• 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 invention relates to the field of the oil industry and makes it possible to increase the efficiency of the method of tretining oil production using a stimulating agent. . , ether sulfonates. As a stimulating agent, aqueous solutions are used that contain 0.1–3.0 wt.% Of triisobutylphenol sulfonate (TIBPS) of the general formula (OCH2CH2V-S03n 9 where X 4-12; M is Na or K, or N11.. TIBPS is surface active substance (surfactant) that is stable over a wide range of temperatures and pH values.Aqueous TIBPS solutions increase the surface tension at the surfactant phase boundary / air by a value of POIR of about 25-30 mNm and the surface tension of an oil / surfactant solution by 1 -10 (by Di Nony). Based on the activity and stability of TIBFS suitable for alkaline and acid deleterious metal cleaning process. In various salt-prefecture Content
    公开号:SU1274631A3
    申请号:SU843754755
    申请日:1984-06-27
    公开日:1986-11-30
    发明作者:Вестер Норберт；Уль Клаус；Гульден Вальтер；Шнайдер Герхарт
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:

     The invention relates to a non-fusion industry and relates to a method for tertiary oil production. The aim of the invention is to increase the efficiency of the method. Tri-isobutylphenol sulfonates TIBPS are surfactants that are stable in a wide range of temperatures and pH values. Aqueous solutions of these compounds reduce the surface tension at the interface between the surfactant / air solution in the order of 2530 mNm and the surface saturation of the oil / surfactant solution J value of 10 mNm (according to Di Nony). Because of their activity and stability over a wide range of pH values, these compounds are suitable for the alkaline and acid method of cleaning metals. In addition, they are with effective emulsifiers for emulsion polymerization and are suitable as stabilizers for latex and other polymer polymer emulsions. The usual interest is also in the use of these compounds in oil production, for example, in stimulation of wells and F-treatment of oil fields. At the same time, the surrounding area of the well due to the treatment with acid or due to the breakthrough of the reservoir due to the application of very high pressure becomes more permeable to oil. The use of the proposed compounds in this method yields oil. In all i cases, the surfactant is used in amounts of 0.01-10, preferably 0.05-3%. The proposed TIBFS receive as follows. The compound of the formula AND (OCH2CH2) x-Gal, where Gal is a halogen atom, in an aqueous solution is subjected to interaction with sodium or potassium sulfate in the presence of lower alcohols, polyols, mono- or polyethylene glycol or their alkyl ethers. Consequently, specific alcohols are added as solubilizing agents. Suitable for this purpose are Cj-C-alkano, ly, polyols, preferably glycerol, ethylene glycol or polyethylene glycols, in particular diethylene glycols, their C, -C-alkyl, mono- or di-esters. Work preferably with mono-, di- or triethylene glycol. The amount of this alcohol in the reaction batch is about 2-60, preferably 10-40% by weight, calculated on the halide ester. The reaction is carried out at 120-200 ° C, preferably 160-180 ° C. The reaction time is 2-10, preferably 3-6 hours. Sulfite in the form of sodium or potassium sulphite is used in a small: ..: bull. Water is the reaction medium, and the concentration of both starting compounds in the reaction mixture is preferably about 40%. Conventional catalysts for substitution reactions, such as alkali metal iodides, can be added to accelerate. According to this method, ether sulfonates are obtained in a yield of more than 80%. The resulting aqueous solutions of ether sulfonatosis can be applied directly, without isolating the ether sulfonates. Due to their type of alcohols of the type described above, these solutions have a reduced gelling tendency. Compounds of this formula can be obtained from tributylphenol, preferably from the technology available mixtures of 2.4-6-isotributylphenol and a small proportion of 2,4,5-isotributylphenol, and these mixtures also contain minor amounts of isodibutylphenol and isotetrabutylphenol. An example would be a mixture consisting of 1.4-2% 2,6-isobutylphenol, 0.3-0.8% 2,4-isodibutylphenol, 1.2-2.2% 2.5-isodibutylphenol, 70- 80% of 2,4,6-isotributylphenol, 9-12%, 2,4,5-isotributylbenbl and 6-7% 2,4,5,6-isotetrabutylphenol, with a total fraction of three isodibutyl isomers about 3%. Example 1. Tributylphenol x 7.5 X ethylene oxide (EO) sulfonate. 452 g (0.75 mol) of chloride obtained by the interaction of tributylphenol plus 7.5 mol of ethylene oxide (OH 96) with 50 С1 g, 104 g (0.825 mol) NajjSOj, NaJ - at the tip of shpigtel, 83 g of diethyl glycol and 751 g of water are placed in an autoclave with a capacity of 2 l and stirred at 175 C for the initial pH value of 10-11 for 3 h. Pe, the reaction mixture is allowed to cool to -50 C and unloaded. The reaction product is a viscous, orange-colored transparent mass containing 30.4% of the basic substance (corresponding to 84% of the calculated amount of sulfonate based on mole. 670 Example 2. Tributylphenol X 7.5 EO sulfonate. Corresponding Example 1, however, instead of diethylene glycol, triethylene glycol was used as a solubilizing agent. Content was 30.1% (83.2% of the calculated one). Example 3. Tributylphenol X 10 EO-sulfonate. 385 g (0.5 mol of the chlorine compound obtained by the interaction tributy phenol plus 10 moles of ethylene (OH-number 75) with SOC12, 69, 3 g (0.55 mol) of NaJ - at the tip of the spatula, 69 g of diethylene glycol and 618 g of water are put into an autoclave with a capacity of 2 liters and at an initial pH of 10-11 are stirred for 5 hours at a reaction mass temperature of 175 C. the reaction mass is allowed to cool to 50 ° C and discharged.The reaction product is a yellow, viscous, clear liquid with a content of 29.0% of the main product (80.4% of the calculated mol / mol). at. 824). Example 4. Tributylphenol x. X 10 EO sulfonate. The same load as in example 3 but with triethylene glycol as a solubilizing agent. The content of 29.6% (82% of the calculated). Example 5. 440 g (0.5 mol) of chloride, obtained by the interaction of tributylphenol plus 13 mol of ethylene oxide (OH number 65) with SOCl, are loaded together with 69.3 g (0.55 mol), .NaJ - on the spatula tip , 75 g diztilenglykol and 690 g of water in an autoclave with a stirrer with a capacity of 2 liters and at the initial pH value of 10-11 is stirred for 6 hours at 175 C. A brown viscous liquid is obtained containing 29.9% (80.2% of the calculated per mole) . v. 349) of the main product. Example 6. Alfol 14 plus 3 mol EO-sulfonic acid. 14 350 g (0.94 mol) of chloride obtained by the interaction of alfol plus 14 mol of ethylene (OH number 159) 6 thionyl chloride, are loaded together with 130.6 g (1.04 mol) of Na, SO ,, .NaJ -.on spatula tip, 72 g of diethylene glycol and 650 g of water in an autoclave with a capacity of 1 l and at the initial value; pH 10-11 is stirred for 6 hours at 175 C. The reaction mixture is cooled to 60 ° C and unloaded. The target product contains 31.4% of the basic substance (91.3% of the calculated per mole, V. 439). To determine the effectiveness of Tributylphenol ether sulfonates, a well-known microcapillary solution method is used, and the determination of surface tension is carried out using the Spinning method Drop - interfacial - Teusinut er. In the case of a microcapillary solution, Drunemondi Seientifie Co (CCL) glass microcapillaries are used as a model for the pore space of the field, which, with a volume of 5 ml, are 30 mm long and 0.45 mm in diameter. Microcapillaries are sealed at one end, air is pumped out in a desiccator and filled with oil. The capillaries in surfactant solutions (tubes J, thermostated in a water bath, are installed vertically from the top, upwards and visually register the penetration of oil depending on time. When using the next rating scale, determine the effectiveness of the surfactant depending on its concentration, salt concentration, pH, temperature and composition of oil: 9 - complete emptying (30 mm) after 10 minutes; the same, after 1 h; - same, after 3 hours; - same, after 20 hours; - emptying after 20 hours 1625 mm - the same, 9-15 mm; - same, 4-8 mm; - same, 1-3 mm; - same, traces; O - does not change after 2 0 h. The advantage of this method is that, with a small diameter of microcapillaries, the viscosity and density of the oil does not have a large effect on the extraction of oil; therefore, it is possible to work with oil and water deposits.
    It is known that surfactants are only suitable for tertiary oil production when the surface tension at the oil / brine interface decreases by less than 10 mNm. For this definition of the surface tension at the oil / water interface, Wade and Burkovsky Spinning - DropInterfacial - tensitometer.
    The method is based on the fact that a drop of oil is deformed, which is placed in a rotating fluid around a horizontal axis of a capillary containing a liquid (silen water + surfactant) with a high density.
    The droplet is drawn until an equilibrium of deforming forces and surface tension is reached.
    According to Vounegat, the surface tension is calculated from the measured diameter of a drop of oil R, the rotational speed c and the difference in the densities U6i using the formula:
    & d CO R
    U-1/2
    The values measured by this method are presented in table. 1-19,
    In tests, the results of which are presented in Table. 1-9), respectively, 1% aqueous solutions of surfactants are used.
    Nonylphenol and dinonylphenol hydroxy sulfonates are tested as reference products.
    /
    Test with oil field K. Salt content, g / l: NaCljlSO CaClj 20, pH 8.5, temperature 40 ° С,
    i T a b l i c a 1
    Test with oil field K. NaCl content 100 g / l, -pH 8.5,
    Product
    tributyl .-- Q) -0 () CH2CH2S03lsla dinonyl K.O (CH2CH20) bN2CH2 $ 0 a
    temperature 40 C.
    .Table 2
    Surface
    tension
    one
    mnm
    -g
    1-10
    -g
    8-10 71274631 Paraffin oil test. CaCIj Salt content, g / l: NaCl 135,
    Aromatic oil test. Salt content, g / l: NaCl 70,
    Product
    tributyl (CH2CH20l8CH CH2S03Na nonyl h (L-) -0 (CH2CH20) eCH2CH2S03Na
    Dinonil Aromatic Oil Test. 15, -pH Salt content; NaCl 135; CaCl 45
    Tributyl - (QbO (CH2CH20) 6CH2CH2S03Na Nonyl noco (CH2CH20) bCH2CH280zNa
    CaClz 30, -PH, temperature.
    Table 4
    Surface
    tension
    -2
    1.3 -10
    -2
    8 - 10
    -3
    3 10
    rZ
    1 0 (CH2CH20) 8CH2CHN2 VOSY. h, 8 - 8 IS.-pH 8.5, temperature 60 ° C. .Table 3 8.5. temperature up to C. Table 5 Nonyl Dinonyl
    Aromatic oil test. Salt content g / l: NaCl 195, Tributyl Nonyl) Nonyl Dinonil
    Test with naphthenic mixture. Salt content, g / l: NaCl 135,
    CaClz 45, -PH 8.5, temperature 40 ° С
    Table 6
    CaCl-j 15, -pH 8i, 5, temperature 60 ° C,
    Table. 7 (SN2SN20) bSN2SN 80zK 2O (SN2SN.20) bSN2SN2VOzKa 8 - 0 (CH7CH20) 6CH2CH2S03lSl (0 (SH2SN20) bSN2SN2SN280zK 0 (SN2SN20) bSN2SN2 OzYa $ 1 - 10 Feb. 10 I 10 10 July 10 August
    -four
    9 10
    /
    -0 (СН7, СН20) бШ2СН280з a
    Nonil Nonil Dinonil.
    -2
    3-10 0 (СН2СН20) bSN2СН2СН280зК i th about (СН2СН20) bСН2 СН280зМ
    eleven
    Test with naphthenic oil. Salt content, g / l: NaCl 140,
    tributyl-n ((CH2CH20) 8CH2CH280z a nonyl (CH2CH20) 8CH2CH2SO a dinonyl - /
    Test with paraffin (a), naphthenic (b) and aromatic (c) oil.
    Product
    Tributyl-O-0 (CH2CH20) 8CH2, CH2SO a Nonyl Dinonil tab. 9, it can be seen that TIBPS results of testing stimulating different salt levels (50 agents at concentrations of 0.1 and
    200 g / l are superior to the known 3% given in Table. 10-19.
    oil mobilization compounds. Test with oil field K (1)
    Phenol ether sulfonates are effective and the salt content, g / l: NaCl 60,
    at other concentrations .CaCl eo, -PH 6.5, temperature 8Q C.
    1. Tributyl - (VO (CH2CH20) i2-CH2CH2S03NHfi.
    Y /
    VA () w-CH2CH2BACK
    2. Nonil
    1274631-12
    CaClj 60, -PH 6., 5, bOS temperature.
    Table 8
    LZ
    2 IO
    -g
    3 -1-0
    The salt content is 150 g / l, pH 6.5, temperature,
    Gt ab faces 9.
    Surface tension
    -z
    -one
    1.3 10 4.2-10 1.9-10 -0 (CH2CH20) bCH2eH2BOZYa 6. (CH2CH20) gCH2CH2S03Na: 9.4.10-4.5-10-4.8-10 OeCH CH SOsT a 8 10
    3. Dinonil
    -CH2CH2S03Na
    Test with oil field K. Salt content, g / l: Wad 180. 1. C ibutyl 2. Nonyl 3. Dinonil
    Test with oil field. The content of NaCl 100 g / l, pH 8.5,
    1. Tributyl (CH2CH20) / tCH2CH2S03Na.
    2.dnonyl (СН2СН20) бСН2СН230 а.
    jCaGlii 20, -PH 8.5 temperature 40 ° C,
    . temperature 40 ° С, -4Q-0 (CH2CH20) QCH2CH2S03Na. (СН2СН20) 8СНгСН250з№. / JhO (CH2GH20) 6CH2CHiS03Na. Table
    15
    -2
    2 10
    -2
    9-10
    Paraffin oil test. Salt content, g / l: NaCl 135,
    /
    . tributyl - (Y 0 (CH2CH20) bSNgSN280 Na.
    one
    2.non 4Q) -0 (CH2CH 0) 6CH2CH2SOsNa.
    3. nonyl (CH2CH20) 6CH2CH2CH S03Na.
    4. Dinonil // v
    Aromatic oil test. Salt content, g / l: NaCl 70,
    1. Tributyl
    0 (CH2CH20) zSN2CH2BoZ-Na,
    2. Nonyl l, nonyl HQKO (CH2CH20) 8CH2CH2S03Na.
    sixteen
    1274631 Table 12
    7 o
    7 o
    2 10
    8 10
    SAS1g 15, -PH 8.5, temperature 60 C.
    d) bSN2CH280 Ka.
    Table 13
    CAC 30, -PH 6.5, temperature
    OlflCHoCHoSO Na.
    17
    I 2 3
    Aromatic oil test. Salt content, g / l: NaCl 135,
    1. Tributyl
    2. nonyl - (Q) -0 (CH2CH20) 6CH2CH2S03Na.
    3. Nonyl (СНгСН20) бСН2СН2СН280зК,
    4. dinonyl n (2) -0 (СН2СН20) bСН2 СН280зЫа.
    The test with aromatic oil, a CaCl 45, -PH 8.5, temperature 40 ° C. Salt content, g / l: NaCl 05,
    1. Tributyl, (СН2СН20) бСН2СН280зНa. 12. nonyl-O-0 (CH2CH20) bCH2CH230sMa.
    127463118
    -Table 14
    1 - 10
    -g
    4 10
    -g
    7.5 10
    CAC 15, -PH 8.5, temperature 40 ° C.
    laO eCHoCHoSOsNa.
    Table 15
    - (OY () BSN2CH2CH230ZK,
    3. Nonyl 4. dinonyl (СН2СН О) bСН2 СН250зНa.
    Test with naphthenic oil. Salt content, g / l: NaCl 135,
    (СН2СН20) бСН2СН230зНа, -НОНО (СН2СН20) бСН2СН230з№) -0 (CH2CHiO) 6CH2CH2CH2S03Na.
    (СН2СНгО) бШГСН250з№.
    .Table 16
    CaClj 15, -pH 8.5, temperature.
    -Table 17
    -3
    ten
    8 O O
    ABOUT
    -2
    ten
    Ltd
    ten
    -2
    0
    O 21 Test with naphthenic oil. CaCl, Salt content, g / l: NaCl 140,
    one . Tributyl „y / V
    (CH2CH20) 8CH2CH2S03-Na.
    2. NONIL
    OlCHjCHjWaCHgCHjSOjNa. 3. d „„ o „, V / Vo (CH, CH20) teCH, CH, S03Ka. paraffin (a), naphthenic (b) and aromatic (c) oil.
    -0 (CH2CH20) 8CH2CH250z a.
    one . Tributyl // v
    2. nonyl (CH2CH20) 8CH2CH S03Na.
    权利要求:
    Claims (1)
    [1]
    3. dinonyl 3 I2CH20) dCH2CH280zKa. Surface tension, mNm, Product TIZI 5 10,240 1. lO 2 10 9.7-1SG A, IO 4.510 3.1 1274631 4.1 9 10 22 60, -pH 6.5. temperature . The content of NaCl 150 g / l, pH 6 5 temperature, table 19 when the concentration of the product,%. Li ..., J. 2 lo lo 3.2 1 o 5 -.10 The ester sulfonates can also be used in combination with other anionic surfactants such as benzinsulfonates, fluoroalkylsulfonates, ob-olefin sulfates, and nonionic surfactants such as alkyl or alkylphenol polyglycol ethers. Alcohols and glycol ethers can be used as other additives. The viscosity of the water flow can also be increased by using polymers, such as hydroxyethylcellulose, polyacrylamides or polysaccharides. Claims of the method of tertiary oil production using ether sulfonates as a stimulating agent, characterized in that, with the aim of increasing the efficiency of the method, aqueous solutions containing 0.1-3.0 wt.% Of triisobutyl phenyl sulfonate of the general formula (OCH2CH2) x -SO C / tHg where X. D-12; M - Na or K, or NH. Priority on the grounds of 02/17/83 when using ether sulfonates; 12.23.83 when using aqueous solutions containing 0.1-3.0 wt.% Of triisobutylphenol sulfonate of the specified formula.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2115192A|1936-06-20|1938-04-26|Rohm & Haas|Aryloxy polyalkylene ether sulphonates|
    US2148432A|1938-01-27|1939-02-28|Rohm & Haas|Water-soluble capillary-active sulphonates|
    US3082249A|1958-05-13|1963-03-19|Monsanto Chemicals|Sodium 3-tridecyloxy-2-propanol-1-sulfonate|
    BE632843A|1962-05-29|
    US3541140A|1968-12-17|1970-11-17|Gulf Research Development Co|Process for preparing detergent sulfonates|
    US4091014A|1976-12-01|1978-05-23|Texaco Development Corporation|Process for making ether sulfonates|
    CA1157598A|1979-10-03|1983-11-22|Paritosh M. Chakrabarti|Polyethyleneoxy sulfonate surfactants|
    US4343711A|1980-03-17|1982-08-10|Texaco Inc.|Surfactant fluid suitable for use in waterflood oil recovery method|DE3347578A1|1983-12-30|1985-07-11|Hoechst Ag, 6230 Frankfurt|TRIBUTYLPHENOLETHERGLYCIDYLSULFONATES, METHOD FOR THE PRODUCTION AND USE THEREOF|
    CA1236482A|1984-03-16|1988-05-10|Werner A. Lidy|Preparation of sulphonates|
    GB8515225D0|1985-06-15|1985-07-17|British Nuclear Fuels Plc|Preparation of surfactants|
    DE3767119D1|1986-10-24|1991-02-07|Hoechst Ag|STYRYLARYLOXY ETHERSULFONATES, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF FOR PETROLEUM PRODUCTION.|
    DE3931840A1|1989-09-23|1991-04-04|Basf Ag|METHOD FOR PRODUCING REFRIGERABLE ALKANOLIC-AQUEOUS SOLUTIONS OF POLYETHERSULFONATES|
    US5167281A|1991-11-07|1992-12-01|Texaco Inc.|Dialkylate additives for surfactant sytems|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE3305328|1983-02-17|
    DE3346676A|DE3346676A1|1983-02-17|1983-12-23|TRIBUTYLPHENOL ETHERSULFONATES, THE USE THEREOF AND METHOD FOR THE PRODUCTION OF ETHERSULFONATES|
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