• 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:
    Polymer compounds resulting from the condensation of polyacrylic acids having a molecular weight comprised between 10,000 and 2,000,000 and alkylamines containing at least 12 carbon atoms in their chain. These products constitute paraffin deposit inhibitors and pour point depressants for crude petroleum oils.
    公开号:SU1766281A3
    申请号:SU874028820
    申请日:1987-01-09
    公开日:1992-09-30
    发明作者:Лопез Дени；Мальдонадо Поль；Менье Жиль；Наваки Люк
    申请人:Сосьете Насьональ Елф Акитэн (Фирма)；С.Е.К.А.С.А. (Фирма)；
    IPC主号:
    专利说明:

    (L
    WITH
    This invention relates to the chemistry of high molecular weight compounds, specifically, to the preparation of high molecular weight paraffin inhibitors in oil and can be used in the technology of oil production and the production of oils based on it.
    The aim of the invention is to reduce paraffin deposits and improve the flow properties of crude oil.
    Example 1. 600 hours of acrylic acid (AA), 3 hours of azoisobutyronitrile, 16 hours of thioglycolic acid and 343 hours of water are mixed and polymerized by heating for 4 hours at 85 ° C to obtain an aqueous solution of polyacrylic acid (PAA), molecular weight which is approximately 14,000.
    This acid is then condensed with a fatty monoamine with approximately 22 carbon atoms. It uses industrial behenylamine, produced
    for sale by SEKA SA called Noram 42 and characterized by alkalinity of 3.2-3.4 milliequivalents per gram. To this end, 422 hours of amine containing 14.5% dry extract, 320 hours of Solvesso 200 (aromatic solvent, boiling point from 220 to 292 ° C) and 3 hours of zinc oxide are added to the previous solution of polyacrylic acid playing the role of a catalyst for dehydration. The temperature is brought to 60 ° C and introduced into a mixture of 255 parts of Norama 42. The temperature is gradually increased to 240 ° C, with continuous removal of water introduced by polyacrylic acid or formed during the condensation reaction. When water is removed from the solvent, the heating is continued for ten minutes. In this way, a hydrocarbon solution is obtained with 50% of the active substance, the molecular weight of which is between 1000 and 9000.
    h o and y
    00

    Gj
    Example 2. A high molecular weight polyacrylic acid is obtained by polymerizing a monomeric mixture comprising 123 hours of acrylic acid (60% aqueous solution), 186 hours of water, 1.4 hours of potassium persulfote, and 0.7 hours of potassium metabisulphite , heating 1 hour to 55 ° C. An aqueous 2% polyacrylic acid solution is obtained in this way, the molecular weight of which is approximately 120,000.
    As in Example 1, this polyacid is amidated with amine to burrows 42, the amounts of reagents are as follows:
    Polyacrylic acid332ch
    Diluted 20%
    water solution
    PAK / Noram 42300h
    ZnO4 h
    A hydrocarbon solution is obtained in this way with 50% of the active substance, the molecular weight of which is 20000-3000.
    Examples Zi4. The inhibitor is prepared as described in example 1, by changing the amount of azoisobutyronitrile and thioglycolic acid in order to change the molecular weights.
    Examples 5-8. The experiments were carried out as described in Example 2 and the polymerization of acrylic acid by the redox system of metabisulfite persulfate was carried out, changing the conditions of condensation of the amine of begonic acid,
    Example 9. The experiment was carried out by condensing a commercial polyacrylic acid with a low molecular weight (6000). The amidation conditions are the same as in Example 1. An amidated polymer with a molecular weight of about 5,000 is obtained.
    Examples 10-12. The polyacrylic acid obtained as in Example 2 is condensed with stearylamine, distearylamine and behenyl propylene diamine, marketed by SEKA C.A. under the names Norah, Norah 2-18 and Dinoram 42. The condensation conditions are similar to those described in Example 2.
    Example 13. The effectiveness of the products of the invention as additives improving the flow properties of crude paraffinic oil, differing from 20-25% paraffin and its viscosity, 8, m2 / s at 50 and 5 m2 / s at 50 °, is tested. WITH. The experiment was carried out according to the norms of NFT 60105 with the addition of an additive in oil using 600 ppm inhibitors. Compare the products according to the invention with
    trading products, Shell Swimin S.K. which is a C 20/22 alcohol acrylate homopolymer.
    The paraffin content of the test feedstock is measured by conventional isochromatography methods.
    The yield point of the feedstock is measured according to NFT 60105 standards, but in some cases a dynamic flow test was also carried out. This test measures the maximum mileage that the oil can carry out, the output from the tank through the cooled pipeline. The oil contained in the tank is maintained at a temperature that is approximately 10 ° above its pour point. This receiving tank is connected with a wide-bore crane with a calibrated glass tube 40 cm long, 3 mm inside diameter and inclined 5 ° to the horizontal. Due to the thermostat, this pipe is maintained at a temperature of 0, 5, 10, or 15 ° C, the choice of this temperature depends on the performance characteristics of the oil and on the test compound. The initial level of oil in the receiving tank is of great importance. It is simply kept constant from one comparative test to another. In practice, the receiving tank is loaded with a constant volume of oil (for example, 10 ml). The measurement is carried out by reading the maximum distance traveled in the cooled pipe before the oil stops due to solidification.
    Finally, the ability of the additive to limit the formation of paraffin deposits is measured by experience, called plate testing, which consists in circulating crude oil, maintained at a constant temperature, tangentially to two plates, maintained at a constant temperature that differs from crude oil, and which in all cases is lower than the temperature of crude oil, and which in all cases is lower than the temperature of the starting crystallization of the paraffins in the feed, it is determined, for example p, differential calorimetric analysis. After a certain period of formation, the deposition is collected, weighed and, if necessary, analyzed.
    The results of yield tests are presented in Table. four.
    Example 14. The effectiveness of the products according to the invention was tested as additives which improve the flow properties of paraffinic oil, the paraffin content of which is 22% and the pour point of 26 ° C.
    The inhibitor dosages here are 600 and 2000 ppm (0.06 and 0.20 wt.%).
    Example 15: The effectiveness of the products of the invention as additives improving the flow properties of crude oil in an experiment with dynamic flowability is tested.
    Here, crude oil with a paraffin content of 27.5% is used and its pour point is 27 ° C. Control experience on the proposed method of work gives zero mileage in a pipe cooled to 10 ° C. Shell Swimin S.X. is taken as an element of comparison. Example 13. The test was carried out with 1000 ppm (0.1% by weight) of the additive.
    Example 16. The example shows the specific feature of products derived from monoamine with a long chain.
    The effectiveness of the products is tested according to NFT 60105 standards by measuring the yield point of crude oil of Example 13, with additives of 600 ppm (0.06 wt%) additives.
    The results of the table below confirm the greater efficacy of polybenyl acrylamide.
    Example 17. The efficacy against paraffin deposition of a product according to the invention is determined by experience with plates carried out with crude oil, having a paraffin content of 8.5%, at which the crystallization temperature starts at 22 ° C, the test is carried out on plates supported
    at 20 ° C for 17 hours. The experiment was carried out with 300 ppm (0.03 wt.%) Of additives, the product for comparison DAAM was an amino derivative of an acrylic copolymer.
    acids (maleic anhydride modified with fatty amine and fatty alcohol.
    In addition, analysis of the formed sediments shows that they consist of a paraffinic feedstock, in which 40% by weight represents paraffins with a molecular weight above 350 (25 carbon atoms or more) versus 33% for the feedstock treated with DAAM and
    10% for the feedstock containing the compound of Example 7, and that, therefore, this compound not only limits quantitatively such deposition, but also reduces the ability to precipitate the raw material.
    by reducing very heavy paraffins.
    权利要求:
    Claims (1)
    [1]
    Claim Method Inhibiting Paraffin
    deposits in crude oil by introducing into it a high molecular weight inhibitor based on acrylic acid in an amount of 0.06-0.20 wt.%, characterized in that, in order to reduce paraffin blend and improve the rheological properties of crude oil, as a high molecular weight inhibitor use the product of the interaction of polyacrylic acid, mol. May 1400-120000 behenyl or stearylamine in the form of a 50% hydrocarbon solution.
    Table 1
    table 2
    Table 3
    Table 4
    Table 5
    Table 6
    Table 7
    Table 8
    类似技术:
    公开号 | 公开日 | 专利标题
    Kuzmić et al.2008|Studies on the influence of long chain acrylic esters polymers with polar monomers as crude oil flow improver additives
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    GB2121808A|1984-01-04|Cloud-point-lowering copolymer additives for fuel compositions
    El-Gamal et al.1998|Nitrogen-based copolymers as wax dispersants for paraffinic gas oils
    KR20060026411A|2006-03-23|Fuel compound exhibiting improved cold flow properties
    SU1508970A3|1989-09-15|Method of inhibition of crystallization of paraffins in crude oil recovered from well
    JP4783209B2|2011-09-28|Fluidity improver for fuel oil and fuel oil composition
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    El‐Gamal et al.1994|Synthesis and evaluation of acrylate polymers for improving flow properties of waxy crudes
    Farag2008|Poly | as flow improver for Egyptian waxy crude oils
    CA1334013C|1995-01-17|Copolymers of | acrylic acid esters as flow improvers in petroleum oils
    US4022590A|1977-05-10|Low pour waxy residual fuel oils
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    US4772673A|1988-09-20|Ethylene copolymers
    同族专利:
    公开号 | 公开日
    FR2592885A1|1987-07-17|
    FR2592885B1|1988-08-05|
    GB2185259B|1990-03-21|
    DE3700518A1|1987-07-16|
    OA08459A|1988-06-30|
    US4870137A|1989-09-26|
    GB8700451D0|1987-02-11|
    CA1298030C|1992-03-24|
    AR243904A1|1993-09-30|
    GB2185259A|1987-07-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3005784A|1958-03-31|1961-10-24|Goodrich Co B F|Polymers containing amide and carboxylic groups|
    DE1123471B|1958-03-31|1962-02-08|Goodrich Co B F|Process for the production of partial amides or partial esters from anhydride polymers|
    FR2528435B1|1982-06-09|1986-10-03|Inst Francais Du Petrole|NITROGEN ADDITIVES FOR USE AS DISORDERS TO REDUCE THE POINT OF MEDIUM HYDROCARBON DISTILLATES AND COMPOSITIONS OF MEDIUM HYDROCARBON DISTILLATES CONTAINING THE ADDITIVES|
    US4520182A|1982-12-29|1985-05-28|Exxon Research & Engineering Co.|Acrylamide-alkylacrylamide copolymers|US5110874A|1989-07-18|1992-05-05|Petrolite Corporation|Methods and compositions for reduction of drag in hydrocarbon fluids|
    US5075390A|1990-07-06|1991-12-24|Nalco Chemical Company|Synthesis of hydrophobic/alkoxylated polymers|
    US5084520A|1990-07-06|1992-01-28|Nalco Chemical Company|Synthesis of hydrophobic/alkoxylated polymers|
    US5395897A|1994-01-18|1995-03-07|Nalco Chemical Company|High molecular weight substituted amides from polycarboxylic acids|
    GB9422093D0|1994-11-02|1994-12-21|Zeneca Ltd|Rheology modifier for solvent-based coatings|
    US5969052A|1996-12-31|1999-10-19|Kimberly Clark Worldwide, Inc.|Temperature sensitive polymers and water-dispersible products containing the polymers|
    CN105062450A|2015-08-25|2015-11-18|中国石油化工股份有限公司|Oil-based paraffin remover and inhibitor|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8600291A|FR2592885B1|1986-01-10|1986-01-10|NOVEL POLYAMIDE-N-SUBSTITUTED POLYMERS, PROCESS FOR THEIR PREPARATION AND THEIR USE AS ADDITIVES FOR CRUDE OIL|
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