt.% Residues of the general formula
    -sn, -snI
    СО nh 2 , (III) where Y is a direct bond or the remainder of the formula
    —CO — NH — C (CH ) G —CH 2 -,
    X® cation.
    If Y is a direct bond, then R, is hydrogen; R2 is hydrogen; methyl or ethyl; if Y is the remainder of the formula
    —CO — MH — C (CH } ) g — CH—, then R, is hydrogen, methyl or ethyl; R 2 hydrogen, methyl or ethyl, or R, IR 2 taken together mean trimethylene.
    [2]
    2. The method according to p, 1, characterized in that, in order to reduce the amount of copolymer, the additive to water additionally contains boric acid in an amount of 2.5-35 wt.% By weight of the copolymer.
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    法律状态:
    优先权:
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