DE2922928A1 - METHOD FOR OBTAINING OIL USING AQUEOUS SOLUTIONS OF PERFLUORED SURFACTORS - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann i Dir: T? - Koerogsberger Dipl.-Phys. R. Holzbauer - Dipl.-Ing. F. Klingseisen - Dr: F.ZumsteiYi jun.

PATENT LAWYERS

80OOMünchen 2 ■ Bräuhausstrasse 4 -Telephone, collective no. 22 5341 ■ Telegrams Zumpat · Telex 529979

• 5 ··

61-12042 / CGC 872 / +

CIBA-GEIGY AG, CH-4-002 Basel / Switzerland

Process for obtaining oil using aqueous solutions of perfluorinated surfactants

When extracting oil from oil-bearing reservoirs, it is generally only possible to use a smaller proportion of the originally existing OeIs through so-called primary extraction methods, which only those in the Take advantage of existing natural forces.

Un the economic oil yield over the under application To increase such natural forces achieved beyond, there have been various methods of increasing the stimulation developed. One of the most widely used methods of increasing extraction is flooding the reservoirs with water. The water is pressed into the reservoirs in the usual way, to drive the crude oil to the wells. The amount of oil obtained by this method depends on factors like that Interfacial tension between water and crude oil, the relative mobilities of the crude oil and water and the Wetting properties of the OeI in the deposit holding rocks dependent.

To increase the effectiveness of the water flooding method, surfactants have been added to the water. That Surfactant lowers the surface tension of the aqueous liquid and the interfacial tension between them and the petroleum and increases its water wetting properties, thereby reducing the capillary forces in the relevant underground formation. This supports the displacement of the OeI from the

030015/0669
Ή ".. ' ^: ^^ ' ■ - ORIGINAL INSPECTED

earthly sand and rock formations. Most aqueous compositions containing petroleum sulfonates have been used, conveniently in conjunction with controlled amounts of common salt. Sodium carbonate and / or sodium tripolephosphate can also be added to such a composition as an aid in order to protect the petroleum sulfonate surfactant against losses as a result of precipitation reactions with divalent cations. The use of thickeners has also been proposed in order to increase the clearing effect of the water flooding. Another water flooding method is the application of a first rinse (flooding). To reduce the amount of divalent cations (e.g. Ca ⁺ , Mg ⁺ ) that the surfactant would precipitate or absorb to a minimum, a surfactant-containing rinse to loosen the oil and detach it from the sand and rock, and a mobility buffer rinse that acts as counterpressure can be used on the surfactant system.

The pre-rinse solution does not contain any cations that have a disruptive influence on the surfactant and can be solutions contain or consist of sodium carbonate and sodium tripolyphosphate and the like. Possibly you can then inject brine in order to optimize the salt concentration for the purpose of better surfactant performance. The sodium ions also displace the calcium and magnesium ions. Strong acids are useful to form a carbonate rock formation to unlock. After the aqueous surfactant solution has been pressed in, the mobility buffer solution is injected. The mobility buffer usually contains a water-soluble polymer such as polyacrylamide or a biopolymer (e.g. a natural rubber).

After pressing in the mobility buffer (control) a propellant fluid is injected to move the previously injected fluids through the sand or pushing through the rock formation. the

030015/0669

ORIGINAL INSPECTED

Driving fluid is not critical in its nature and can for example, consist of locally available water. The propellant fluid, however, should not be mixed with the underground Formation incompatible. In a further embodiment of the mentioned method using Of the various solutions, the so-called surfactant solution contains an aqueous microemulsion from OeI, combined with petroleum sulfonates and auxiliary surfactants such as alcohols and electrolytes.

The present invention is a method of treating subterranean formations to reduce the flow of oil stimulate therefrom, as well as surfactant compositions for use in such treatments.

In particular, the present invention relates to a method for extracting oil from underground Deposits by injecting an aqueous surfactant composition, to displace the OeI from these deposits, which is characterized by the fact that Surfactant a compound of the formula

(1) VZ _1n -AQ _n

is used, wherein R _{f is} a hydrophobic-oleophobic fluoroaliphatic group with 4 to 24 carbon atoms, Z is a divalent bridging group, A is ·! divalent hydrophilic organic radical, Q is a divalent bridging group, R is a hydrophobic-oleophilic aliphatic radical with 6 to 24 carbon atoms or an araliphatic radical with at least 9 carbon atoms and m and η are independently 0 to 1, and the surfactants have a solubility in water of at least 0.01% by weight at 30 ° C, a surface tension of less than 30 dynes / cm in deionized water at a concentration of 0.1% by weight, and an interfacial tension measured against cyclohexane in deionized water of less than 12 dynes / cm at a concentration of 0.1% by weight.

030015/0669

^ ORIGINAL INSPECTED

-A-

Optionally, the aqueous surfactant composition contains further surfactants, e.g. of the non-fluorinated ones Type, such as anion-active, mixtures of anion-active and non-ionic surfactants or cation-active surfactants. The solubility of the surfactants in question in deionized water can be lower than that of the Measurement of surface and interfacial tension concentration used (0.1 wt% in deionized water). In such cases the measurements are carried out on a saturated heterogeneous aqueous system containing 0.1% of the fluoroaliphatic surfactant in deionized water.

Preferably the fluoroaliphatic surfactant

at a concentration of 0.1% in deionized water a surface tension of about 16 to 28 dynes / cm and an interfacial tension measured in deionized water versus cyclohexane of less than 12 dynes / cm, for example about 4 to 10 dynes / cm.

The fluoroaliphatic surfactants usually contain at least 2 to 50 weight percent fluorine, and preferably 5 to 35 wt. 96 fluorine.

The R _f radical is expediently a straight-chain or branched perfluoroaliphatic radical which contains 4 to 24 carbon atoms and can be interrupted by oxygen.

In a preferred embodiment, the R ^ group is straight-chain or branched perfluoroalkyl with 4 to 20 carbon atoms, straight-chain or branched perfluoroalkenyl with 4 to 20 carbon atoms or straight-chain or branched perfluoroalkyl-polyperfluoroalkoxy-perfluoroalkylene with up to 24 carbon atoms.

Suitable R _f groups are those of the following formulas:

030015/0669 ORIGINAL INSPECTED

(2) CF,

'η 2η + 1
wherein η is 4 to 20;

(3) C F-

ϊΓ2η - 1

wherein η is 4 to 20;
and

where m is 1 to 3, ρ 2 to 4, q is 0 to 6 and r is 1 to 10 with the proviso that the sum (m + ρ + q + r) is at least 4.

Suitable R ~ groups of the formula (2) are CF, (CF ~) -, in which χ is 3 to 19, and mixtures thereof as well as those of the formula

^CF 3 \

and their mixtures.

Suitable R groups of the formula (3) are such

of the formula CF, (CF ₂ ) o_8 ~ ^{CF = CF} ^ ^CF 2 ^ T ⁼ '5 ^and their mixtures and branched analogs "such as Z ₄ B.

Exemplary R _f groups of the formula (4) are those of the formula

030015/0 66 9

: - ■ "'ORIGINAL INSPECTED

ß -

^CF 3 \

and their mixtures.

The R _f radical can also contain substituents other than fluorine, such as chlorine and hydrogen. Usually, however, not more than 20% of such substituents should be different from fluorine, so that the remainder retains its hydrophobic-oleophobic character.

Suitable R ^ radicals containing such other substituents include the following

and

Cl Cl

03001 5/0669

ORIGINAL INSPECTED

wherein a is 0 to 8 and b is 0 to 8, with the Provided that (a + b) is between 2 and 16.

The type of divalent bridging group Z which may be present is not critical as long as it has the essential function, the fluoroaliphatic group R ~ To bind covalently to the hydrophilic organic residue .A, fulfilled.

Thus, Z can be selected, for example, from the following: -Cj-Cg-alkylene-, -phenylene-, - (C ₁ -Cg-AIlCyIen) -R ₁ - (Oj-Cg-alkylene) -, - (C ₁ -Cg-ABy ^ n) -R ₁ ), -R ₁ - (C ₁ -Cg-alkylene) -, -R ₁ - (C - ^ - Cg-alkylene-R- ^) -, -R ₁ -, -R _n - Phenylene- (C _n -C ^ -alkylene-R-,) -, -R-, -phenylene- or

J-, XD J. J.

-Phenylene-R. ,, wherein this is alkylene and phenylene, respectively independently of one another, optionally by hydroxyl, halogen, nitro, carboxyl, C -, - Cg-alkoxy, C -, - Cg-alkanoyl, C-j-Cg-carbalkoxy, Cn-Cg-alkanoyloxy or C-j-Cg-alkanoylamino are substituted. The alkylene radical can be straight-chain or branched.

R-, and R ₁ are independently of one another

R 0

Ϊ2 Il

-N-, -CO-, -NR ₂ CO-, -CONR-, -NR ₂ CO-, -OCONR ₂ -, -0-, -S-, -SO-,

-SO -, -NR SO, -, SONlL-, -NR CONR--, -NR-SO -NR - -CO- J

P. ff

-SO ₂ O-, -OSO ₂ -, -OSO ₂ O-, -OCO-, -OP-O-,

OR ₂

I η s

-P-, -P-o-odep-o-p-

Rp is hydrogen or _{Cj-Cg-alkyl which is optionally substituted by C 1} -Cg -AlkOXy, halogen, hydroxyl, carboxyl, C - ^ - Cg-carbalkoxy, C -, - Cg-alkanoyloxy or Cj-Cg-alkanoylamino.

In addition, Z can contain a cycloaliphatic or heterocyclic radical.

030015/0669

■ 43 ·

So kana R-, for example a remainder of the

formula

COR,

be, wherein R- -OR ₉ , -OM, where M has the meaning given below, or -NHR ₂ ,

R ^ -0- or -N- and R _{5 is} hydrogen, halogen, Ο -, - C / - alkyl or C-, -Cr-alkoxy, or R ₁ is a radical

JL O Jl O X

of the formulas · COR.

-S-

or

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ORIGINAL INSPECTED

. 4S-

Suitable hydrophilic radicals A are, for example, those hydrophilic divalent radicals of the following formulas:

- {ch, ch-o-4

ί ι S

wherein R, is hydrogen or hydrogen and methyl (mixture), with the proviso that R, - is preferably hydrogen is;

OH

-CH -N> 2. 2 ι S

where Ry is hydrogen, lower alkyl or hydroxyethyl is;

[ s

CONR,

where R,

y is hydrogen or hydroxyethyl;

- (CH ₂ -C ₄ -alkylene-N ^A ^

Ro

where t 1 to 3 and Rg lower alkyl, hydroxynie

deralkyl or - (CH ₂ CH ₂ O) ₃ H;

030015/0663

ORIGINAL INSPECTED

- ίο -

™ "Λ Cl! Λ /

where t "1 to 3, T -SO ₃ M, -COOM, -PO ₃ M, -OSO, M or -OPO ₃ M ₂ and M is hydrogen, ammonium or an alkaline cation; or

4CH..CH) -

J ⁹

^R io

- ^R ii

wherein Rg, R-, q and Rq are independently hydrogen, C - ^ - C ^ -alkyl or C ₂ -C ^ -alkyl substituted by hydroxyl, C ^ -C ^ -alkoxy or hydroxy-Cg-C ^ -alkoxy and one of the substituents R., and R ,, _ additionally also

Can represent benzyl, u is 0 or 1, R ₁₁ additionally also by sulfc or carboxyl substituted Cj-Cg-alkylene, X is an acetate, halogen, methosulfate or hydroxyl anion, if u 1 and R ^ are not Cj ^ -Cg- Is alkylene and t is 1-3.

Where s appears in the above formulas, it is 2 to 60, preferably 5 to 25, in each case.

'Mixtures of the aforementioned hydrophilic There are residues.

Furthermore, hydrophilic divalent radicals come into consideration, in which the hydrophilic character is at least partially originates from substituents such as a divalent radical of the formulas

(CH ₂ CH ₂ O ^ -H

wherein U _{1 is} 0-20 and n ₂ is 1-20.

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ORIGINAL INSPECTED

away

- { CH ₂ CH ₂ O) ^ - CH ₂ CH ₂ -N (C ₂ -C ₄ alkylene) -N (CH ₂ CH ₂ O ^

where η- and η, independently of one another, are 0 to 20 and n ₂ and n ^ are independently of one another 1 to 20;

-CH ₂ CH ₂ -N

wherein the n, - independently of one another 2 to 20 and the ng are independently 1 to 10.

^R l4

I η

₁ -C.-alkylene) -C- (C ₁ -C ₄ -alkylene

40CH ₂ CH ₂ - ^ OH

wherein R ₁ ^ hydrogen, C ^ -C ^ -alkyl or (OCH ₂ CH ₂ ) -OH, y-j_ and y ₂ independently of one another 0 to 4, y, 1 to 8 and n ₂ and n ^ independently of one another 1 to 20 .are. ^r

Q represents a divalent bridging group and, like Z, is not critical as long as it fulfills _{the essential puncture of covalently binding the hydrophilic organic radical A to the hydrophobic-oleophilic group Rtj C.}

The bridging group Q is thus selected independently from those groups listed above for Z, with the proviso that Rtt _{C is} a hydrophobic-oleophilic, aliphatic

Ö30015 / 0669

ORIGINAL INSPECTED

-ν-

or araliphatic ^ monovalent group when R ₁ or R ₁ are bonded directly to A and A is in an oxy or

Aminoliganden ends as well as R ₁ in this position 0 ^x

of μ
-OC

NR ₂ -

-s-, -oco-, -oc-, -OSO ₂ -, -OSO ₃ -, -oip-o-,

0 ^

-0-P- or -0-

is different.

Suitable R _{H (} -, - groups include hydrophobic-oleophilic higher alkyl or alkenyl with 6-24 carbon atoms, which are optionally replaced by chlorine, bromine, alkoxy with up to 18 carbon atoms, nitro, alkanoyl with up to 18 carbon atoms, alkyl mercapto with up to to 18 carbon atoms, amino, C ^ -C- ^ g-alkylamino or di-C- | -C-, Q-alkylamino are substituted.

Preferably R ™ represents such alkyl or Alkenyl having at least 8 carbon atoms. The alkyl and alkenyl groups can be straight-chain or branched be. Their mixtures can also be used.

In addition, the RpiQ group of formula

ι ⁵ ι ⁵

CHO ^ CH ₂ CH-OR ₆

'correspond to where R _{5 is} C.-Cg-alkyl, n_ 5 to 20 and R ,. Are hydrogen or alkyl of up to 24 carbon atoms.

Furthermore, the R _H p group can be a hydrophobic-oleophilic araliphatic radical having at least 9 carbon atoms. . ·

030015/0669 ORIGINAL INSPECTED

Suitable groups of this type include those of the formula:

(C ₁ -C / -

^R 16

wherein n ₈ 0 to 1, R ₁₅ alkyl with up to 20 carbon atoms, alkoxy with up to 20 carbon atoms, alkanoyl with up to 20 carbon atoms, mono- or dialkylamino with up to 20 carbon atoms, alkyl mercapto with up to 20 carbon atoms, alkanoyloxy with up to to 20 carbon atoms or carbalkoxy of up to 20 carbon atoms and R-jg is hydrogen, halogen, nitro or R - ,, -.

There are also hydrophobic-oleophilic groups of formula

15 16 n ₈

in which n ₈ , R ₁₅ and R-, g have the meanings given above, into consideration.

In addition, the group -Q _n -RjJQ niit η = 1 can be a group of the formula

(C ₂ -C ₄ alkylene) -

^R 18

represent, wherein R _n - and R _no independently of one another

i. / Io

are higher alkyl groups with 6 to 24 carbon atoms,

or the
Group - ^ Cp-Cg-Alkylene-} O-CHCOOR ^ q

CH ₂ COOR20

030015/0669. _; . . :. ..--, - .., ORIGINAL INSPECTED

-levorin R ₁₉ and R _{20 are} higher alkyl having 6 to 24 carbon atoms.

Preferred compounds are those which are largely non-ionic, i.e. free of strongly acidic groups like -SCuH and -ΡΟ, Η and free of strongly basic quartz

3 3
are tary ammonium groups.

Among such preferred, largely nonionic surfactants, particular emphasis is placed on those which not only have a surface tension of about 16 to 28 dynes / cm at a concentration of 0.1% by weight in deionized water, a solubility in water of at least 0.01% by weight %, at a concentration of 0.1% by weight in deionized water have an interfacial tension measured against cyclohexane of less than 12 dynes / cm, but also in the corresponding hydrocarbon surfactant R ₁₁ P ^- Q -A-OH the apparent HLB (hydrophilic-lipophilic balance in the range from about 5 to 24, and preferably in the range from about 12 to 18).

The HLB of a largely non-ionic hydrocarbon surfactant is a well known indicator of this percentage weight of the hydrophilic content in the nonionic hydrocarbon surfactant molecule. See for Example Ind. And Eng. Chem., Anal. Ed., Volume 18, page 500 (1946).

A particularly preferred class of fluorochemical surfactants are those of the formula

(5) ν ^Ζ

wherein R _f straight-chain or branched perfluoroalkyl with 4 to 20, in particular 4 to 12, carbon atoms, R _HC alkyl with 6 to 24, preferably 12 to 18, carbon atoms or on the remainder of the formula

030015/0669 ORIGINAL INSPECTED

-ISf-

where Rp, alkyl having 3 to 20, preferably 6 to 12, carbon atoms and R _{22 is} hydrogen, halogen (chlorine, bromine, fluorine), nitro or Rp-, m is O or 1, s 5 Ms 30, Z - COO-, -SO, -, -0-, -C ₁ -C ^ -alkylene-COO-, -C ^ -C ^ -alkylene-SO ,, ·

- or

COOH

-C ₁ -C ^ -alkylene-S-CH ^ HCHgO-, η O or 1 and Q

OH

-CO- or -SO ₂ -.

Preferred compounds of the formula (5) are those in which R-, Rjrp and s have the meanings given and m and η are zero.

Also preferred are those compounds of formula (5) in which Z is -C-j-C ^ -alkylene-S-CHCOOH, such as

e.g. the formula

CH ₂ COO-

(6) R _f -CH ₂ CH ₂ -S-CH-COOH

CH ₂ -COO (CH ₂ CH ₂ O)

or wherein Z is -C ₁ -C ₄ -AlCylen-S-CH ₂ -CH-CE ₂ O,

OH such as the formula

(7) R _f -CH ₂ -CH ₂ -SCH ₂ -CH-CH ₂ -O (CH ₂ -CH ₂ -O)

OH

030015/066 9

ORIGINAL INSPECTED

- 16 -

wherein R _f , Rjj _C and s have the meanings given above.

The fluorochemical surfactants used in the present invention can be prepared by known methods produce. For example, the fluorochemical surfactants can be prepared by reacting known hydrocarbon surfactants the formula

or

with a fluoroaliphatic acid halide in one produce inert solvents.

For example, one described in U.S. Patent 2,759,019 prepared CF ₃ (CF ₂₎ ^ SO ₂ F with H- (0CH ₂ CH _{2) 5} _ ₂₀ N- (stearyl) ₂ in diethyl ether as a solvent and pyridine or triethylamine as Acid acceptor implement what is the corresponding ester of the formula CF ₃ (CF ₂ ) _? S0 ₂ (OCS ₂ CH ₂ ) 2Q-N- (stearyl) ₂ results.

_{Analogously, the ^ C 3} F ₇ OCF (CF ₃ ) COF disclosed in Canadian patent 725 740 can be used in the presence of diethyl ether and pyridine as the acid acceptor with octylphenoxy-poly (ethyleneoxy) ethanol of an average molecular weight between 514 and 778 to give the corresponding ester realize.

Furthermore, an alpha-perfluoroalkene of the formula C Fp _n τ with η = 6-20 in the presence of potassium carbonate in an inert solvent such as methyl ethyl ketone ^{or acetone, at a temperature of 20-70 0} C with a hydrocarbon _{surfactant of the formula R HC -Q n} -A-0H be converted to the corresponding fluoroaliphatic ether.

For example, an oleic acid-ethylene oxide condensate (molecular weight about 680) can be converted into a product of the formula C ₁ QF ₁ QO (CH ₂ CH ₂ O) ₁₀ COC ₁ CH ₂ Q in the presence of potassium carbonate in acetone with tetrafluoroethylene pentamer. If a mixture of cetyl / oleylethylene oxide condensate (molecular weight about 550) is used,

030015/0669 ORIGINAL INSPECTED

- 37 -

holding the corresponding cetyl / oleyl ether product of the formula C ₁₀ F ₁ QO (CH ₂ CH ₂ O) ₁₀ C ₁₆ H ₃₁ Z ₃₃ .

Such compounds and their preparation are known from British patent specification 1,371,054.

Fluoroaliphatic isocyanates or carbamic acid halides can also be reacted with hydrocarbon surfactants of the formula RgQ-Q _n -A-OH or Rg ₁ J ₀ -Q _n -A-NHR ₂ to give the corresponding urethanes or ureas. Suitably, the reactions are carried out in the presence of an inert medium at temperatures of 20 to 50 ⁰ C. If a reactant a fluoroaliphatic carbamic acid halide, so Substituting advantageously a tertiary amine such as triethylamine or pyridine to promote the reaction and remove the hydrogen halide formed to.

For example, 1,1-DIhydroperfluorooctylcarbamyl chloride of the formula CyF ₁ CCH ₂ NHCOCl prepared according to German patent specification 1 145 606 is slowly added to ethoxylated (15 mol) coconut fatty acid in diethyl ether in the presence of triethylamine as HCl binder with stirring. The product thus obtained has the formula CyF ₁ CCH ₂ NHCOO- £ CH ₂ CH ₂ -04jrC0R _HC , where R _{HC is} the coconut fatty acid hydrocarbon radical.

In a similar way, CF ₃ (CF ₂ ) ^ NCO prepared according to US Pat React solvent to form a product of the formula CF ₃ (CF ₂ JgNHCO (NHCH ₂ CH ₂ ^ TPrNHCO-RTTp, in which R " _{c is} the hydrocarbon residue of stearic or lauric acid.

The product can be neutralized with aqueous HCl or H ₂ SO ^ to obtain the appropriate salts, or it can be alkylated with dimethyl sulfate or a methyl halide such as methyl bromide to form its tertiary and quaternary ammonium derivatives.

0 3 Q 0 1 5/0: 6 6 9

ORIGINAL INSPECTED

- ie -

The product can also be used in the presence of an HCl catalyst with ethylene oxide, e.g. in amounts of 4 to 15 moles per mole of product, to form its ethoxylated derivative realize.

Analogously, phosgene can be reacted with non-ionic hydrocarbon surfactants of the formula R ^ -Q _n -A-OH to form the corresponding chloroformic acid ester and the acid chloride with a fluoroaliphatic alcohol or amine to form the corresponding carbonate or urethane. The reactions are advantageously carried out in the presence of a tertiary amine such as triethylamine and an inert diluent.

For example, C ₁₂ H ₂₅ S (CH ₂ CH ₂ O ^ -QH in the presence of triethylamine with phosgene to the corresponding acid chloride C ₁₂ H ₂₅ S (CH ₂ CH ₂ O) ₁₀ COCl ^imse ' ^izen > which in turn in the presence of triethylamine in diethyl ether with a fluoroaliphatic alcohol such as that disclosed in US Pat. No. 3,697,564. (CF ₃ ) ₂ CFO-CF ₂ CF ₂ -CH ₂ CH ₂ CONH (CH ₂ ) ₃ OH to a product of the formula

(CF ₃ ) ₂ CF0-CF ₂ CF ₂ CH ₂ CH ₂ CONH (CH _£ ) ₃ <Χ0 (OCH ^^ - ^ SC- ^ H ^ is implemented.

_{C 10} F-JQOCgH ^ SO ₂ Cl, as described in British Patent Nos. 1,130,822 and 1,270,662, can also be reacted in the presence of triethylamine in an inert diluent with polyoxyethylene (20) sorbitan monolaurate to give the corresponding ester.

Suitably can fluorochemical surfactants by reaction of a hydrocarbon surfactant of the formula RjJp-Q _n -A-OH with an equimolar amount of tolylene diisocyanate to form the l: l-urethane adduct and reaction of the Ure-thanmonoisocyanats with a polyfluoraliphatischen amine or alcohol produced.

So you can Nonylphenoxypolyäthoxyäthanol with an average of 4 moles of ethylene oxide with one mole Convert toluene diisocyanate to the corresponding l: l adduct, which in turn with a perfluoroalkylalkylamine

030015/0669 ORIGINAL INSPECTED

- VB -

of the formula CgF ^ y (CHp) ₅ NH ₂ , which can be prepared according to US Pat. No. 3,257,407, is converted to the corresponding urea derivative.

Analogously, numerous fluorochemical surfactants of the formula R 1 -Z _n -A-OH can be reacted with suitable aliphatic or araliphatic acid halides, isocyanates and the like to form fluorochemical surfactants suitable for use in accordance with the invention.

_{For example, the CgF 17} SO ₂ N (C ₂ H ₅ ) -CH ₂ CH ₂ C OCH ₂ CH ₂ O ₁₀ -OH known from US Pat. No. 2,915,554 can be converted in the presence of triethylamine with dodecylbenzenesulfonyl chloride in diethyl ether to give the corresponding sulfonate ester.

Surfactants suitable for use in accordance with the invention can also be prepared by reacting a fluoroaliphatic thiol with an ethylenically unsaturated dicarboxylic acid anhydride and the anhydride condensate thus obtained with an equimolar amount of a hydrocarbon surfactant of the formula RjTp-Q _n -A-OH or Rjj _C -0 - A-NH ₂ can react in order to obtain the half-ester or the half-amide that is formed in the process. Instead, the ethylenically unsaturated dicarboxylic acid anhydride can be reacted with an equimolar amount of a hydrocarbon surfactant, for example of the formula Rrrp-GL-A-OH or Rtt _C -QA-NH ₂ , and the reaction product with a fluoroaliphatic thiol.

For example, dodecylphenoxypolyethoxyethanol (with 9 moles of ethylene oxide) with an equimolar amount of maleic anhydride in an inert diluent like sulfolane to the corresponding half ester of the formula:

y COOH

(8) HC

HC

0300 15/0669

ORIGINAL INSPECTED

such as piperidine at 20 to 75 ° C, for example to convert a pro.

The half ester can then be reacted with a fluoroaliphatic thiol, such as the CgF ^ C ^ H ^ SH obtained according to US Pat. Nos. 3,172,910 and 3,088,849. The reaction is conveniently carried out in largely stoichiometric amounts in aqueous ethanol in the presence of small amounts of sodium hydroxide and a tertiary amine such as piperidine
product of the formula:

(9)

C ₉ F ₁₉ C ₂ H ₄ -S-CH

to build.

The compound of the formula

(10)

C ₉ F ₁₉ CH ₂ CH ₂ SCHCO

CH ₂ CO

according to U.S. U.S. Patent 3,471,518, with the method disclosed in U.S. Pat. U.S. Patent 2,341,846 the formula

(11) H (OCH ₂ CH ₂ ) ₆ -0-CH-C00C ₈ H ₁₇

CH ₂ COOC ₈ H ₁₇

by refluxing fiquimolar amounts in dioxane to implement the corresponding half-ester.

The compound of the formula prepared by reacting norbonene anhydride and R ^ CH ₂ CH ₂ SH in the presence of a small amount of azobutyronitrile as a catalyst can also be used

030015/0669 ORIGINAL INSPECTED

(12)

wherein R- is mixed Cg-C-, Q-perfluoroalkyl, at temperatures from 20 to 5O ⁰ C in an inert diluent such as toluene with 3- (n-dodecylamino) propylamine in equimolar amounts and the product by azeotropic distillation of the Dehydrate water to the corresponding imine, which in turn in an acidic aqueous medium with 10 mol of ethylene oxide to a product of the formula:

(13)

N- (CH ₂ ) ^ ₁ -

can be ethoxylated. ,

Some of the fluorochemical surfactants which can be used according to the invention are known compounds.

As defined above and according to the invention Using suitable fluorochemical surfactants can be easily prepared from known starting materials according to conventional Methods such as those mentioned above and as illustrated in the examples below, prepare.

0 30015/06 69 ORIGINAL INSPECTED

Advantageously, the fluorochemical Surfactants on their own in an aqueous system or in combination with a conventional water flooding surfactant applied. Such surfactants for increased oil production are well known and include anionic surfactants such as petroleum sulfonates, synthetic alkyl aryl sulfonates and the like, anionic / nonionic surfactant systems such as those described in U.S. Patents .3 811 504, 3,792,731 and 4,005,749, as well as cation-active surfactant systems.

Mixtures of cationic and anionic

Active surfactants should generally be avoided as they can be incompatible because of their interaction.

The total amount of surfactant, based on the aqueous medium, can vary within wide limits, for example between 0.01 and 40 percent by weight, usually 0.05 to 20 percent by weight. When using a mixture of fluorochemical surfactant according to the invention and a conventional water flood surfactant, there is usually at least 1%, preferably at least 4%, fluorochemical surfactant, based on the amount of non-fluorochemical surfactant.

The aqueous surfactant solution can advantageously contain suitable auxiliary surfactants such as aliphatic or alkylaryl alcohols with a molecular weight of 40 to 220 in amounts of up to 10% by volume of the solution. Furthermore, a monovalent salt can be present in the aqueous medium in amounts of up to 5% by weight , based on the aqueous medium, in order to control the salinity.

You can also use various thickeners such as guar gum or a polysaccharide, as well as consumable ones Agents such as inorganic polyphosphates or alkali carbonates may be present.

In one embodiment of the invention, the so-called surfactant solution can be an aqueous petroleum emulsion, which contains 0.5 to 40 wt .-% OeI, based on the weight

030015/0669
ORIGINAL INSPECTED

2322928

contained in the aqueous phase.

In a further embodiment of the invention, the last portion of the aqueous surfactant solution of the aqueous petroleum emulsion has a lower concentration of non-aqueous components than the first in the Deposits injected portion from which the OeI is extracted. The use of such a concentration gradient thus reduces that in the oil recovery process total amount of surfactant required.

The following examples serve only to illustrate the present invention and are not intended to limit its scope in any way. Unless otherwise stated, parts are always parts by weight. Example 1 :

In one with thermometer, stirrer and nitrogen inlet A 500 ml vessel is equipped with 84.2 g (0.075 mol) of polyethoxylated cetyl alcohol with an average of 20 ethoxy units, of the formula

(ιοί) ⁰

and stirred at 50-55 ⁰ C under a nitrogen blanket. Boron trifluoride in the form of the diethyl ether complex (47.3% BF) is added in an amount of 0.4 g. Then there are added slowly while maintaining the temperature at 50-60 ⁰ C in the course of about 10 minutes with 6.1 g of epichlorohydrin (0.066 mol). The mixture is then stirred for a further 30 minutes at a temperature of 50 to 60.degree. The product formed has the formula

(102) ^C1 - ^CH 2 ^OH -

OH

140.3 g of anhydrous isopropyl alcohol and 27.9 g of R _f CH ₂ CH ₂ SH are then added to this reaction product, where R _{f represents} straight-chain perfluoroalkyl with the following R _f distribution: 0.9% C ^ F _g -, 32, 9% ^c 6 ^F i3 ~ »

030015/0 669

ORIGINAL INSPECTED

2322928

- 24 -

37.5% C ₈ F ₁₇ -, 22.99% C ₁₀ F ₂₁ -, and 5.3% C ₁₂ F ₂₅ - (average molecular weight about 465), and the mixture is stirred at about 5O ⁰ C. then added slowly 5 , 4 g of 50% aqueous NaOH (0.0672 mole) as to the fact that the reaction mixture remains at 50 to 60 ⁰ C. A white precipitate of NaCl forms. The mixture is stirred for one hour at 50-55 ⁰ C and suggests doing of farbblos on pale yellow to. To remove the by-product NaCl, it is then filtered off. On drying, 73.6 g of product are obtained (about 70% yield). The product conforms to the formula

(103) .RfCH ₂ CH ₂ SCH ₂ CHCH ₂ OtCH ₂ CH ₂ O ^ jC ₁₆ H ₃₃ .

OH
Example 2 :

Following the procedure of Example 1, polyethoxylated stearylamine of the formula is brought

(104)

^CH 2 ^H 2 ° * r ^H

(with q + r- = 15)

in an amount of 54.69 g (0.063 mol) in the presence of 0.3 g of BF / diethyl ether complex with 5.09 g (0.055 mol) of epichlorohydrin for the reaction and sets the resulting reaction product in the presence of 4.48 g of 50% iger aqueous NaOH in 98.85 g of isopropanol with 23.25 g of R ^ CH ₂ CH ₂ SH according to Example 1. The mixture is stirred for two hours before filtering off, 151.47 g of an amber-colored, cloudy solution being obtained. Filtering again gives 142.01 g of a clear amber solution. On drying, 46.43 g of a product of the formula are obtained

030015/0669 "ORIGINAL INSPECTED

- 25 -

⁽¹⁰⁵⁾

- I.

(CH ₂ CH ₂ P) _r H.

Example 5 t

Following the procedure of Example 1, 264.0 g of ethoxylated (15) p-nonylphenol of the formula are introduced

(106)

in the presence of 1.6 g of BF / diethyl ether complex with 24.42 g of epichlorohydrin for reaction and then sets the product obtained in the presence of 21.50 g of 50% aqueous sodium hydroxide solution and 460, ^ g of isopropyl alcohol with 111.6 g of R ^ CHpCH ₂ SH around. R _f has the distribution as given in Example 1. The resulting reaction product corresponds to the formula

(107)

Example 4 ;

2.55 g of maleic anhydride and 2.55 g of suIfolan are added as solvents to 36.45 g of polyethoxylated (24) Dinonylphenol of the formula '

(108)

030015/0669

ORIGINAL INSPECTED

2322928

and stirred for 20 hours at 60 ^° C., the reaction mixture that forms being a half-ester of the formula

(109)

HCCOOH

HCCOOH J TV- ^C 9 ^H 19

contains.

_{0.1 g of triethylamine and 11.63 g of R f} CH ₂ CH ₂ SH with the R _f distribution as in Example 1 are then added under a nitrogen blanket and the mixture is stirred ^{at 60 °} C. for about 7 hours. The product corresponds to the formula

(HO)

_r " _r " _c C _n H-

Example 5 ;

To examine the effectiveness of the fluorochemical surfactant in displacing oil from an oil-bearing underground Measuring formation by increasing the efficiency of the aqueous medium is the following orientational Method used:

Working method ; 20 g of sand / oil mixture (10% ASTM-OeI No. 3 and 90% Ottawa standard sand with a sieve size of 20-30) are placed in a 25 χ 150 mm test tube. The test solution (25 ml with 0.1% active substance of the sample in deionized water) is carefully covered over the sand / oil mixture. The system is then left undisturbed for 18-20 hours. Any oil that penetrates the surface is drawn off with a pipette and weighed. The results are reported as percent recovered (ie weight

030015/06 6-9
• ORIGINAL INSPECTED

- 27 -

of the recovered oil versus the theoretical Maximum of 2.0 g OeI in the glass). To form an average value, 3 to 5 tests are carried out with each sample performed.

For the tables below, the compounds are investigated for orientation at 0.10% active ingredient in deionized water; the surface and interfacial tensions are measured against cyclohexane. Unless otherwise stated, the R _f distribution in the perfluoroalkyl surfactants is: 0.9% C 1 -C ₉ , 32.9% C ₆ F ₁₅ , 37.5% C ₈ F ₁₇ , 22.9% C ₁₀ F ₂₁ - and 5.3% C ₁₂ F ₂₅ -.

030015/0669

ORIGINAL INSPECTED

- / 28 -

Table 1

Compounds of the formula prepared according to the procedure given in Examples 1 to 3

(111) P f * H ΓΗ ζΓΗ

f 2 2 ,,
OH

Proximity- Rxeent surface- Grenzflädsi-

No. run ^ '/ ert R ^ back-cheaspan-tension

from s gswome- nung (dyn / cmT

nes OeI

1 15th 1 4OCH ₂ CH / X 2 20th q + r = 15, -C ₁₆ H ₃ , 3 • 20th " ^C 18 ^H 37 4th 15th ~ ^C 13 ^H 27 R.
I. 5 '.f ^ ~ N- (CH R ^ stearyl

61.4 24.09 6.2 52.0 22.6 6.5 46.8 20.7 7.0 36.7 19.9 6.0

69.8 25.6 7.3

6 24 - \ C- 40.2 22.3 5.4

7 5 · _ / ~ \ _ _Γΐί 10.2 20.7 18.6

/ 9 19

• K *

8 11 - /; - ^C 9 ^H 19 ^{46> 0 23> 4 10} ' ⁷

9 20 ~ \ / * ~ ^C 9 ^H 19 35.4 20.7 5.0

10 30 \ ../ "9 19 27.0 24.9 5.5

030015/0669
ORIGINAL INSPECTED

Table 2

Compounds of the formula prepared according to the procedure given in Example 4

(- \ - \ n \ R-CH-CH-SCHCOOH

CH ₀ COO (CH-CH ₀ O) R ^

Proximity Erceent Surface Grenzflfidsl -

No. run ^ value R _HC back-chais voltage

from s —— become
nes OeI tion 6th m / cm; 5 11 24 " ^x K
χ Η
9 19 44.7 29.2 , 6 12th 20th ~ ^C 18 ^H 37 68.1 27.1 ,1

· - ·

13 15 -. (/ -C ₉ H ₁₉ 86.9 24.2 7.1

14 ^υ 20 - () ^# -C ₉ H ₁₉ 59.9 26.3 5.3

15 '5 -. () -C _g H ₁₉ 36.6 24.5 7.5

R.
I.

16 - (OCH ₀ CH ^ N eCH-CH-03-H '

II q 2 2 r

q + r = 15, R ^ stearyl

R _f '252 C ₆ F ₁₃ -, 5OZ CGF ^ -, 25Z

030015/0669

ORIGINAL INSPECTED

- 50 -

Example 6 ;

In the table below, formulations of various hydrocarbon surfactants with representative fluorochemical surfactants and their effectiveness in displacing oil in accordance with the procedure set out in Example 5 are listed. The hydrocarbon surfactant (A) is a commercially available anionic sulfate surfactant (Conco EL-30 - trademark), the hydrocarbon surfactant (B) is a non-ionic polyethoxylated nonylphenol surfactant (Igepal CO-710 - trademark) and the surfactant (c) is an anion-active petroleum sulfonate surfactant (Petronate L - trademark;
Table 3

No. Active ingredient in
solution % recovered
OeI A. 0.09% 19.5 B. 0.09% 51.7 C. 0.10% 8.1 5 0.01% 13.5 1 0.01% 45.6 13th 0.01% 31.2 5
A. 0.01%
0.09% 34.9 5
B. 0.01%
0.09% 57.5 5
C. 0.01%
0.09% 13.2 1
A. 0.01%
0.09% 28.3 1
B. 0.01%
0.09 57.5 1
C. 0.01%
0.09% 12.2 13th
A. 0.01%
0.09% 29.2 13th
B. 0.01%
0.09% 67.0 13th
C. 0.01%
0.09% 14.4

030015/0689
ORIGINAL INSPECTED

Active ingredient in% recovered

No. Solution - ■ OeI

13 0.05% '77.9 B 0.05%

The results in the table above show those obtained using conventional hydrocarbon formulations toff tens ide together with the fluorochemical surfactants achievable advantages in tertiary oil production.

030015/0 669

ORIGINAL IWSPECTED

Claims (13)

Claims t 1. Process for extracting oil from underground oil deposits by injecting an aqueous surfactant composition to displace the oil from this deposit, characterized in that the surfactant used is a compound of the formula is used, wherein R- is a hydrophobic-oleophobic fluoroaliphatic Group with 4 to 24 carbon atoms, Z a divalent bridging group, A a! divalent hydrophilic organic radical, Q a divalent bridging group, R "_ a hydrophobic-oleophilic aliphatic radical with 6 to 24 carbon atoms or an araliphatic radical with at least 9 carbon atoms and m and η are independent are from each other 0 to 1, and the surfactants have a solubility in water of at least 0.01 wt .-% at 30 ° C, a surface tension less than 30 dynes / cm in deionized water at a concentration of 0.1% by weight, and an interfacial tension measured against cyclohexane in deionized water of less than 12 dynes / cm at a Have concentration of 0.1 wt .-%. 2. The method according to claim 1, characterized in that the aqueous surfactant compositions additionally non-fluorinated surfactants such as anion-active, mixtures of anion-active and non-ionic surfactants or contain cationic surfactants. 3. The method according to claim 1, characterized in that the fluorochemical surfactant at a concentration of 0.1% in deionized water has a surface tension of about 16-28 dynes / cm and one measured against cyclohexane Has interfacial tension of less than 12 dynes / cm. 4. The method according to claim 3, characterized in that the fluorochemical surfactant is substantially non- 030015/0669 ORIGINAL INSPECTED is ionic. 5. The method according to claim 4, characterized in that in the surfactant HO-AQ _n -RtTp, which ^{corresponds to the fluorochemical surfactant Rf -} ^ j _n -AQ-RjTp, the apparent hydrophilic / lipophilic balance is in the range of about 4-24. 6. The method according to claim 5, characterized in that the apparent hydrophilic-lipophilic balance in _{the surfactant HO-AQ n} -R _{HC is in the range of about 12-18.} 7. The method according to claim 5, characterized in that the fluorochemical surfactant of the formula R _f -Z _m (CH ₂ CH ₂ 0) _s Q _n -R _HC wherein R _f 'is straight-chain or branched perfluoroalkyl with 4 to 20 carbon atoms, R _{HC is} alkyl with 6 to 24 carbon atoms or a radical of the formula is / where R21 is alkyl with 3 to 20 carbon atoms and R _{22 is} hydrogen, halogen, nitro or R ₂₁ , m is 0 or 1, s is 5 to 25, Z is -COO-, -SO, -, -0-, -C ₁ -C ^ -alkylene-COO-, -C ^ -C ^ -alkylene-SO ^, COOH -C ₁ -C ₄ -alkylene-S-CH-CH ₂ C00- or
-C ₁ -C _Zf -alkylene-S-CH ₂ CHCH ₂ 0, η 0 or 1 and Q OH -CO- or -SO ₂ -. 8. The method according to claim 7, characterized in that R _£ straight-chain or branched perfluoroalkyl with 4 to 20 carbon atoms, R _HC alkyl with 6 to 24 carbon atoms or a group of the formula 030015/0669
ORIGINAL INSPECTED Hi is, m and η are zero and s, R ₂₁ and R _{22 have} the meanings given in claim 7. 9. The method according to claim 7, characterized in that the fluorochemical surfactant of the formula. R _f -CH -CH - S-CHCOOH r t ί ! CH ₉ -C- (KCH ₀ CH ₀ OJ- R ^ II 2 2 ε IC OH wherein R _f , R _HC and s have the meanings given in claim 7, corresponds. 10. Aqueous surfactant compositions for carrying out the method according to one of claims 1 to 9, characterized characterized in that they contain 0.01 to 40 wt .-% fluorochemical surfactant and optionally a water flood include common non-fluorochemical surfactant. 11. Compositions according to claim 10, characterized in that that they contain at least 1% by weight of fluorochemical surfactant, based on the weight of the non-fluorochemical Surfactants. 12. Compounds of the formula OH
030015/0669 ORIGINAL INSPECTED - 35 - wherein R 1 is a hydrophobic-oleophobic fluoroaliphatic group having 4 to 20 carbon atoms, s 5 to 30 and Rtj _{C is} a hydrophobic-lipophilic aliphatic radical having 6 to 24 carbon atoms or a group of the formula where Rp-, alkyl having 3 to 20 carbon atoms and R _{22 are} hydrogen, halogen, nitro or R ₂₁ . 13. Compounds according to claim 12, characterized in that R _f '■ perfluoroalkyl with 6 to 20 carbon atoms and Rtt _C alkyl with 6 to 24 carbon atoms or a group of the formula ^R 22 where R _{21 is} alkyl having 6 to 12 carbon atoms and R _{22 is} hydrogen or R ₂₁ . 030015/0669 ORIGINAL INSPECTED