NO853356L - MOBILITY CONTROL OF CUT, SLOT OR PORE FLOWS - Google Patents

Description

In the technique, it is often desirable to 1anxiety or

to control flows of fluids through slits, slits or pore spaces. Thus, e.g. minimizing leakage losses through gaps in hydraulic systems, or achieving the slowing down of drip flows in waste dumps or building screws, which can mean a considerable technical advantage. In the case of the so-called tertiary crude oil transport (crude oil intensive transport), finally, it is necessary, among other things, to have a mobility control of the flow which will displace the crude oil from porous formations in order to achieve the highest possible degree of de-oiling. It is known that the slowing down of these gap or pore flows can be achieved by additions that increase the shear viscosity of the flow medium. Especially for crude oil-intensive transport, numerous methods have already been discussed which rely on a shear viscosity-increasing effect of the aqueous flow front. For increasing the viscosity, it is therefore recommended over high polymer soluble additives (US patent 3 724 545).

However, those with high-polymer thickeners have a number of disadvantages in practice. Thus, e.g. the viscosity-increasing effect of high polymers in ordinary strong by the temperature and by the addition of electrolytes. Under the conditions of petroleum formations with elevated temperature and salinity of the formation water, the thickening effect of the polymers usually decreases rapidly. Even if, however, it succeeds, at extremely high concentrations of the polymer or by using special polymers in the flow water, to achieve approximately the required temperature and electrolyte stability, these additions, however, simultaneously slow down the mobility of the flow in all pore areas. This means that the flow channels broken through (fingering) by the push-in probes of the transport probes in the pore space flow, as before, the main part of the flooding water past the oil-bearing areas, albeit slowly.

In order to avoid this disadvantage in particular, it was proposed in the European application 80 104 489.2 to use special polymer mixtures which only show a drastically increased flow resistance in the places where the flow liquid breaks through to the transport probe. Although this method is a significant advance, it does not, however, remove the disadvantages that are generally associated with the use of polymers such as e.g. their temperature and electrolyte sensitivity, and above all shear sensitivity. Because of these disadvantages, the polymers can be relatively easily broken down and destroyed, and thus quickly lose at least a large part of their thickening effect.

Surprisingly, it was now found that instead of these polymers, certain fluorinated cationic compounds can also be used which do not show the disadvantages of the polymers. These fluorinated cationic compounds flow-actively increase the flow resistance of the flow medium in a certain velocity range and thus affect its mobility in the desired way.

Furthermore, it was found that the compounds listed below

in pure form also without any additives in aqueous solution even in the smallest concentrations even in the presence of hydrocarbons they do not lose their flow resistance-increasing effect in gap, slot or pore flows and also under permanent stress, retain their effectiveness.

The object of the invention is thus a method for mobility control of the aqueous slit, slit or pore flows, the method being characterized by adding a compound of formula to the aqueous medium

while

R means n-fluoroalkyl, n-fluoroalkenyl, n-alkyl, n-alkenyl or a group of formula „

Rf-(CH2)yB(CH2)x-

R^means n-fluoroalkyl or n-fluoroalkenyl, R^means hydrogen methyl or ethyl, X means an integer from 2 to 6, y means 0, 1 or 2, B means an oxygen or sulfur atom,

K<+>means a cation with formula

vy' +N_R2

<*>4 ;R2 means hydrogen, C-^-C^-hydroxyalkyl, C1-C5-alkyl, benzyl or phenyl, R^ means hydrogen, methyl or ethyl, R4resp. may be the same or different, and mean hydrogen or ε 1 -C 2 -alkyl and a in the case that the fluorinated groups under the meaning of R mean an n-alkyl-, m-alkenyl- or n-fluoroalkylsulfonate anion, a n -alkyl-, -n-alkenyl- or n-fluoroalkenylcarboxylate anion, a benzoate, phenylsulfonate, naphthoate, iodide, rhodanide anion or an anion of the formula C n Cl2n n+1 COO- with n = 1, 2 or 3, and A~ for the case of non-fluorinated groups under the meaning of R means an n-alkyl, n-alkenylcarboxylate anion, an n-fluoroalkyl or n-fluoroalkenylcarboxylate anion, or an n-fluoroalkylsulfonate or n-fluoroalkenyl sulfonate anion, the compounds being excepted for the cases R^= fluoroalkyl, K+ trialkylammonium, A : iodide, R = alkyl, K+ = N<+>H_., A = fluoroalkylcarboxylate, and R-K = ( C-^- C ^)-trialkylammonium, A = fluoroalkyl sulfonate and fluoroalkyl carboxylate, as well as the salts with the formulas; ; for n = 12-14, and ;x = 1-3. Preference is hereby given to such compounds with the formula R-K<+>A~, where R means C]_8~ci4~n-fluoroalkyl, Cg-C-^-n-fluoroalkenyl, C^-C^-n-alkyl, or C , -C94-n-alkenyl, or a group of the formula; Rf means C 8 -C 1 -n-fluoroalkyl or C 8 -C 1 -n-fluoroalkenyl, R 1 means raethyl or ethyl, X means an integer from 2 to 6, y means 0 or 1, or e.g. an oxygen or sleeping atom, R^ means hydrogen, R^ means hydrogen or methyl or ethyl, and A~ in the case that fluorinated groups under the meaning of R means a C^-Cg-n-alkyl or n-alkenyl sulfonate anion, a trifluoromethyl or pentafluoroethylsulfonate anion, a Cg-Cg-n-alkyl or n-alkenylcarboxylate anion, a C-^-C^-n-perfluoroalkyl or C^-C4~n-perfluoroalkenylcarboxylate anion, an anion with the formulas; R5-COO~ or ~SO3~ Rg means C^-Cj--alkyl, C2-C(--alkenyl or C-^-C^-alkoxy in positions 3, 4 or 5, to R^, R^ means hydrogen or hydroxy in position 2 or 3 to R,., or R7 means NO2~, F-, Cl", Br", or J~ in position 3 to R5, ;Rg means hydrogen or methyl, or A~ means an iodide, rhodanide -anion, or an anion of the formula C2Cl2n+^COO; with n = 1, 2 or 3, and a" in the case of non-fluorinated groups under the meaning of R means an n-fluoroalkyl or n-fluoroalkenylcarboxylate anion, the sum of (2 x + n) must be an integer from 19 to 24 when x is the number of C atoms in the carboxylate anion, and n is the number of C atoms in the group R, an n-fluoroalkyl or n-fluoroalkenyl sulfonate anion, the sum of (2y + n) must amount to 17 or 18, when y is the number of C atoms in the sulfonate anion and n is the number of the C atom in the group ;R, or A means n-alkyl or n-alkenylcarboxyl anion , as the sum (z + n) must be an integer greater than 23 except for n = 16, when z is the number of C- the atom in the carboxylate anion and n is the number of C atoms in the group R. Particularly preferred are the compounds of formula R-K+A, where R-K+ means a cation of formula; ; R means a group of formula; C F_..-C.H,.-, C F_ -C„, ,-C,H..-, C F_ -CONR, C, H01 - or ;n 2n+l 1 21 n 2n 21-1 11 n 2n+l 1 k 2k C F, ,,- C- R. SC, H„. -, C F- ^ S0oNR,C, H01 -, ;n 2n+l 2 4 k 2k ' n 2n+l 2 1 k 2k ;n means a number from 2 to 10, 1 means a number from 2 to 20, k means a number from 2 to 6, as the sum (2n+l) must amount to--a number from 2 to 24, R4 means methyl or ethyl, R4' means methyl, ethyl, hydroxymethyl or hydroxyethyl, R^ means methyl or ethyl, ;A~ means a 2-hydroxyphenylsulfonate, m-halobenzoate or salicylate anion, an anion of formula wherein ; ; Rc means COO or SO_ and R means C H„ or C H_ - 5 J 3 ^ 61n 2n+l n 2n ;or<c>nH2n+i~°~ with n a number1 from .1 to11 4 1 positions 3, 4 or 5 to R,, or A~ means a 2-hydroxy-1-naphthoate-, ;3- or 4-hydroxy-2-naphthoate-, 2-hydroxy-naphthalene-1-sulfonate-, 3- or 4-hydroxy-naphthalene -2-sulfonate anion, or A~ means an anion of formula CF_SO_- or n-C H_ ,,-SO--, where x is ;3 3 x 2x+l 3 ;6, for which case (2n+l) is at least 18, x is 7 for that case (2n+l) at least 16, or x is 18 for that case (2n+l) is a number from 14 to 18, or A~ is an anion of the formula n~cxF2X+ l-C00~' where x is 2 or 3, when (2n+l) is a number from 16 to 22, or x is 4 or 5, when (2n+l) is a number from 14 to 20 or x is a numbers from 6 to 9, when (2n+l) is a number from 14 to 22, or A~. means an anion of formula SCH<->, J- or CCl3COO~ for the case where n is at least 6, and' (2n+l) is at least 16. Particularly preferred are also the compounds of formula R-K+A, where R-K <+>means a cation of formula ; ; n means a number from 1 to 22, R^ means methyl or ethyl, ;R^' means hydrogen, methyl, ethyl, hydroxymethyl or hydroxyethyl, A means an anion with the formula n-C2F2x+^-COO , where x is 2 or 3y and n+2X a number from 4 to 28, or x is 4 or 5 when n+2x is a number from 20 to 26, or x is a number from-__ ;6 to 9 when n+2x is a number from 19 to 22, A~ is an anion with the formula n-C H_ ,COO-, where x is a number from 7 to 9, when (n+x) is a number from 23 to 31 except for the case n = 16, or A is a anion with formula n-C F„ ,,-SO_-, where x is a number ;x 2x+l 3 which is chosen so that the sum (2x+n) amounts to 17 or 18. Of particular interest are the compounds with formula (CgF^ SO^ ) ;(R4~N(R1, R2, R3))fidet R1 means methyl or ethyl, R2 means methyl or ethyl, R^ means hydrogen, ethyl or methyl and R^ means hydrogen, methyl or ethyl, and of formula (cnH2n+ ]_+ NH3)(CxF2+1COO~), where n means a number from 14 to 18, and x a number from 1 to 3, especially 1. The production of the fluorinated compounds can take place in the following ways. In the case of ammonium iodides containing perfluoroalkyl groups, the appropriate starting point is the corresponding dimethylamines, resp. amidamines with dimethylami structures and quaternize with methyl iodide. The reaction can take place in lower alcohols such as methanol, ethanol, isopropanol, etc., as a solvent. Formed trimethylammonium iodides are in this case soluble in the mentioned alcohols. However, the quaternization can also be carried out in aprotic solvents such as Cl 2 , CHCl 3 , CH 2 Cl 2 or 1,1,2-trichloro-1,2,2-trifluoroethane. The reaction proceeds during the resp. solvent reflux temperature. In order to increase the reaction rate, however, it is appropriate to carry out the temperature at 100 or 120°C, since, however, due to methyl iodide's low boiling point, work must be done under pressure. ;Hexahydro- resp. octahydroperfluoroalkyltrimethylammonium iodide of the general formula; ; can also be prepared by direct alkylation of trimethylamine with the corresponding iodides containing perfluoroalkyl groups. If the desired perfluoroalkyltrimethylammonium carboxylates are to be prepared, it is appropriate to first prepare the silver salts of the carboxylic acid in question. In addition, the carboxylic acid is mixed with a stoichiometric amount of alkali. The silver nitrate solution is added to the water-soluble alkali salt. The slightly water-soluble silver carbonate oxylate that forms precipitates out and can be sucked off and dried. The production of the perfluoroalkyltrimethylammonium carboxylates takes place best in anhydrous solvents such as methanol, ethanol or isopropanol by mixing stoichiometric amounts of silver carboxylate and perfluoroalkyltrimethylammonium halide at temperatures of 50-60°C. After cooling, the formed silver halide is sucked off and by evaporation of the filtrate the desired trimethylammonium carboxylate containing perfluoroalkyl groups is recovered. A further purification can take place by recrystallization from solvents such as acetic acid ethyl ester, acetone, acetonitrile. A further production possibility for the desired perfluoroalkyl group-containing trimethylammonium carboxylates also consists in the production of alkyl trimethylammonium hydroxide solution by treating alkyltrimethylammonium halide or other salts with a strong basic ion exchanger, which is to be carried out in an anhydrous solvent such as methanol or ethanol. It is then neutralized with the desired carboxylic acid, and the salt is recovered from the solution by evaporation. The compounds mentioned are suitable for increasing the flow resistance of aqueous media in slit, slit or pore flows. They are added in concentrations of 0.05 to 5% by weight, preferably of 0.05 to 1% by weight, particularly preferably of 0.1 to 0.5% by weight. For each surfactant, however, depending on the temperature, there exists a different lower critical concentration limit for a sufficient effect as a flow resistance increaser (FWE), which, however, as discussed in more detail below, can be determined by a simple preliminary test. The effect as FWE is temperature dependent. Said compounds act together in a temperature range from 0 to 13 5°C, a single surfactant shows an effect like FWE, however, only over a temperature range of approx. 40°C (+ 15°C) The lower temperature limit for all surfactants is the solubility temperature (isotropic dissolution) or better power point. If the surfactant is temporarily in solution, the solubility temperature can in most cases be lowered for a few hours to weeks at around 5 to 25°C without loss of effect as FWE. ;The effect of the mentioned compounds such as FWE has not only been investigated in deionized water (E-water) at a pH value of 5 to 7, but various salts (foreign electrolytes) such as e.g. NaCl or CaC^ and others, or the solution's pH value varied by adding NaOH or HC1. It turns out that the addition of foreign electrolytes leads to no effect (Example 8) to a reduction (see Example 7) of the effect as FWE. An analogous relationship occurs when the pH value changes. The amount of foreign electrolyte that can be added to the aqueous surfactant solution is limited upwards by the concentration at which the salting-out effect for the surfactant occurs associated with a decrease or complete disappearance from the business as FWE (see example 7). The maximum concentration is also determined by the external electronegativity and is the lower the higher the value (charge) of the anion or cation. Instead of adding the surfactants mentioned according to the invention, one can also proceed so that the halogen salt of the cation R-K+Ha-, which e.g. ; or corresponding pyridinium compounds with Hal = Cl or Br in a 1:1 molar ratio mixed with an alkali salt of the anion NaA, such as e.g. sodium salicylate or other sodium hydroxybenzoates or sodium 3-hydroxy-2-naphthoates or sodium hydroxynaphthoates or sodium salts of the aforementioned carboxylic and sulfonic acids are used as flow resistance modifiers. The effect is then similar to the effect achieved with the pure surfactants with the addition of alkali halides. Also mixtures that deviate from the molar ratio 1:1 such as exL 1:2 show effects as FWE. The maximum effect that increases flow resistance also depends on the time that has passed since the preparation of the aqueous surfactant solution. It is true that the surfactant solution already works immediately after the solutions are prepared, an effect that increases flow resistance, however, this effect can change clearly within a week. The time required to absorb a constant effect can be easily determined in the individual case by simple experiments. In most cases, a constant effect is achieved after 1 to 3 days, in some cases after 1 week. A change, i.e. improvement or decline in the effect of FWE then no longer occurs. ;Of some surfactants such as e.g. hexadecylpyridinium salicylate, it is known (H. Hoffmann et al. Ber. Bunsenges. Phys. Chem. 85 (1981) 255), that from a completely determined'for each surfactant characteristic concentration CMC.^build up large non-spherical for the mostly small-scale micelles of the individual surfactants and counterions. Surprisingly, it was now found that the surfactant in aqueous solution is always effective as flow resistance enhancers, when they are for concentrations greater than CMCj-j. form non-cool worm-ed, preferably small-scale micelles. Non-spherical, ~~ preferably small steel-shaped micelles are present when, by examination of the isotropic tension resolution using the methods of electric birefringence with a pulsed, square-shaped electric field (E. Fredricq and C. Houssier, Electric Dichroism and Electric Birefringence, Claredon Press, Oxford 1973 and H. Hoffmann et al. Ber. Bunsenges. Phys. Chem. 85 (1981) 255) there is a measurement signal whose fall allows a reation time of numbers greater than 0.5 ys to be determined. The lower concentration limit from which a surfactant in aqueous solution is effective as FWE is therefore always determined at the CMC^^, preferably at 1.3 to 2 times the concentration value of the CMC. ^. The determination of CMC^ is e.g. possible by measuring the electrical conductivity of the surfactant solution as a function of the surfactant concentration, as discussed in H. Hoffmann et al. (Ber. Bunsenges. Phys. Chem. 85 (1981) 255). It was found that the value of CMC^-j. is temperature dependent, and increasing temperature shifts to higher surfactant concentrations. To determine the surfactant concentration that is minimally necessary to achieve a sufficient effect as FWE in a certain temperature range, the determination of the CMC at the application temperature by means of electrical conductivity is a suitable preliminary test. The investigation and the mentioned surfactants on their effect on increasing the flow resistance of flow media in porous media or similar flow geometries took place with the help of the apparatus mentioned in DE-OS 29 04 848, in which for the respective aqueous solution of the surfactant, pressure was measured drop AP over the stretch AL during flow through a measuring tube filled with solid particles with diameter D for the different filter speeds V. From these values it is possible to calculate the dimensionless quantities, friction coefficient f and Renoldstall Re, according to ; where 5 is the density, q the dynamic shear viscosity, d the average diameter of the solid particles and n the volume porosity of the storage. Usually used for £ and n resp. the corresponding values of pure solvents, water. The thus obtained values f and Re are obtained as a product of these two quantities, a resistance characteristic number which, for the investigated surfactant solutions, was compared to the usual double logarithmic plot against Re with the corresponding value for pure water. As can be seen from fig.l, the pure water flow through a porous medium gives a resistance characteristic number A-l^O, which for Re i 5 is independent of the Rey-zero number Re. A resistance-increasing effect or also an extensional viscosity increase occurs when 4-TL - AJ^O, >0, for Re = constant, when the relative resistance characteristics <p>-^-R =^TL/"^H 0 exceed the value 1. ( -4^= resistance characteristic number of the surfactant solution). determined Reynolds number Remax'me^ maximum resistance increase decreases again. The degree of the effect of the tension solution as a resistance or expansion viscosity increaser .. medium shall in the following be characterized by the relative resistance characteristic number -4^ consequently a tension solution with = 20 has a better effect as a flow resistance increaser medium than a tensor resolution with = 10. The particularly effective tensor resolution „ can often the very small application Reynolds numbers measured knish only difficult to achieve (cf. fig. 1), so that in such cases when specifying or-^- K. at a specific Reynolds number, FWE is sufficiently described. The investigations of the surfactant solution only gave reproducible results, when the aqueous solutions of the surfactant salts before the measurements or was stored for approx. 1 week at measuring temperature. Admittedly, the solutions also show an effect as a resistance-increasing medium immediately after the conversion, which, however, can change clearly in the course of a week. The thus pretreated surfactants were subjected to a number of tests. Thus, pressing through the same surfactant solutions several times as shown in example 4 showed that the listed surfactants do not show a decrease in their flow resistance-increasing effect, mechanical or chemical degradation. Furthermore, it turned out that a flow resistance-increasing effect of the mentioned surfactants increases with increasing concentration, as the simultaneous increase in shear viscosity with increasing surfactant concentration of this can be determined in an ordinary viscometer compared to the flow resistance-increasing effect in a porous medium is relatively small. It also turned out that a reduction in the mean particle diameter of the storage leads to a lower applied Reynolds number or lower applied filter rates of the flow resistance-increasing effect, while the maximum value of the achievable resistance increase remains constant. It was also found that the aforementioned flow resistance-increasing effect of the surfactant solutions, on the one hand, occurs in bearings made from spherical, uniform grains, in bearings made from spherical grains with a wide particle diameter distribution, on the other hand, in sand packings made from angular grain material with a narrow or wide diameter distribution . Conducted investigations show that the aforementioned surfactant salts are suitable as flow resistance detectors wherever aqueous flows through slits or slits or pore spaces are to be controlled and/or slowed down. In particular, with the use of surfactant salts during crude oil-intensive transport (tertiary crude oil transport), the dreaded fingering ("fingering") of the flow front with subsequent breakthrough to the transport probe can be prevented, and thus crude oil yield is increased. To achieve an optimal effect as FWE, the dilute aqueous solutions of surfactant salts should be placed one to several hours before use in e.g. storage tanks by stirring, and possibly by heating before the solution is pressed into the formations in the usual way by pumping. It is also possible to store the diluted solutions in the storage tank over days to weeks without a decrease in effectiveness, as long as the solubility temperature of the resp. surfactant salts are not clearly exceeded. ;Example 1; ; (abbreviated: (CF)t» s (CH) 4. Ta salt) a concentration range of 250, 500 and 1000 ppm by weight was formed in E-water, the corresponding weight amounts of 0.625, 1.25 and 2 .5 g of the (CF)g (CH)4Ta salt in E-water was weighed to 2500 g. During the solution (solubility temperature approx. 40°C), the solutions were briefly heated to 90°C, and after cooling to 40°C stored for 1 week without stirring at this temperature. The investigation of the increase in flow resistance then took place in a pore flow apparatus (cf. DE-PS 29 04 848), as a quantity of liquid of 2500 cm from a thermostatizable supply container under pressure was pressed through the measuring tube filled with solid particles and likewise tempered. Through an adjustable valve at the end of the measuring device, the flow was controlled and measured by determining the flowing volume per unit of time, so that by simultaneous measurement of the pressure loss along the pore measuring section, the through-flow characteristic of the pore body could be determined. The diameter of the measuring tube was D = 25 mm, the total length L = 18.9 mm, measurement length for determining the pressure loss AL = 8.9 mm, and the approach length in the first pressure measurement bore LA = 5 mm. The measurement was carried out in such a way that it started at the highest flow rate, and the rate was then gradually lowered. The pore body was a random storage of narrowly fractionated glass spheres with a particle diameter d = 100 ym. Table 1 summarizes the results obtained with the solutions of different concentrations, with three Reynolds numbers (10, 10, 10) indicating the resistance characteristic number A as well as the relative resistance characteristic number A R. In fig. . 1 shows the overall progress of the measurement of the 1000 ppm solution in the formation against Reynolds number. The water-straight solid line corresponds to the A values obtained with the pure water flow. ;Example 2;Solutions of (CF)g(CH)4TA-Sal were prepared in concentrations of 250, 500 and 1000 ppm, as described in example 1 and measured at 55°C. They achieved television. and -<A_> values are given in Table 2. ;Example 3;The same solutions as in Example 2 were measured at 70°C. The results are summarized in table 3. ;Example 4;A solution of (CF)g(CH)4TA-Sal was prepared in a concentration of 500 ppm iE-water and examined in pore flow apparatus with d = 100 ym at T-55 °C. The same solution was successively pressed 50 times through the measuring section at a Reynolds number of 0.1. The -^- value initially amounted to 3800, and remained constant until the 50th measurement.;Example 5;A solution of Z~c10F2lC4H8N(CH3* 3-^ Sal<9>(Sal = sali~cylate) of 1000 ppm in E-water was formed as in example 1, and measured in the pore flow apparatus at 70°C (d = 100 ym).

At a Reynolds number of 0.1, an A value of

22100 (AR= 119.5) .

Example 6

The solution of (C9FigCF=CHCH2N(CH3)3)®Sal9 with concentrations of 500, 750 and 1000 ppm was formed in E-water according to example 1, and measured at 55°C in the pore flow apparatus. The results are shown in table 4.

Example 7

DSeat l become e edn aknonent sen5 tropapsljoøn snpinå ge7r 50 of ppm (CQsFom , f.Ci F=eCkHsCemHp„N el (CH6_ , ) b_ a)(rBe with different NaCl concentration (0, 5.IO<-4>, 5.IO<-3>, 5.10~<2>and 1 mol/l NaCl) and measured at 55°C in the pore flow apparatus according to example 1. The results are given in table 5.

Example 8

The procedure was as in example 7, in that instead of N5a.C1l 0 -b3 l, e 1a.n1v0 -en2d, t 1f.i1r0 -e 1 fmoorslk/CjaeClll2ig. e CRaeCsull„-toaptpenløe sner ingaengr it(t 5.1i0 -4, table 6.

Example 9

A solution of (CgF19CF=CHCH2-N(CH3) C2H40H)<®>Sal<9> was formed as in example 1 with a concentration of 1000 ppm, and measured in a pore flow apparatus (d = 100 ym at 40°C. The measured values are listed in Fig. 2. From Fig. 2 it appears that Re<2.10 3 er-A-R again = 1, i.e. at very low speeds the effect FWE disappears again as well as at high speeds (Re> 6). The maximum A-value is at Re = 0.16 2100 C^-R = 11.4'}-.

Example 10

Solutions of 500, 1000 and 2000 ppm of the compound ffi0(CgF^C^HgN (CH^) 3) J were formed as discussed in example 1, and measured at 40 C as in example 1. The measured value is given in table 7.

Example 11

A solution of 1000 ppm of the compound (CQF,QCF=CHCH_N © 9 (CH 3 ) 3 ) C 2 F 1 -C 00 was prepared as described in Example 1 and measured at 55°C. At the maximum value of 31,000 (AR=168) a Re number of 0.23 was achieved. FWE started at a Re number of _ o 1.10 and disappears again from Re >10.

Example 12

A solution of (C16H33N(CH3)3)C3F7C00 was formed as described in Example 1, and measured at 25°C. At Re = 0.01 accounted for

■A. = 5200 (AR=28.1) and at Re = 0.1, A. =2300 (AR=12.4).

Example 13

A solution of 1000 ppm of the compound (N(C9H[.) . C7F17S03 9 was formed as in example 1 and measured (T=25 oC).

The maximum FWE with = 2400 ( A„= 13) was obtained at Re=8.10 .FWE disappears ( A. K„.=1) at Re 2.10 and Re> 8.

Example 14

A solution of 3000 ppm of the compound (C,,<H>00 N(CH_)_) CgH^7C00 was formed as in Example 1 and measured (T = 25 C). At a Re number of 0.01, one-A was measured. -value of 28,000 (AR= 151.4) .

Example 15

ffl 9 The compound (C^HgN(CH3)3) CgFigCOO was formed with a concentration of 2000 ppm analogous to example 1 and measured (T = 55°C) at Re = 6.10<-2>er A = 420 '(^=2 ,3).

Claims (5)

1. Method for mobility control of aqueous gap, slit or pore flows, characterized in that a compound of formula R-K <+> A~ is added to the aqueous medium, where R means n-fluoroalkyl, n-fluoroalkenyl, n-alkyl, n-alkenyl or a group of formula Rf means n-fluoroalkyl or n-fluoroalkenyl, R^ means hydrogen, methyl or ethyl, x means an integer from 2 to 6, y means 0, 1 or 2, B means an oxygen or sulfur atom, K <+> means a cation with the formulas R 2 means hydrogen, C 1 -C 2 -hydroxyalkyl, C 1 -C 8 -alkyl, benzyl or phenyl, R 2 means hydrogen, methyl or ethyl, R 2 can be the same or different and mean hydrogen or C 2 -C 3 -alkyl, and A in the case of fluorinated groups under the meaning of R means an n-alkyl-, n-alkenyl or n-fluoroalkyl sulfonate anion, an n-alkyl-, n-alkenyl or n-fluoroalkenyl carboxylate anion, a benzoate, phenylsulfonate, naphthoate, iodide, rhodanide anion or an anion of the formula C Cl~ ,, ' _ n 2n+l COO~ with n = 1,2 or 3, and A for the case of non-fluorinated groups.under the meaning of R, means an n-alkyl, n-alkylcarboxylate anion, an n-fluoroalkyl or n-fluoroalkenylcarboxylate anion, or an n-fluoroalkylsulfonate or n-fluoroalkenylsulfonate anion, the compound being excepted for the cases R = fluoroalkyl, K <+> trialkylammonium, A : iodide, R = alkyl, K <+> = N+H , A = fluoroalkylcarboxylate and R-K ■ + = (C^ -C2 )-trialkylammonium, A — = fluoroalkylsulfonate and fluoroalkylcarboxylate , likewise hall tene with the formulas 2., Method according to claim 1, characterized in that a compound of formula R-K <+> A~ is added to the aqueous medium, where R means <C> g <-> C^ -n-fluoroalkyl, Cg-C14~ n -fluoroalkenyl, c1~C24 -n-alkyl or C^-C^-n-alkenyl, or a group with Rf-(CH2 )yB(CH2 )x - Rf means Cg-C-^-n-fluoroalkyl or Cg-C-^-n-fluoroalkenyl, R1 means methyl or ethyl, x means an integer from 2 to 6, y means 0, 1 or 2, B means an oxygen- or sulfur atom, R 3 means hydrogen, R 4 means hydrogen or methyl or ethyl, and A in the case of fluorinated groups under the meaning of R means a C 1 -C 8 n -alkyl or n -alkenyl sulphonate anion, a trifluoromethyl or pantafluoroethyl sulphonate anion, a Cg-Cg-n-alkyl or n-alkenylcarboxylate anion, a C-^-C^-n-perfluoroalkyl or C-^-C^-n-perfluoroalkenylcarboxylate anion, an anion of the formula R5 -COO~ or -SO3~, Rg means C^-C^-alkyl, C2-C5~ alkenyl or C^-Cg- alkoxy in the position 3, 4 or 5 to R,-, R7 means hydrogen or hydroxy in the positions 2 or 3 to Rj-, or R7 means N02 ~ , F~, Cl <-> , Br~ or J~ in position 3 to R^fRg means hydrogen or methyl, or A~ means an iodide, rhodanide anion or an anion of formula C2Cl2n+1COO with n =1,2 or 3, and A" for the case of non-fluorinated groups under the meaning of R means an n-fluoroalkyl or n-fluoroalkenyl carboxylate anion, the sum of (2x + n) shall be an integer from 19 to 24, when x is the number of C atoms in the carboxylate anion and n is the number of C atoms in the group R, an m-fluoroalkyl or n-fluoroalkenylsulfonate anion, the sum of (2y + n) must amount to 17 or 18, when y is the number of C atoms in the sulfonate anion, n is the number of C atoms in the group R, or A means an alkyl or n-alkenyl carboxylate, as the sum (z + n) must be an integer such as 23 except n = 16, when z is the number of C atoms in the carboxylate anion and n the number of C atoms in the R group. 3. Method according to claim 1, characterized in that a compound with formula is added to the aqueous medium where R-K <+> means a cation with formula R means a group of formula C F_\ n-C,Hon -, C F- .n -Cn Hn -f C F_ , -CONR, C, H01 - or n 2n+l 1 21 n 2n+l 11' n 2n+l 1 k 2k C F_ ,,-C-H.SC, H..-, C F_ SO„NRnC, H0, -, n 2n+l 2 4 k 2k n 2n+l 2 1 k 2k n means a number from 2 to 10, 1 means a number from 2 to 20, k means a number from 2 to 6, the sum being (2n+l) to make up in a number from 12 to 24, R4 means methyl or ethyl, R4 means methyl, ethyl, hydroxymethyl or hydroxyethyl, R^ means methyl or ethyl, A means a 2-hydroxyphenylsulfonate, m-halobenzoate or salicylate anion, an anion of formula wherein Rc means C00 or SO ~ and Rr means C H_ ,,- or 5 J 3 6 n 2n+l C H_ or C H_ ,,-0- with n a number from 1 to 4 in position n 2n- n 2n+l ^ 3, 4 or 5 to R^ , or A means a 2-hydroxy-n-naphthoate-, 3- or 4-hydroxy-2-naphthoate-, 2-hydroxy-naphthalene-l- sulfonate, 3- or 4-hydroxy-naphthalene-2-sulfonate anion, or A means an anion of formula CF^O^ - or n-cx H2X +l~ <S> 03~' where x is 6, for the case (2n+l) is at least 18, x is 7 for the case (2n+l) is at least 16, or x is 8 for the case (2n+l) is a number from 14 to 18 or A is an anion of formula n- Cx F2x+1 -C00~, where x is 2 or 3, when (2n+l) is a number from 16 to 22, or x is 4 or 5, when (2n+l) is a number from 14 to 20, or x is a number from 6 to 9, when (2ri+-l) is a number from 14 to 22 or A~ means an anion of formula SCN-, J- or CC13 C00~, for the case n is at least 6, and ( 2n+l) is at least 16. 4. Method according to claim 1, characterized in that a compound of formula is added to the aqueous medium wherein R-K <+> is a cation of formula n is a number from 1 to 22, R4 means methyl or ethyl, R4<1> means hydrogen, methyl, ethyl, hydroxymethyl or hydroxyethyl, A~ means an anion of the formula n-C2 F2x+1 -COO~, where x is 2 or 3, when n+2x is a number from 20 to 28, or c is 4 or 5, when n+2x is a number from 20 to 26, or x is a number from 6 to 9 when n+2x is a numbers from 19 to 22, or A is an anion of formula n-CxH2X+lC00 , where x is a number from 2 to 9, when (n+x) a number from 23 to 31, except in the case of n = 16, or A is an anion with formula n-C F_ ,,- x 2x+l SO^ , where x is a number chosen so that the sum (2x+l) amounts to 17 or 18. 5. Method according to claim 1 for mobility control of flow water in the tertiary crude oil transport.