• 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:
    This invention relates to polymeric additives useful for inhibition of the deposit of paraffins and improvement of the flow properties of crude oils and to compositions containing crude oils and such additives. The polymeric additive according to the invention consists of a polymer formed by units derived from one or more alkyl esters of unsaturated monocarboxylic acids, one or more unsaturated alpha, beta-dicarboxylic compounds in the form of diacids, low alkyl diesters or anhydrides and one or more monomers having ethylenic unsaturation of the general formula CH2=CZ1Z2, in which Z1 and Z2 are the same or different and represent hydrogen, a halogen, a saturated, unsaturated or aromatic hydrocarbon group or an ester or ether group. Compounds containing a crude oil and 5 to 4000 ppm and preferably 100 to 1500 ppm of the additive have much improved flow properties.
    公开号:SU1508970A3
    申请号:SU853916002
    申请日:1985-06-19
    公开日:1989-09-15
    发明作者:Менье Жиль；Бруард Рене；Мальдонадо Поль；Волль Жан-Люк
    申请人:Сосьете Насьональ Елф Акитен (Фирма)；Сека С.А. (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to the field of inhibiting the crystallization of paraffins in crude oils when extracting oil from a well.
    The aim of the invention is to increase the efficiency of inhibition.
    The polymer additive according to the invention is prepared by polymerizing 80%, n-alkyl acrylate, 10% maleic anhydride and 10% vinyl acetate or styrene.
    The polymerization can be carried out in bulk, therefore, without a solvent or else in an organic solvent in which both monomers and copolymers are soluble. Among these solvents are hydrocarbon solvents with an aliphatic or aromatic structure that is chemically inert with respect to the monomers.
    Preferably, the solvents are, for example, xylene or toluene, or an aromatic fraction of o
    When the polymerization is carried out in a solvent, the total monomer concentration can reach 10-100 1 of a solvent, preferably 20 to 60%, in order to have a solution after palimerization and a solution that can be pumped at a temperature close to room temperature.
     The polymerization temperature can vary within fairly wide limits, e.g. 50-150 ° C, preferably 70-120 ° C.
    The pressure is selected depending on the structure of the monomers, it can vary between atmospheric and elevated in the order of 100 bar.
    Ian

    s
    Unsaturated cd, d-dicarboxylic compound and ethylenically unsaturated monomer each use 0.05-0.5 mol of unsaturated monocarboxylic acid alkyl ester.
    The catalyst is generally chosen from compounds that are sources of free radicals soluble in the reaction medium, such as, for example, benzoyl peroxide, acetyl peroxide, di-tert-butyl peroxide, or azo compounds, such as azo-bis-isobutinitrile . Usually, 10 - mol of catalyst is used, preferably 5-10 - 10 mol / mol of monomer.
    Molecular weight in most polymers can vary from 5,000 to 300,000, preferably 20,000 to -150000. Polydispersity may be 2-7. Molecular weights are determined by chromatography by permeation gel (GPC),
    The additive according to the invention is introduced into crude oils with a weight concentration of 5-400 ppm, preferably 100-1500. Inclusion is carried out at a temperature exceeding by 20 the pour point of the blank material, with stirring.
    The degree of polymerization of the copolymers is measured by gel permeation chromatography (GPC), which makes it possible to measure the molecular weights in the range equivalent to polystyrene, and the polydispersity index. Infrared spectrometry is used to dose the amount of maleic anhydride introduced into the polymer, based on the initial monomer mixture.
    To determine the effectiveness of these copolymers as inhibitors — paraffin precipitation — three different measurements are used: ASTM D97B test point yield point; a dynamic test called dynamic, which takes into account the possible shear force encountered during the transportation of crude oil and consists in measuring (cm) the distance that the raw oil passes along the pipeline with a slope of 5 ° and maintained at a temperature of 10 ° C below the hardening point of the oil; test
    sedimentation on cold pipes, the swarm consists in the study of the quantity and nature of the precipitation of paraffins on cold: machine tools, immersed in crude oil. A photocell is immersed in oil in which its production temperature is maintained; the photocell includes two plates whose temperature is set at about 20 below the temperature of the oil. The weights of precipitation found in raw oils without additives and in oils containing additives according to the invention are compared. The value (E), representing the effectiveness of the additives, is determined by the ratio:
    (E) Yo
    100
    0 5
    0
    50
    five
    0
    where E (- weight of sediment in crude oil
    without additive; E - weight of sediment in crude oil,
    containing additive. Example 1 (preparation of a copolymer additive). Into a 1 liter reactor, 122 g (0.33 mol) of n-alkylacrylate with an average chain length Cd-Cr, 4.2 g (mol) of maleic anhydride and 3.6 g (0.042 mol) of vinyl acetate in 240 g of xylene are introduced, the reactor is preliminarily brought into a nitrogen atmosphere. The reactor temperature is adjusted to 80 ° C. In the beginning;
    , 0.34 g of benzoyl peroxide was added to the reaction and the temperature was maintained at 80 ° C while the reaction mixture was cooled. After 1, 2 and 3 hours of reaction, the same amount of benzoyl peroxide is added in such a way that the total amount of catalyst used is 1.36 g. The total polymerization time is 6 hours.
    The reaction yield is 78% and the weight amount of maleic anhydride, determined by infrared spectrometry, 3.3%. The amount included
     melein anhydride ivinyl acetate 100% ..
    Molecular weights determined by gel permeation chromatography are: M
    P
    13,700;
    Mw
    33,000.
    Example 2 122 g of n-alkyl acrylate, 4.2 g of maleic anhydride and 4.4 g of washer were placed in the reactor of example 1 and polymerized under the same conditions. The total polymerization time is 6 hours. The reaction yield is 79% and the amount of maleic anhydride in the copolymer, determined by infrared spectrometry, is 3%. The amount of maleic anhydride included is 94%, the amount of styrene is 100%.
    The molecular weights determined by gel permeation chromatography are: M f, 11,000; My, 34000.
    - Example 3. Amounts equivalent to example 1 are introduced into 136.5 g of xylene, the reactor is pre-filled with nitrogen. The temperature of the reactor is adjusted to 80 ° C. 1.36 g of benzoyl peroxide in solution in a few cm of xylene are continuously added over 6 hours. Dilute the solution; w 37% by weight solids with xylene by the end of the reaction. The reaction yield is 89% and the amount of maleic anhydride determined by infrared spectrometry is 3.3%. The amounts of maleic anhydride and vinyl acetate included are 100%.
    The molecular weights determined by gel permeation chromatography are: M 15000; M 41000.
    Example 4. Synthesis is equivalent to Example 3, but 4.4 g of vinyl acetate is replaced by 4.4 g of styrene. The yield of the reaction is 95% and the amount of maleic anhydride determined by infrared pentrometry is 3.1%. The amount of maleic anhydride included is 94%, the amount of styrene is 100%.
    The molecular weights determined by gel permeation chromatography are: M = 13000J MV, 39000.
    Example 5 (comparative). As a comparison, 137.4 (0.375 mol) of average chain length n-alkylacrylate and 4.2 g (0.042 mol) of malic anhydride are polymerized under the same conditions as in example 1, the yield of the reaction is 77%, the amount of maleic anhydride determined infrared spectrometry, 1.9%. The amount of maleic anhydride included, and 64%.
    .3
    0
    five
    0
    .five
    0
    five
    .;.; . --but , :. , : -. with:., .- .i: .-- s, tgfon15ka) o; ts1, / M; I, are: M, ibOCO, i vv -i iA.
    Example t (srann; g1 ate GM1-1. 1Y) as article # 39; s ibf.G; (0.4: K-alkylacrylate sy,:,;.: ,,; with l. Anaiu.j chain. Polymerized under the same conditions as in Example 1, Reaction yield 88%.
    Molecules p; {b) .2 nsc, determined by gel permeation chromatherapy, are: M „19000; M, 58,000.
    Table 1 shows the characteristics of the test raw m; sel, table 2-7 yield points and the test results for the dynamic fluidity of oil without additives and measurement Shen emygat kont.ntrapi r-Fri prisadsk. obtained in examples 1-5 .; In tabl. 8 - test results
    OS-Chu .; Ziiz
    Kpor.fe tox, when tested in; -ie, stolstseni in skka: for psh. Use of Tk / jiojib oBaiine oil 1000 ppin additives. L linciinicu in liOH- measure 3, allowed TpajicnopTHponaTb this oil refiner: p1;, for the current 15 km, yy7 y; -1 1; psolosti and оСо: И-1ени1; ара1 {: ;;: 1: п
    Osaz, aim gar: |}; ins, itj number of automatic telephone exchange: .ov ug; ь.ro; (1 p: ..; ri. Reda (en:; oh oh omgo ..- ga {1 htc: g phase, practical;; -. L.
    Ф о рм ул р и ч ii 1 р С: 1 е ;:
    Method 1P NbPR; -T Yi1; - Kr1 G1 GLL Gsash-; parafsh og iz izzle-h ° iiii i ;; oi way up to 1PG oil | -. 00 rr; Vinylacesh copolymer, d, o tl and h a - y; c and with ti. -i, vro. with dszazyu nosjbi-eu effect1; g .1os. U and L- ibirovi ;; n, as conojiiif- i: B :)); ialtsi Gs1.ta.is used cono.4i-; i-; c 11 80 mol.%,. } 1-alk1: lp1l. 1: 1 a, 10 mol.% MaleinoEogo aiiri:; pi :: ii; f 10 mog.,
     33000-39000.,
    v
    Ta lb and c
    Note-. Indian oil
    of origin
    Table 3
    Note Raw oil of Indian origin.
     .150897010
    ;;. J ..
    Additive Distance, cm, at the point of use, С
    O700
    12715
    22715
    32712
    4 2712 5 (compare) 27 21 Prototype 18
    Note. Oil is of Alsatian origin.
    Table 5
    Additive Distance, cm, at a rate of yield point, C ru.
    OI700
    1127
    21 28.4
    3127.5
    41 28.6. 5 (compare), 1. 19.3 Prototype 21.2
    Table 6
    spacing Distance, cm, at the point of flow, for example, C
    About T 100 I 200 700
    1. 30 18 15 12
    230 1815 9
    330181512
    4301815 9 (compare.) 30242118 roto272721.
      - - - -
    Note. Nigerian crude oil
    origin.
    Table 7
    raskad Distance, cm at a temperature about an example of fluidity, ° C
    About I 100 I 200 I 700
    19.5 33.6 38.5 44
    29.5 32.5 37 44
    3 9.5 34.5 38.9 44
    49.5 33.1 37.8 44 (cf.) 9.5 27 30 37 rototype25 27 35
    eleven
    Note. Cheese oil of Gabonese origin. Concentration of 2000 ppm.
    150897012
    Table 8
    权利要求:
    Claims (1)
    [1]
    For m u and a l in b p ι they
    The method was inhibited by CO! ' .-'ABOUT 1 “ paraffinen’s nation’s cheese;Ori extracting nefep from ыжyzhl u ip in order additions to oil 1E0—700 horn: S. 1) “ vinyl acetate polymer .G * and h a - y in; and th with i in order to Job
    effective. ·! and nibbed! I, as a copolymer of vinyl acetate, use a copolymer of 80 MOL.%, C ao- C g2 . b-aluschakroat, 10 mol.% maleic anhydride and 10 mog..% vinyl acetate or styrene with M sv = 33000-39000.
    Ί
    Table 1
    Indicators Origin crude oil Gabon India Nigeria France(Alsace)
    Density, kg / m
    at 15 ° C 852 820 873 830 Yield point ° C eighteen 27-30 40 27 Paraffin content new,% * fifteen 20-25 39 27.5 Viscosity '40 e C t 50 th C. 8.6 22-27 50 ° C 4.3 60 ° C8.4 60 ° C 5.9 20 ° C 60’s 3.6 5,0
    Chromatography in the gas phase.
    table 2
    Example additive Distance, cm, at pour point, ° C 0 | one hundred | 200 | 700 one 30 27 21 fifteen 2. 30 24 21 12 3 30 24 eighteen 12 four 30 24 eighteen 9 5 (counter. ) 30 27 27 21 Famousterpolymer. 30 30 27 27
    Note·. Crude oil of Indian origin.
    Example additive Distance, cm, at pour point, ° C one hundred 200 ' one' 0 27.6 34 2 0 27.5 38.5 3 0 28.8 40 four 0 28.7 34 5 0 13.5 26
    Known; terpoli-. measures 0
    5 15
    Note. Crude oil of Indian origin.
    T _a__b_l_i_a ___ 4
    Example additive Distance, cm, at yield point, C 0 700 one 27 fifteen 2 27 fifteen 3 27 12 four ’27 12 5 (compare. ) 27 21 Prototypeeighteen Prim e n e Raw oil alsatian origin. T a blitz '5 Additive Distance, cm, at according to flow rate, C RUg 0 700 one one 27 2 one ' 28,4 3 one 27.5 four one 28.6 5 (compare. ) one 19.3 Prototype21,2
    Table 6
    -. - -. ">""M ~ m - - m _ m" and - m m b.
    Example additive Distance, cm, О pst, s at the point of flow ° 1 one hundred | 200 II aboutI aboutI g- "I 'I IIf ---------------------- 1eleven one thirty eighteen fifteen 12 2 thirty eighteen fifteen 9 3 thirty eighteen fifteen 12 four thirty eighteen fifteen 9 5 (. Compare) thirty 24 • 21 eighteen Prototype27 24 21.
    Note. Crude oil of Nigerian origin.
    T a b l Ts a 7 Example additive Distance, cm at pour point, ° C ° I one hundred | 200 700 one 9.5 33.6 38.5 44 2 9.5 32,5 37 44 3 9.5 34.5 38.9 44 four 9.5 33.1 37.8 44 5 (compare) 9.5 27 thirty 37 Prototype25 27 35
    Table 8
    Additives for example E (reduction of deposition),% one fifty 2 60 5 (compare) 40 6 twenty Prototype thirty
    Note. Crude oil of Gabon origin. Concentration = 2000 ppm.
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    同族专利:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8409747A|FR2566288B1|1984-06-21|1984-06-21|POLYMERIC ADDITIVES FOR USE INHIBITING THE DEPOSITION OF PARAFFINS IN RAW OILS|
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