WO2002020691A2 - Utilisation de desemulsionneurs hydrosolubles permettant de separer des huiles d'hydrocarbures et des argiles - Google Patents

Utilisation de desemulsionneurs hydrosolubles permettant de separer des huiles d'hydrocarbures et des argiles Download PDF

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Publication number
WO2002020691A2
WO2002020691A2 PCT/US2001/027408 US0127408W WO0220691A2 WO 2002020691 A2 WO2002020691 A2 WO 2002020691A2 US 0127408 W US0127408 W US 0127408W WO 0220691 A2 WO0220691 A2 WO 0220691A2
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Prior art keywords
clay
hydrocarbon oil
dispersion
group
water
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PCT/US2001/027408
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English (en)
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WO2002020691A3 (fr
Inventor
Jeffrey M. Carey
Alvin E. Haas
Thomas M. Keir
John S. Manka
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The Lubrizol Corporation
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Publication date
Application filed by The Lubrizol Corporation filed Critical The Lubrizol Corporation
Priority to MXPA03001866A priority Critical patent/MXPA03001866A/es
Priority to EP01968445A priority patent/EP1325208A2/fr
Priority to CA002419953A priority patent/CA2419953A1/fr
Priority to US10/344,911 priority patent/US20030222026A1/en
Priority to AU2001288691A priority patent/AU2001288691A1/en
Publication of WO2002020691A2 publication Critical patent/WO2002020691A2/fr
Publication of WO2002020691A3 publication Critical patent/WO2002020691A3/fr

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    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
    • E21B21/06—Arrangements for treating drilling fluids outside the borehole
    • E21B21/068—Arrangements for treating drilling fluids outside the borehole using chemical treatment

Definitions

  • FIELD OF INVENTION Dispersions of particulate matter in hydrocarbon oils are used in a variety of applications (such as oil well drilling fluids) where a high viscosity lubricious composition is desired. At some point in the life of a drilling mud it has to be disposed of or recycled due to contamination or the completion of drilling in a particular location. The presence of emulsified water, inorganic particulate, hydrocarbons, etc. in a single high viscosity mixture makes reclamation of components difficult or disposal environmentally risky. Two methods of separating the solids from the hydrocarbon oil phase are set forth.
  • Drilling fluids are available in a variety of forms including water based muds, oil based muds, and muds using a combination of oil and water.
  • the muds become contaminated with debris removed by the drilling bits and with liquids (water, brines, etc.) that enter the hole from above or from liquids that leach into the hole from deposits in the ground.
  • the mud composition can change due to liquid contaminants.
  • Many of the solid contaminants can be removed by screening or other mechanical separations based on density or particle size. Mechanical separation of oversized solid material (drilling debris) typically takes with it a liquid layer of the drilling mud which generally is removed before the solid material is discarded.
  • a simple mechanical separation of such clay from the oil generally cannot remove all of the trapped oil between the layers of the clay.
  • Simple dilution of a spent drilling mud with water or oil generally generates more waste material with only a slight decrease in viscosity.
  • Emulsified water or brine that may be present in the drilling mud further complicates the separation process and may build viscosity.
  • HLB hydrophile-lipophile balance
  • the high HLB surfactant can be characterized by its chemical structure and the fact that it has high solubility in water (e.g. at least soluble to 5 g/100 g of water). The separation of these three layers from an oil based drilling mud can be expedited or facilitated by mixing and centrifugation of the mixture.
  • While a high HLB surfactant of the disclosed structure will consistently break dispersions of clay in hydrocarbon oil with the use of a centrifuge, it is desirable in another embodiment to break the dispersion and separate a majority of the clay or other fine particle inorganic matter from the hydrocarbon without the initial used of a centrifuge to expedite the separation.
  • a process using a blend of the high HLB surfactant and a surface active compound comprising the ester/salt reaction product of an alkenyl substituted succinic anhydride or similarly substituted succinic acid with a dialkylalkanolamine has been found to effectively break the dispersion of clay in hydrocarbon oil into three layers (top oil layer, middle water layer, and bottom clay layer) without the need for a centrifuge for the initial crude separation.
  • significant amounts of the recovered water phase can be recycled and used to break addition samples of clay dispersed in hydrocarbon oil, optionally with some addition high HLB surfactant and, in the second embodiment, the surface active agent to replace lost surfactant and lost surface active agent.
  • both the recovered water and oil phase can be recycled and used to break additional dispersions of clay in hydrocarbon oil. Recycling saves not only the water and oil phases but also saves significant amount of the high HLB surfactant and surface active agent.
  • the two liquid layers and any flock layers therein or there between can be centrifuged (or other mechanical forces applied) to further purify the hydrocarbon oil layer, water layer or clay (inorganic) layer.
  • the present invention provides a method for destabilizing an oil based dispersion of inorganic material in hydrocarbon oil, comprising:
  • each R is independently a hydrocarbyl group containing at least 8 carbon atoms, n is at least 1, W is a group containing at least 6 carbon atoms and at least one ether linkage for every 6 carbon atoms thereof, and each X is selected from the group consisting of
  • each Y is independently -O- or -NR'-
  • each Z is independently OM or NR' 2
  • each R' is independently hydrogen or a C ⁇ to C 18 alkyl group
  • the present invention further provides surfactants suitable for such use, including a composition represented by the structure
  • R is independently a hydrocarbyl group containing at least 8 carbon atoms
  • W is a group containing at least 6 carbon atoms and at least one ether linkage for every 6 carbon atoms thereof, having no unreacted amino groups and where X is selected from the group consisting of
  • Y is -O- or -NR'-
  • the second embodiment also provides for inclusion of a surface active agent comprising the half ester of the reaction of an alkenyl substituted succinic anhydride or similarly substituted succinic acid reacted with a dialkylalkanolamine in the process for breaking the emulsion.
  • a surface active agent comprising the half ester of the reaction of an alkenyl substituted succinic anhydride or similarly substituted succinic acid reacted with a dialkylalkanolamine in the process for breaking the emulsion.
  • a hydrocarbon solvent which can be the same as the hydrocarbon oil, helps separate the hydrocarbon oil from the clay and break the dispersion.
  • the process of the second embodiment is preferably set up as a continuous process where the water rich phases and hydrocarbon oil and/or solvent phases are reused at least several times in breaking additional dispersions of clay in hydrocarbon solvent.
  • the water and hydrocarbon oil recovered are reused significant amounts of the high HLB surfactant and the surface active agent would be carried back into the process minimizing the additional amounts needed in subsequent batches.
  • the byproducts of the process would be recovered hydrocarbon oil and a solid clay component with significantly reduced hydrocarbon oil content.
  • hydrocarbon oil is used in its common meaning that the component is a liquid at room temperature and is primarily composed of hydrogen and carbon atoms. It may include unsaturation and single or multiple aromatic rings. It may include some small percentage of atoms other than carbon and hydrogen e.g. less than 5 wt.%, more desirably less than 2 wt.% and preferably less than 1 wt.% of atoms other than carbon and hydrogen. While commercially important hydrocarbon fluids are often obtained as petroleum distillates, the hydrocarbon oil of this invention may be other than a petroleum distillate.
  • the hydrocarbon oil of this invention may be a hydrogenated petroleum distillate, hydrocracked petroleum distillate, or even an alpha olefin polymer. It may be a paraffinic oil such as described in U.S. 6,096,690. Alternatively it may be a diesel fuel.
  • the aromatic component of diesel fuel has a toxic effect on some marine life and preferred diesel fuels have an aromatic content of less than 3, more desirably less than 2 and preferably less than 1 wt.% aromatic.
  • the hydrocarbon oil has a viscosity of less than 5 centapoise at 25 °C and more preferably less than 1.5 centapoise. Desirably the hydrocarbon oil has a minimum flash point above 60°C.
  • hydrocarbon solvent used to facilitate separation in the second embodiment can be a hydrocarbon oil as described above or another hydrocarbon chemical.
  • a hydrocarbon solvent with a lower flash point than the hydrocarbon oil used in the dispersion can be tolerated in the process.
  • the surfactant can be represented by the structure (R-X-) n -W.
  • the expression "represented by the structure” is meant to include obvious variants and equivalent of a given structure, including isomers, tautomers, and the like.
  • each R is independently a hydrocarbyl group containing at least 8 carbon atoms, and preferably up to 40 carbon atoms.
  • Preferably each R is an alkyl or alkenyl group of 12 to 32, or more preferably 16 to 18 carbon atoms.
  • the R groups are intended to provide a measure of hydrophobic character to the surfactant molecule.
  • each X is a carbonyl-containing linking group, represented by one or more of the structures
  • each Y is independently -O- or -NR'-
  • each Z is independently OM or NR 2
  • each R' is independently hydrogen or a Ci to C 18 alkyl group
  • M is hydrogen, a monovalent metal or one valence of a polyvalent metal, a quaternary ammonium ion, a Ci to C 18 alkyl group, or -(CH CHR"O) a -H, R" is hydrogen or methyl, and a is 1 to 40.
  • X is a structure containing two carboxylic moieties, that is, a succinic or maleic acid-type structure.
  • Y is NR', or optionally NH.
  • Z is OM and preferably M is a monovalent metal, preferably an alkali metal, more preferably sodium.
  • each X group is represented by the structure
  • Alkyl and alkenyl-substituted succinamides are well known materials which have been set forth, i.e., in U.S. 4,664,834. They can be prepared by, first, reacting an olefin (providing the R group) with the desired unsaturated carboxylic acid such as fumaric acid or a derivative of such an acid such as maleic anhydride at a temperature in the range of, for example, 160°C to 240°C, preferably 185°C to 210°C. Generally these reactions are conducted at an atmospheric pressure, although elevated pressures can also be used. Free radical inhibitors (e.g., t-butyl catechol) can be used to reduce or prevent the formation of polymeric by-products. Further details can be found in Benn et al.,
  • n is at least 1 but is normally 2 or more, preferably
  • W is a mono- or polyvalent group.
  • the W group of the surfactant is believed to provide a measure of hydrophilic character to the molecule.
  • the group W is preferably a polyvalent group, normally a divalent group, so that n in the above formula is normally 2.
  • the W group contains at least 6 carbon atoms, and preferably 20 to 300 carbon atoms, more preferably 40 to 200 carbon atoms, and moreover contains at least one ether linkage for every 6 carbon atoms, and preferably for every 4 carbon atoms.
  • the group W preferably comprises polymerized ethylene oxide monomers and propylene oxide monomers. In one embodiment, W is represented by the structure
  • n is at least 2 and each R" is independently hydrogen or methyl. That is, monomer units derived from ethylene, propylene, or mixtures thereof can be used.
  • W is represented by the structure
  • a and c are integers which together equal 2 to 20 (preferably 3 to 20) and b is an integer in the range of 5 to 80 (preferably 5 or 10 to about 30 or 40).
  • the reactant used to form the W group is terminated by amine functionality, to provide the amides characteristic of the preferred X groups, above.
  • W then represents the central moiety of an amine- terminated poly(oxyalkylene).
  • Preferred examples of such amine terminated materials can be described as alpha, omega diaminopolypropyleneoxide-capped poly(oxyethylene)s, when n is 2. If n is 1, W would be a corresponding monoamino polyoxyalkylene moiety, the non-nitrogen terminated end of which would normally be terminated with a nonreactive group such as an alkyl (e.g., methyl, ethyl, propyl) group. It is also possible that additional amino groups are present within the structure of W.
  • alkyl e.g., methyl, ethyl, propyl
  • HuntsmanTM XTJ-502 also referred to as JeffamineTM ED- 2003
  • JeffamineTM ED- 2003 which is an alpha,omega diamino poly(oxyalkylene) is particularly preferred.
  • a preferred surfactant for use in the present invention is a sodium salt represented by the structure
  • a and c are integers which together equal 4 to 6
  • c is a positive integer
  • b is an integer in the range of 5 or 10 to about 30 to 40, and more preferably about 10 to 30.
  • Such materials have good resistance to Ca ion (water hardness) and low sorption onto soil.
  • W can be a monovalent moiety containing at least 20 carbon atoms and at least one ether linkage for every 6 carbon atoms thereof, having no unreacted amino groups.
  • One species of W, in this case, is represented by the structure
  • a preferred species of W is that represented by the structure
  • each R" is independently hydrogen or methyl
  • R'" is hydrogen or a Ci to C 4 alkyl group
  • n is at least 5.
  • the ratio of the hydrogen to methyl groups of R" is 3:1 to 8:1, preferably 5:1 to 8:1, (e.g., about 19:3)
  • R'" is a methyl group
  • n is 5 to 42, preferably 8 to 42, or 15 to 42, or more preferably 20 to 24 (e.g., about 22).
  • the preferred surfactant can be described as a reaction product of a hydrocarbyl-substituted succinic anhydride or a reactive equivalent thereof (e.g., diacid form of anhydride) with at least one water-dispersible amine-terminated poly(oxyalkylene).
  • the components are typically prepared by reacting the hydrocarbyl-substituted succinic anhydride with the amine-terminated poly(oxyalkylene) at temperatures of 60°C to about 160°C, preferably 120°C to 160°C.
  • the ratio of the anhydride to the diamine is typically 0.1:1 to 8:1, preferably 1:1 to 4:1, and more preferably about 2:1.
  • the resulting material is normally an amid/acid, that is, a half amide.
  • the product can be neutralized with a basic material using methods well known in the art, to form a salt, preferably a sodium salt. Such materials and their preparation are described in greater detail in U.S. Patent 4,664,834.
  • the above-described high HLB surfactant is used in the application (e.g. in water, clay, hydrocarbon oil etc.) generally at a concentration of about 0.5, 1, or 5 to about 50 weight percent, and preferably from about 0.5 or 1 to about 10 or 20 wt.% based on the weight of the dispersion of clay in hydrocarbon oil, water, high HLB surfactant and optional surface active agent.
  • the high HLB surfactant is made up in water or another polar diluent at a concentration about 10 to 40 or 50 wt. percent and more preferably about 15 to 35 percent (based on active chemical).
  • Diluents other than water include polar solvents such as C ⁇ -C 4 alcohols, acetone, etc.
  • the diluent e.g. water phase is desirably at least 50 wt.% of the blend, more desirably at least 75 wt.% of the blend.
  • the amounts can be adjusted, as needed, to optimize performance for a particular drilling fluid.
  • the surfactant can be dissolved or otherwise dispersed in the water; preferably the surfactant is dissolved.
  • the surfactant in water can be recycled along with some of the water recovered as the water phase from the separation of the drilling fluid into three components.
  • the surface active agent which can be used in addition to the high HLB surfactant, is comprised of the ester salt (also known as a half ester salt) of the reaction of an alkenyl substituted succinic acid or succinic anhydride reacted with a dialkylalkanolamine or an alkyldialkanolamine or similar amines having at least one alkanol group.
  • ester salt also known as a half ester salt
  • the succinic acids and anhydrides are described as hydrocarbyl- substituted carboxylic acids, anhydrides, esters and amide derivatives thereof.
  • the above-surface active agent is used in the application (e.g. in water, clay, hydrocarbon oil etc.) generally at a concentration of about 0.5, 1, or 5 to about 50 weight percent, and preferably from about 0.5 or 1 to about 10 or 20 wt.% based on the weight of the dispersion of clay in hydrocarbon oil, water, high HLB surfactant and optional surface active agent.
  • Reactive equivalents of the alpha-beta olefinically unsaturated carboxylic acid reagents include the anhydride, ester or amide functional derivatives of the foregoing acids.
  • a preferred alpha-beta olefinically unsaturated carboxylic acid is maleic anhydride.
  • the succinic agent of this invention is a hydrocarbyl- substituted succinic acid or anhydride represented correspondingly by the formulae
  • R is hydrocarbyl group of about 12 to about 16 or 32 carbon atoms.
  • R in formula (C-I-3) is a hexadecenyl group.
  • the “succinic groups” are those groups characterized by the structure
  • X and X' are the same or different provided that at least one of X and X' is such that the substituted succinic agent can function as a carboxyl acylating agent. That is, at least one of X and X' must be such that the substituted succinic agent can form, for example, half ester salts with dialkylalkanolamines, and otherwise function as a conventional carboxylic acid acylating agent. Transesterification and transamidation reactions are considered, for purposes of this invention, as conventional acylating reactions.
  • X and/or X' is usually -OH, -O-hydrocarbyl, -O-M + where M + represents one equivalent of a metal, ammonium or amine cation, -NH 2 , -CI, -Br, and together, X and X' can be -O- so as to form the anhydride.
  • M + represents one equivalent of a metal, ammonium or amine cation, -NH 2 , -CI, -Br, and together, X and X' can be -O- so as to form the anhydride.
  • the specific identity of any X or X 1 group which is not one of the above is not critical so long as its presence does not prevent the remaining group from entering into acylation reactions.
  • X and X' are each such that both carboxyl functions of the succinic group (i.e., both -C(O)X and -C(O)X') can enter into acylation reactions.
  • One of the unsatisfied valences in the grouping of formula (C-I-4) forms a carbon-carbon bond with a carbon atom in the hydrocarbyl substituent group. While other such unsatisfied valence may be satisfied by a similar bond with the same or different substituent group, all but the said one such valence is usually satisfied by hydrogen; i.e., -H.
  • the succinic groups correspond the formula
  • R and R' are each independently selected from the group consisting of -OH, -CI, -O-lower alkyl, or when taken together, R and R' form -O-.
  • the succinic group is a succinic anhydride group. All the succinic groups in a particular succinic acylating agent need not be the same, but they can be the same. In one embodiment, the succinic groups correspond to CH — COOH
  • hydrocarbyl-substituted succinic agents wherein the succinic groups are the same or different is within the ordinary skill of the art and can be accomplished through conventional procedures such as treating the hydrocarbyl substituted succinic acylating agents themselves (for example, hydrolyzing the anhydride to the free acid or converting the free acid to an acid chloride with thionyl chloride) and/or selecting the appropriate maleic or fumaric reactants.
  • Partial esters of the succinic acids or anhydrides can be prepared simply by the reaction of the acid or anhydride with a dialkylalkanolamine.
  • Particularly useful alkyl groups in the dialkyl and alkanol are the lower alkyl groups of 1 to 6 carbon atoms and the lower alkanol groups of 1 to 6 carbon atoms such as methyl, ethyl, and propyl along with alcohols such as methanol, ethanol, allyl alcohol, propanol, cyclohexanol, etc.
  • Preferred alkyl groups are methyl and ethyl and a preferred alkanol is ethanol.
  • Esterification reactions are usually promoted by the use of alkaline catalysts such as sodium hydroxide or alkoxide, or an acidic catalyst such as sulfuric acid or toluene sulfonic acid.
  • alkaline catalysts such as sodium hydroxide or alkoxide
  • an acidic catalyst such as sulfuric acid or toluene sulfonic acid.
  • a partial ester or half ester can be represented by the formula
  • the alkylene substituted succinic anhydride of the present invention can also be made via a direct alkylation procedure that does not use chlorine.
  • the product of the reaction between any residual COOH groups of the succinic group and any amine such as the amine portion of dialkylalkanolamine comprises at least one salt.
  • This salt can be an internal salt involving residues of a molecule of the succinic group, and the amine portion of the dialkylalkanolamine attached to the succinic group via an ester linkage, wherein one of the carboxyl groups becomes ionically bound to a nitrogen atom within the same group; or it may be an external salt wherein the ionic salt group is formed with a nitrogen atoms is not part of the same molecule.
  • the product of the reaction between succinic group and alkanolamines can also include other compounds such as a half ester and half salt, i.e., an ester/salt.
  • the surface active component is made by reacting a linear or branched alkenyl substituted succinic anhydride or diacid with dialkylalkanolamine in a mole ratio of about 1: about (0.4-1.25) respectively, and in one embodiment in an mole ratio of about 1:(0.8-1.2) respectively.
  • surface active component is made by reacting a hexadecenyl succinic anhydride with N,N-dimethylethanolamine in an equivalent ratio of about 1: about (0.4-0.6) (which also corresponds to a mole ratio of about 1: about (0.8-1.2)) respectively, and in one embodiment in an equivalent ratio of about
  • one or more additional surfactants can be used along with the above-described materials.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art.
  • hydrocarbyl groups examples include:
  • hydrocarbon substituents that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form an alicyclic radical);
  • aliphatic e.g., alkyl or alkenyl
  • alicyclic e.g., cycloalkyl, cycloalkenyl
  • aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form an alicyclic radical);
  • substituted hydrocarbon substituents that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
  • hetero substituents that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms.
  • Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
  • no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.
  • the drilling fluids of this invention typically include a particulate material, usually inorganic, added to build viscosity and density; an emulsifier(s) to help suspend particulate material and aid wetting; wetting agents to help wetting of the variety of substrates that the fluid comes in contact with; viscosifiers that help increase or control fluid viscosity; fluid loss control agents; proppants; and optionally water.
  • the particulate material can be any material that is readily dispersed in hydrocarbon oil, optionally with an emulsifier or wetting agent.
  • hydrocarbon oil optionally with an emulsifier or wetting agent.
  • it is a clay due to the low cost of clays and their high density relative to water and hydrocarbon oil. While water has a density of about 8 pounds per gallon, drilling fluids often have densities of values such as 18 pounds per gallon due to the addition of high density materials such as clays. This higher density may help stabilize the relative position of fluids in the drilling operation and help the pumping of the drilling debris up from the bottom of the well.
  • the particulate material e.g.
  • clay is at least 5 wt.%, more desirably at least 10 wt.% and preferably from about 10 or 20 to about 50 wt.% of the drilling fluid.
  • the particulate material is or is predominantly clay.
  • the clay may include organically modified clay which is generally referred to as clay modified to increase their compatibility and swelling with oils. These are well known to the art.
  • Water and/or brine may be present in the drilling fluid. Its amount can vary from about 0 to about 40wt.% and more desirably from about 5 to about 35 wt.% based on the weight of the clay dispersed in hydrocarbon oil.
  • the water can include from about 0 to about 55 wt.% inorganic salts such as sodium chloride, magnesium chloride, sulfates, etc. known to be available commercially or naturally occurring in brines. These components can be added when the drilling fluid is first formulated or can be contaminants picked up as the drilling fluid is used to drill wells.
  • Emulsifiers can be present in the drilling fluid. They help suspend particulates and emulsify any water that enters the drilling fluid. These are often low HLB materials (surfactants) such as fatty acid soaps. They are further taught in
  • a glass lined, jacketed reactor vessel equipped with an agitator, condenser, and nitrogen flow, and is heated to 85°C.
  • To this vessel is charged 100 parts by weight JeffamineTM ED-2003 (a diamine with terminal amine groups, internal ether linkages, and a molecular weight of about 2,000), with stirring.
  • To the vessel is added 30.9 parts hexadecenyl succinic anhydride over 30 minutes, during which time the reaction temperature increases to about 93 °C. Thereafter the mixture is heated to about 100°C and maintained at temperature for 3 hours.
  • reaction mixture is cooled to 45°C and 131 parts water is added as diluent, as well as 0.8 parts silicone antifoam agent.
  • the mixture is maintained, with stirring, at 40°C for 1 hour.
  • 9.0 parts of 50% aqueous sodium hydroxide solution over 15 minutes, during which time the temperature is maintained at below 50°C; stirring is continued to effect complete reaction.
  • Example 2 is substantially repeated except that the JeffamineTM ED-2003 amine is replaced by 300 parts by weight of a similar material of about 6000 molecular weight. The amount of diluent water added is adjusted accordingly to provide a 50% by weight concentration of chemical in the resulting mixture.
  • Example 4 is substantially repeated except that the JeffamineTM ED-2003 amine is replaced by 300 parts by weight of a similar material of about 6000 molecular weight. The amount of diluent water added is adjusted accordingly to provide a 50% by weight concentration of chemical in the resulting mixture.
  • Example 3 is substantially repeated except that the amine is replaced by 60 parts by weight of a similar material of about 600 molecular weight.
  • Example 5 is substantially repeated except that the amine is replaced by 60 parts by weight of a similar material of about 600 molecular weight.
  • Dodecenyl-succinic anhydride is prepared by a method similar to that of Example 1 A and B, except that a C12 alkyl group is provided.
  • Example 6 After a total of 4 hours at 100°C, the composition is allowed to cool to 44°C. To the composition, 633 g water is added in one portion, causing the mixture to become slightly foamy. At 44°C, 40 g of 50% aqueous sodium hydroxide solution is added dropwise over 20 minutes. During this addition, the temperature of the composition increases to 49°C. After maintaining the composition at temperature for 40 minutes, it is poured into jars without filtration. The product is a dark brown foamy liquid.
  • Example 6 Example 6
  • Example 7 100°C with stirring. After a total of 1 hour at 100°C, the composition is allowed to cool to 45°C and 736 g water is added in one portion. At 45°C, 40 g of 50% aqueous sodium hydroxide solution is added dropwise over 20 minutes and the reaction mixture is maintained below 50°C. After maintaining the composition at temperature for 1 hour, it is poured into jars without filtration. The product composition is an orange liquid.
  • CMC critical micelle concentration
  • the solubility of Surfactant A in the presence of calcium ion is determined at 22°C.
  • Mixtures of Surfactant A are prepared using water containing 0.001M, 0.01M, and 0.2M CaCl 2 .
  • the critical micelle concentration that is, up to 0.20 weight percent
  • the surfactant dissolves to form a clear solution without formation of precipitate.
  • Formation of precipitate is determined by the use of pinacyanol dye as in Example 7. Since micelles and precipitate cannot coexist thermodynamically for single surfactant systems, the presence of a blue color, indicating the existence of micelles, likewise indicates the absence of precipitate. The absence of precipitate at all the concentrations evaluated indicates excellent hardness tolerance of Surfactant A.
  • a commercial diesel fuel based drilling mud was treated with at the 20 wt.% level with a 20 wt.% solution of an emulsifier according to Example 1 where the succinic anhydride is hexadecenyl succinic anhydride and the diamino terminated propylene oxide capped polyoxyethylene had a number average molecular weight of about 1000.
  • the resulting solution was mixed thoroughly.
  • a portion of the material was placed in a test tube and centrifuged for 30 minutes at a preset centrifuge speed.
  • the resulting product had three distinct phases after centrifuging comprising a top hydrocarbon , a middle water and surfactant layer and a bottom clay layer.
  • a drilling mud of this type can be prepared from 55% diesel fuel, 5% asphalt, 3% low HLB emulsifier, 2% organically modified clay, and 35% by wt. barite.
  • a mixture of 1000 parts (1.69 equivalents) of the polyisobutene-substituted succinic acylating agent having a ratio of succinic groups to equivalent weights of polyisobutene of about 1.91 (prepared according to Example 1 of EP 0 561 600 A2) and 1151 parts of a 40 Neutral oil are heated to 65-70°C with stirring.
  • N,N- dimethylethanolamine 151 parts; 1.69 equivalent
  • the reaction mixture is heated to 93°C and held at that temperature for 2 hours.
  • the temperature is adjusted to 160°C, and held at that temperature for several hours (10-15 hours), and then filtered and cooled to room temperature to provide the product.
  • the product has a nitrogen content of 0.90% by weight, a total acid number of 13.0, a total base number of 39.5, a viscosity at 100°C of 50.0 cSt, a viscosity at 40°C of 660 centistoke (cSt), a specific gravity of 0.925 at 15.6°C, and a flash point of 75°C.
  • the product is an ester/salt.
  • the first component being the surfactant of Examples 1-6 where the anhydride is hexadecenyl succinic anhydride and the Jeffamine is a diamino terminated propylene oxide capped polyoxyethylene of about 1000 molecular weight with the second component being a surface active agent generally comprised of the half ester of a hexadecenyl succinic anhydride reacted with dimethylethanolamine in a mole ratio of about 1:1
  • the composition of the drilling mud was very similar to that set forth in the example above but being a used drilling mud may have contained some contaminants.
  • muds are well known and readily commercially available.
  • the blend of surfactant, surface active agent, water, and drilling mud were shaken to mix and settled over several minutes to form a yellow flock layer and a dark solid layer.
  • This clay may be further cleaned and possibly sent to a landfill.
  • a centrifuge designed for separating liquids of different densities might be used to further purify water or fuel layers that didn't go back into processing further clay dispersions in hydrocarbon oil.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mining & Mineral Resources (AREA)
  • Geology (AREA)
  • Fluid Mechanics (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

les liquides de forage à base d'huile (boues) qui renferment des argiles peuvent être subdivisés en trois couches correspondant à leurs éléments constitutifs respectifs (huile, eau et argile) par adjonction de quelques unités en pourcentage de poids d'un tension actif à rapport hydrohpile-lipophile élevé dilué dans l'eau. La centrifugation peut accélérer le processus de séparation. Les couches d'huile, d'eau et d'argile qui en résultent peuvent ensuite être recyclées ou évacuées de façon plus économique. Selon un autre mode de réalisation, on ajoute un agent de surface actif supplémentaire afin de faciliter le fractionnement de la boue de forage entre au moins trois phases sans centrifugation.
PCT/US2001/027408 2000-09-05 2001-09-04 Utilisation de desemulsionneurs hydrosolubles permettant de separer des huiles d'hydrocarbures et des argiles WO2002020691A2 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
MXPA03001866A MXPA03001866A (es) 2000-09-05 2001-09-04 Uso de desemulsionantes solubles en agua en la separacion de aceites hidrocarbonados de las arcillas descripcion.
EP01968445A EP1325208A2 (fr) 2000-09-05 2001-09-04 Utilisation de desemulsionneurs hydrosolubles permettant de separer des huiles d'hydrocarbures et des argiles
CA002419953A CA2419953A1 (fr) 2000-09-05 2001-09-04 Utilisation de desemulsionneurs hydrosolubles permettant de separer des huiles d'hydrocarbures et des argiles
US10/344,911 US20030222026A1 (en) 2001-09-04 2001-09-04 Use of water soluble demulsifiers in separating hydrocarbon oils from clays
AU2001288691A AU2001288691A1 (en) 2000-09-05 2001-09-04 Use of water soluble demulsifiers in separating hydrocarbon oils from clays

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US23011300P 2000-09-05 2000-09-05
US60/230,113 2000-09-05

Publications (2)

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WO2002020691A2 true WO2002020691A2 (fr) 2002-03-14
WO2002020691A3 WO2002020691A3 (fr) 2002-08-15

Family

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PCT/US2001/027408 WO2002020691A2 (fr) 2000-09-05 2001-09-04 Utilisation de desemulsionneurs hydrosolubles permettant de separer des huiles d'hydrocarbures et des argiles

Country Status (5)

Country Link
EP (1) EP1325208A2 (fr)
AU (1) AU2001288691A1 (fr)
CA (1) CA2419953A1 (fr)
MX (1) MXPA03001866A (fr)
WO (1) WO2002020691A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008031806A1 (fr) * 2006-09-14 2008-03-20 Lamberti Spa Inhibiteurs de gonflement pour argiles et schistes
US7867399B2 (en) 2008-11-24 2011-01-11 Arkansas Reclamation Company, Llc Method for treating waste drilling mud
US7935261B2 (en) 2008-11-24 2011-05-03 Arkansas Reclamation Company, Llc Process for treating waste drilling mud

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5723423A (en) * 1993-12-22 1998-03-03 Union Oil Company Of California, Dba Unocal Solvent soaps and methods employing same
GB2347682A (en) * 1999-03-12 2000-09-13 Univ Napier A method for the extraction of oil by microemulsification

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5723423A (en) * 1993-12-22 1998-03-03 Union Oil Company Of California, Dba Unocal Solvent soaps and methods employing same
US5780407A (en) * 1993-12-22 1998-07-14 Union Oil Company Of California Solvent soaps and methods employing same
GB2347682A (en) * 1999-03-12 2000-09-13 Univ Napier A method for the extraction of oil by microemulsification

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008031806A1 (fr) * 2006-09-14 2008-03-20 Lamberti Spa Inhibiteurs de gonflement pour argiles et schistes
US7867399B2 (en) 2008-11-24 2011-01-11 Arkansas Reclamation Company, Llc Method for treating waste drilling mud
US7935261B2 (en) 2008-11-24 2011-05-03 Arkansas Reclamation Company, Llc Process for treating waste drilling mud

Also Published As

Publication number Publication date
EP1325208A2 (fr) 2003-07-09
MXPA03001866A (es) 2003-06-24
WO2002020691A3 (fr) 2002-08-15
CA2419953A1 (fr) 2002-03-14
AU2001288691A1 (en) 2002-03-22

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