• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention provides grafted ethylene copolymers usable more especially as additives for inhibiting the depositions in crude oils. Said copolymer being formed of ethylene and at least one monomer with ethylenic unsaturation, chosen from vinyl esters of C2 to C18 monocarboxylic acids, the alkyl esters in the C1 to C12 range of unsaturated monocarboxylic acids from the C3 to C12 range and the alpha , beta -unsaturated dicarboxylic compounds, on which are fixed the grafts of a homo or copolymer of an alpha , beta -unsaturated monocarboxylic acid ester with at least one alkanol of a chain length equal to or greater than C12 and at least 20% of which is of a chain length equal to or greater than C22. Such copolymers may be used more especially as additives for inhibiting the deposition of paraffins and for improving the flow properties of the crude oils.
    公开号:SU1660588A3
    申请号:SU853979471
    申请日:1985-10-24
    公开日:1991-06-30
    发明作者:Менье Жиль；Дамэн Бернар；Бруард Рене；Лопез Дени
    申请人:Сосьете Насьональ Елф Акитэн (Фирма)；Сека С.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to inhibiting the precipitation of paraffins and improving the flow properties of crude oils.
    The purpose of the invention is to increase the effectiveness of preventing the crystallization of oil.
    The additives according to the invention are easily merged with crude oils. They slow down the crystallization of paraffins, reduce the flow temperature and viscosity of these oils and facilitate the transportation, storage and processing of these oils. In addition, these additives are copolymers formed by the main part (stem) obtained from an ethylene copolymer with at least one ethylenically unsaturated monomer, on which grafts of an α, ω-unsaturated monocarboxylic ester copolymer are fixed. - chain alkanol.
    The structures according to the invention also have paraffin sequences in the main part (stem) of the polymer, derived from ethylene, as in the graft, derived from ester a, / 3 -saturated monocarboxylic acid with a long-chain alkanol. These paraffin sequences provide the affinity of these graft copolymers with crude oil paraffins and improve the solubility of the additive.
    The graft copolymer contains 5-95 wt.% And preferably 40-75 wt. % copolymer of ethylene, forming the main part (trunk). The ethylene copolymer contains 50-90 wt.%, Preferably 70-90 wt.% Ethylene and 1-50 wt.%, Preferably 10-30 wt.%, At least one
    about
    S
    ate
    00 00

    s
    monomer with ethylene unsaturation selected in the group formed by: vinyl esters of monocarboxylic acids with C2-C18, preferably with alkyl esters of Ci-Ci2 esters of unsaturated monocarboxylic acids with Cz-C-12, unsaturated a, j3-dicarboxylic compounds in the form of a di-acid, a complex alkyl diester or anhydride.
    Of the vinyl esters, preferably vinyl acetate is used.
    Of the esters of unsaturated monocarboxylic acids, preferably alkallacrylates or methacrylates are used, preferably with a Ci-Cs-alkyl moiety,
    Unsaturated a, {3-dicarboxylic compounds are preferably methyl, ethyl or propyl diester of maleic, alkylmaic, fumaric or alkyl fumaric acid.
    The grafting may be an #, / -unsaturated monocarboxylic acid homo- or copolymer with at least one alkanol with a chain length equal to or more than Ci2, and at least 20% of which has a chain length equal to or more than C22. Preferably, acrylic and methacrylic acid are used as α, α-unsaturated monocarboxylic acid.
    The esters are obtained by reacting acrylic or methacrylic acid or their esters with mixtures of fatty alcohols.
    The fatty alcohols used are mixtures of alcohols with different chain lengths, the distribution of which lies in the following limits, wt.%:
    About Ci2-Cie Yu
    About Cie-Ci8 40
    About C20 80
    20 100.
    The mixture of alcohols according to the invention has the following composition, wt.%: Ci80-30
    S20Y-70
    С22-Сзо20-90
    If the graft is a copolyme, it contains 20-90 wt. %, preferably 60-99 weight. % of a complex of a, ft-unsaturated monocarboxylic acid with an alkanol having at least 12 carbon atoms in its molecule, m at least one co-homogomer selected in the group with: monomers of the general formula
    Zi 5CH2

    Z2
    in which Zi and Z2 are the same or different, they mean hydrogen, halogen, saturated, unsaturated or aromatic hydrocarbon radical with Ci – Cso, the group –0 – CO – RI, where RI is an alkyl radical with Ci – Cg. or the group -OR2, where R2 is an alkyl radical with
    C1-C12,
    unsaturated a, 3-dicarboxylic compounds in the form of a diacid, a light dialkyl ester, or an anhydride. From comonomers of general formula
    /
    Zi
    CH2 C
     Z2 is preferred by those in which Zi is hydrogen, and Z2 is an alkyl radical with Ci-Cie, an aromatic radical with Ce-Ci2, a group -O-00-Ri, where RI is an alkyl radical with Ci-C3, or a group - OR2, where R2 is an alkyl radical with Ci-Ce.
    Preferred comonomers are octadecene-1, styrene and vinyl acetate. They also facilitate the copolymerization of ester, / - unsaturated monocarboxylic acids and especially acrylates or methacrylates with unsaturated, dicarboxylic compounds.
    Among the unsaturated a, / 3 -dicarboxylic compounds that are part of the grafts, maleic or alkyl maleic acid, methyl, ethyl or propyl diester of such an acid or maleic or alkyl maleic anhydride can be specified,
    The graft copolymers are prepared by grafting an unsaturated monocarboxylic acid alkyl ester and, in known cases, the other monomers mentioned, onto an ethylene copolymer dissolved in an organic solvent. A solvent is selected in which both the copolymer and the graftable monomer or the graftable monomers are soluble. Of these solvents, the hydrocarbon solvents of the aliphatic or aromatic structure are chemically inert with respect to the monomers.
    Preferred solvents are, for example, xylene or toluene or
    fractions with aromatic character. The total monomer concentration can reach 10-100% by weight of the solvent, preferably the concentration is up to 20-60% by weight, so that after polymerization
    have a solution that is pumped at a temperature close to room temperature. The polymerization temperature can vary quite widely, e.g. 50 ° - 150 ° C, preferably at 70-120 ° C. The pressure is selected depending on the structure of the monomers, it can vary from atmospheric pressure to elevated pressures, in the order of 100 bar.
    Catalysts are usually chosen from compounds that give free radicals and are soluble in the reaction medium, for example, peroxides, namely benzoyl peroxide, acetyl, di-tert-butyl peroxide, tert-butyl peroctoate, or azo compounds, for example azo-bis-isobutylronitrile. Usually use a mole of catalyst, preferably 5-10 -10 mol per mole of monomer.
    The degree of polymerization is measured using gel permeation chromatography (GPC), which allows to obtain a weight average molecular weight in the form of an equivalent polystyrene number and polymer polydispersity indexes. The degree of grafting is determined by increasing the molecular weight obtained by GPC.
    The molecular weight of the target polymer can vary from 5,000 to 300,000, preferably from 20,000 to 15,000. Only a small percentage of the unvaccinated polymer is formed, and this percentage changes with the composition of the starting mixture. Due to the compatibility effect of the graft polymer, this polymer forms a stable mixture of ethylene copolymers.
    The additive according to the invention is included in crude oils in a weight concentration reaching up to 5-4,000 ppm, preferably 100-1,500 ppm. The introduction is carried out at a temperature of 20 ° C above the flow temperature of the crude oil, with stirring.
    Examples 1-5 describe graft copolymerization (graft copolymerization) of variable amounts of polyacrylates on EVA copolymer, while Example 7 deals with the graft copolymerization of three monomers - alkyl acrylate, styrene and maleic anhydride - on the same. Copolymer. In examples 6 and 8, a polyalkylacrylate and a copolymer of alkyl acrylate with styrene and maleic anhydride are prepared as a comparison.
    Example 9 describes, as an example, the synthesis of EVA to which an alkyl acrylate is grafted, not including C22-alkyl.
    Examples 10-12 relate to graft copolymerization on the main parts (trunks) formed by ternary copolymers.
    The yield is indicated as a percentage of the monomers reacted with respect to the initial monomer. The percentage of graft copolymer present in the final polymer is also indicated as a percentage, which is estimated from the chromatogram obtained with
    With the help of gel permeation chromatography (GPC), the ratio of the areas corresponding to the maximum (peak) of small masses (not subjected to the grafting product) and the maximum (peak) of higher masses (graft copolymer) was obtained to the composition of the initial mixture. The ultimate molecular weight (m) corresponds to the maximum recorded by GPC, it is given as a comparison to show
    0 increase in molecular weight due to graft copolymerization.
    Example 1: 60 g (1.36 mol) of a copolymer (weight average molecular weight
    5 weight 28.000. The number average molecular weight is 18,000, the molecular weight is 50,000) ethylene with vinyl acetate (EVA) containing 28% by weight of vinyl acetate in 440 g of xylene, and a nitrogen atmosphere is preliminarily created in the reactor. Bring the mixture to 90 ° C to achieve a copolymer dissolution. Then 6.67 g of alkyl acrylate with an average C2Q-C22 chain length containing 70% C22 is added, followed by a 5% complete dissolution of the alkyl acrylate 0.136 g of t-butyl peroctoate. After 1.2 and 3 hours of reaction, the same amounts of radical initiator (polymerization) are added so that the total amount
    0 catalyst used was 0.554 g. Total polymerization time was 4 h.
    Yield 92%, of which graft copolymer 94%. The ultimate molecular weight is 55,000.
    5 Example2. The same operating conditions are repeated as in Example 1, but using 20 g of alkyl acrylate and 0.408 g of tert-butyl pero-cocoate. Yield 91%, of which graft copolymer 85%. Limiting p0 molecules to mass 65.000.
    Example 3. The same operating conditions are repeated as in Example 1, but using 30 g of alkyl acrylate and 0.625 g of t-butyl peroctoate. 93% yield, of which grafted
    5 copolymer 74%. The ultimate molecular weight is 80.000.
    Example 4. The same operating conditions as in Example 1 are repeated. But 60 g of alkyl acrylate and 1.225 g of tert-butyl peroctoate are used. Yield 94%, of which grafted
    copolymer 54%. Ultimate molecular weight 85.00.
    Example 5 The same operating conditions as in Example 1 are repeated, but using 60 g of alkyl acrylate and 1.836 g of t-butyl peroxo. Yield 89%, of which graft copolymer is 46%. The ultimate molecular weight is 85,000.
    Example 6 As a comparison, the alkyl acrylate is polymerized under the conditions of Example 1, but without the presence of an EVA copolymer. Yield 93%. 12.000 average number average molecular weight.
    Example 7. The same operating conditions were repeated as in Example 1, but using a mixture of three monomers — 53.36 g of alkyl acrylate, 2 g of styrene and 1.89 g of maleic anhydride — in the presence of 0.86 g of butyl peroctoate. Yield 088%, of which graft copolymer 54%. Ultimate molecular weight 84.00.
    Example 8. As a comparison, alkyl acrylate, styrene and maleic anhydride are polymerized under the conditions of Example 7, but without the presence of an EVA copolymer. Yield 89%. The number average molecular weight is 10,500.
    Example 9. The same operating conditions as in Example 1 are repeated, but alkyl alkylacrylate with C18-C20 is used, not including C22-Yield 93%, of which grafted copolymer is 53%. The ultimate molecular weight is 85,000.
    Example 10. The same operating conditions were repeated as in Example 1, but replacing an ethylene-vinyl acetate copolymer with an ethylene-vinyl acetate-maleic anhydride terpolymer (weight average molecular weight of 26,000, number average molecular weight of 15,000, molecular weight of 40,000) comprising 28% by weight of vinyl acetate and 1% by weight of maleic anhydride, and 60 g of alkyl acrylate and 1.83 g of t-butyl peroctoate are used. Alkyl acrylate has and includes 70% C22. Yield 91%, of which graft copolymer is 49%. The ultimate molecular weight is 80.000.
    Example 11. The same operating conditions were repeated as in Example 1, but replacing a copolymer of ethylene with vinyl acetate with a terpolymer of ethylene with vinyl acetate and dilauryl fumarate (molecular weight, 38,000), prepared according to a known method of synthesis, and using 60 g of alkyl acrylate and 1,836 tert-butyl peroctoate. The alkyl acrylate has Cs-Cm and includes 70% C22. Yield 90%, of which graft copolymer 47%. The ultimate molecular weight is 78,000.
    Example 12. The same operating conditions were repeated as in Example 1, but replacing a copolymer of ethylene with vinyl acetate with a terpolymer of ethylene with vinyl acetate and alkyl methacrylate with Ci2, prepared according to a known method of synthesis, and using 60 g of alkyl acrylate and 1.836 g of tert. -butylperoctate. Alkyl acrylate is Ci8 C22 and includes 70% C22. Yield 89%, of which graft copolymer is 45%. The ultimate molecular weight is 85,000.
    To determine the effectiveness of these polymers as inhibitors of paraffin precipitation (release), two different measurements (measures) were used:
    pour point according to ASTM D 97 B
    temperature of onset of crystallization of paraffins by differential calorimetric analysis.
    This measurement makes it possible to determine in a very precise way the temperature of the appearance of the first paraffin crystals. Results are obtained by comparing the onset temperatures of the onset of crystallization of crude formation oils and that of crude oils, including the additives according to the invention.
    The magnitude of the DT, characteristic of the effectiveness of additives, is determined by the dependence
    AT Tf-T2l
    where Ti is the temperature of the onset of crystallization of reservoir crude oil;
    T2 - the temperature of the onset of crystallization of crude oil in the presence of additives.
    For some crude oils, there are two crystallization start temperatures, one for heavy paraffins above C45, another for lighter paraffins below C45.
    Table 1 shows the characteristics of the crude test oils (the paraffin content in the crude oil was determined by gas chromatography; the viscosity was measured in the RHEOMAT 30 apparatus),
    In tab. 2-5 show the onset temperatures (incipient) of crystallization or the flow temperature of crude oils of various origins in the presence of varying concentrations of additives;
    Thus, during the test at the wells in the crude Gabon oil well, the use of 300 ppm of the additive of Example 4 makes it possible to receive and transport this oil through pipelines over a distance of 15 km without any problem of viscosity and paraffin deposition.
    权利要求:
    Claims (1)
    [1]
    At the temperature of measuring the crude oil, the oil behaves like a Newtonian liquid .5 Claims of Invention
    t
    to increase the efficiency of the process, as a graft copolymer, a graft copolymer of C20 C22-alkylacrylate or maleic anhydride and a copolymer of ethylene, vinyl acetate is used. or a copolymer of ethylene, vinyl acetate and maleic anhydride, or a copolymer of ethylene, vinyl acetate and dilauryl fumarate, or a copolymer of ethylene, vinyl acetate and Cia methacrylate. a b and c a 1
    11166058812
    Table
    The temperature of the onset (onset) of crystallization of crude oil of Tunisian origin at T,
     28,
    Tabli-csa
    Pour point, C, crude oil origin from Niger
    Ethylene copolymer with vinyl acetate
    (comparison) + 24 + 24 + 12 O
    Product of Example 6
    (comparison) +2424 + 9O
    Mixture (50/50) of ethylene copolymer with vinyl acetate + product of example 6 + 24 2460 product of example 5 +24 2+ O-3 product of example 9
    (comparison) + 24 + 24 + 12 +3
    Product of Example 10 + 24 + 21-3-3
    Product of Example 11 + 24 + 21О-3
    Product Example 12 + 14 + 21 + 3O
    US Patent No. 4178951 + 24 + 24 + 10 O
    USSR Patent No. 391002 (Example 8) + 24 + 22 + 5O
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
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