WO2019144086A1 - Désémulsifiants biodégradables - Google Patents

Désémulsifiants biodégradables Download PDF

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Publication number
WO2019144086A1
WO2019144086A1 PCT/US2019/014433 US2019014433W WO2019144086A1 WO 2019144086 A1 WO2019144086 A1 WO 2019144086A1 US 2019014433 W US2019014433 W US 2019014433W WO 2019144086 A1 WO2019144086 A1 WO 2019144086A1
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Prior art keywords
carboxylic acid
demulsifier
group
dendrimer
functionalized
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PCT/US2019/014433
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English (en)
Inventor
Rachael Anne COLE
Tore NORDVIK
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Schlumberger Norge As
M-I L.L.C.
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Publication of WO2019144086A1 publication Critical patent/WO2019144086A1/fr
Priority to DKPA202070494A priority Critical patent/DK181100B1/en
Priority to NO20200842A priority patent/NO20200842A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • 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
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/047—Breaking emulsions with separation aids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules
    • C08G83/006—After treatment of hyperbranched macromolecules
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/003—Dendrimers
    • C08G83/004—After treatment of dendrimers
    • 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
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/26—Gel breakers other than bacteria or enzymes

Definitions

  • crude oil refers to the desirable (and undesirable) hydrocarbon products extracted from the ground together with the associated aqueous phase and minor amounts of solids. Crude oils differ in their composition from deposit to deposit. In addition to water, the crude oil generally also comprises from 0.1 to 25% by weight of salts and solids. Water, salts and solids have to be removed before the crude oil can be transported and can be processed as crude oil in the refinery.
  • the proportion of hydrocarbons in crude oils varies from 5% to almost 100%, and includes thousands of different molecules that may be grouped into four families of compounds: saturates, aromatics, resins and asphaltenes. Saturates generally constitute the lightest fraction of the crude oil while within the saturates family, Cix- long-chain linear paraffins represent the heavy fraction of the saturates and are responsible for wax deposit formation.
  • water which is comprised in the crude oil is emulsified in particular by natural emulsifiers, such as naphthenic acids, which reduce the interfacial tension between water phase and oil phase, stabilizing the emulsion.
  • natural emulsifiers such as naphthenic acids
  • such emulsions may also occur artificially resulting from one or more of numerous operations encountered in various industries. For example, such emulsions may be obtained from producing wells (as a result of enhanced oil recovery methods but much more generally than this) or from the bottom of crude oil storage tanks.
  • these crude oil emulsions may be broken into the oil fraction and the water fraction.
  • the breaking of crude oil emulsion is carried out for economic and technical reasons, in order firstly to avoid the uneconomical transport of water, to prevent or to at least minimize corrosion problems, and in order to reduce the use of energy for the transport pumps.
  • the breaking of the crude oil emulsion is thus a substantial process stage in crude oil production.
  • emulsion breakers i.e. interface-active substances, which enter the oil-water interface and displace the natural emulsifiers there, coalescence of the emulsified water droplets can be achieved, which finally leads to phase separation.
  • emulsion breakers i.e. interface-active substances
  • Petroleum demulsifiers may be surface-active polymeric compounds which are able to affect the desired separation of the emulsion constituents within a short time.
  • demulsifiers are increasingly desired which have good biodegradability and low bioaccumulation in order to replace the controversial products based on alkylphenol.
  • embodiments disclosed herein relate to a method of breaking an emulsion, the method including contacting an emulsion with a demulsifier, where the demulsifier is a dendrimer functionalized with a carboxylic acid derivative and separating the emulsion into two distinct phases.
  • embodiments of the present disclosure relate to a method of producing crude oil, the method including extracting a hydrocarbon fluid from a subterranean formation; adding a demulsifier to the hydrocarbon fluid, where the demulsifier is a dendrimer functionalized with a carboxylic acid derivative and separating the crude oil emulsion into two distinct phases.
  • embodiments of the present disclosure relate to a composition that includes a demulsifier, where the demulsifier is a dendrimer functionalized with a polyoxyalkylene alkyl ether carboxylic acid having at least one oxyalkylene unit.
  • FIG. 1 is a representation of Boltorn H20.
  • FIG. 2 is a representation of Boltorn H30.
  • FIG. 3 is a representation of Boltorn H40.
  • FIG. 4 depicts OECD 306 biodegradation screening test results, according to the present embodiments.
  • FIG. 5 depicts the water drop (volume versus time) according to the present embodiments.
  • embodiments disclosed herein are directed to compositions and methods of using the same for treating hydrocarbon fluids. More specifically, embodiments disclosed herein are directed to compositions and methods of using the same for breaking crude oil emulsions.
  • the inventors of the present disclosure have found that compositions that include dendrimers functionalized with a surfactant, such as a carboxylic acid derivative, may be used as demulsifiers in demulsifier packages.
  • the functionalized dendrimers of the present disclosure may be used as demulsifiers in environmentally sensitive areas such as the North Sea, as they are environmentally acceptable, exhibiting low toxicity and high biodegradability compared to conventional demulsifiers which are poorly biodegradable.
  • the term“environmentally acceptable” is defined as chemicals or formulations that can pass the most stringent environmental testing criteria as described below.
  • the term“environmentally unacceptable” is defined as chemicals or formulations that do not pass the most stringent environmental testing criteria.
  • sample biodegradation is marine biodegradation data as outlined in Organization for Economic Cooperation and Development, Procedure OECD 306 or BODIS. . . OECD 306, the rules governing offshore chemical use set forth three tests: bioaccumulation, biodegradation and toxicity.
  • biodegradation is greater than 60%, if less than 20% it is automatically marked for substitution; (2) bioaccumulation as measured by octanol/water partitioning coefficient (log Po/w) is below 3 (or have a molecular weight >700); and (3) toxicity to the most sensitive marine species (often Skeletonema) is greater than LC50 or EC50 of 10 ppm.
  • components of the production chemical treatment fluid in some embodiments may be selected such that they meet the requirements for biodegradation and aquatic toxicity.
  • the geographic location with the most stringent environmental and discharge testing criteria for well treatment operation is the North Sea, but the definition of either of these terms should in no way be limited to any past, present or future North Sea environmental testing criteria. Further, the test criteria also in no way limit the geographical region of use of the fluid, but provides an indication of the environmental friendliness of a product (or fluid containing a product).
  • the compositions as described herein may include a demulsifier, where the demulsifier may be a hyperbranched polymer having functional groups, such as a functionalized dendrimer.
  • Particular dendrimers that may be used in embodiments of the present disclosure may be selected from the group of polyester polyols.
  • the molecular weight of such polyester polyols may be at least 1700. In one or more embodiments, the molecular weight of the polyester polyol may be at least 3500. It is also envisioned that polyester polyols with higher molecular weights may be used.
  • the dendrimers as described herein may be functionalized with at least a surfactant.
  • the dendrimer may have at least one terminal hydroxyl group esterified by the surfactant.
  • the functionalized dendrimer may have a degree of functionalization of at least 50%.
  • the degree of functionalization may be 70% or 90%.
  • the dendrimers of the present disclosure may include a branched dendritic core including a first quaternary carbon center bonded to four second carbon atoms, wherein each of the four second carbon atoms is bonded to a plurality of branched ligands to produce the branched dendritic core, wherein the branched dendritic core has greater than or equal to about 16 terminal hydroxyl groups, wherein at least one of the terminal hydroxyl groups is esterified with at least one carboxylic acid moiety comprising from 6 to 30 carbon atoms. It is also envisioned that a carboxylic acid moiety having a higher number of carbon atoms (such as 40 carbon atoms) may be used.
  • the dendrimers as described herein may be functionalized with at least one surfactant.
  • Suitable surfactants may include nonionic surfactants, cationic surfactants, and anionic surfactants.
  • anionic surfactants such surfactants may contain anionic functional groups at their head, such as sulfate, sulfonate, phosphate and carboxylates.
  • the surfactants may be selected from the group of carboxylic acids and their derivatives.
  • particular surfactants that may be used are selected from the group of polyoxyalkylene alkyl ether carboxylic acids.
  • the alkyl may be selected from the group of linear and branched alkyl groups.
  • the alkyl may be selected from the group of saturated alkyl groups or unsaturated alkyl groups, such as alkenyls.
  • the number of carbon atoms in the alkyl group may be at least 1. It is also envisioned that the alkyl group may have more than one carbon atom.
  • the alkyl group may have at least 8 carbon atoms. In one or more embodiments, the number of carbon atoms present in the alkyl group may range from about 8 to about 18. It is also envisioned that the alkyl group may have up to 24 carbon atoms. In yet another embodiment, the number of carbon atoms present in the alkyl group may be higher than 24.
  • the carboxylic acid derivative may contain polyoxyalkylene units.
  • the oxyalkylene units present on the carboxylic acid derivative may range from 1 to 10, or from 1 to 15. It is also envisioned that the number of oxyalkylene units present on the carboxylic acid derivative may be even higher than 15.
  • the oxyalkylene units are selected from the group of oxyethylene, oxypropylene, oxybutylene and combinations of thereof.
  • the carboxylic acid derivative may include oxyethylene units. It is also envisioned that the carboxylic acid derivative may include combinations of oxyalkylene units, such as for example, oxyethylene and oxypropylene units, or oxyethylene and oxybutylene units. However, other combinations are envisioned as well.
  • the polyoxyethylene alkyl ether carboxylic acids have the following general formula:
  • R is an alkyl group and n is the number of oxyethylene units, or the degree of polymerization.
  • R may be selected from the group of linear, branched, saturated or unsaturated alkyl groups. In such embodiments, R may have at least one carbon atom. It is also envisioned that R may have a higher number of carbon atoms. For example, in one or more embodiments, R may have at least 8 carbon atoms. In yet another embodiment, R may have up to 24 carbon atoms. It is also envisioned that R may contain even more than 24 carbon atoms. Examples of polyoxyethylene alkyl ether carboxylic acids will be presented later in greater detail.
  • Dendrimers are three-dimensional highly-ordered oligomers or polymers. They are obtainable by reiterative reaction sequences starting from an initiator core having one or more reactive sites. To each reactive site is attached one functional group of a polyfunctional reactant. The reactant is then caused to react through its remaining functional group or groups with additional molecules either the same as the original core if it is polyfunctional or a different, polyfunctional, molecule or molecules, and so on, in each case under reaction conditions such that unwanted side reactions, for example, crosslinking, are avoided. In this way, a dendritic body is built up around the central core, each reiterative reaction sequence adding further reactants (or‘units’) to the ends of the dendrites.
  • polyamidoamine (PAMAM) dendrimers may be made based on ammonia as a core, which is caused to react by Michael addition with methyl acrylate (Stage A).
  • the carboxyl group of the acrylate molecule is caused to react with one amino group of ethylene diamine (Stage B).
  • the resulting triamine core cell is referred to as Generation 0; a further repetition of stages A and B provides a hexamine, referred to as Generation 1. Further repetitions of stages A and B produce higher generations which after Generation 4 result in concentric spheres of cells, the outermost sphere carrying external reactive groups.
  • Other dendrimers may include, but are not limited to, polyethylenimine, hydrocarbon, polyether, polythioether, polyamide, polyamido-alcohol and polyarylamine dendrimers.
  • branched, hyperbran ched, and/or dendritic macromolecules ⁇ i.e., dendrimers) suitable for use herein may generally be described as three dimensional highly branched (i.e., hyperbranched) molecules having a tree-like structure.
  • Suitable branched dendrimers may be highly symmetric, while similar macromolecules designated as branched, may, to a certain degree, hold an asymmetry, yet maintaining a highly branched tree-like structure.
  • Dendrimers can be said to be monodispersed variations of branched macromolecules.
  • branched dendrimers suitable for use herein comprise an initiator or nucleus having one or more reactive sites and a number of surrounding branching layers and optionally a layer of chain terminating molecules. As is known in the art, the layers are called generations, a designation hereinafter used. Branched dendritic or near dendritic macromolecules, also referred herein as a branched dendritic core, may have three or more generations. Embodiments of the branched dendritic core may be illustrated by Formulae (II) and (III),
  • X is a first quaternary carbon center bonded to four second carbon atoms Y, where each of the four second carbon atoms Y is each bonded through one or more chain extender ligands, which may be linear or branched, to produce the branched dendritic core.
  • a and B are chain extender ligands having two or four reactive sites each. Suitable examples may include poly functional ligands comprising hydroxyl groups, epoxides, carboxylic acids, and the like.
  • each of the chain extender forms one generation in the branched dendritic core.
  • a and/or B may include a plurality of chain extenders, linked together, each providing a branching point which is eventually terminated by a T functional group.
  • Each of the A and B chain extenders may be the same or different.
  • the branched dendrimer core, including the branches and terminating chains does not include nitrogen atoms.
  • the branched dendrimer core, including the branches and terminating chains may include carbon, hydrogen and oxygen.
  • a and B may be carbon, hydrogen and/or oxygen.
  • T is a terminating chain stopper forming the last generation. T may either be monofunctional or give a suitable terminal functionality.
  • T may be selected from at least one of a hydroxyl, carboxyl or epoxide group. Each T may be a terminal hydroxyl group or a terminal hydroxyl group esterified with at least one carboxylic acid moiety having from 6 to 30 carbon atoms.
  • a carboxylic acid moiety having a higher number of carbon atoms may be used.
  • the branched dendritic core may have greater than or equal to about 16 terminal hydroxyl groups, wherein at least one of the terminal hydroxyl groups is esterified with at least one carboxylic acid moiety comprising from 6 to 30 carbon atoms, or even a higher number of carbon atoms, such as for example 40 carbon atoms
  • the branched dendritic core may be represented by Formula IV below.
  • the Formula IV branched dendritic core may not include nitrogen functionality, and more specifically may not include amine or amide functionality.
  • Each R may be a hydrogen (z.e., a hydroxyl terminal group) or an esterified hydroxyl group which has been esterified with at least one carboxylic acid moiety selected from the group including: greater than or equal to about 6 carbon atoms, greater than or equal to about 10 carbon atoms, and from 6 to 40 carbon atoms, with from 6 to 30 carbon atoms.
  • the branched dendritic core prior to being esterified with the carboxylic acid, has a hydroxyl number of greater than or equal to about 490 mg KOH/g, wherein the hydroxyl number represents the hydroxyl content of a dendritic core, and is derived by acetylating the hydroxyl and titrating the resultant acid against KOH, as is known in the art.
  • the hydroxyl number is thus the weight of KOH in milligrams that will neutralize the acid from 1 gram of the dendritic core prior to being esterified with a carboxylic acid.
  • the branched dendritic core may include at least one carboxylic acid derivative moiety having from 6 to 30 carbon atoms, or from 8 to 24 carbon atoms, or from 6 to 40 carbon atoms, where the terminal hydroxyl groups of the branched dendritic core are each esterified with at least one carboxylic acid derivative moiety having from at least 8 carbon atoms.
  • the terminal hydroxyl groups on the branched dendritic core may be esterified with a corresponding number of the same carboxylic acid derivative moiety.
  • the carboxylic derivative moiety may be individually selected from a polyoxyalkylene alkyl ether carboxylic acid moiety having six to 30 carbon atoms or more.
  • the polyoxyalkylene alkyl ether carboxylic acid moiety may have from 8 to 30 carbon atoms, or from 8 to 24 carbon atoms.
  • the oxyalkylene unit may be selected from the group of oxyethylene, oxypropylene, oxybutylene and combinations thereof.
  • the alkyl group may be selected from the group of linear, branched, saturated and unsaturated alkyl groups, where the unsaturated alkyl is an alkenyl group.
  • the branched dendritic core may include terminal carboxylic acid derivative moieties selected from the group of polyoxyalkylene alkyl ether carboxylic acids having six to 30 carbon atoms, or six to 40 carbon atoms, or 8 to 24 carbon atoms, or having 12, 14, 16, 18, 20, 22 and 24 carbon atoms, and combinations thereof.
  • branched dendritic core refers to a branched dendritic core wherein at least one of the terminal hydroxyl groups is esterified with at least one polyoxyalkylene alkyl ether carboxylic acid moiety including from 6 to 30 carbon atoms, or from 6 to 40 carbon atoms, or from 8 to 24 carbon atoms.
  • the carboxylic acid moiety is a substituted carboxylic acid moiety which is substituted with at least one functional group including elements from one or more of Groups 13-17 of the periodic table of the elements.
  • the carboxylic acid moiety is a substituted carboxylic acid moiety which is substituted with at least one functional group including elements from one or more of Group 13, 14, 16, or 17 of the periodic table of the elements.
  • the at least one functional group may include carbon, hydrogen, oxygen, sulfur and/or a halogen.
  • the substituted carboxylic acid moiety may include a hydroxyl functional group, a halogen functional group, or a combination thereof.
  • the substituted carboxylic acid moiety may be a hydroxy substituted carboxylic acid. In such an embodiment, the substituted carboxylic acid moiety is 12 hydroxy stearic acid.
  • branched dendritic cores prior to esterification which are suitable for use herein may include polyols sold by Perstorp AB Corporation Sweden under the name Boltorn®, (Perstorp, Sweden), including Boltorn® H20 (See FIG. 1), Boltorn® H30 (see FIG. 2), Boltorn® H40 (see FIG. 3), and the like.
  • the dendrimers of the present disclosure are functionalized with carboxylic acid derivatives.
  • Tables 2 and 3 presented below show examples of polyoxyethylene alkyl ether carboxylic acids. However, the embodiments of the present disclosure should not be limited to such examples.
  • carboxylic acid derivatives used for the functionalization of the dendrimers as disclosed herein may be selected from the group of alkyl-(aryl) alkoxylated carboxylic acids.
  • Table 4 presents examples of such acids. However, the embodiments of the present disclosure should not be limited to such examples. Table 4. Examples of alkyl-(aryl-) alkoxylated carboxylic acids.
  • compositions of the present embodiments may be used as demulsifiers in breaking emulsions.
  • breaking emulsions Such operations are known to persons skilled in the art and involve adding a functionalized dendrimer to a water-in oil or an oil-in-water emulsion.
  • the polymer solutions may be added to crude oils, i.e. in the oil field during oil production and processing.
  • the crude oil emulsion may comprise oil and water or oil and salt water.
  • the breaking takes place at a temperature as low as that of the freshly conveyed crude oil emulsion at a speed such that the emulsion can be broken on the way to the processing plant. This broken emulsion is then separated into pure oil and water or salt water in an optionally heated separator and possibly with the aid of an electric field.
  • the demulsifiers are added as a formulation.
  • Commonly used solvents for demulsifiers are mutual solvents/glycols such as for example ethylene glycol monobutyl ether.
  • the temperature at which the formulation is dosed may vary. Demulsifier testing may be designed to follow the temperature in the oil production process.
  • the dosage rate of demulsifier formulations may vary, depending on the system, the temperatures and the crude oil/water emulsion. For example, in one or more embodiments, the dosage rate of demulsifier formulations for a normal light crude oil may range from 2 to 20 ppm. In one or more embodiments, the dosage rate of the demulsifier formulation for a medium crude oil may range from 10 to 100 ppm.
  • the dosage rate of the demulsifier formulation may range from 80 to 200 ppm. It yet another embodiment, the dosage rate of the demulsifier formulation used for extra heavy crude oils may be up to 500 ppm. It is also envisioned that in all the above-mentioned embodiments, the dosage rate of the demulsifier formulation may be higher, such as three times higher. According to one or more embodiments, the active concentration of the demulsifier in the formulation may range from 30% to 50%, where the lower limit can be any of 30%, 32%, or 35% and the upper limit can be any of 45%, 48% or 50% where any lower limit can be used with any upper limit. However, it is envisioned that other concentrations may be used.
  • the demulsifiers as described herein may be used for water-in-oil or oil-in-water emulsions comprising in general from 0.1 to 99% by weight of water or salt water.
  • Suitable oils which can be dewatered in this manner are crude oil emulsions of any origin.
  • One embodiment of the present disclosure includes a method of breaking an emulsion, such as for example a crude oil emulsion.
  • the method involves contacting an emulsion with a demulsifier and separating the emulsion into two distinct phases.
  • the demulsifier is a dendrimer functionalized with a carboxylic acid derivative, where the degree of functionalization of the functionalized dendrimer may be at least 50%. It is also envisioned that a functionalized dendrimer having a degree of functionalization higher than 50% may be used as well. For example, in one or more embodiments, the degree of functionalization may be at least 70%. In yet another embodiment, the degree of functionalization may be 90%.
  • the dendrimer is a polyester polyol that has at least one terminal hydroxyl group esterified by the carboxylic acid derivative.
  • the dendrimer may be functionalized with a polyoxyalkylene alkyl ether carboxylic acid.
  • the dendrimer may be functionalized with a polyoxyalkylene alkyl ether carboxylic acid, where the oxyalkylene units are selected from the group of oxyethylene, oxypropylene, oxybutylene and combinations thereof.
  • the alkyl group may have at least one carbon atoms. It is also envisioned that the alkyl group may have more than one carbon atom.
  • the alkyl group may have at least 8 carbon atoms and up to 24 carbon atoms. It is also envisioned that the dendrimer may be functionalized with an alkyl-(aryl) alkoxylated carboxylic acid.
  • One or more embodiments of the present disclosure involve a method of producing crude oil.
  • the method involves extracting a hydrocarbon fluid from a subterranean formation by means of a well, adding a demulsifier according to any one or combination of embodiments disclosed herein to the hydrocarbon fluid and separating the crude oil emulsion into two distinct phases.
  • the dendrimer functionalized with a carboxylic acid derivative is added to the hydrocarbon fluid after the hydrocarbon fluid is extracted from the well.
  • the hydrocarbon fluid is a hydrocarbon fluid produced during extraction of hydrocarbons from a well, crude oil, a crude oil condensate, a middle distillate, a fuel oil, diesel, or a combination thereof. Also included are refined streams including various fuel oils, diesel fuel, kerosene, gasoline, and the like.
  • the well is located underwater.
  • the demulsifier may be added to a hydrocarbon fluid produced from a well at the well head or at the surface.
  • demulsifiers are used topside, but they may also be added at the wellhead or subsea. They are generally added prior to the separators to ensure that water separates from the hydrocarbon fluids in a good location. It is also envisioned that the demulsifier may be added to a hydrocarbon fluid prior to transporting the hydrocarbon fluid in a pipeline or a tank.
  • the dendrimers as described herein may be functionalized with a polyoxyalkylene alkyl ether carboxylic acid.
  • the dendrimer may be functionalized with an alkyl-(aryl) alkoxylated carboxylic acid.
  • the superior performance of the formulations of this disclosure was determined by conducting the Relative Solubility Number (RSN) test as described below.
  • the RSN number of a demulsifier is a measure of its solubility properties (such as the solubility hydrophile- lyophile balance of surfactants).
  • the RSN is a factor in the demulsifier selection since solubility properties dictate whether the chemical will be capable of working effectively as a surface-active agent at the water/oil interface.
  • the RSN is an industrially accepted measurement used to describe the hydrophile-lyophile balance of oilfield demulsifiers. It is a simple measure of water solubility and relates to a water/oil partition coefficient.
  • OECD 306 Biodegradability in Seawater
  • This Test Guideline describes two methods for biodegradability in seawater.
  • the shake flask method involves dissolution of a pre-determined amount of the test substance in the test medium to yield a specific concentration of dissolved organic carbon (DOC).
  • DOC dissolved organic carbon
  • the solution of the test substance in the test medium is incubated, under agitation in the dark or in diffuse light under aerobic conditions, at a fixed temperature (such as l5-20°C).
  • the recommended maximum test duration is about 60 days.
  • Degradation is followed by DOC measurements (ultimate degradation) and, in some cases, by specific analysis (primary degradation).
  • the closed bottle method involves dissolution of a pre-determined amount of the test substance in the test medium in a specific concentration.
  • Two hyperbranched dendrimers were functionalized by an esterification reaction with the formation of functionalized dendrimers, namely sample 1 and sample 2.
  • the synthesis was completed using the reaction carousel in the presence of xylene as a solvent.
  • the desired dendrimer and the corresponding polyoxyalkylene alkyl ether carboxylic acid were mixed with 100 mL of solvent.
  • a dodecylbenzenesulphonic acid (DDBSA) was used as a catalyst to promote the esterification. It is also envisioned that other acid catalysts may be used.
  • the synthesis may be carried in the absence of a solvent.
  • the desired dendrimer, polyoxyalkylene alkyl ether carboxylic acid and catalyst such as DDBSA, a sulphonic acid catalyst
  • the mixture was heated to l50°C under vacuum. Water was removed by distillation during the esterification reaction. The reaction was monitored by the amount of water produced and acid number.
  • EGMBE is ethylene glycol mono butyl ether
  • the classification scheme is based on aquatic biodegradation, toxicity and bioaccumulation tests. Red category products, as for instance several products in production chemicals, are not allowed to discharge and will need to be shipped onshore for cuttings waste treatment.
  • Screening tests performed on the two functionalized dendrimers have demonstrated a biodegradation over 40% in the OECD 306 test, as shown in Table 7 and FIG. 4. Screening of the toxicity to the Skeletonema has also been performed. The screening test shows that sample 1 has a toxicity between 33 and 103 mg/L, while sample 2 has a toxicity between 3.2 and 10 mg/L.
  • a preliminary classification indicates that sample 1 falls in the yellow category (Y2), while sample 2 falls in the red category.
  • the water cut (the ratio of water produced compared to the volume of the total liquids produced) and emulsions was determined by using Hot Spin centrifuge.
  • the crude oil sample contained zero water and emulsion according to the test.
  • the synthetic water used was 3% sodium chloride brine which was preheated to 70 C.
  • the emulsion was prepared by adding 20 vol% synthetic water and crude oil. The mixture was kept at 40°C in a water bath. ETltra turrax mixing at 24,000 rpm for 7 minutes gave a stable emulsion (>l hour).
  • the bottles were heated to 40°C, and the demulsifier was injected to each bottle, except for the blank.
  • middle cut (level 50%) were performed on the test bottles.
  • water drop is the amount of water/brine separated from the crude oil and/or emulsion
  • middle cut represents the level that a sample is taken above the interface to see how much residual water/emulsion is left in the crude oil.
  • middle cut indicates how dry is the crude oil.
  • a hotspin centrifuge was used to identify the residual emulsion.
  • the results as depicted in FIG. 5 show the comparison of a commercial dendrimer (“dendrimer”) and new demulsifier samples, namely sample 1 and sample 2 at the same dosage of 100 ppm.
  • the commercial dendrimer is a finished product with at least 3 different active components developed for North Sea market to meet the environmental requirements. It is normal for demulsifier formulations to have multiple components, as different chemistries work to separate the oil and water, clean the interface, and give both dry oil and clean water.
  • Both sample 1 and sample 2 are single components and match the performance of commercial products, i.e. fast water drop, good interface and good water quality and dry crude.
  • embodiments of the present disclosure may provide biodegradable demulsifier compositions and methods for using the same.
  • the use of dendrimers functionalized with a carboxylic acid derivative may allow for breaking emulsions, in particular in the production of crude oil.
  • dendrimers functionalized with a carboxylic acid derivative are environmentally acceptable, exhibiting low toxicity and high biodegradability for potential applications in the North Sea.

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Abstract

La présente invention concerne un procédé de rupture d'une émulsion comprenant la mise en contact d'une émulsion avec un désémulsifiant, le désémulsifiant étant un dendrimère fonctionnalisé avec un dérivé d'acide carboxylique et la séparation de l'émulsion en deux phases distinctes. L'invention concerne également un procédé de production d'huile brute comprenant l'extraction d'un fluide hydrocarboné d'une formation souterraine ; l'ajout d'un désémulsifiant au fluide hydrocarboné, le désémulsifiant étant un dendrimère fonctionnalisé avec un dérivé d'acide carboxylique ; et la séparation de l'émulsion d'huile brute en deux phases distinctes.
PCT/US2019/014433 2018-01-22 2019-01-22 Désémulsifiants biodégradables WO2019144086A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070100002A1 (en) * 2003-07-02 2007-05-03 Dirk Leinweber Alkoxylated dendrimers and use thereof as biodegradable demulsifiers
US20140224495A1 (en) * 2011-07-29 2014-08-14 Schlumberger Norge As Hydrocarbon fluid flow improver
US20160222278A1 (en) * 2014-11-04 2016-08-04 Schlumberger Norge As Encapsulated Production Chemicals
WO2017192658A1 (fr) * 2016-05-04 2017-11-09 M-I L.L.C. Produits chimiques de production encapsulés

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070100002A1 (en) * 2003-07-02 2007-05-03 Dirk Leinweber Alkoxylated dendrimers and use thereof as biodegradable demulsifiers
US20140224495A1 (en) * 2011-07-29 2014-08-14 Schlumberger Norge As Hydrocarbon fluid flow improver
US20160222278A1 (en) * 2014-11-04 2016-08-04 Schlumberger Norge As Encapsulated Production Chemicals
WO2017192658A1 (fr) * 2016-05-04 2017-11-09 M-I L.L.C. Produits chimiques de production encapsulés

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