CA1216416A - Method of increasing hydrocarbon production by remedial well treatment - Google Patents

Abstract

METHOD OF INCREASING HYDROCARBON PRODUCTION
BY REMEDIAL WELL TREATMENT

Abstract of the Disclosure Methods of increasing hydrocarbon production from subterranean hydrocarbon-containing formations having impaired permeability are provided wherein the formations are contacted with a penetrating solvent and cationic perfluoro compounds represented by the following formula:

Description

METHOD OF INCREASING HYDROCARBON PRODUCTIOM
BY REMEDIAL WELL TREATMENT

_ackground of the Invention Field of the Invention:
The present invention relates to a method of increasing hydrocarbon production from a subterranean for-mation having impaired permeability as the result of well drilling or prior stîmulation treatments.

Description of the Prior Art:
Various procedures have been developed and utilized heretofore to increase the flow of hydrocarbons from hydrocarbon-containing subterranean formations penetrated by well bores. For example, a commonly used production stimu-lation technique involves creating and extending fractures in the subterranean formation to provide flow channels therein through which hydrocarbons flow from the formation to the well bore. The fractures are created by introducing a fracturing fluid into the formation at a flow rate which exerts a sufficient pressure on the formation to create and extend fractures therein. Solid fracture proppant materials, such as sand, are commonly suspended in the frac-turing fluid so that upon introducing the fracturing fluid into the formation and creating and extending fractures therein, the proppant material is carried into the fractures and deposited therein whereby the fractures are prevented from closing due to subterranean forces when the introduc-tion of the fracturing fluid has ceased.
S In such formation fracturing and other production stimulation procedures, at least a portion of the stimula-tion fluid or fracturing fluid will leak off into the for-mation and will reduce the relative permeability of the invaded region of the formation. After fluid injection has ceased, imbibition will begin to alter the fluid distribu-tion within the formation, and when production begins, the ~luid will move from the formation into the fracture. It is important to leave the formation after treatment with the maximum permeability or conductivity possible whereby hydro-carbons contained in the formation will flow to the well bore with the least possible restriction. However, substantially all stimulation fluids or fracturing fluids, no matter how carefully they are selected, will do some damage to the formation adjacent to the fracture. In order to achieve maximum conductivity of hydrocarbons from sub-terranean formations, whether or not such formations have been fractured or otherwise stimulated, it has heretofore been the practice to cause the formation surfaces to remain water wet after treatment. Such water wetting has been shown to provide an improved flow of hydrocarbons through ~2~
flow channels and capillaries in the magnitude of about three times greater than when the formation surfaces are hydrocarbon wet.
The water wetting of solid surfaces in subterranean hydrocarbon-containing formations as well as the surfaces of solid proppant material deposited therein has heretofore been accomplished using surfactants in the stimulation fluids or fracturing fluids whereby a layer of water or water and surfactant is spread over the solid surfaces.
Such layers of water or water and surfactant are extremely viscous near the interface of the layer and the solid sur-face, and while the layer provides a slippage or lubricating effect at the interface thereof with hydrocarbons which decreases the resistance to flow, the layer reduces the effective diameter of capillaries and flow channels. This reduction of effective diameter restricts fluid flow, and in very small capillaries or flow channels becomes highly si~nificant.
If the formation relative permeability has been damaged by the invasion of the stimulation fluid or frac-turing fluid into the formation and this damage results in an increase in the capillary pressure in the damaged region~
the capillary pressure in the damaged region then acts as a pressure sink drawing additional water to the damaged region. Unless the pressure drawdown upon attempting pro-:3L2~6g,t31~i duction is large enough to overcome the increased capillary pressure, a complete blocking of the formation in the damaged region will occur. Even when the pressure drawdown is sufficient to overcome the capillary pressure, production can be reduced because of the decrease in the capillary radius of the flow channels caused by the layer of water coating the solid surfaces in the formation.

~6~G
Summary of the Invention By the present invention, methods are provided whereby certain fluids are employed to strip water or other aqueous fluids from the formation solids and certain com-pounds then are caused to be adsorbed onto the solid sur-faces in the subterranean hydrocarbon-containing formations in a very thin layer~ i.e., a layer which is preferably one molecule thick and significantly thinner than a layer of water or a water-surfactant mixture. The compounds so adsorbed on the surfaces resist or substantially reduce the wetting of the surfaces by water and hydrocarbons and pro-Yide high interfacial tensions between the surfaces and water and hydrocarbons which allows slippage of hydrocarbons at the hydrocarbon-surface interface and significantly increases the flow of hydrocarbons through capillaries or flow channels in the formations.

Description of the Preferred Embodiment The present invention provides methods for - increasing the production of hydrocarbon from a hydrocarbon-containing subterranean formation having impaired per-meability as a result of formation invasion by aqueous fluids. The fluid invasion generally results in a coating of the solid surfaces of the formation with the aqueous fluid which results in a decrease in the open cross-sectional area of the capillaries or flow channels in the formation.
The fluids which are utilized in accordance with the methods of this invention to stxip the water or aqueous fluid coating from the solid surfaces within the sub-terranean formation comprise a penetrating solvent. The penetrating solvent can comprise a lower alcohol such as methanol, ethanol, propanol or any other alcohol containing from about 1 to about 5 carbon atoms. The penetra~ing solvent also can be comprised of acetone or any other fluid which is capable of disrupting the water layer which coats the solid surfaces in the formation.
The compounds which are utilized in accordance with the methods of this invention to prevent solid surfaces from becoming water or hydrocarbon wet while not creating either or both significantly thick or viscous layers thereon are certain cationic perfluoro compounds and mixtures of such compounds represented by the formula:

~z~

F ( CF2 ) x _CH2CH20_~ CE~21 H ~W--( C~12CHO ) 5T ( CH2CHO ) z~

I I(+) A(-~

wherein x is an integer from 2 to 12 or an integer or frac-tional integer represen~ing an average value of from 2 to i2; w and y are both individually integers from 0 to 20 or are integers or fractional integers representing average values of from 0 to 20; z is an integer of from 0 to 20 or an integer or fractional integer representing an average value of from 0 to 20; the sum of y and z being from l to 20; R is a hydrogen, methyl, ethyl or propyl radical, or mixtures thereof; A is a halogen chosen from the group con-sisting of chlorine, bromine or iodine and may be present as either a halo radical bonded to carbon or as an anion; and Q
is a cationic nitrogen-containing radical from the group consisting of:
(i) an aromatic or heterocyclic amino radical formed from the following compounds:

2-H-pyrrole, pyrrole, imidazole, pyra-zole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, isoindole~
3H-indole, indole, lH-indazole, purine, 4H-quinolizine, quinoline, isoquinoline, phthalaæine, naphthyridine, quinoxaline, quinazoline, 4-H-carbazole, carbazole, -carboline, phenanthridine, acridine, phenathroline, phenazine, imidazolidine, phenoxazine, cinnoline, pyrrolidine, pyrroline, imidazoline, piperidine, piperzine, indoline, isoindoline, quinuclindine, morpholine, azocine, aze-pine, 2H-azepine, 1,3,5-triazine, thiazole, pteridine, dihydroquinoline, hexa methylene imine, indazole; and (ii) an amine radical represented by the formula:

R1 _ N__~R3 wherein Rl, R2 and R3 are from the group con-sisting of aliphatic hydrocarbon radicals con-~2~

taining from 1 to 30 carbon ato~s, aromatic hydrocarbon radicals such as phenyl and any alkyl substituted phenyl radical, and hydrogen radicals, provided that at least one of Rl, R2 and R3 is an aliphatic hydrocarbon radical containing from 1 to 30 carbon atoms or an aromatic hydrocarbon~ and that when any one of the Rl~ R2 and R3 radicals contains more t.han four aliphatic carbon atoms or an aromatic hydrocarbon, the other two radicals are each chosen from the group consisting of hydrogen, methyl, and ethyl radicals.
In the above formula, x is preferably an integer of from 4 ~o 10 or an integer or fractional integer repre-senting an average value of from 4 to 10; w is preferably an integer of from O to 12 or is an integex or fractional integer representing an average value of from O to 12; y is preferably O; z is preferably an integer of from 1 to 8 or an integer or fractional integer representing an average value of from 1 to 8; ~ is preferably chosen from the group consisting of hydrogen and methyl radicals, or mixtures thereof; A is preferably chlorine; and Q is preferably cho-sen from the group of cationic nitrogen-containing radicals formed by reacting trimethylamine, pyridine, quinoline, iso-quinoline, N,N-dimethyl aniline, N-methyl morpholine, or morpholine with a chloro radical functional group.
Most preferably, in the above formula ~ is an integer of from 6 to 8 or an integer or fractional integer representing an average value of from 6 to 8; w is an integer of from 0 to 8 or an integer or fractional integer representing an average value of from 0 to 8; y is 0; z is an integer of from 1 to 4 or an integer or fractional integer representing an average value of from 1 to 4; R is from the group of hydrogen radicals and methyl radicals and/or mixtures thereof; A is chlorine; and Q is from the group of cationic nitrogen-containing radicals formed by reaction of trimethylamine, pyridine, quinoline, morpholine, and isoquinoline with a pendent chloro radical.
The term "integer or fractional integer repre-senting an average value" indicates that the formula may represent an admixture of compounds wherein the average values of x, w, y and z can be any integer in the range given such as 8 or a fractional integer such as 7.5, 7.8, 8.5 and the like.
A preferred group of nitrogen-containing cationic perfluoronated compounds for use in accordance with the methods of this invention is represented by the following formula:

F(CF2)x. CH2CH2 (CH2cHO)w (CH2CHO)z___H
I

Q(~j A(-) wherein x is an integer from 2 to 12 or an integer or frac-tional integer representing an average value of from 2 to 12; w is an integer from 1 to 20 or an integer or fractional integer representing an average value of from 1 to 20; z is an integer from 1 to 20 or a fractional integer representing an average value of from 1 to 20; R is from the group of hydrogen~ methyl, ethyl, propyl radicals and mixtures thereof; A is a halogen anion from the group consisting of chlorine, bromine and iodine; and Q is a cationic nitrogen radical from the group consisting of an aromatic amino radi-cal, a heterocyclic amino radical, and an amine radical represented by the formula:

Rl N___R3 I

wherein Rl, R2 and R3 are from the group consisting of hydrocarbon radicals containing from 1 to 30 carbon atoms, aromatic hydrocarbon radicals such as phenyl and any alkyl substituted phenyl radical, and hydrogen radicals, provided that at least one of Rl, R2 and R3 is an aliphatic hydrocar-bon radical containing from 1 to 30 carbon atoms or an aro-matic hydrocarbon and that when any one of Rl, R2 and R3 radicals contains more than four aliphatic carbon atoms or an aromatic hydrocarbon, the other two radicals are each chosen from the group consisting of hydrogen, methyl and ethyl radicals.
Of this group of compounds, when Q is an aromatic/-heterocyclic amino radical, the most preferred compounds are those wherein x is an integer representing an average value of 8; w is an integer or fractional integer representing an average value of from 6 to 10; ~ is an integer or fractional integer representing an average value of ~rom 1 to 3; R is methyl; and Q is a pyxidino or quinolino radical.
When Q is an amine radical, the most preferred com~

pounds are those wherein x is an integer representing an average value of 8; w is an integer or fractional integer representing an average value of Erom 6 to 8; ~ is an integer or fractional integer representing an average value of from 1 to 3; R is methyl; Rl, R2 and R3 are all methyl and A is chlorine.
Another preferred group of compounds are repre-sented by the formula:

F ( CF2 ) x CH2CH20_( CH2tHO ) Z ~1 C~2 III

R3~ _N(+) ~1 I

wherein x is an integer from 2 to 12 or an integer or frac-tional integer representing an average value of from 2 to 12; z is an integer from 1 to 20 or an integer or fractional integer representing an average value of from 1 to 20; Rl, R2 and R3 are each chosen from the group consisting of lower aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms; and A is a halogen anion chosen from the g.roup con-sisting of chlorine, bromine and iodine.
Of this yroup of compounds, the most prefer.red is where x is an integer representing an average value of 8; z is an integer or fractional integer representing an average value of from 1 to 3; Rl, R2 and R3 are all methyl and A is chlorine.
Yet another preferred group of compounds for use in accordance with the methods of the present invention are represented by the formula:

~6~

F(CF2)x CH2CH2O (C~12CHO)z Q(+) A(-) wherein x is an integer from 2 to 12 or an integer or frac-tional integer representing an average value of from 2 to 12; z is an integer from l to 20 or an integer or fractional integer representing an average value of from l to 20; Q is a nitrogen-containing heterocyclic/aromatic cationic radi-cal; and A is a halogen anion chosen from chlorine, bromine and iodine anions.
Of this group of compounds, the most preferred is where x is an integer representiny an average value of 8; z is an integer representing an average value of from l to 3;
Q is a pyridino or quinolino radical; and A is chlorine.
The most preferred compounds for use in accordance with the present invention are those represented by Formula II above wherein x is an integer representing an average value of 8; w is an integer or fractional integer repre-senting an average value of from 6 to 8; z is an integer or fractional integer representing an value of l to 3; Q is an amine radical wherein Rl~ R2 and R3 are all methyl; and A

is chlorine.
In carrying out the methods of the present inven-tion to improve the productivity of a subterranean formation having impaired permeability, the penetrating solvent is introduced into the formation by pumping down a well bore penetrating the subterranean formation. The penetrating solvent disrupts the water or other aqueous fluid layer coating upon the solid surfaces in the subterranean for-mation, including the surfaces of any proppant material that may be present, to permit contacting with the cationic perfluoro compound or compounds. The cationic perfluoro compound or compounds can be applied directly to a sub t~rranean formation whereby the surfaces thereof are con-tacted by the compounds and adsorbed thereon. ~owever, preferably, the cationic per~luoro compound or compounds utilized are dissol~ed or dispersed in a carrier Eluid which is in turn introduced into the formation through the well bore penetrating the same whereby the carried cationic perfluoro compounds are distributed in the formation and contact solid surfaces therein whereby they are adsorbed thereon. Aqueous or hydrocarbon base carrier fluids can be utilized in the form of liquids, foams, emulsions, etc. The particular quantity of perfluoro compounds combined with the carrier fluid can vary widely depending`upon the type of ~5 ormation to be treated and other factors, but generally the 9 ~6~

cationic perfluoro compounds utilized are combined with the carrier fluid in an amount in the range of from about 0.01%
to about 10% by weight of the carrier fluid. Particularly preferred carrier fluids are 50% alcohol foams.
In a preferred embodiment of the invention, the penetrating solvent employed to disrupt the water or aqueous fluid coating and the carrier fluid are the same fluids. In this instance, the penetrating solvent and cationic perfluoro compound or compounds are introduced together such that as the solvent disrupts the water coating the cationic perfluoro compound or compounds contact the water-free solid surfaces and are adsorbed thereon such that the solid sur-faces now remain substantially non-wettable by water or hydrocarbons. When a proppant material has been placed in fractures formed in the subterranean formation by prior sti-mulation treatments, the penetrating solvent also disrupts the water coating on this material and the cationic perfluoro compound or compounds are adsorbed thereon. Thus, both the surfaces of the forrnation and the surfaces of the proppant material have cationic perfluoro cornpounds adsorbed thereon whereby such surfaces are substantially prevented from being wetted by water or hydrocarbons and the flow of hydrocarbons through the formation and proppant material is significantly increased.
In order to facilitate a clear understanding of the ~6~6 methods of the present invention, and not by way of limita-tion, the following examples are provided.

Example I
Various cationic perfluoro compounds of structural Formula II above are tested to determine their effectiveness in producing a non-wetting surface.

Test Procedure 40-60 Ottawa ~fxom Minnesota) sand is sieved three times through a 50 mesh screen. The sieved sand (93 g) is placed in 300 ml. of methanol containing .01% by weight of the cationic perfluoro compounds to be tested. The slurry is stirred vigorously to insure complete solution sand con-tact, and the methanol is evaporated. The treated sand is cooled to room temperature and then placed in a horizontally positioned l~n I~Do x 12" cylindrical polypropylene tubing.
The ends of the packed column are stoppered with a 13"
diameter 60 mesh screen and a number 0 stopper with a 9 mm.
hole. The column fluid entry point is equipped with a piece of 'Y' shaped 9 mm. tubing with a stopcock on each arm of the 'Y'; one arm leads to the column; the other two arms lead to 500 ml. water and oil reservoirs, which are placed 18" above the horizontal column to provide a constant head.
The fluid exit point of the column is equipped with a 3", 120~ elbow fashioned from 9 mm. glass tubing. A 1" piece of 5 mm. glass rod is annealed to the bend point of the elbow to direct flowing fluid into a collecting vessel. The elbow is pointed upward in order to maintain a constant, maximum fluid volume (no air entrapment).
Distilled water is flowed through the column for 10 minutes ~ 5 column volumes), followed immediately by Phillips Soltrol 160 (a refined aliphatic oil). The time for the oil to displace the water is noted, and the flow rate of the oil is measured (from the time of the first collected drop) for 10 minutes. Each ~est is run in dupli-cate or triplicate.
The results of these tests are shown in Table I
below.

,4~ E;

TABLE I
EFFECTIVENESS OF CATIONIC PERFLUORO COMPOUNDS
IN PRODUCING NON-WETTING SAND SURFACES

Cationic Perfluoro Compounds Tested Averagel Flow Rate of (Structural Formula II above) _ Soltrol 160 Following x w R z A Q Water tml./min.) 8 0 - 1.5 Cl pyridine 4.0 8 0 - 3.0 Cl pyridine 3.5 8 0 - 3.0 Cl quinoline 3.2 8 0 - 1.5 Cl trimethylamine 3.8 8 0 - 2.0 Cl ~imethylamine 3.6 8 0 - 3.0 Cl trimethylamine 3.5 8 2 -~13 1.5 Cl trimethylamine 3.8 8 2 -CH3 2.0 Cl trim~thylamine 3.6 ~4 -CH3 1.5 Cl trimethylamine 4.0 8 6 -CH3 1.5 Cl trimethylamine 4.3 8 8 -CH3 1.5 Cl trimethylamine 4.5 8 12 -CH3 1.5 Cl tri~.ethylamine 3.8 8 6 H 1.5 Cl pyridine 2.3 8 6 ~I 1.5 Cl pyridine 1.7 lVariation between flow rates of duplicate r~ms averaged 5%

In runs of oil following water on untreated sand, no flow of oil is detected for 15 minutes and only 2 mlO of oil are collected within one hour. In runs in which the sand is treated with cationic perfluoro compounds (Table I
above), the time required to displace the water in the sand pack is less than four minutes, and subsequent oil flow rates are in the range of 2 to 5 ml./min., depending on the particular structure of the cationic perfluoro compound.
The greater the sustained flow rate of oil following water~

the more pronounced is the non-wettiny effect of the sample.

~xample II
The procedure of Example I is repeated using cationic perfluoro compounds and several conventional hydro-carbon surfactants. The results of these tests are given in Table II below:

TABLE II

COMPARISON OF NON-WETTING BROUGHT ABO~T BY
VARIOUS SURFACTANTS

Relative ~ Flow Quantity of Rate of Oil Surfactant Surfactant Used Achieved 0.01~ by Cationic perfluoro compounds Weight (Structural Formula XI, x=8, w=B, R=CH3, z=1.5, A=Cl, Q=trimethylamine~ 100.00%

0.5% by N~4 Salt of Sulfatedi ekhoxy-Volume lated C12_14 Alcohol 0.74%

0.5% by C12_16 trialkyl ammonium chloride Volume formulationl 4.2%

0.5% by NH4 Salt of C12 diphenylether Volume sulfonate formulationl 42.00%

Added to water phase From Table II it can be seen that the cationic perfluoro compounds are much more effective in preventing the wetting of solid surfaces than conventional hydrocarbon :~z~

surfactants.

Example III
A cationic perfluoro compound of Structural Formula II above is tested with a penetrating solvent to determine their effectiveness in treating a water block.

est Procedure 40-60 Ottawa sand is sieved through a 50 mesh screen and placed in a horizontally positioned column comprising 1~" I.D. x 12" cylindrical polypropylene tubing.
The ends of the packed column are stoppered with a 1~"
diameter 60 mesh screen and a number 0 stopper with a 9 mm.
hole. The column fluid entry point is equipped with a piece of 'Y'-shaped 9 mm. tubing with a stopcock on each arm of the 'Y', one arm leads to the column; the other two arms lead to 500 ml. water and oil reservoirs, which are placed 18" above the horizontal column to provide a constant head.
The fluid exit point of the column is e~uipped with a 3"
120 elbow fashioned from 9 mm. glass tubing. A 1" piece of 5 mm. glass rod is annealed to the bend point of the elbow to direct flowing fluid into a collecting vessel. The elbow is pointed upward in order to maintain a constant, maximum fluid volume tno air entrapment).
The column is filled with distilled water and followed ~2~

with one column volume of a test solution. This is followed immediately with Isopar L (a refined aliphatic oil). The time for the oil to displace the test solution is noted and the flow rate of the oil is measured (from the time of the first collected drop) for ten minutes.
The results of the tests are shown in Table III
below.

TABLE III
Cumulative Test Break- Time,Oil Flow, Solution through (Min.) (ml.) 1. 500 gal./1000 gal. MeO~, 4 min.
5 gal./1000 gal. concen- 1 1.5 trated 28~ HCl, 2 gal./1000 2 3.5 gal. Clo - C12 alcohol alkox- 3 5.0 ylate formulation and 2~ KCl 4 8.0 solution to provide 1000 gals. 5 10.5 6 13.5 7 1~.0 8 1~.5 9 21.0 23.5 Average oil flow rate 2.35 ml./min.

2. Same as above plus 0.01~ 2.5 min.
by weight cationic perfluoro 1 4.0 compounds (Structural 2 8.5 Formula II, x=81 w=8, R=CH3, 3 13.0 7.=l . 5, A~Cl, Q=trimethylamine 4 18.5 22.0 6 26.0 7 31.0 44.0 Average oil flow rate 4.4 ml./min.

-2~-64~

From Table III it can be seen that the method of the present invention is effective in treating water blocked formations.

Example IV
To further illustrate the effectiveness of the pre-sent inv~ntion in treating water blocked sandstone for-mations, the following test is performed.
A well in Moffat County, Colorado, is producing 100 MCF of gas per day from the Fort Union Sand Formation. The formation has a permeability of 0.1 millidarcy.
The well is treated in accordance with the methods of the present invention employing a fluid comprising 50 volume percent methanol, 2 gal~/1000 gal. Cl~ - C12 alkoxy-late formulation (foaming agent), 0.01 weight percent cationic perfluoro compounds (Structural Formula II, x=8, w=8, R=CH3, z=1.5, A=Cl, Q=trimethylamine), 40 volume per-cent liquid nitrogen to provide a gas assist in fluid reco~
very and 2% KCl solution.
The well, after treatment, is producing 3Q0 MCF of gas per day.
While that which is considered to be the preferred embodiment of the present invention has been described herein, it is to be understood that modifications, changes ~L216~G
or the like can be made in the methods and compositions disclosed w.ithout departing from the spirit or scope of the invention as defined in the appended claims.

Claims (13)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-

1. A method of increasing the production of hydrocarbons from a hydrocarbon-containing subterranean for-mation having impaired permeability as a result of formation invasion by aqueous fluids comprising contacting said for-mation with a penetrating solvent capable of disrupting at least a portion of any aqueous layer present on solid sur-faces within said formation and a cationic perfluoro com-pound whereby said compound is adsorbed onto said solid surfaces of said formation said cationic perfluoro compound being selected from the group consisting of a compound or mixtures of compounds represented by the formula:

wherein x is an integer from 2 to 12 or an integer or fractional integer representing an average value of from 2 to 12; w and y are both individually integers from 0 to 20 or integers or fractional integers representing average values of from 0 to 20; z is an integer from 0 to 20 or an integer or fractional integer representing an average value of from 0 to 20, the sum of y and z being from 1 to 20; R is a hydrogen, methyl, ethyl or propyl radical, or mixtures thereof; A is a halogen chosen from chlorine, bromine or iodine; and Q is a cationic nitrogen radical from the group consisting of an aromatic amino radical, a heterocyclic amino radical, and an amine radical represented by the for-mula:

wherein R1, R2 and R3 are from the group consisting of hydrocarbon radicals containing from 1 to 30 carbon atoms, aromatic hydrocarbon radicals and hydrogen radicals, provided that at least one of R1, R2 and R3 is an aliphatic hydrocarbon radical containing from 1 to 30 carbon atoms or an aromatic hydrocarbon and that when any one of R1, R2 and R3 radicals contains more than four aliphatic carbon atoms or an aromatic hydrocarbon, the other two radicals are each chosen from the group consisting of hydrogen, methyl and ethyl radicals.

2. The method of Claim 1 wherein said contacting of said formation with said cationic perfluoro compound or compounds is brought about by dissolving or dispersing said compound or compounds in a carrier fluid and introducing said carrier fluid into said formation.

3. The method of Claim 2 wherein said cationic perfluoro compound is present in said carrier fluid in an amount in the range of from about 0.01% to about 10% by weight of said carrier fluid.

4. The method of Claim 1 wherein said cationic perfluoro compound is selected from the group consisting of a compound or mixture of compounds represented by the for-mula:

wherein x is an integer from 2 to 12 or an integer or fractional integer of from 2 to 12; w is an integer from 1 to 20 or an integer or fractional integer of from 1 to 20;
z is an integer from 1 to 20 or an integer or fractional of from 1 to 20, R is selected from the group of hydrogen, methyl, ethyl, propyl radicals and mixtures thereof; A is a halogen anion from the group consisting of chlorine, bromine and iodine; and Q is a cationic nitrogen radical from the group consisting of an aromatic amino radical, a hetero-cyclic amino radical, and an amine radical represented by the formula:

wherein R1, R2 and R3 are from the group consisting of hydrocarbon radicals containing from 1 to 30 carbon atoms, aromatic hydrocarbon radicals and hydrogen radicals, provided that at least one of R1, R2 and R3 is an aliphatic radical containing from 1 to 30 carbon atoms or an aromatic hydrocarbon and that when any one of R1, R2 and R3 radicals contains more than four aliphatic carbon atoms or an aromatic hydrocarbon, the other two radicals are each chosen from the group consisting of hydrogen, methyl and ethyl radicals.

5. The method of Claim 4 wherein x is 8; w is from 6 to 10; z is from 1 to 3 R is a methyl radical; A is chlorine; and Q is a cationic nitrogen radical selected from the group consisting of pyridino and quinolino.

6. The method of Claim 4 wherein x is 8; w is from 6 to 8; z is from 1 to 3; A is chlorine; and Q is a trimethylamino radical.

7. The method of Claim 1 wherein said cationic perfluoro compound is selected from the group consisting of a compound or mixture of compounds represented by the for-mula:

A( -) wherein x is an integer from 2 to 12 or an integer or fractional integer representing an average value of from 2 to 12; z is an integer of from 1 to 20 or an integer or fractional integer representing an average value of from 1 to 20, R1, R2 or R3 are each chosen from the group con-sisting of lower aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms; and A is a halogen anion chosen from the group consisting of chlorine, bromine or iodine.

8. The method of Claim 7 wherein x is 8; z is from 1 to 3; R1, R2 and R3 are each methyl radicals; and A
is a chlorine anion.

9. The method of Claim 1 wherein said cationic perfluoro compound or compounds are represented by the for-mula:

wherein x is an integer from 2 to 12 or an integer or fractional integer representing an average value of from 2 to 12; z is an integer of from 1 to 20 or an integer or fractional integer representing an average value of from 1 to 20, Q is a nitrogen-containing heterocyclic or aromatic cationic radical; and A is a halogen anion chosen from the group of chlorine, bromine or iodine anions.

10. The method of Claim 9 wherein x is 8; z is from 1 to 3; Q is a cationic nitrogen radical selected from the group consisting of pyridino and quinolino radicals; and A is a chlorine anion.

11. The method of Claim 4 wherein x is 3; w is from 6 to 8; z is from 1 to 3; Q is a trimethylamino radi-cal; and A is the chlorine anion.

12. The method of Claim 1 wherein x is from 4 to 10; w is from 0 to 12; y is 0; z is from 1 to 8; R is from the group of hydrogen and methyl radicals, and mixtures thereof; A is chlorine; and Q is selected from the group of trimethylamino, pyridino, quinolino, isoquinolino, N,N
dimethyl anilino, N-methyl morpholino and morpholino radi-cals.

13. The method of Claim 1 or Claim 4, wherein R1, R2 and R3 are selected from the group consisting of phenyl and any alkyl substituted phenyl radical.