Oil-in-water emulsion for secondary and tertiary production of petroleum

专利摘要:
This invention relates to an oil-in-water emulsion containing xanthan gum. The emulsion can be used for secondary and tertiary oil production. The aim of the invention is to obtain a stable emulsion at high concentrations of xanthan gum. This is achieved by the fact that the emulsion contains, in wt.%: Xanthan gum, 9.1-38.2; oil 1.1-48; surfactant 1,6-25,9; water the rest is up to 100%. As an oil, it contains a mixture of aromatic Cio-Cia-yr-hydrogens with TCip. 225-290 ° C or a mixture of aliphatic Cc-C15 hydrocarbons with batch. 205-265 ° C, as the surfactant - tristirilfenoksie- Thielen, dodetsilbenzolsu fonat calcium alkilarilfenol- ethoxylated Ca-phosphate having a degree of ethoxylation of 25, an ethoxylated lauryl alcohol with ethoxylation degree of 2, polietok- silirovanny nonylphenol with a degree of ethoxylation 14 , Ce-alkylaryl polyetherphosphate with a degree of ethoxylation of 6 or polyethoxylated linear alcohol Ct2-Ci4 with a degree of ethoxylation of 3. 5 table. sl C
公开号:SU1681734A3
申请号:SU843755477
申请日:1984-07-03
公开日:1991-09-30
发明作者:Пейнье Мишель；Гарсиа Мишель；Сенешаль Ален；Гань Пьер；Леспинасс Доминик；Шо Жан-Бернар
申请人:Рон-Пуленк Спесьялитэ Шимик (Фирма)；
IPC主号:

专利说明:

The invention relates to a heteropolysaccharide emulsion and microbial origin (xanthan gum, which has thickening properties) and can be used in the oil industry.
The aim of the invention is to achieve stability at high concentrations of xanthan gum,
The composition used the following commercial products:
oils: Solvesso 200 - a mixture of aromatic CU-Sp hydrocarbons with a boiling point of 225-290 ° C; Exosol D-100 is a mixture of aliphatic Cs-C15 hydrocarbons with a boiling point of 205-265 ° C; surfactants: Cemulsol LA30 - polyethoxylated linear C12-C-alcohol with a degree of ethoxylation of 3; Sokrofor ZD 33 - C2 - alkyl arylphenol phosphate, ethoxylated with a degree of ethoxylation of 25; Semulsol LA 20 - ethoxylated lauryl alcohol with a degree of ethoxylation 2; Semulsol NP 14 is a polyethoxylated nonylphenol with a degree of hydroxyethylation of 14; Semulsol RF 17-Сe-kilaryl polyether phosphate with degree of ethoxylation 6; Saprofor S 25 - tristyrylphenoxyethylene; - Saprofor 70 - calcium dodecylbenzenesulfonate; Celanol PA 17 - the same as Semulsol RA 17.
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Example 1. A 395 g Solvesso 200, then 20 g tristirylphenoloxyethylene, 20 g calcium dodecylbenzenesulfonate and 15 g ethoxylated alkylarylphenol phosphate (trade name Sophophorus 25, Soprophorone 70, Soprofor, ZD 33, produced by Ro-nPulek).
After dissolving the emulsifying system, 250 g of xanthan gum powder (Rodopol 23 grade), produced by the Ron-Poulenc form, are added.
Particle size: 200z m 77.5%; between 200-250, they are 14%; 250 / g m 8.5%.
After the powder was thoroughly dispersed in the solvent, 300 g of water was continuously added over 15 minutes with constant stirring.
A very homogeneous oil-in-water emulsion is obtained, which is not separated into phases after settling for 20 days at room temperature.
An aqueous solution is prepared from this emulsion with 0.3% xanthan gum. The viscosity of the resulting sol is measured and compared with a sol of the same concentration (control) prepared from Rhodopol powder.
The conditions for the preparation of sols are as follows.
For each experiment, 400 g of ashes are prepared. In a beaker equipped with a stirring system, rotating at a speed of 500 rpm, in water t400 g of tap water, the composition or powder is quickly poured in the desired amount, the duration of stirring is less than 30 seconds, then the stirring is continued for 1 minute after the introduction .
The viscosity measurement is carried out at 23 ° C on a Bruukfield viscometer.
The measurements were made after 10, -30, 60 minutes, then after 24 hours of settling. Duration of re-viscosity, MPa.s. mixing, min. Example 1 Control
10220110
30540320
60740560
24 h860740
Example 2. The same components are used in the same amounts as in Example 1, but they work as follows.
The emulsifiers are introduced into Solvesso 200. After dissolving, water is added slowly with stirring, then xanthan gum powder.
A stable emulsion is obtained, no phase separation is observed after 20 days of settling.
Example 3. In a reactor equipped with a stirring system and a thermostatically controlled bath, 500 g of a crude culture liquid, concentrated by ultrafiltration to a xanthan gum content of 7.6%, are introduced.
74.5 g of a mixture containing 67 g Solvesso 200, 2.75 g Soprofor 70, 2.75 g Soprofor S 25 and 2 g Soprofora 3 D 33 are mixed with water (500 v / mn).
Stirring is continued for 10 minutes, then a reduced pressure is created in the reactor (200 000 - 21 33 Pa) and the temperature is raised to 80-85 ° C. Evaporation is continued for 3 h.
An emulsion is obtained with the aqueous phase, which has the following mass composition,
%:
Xanthan gum23
Water44
Oil28,5
Surfactant4,5
This emulsion is homogeneous and fluid. No separation of the phases after a month of settling at room temperature is observed. The viscosity change is measured as a function of various velocity gradients compared to a sol containing 2% xanthan gum (Rodopol 23) prepared by dissolving the powder in tap water and with the original culture fluid.
The results are shown in Table. one.
The rheology of solutions of various concentrations prepared from emulsion is tested in Rheomat and compared with solutions of the same concentrations prepared from the initial culture liquid.
For each concentration, the rheogram, taken 24 hours after the end of preparation, makes it possible to calculate the critical stress of the flow threshold and apparent viscosity at various velocity gradients and to estimate the pseudoplasticity.
The results are shown in Table. 2
The same measurements made after 10 days of aging at 23 ° C give identical results.
Compared to the original culture liquid, an improvement in the emulsion performance with respect to the flow threshold and viscosity is noted, whatever the concentration of the solutions. In any case, the pseudoplasticity increases with increasing sols concentration.
A comparative study of solutions prepared on tap water and
salt water, shows a favorable effect on the yield strength and viscosity of salt water, the pseudoplastic behavior remains identical.
Example 4. Preparing an emulsion according to the method of example 3, using 500 g of culture liquid containing 78% xanthan gum, calculated on a dry material, 60 g Solvesso 260.7.5 g Semulsol LA 20, 7.5 g Semulsol NP14.
After evaporation (concentration), an emulsion is obtained, which has the following weight composition,%:
Xanthan gum 22.3
Water40,5
Oil28,6
Surfactant8,6
Example 5. Preparing an emulsion according to the procedure of Example 3, using for the aqueous phase 87 g of culture liquid containing 7.8 wt.% Xanthan gum, and for the oil phase 11 g Exosol D 100, 1 g Cemulsol L 20, 1 g Semulsol RA 17.
After concentrating by evaporation (70 ° C at a pressure of 20,000 to 21,500 Pa), the emulsion is ready and has the following composition,%:
Xanthan gum 25.2
Water29.0
Oil38,1
Emulsifiers7.7
. The rheology and filterability of the diluted aqueous solutions prepared from this emulsion and from the culture fluid used to prepare the emulsion (control) is determined.
Rheologists. The emulsion (or culture liquid) is diluted with salt water (50 g / l NaCI and 5 g / l CaCte) to obtain a solution containing 1000 ppm of xanthan gum.
The apparent viscosity is measured at various shear rates.
Flow or filtration test at constant flow.
This test allows one to prove the appearance of kelmatase, which can occur when a dilute biopolymer solution is injected into the oil field, and, therefore, to measure the suitability of the biopolymer solution for use in auxiliary oil recovery.
The principle of testing is to create a circulation of diluted solutions with a constant flow rate through a calibrated filter. Head loss (DH) occurring at the ends of the filter as it passes
xanthan gum solution, characterized by the ability to filter.
In order to comply with the conditions of use in the field, the solutions are tested with identical viscosity (and not with the same concentration).
The tests are conducted under the following conditions:
temperature 30 ° С, flow rate 22.5% ml / h, Millipore filters with a diameter of 47 mm, pore diameter of 8 ft m and 12 cm.
Preparation of solutions. The culture fluid is diluted with salt water (50 g / l NaCI and 5 g / l CaCIa) so that the resulting solution has a viscosity of 35 mPa-s measured on a Brook-Field viscometer at 30 ° C, shear rate 7, 3 sec.
The loss of head pressure L P is measured by filtering 350 ml of solution. If the pressure exceeds 50 mb, the number in brackets indicates the volume of the solution that was filtered when the pressure reached 50 mb.
Injection test at constant pressure.
This test allows one to prove the injectability properties of diluted xanthan gum solutions. The principle is to create a solution circulation at constant pressure through a calibrated filter. The ejected volume, depending on time, characterizes injectability.
Operate in the following conditions: Millipore filters with a diameter of 47 mm, pore diameter b ft m - 12 // m; pressure 3 bar; preparation of solutions: identical to the filterability test at a constant flow rate, viscosity 35 mPa s.
Note the flow time for the passage of 1000 ml of solution. If the time exceeds 10 min, the amount of breakdowns indicates the volume of the filtered solution.
The results are shown in Table. 3
Example 6 A mixture of 38.1 g of an aliphatic hydrocarbon (Exosol D100) and 7.7 g of an emulsifier (Semulsol LA 20 and Semulsol PA) are added to 700 g of culture liquid containing 15 g / kg of xanthan gum and with stirring. 17, 50:50 ratio).
The emulsion is concentrated by ultrafiltration.
Initial pressure 5 bar inlet, 3 bar outlet.
Final pressure 7 bar inlet, 3 bar outlet.
The ultrafiltration is stopped when the concentration of xanthan gum reaches 12% by weight.
The apparent viscosity is measured as a function of the shear gradient. For comparison, the initial culture liquid is concentrated by ultrafiltration to achieve the same value (12%). The results are shown in Table. four.
Example 7. According to the method of Example 1, an emulsion containing 8.9% xanthan gum is obtained, using: xanthan gum 16 g; water phase 144 g; oil Exsol D100 15 g; Cemulsol A 30 1.4 g. Surface-active substances Celanol PA 17 1.6 g.
The resulting homogeneous and stable emulsion contains:
91.4 parts of the aqueous phase containing 10% xanthan and 90% water; 8.6 h, Exsol D100 oils, 1.68% surfactants with respect to the mixture (a + b).
Example 8. Get the emulsion oil in water from 250 g of xanthan wort with 8% dry matter, 1 g of oil (Exsol D100), 17 g of Cemulsol LA30 and 17.5 g of Celanol PA17,
The emulsion is concentrated by evaporation of water to obtain an emulsion containing 20% by weight of xanthan gum, 98.5% of the aqueous phase, containing 31.25% of xanthan gum, 1.5 parts of oil, 35% of surfactants with respect to to (a1 + b).
The oil-in-water emulsion remains stable.
Example 9. Get the emulsion oil in water from 300 g of wort xanthan gum with a content of 8% solids, 45 g of oil Exsol D100. 12 g of surfactants (50:50 mixture of Cemulsol A30 and Celanof PA 17).
After concentration by evaporation of water, an emulsion containing 24% by weight of xanthan gum, of the following composition is obtained: 45.5 parts of an aqueous phase containing 60% xanthan gum and 40% water; 54.5 hours, oils, 13.6% surfactants with respect to (A + B).
The oil-in-water emulsion remains stable.
Example 10. An oil-in-water emulsion is prepared according to the method of Example 7 using 38.2% xanthan gum; oil Exsol D100 30.6, surfactant 4.2 g and water 27 g
The resulting stable emulsion contains 68 parts of the aqueous phase, containing 58.6% xanthan and 41.4% water, 32 parts oil and 4.2% surfactants with respect to (a + b).
Data on the composition of the compositions are presented in table. five.
The proposed emulsion, containing 9.1-38.2 wt.% Xanthan gum, is not susceptible to gelatinization for a long time (more than a month) and can be further diluted to the desired concentration in order to obtain solutions used for secondary or tertiary oil production. .
The known emulsion, which is also stable, contains xanthan gum in much lower concentrations — 0.05% and has a viscosity below 100 // P c s at 1.

权利要求:
Claims (1)
[1]
Claims of the invention Oil-in-water emulsion for secondary or tertiary oil production, including xanthan gum, oil, surfactant and water, characterized in that, in order to achieve emulsion stability
high concentrations of xanthan gum; as an oil, it contains a mixture of aromatic CU-C1Z-hydrocarbons with a boiling point of 225-290 ° C or a mixture of aliphatic C-C15 hydrocarbons with a boiling point of 205-265 ° C, as a surfactant - compound selected from the group comprising tristyrylphenoxyethylene. Calcium dodecylbenzenesulfonate, ethoxylated C2 alkylarylphenol phosphate with a degree of hydroxyethylation of 25, ethoxylated lauryl alcohol with a degree of hydroxyethylation 2, polytoxylated nonylphenol with a degree of hydroxyethylation of
14, Cg-alkylaryl polyether phosphate with degree of ethoxylation 6, polyethoxylated linear alcohol Ci2-Cu with degree of ethoxylation 3, with the following content of components, wt%:
Xanthan gum9,1-38,2
Oil1,1-48
Surfactant1,6-25,9
WaterEverything
Table 1
Example 3
table 2
Culture fluid 12% (control)
13,000
T a b l and c a4i
1800
290
46
T a b l and c a 5

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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FR8311060A|FR2548676B1|1983-07-04|1983-07-04|BIOPOLYMER COMPOSITIONS AND THEIR PREPARATION PROCESS|

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