• 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:
    A process for inhibiting the deposit of paraffins in crude oils and petroleum fractions incorporating additives of the family of N-substituted succinimide ethers. The additives according to the invention make it possible, on the one hand, to maintain in dispersion the whole range of paraffins improving the flowing properties of crude oils and, on the other, to prevent the deposit of the heavier paraffins on the walls. Therefore, the process is effective during both the storage and the transportation of crude petroleum.
    公开号:SU1314961A3
    申请号:SU843775307
    申请日:1984-07-20
    公开日:1987-05-30
    发明作者:Дамен Бернар；Фор Ален；Мальдонадо Поль；Волль Жан-Люк
    申请人:Сосьете Насьональ Елф Акитан (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a method of preventing paraffin deposits in oil by using additives.
    The purpose of the invention is to develop a SporO alkoxylated alcohol of formula (VI) using polyhydroxypropyl lauric alcohol to obtain either anhydrides of formula (III), for example, 21 propylene syrup units, tridecyl alcohol trioxypropyl, hydroxypropyl alcohol
    Soba, which retains its effectiveness both during storage and during the transportation of oil with respect to heavy paraffins.
    The method consists in adding to the paraffinic oil additives from the family O hydroxyethyl tridecyl alcohol, va substituted M-succinimide esters. Among the amines of formula (IV), the mass concentration is 100-1500 ppm.
    Substituted N-succinimide esters respond to tuyeres
    Mules (I) of the invention of -N-oleylprodiamine of the formula Cg (CH), -N N-isohridecylpropanediamine of the formulas C |, H NH- (CH.), isotridercyloxy-3-propylamine-1C13 flj -., 0- (CK2), undecyloxy-3-propylamyl- formula C, H.N.-0- (SI., Tridcyloxy-3 propylamine-1 forms C, Ji ..- 0 - (, J., j —NH,.; (Ethyl-2 g strength) hydroxy-Zpropylamine-1 of formula
    ABOUT
    //
    Rv- (OAV-0Jl -lBXlm-R (1)
    0
    Rdqal
    ro-Qr NHVB- N (-I) ,,, - R
    where R and Rj are linear C, -C-alkyl, A and B are C, .- Cj-alkyl,
     X is a group - N11 or -O, p is an integer of 5-40, m is an integer of 1-4, Z is an integer of 1-3, Products of the invention that meet formulas () and (11) can be obtained in the course of reactions, at least Nfc re, of one anhydride, corresponding to the general formula
    ABOUT
    go
    -U
    P
    o (iii)
    with an amine, responsible either to the general formula
    The reaction temperature is usually 65 - and preferably 80-160 ° C, 45. The reaction time is 0.5-6 h and preferably 1-3 h,
    The amines of formula (IV) are usually used at the rate of 1.02-1.2 mol, etc.
      NH, (IV)
    or the general formula:
    H.N-fBNHf- H (V) - 1 preferably, 1.05-1.1 mol per mole
    The anhydride of formula (III) can be an anhydride of formula (111), obtained by reacting maleic anhydride with a secondary or tertiary alkoxylated alcohol; the amines of formula (V) are usually used at the rate of 1.02-1.2 mol and, preferably, 1.05- 1.1 mol to 2 mol of anhydride of formula (III). 55 To obtain the products of the invention, maleic anhydride, oxyalkylated alcohol of formula (VI) and amine of formula (IV) or (V) can also be condensed into one step.
    the general formula
    R, - (- O -
    (Vi)
    In the above formulas (ITI), (IV), (V) and (VI) A, B, R ,, R ,;
    n, t, z, x ike the above values,
    Among the alkoxylated alcohols of the formula (VI), to obtain anhydrides of the formula (III), polyoxypropyl lauric alcohol is used, containing, for example, 21 propylene oxide unit, trioxypropyl alcohol, tridecyl alcohol, oxypropyl alcohol
    hydroxyethyl tridecyl alcohol, Among the amines of formula (IV) is
    hydroxyethyl tridecyl alcohol, Among the amines of formula (IV) is
    Formula (I) of the invention of -N-oleylpropanediamine of the formula C g (CH), N-isohydridyl propanediamine of the formula C |, H NH- (CH.), isotridocyloxy-3-propylamine-1 C 13 flj -., 0- (CK2), undecyloxy-3- -propylamyl- formula C, N.-0- (SI.,) - LH tridcyloxy-3 propylamine-1 of formula C, Ji ..- 0 - (, J., j-NH,.; (Ethyl-2 hexyl) oxy-Zpropylamine-1 of formula
    НЗС- (СНо) -ШНО-0- (СН21з- Н2
    SNG Cib
    Among the diaminone forgguli (IV), for the preparation of the products (II) of the invention, typenediamic, diethy. Pentaitine, tetraethylene pentamine, dipropylenetriamine, tetrapropylenepentamine,
    In order to obtain the products of the invention, it is possible to carry out the condensation of reagents of a solvent-free post, however it is preferable to be concentrated with a solvent, for example an aromatic hydrocarbon with a boiling point. 70-200 ° C, remove the water, Jo;) LZOEnnnuyu during the reaction.
    The reaction temperature is usually 65% and preferably 80-160 ° C., the reaction time is 0.5-6 hours and preferably 1-3 hours,
    The amines of formula (IV) are usually used on the basis of 1.02-1.2 mol and
    respectfully, 1.05-1.1 mol per mole
    anhydride formula (111),
    The amines of formula (V) are usually used at a rate of 1.02-1.2 mol, and preferably 1.05-1.1 mol, per 2 mol of anhydride of formula (III). To obtain the products of the invention, maleic anhydride, oxyalkylated alcohol of formula (VI) and amine of formula (IV) or (V) can also be condensed in one step.
    The structure of the nsuccinimide-substituted esters of the products of the invention can be confirmed by infrared spectrometry: the infrared spectra of the absorption bands of the succinimidor are 1700 cm and the absorption bands of the esters are 1110.
    The effectiveness of the additives has been tested both in the laboratory and in the field.
    Example 1. 715 g (0.5 mol) of polypropylene glycol monolauryl ether (i.e. polyoxyprokylated lauryl alcohol containing about 21 groups of propylene oxide per molecule) is introduced into a two-liter vessel and heated in nitrogen with stirring to 185 with. Then, 58.9 g (0.55 mol) of maleic anhydride are added and the reaction is carried out in nitrogen at 185 ° C for 15 hours.
    After cooling, a yellow sulfur oil is obtained, the infrared spectrum of which corresponds to the structure of an ob-pipropoxyl succinic anhydride.
    153.8 g of this oil are added to a solution of 39.6 g (0.12 mol) of N-oleylpropanediamine in 250 ml of xylene,
    The mixture is heated in reflux for 3.5 hours to 144 ° C with azeotropic distillation of the water formed during the reactions. 378 g of a 50% solution are obtained in the xysol of the product, the N-alkenyl-succinimide is the oi-polypropoxy structure of which is confirmed by infrared spectrometry,
    Example 2, In a 500 ml reactor, 9.8 g (O, 1 mol) of maleic anhydride and 145 g (O, 1 mol) of monolauryl ether, propylene glycol (t, e, polyoxypropyl duror alcohol containing about 21 groups of propylene oxide) are dissolved per molecule) in 150 ml of xylene. After heating in reflux for 3 hours, the mixture is cooled to room temperature, then 36 g is added.
    (0.1 mol) N-oleylpropanediamine,
    The mixture is again heated in reflux to 145 ° C for 3 hours with azeotropic separation of the water formed.
    A 50% solution is obtained in xylol of the product, whose structure by infrared spectrometry is identical to that obtained in the previous example.
    EXAMPLE 3 The same operations were carried out as in example 1, but 153.8 g of the oil formed in the first stage, polypropoxyl succinic anhydride, solution 9.90 g (0.06 g) was added to the procedure. mole) of tetraethylenepentamine in 250 ml of xylene. The mixture is heated in reflux to 144 ° C. for 3.5 hours with azeotropic distillation of the water formed during the reaction. A 50% solution in xylene of the product is obtained, the triamino-bis-succinimide -o-polypropoxy structure of which is confirmed by infrared spectrometry,
    PRI me R 4. The effectiveness of the products of the invention was tested in the laboratory by testing paraffin deposits on cold walls immersed in oil. The oil kept at its production temperature immersed the cell containing two plates whose temperature is 20 ° C lower than the crude temperature. of oil.
    The results are obtained by comparing the weight of sediments selected in crude oil without additives and in crude oil containing additives according to the invention.
    The value of E, reflecting the effectiveness of the additives, is determined by the formula
    E
    HER,
    100%
    where E, is the mass of sediment in oil without
    additives; E is the mass of deposits in oil,
    containing additives according to the invention,
    Table 1 gives the characteristics of the tested crude oil.
    The paraffin content is determined by excretion using methyl isobutyl acetone with further crystallization at -30 ° C. Possible asphaltenes should be preliminarily treated by adsorption on bleaching earth.
    Example 5, Efficiency of additives according to the invention in the inhibition of heavy paraffins.
    Paraffins are deposited on a cold plate in Example 4, Deposits are weighed, and the molecular weight distribution is determined by chromium,
    5i
    Table 2 shows the reduction (R) in percent of the mass of heavy N-paraffins in sediments in crude oil of the Paris Basin containing 100 ppm, the additives obtained in examples 3 and 10. Paraffins C are completely removed.
    Example In a 500 ml reactor, 0.1 mol of maleic anhydride and O, 1 mol of monohelenyl ether (bshenyl-C) polyethylene glycol, containing about 5 ethylene oxide units per molecule in 150 ml of xylene, are dissolved. After heating in reflux for 3 hours, the mixture is cooled to ambient temperature, then 0.1 mol of N-lauryl tetraethylenepentamine is added. The mixture was again fiarpeted in reflux for 3 hours. The structure of the polyethoxylated substituted N-succinimide was confirmed by infrared spectrometry.
    Example 7. In the example 6, 0.1 mol of maleic anhydride is reacted with O, 1 mol of polypropylene glycol mono-olether containing about AO ethylene oxide units, then O, 1 mol of progeny (α-propylene glycol).
    The structure of the product is confirmed by infrared spectrometry.
    Example 0.1 mol of maleic anhydride with O, 1 mol of polyethylene glycol monohehenyl ether containing about 5 units of ethylene oxide per molecule is reacted according to Example 7, then a solution in xylene of 0.06 mol of diethyl, and triamine is added.
    The texture of polyethylated oi-a-1-no-bis succinimide is confirmed by infrared spectrometry.
    EXAMPLE 9. The reaction according to Example 8 O, 1 mol1, maleic anhydride with O, 1 mole of polyurethane glycol laureate, containing about 40 units of propylene oxide per molecule, is added, then a solution in xylene of 0.06 mole of di - propylene triamine.
    The structure of the polypropoxylated of-a-bic-cyquinimide is confirmed by infrared spectrometry.
    sixteen
    Example 10 (comparative) 100 g of an ELVAX 40 copolymer are mixed with 200 g of lauric alcohol and 200 g of beeswax.
    Table 3 summarizes the results of the paraffin deposition tests of Example 4 and the effectiveness of additives with various types of oil.
    The data show the advantage of the proposed method. For each type of oil, an additive can be selected that is much more effective than the known product, i.e. additives can be adapted to the nature of the oil, while the deposition of heavy paraffins is more fully prevented.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    A method of preventing paraffin deposits in oil by adding an additive, from. finding out
    that, in order to increase the effectiveness of preventing the precipitation of heavy paraffins, substituted l-succinimide ester, of the general formula
    Ri- (OA) n-0Ч
    about
    , N- (BXV-H2 0
    or
    about o
    R -1PA P l / W-KN1g-B-1 "1-HOA), - 0-MD oV-Lo-tAOln-Rv
    where R ,, R, is a linear C-C-alkyl; A, B is j-alkyl;
    X is the group NH or -O, p - 5-40; m is 1-4;
    Z - 1-3,
    which is administered in an amount of 100 to 1500 ppm.

    -
    810
    32
    26,
    0,
    Chain length
    ha
     24
    28
    thirty
    and
    36
    40
    44
    Table 1
    901
    855
    32
    -12
    -12
    26.9
    4.75
    11.8
    0.18
    2.75
    0.01
    table 2
    R MVS% examples
    7
    one
    ten
    35 38 40 43 46 47 50 50
    I3I496I
    10 Table
    eleven
    Editor V.Kovtun
    Compiled by L.Ivanova
    Tehred L. Serdyukova Proofreader A.T.
    Download 2224/58 Circulation 453 Subscription
    VNIIPI USSR State Committee for Inventions and Discoveries 4/5, Moscow, Zh-35, Raushsk nab. 113035
    Production and Printing Enterprise, Uzhgorod, ul. Project, 4
    I3u961
    12 Continuation of table 3
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    同族专利:
    公开号 | 公开日
    OA07752A|1985-08-30|
    FR2549487B1|1986-08-29|
    GB2144448A|1985-03-06|
    IN161323B|1987-11-14|
    CA1231908A|1988-01-26|
    FR2549487A1|1985-01-25|
    US4937007A|1990-06-26|
    AR240187A1|1990-02-28|
    GB8418201D0|1984-08-22|
    GB2144448B|1987-07-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    NL111349C|1958-01-14|
    US3244188A|1962-10-03|1966-04-05|Dow Chemical Co|Inhibition of deposition of hydrocarbonaceous solids from oil|
    DK128287A|1967-10-24|
    US3897454A|1968-10-08|1975-07-29|Atlantic Richfield Co|Polyalkylene glycol polyalkylene polyamine dispersants for lubricant fluids|
    US4005020A|1973-07-19|1977-01-25|Petrolite Corporation|Paraffin removing compositions|
    US4045360A|1975-09-22|1977-08-30|Union Oil Company Of California|Inhibiting wax deposition from a wax-containing oil|
    FR2476119B1|1980-02-15|1985-07-26|Inst Francais Du Petrole|N-SUBSTITUTED SUCCINIMIDE ETHERS, THEIR PREPARATION AND THEIR USE AS FUEL ADDITIVES|
    US4329239A|1980-05-12|1982-05-11|Texaco Inc.|Hydrocarbyl dihydrouracil, its method of preparation and lubricating oil composition containing same|
    US4303535A|1980-05-12|1981-12-01|Texaco Inc.|Hydrocarbyl carbamidopropanamide, its method of preparation and lubricating oil composition containing same|US5202058A|1991-11-06|1993-04-13|A.S. Incorporated|Corrosion inhibiting method and inhibition compositions|
    US5989322A|1991-11-06|1999-11-23|A.S. Incorporated|Corrosion inhibition method and inhibitor compositions|
    EP0662504A1|1994-01-10|1995-07-12|Nalco Chemical Company|Corrosion inhibition and iron sulfide dispersing in refineries using the reaction product of a hydrocarbyl succinic anhydride and an amine|
    US6176243B1|1998-03-30|2001-01-23|Joe A. Blunk|Composition for paraffin removal from oilfield equipment|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8312074A|FR2549487B1|1983-07-21|1983-07-21|PROCESS FOR THE INHIBITION OF PARAFFIN DEPOSITION IN CRUDE OILS AND OIL FRACTIONS|
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