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  • 专利说明
  • 权利要求
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  • 优先权
    • 专利摘要:
    A micellar slug for use in the recovery of oil, consisting essentially of a surfactant and an aqueous medium, which may contain an inorganic salt. The surfactant contains, as essential constituents, (a) at least one internal olefin sulfonate having 10 to 26 carbon atoms; and (b) 0.1 to 60 parts by weight, based on 100 parts by weight of the internal olefin sulfonate, of at least one ether sulfonate having the general formula: R1-O-(R2O)m-(R3O)n-R4-SO3X (I) wherein R1 represents an alkyl or alkenyl phenyl group having 12 to 26 carbon atoms or an alkyl or alkenyl group having 10 to 24 carbon atoms, R2 represents C2H4 or C3H6, R3 represents C2H4 or C3H6, R4 represents C2H4, C3H6, or CH2CH(OH)CH2, n>/=0, m>/=0, and n+m=0 to 15, and X represents an alkali metal or an alkaline earth metal.
    公开号:SU1650016A3
    申请号:SU853983323
    申请日:1985-12-05
    公开日:1991-05-15
    发明作者:Морита Хироси；Кавада Ясуюки；Ямада Юнити；Укигай Тосиюки
    申请人:Лион Корпорейшн (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to the oil industry, namely, a micelle slug capable of absorbing large quantities of oil and saline in the resulting microemulsions and having good stability and high ability to extract oil from underground oil bearing formations.
    The purpose of the invention is enhanced oil recovery.
    Micellar slug is used in oil recovery. Slug consists in
    mainly from a surfactant and an aqueous medium that may contain an inorganic salt. The surfactant contains as the main components intramolecular olefin sulfonate (10-26 carbon atoms), 100 May. h. and 0.1-60 masoCH "ether sulfonate of the general formula
    R h-0- (kgO) I1- (RjOJn - R. - S03X,
    where R is an alkyl or alkenylphenyl group containing from 12 to
    Re
    s
    26 carbon atoms, or alkyp or
    alkenyl group containing 1024 carbon atoms}
    Ra-. or C3HS;
    RJ -. or C3H6;
    four- . or or CH4CH (OH) SNg;
     (0-10);
    njyO; (0-1Q)
    t + n is 0-15 (1-Yu)
    X - alkali or alkaline earth metal with
    The drawing shows graphically the ratios between the proportion of the mixed surfactants, t, e, and ether sulfonate and intramolecular olefypsulfonate, the solubility parameter and the optimal salinity,
    Micellar slugs used to extract oil are clear or dispersed liquids containing 0.1 to 15% by weight of the surfactant in an aqueous medium.
    Intramolecular olefinosulfonates (BOC) are substances obtained by the sulfonation of intramolecular olefins containing mono-olefins as the main component,
    Vinylene type containing 10-26 (preferably 12-24 carbon atoms) of the general formula:
    R - CH CH R
    where R and R - are, independently of each other, straight or branched-chain saturated hydrocarbon groups containing one or more carbon atoms, provided that the total number of carbon atoms in R and R t is 8-24, they can contain about 33% (about one-third of olefins) or less trisubstituted mono-olefins with sulphonated products are neutralized with suitable bases, and then hydrolysis of the neutralized products is possible, the intramolecular olefinsulfonates obtained in this way usually contain about 10- 60 wt.% lkenil- sulphonates double bond and about 90-40% oksialkansulfonatov and about 80% or more monosul- sulfonate and 20% or less disulfona- tov "can use other intramolecular olefin with another protsedtnym content koto
    50
    five
    0
    five
    0 45 50
    These can be obtained by appropriate selection of sulfonation and hydrolysis conditions.
    An increase in the number of carbon atoms of the intramolecular olefin leads to an increase in the percentage of alkenyl sulfonate. On the other hand, an increase in the molar ratio between the sulfonating agent and the intramolecular olefin during the sulfugation leads to an increase in the percentage of disulfonate.
    Intramolecular olefin sulfonates suitable for use should contain 40% or more, preferably 45-90%, hydroxyalkanesulfonates and 20% or less, preferably O, 1-15%, disulfonate. When these intramolecular olefin sulfonates are used, microemulsions may be formed having a sufficiently low surface tension, thereby increasing the efficiency of oil recovery.
    Intramolecular olefin sulfonates can be used in the form of alkali metal salts, aluminum salts and their organic amino salts. Preferred cations are Na, K, III and alkanolammonium.
    Intramolecular olefin sulphonates used in the formation of micellar slugs: intramolecular olefin sulfonates containing 12, 13,14,15,16,18,20,22,24, 12-16, -13-14, 14-16, 14-18, 15-17, 16-18, 17-20 and 20-24,26 carbon atoms. These sulfonates can be used individually or in any combination with each other.
    Ester sulfonates are substances having the general formula
    R, - O - (RgO) - () n - Rf- so, x,
    where R, p R2, Rj, RH, X, m, n - are indicated.
    These ester sulfonates can be obtained as follows:
    Alkylene oxides with 2–4 carbon atoms (preferably 3 carbon atoms) are reacted with alkyl phenols with 12–26 carbon atoms (preferably 14–24 carbon atoms) or aliphatic alcohol with 8–24 carbon atoms (preferably with 10–20 carbon atoms). carbon) in
    resulting in the formation of alkylphenyl or alkyl esters. The resulting alkylphenyl or alkyl ethers, react with sodium isothiocyanate, propanesulfone or epichlorohydrin, followed by reaction with sodium sulfite. The alkylphenols used to prepare the sulfonate esters may contain saturated or unsaturated, straight or branched alkyl groups. Aliphatic alcohols can be saturated or unsaturated straight or branched primary or secondary alcohols. For the preparation of ether sulfonates, alkylene oxides such as ethylene oxide and propylene oxide are used in an amount of 1-20 (preferably 1-10) grams of molecules. Suitable cations are alkali metal ions, alkaline earth metal ions and organic ammonium ions. Preferred cations Na, K and N11 f,
    Ester sulfonates suitable for use in micellar slug are sulfonic acid esters derived from nonylphenol ethoxylates (P 1 -10), octylphenol ethoxylates (P 1-10), ethoxylate of lauryl alcohol (P 2,3,4,5,7 and 10) ethoxylates of synthetic alcohols with 10-12 carbon atoms (P 2,3,5,7,9) and ethoxylates of synthetic alcohols with 12-14 carbon atoms (P 2,3,5, 7 and 9).
    The ester sulfonates are introduced into the micelles in a quantity of 0.1-60 mash. (preferably 0.5-50 wt.h.). When too little ether sulfonate is used, the formation of the desired microemulsion is difficult. If too much ether sulfonate is used, the effect achieved by the introduction of the micellar slug is reduced due to a decrease in solubility.
    Water or brine containing an inorganic salt at a concentration of 0-20% (preferably 0.1-15%) is used as an aqueous medium to obtain micellar sludge, since the surfactants used in the micellar slug resist the effects of salt. and hard water. The aqueous medium used in the formation of the micellar sludge consists of soft water, dispersed
    ten
    15
    20
    25
    $
    la and water from subterranean strata, for example, rain, river, lake, groundwater, bottom and sea. NaCl, KCl, MgCl, CaCl2 are used as inorganic salts contained in the brine. Bivalent metal ions, in particular, Mg ion and Ca ion, are used in an amount of up to 5000 hours per million ppm.
    A micelle slug suitable for use in oil extraction may contain auxiliary surfactants, in particular anionic surfactants and non-ionic surfactants such as petroleum sulfonates, alkyl benzene sulfonates, polyoxyethylene alkyl ether sulfonates, dialkyl sulfonic succinates, o-olefin sulfonates, soaps, alkylphenol ethoxylates, higher alcohol ethoxylates, polyester esters, fatty acid alkylamides, and polyoxyethylene fatty acid amides.
    When it is necessary to control the viscosity of the micelle slugs, known thickening agents, such as water soluble polymers, lower alcohols and hydrocarbons, in particular, heteropolysaccharides produced by microbes, formaldehyde naphthalene sulfonic acid condensates, polyacrylamides, can be added to the micelle aggregates - lyacrylate, hydroxyethylcellulose and carboxymethylcellulose. As lower alcohols, straight and branched alcohols with 1-8 carbon atoms can be used in sludge. However, since the use of too much of these lower alcohols leads to a decrease in oil recovery, the higher alcohols, if used, in an amount of 2% or less by weight. Hydrocarbons are petroleum, liquefied petroleum gas, crude gasoline (naphtha), kerosene, diesel fuel, and fuel oil. Preferably, the produced oil is used due to its low cost and availability, and also because of its composition, which is identical or similar to the composition of oil remaining in the oil-bearing formation.
    When using micelle sludge high, oil recovery efficiency can be achieved even in cases where microemulsions in subterranean formations are diluted with oil and water. The amounts of oil and water absorbed
    five
    0
    0
    microemulsions, can increase markedly.
    The micelle lesions can be easily made by any known method. For example, ingredients including surfactants and an aqueous medium can be mixed in any order using conventional mixers (mixers), mixing temperatures and pressures of
    Oil from subterranean formations, using the proposed micelle weaknesses, can be produced by any method, for example, by the method by which slug is supplied under pressure in at least one injection well into an underground oil bearing formation; and then at least one displacement liquid, such as water for flooding and / or an aqueous solution of the above thickener (i.e., biopolymers, such as xanthan gums, hydrophilic polymers, such as polyacrylamides and polysaccharides, and cellulose derivatives, such as as carboxymethylcellulose and hydroxyethylcellulose) are injected into the injection well in order to push the remaining oil in the reservoir towards the production well and extract oil through it. The appropriate amount of micelles is pumped into the injection well. in the amount of 5-200% of the pore volume of underground reservoirs, but this amount is non-critical.
    Example 1 o Aqueous solutions of surfactants are obtained by dissolving 7: 3 (by weight) mixture of C (BOC-Na and synthetic with “. C 13 ethoxy alcohol () -propanesulfonate as a surface-active component in various concentrations of x- in an aqueous 1-15% solution of NaCl, 5 ml of each of the obtained surfactant solutions are stirred for 10 minutes at 5 ° C. with 5 ml of Sarukawa crude oil.
    The results are shown in Table 1 (the concentration of NaCl solution varies from 1 to 15% for each concentration of surfactant listed in Table O
    Comparative Example 1a Use 7: 3 (by mass mixture of C + g-C j BOC
    0
    five
    0
    five
    0
    five
    0
    five
    Na and isobutanol instead of a mixture of CftBOC-Na is a sulfonic ester.,
    EXAMPLE 2: Mixtures of Cta-C2o BOC-Na and synthetic C1g-C branched secondary alcohol ethoxy () propanesulfonate, mixed in various proportions as a surfactant with 5 ml of an aqueous solution of NaCl at various concentrations and 5 ml of dodecane are placed in tubes so that the concentration of surfactant is 4% o
    I
    The contents of the tubes are mixed for 10 minutes at 50 ° C. After the sludge, a microemulsion is formed.
    The results of these experiments determine the optimal concentration of sodium chloride (the amount of dodecane and an aqueous solution of sodium chloride embedded into the microemulsion of the middle phase should be the same). The measure of solubility is the amount of n-dodecane or an aqueous solution of sodium chloride per 1 g of surfactant at the optimum salt concentration.
    The correlation between the optimum salt concentration and solubility and the ratio of surfactants in the mixture is shown in the drawing.
    Comparative example 2a. Carried out as in example 2, but using an aqueous solution of NaCl containing 4% BOC-Na and 2% amyl alcohol. The optimal salinity and solubility parameter in this case are 1.8% and 8.1 cm3 / g, respectively.
    PRI me R 3. A translucent, homogeneous liquid for oil production is obtained by mixing 2% C ig – C to BOC-Na and 2% C 1 C – C 20 BOC-Na, 1% oxyphenol ethoxy () ethanesulfonate 10% heptane and 90% brine containing 3.6% NaCl, 0.2% CaCl and 0.1% MgCl. The experience in oil extraction is carried out on a core from Berea sandstones with a length of 28 cm and a diameter of 3.8 cm with a permeability of 200 mD and a porosity of about 20%. A core sufficiently saturated with brine containing 6.2% NaCl, 0.3% CaCl, and 0.01% MgClz was placed in the core holder. Fuel oil was pumped into it under pressure at a rate of
    91650016
    6 cm3 / min until discontinued
    The mining experience is not the same as in Example 3 using for the micelles obtained by ZOM. In this experiment with NaCl 4.56; The polymer saturation is the final salinity, and n-dodecane is used as a carbohydrate.
    25
    brine. Then, the brine under pressure was injected at the same rate into the water of the water flooding until the content of fuel oil in the stream fell below 0.1%. As a result, the oil was recovered. After the water flooding, the core holder and slug micelles are placed in a constant bath. temperature of 80 ° C. Yu
    The slug of micelles is first injected into the core under pressure in an amount of 10% by volume of the porous space, then a 1% aqueous solution of NaCl containing 1500 ppm of xanthan resin, 15 in Example 5, is pumped under pressure in an amount of 100% of the volume of the porous space and, finally, a 1% aqueous solution of NaCl is pumped under pressure in a volume of 100% of the volume of the porous 20 space. As a result, remove fuel oil. The injection rate under pressure is 0.3046 m per day.
    The efficiency of oil recovery is determined by measuring the amount of water in the core after the experiment by an azeotropic method in toluene in terms of production, the amount per fuel oil. Oil recovery is 93%,
    Example 4 A translucent slug of micelles for oil production is prepared by stirring 3% Cij-Cf BOC-Na, 3% about. -Tilphenol epoxy () - propanesulfonate and 94% brine containing 10.4% NaCl, 1, 3% CaCl2 and 0.2% MgCl,
    The oil recovery experiment was carried out as in Example 3, using the micelle slug obtained at 50 ° C for oil production, but the brine used in the preparation of the slug for oil production was also used as a core pumped brine, and to prepare a polymer solution.
    The oil recovery in this experiment is 89%.
    Example 5 0 A translucent slug of micelles for oil production was prepared with stirring 0.9% C 15-C 1 BOC-Na, 3.5% BOC-Na, 0.6% C12-C 4 CBS branched secondary ethoxy alcohol () -hydroxypropanesulfate, 4% n-dodecane and 91% brine, containing 2.2% NaCl, 0.49% CaClz, and 0.1% MgCl2.
    thirty
    Oil return to this
    In Table 2 presents
    权利要求:
    Claims (1)
    [1]
    Formula iso
    The micelle sludge containing the main medicinal agent and the aqueous salt of the salt, except that, with oil recovery, as an active agent, the mitz contains a mixture of internal olefin sulfonate, with up to 26 carbon atoms
    KG0- (Kar) „G (R, 0
    where R4 is alkyl or 35 is a phenyl group, soda gas is up to 26 carbon atoms per or alkenyl g, having 10-24 carbon atoms, RЈ is C2H or CEN R, is CrH4 or C3H R4 is CrH4, CjHg or cn O; m O and n + m
    X - alkali or nano metal, with the following components, May “Intramolecular olefin sulfonate 10
    Simple sulphonate
    ether0,
    moreover, surface-a in micelle slug with a concentration of 0.1-15 m
    40
    45
    ten
    The experience in oil extraction is carried out in the same way as in Example 3 at 50dC using the slope of micelles obtained in this way for oil production. In this experiment, the composition of the brine,%: NaCl 4,56; MgCl2 0.21, the salinity of the polymer solution of 1% NaCl, the salinity of the final brine 0.5% NaCl and n-dodecane was used as the hydrocarbon.
    Cent in example 5,
    values according to example 5,
    Oil output in this experience is 91%.
    Table 2 presents the data
    Cent in example 5,
    Invention Formula
    Micellar slug for oil production, containing the main surface-active agent and an aqueous solution of an inorganic salt, characterized in that, in order to enhance oil recovery, the micelle slug contains a mixture of intramolecular olefinsulfonate containing from 10 to 26 carbon atoms, and an ether sulfonate of the general formula
    KG0- (Kar) „G (R, 0) h- R4-S09X,
    where R4 is an alkyl or alkenyl phenyl group containing from 12 to 26 carbon atoms, or an alkyl or alkenyl group containing 10-24 carbon atoms, RЈ is C2H or CEN6, R, is CgH4 or C3H6 R4 - CgH4, CjHg or CH2CH ( OH) SNg with p O; m O and n + m from 0 to 15,
    X - alkali or alkaline earth metal, with the following ratio of components, May „h. Intramolecular olefin sulfonate100
    Simple sulphonate
    ether0,1-60
    moreover, the surface-active agent in the micelle slug is contained in a concentration of 0.1-15 wt%.
    II
    1650016
    Table 1
    12
    Note. O- observed the formation of a microemulsion in the middle phase of the mixture.
    X - microemulsion formation was not observed in the middle phase of the mixture
    R - OCCHgCHjp CHjCHjCHjSOjNa- - R - С1г-С, 5
    Spreadsheets
    OS, / 5
    .
    Ago0.07
    ether sulfonate,%:
    Octylphenol ethoxyethane sulfonate () Dodecylphenolate oxyhydroxypropane sulfonate () - 0.5
    C 0iЈ-synthetic alcohol ethoxypropane sulfonate
    () 0.03
    .-synthetic alcohol ethoxy-propane sulfonate () -0.1
    10.0
    5.0
    13
    Aqueous solution of sodium chloride,%
    Concentration of sodium chloride,%
    Salt concentration in oil layer water,% sodium chloride
    The amount of liquid injection,% well volume
    Oil production,%
    OilOO 20/60
    40J60 60/40 Wo / 20 100/0 NP
    Compiled by I., Lopakova. Editor L. Pcholinsk - Tehred M. Morgen. Corrector T. Paliy
    Order- 1527
    Circulation 373
    VNIIPI State Committee for Inventions and Discoveries at the State Committee on Science and Technology of the USSR 113035, Moscow, Zh-35, Raushsk nab. 4/5
     1650016
    14 Continued table. 2

    99.5 2.1
    2.4
    100 88
    85.0 7.3
    8.1
    7.5 91
    80.0 6.1
    7.0
    5.0 92
    Subscription
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    引用文献:
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    US3506070A|1967-12-26|1970-04-14|Marathon Oil Co|Use of water-external micellar dispersions in oil recovery|
    US3808156A|1971-11-22|1974-04-30|Ethyl Corp|Chemical composition|
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    US4293428A|1978-01-18|1981-10-06|Exxon Production Research Company|Propoxylated ethoxylated surfactants and method of recovering oil therewith|
    JPH0157235B2|1982-01-28|1989-12-05|Lion Corp|
    US4556108A|1982-01-28|1985-12-03|Lion Corporation|Micellar slug for oil recovery|
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    法律状态:
    优先权:
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    JP25645084A|JPS61136577A|1984-12-06|1984-12-06|Fluid for petroleum recovery|
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