WO2000056835A1

WO2000056835A1 - Invert emulsion fluids suitable for drilling

Info

Publication number: WO2000056835A1
Application number: PCT/US2000/007860
Authority: WO
Inventors: Arvind D. Patel
Original assignee: M-I L.L.C.
Priority date: 1999-03-24
Filing date: 2000-03-24
Publication date: 2000-09-28
Also published as: AU3918400A

Abstract

A new invert emulsion fluid has been invented which comprises an oleaginous liquid, a non-oleaginous liquid, and a protonated amine having the structure R-N+-H3 B- wherein R represents a C¿12?-C22 alkyl group or a C12-C22 alkenyl group, a C3-C8 cycloalkyl group substituted with a C9-C14 alkyl or alkenyl group, or a C9-C14 alkyl or alkenyl group substituted with a C3-C8 cycloalkyl group and B?-¿ is the conjugate base of a water soluble acid and the protonated amine is in an amount sufficient to stabilize the invert emulsion. Such fluids are acidic and thus useful in drilling wells in which acidic gases such as CO¿2? or H2S are likely to be encountered and break, i.e. de-emulsify, the drilling fluid. The fluids may also be utilized in combination with acidic brine solutions to increase the density of the drilling fluid.

Description

INVERT EMULSION FLUIDS SUITABLE FOR DRILLING BACKGROUND OF THE INVENTION

Invert emulsion fluids, i.e. emulsions in which the non-oleaginous fluid is the dispersed phase and the oleaginous fluid is the continuous phase, are employed in drilling processes for the

5 development of oil or gas sources, as well as, in geothermal drilling, water drilling, geoscientific drilling and mine drilling. Specifically, the invert emulsion fluids are conventionally utilized for such purposes as providing stability to the drilled hole, forming a thin filter cake, lubricating the drilling bore and downhole, and penetrating salt beds without sloughing or enlargement of the drilled hole.

10 Invert emulsion fluids generally consist of a three-component system, namely an oleaginous liquid such as oil which serves as a continuous phase, a non-oleaginous liquid such as water which serves as a discontinuous phase, and an emulsifying agent. The emulsifying agent serves to lower the interfacial tension of the liquids so that the non-oleaginous liquid may form a stable dispersion of fine droplets in the oleaginous liquid. A full description of such invert ι₅ emulsions may be found in Composition and Properties of Drilling and Completion Fluids. 5th Edition, H. C. H. Darley, George R. Gray, Gulf Publishing Company, 1988, pp. 328-332, the contents of which are hereby incorporated by reference.

The use of organophilic clay as a suspending agent in oil based drilling fluids should be well known to one of skill in the art. Generally, organophilic clays are made in a cation

20 exchange reaction of hydrophilic clay with cationic organoamine compounds such a quaternary cationic amine compounds. Chemically, the cationic organoamine compound exchanges with the sodium, potassium, calcium and magnesium ions on the surface of the clay thus ionically binding the organoamine compound to the clay surface. Once bound to the clay surface, the organic groups of the organoamine compounds render the clay organophilic and thus capable of s becoming "oil-wet." In order to maximize yield, the above cation exchange reaction is typically carried out separately from the formulation of the drilling fluid itself. However, early attempts to achieve the formation of organophilic clay invert emulsions are known in the literature. For Example U.S. Patent No. 2,900,336 issued to William E. Brown, William J. McVeagh and Thomas H. Wallace describes such an attempt at the formation of organophilic clay in an invert

30 emulsion drilling fluid so as to increase the suspending properties of the resulting fluid. As is noted in Column 2, lines 39-44 of U.S. Patent No. 2,900,336, the amount of organic compound added to the drilling fluid should be sufficient to maintain in suspension substantially all of the solid material added to the drilling fluid. However, due to the many components of a drilling fluid and the high potential for side reactions, this method of forming a useful invert emulsion drilling fluid with organophilic clay suspending agent fails to give an invert emulsion drilling fluid with measurable properties typical of a drilling fluid such as plastic viscosity; yield point; apparent viscosity; "GELS" ; API filtrate loss; or high temperature high pressure fluid loss.

In addition to organophilic clay and other suspending agents, lime or other alkaline materials are added to conventional invert emulsion fluids to maintain a reserve alkalinity when the invert emulsion fluid is to be used in drilling. See, for example, API Bulletin RP 13B-2, 1990, p. 22 which describes a standard test for determining excess lime in drilling mud. See also, for example, U.S. Patent No. 5,254,531 which employs lime along with an ester oil, a fatty acid, and an amine and EP 271943 which employs lime along with oil, water, and an ethoxylated amine. In some areas acidic gases such as CO₂ or H₂S are encountered during drilling. The acidic gases often weaken conventional invert emulsion fluids to the point of failure and render the invert emulsion fluids useless. Another aspect of invert emulsions that is typically encountered during drilling is the need to increase the density of the drilling fluid. Conventionally this is done by the addition of solid weighting agents or by the use of brines of salts that form basic or neutral aqueous solutions. The use of brines of salts that form acidic aqueous solutions, for example a transition metal halide solution, is difficult because of the addition of the acidic brine would tend to make the invert emulsion fluids unstable. Further, due to the alkaline reserve noted above, the transition metal ion would precipitate out due to the formation of hydroxide complexes. However the use of acidic brine solutions is desired due to their higher density imparted by the metal cation.

Thus, it would be desirable if an invert emulsion could be invented which did not fail or weaken when subjected to acidic gases such as CO or H S or mixed with acidic aqueous solutions or brines. In this manner, the invert emulsion could be employed as a drilling fluid in potentially acidic environments without apprehension of adverse affects before, during or after drilling.

SUMMARY OF THE INVENTION A new invert emulsion fluid has been invented which comprises an oleaginous liquid, a non-oleaginous liquid, and a protonated amine having the structure R-N⁺-H₃ B^" wherein R represents a C₁ -C₂₂ alkyl group or a Cj₂-C₂ alkenyl group, a C₃-C₈ cycloalkyl group substituted with a C₉-Cι₄ alkyl or alkenyl group, or a C₉-Cι₄ alkyl or alkenyl group substituted with a C -C₈ cycloalkyl group and B^" is the conjugate base of a water soluble acid and the protonated amine is in an amount sufficient to stabilize the invert emulsion. Such fluid is particularly useful in the drilling of wells in which CO₂, H S or other acidic gases will be encountered and break or adversely affect conventional invert emulsions. Such fluids may also be useful in the formulation of "solids free" invert emulsion drilling fluids with an acidic brine internal phase. DETAILED DESCRIPTION OF THE INVENTION As used herein, the term "invert emulsion" is an emulsion in which a non-oleaginous fluid is the dispersed phase and an oleaginous fluid is the continuous phase. The novel invert emulsion fluids of the present invention are useful in a similar manner as conventional invert emulsion fluids which includes utility in preparation for drilling, drilling, completing and working over subterranean wells such as oil and gas wells. Such methods of use of conventional inverse emulsion fluids are described in, for example, Composition and Properties of Drilling and Completion Fluids. 5th Edition, H. C. H. Darley, George R. Gray, Gulf Publishing Company, 1988, the contents which are incorporated by reference, as well as, U.S. Patent No. 5,254,531 and EP 271943 which are incorporated by reference. The advantage of the instant invert emulsion fluids is that due to the protonation of the amine it will normally not be necessary to add significant amounts of lime or another basic material to the invert emulsion fluid when an acidic substance such as CO₂ or H S comes into contact with the fluid. Another advantage of the invert emulsion fluids of the present invention is that brines including acidic transition metal salts may be used to increase the density of the drilling fluid without the addition of solids or the formation of undesirable metal hydroxide precipitates.

As used herein, the term "oleaginous liquid" means an oil which is a liquid at 25°C and immiscible with water. Oleaginous liquids typically include substances such as diesel oil, mineral oil, synthetic oil, glycerides of fatty acids, aliphatic esters, aliphatic ethers, aliphatic acetal, dialkylcarbonates, or other such hydrocarbons or mixtures of these compounds that may be used in the formulation of a drilling fluid.

The amount of oleaginous liquid in the invert emulsion fluid may vary depending upon the particular oleaginous fluid used, the particular non-oleaginous fluid used, and the particular application in which the invert emulsion fluid is to be employed. However, generally the amount must be sufficient to form a stable emulsion when utilized as the continuous phase. Typically, the amount of oleaginous liquid is at least about 30 percent by weight per volume of drilling fluid, preferably at least about 40 percent by weight per volume of drilling fluid, more preferably at least about 50 percent by volume of the total fluid. As used herein, the term "non-oleaginous liquid" mean any substance which is a liquid at

25°C and which is not an oleaginous liquid as defined above. Non-oleaginous liquids are immiscible with oleaginous liquids but capable of forming emulsions therewith. Typical non- oleaginous liquids include aqueous substances such as sea water or brine containing inorganic or organic dissolved salts, as well as, mixtures of water with water-miscible organic compounds. The amount of non-oleaginous liquid in the invert emulsion fluid may vary depending upon the particular non-oleaginous fluid used and the particular application in which the invert emulsion fluid is to be employed. Typically, the amount of non-oleaginous liquid is at least about 1 percent by volume, preferably at least about 3 percent by volume, more preferably at least about 5 percent by volume of the total fluid. Correspondingly, the amount should not be so great that it cannot be dispersed in the oleaginous phase. Therefore, typically the amount of non- oleaginous liquid is less than about 90 percent by volume, preferably less than about 80 percent by volume, more preferably less than about 70 percent by volume of the total fluid.

As used herein, the term "amine" refers to compounds having the structure R-NH wherein R represents a Cj -C ₂ alkyl group, a Cj₂-C alkenyl group, a C₃-C₈ cycloalkyl group substituted with a C₉-C]₄ alkyl or alkenyl group, or a C₉-Cι₄ alkyl or alkenyl group substituted with a C₃-C₈ cycloalkyl group. Preferable R groups include straight or branched dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, as well as, mixtures and unsaturated derivatives thereof. Preferable unsaturated derivatives include soyaalkylamine (Armeen S™ available from Akzo Chemicals Inc.) and tallowalkylamine (Armeen T™ available from Akzo Chemicals Inc.). Many of the other above amines are also commercially available from Akzo Chemicals Inc. under the tradename Armeen™.

The aforementioned amines of the formula R-NH are protonated for use in this invention. The term "protonated" means that the amine is substantially converted to the structure R-N⁺-H₃ B^". Typically, such protonation occurs due to reaction of the amine with an acid. Depending upon the conditions of such a reaction, an equilibrium may be established between the protonated amine and the conjugate base of the acid, and unprotonated amine and acid. Such a condition can be represented by the equation:

R-NH₂ + HB < > R-N⁺-H₃ B^".

In such cases the equilibrium established will depend upon the relative strength of the acid. With regard to the present invention, it is only important that the protonated amine be present in a concentration so as to stabilize the invert emulsion. Generally, the type of counter- ion, B^", is not particularly critical so long as it does not adversely affect the performance and characteristics of the resulting emulsion as is disclosed herein. Examples of the counter-ion include the conjugate bases of the water soluble acids described below. The protonated amines of the present invention function in the instant invention as a surfactant to lower the interfacial tension of the liquids so that the non-oleaginous liquid may form a stable dispersion of fine droplets in the oleaginous liquid. One of ordinary skill in the art should appreciate that the function of the protonated amine compounds in the present invention is different from that of a suspending agent. Generally a suspending agent is chemically associated with the solid components of a drilling fluid or mud. For example, organophilic clay is a suspending agent used in oil based muds. Organophilic clay is made by a process of cation exchange prior to formulation of the drilling fluid in which normally hydrophilic clay is reacted with quaternary ammonium salts to form a product that can be dispersed in oil. The function of such organophilic clays and other suspending agents is to enable the invert emulsion to suspend particles in the drilling fluid. This is in contrast to the function of the protonated amines of the present invention which, as previously noted, function as a surfactant to lower the interfacial tension of the liquids so that the non-oleaginous liquid may form a stable dispersion of fine droplets in the oleaginous liquid.

In view of the above function, the amount of protonated amine should be sufficient to enable the non-oleaginous liquid to form a stable dispersion of fine droplets in the oleaginous liquid. That is to say the protonated amine should be present in a concentration sufficient to stabilize the invert emulsion and thus serve as the basis for the formulation of a useful invert emulsion drilling fluid. While this amount may vary depending upon the nature and amount of the oleaginous liquid and non-oleaginous liquid, typically the amount of protonated amine is at least about 0.1 percent by weight per volume of drilling fluid, preferably at least about 5 percent by weight per volume of drilling fluid, more preferably at least about 10 percent by weight per volume of drilling fluid of the total fluid. Correspondingly, the amount should not be so great to interfere with the stability of the invert emulsion fluid or the performance of the invert emulsion as a drilling fluid.

As used herein, the term "acid" or "water soluble acid" refers to water-soluble, i.e. at least 10 percent by volume of the acid dissolves in water, compounds which are suitable to protonate the amine and render a stable non-oleaginous fluid in oleaginous fluid emulsion. The term acid refers to both inorganic acids such as sulfuric, nitric, hydrofluoric, hydrochloric and phosphoric acid and organic acids such as citric, acetic, formic, benzoic, salicyclic, oxalic, glycolic, lactic, glutaric acid, and carbonic acid. Fatty acids such as oleic, palmitic, and stearic acid are not within the definition of acid as used herein because such acids are not water-soluble. Compounds that generate acidic solutions upon dissolution in water are also considered "acids" as the term is used herein. For example such acids may include, acetic anhydride, hydrolyzable esters, hydrolyzable organosulfonic acid derivatives, hydrolyzable organophosphoric acid derivatives, phosphorus trihalide, phosphorous oxyhalide, acidic metal salts, sulfur dioxide, nitrogen oxides, carbon dioxide, and similar such compounds. Thus in one embodiment, the acidic solution is formed by the dissolution of an acidic metal salt in water. That is to say the upon dissolution of the metal salt, a sufficient concentration of protons are produced the resulting solution is capable of protonating the amine and render a stable non-oleaginous fluid in oleaginous fluid emulsion. In another embodiment the acidic solution is a brine formed by the dissolution of a neutral metal salt and an acidic metal salt in water. In yet another embodiment, an acidic solution may be formed by the dissolution of an acid compound and a neutral salt.

In a particularly preferred embodiment of this invention, brines, such as zinc bromide brine or zinc bromide and calcium bromide brine, are acidic in aqueous solutions, and these brines are acidic enough to protonate the amines of this invention to form invert emulsions. Other transition metal salts may demonstrate utility in this invention, for instance acidic metal salt brines may be formed by the dissolution of a variety of first row transition metal salts in aqueous solution with or without other acids. The preferred acidic metal salts are transition metal salts of neutral or acid anions, especially preferred are the first row transition metal slats due to the high cost of second and third row transition metal salts. The anion of these salts may include halide, sulfate, sulfite, nitrate, hyrdosulfate and the like. One distinct advantage of the use of these materials is the ability to build weight in drilling fluids without adding solid weighting materials, such as those described below.

The amount of acid must be sufficient to protonate the amine without rendering the invert emulsion fluid so acidic that it is unstable. As one skilled in the art will appreciate, the amount of acid will necessarily vary tremendously with the strength of the acid and the particular amine to be protonated. Nevertheless, one skilled in the art having the benefit of this specification may readily determine the necessary amount of acid via routine experimentation.

The method of preparing the drilling fluids of the present invention is not particularly critical so long as an invert emulsion is formed. Generally, the components may be mixed together in any order under agitation condition. A representative method of preparing said invert emulsion fluids comprises mixing an appropriate quantity of oleaginous fluid and an appropriate quantity of amine together with continuous, mild agitation. A non-oleaginous fluid and acid is then added while mixing until an invert emulsion is formed. If weight material, such as those described below, are to be added, then the weight material is typically added after the invert emulsion fluid is formed.

One skilled in the art may readily identify whether the appropriate ingredients and amounts have been used to form an invert emulsion by using the following test:

INVERT EMULSION TEST A small portion of the emulsion is placed in a beaker which contains an oleaginous fluid. If the emulsion is an invert emulsion, the small portion of the emulsion will disperse in the oleaginous fluid. Visual inspection will determine if it has so dispersed. Alternatively, the electrical stability of the invert emulsion may be tested using a typical emulsion stability tester.

Generally the voltage applied across two electrodes is increased until the emulsion breaks and a surge of current flows between the two electrodes. The voltage required to break the emulsion is a common measure of the stability of such an emulsion. Other tests are described on page 166 of the book, Composition and Properties of Drilling and Completion Fluids. 5th Edition, H. C. H.

Darley and George Gray, Gulf Publishing Company, 1988, the contents of which are hereby incorporated by reference.

The properties of invert emulsion drilling fluids and muds formulated in accordance with the present invention should include those commonly expected of a useful invert emulsion drilling fluid. Such properties include measurable properties typical of a drilling fluid including: plastic viscosity; yield point; apparent viscosity; "GELS" ; API filtrate loss; or high temperature high pressure fluid loss.

Various surfactants and wetting agents conventionally used in invert emulsion fluids may optionally be incorporated in the fluids of this invention. Such surfactants are, for example, fatty acids, soaps of fatty acids, amido amines, polyamides, polyamines, oleate esters, imidazoline derivatives, oxidized crude tall oil, organic phosphate esters, alkyl aromatic sulfates and sulfonates, as well as, mixtures of the above. Generally, such surfactants are employed in an amount which does not interfere with the fluids of this invention being used as drilling fluids.

Suspending agents also referred to herein as viscosifying agents, for example, organophilic clays, may optionally be employed in the invert drilling fluid compositions of the present invention. Usually, other viscosifying agents, such as oil soluble polymers, polyamide resins, polycarboxylic acids and fatty acid soaps and combinations of the above noted suspending agents may also be employed. The amount of viscosifying agent used in the composition will necessarily vary depending upon the end use of the composition. Usually such viscosifying agents are employed in an amount which is at least about 0.1 percent by weight per volume of drilling fluid, preferably at least about 2 percent by weight per volume of drilling fluid, more preferably at least about 5 percent by weight per volume of drilling fluid of the total fluid. VG-69™ and VG-PLUS™ are organoclay materials and Versa HRP™ is a polyamide resin material manufactured and distributed by M-I L.L.C. which are suitable viscosifying agents.

The invert emulsion drilling fluids of this invention may optionally contain a solid weight material. The quantity and nature of the solid weight material depends upon the desired density and viscosity of the final composition. The preferred solid weight materials include, but are not limited to, barite, iron oxides, calcium carbonate and the like. The solid weight material is typically added in order to obtain a drilling fluid density of less than 24 pounds per gallon, preferably less than 21 pound per gallon, and most preferably less than 19.5 pounds per gallon.

The invert emulsion drilling fluids of the present invention may also be weighted by the use of acidic metal salt brines. Like solid weight materials, the quantity and nature of the acidic metal salt brine depends upon the desired density and viscosity of the final composition. As noted above, acidic metal salt brines may be formed by the dissolution of an acidic metal salt in aqueous solution with or without other acids. The preferred acidic metal salts are transition metal salts of neutral or acid anions. For example, such anions include halide, sulfate, sulfite, nitrate, hyrdosulfate and the like. In one such embodiment, the acidic metal salt is selected from the group including zinc chloride, zinc bromide, the hydrates of these salts, and their mixtures. In another preferred embodiment the acidic metal salt is zinc bromide. Yet a third embodiment includes a mixture of a neutral salt, such as calcium halide, or alkali metal halide, nitrate or sulfate, and an acidic metal salt is selected from the group including zinc chloride, zinc bromide, the hydrates of these salts, and their mixtures. Thus in one embodiment a mixture of zinc bromide and calcium bromide is used to generate a brine solution. Depending upon the increase in density desired, the concentration of the salt in solution can be varied. In one such embodiment a mixture of zinc bromide and calcium bromide is used to achieve a solution having a density of 19.2 pounds per gallon. One skilled in the art should readily be able to formulate any such solution. One method of doing this is to form a saturated aqueous solution of the selected salt or mixture of salts and measuring the density of the decanted solids free solution. The density of the saturated salt solution can be lowered by systematically diluting with small portions of water until the desired density is obtained. If a higher density solution is desired, a more soluble form of the metal salt may be selected or a combination of salts may be utilized. It should be noted that in some cases environmental concerns regarding the toxicity of the metal ion in solution should be considered when selecting the salt to be used to form the brine.

Fluid loss control agents such as modified lignite, polymers, oxidized asphalt and gilsonite may also be added to the invert drilling fluids of this invention. Usually such fluid loss control agents are employed in an amount which is at least about 0.1 percent by weight per volume of drilling fluid, preferably at least about 1 percent by weight per volume of drilling fluid, more preferably at least about 5 percent by weight per volume of drilling fluid of the total fluid. The following examples are submitted for the purpose of illustrating the performance characteristics of the drilling fluid compositions of this invention. These tests were conducted substantially in accordance with the procedures in API Bulletin RP 13B-2, 1990 which is incorporated herein by reference. The following abbreviations may be used in describing the results of experimentation: "E.S." is electrical stability of the emulsion as measured by the test described in

Composition and Properties of Drilling and Completion Fluids. 5th Edition, H. C. H. Darley, George R. Gray, Gulf Publishing Company, 1988, pp. 116, the contents of which are hereby incorporated by reference. Generally, the higher the number, the more stable the emulsion.

"PV" is plastic viscosity which is one variable used in the calculation of viscosity characteristics of a drilling fluid, measured in centipoise (cp) units. "Yp" is yield point which is another variable used in the calculation of viscosity characteristics of drilling fluids, measured in pounds per 100 square feet (lb/100ft²).

"AV" is apparent viscosity which is another variable used in the calculation of viscosity characteristic of drilling fluid, measured in centipoise (cp) units.

"GELS" is a measure of the suspending characteristics, or the thixotropic properties of a drilling fluid, measured in pounds per 100 square feet (lb/ 100 ft²).

"API F.L." is the term used for API filtrate loss in milliliters (ml).

"HTHP" is the term used for high temperature high pressure fluid loss, measured in milliliters (ml) according to API bulletin RP 13 B-2, 1990.

The following experiments were conducted using standard laboratory techniques and equipment. Except as noted commercially available materials were utilized. Example 1 * (Prior Art)

In the following example attempts were made to prepare invert emulsion drilling fluids in accordance with the teachings of U.S. Patent No. 2,900,336.

Preparation of Alkylamine JM-T Acetate: The emulsifier Alkylamine JM-T acetate was not commercially available at the time of these experiments. Based on a knowledge of the art and the teachings of U.S. Patent No. 2,900,336, a chemically equivalent compound was prepared by mixing about 8.5 g of Alkylamine JM-T with about 2.0g glacial acetic acid (1 :1.05 mol ratio) for about 2 minutes.

Preparation of Bentonite Gel Slurry: A bentonite gel slurry was prepared by mixing about 75 ml of distilled water with about 0.75 g Wyoming bentonite (M-I GELL Supreme) for about 15 minutes.

Preparation of EUenberger Field Crude Oil: EUenberger Field crude oil was not commercially available at the time of the these experiments. Based on a knowledge of the art and the teachings of U.S. Patent No. 2,900,336, diesel #2 was utilized as a substitute for the asphaltene-free and processed EUenberger Field crude oil utilized in U.S. Patent No. 2,900,336. Preparation of Invert Emulsion: The alkylamine JM-T acetate (8.25 g) was dissolved in about 225 ml of diesel #2. The diesel solution was added to the bentonite gel slurry and mixed on a Hamilton Beach mixer for about 15 minutes. The resulting mixture was allowed to stand at room temperature and separated into two layers (a predominately diesel layer and a predominately water layer) upon standing for about 20-30 minutes.

After standing overnight at room temperature, 140 g of barite was added and the combination was mixed for about 15 minutes on a Hamilton Beach mixer. Upon stopping of the agitation, the mixture separated into three layers ( a predominately diesel layer, a predominately water layer and a settled barite solid layer) with the emulsion breaking and the barite settling to the bottom as water wet barite. The amount of Alkylamine JM-T acetate was about 3% by weight.

The above example was repeated using Armac 18D, Armeen- 12D Acetate and Alkylamine JMT Acetate at the concentrations shown below.

Alkylamine JMT-Acetate Armeen- 12D Acetate Armac 18D

Weight Percent Weight Percent Weight Percent

(g) weight (g) weight (g) weight

13.75 5 12.5 4.5 17.0 6.1

8.25 3 7.5 2.7 10.25 3.7

2.75 1 2.5 0.9 3.4 1.22

In all of the above experiments the emulsion separated upon standing and the barite settled and appeared water wet. For each of the above drilling fluids, which were formulated in accordance with the teachings of the U.S. Patent No. 2,900,336, the following observations were made: a) In all of the above formulated drilling fluids the mixture formed by the combination and mixing of diesel #2 with organic amine compound, and bentonite gel slurry separated over the course of 20-30 minutes upon cessation of agitation. b) In all of the above formulated drilling fluids the mixture formed by the addition of barite to the combination of diesel #2 with organic amine compound, and bentonite gel slurry followed by mixing separated over the course of 20-30 minutes upon cessation of agitation with the barite settling and appearing to be water wet. c) In all of the above formulated drilling fluids the resulting mixture does not exhibit measurable properties typical of an invert emulsion drilling fluid including: plastic viscosity; yield point; apparent viscosity; API filtrate loss; or high temperature high pressure fluid loss. One of ordinary skill in the art should understand and appreciate upon review of the above experimental data that the teachings of U.S. Patent No. 2,900,336 fail to give an invert emulsion that may be used in the formulation of a drilling fluid. Further a drilling fluid formulated in accordance with the teachings of U.S. Patent No. 2,900,336 does not exhibit measurable properties of typical of a drilling fluid including: plastic viscosity; yield point; apparent viscosity; "GELS" ; API filtrate loss; or high temperature high pressure fluid loss.

Example 2

The following drilling fluids were prepared utilizing amines of this invention. Formulation 1

Materials Amount in Grams

I.O. Cι₆ ^" Cι₈™ Oil (Isomerized olefin available from 125

Amoco)

Lime 0

Organophilic clay (VG-PLUS™ available from M-I 2.0

Drilling Fluids)

Adogen - 151™ (Tall Oil Primary amine available from 10

Witco Chemical Company)

25% CaCl₂ Brine 90

CaCO₃ 293

The above formulation was prepared according to the following procedure: First, oil and organophilic clay were mixed in a glass jar on a Hamilton Beach mixer for 15 minutes. Then, Adogen-151™ was added and mixed for 10 minutes. Brine was then added and mixed for 15 minutes. CaCO₃ was then added and mixed for 15 minutes.

The above formulation was heat aged at 150° for 16 hours.

Initial and heat aged properties were measured at room temperature.

Initial Heat Aged

E.S. 343 378

PN. 54 41

Y.P. 23 40

GELS

10 sec. 13 18

10 min. 14 20

5.0 grams of lime were added to the heat-aged formulation and heated at 150°F. The invert emulsion broke in 4 hours and the solids were water-wet. Electrical stability (E.S.) dropped to 6. To the above water-wet solids formulation, 15 ml of 17.5% hydrochloric acid were added. The formulation was mixed for 10 min. The water- wet solids became oil- wet and an invert emulsion was obtained. The emulsion stability increased to 280. The following properties were measured on the acid treated formulation.

E.S. 280

PN. 50

Y.P. 20

GELS

10 sec. 6

10 min. 9

5.0g of lime were added to the acid treated formulation above and mixed for 10 min. The formulation was then heat aged at 150°F for six hours. It was then noted that the emulsion broke and the solids became water-wet. The fluid had an electrical stability of 6. To the above water- wet solids mixture, 10 ml of glacial acetic acid were added. The water- wet solids became oil-wet again. The electrical stability increased to 295.

The above example shows that the protonation of the amine makes the invert emulsion and upon deprotonation, the emulsion is broken.

Example 3 The following formulation was prepared to demonstrate the utility of amine surfactant of this invention in 50/50 oil to water ratio oil base mud. Formulation 2

Materials Amount in Grams

I.O. Cι₆ - Ci8™ 121

VG-PLUS™ 2.0

Adogen - 151™ 12.0

25% CaCl₂ Brine 200

CaCO₃ 61

The above formulation was prepared in a manner similar to Example 1 and heat aged at 150°F for 16 hours. The following initial and heat-aged properties were measured. Initial Heat Aged

E.S. 156 150 PN. 34 37 Y.P. 38 43 GELS

10 sec 18 20

10 min 18 22

5.0g lime was then added to the above formulation and it was heat-aged to 150°F for 4 hours.

The solids became water- wet. The electrical stability was 6.

15.0 ml. of 17.5% hydrochloric acid were then added to the water-wet formulation above and mixed for 10 min. The water- wet solids became oil-wet. The electrical stability increased to

208. The mud was oil dispersible.

The above example shows that the protonation of amine-surfactant of this invention makes stable water-in-oil emulsions.

Example 4

The following formulation was prepared in a manner similar to Example 1 to demonstrate the use of amine surfactant in protonated form to make stable water-in-oil emulsions. Formulation 3

Materials Amount in Grams

I.O. C₁₆ - Ci8™ 12.1

VG-PLUS™ 2.0

Jet-amine-PS ™ (primary soya available from Jetco Chemical) 12.0

17.5% HC1 10.0

25% CaCl₂ Brine 190

CaCO₃ 61

The above formulation was heat-aged at 150°F for 16 hours. The following properties were measured after heat-aging.

E.S. 216

PN. 39

Y.P. 51

GELS

10 sec 22

10 min 23

lOg of lime were mixed with the above formulation and the resulting formulation was heat-aged at 150°F for 5 hours. The emulsion was converted to an oil-in-water emulsion with electrical stability of 10. The following properties were measured on this oil-in-water emulsion E.S. 10

PN. 20

Y.P. 18

GELS

10 sec 6

10 min 13

15 ml of 17.5% hydrochloric acid was then mixed with the above formulation and it was converted to an oil-base mud with electrical stability 153.

The above example establishes that the amine emulsifier in protonated form of this invention forms a water-in-oil emulsion. Upon deprotonating with lime, it forms an oil-in-water emulsion. Example 5

The following formulations, Formulations 4, Formulation 5 and Formulation 6, were prepared in a manner similar to Example 1 to demonstrate the use of synthetic oils in preparing invert emulsions of this invention.

Formulation 4

Formulation 4 Formulation 5 Formulation 6

Materials £g) (g) (ε)

Sarapar™ - 147 (oil 121 121 21 available from Shell Oil)

VG-PLUS™ 2.0 2.0 2.0

Emulsifiers Jet-Amine P.T ™ Jet-Amine P.S.™ Adogen - 151™

(Primary Tallow (Primary Soya (Tall Oil Primary amine available form amine available amine)

Jetco Chemical) from Jetco

12.0 Chemical)

12.0 12.0

17.5% HC1 10 10 10

25% CaCl₂ 200 200 200

Barite 66 66 66

The following initial properties were measured on the above formulations.

Formulation 4 Formulation 5 Formulation 6

E.S. 159 160 125

PN. 34 27 24

Y.P. 73 44 14

GELS

10 sec 28 14 7

10 min 34 20 8

The above formulations were then heat-aged at 150°F for 16 hours. The following properties were then measured at room temperature.

Formulation 4 Formulation 5 Formulation 6

E.S. 258 188 105

PN. 29 26 21

Y.P. 36 36 15

GELS

10 sec 18 18 7

10 min 26 19 9

10 grams of lime were added to each of the above heat aged Formulations 4-6. The solids became water- wet. Electrical stability dropped to 25, 22 and 10 respectively. The water-in-oil emulsions were broken.

Glacial acetic acid was then added to each of the above water-wet solids mix to neutralize the lime and protonate the amine surfactant. Upon protonating the amine surfactant, the formulations became water-in-oil invert emulsions. Electrical stability increased to 121, 138 and 110, respectively. The above example demonstrates the use of amine surfactant in protonated form to make the invert emulsion of this invention.

Example 6

The following formulations were prepared to demonstrate the utility of the amine surfactant of this invention in preparing solids free invert emulsions using zinc bromide brine as internal phase.

Materials Formulation 7 Formulation 8 Formulation 9 Formulation 10

(gm) (gm) (gm) (gm)

I.O. C16-C18™ 120 108 84 60

Adogen-151™ 12.0 12.0 15.0 15.0

ZnBr₂ brine (19.2 ppg) 345 379 448 517

The density of the zinc bromide brine solution was adjusted to achieve the desired density by either adding additional salt to increase the density or adding additional water to decrease the density. The above formulations were prepared in a manner similar to Example 1 and heat aged at 150°F for 16 hours. The following heat aged properties were measured at room temperature.

Formation 7 Formation 8 Formation 9 Formation 10

ES 306 352 205 175

PV 18 22 32 101

YP 8 8 17 69

GELS

10 sec 3 4 6 19

10 min 7 5 7 26 The above example demonstrates the use of a acidic metal salt brine (i.e. zinc bromide brine) with the amine surfactant in a protonated form to make an invert emulsion of this invention which is weighted (i.e. has a density greater than the emulsion when water replaces the brine) but does not contain solid weight materials.

While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the processes and compositions described herein without departing from the concept, and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope and concept of the invention as set out in the following claims.

Claims

CLAIMS:

1. An invert emulsion fluid comprising: a) an oleaginous liquid; b) a non-oleaginous liquid; and c) a protonated amine having the structure

R-N⁺-H₃ B^" wherein R is a C₁ -C ₂ alkyl group, a Cj -C₂₂ alkenyl group, a C₃-C₈ cycloalkyl group substituted with a C₉-C] alkyl or alkenyl group, or a C -Cι₄ alkyl or alkenyl group substituted with a C₃-C₈ cycloalkyl group and B^" is the conjugate base of a water soluble acid and wherein said protonated amine is in an amount sufficient to stabilize said invert emulsion.

2. The invert emulsion fluid of claim 1 wherein said oleaginous liquid comprises from about 30 to about 99 percent by volume of said fluid.

3. The invert emulsion fluid of claim 1 or 2 wherein said oleaginous liquid is diesel oil, mineral oil, a synthetic oil, or a mixture thereof.

4. The invert emulsion fluid of claims 1 , 2, or 3 wherein said oleaginous liquid comprises from about 5 to about 100 percent by volume of an aliphatic ester, an aliphatic ether, an aliphatic acetal, a dialkylcarbonate, a hydrocarbon, or a mixture thereof.

5. The invert emulsion fluid of claim 1 wherein said non-oleaginous liquid is an acidic metal salt brine and comprises from about 1 to about 70 percent by volume of said invert emulsion fluid.

6. The invert emulsion fluid of claim 1 wherein R is an alkenyl group.

7. The invert emulsion fluid of claim 6 wherein R contains one double bond.

8. The invert emulsion fluid of claim 1 wherein said acid is an organic acid, an inorganic acid, or a mixture thereof.

9. The invert emulsion fluid of claim 8 wherein said organic acid is citric, acetic, formic, benzoic, salicyclic, oxalic, glycolic, lactic, glutaric, or carbonic acid.

10. The invert emulsion fluid of claim 8 wherein said inorganic acid is sulfuric, nitric, hydrofluoric, hydrochloric, or phosphoric acid.

11. An invert emulsion fluid comprising: a) an oleaginous liquid, said oleaginous liquid comprising from about 30 to about 99 percent by volume of said fluid; b) a non-oleaginous liquid, said non-oleaginous liquid comprising from about 1 to about 70 percent by volume of said fluid and wherein said non-oleaginous liquid is an acidic metal salt brine; and c) a protonated amine having a structure of: R-N⁺-H₃ B^" wherein R is a Cι₂-C ₂ alkyl group, a Cι₂-C₂ alkenyl group, a C₃-C₈ cycloalkyl group substituted with a C₉-Cι₄ alkyl or alkenyl group, or a C₉-Cι₄ alkyl or alkenyl group substituted with a C₃-C₈ cycloalkyl group and B^" is the conjugate base of a water soluble acid said protonated amine comprising from about 0.1 to 5.0 percent by weight per volume of drilling fluid of said fluid; and wherein said amine is present in an amount sufficient to stabilize said invert emulsion for use as a drilling fluid.

12. The invert emulsion fluid of claim 11 wherein said oleaginous liquid is diesel oil, mineral oil, a synthetic oil, or a mixture thereof.

13. The invert emulsion fluid of claim 11 wherein said oleaginous liquid further comprises from about 5 to about 99 percent by volume of an ester, an ether, an acetal, a di-alkylcarbonate, a hydrocarbons, or a mixture thereof.

14. The invert emulsion fluid of claim 11 wherein R is an alkenyl group.

15. The invert emulsion fluid of claim 14 wherein R contains one double bond.

16. The invert emulsion fluid of claim 11 wherein said acid is an organic acid, an inorganic acid, or a mixture thereof.

17. The invert emulsion fluid of claim 16 wherein said organic acid is citric, acetic, formic, benzoic, salicyclic, oxalic, glycolic, lactic, glutaric acid, or carbonic acid.

18. The invert emulsion fluid of claim 16 wherein said inorganic acid is sulfuric, nitric, hydrofluoric, hydrochloric, or phosphoric acid.

19. An invert emulsion fluid comprising: a) an oleaginous liquid selected from diesel oil, mineral oil, a synthetic oil, and a mixture thereof, said oleaginous liquid comprising from about 30 to about 99 percent by volume of said fluid; b) an aqueous non-oleaginous liquid is an acidic metal salt brine containing organic or inorganic salts dissolved therein, a liquid containing water-miscible organic compounds, or a mixture thereof, said non-oleaginous liquid comprising from about 1 to about 70 percent by volume of said liquid; and c) a protonated amine having the structure:

R-N⁺-H₃ B- wherein R is a C₁₂-C ₂ alkyl group, a C₁₂-C₂₂ alkenyl group, a C -C₈ cycloalkyl group substituted with a C₉-Cι alkyl or alkenyl group, or a C -C]₄ alkyl or alkenyl group substituted with a C₃-C₈ cycloalkyl group and B^" is the conjugate base of a water soluble acid said protonated amine comprising from about 0.1 to about 5.0 percent by weight per volume of drilling fluid of said fluid and said protonated amine is present in an amount sufficient to stabilize said invert emulsion for use as a drilling fluid.

20. An invert emulsion fluid comprising: a) an oleaginous liquid; b) an acidic metal salt brine; c) a suspending agent; and d) a protonated amine having the structure

R-N⁺-H₃ B^" wherein R is a Cι₂-C alkyl group, a Cj₂-C ₂ alkenyl group, a C₃-C₈ cycloalkyl group substituted with a C₉-Cj₄ alkyl or alkenyl group, or a C₉-Cι₄ alkyl or alkenyl group substituted with a C₃-C₈ cycloalkyl group and B^" is the conjugate base of a water soluble acid and wherein said protonated amine is in an amount sufficient to stabilize said invert emulsion. 21. An invert emulsion fluid of claim 20 wherein the suspending agent is selected from organophilic clay, oil soluble polymers, polyamide resins, polycarboxylic acids, fatty acid soaps and combinations thereof.

21. An invert emulsion fluid of claim 20 or 21 wherein the suspending agent is an organophilic clay.