EP0374229A1 - Emulsifiers for oil based drilling fluids - Google Patents

Emulsifiers for oil based drilling fluids

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Publication number
EP0374229A1
EP0374229A1 EP89906113A EP89906113A EP0374229A1 EP 0374229 A1 EP0374229 A1 EP 0374229A1 EP 89906113 A EP89906113 A EP 89906113A EP 89906113 A EP89906113 A EP 89906113A EP 0374229 A1 EP0374229 A1 EP 0374229A1
Authority
EP
European Patent Office
Prior art keywords
acid
oil
fatty acid
component
working fluid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP89906113A
Other languages
German (de)
French (fr)
Inventor
Jacqueline Anne Coates
John Martin Farrar
Margaret Helen Graham
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sandoz AG
Original Assignee
Sandoz AG
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Filing date
Publication date
Application filed by Sandoz AG filed Critical Sandoz AG
Publication of EP0374229A1 publication Critical patent/EP0374229A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/22—Amides or hydrazides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
    • C09K8/36—Water-in-oil emulsions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents

Definitions

  • the invention relates to the preparation of improved emulsifier additives for use in oil based drilling fluids and to products so obtained.
  • drilling fluid is circulated from tanks at the wellhead down the inside of the drill-pipe, through the bit and back up the annulus.
  • the fluids are subjected to a number of treatments designed to remove gases or solid materials such as drilled cuttings, sand, colloidal material, etc. from the fluid before being returned to the well via the mud tanks.
  • the properties of the drilling fluid change, due to a number of factors such as ingress of water or fine solids or temperature degradation of the components of the fluid.
  • this treatment generally involves the addition of chemicals.
  • Oil-based fluids are less prone to thermal degradation than water-based fluids and as a result are used to drill deep hot holes.
  • economics dictate that as much of the field as possible should be exploited from each platform.
  • This has led to an increase in the number of deviated wells and also to an increase in the maximum angle of deviation. The latter causes a marked increase in the torque required to maintain rotation of the drill-string.
  • Oil-based drilling fluids exhibit extremely good lubricity compared with water based fluids and have proved particularly effective in the drilling of deviated wells.
  • Drilling through hydratable shales has proved troublesome due to the swelling and sloughing of these formations on contact with aqueous drilling fluids.
  • the problem is common throughout the world and not only leads to wellbores which are out of gauge but also to torgue and stuck-pipe problems. Oil-based drilling fluids do not affect most shales and are ideally suited to drilling through these formations.
  • Oil- based drilling fluids are designed to give a filtrate consisting only of oil and since this is essentially native to the production formation, it does not lead to a reduction in permeability.
  • Aqueous fluids can cause loss of productivity due to pore contraction and blocking as a result of the hydration of clays.
  • Oil-based well-working fluids or muds can be classified as true oil muds and invert emulsion muds.
  • the former contain only a small amount of water whilst the latter may contain up to 40 X or more water as the dispersed phase of an invert (water-in-oil) emulsion.
  • Each of these fluids may contain a number of additives such as emulsifiers, viscosifiers, fluid loss reducing additives and various inorganic salts.
  • Emulsifiers are required to form a stable dispersion of water droplets in an oil phase (invert emulsion mud) and to maintain any solids, for example weighting materials such as barytes or solids encountered during drilling in an oil-wet state.
  • an emulsifier composition comprising
  • component 1 80-99 % of the reaction product (hereinafter defined as component 1) of
  • component i) one or two moles of an amide-amine having at least one free amino group or hydroxy alkyl amide having at least one hydroxy group (herein defined as component i); component i) being free of any imidazoline groups; and
  • component ii one to five moles of a dicarboxylic acid or an acid anhydride (preferably an acid anhydride) (hereinafter defined as component ii); and
  • component 2 all percentages being based on tne weight of actives in the emulsifiers.
  • an emulsifier according to the invention comprises 20-80 % of components 1 and 2 and 80-20 % of one or more solvents.
  • Preferred solvents include hydrocarbon paraffins (e.g. oils) such as diesel oil. Such solvents can be hydrocarbon drilling oil. Preferred components 1 contain at least one free acid group.
  • Preferred C 4-22 alkylphenol ethoxylates are t.butyl-, nonyl- and iso octyl - phenol ethoxylated with 4 to 15 moles of ethylene oxide.
  • Preferred C 8-22 alkyl benzene sulphonic acids are dodecylbenzene sulphonic acids.
  • Preferred straight chain alcohol ethoxylates are C 1-12 alkanols ethoxylated with 4 to 15 moles of ethylene oxide.
  • Preferred carboxymethylates are reaction products of an ethoxylated end/or propoxylated alcohol and chloroacetic acid, e.g. 1 mole C 8-22 alcohol ethoxylated with 4-12 moles of ethylene oxide, reacted with 1 mole of chloroacetic acid.
  • Preferred sulphosuccinates are reaction products of 1-2 moles of an alcohol or ethoxylated and/or propoxylated alcohol with 1 mole of maleic anhydride further reacted with sodium sulphite, e.g. 2 moles ethylhexanol with 1 mole of maleic anhydride and 1 mole of sodium sulphite.
  • an oil-based well working fluid comprising
  • the hydrocarbon drilling oil is diesel oil or a low toxicity drilling oil.
  • drilling oils are also known as oil muds as described in "The Oilman” April, 1983 pages 45-49 in an article entitled “Non-polluting Oil Muds” by J. Hall and P. Grange, the contents of which are incorporated herein by reference.
  • the brine is a calcium brine.
  • Well working fluids according to the invention may also include one or more compounds selected from the following: lime, viscosifiers (e.g. oleophilic bentonites), weighting agents (such as barytes), further fluid loss additives, dispersants, stabilizers and lost circulation additives (such as attapulgites) .
  • viscosifiers e.g. oleophilic bentonites
  • weighting agents such as barytes
  • further fluid loss additives such as barytes
  • component i) is an amide-amine, it is the reaction product of
  • diethylene triaraine with a C 1-22 alkanoic acid, a C 3-22 alkenoic acid, a dimer fatty acid, a trimer fatty acid or a monoether polyacid; or
  • component i) is an amide-amine it is the product of any one of formulae III to VII (in any of the isomeric forms)
  • each R 30 independently, is hydrogen, C 1-21 alkyl or C 2-21 alkenyl; or component i) when an amide-amine is preferably the product of reacting
  • reaction products of component i) are known or may be made from known compounds by known methods.
  • Preferred C 1-22 alkanoic acids and/or C 3-22 alkenoic acids include tall oil fatty acid (which contains oleic acid and linoleic acid).
  • a dimer fatty acid is of 24 to 44 carbon atoms.
  • a trimer fatty acid is of 36 to 66 carbon atoms.
  • Preferred monoether polyacids include oxidised tall oil which contains a compound of the formula VIII
  • component i) is hydroxyalkyl amide it is a compound of formula IX or X
  • R 3 is hydrogen or C 1-4 alkyl (preferably hydrogen); or R 3 is a group of the formula
  • Component 1 (e.g. the reaction products of components i) and ii) is often mixtures of products.
  • component 1 includes a compound selected from those of formulae XII to XVI (in any isomeric form) n
  • R 25 is -X-CO 2 H or
  • R 30 is as defined above; d is as defined above; is a di rect bond , C 1- 1 2 alkylene ; C 2 - 1 2 alkenylene ; -CH 2 -O-CH 2 ;
  • R 6 is hydrogen, C 1-4 alkyl or
  • Preferred dicarboxylic acids of component ii) are of the formula HOOC-Z-CO 2 H where Z is a direct bond, C 1-12 alkylene or C 2-12 alkenylene; more preferably the dicarboxylic acids of component ii) are selected from itaconic acid, maleic acid, succinic acid, glutonic acid and diglycollic acid.
  • Preferred acid anhydrides of component ii) are maleic anhydride, succinic anhydride, glutonic anhydride, diglycollic anhydride and itaconic anhydride.
  • Most preferred components 1 are those of formulae XII and XIII where R 25 is -X-CO 2 H and those of formulae XIII, XIV, XV and XVI.
  • An emulsifier of a well working fluid according to the invention is present in an amount to give a concentration, preferably of from 1 to 20 pounds per barrel(ppb), more preferably 2-10 ppb, based on the weight of the well working fluid.
  • dimer fatty acid and "trimer fatty acid” as used in this Specification mean, respectively, a dibasic acid resulting from condensation of two molecules of an unsaturated fatty acid or ester (dimerization) and a tribasic acid resulting from condensation of three molecules of an unsaturated fatty acid or ester (trimerization).
  • dimer fatty acid and "trimer fatty acid” as used in this Specification mean, respectively, a dibasic acid resulting from condensation of two molecules of an unsaturated fatty acid or ester (dimerization) and a tribasic acid resulting from condensation of three molecules of an unsaturated fatty acid or ester (trimerization).
  • Such products have been known for many years and have been used commercially since the late 1940's. They are discussed in detail in the monograph entitled "The Dimer Acids - The chemical and physical properties, reactions and applications of polymerized fatty acids", edited by Edward C.
  • dimer and trimer fatty acids are commercially prepared by thermal condensation of unsaturated fatty acids in the presence of a clay catalyst, e.g. montmorillonite clay, usually by a Diels-Alder type reaction.
  • Preferred starting materials for the dimer and trimer acids are C 12-22 alkenyl (preferably straight chain) monomeric fatty acids.
  • a particularly favoured source of such acids is tall oil fatty acid comprising oleic and linoleic acid in admixture with lesser amounts of palmitic and stearic acids and other saturated and unsaturated acids.
  • tall oil fatty acid comprising oleic and linoleic acid in admixture with lesser amounts of palmitic and stearic acids and other saturated and unsaturated acids.
  • individual unsaturated acids such as oleic or linoleic acid.
  • dimer acids usually result in mixtures which may contain varying amounts of monomeric by-products and starting materials as well as trimer and higher polymeric acids along with the dimer fatty acid. If desired the components of such mixtures may be separated, e.g. by distillation.
  • reaction mixture is then heated to 140°C and 36 g of water is removed by distillation.
  • the reaction is cooled and yields 637 g of a 2:1 amide of crude oleic acid and diethylene triamine.
  • R 30 is oleyl derived from crude oleic acid.
  • the reaction is then heated up to 160°C under reflux. Water is allowed to distill out when the temperature falls below 150°C. When 18 g of water has been removed the reaction is cooled and discharged to yield 343 g of the monoethanolamide.
  • R 30 is oleyl derived from tall oil fatty acid.
  • an oleic diethanolamide is prepared by reacting 300 g tall oil fatty acid with 52.5 parts diethanolamine, to produce the 2:1 adduct of formula 3b
  • the emulsifier composition of Example 1 is used to prepare 1 laboratory barrel of mud of the following composition:
  • the rheology and electrical stability of the invert mud is measured initially. After hot rolling for sixteen hours at 121°C (250°F), the above tests are repeated and HTHP (high temperature high pressure) fluid loss at 121°C is measured.
  • HTHP high temperature high pressure
  • Example 4 is repeated using an appropriate amount of the emulsifier composition of Example 2 (Example 5) or the emulsifier composition of Example 3 (Example 6).
  • the mud properties (especially emulsion stability and HTHP fluid loss properties) are good.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Lubricants (AREA)

Abstract

Un fluide de travail de puits à base d'huile comprend a) un émulsifiant comprenant le produit de réaction de i) une ou deux moles d'une amide-amine ou d'un hydroxyalkyle amide (ci-défini comme constituant i); avec ii) une à cinq moles d'un acide dicarboxylique ou d'un anhydride acide [de préférence un anhydre acide] (ci-défini comme constituant ii); b) une huile de forage hydrocarbure; et c) de la saumure de sodium, de calcium ou de magnésium.An oil-based well working fluid comprises a) an emulsifier comprising the reaction product of i) one or two moles of an amide-amine or hydroxyalkyl amide (herein defined as component i); with ii) one to five moles of a dicarboxylic acid or an acid anhydride [preferably an acid anhydride] (herein defined as component ii); b) a hydrocarbon drilling oil; and c) sodium, calcium or magnesium brine.

Description

EMULSIFIERS FOR OIL BASED DRILLING FLUIDS
The invention relates to the preparation of improved emulsifier additives for use in oil based drilling fluids and to products so obtained.
In the drilling of wells by the rotary drilling technique, drilling fluid is circulated from tanks at the wellhead down the inside of the drill-pipe, through the bit and back up the annulus. On reaching the wellhead the fluids are subjected to a number of treatments designed to remove gases or solid materials such as drilled cuttings, sand, colloidal material, etc. from the fluid before being returned to the well via the mud tanks. During the course of this circulation the properties of the drilling fluid change, due to a number of factors such as ingress of water or fine solids or temperature degradation of the components of the fluid. As a result the fluid is treated to regenerate the required properties and this treatment generally involves the addition of chemicals.
As the total reserves of oil diminish, it has become necessary to drill in areas which were previously inaccessible due to technological or economic difficulties. This has led to the development of increasing sophisticated drilling fluids and in particular to the widespread use of oil-based fluids. These have a number of advantages over conventional water-based drilling fluids. Oil-based fluids are less prone to thermal degradation than water-based fluids and as a result are used to drill deep hot holes. In order to drill effectively from offshore platforms, economics dictate that as much of the field as possible should be exploited from each platform. This has led to an increase in the number of deviated wells and also to an increase in the maximum angle of deviation. The latter causes a marked increase in the torque required to maintain rotation of the drill-string. Oil-based drilling fluids exhibit extremely good lubricity compared with water based fluids and have proved particularly effective in the drilling of deviated wells.
Drilling through hydratable shales has proved troublesome due to the swelling and sloughing of these formations on contact with aqueous drilling fluids. The problem is common throughout the world and not only leads to wellbores which are out of gauge but also to torgue and stuck-pipe problems. Oil-based drilling fluids do not affect most shales and are ideally suited to drilling through these formations.
In order to achieve a maximum production rate from a well it is important that the fluid, used to penetrate the production zone, and the subsequent completion fluid do not damage the formation.
Oil- based drilling fluids are designed to give a filtrate consisting only of oil and since this is essentially native to the production formation, it does not lead to a reduction in permeability. Aqueous fluids can cause loss of productivity due to pore contraction and blocking as a result of the hydration of clays.
Oil-based well-working fluids or muds can be classified as true oil muds and invert emulsion muds. The former contain only a small amount of water whilst the latter may contain up to 40 X or more water as the dispersed phase of an invert (water-in-oil) emulsion. Each of these fluids may contain a number of additives such as emulsifiers, viscosifiers, fluid loss reducing additives and various inorganic salts.
Emulsifiers are required to form a stable dispersion of water droplets in an oil phase (invert emulsion mud) and to maintain any solids, for example weighting materials such as barytes or solids encountered during drilling in an oil-wet state.
According to the invention, there is provided an emulsifier composition comprising
1) 80-99 % of the reaction product (hereinafter defined as component 1) of
i) one or two moles of an amide-amine having at least one free amino group or hydroxy alkyl amide having at least one hydroxy group (herein defined as component i); component i) being free of any imidazoline groups; and
ii) one to five moles of a dicarboxylic acid or an acid anhydride (preferably an acid anhydride) (hereinafter defined as component ii); and
2) 1-20 % of one of more compounds selected from dimer acids,
C8-22 alkyl benzenesulphonic acids, naphthenic acids, tall oil, oxidised tall oil, C4-22 alkylphenol ethoxylates, straight chain alcohol ethoxylates, carboxymethylates and sulphosuccinates,
(hereinafter defined as component 2) all percentages being based on tne weight of actives in the emulsifiers.
Preferably an emulsifier according to the invention comprises 20-80 % of components 1 and 2 and 80-20 % of one or more solvents.
Preferred solvents include hydrocarbon paraffins (e.g. oils) such as diesel oil. Such solvents can be hydrocarbon drilling oil. Preferred components 1 contain at least one free acid group.
Preferred C4-22 alkylphenol ethoxylates are t.butyl-, nonyl- and iso octyl - phenol ethoxylated with 4 to 15 moles of ethylene oxide.
Preferred C8-22 alkyl benzene sulphonic acids are dodecylbenzene sulphonic acids. Preferred straight chain alcohol ethoxylates are C1-12 alkanols ethoxylated with 4 to 15 moles of ethylene oxide.
Preferred carboxymethylates are reaction products of an ethoxylated end/or propoxylated alcohol and chloroacetic acid, e.g. 1 mole C8-22 alcohol ethoxylated with 4-12 moles of ethylene oxide, reacted with 1 mole of chloroacetic acid.
Preferred sulphosuccinates are reaction products of 1-2 moles of an alcohol or ethoxylated and/or propoxylated alcohol with 1 mole of maleic anhydride further reacted with sodium sulphite, e.g. 2 moles ethylhexanol with 1 mole of maleic anhydride and 1 mole of sodium sulphite.
Further according to the invention, there is provided an oil-based well working fluid comprising
a) 1-5 % of an emulsifier composition according to the invention b) 40-97 % of a hydrocarbon drilling oil; and c) 2-60 % of a sodium, calcium or magnesium brine,
all percentages being by weight of the well working fluid.
Preferably the hydrocarbon drilling oil is diesel oil or a low toxicity drilling oil. Such drilling oils are also known as oil muds as described in "The Oilman" April, 1983 pages 45-49 in an article entitled "Non-polluting Oil Muds" by J. Hall and P. Grange, the contents of which are incorporated herein by reference.
Preferably the brine is a calcium brine.
Well working fluids according to the invention may also include one or more compounds selected from the following: lime, viscosifiers (e.g. oleophilic bentonites), weighting agents (such as barytes), further fluid loss additives, dispersants, stabilizers and lost circulation additives (such as attapulgites) .
Preferably when component i) is an amide-amine, it is the reaction product of
a) ethylene diamine with a C1-22 alkanoic acid, a C3-22 alkenoic acid, a dimer fatty acid, a trimer fatty acid or a monoether polyacid; or
b) diethylene triaraine with a C1-22 alkanoic acid, a C3-22 alkenoic acid, a dimer fatty acid, a trimer fatty acid or a monoether polyacid; or
c) triethylene tetraamine with an C1-22 alkanoic acid, C3-22 alkenoic acid, a dimer fatty acid, a trimer fatty acid or a monoether polyacid; or
d) tetraethylene pentamine with a C1-22 alkanoic acid, a C3-22 alkenoic acid, a dimer fatty acid, a trimer fatty aeid or a monoether polyacid.
Preferably in the reaction to prepare the above reaction products, 1 to 3 moles of amine is used, depending on the number of carboxy groups present.
Preferably in the reaction to prepare the above reaction products, 1 to 4 moles of acid is used, depending on the amine present.
More preferably when component i) is an amide-amine it is the product of any one of formulae III to VII (in any of the isomeric forms)
ε where each R30 independently, is hydrogen, C1-21 alkyl or C2-21 alkenyl; or component i) when an amide-amine is preferably the product of reacting
1 to 3 moles of ethylene diamine with 1 mole of a dimer fatty acid or a trimer fatty acid ; or
1 to 3 moles of diethylene triamine with 1 or 2 moles of a dimer fatty acid or a trimer fatty acid; or
1 to 3 moles of triethylene tetraamine with 1 to 3 moles of an a dimer fatty acid or a trimer fatty acid ; or
1 to 3 moles of tetraethylene pentamine with 1 to 4 moles of a dimer fatty acid or a trimer fatty acid.
The reaction products of component i) are known or may be made from known compounds by known methods.
Preferred C1-22 alkanoic acids and/or C3-22 alkenoic acids include tall oil fatty acid (which contains oleic acid and linoleic acid).
Preferably a dimer fatty acid is of 24 to 44 carbon atoms. Preferably a trimer fatty acid is of 36 to 66 carbon atoms.
Preferred monoether polyacids include oxidised tall oil which contains a compound of the formula VIII
Preferably when component i) is hydroxyalkyl amide it is a compound of formula IX or X
where R3 is hydrogen or C1-4alkyl (preferably hydrogen); or R3 is a group of the formula
in which each d, independently, is an integer from 1 to 15 inclusive; each R4, independently, is hydrogen or C1-4 alkyl; and each R5 independently has one of the significances of R4; and R30 is as defined above.
Component 1 (e.g. the reaction products of components i) and ii) is often mixtures of products. Preferably component 1 includes a compound selected from those of formulae XII to XVI (in any isomeric form) n
where R25 is -X-CO2H or
where R30 is as defined above; d is as defined above; is a di rect bond , C 1- 1 2 alkylene ; C2 - 1 2 alkenylene ; -CH2 -O-CH 2;
or and R6 is hydrogen, C1-4 alkyl or
X is preferably Xa where Xa is -CH=CH-.
Preferred dicarboxylic acids of component ii) are of the formula HOOC-Z-CO2H where Z is a direct bond, C1-12alkylene or C2-12alkenylene; more preferably the dicarboxylic acids of component ii) are selected from itaconic acid, maleic acid, succinic acid, glutonic acid and diglycollic acid.
Preferred acid anhydrides of component ii) are maleic anhydride, succinic anhydride, glutonic anhydride, diglycollic anhydride and itaconic anhydride.
Most preferred components 1 are those of formulae XII and XIII where R25 is -X-CO2H and those of formulae XIII, XIV, XV and XVI.
An emulsifier of a well working fluid according to the invention is present in an amount to give a concentration, preferably of from 1 to 20 pounds per barrel(ppb), more preferably 2-10 ppb, based on the weight of the well working fluid.
The terms "dimer fatty acid" and "trimer fatty acid" as used in this Specification mean, respectively, a dibasic acid resulting from condensation of two molecules of an unsaturated fatty acid or ester (dimerization) and a tribasic acid resulting from condensation of three molecules of an unsaturated fatty acid or ester (trimerization). Such products have been known for many years and have been used commercially since the late 1940's. They are discussed in detail in the monograph entitled "The Dimer Acids - The chemical and physical properties, reactions and applications of polymerized fatty acids", edited by Edward C. Leonard, Humko Sheffield Chemical (1975) of which Chapter 1, "The General Charac teri za t i on o f Dimer Aci ds " , By Be rman and Loeb , i s i ncorporated herein by reference. As discussed in the aforementioned monograph, dimer and trimer fatty acids are commercially prepared by thermal condensation of unsaturated fatty acids in the presence of a clay catalyst, e.g. montmorillonite clay, usually by a Diels-Alder type reaction. Preferred starting materials for the dimer and trimer acids are C12-22 alkenyl (preferably straight chain) monomeric fatty acids. A particularly favoured source of such acids is tall oil fatty acid comprising oleic and linoleic acid in admixture with lesser amounts of palmitic and stearic acids and other saturated and unsaturated acids. However, it is also possible to use individual unsaturated acids, such as oleic or linoleic acid.
Commercial processes for producing dimer acids usually result in mixtures which may contain varying amounts of monomeric by-products and starting materials as well as trimer and higher polymeric acids along with the dimer fatty acid. If desired the components of such mixtures may be separated, e.g. by distillation.
A number of compounds of component (i) are described in EP 49494, the contents and preferences of which are incorporated by reference and GB Published Patent Application No. 2,135,321 B the contents and preferences of which are incorporated by reference.
In this Specification for the avoidance of doubt, where any symbol appears more than once in a formula, its significances are independent of one another, unless indicated to the contrary.
Furthermore where any group is capable of being linear or branched, it is linear or branched unless indicated to the contrary. The invention will now be illustrated by the following Examples in which all parts and percentages are by weight and all temperatures are in °C unless indicated to the contrary.
Example 1
103 g of diethylenetriamine is added to 570 g of a commercially available tall oil fatty acid under an atmosphere of nitrogen and the reaction temperature is maintained below 100 ºC.
The reaction mixture is then heated to 140°C and 36 g of water is removed by distillation. The reaction is cooled and yields 637 g of a 2:1 amide of crude oleic acid and diethylene triamine.
Under an atmosphere of nitrogen, 637 g of the 2:1 amide prepared above are heated to 80°C and 98 g of maleic anhydride are added at such a rate so as to keep the temperaυre below 100°C. When the addition is complete, the reaction is heated to 140°C for two hours. The reaction mixture is then cooled and discharged to yield 416.5 g of a compound of formula 1a
where R30 is oleyl derived from crude oleic acid.
To the compound of formula 1a,95 g of dodecylbenzene sulphonic acid are added together with 250 mis of odourless Kerosene to form the emulsifier composition of Example 1.
Example 2
Under an atmosphere of nitrogen, 61 g of monoethanolamine are added to 300 g of a commercial tall oil fatty acid.
The reaction is then heated up to 160°C under reflux. Water is allowed to distill out when the temperature falls below 150°C. When 18 g of water has been removed the reaction is cooled and discharged to yield 343 g of the monoethanolamide.
Under an atmosphere of nitrogen, 300 g of the alkanolamide prepared above, are heated to 80°C and 42.9 g of maleic anhydride are added at such a rate so as to keep the temperature below 100°C. The reaction mixture is then heated to 160°C under vacuum for six hours. The reaction is then cooled and discharged to yield 335 g of the compound of formula 2a
where R30 is oleyl derived from tall oil fatty acid.
To the compound of formula 2a, 80 g of oxidised tall oil and 200 mis of odourless Kerosene are added to form the emulsifier composi tion of Example 2.
Example 3
Similarly, an oleic diethanolamide is prepared by reacting 300 g tall oil fatty acid with 52.5 parts diethanolamine, to produce the 2:1 adduct of formula 3b
This is then further reacted with maleic anhydride, according to the method of Example 2, by heating 300 g of the amide above with 21.8 g maleic anhydride.
This yield 317.8 g of a compound of the formula 3a
To the compound of formula 3a, 40 g of oxidised tall oil and 40 g of dodecylbenzene sulphonic acid in 250 mis of odourless Kerosene are added to form the emulsifier composition of the Example 3.
Example 4
The emulsifier composition of Example 1 is used to prepare 1 laboratory barrel of mud of the following composition:
low toxic oil: 0.574 bbl water 0.205 bbl
Calcium Chloride 31.7 ppb
Organophillic Clay. 5.5 ppb
(Perchem DMB)
Barite (Barium Sulphate) 20.1 ppb
Lime 6 ppb and
Emulsifier composition 8 ppb
(ppb is pounds per barrel and bbl is barrels).
The rheology and electrical stability of the invert mud is measured initially. After hot rolling for sixteen hours at 121°C (250°F), the above tests are repeated and HTHP (high temperature high pressure) fluid loss at 121°C is measured.
Examples 5 and 6
Example 4 is repeated using an appropriate amount of the emulsifier composition of Example 2 (Example 5) or the emulsifier composition of Example 3 (Example 6).
The mud properties (especially emulsion stability and HTHP fluid loss properties) are good.

Claims

CLAIMS:
1. An emulsifier composition comprising
1) 80-99 % of the reaction product (herein defined as component 1) of
i) one or two moles of an amide-amine having at least one free amino group or a hydroxyalkyl amide having at least one free hydroxy group (herein defined as componenti); component i) being free of any imidazoline groups; and
ii) one to five moles of a dicarboxylic acid or an acid anhydride (herein defined as component ii); and
2) 1-20 % of one or more compounds selected from dimer acids, C8-22 alkylbenzene sulphonic acids, naphthenic acids, tall oil, oxidised tall oil, C4-22 alkylphenol ethoxylates straight chain alcohol ethoxylates, carboxymethylates and sulphosuccinates (hereinafter defined as component 2); all percentages of the emulsifier being based on the weight of actives in the emulsifier.
2. An emulsifier composition according to Claim 1 comprising
20-80 % of components 1 and 2 and 80-20 % of a solvent
all percentages being based by weight of the emulsifier composition.
3. An oil based well- working fluid comprising
a) 1-5 % of an emulsifier according to Claim 1 or Claim 2 b) 40-97 % of a hydrocarbon drilling oil; and c) 2-60 % of a sodium, calcium or magnesium brine.
all percentages being by weight of the well working fluid.
4. An oil based well- working fluid according to Claim 3 in which the hydrocarbon drilling oil is diesel oil or a low toxicity drilling oil.
5. An oil based well- working fluid according to Claim 3 cr 4 in which the brine is a calcium brine.
6. An oil based well- working fluid according to any one of claims 3 to 5 in which component i) is the reaction product of
a) ethylene diamine with a C1-22 alkanoic acid, a C3-22 alkenoic acid, a dimer fatty acid, a trimer fatty acid or a monoether polyacid; or
b) diethylene triamine with a C1-22 alkanoic acid, a C3-22 alkenoic acid, a dimer fatty acid, a trimer fatty acid or a monoether polyacid; or
c) triethylene tetraamine with an C1-22 alkanoic acid, C3-22 alkenoic acid, a dimer fatty acid, a trimer fatty acid or a monoether polyacid; or
d) tetraethylene pentamine with a C1-22 alkanoic acid, a C3-22 alkenoic acid, a dimer fatty acid, a trimer fatty acid or a monoether polyacid.
7. An oil based well- working fluid according to Claim 6 in which any dimer fatty acid is of 24 to 44 carbon atoms and any trimer fatty acid is of 36 to 66 carbon atoms; and
any polyether acid contains a compound of the formula VIII 3
8. An oil based well- working fluid according to any one of claims 3 to 7 in which the dicarboxylic acids of component ii) are of the formula HOOC-Z-CO2H where Z is a direct bond, C1-12alkylene or C2-12alkenylene.
9. An oil based well- working fluid according to Claim 8 in which the dicarboxylic acids of component ii) are selected from itaconic acid, maleic acid, succinic acid, glutonic acid and diglycollic acid and the acid anhydrides of component ii) are selected from maleic anhydride, succinic anhydride, glutonic anhydride, diglycollic anhydride and itaconic anhydride.
10. An oil based well- working fluid according to any one of the Claims 3 to 9 in which the emulsifier composition is present in an amount to give a concentration of from 1 to 20 pounds per barrel(ppb).
EP89906113A 1988-05-16 1989-05-12 Emulsifiers for oil based drilling fluids Withdrawn EP0374229A1 (en)

Applications Claiming Priority (2)

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GB8811574 1988-05-16
GB888811574A GB8811574D0 (en) 1988-05-16 1988-05-16 Improvements in/relating to organic compounds

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WO (1) WO1989011516A1 (en)

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GB8811574D0 (en) 1988-06-22

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