DEMULSIFICATION OF HYDROCARBONS

Abstract

DEMULSIFICATION OF HYDROCARBONS The present invention relates to a use of a composition comprising: - one or more alkoxylated formocardanol resins comprising from 2 to 200 alkoxyl units per phenolic unit, - one or more alkoxylated cardanol compounds comprising from 2 to 200 alkoxyl units per phenolic unit, the mass ratio between said alkoxylated resin(s) and said alkoxylated cardanol compound(s) being between 1:1 and 50:1, preferably between 2:1 and 30:1, more preferably between 3:1 and 25:1, for demulsifying fluids from oil production, and in particular hydrocarbons

Description

Title of the invention: DEMULSIFICATION OF HYDROCARBONS

[0001] The present invention relates to the field of hydrocarbon extraction, and more particularly to the field of additives used to facilitate the treatment of said fluids, and in particular hydrocarbons from oil production. The present invention relates in particular to the use of a specific composition for demulsifying fluids and in particular hydrocarbons from oil production.

[0002] It is known that these production fluids most often comprise an aqueous phase, in a more or less significant quantity. The origin of this aqueous phase can be endogenous and / or exogenous to the underground reservoir containing the hydrocarbons, the exogenous aqueous phase generally coming from an injection of water, also called injection water.

[0003] Extracted fluids (or produced fluids, or production fluids) are understood to mean fluids comprising oil, gas, condensates, water and their mixtures.

[0004] For the purposes of the present invention, the term petroleum means crude oil, i.e. a fluid based on mixtures of hydrocarbons, unrefined, originating from a deposit and most often comprising a more or less significant quantity of endogenous and / or exogenous water.

[0005] Thus, the fluids extracted from deposits are most often found in the form of emulsions. Therefore, an essential step in the process of extracting and treating hydrocarbons consists of breaking these emulsions, that is to say separating the aqueous phase from the organic phase, the latter of which can then be treated.

[0006] The separation step generally uses specific additives called demulsifiers aimed at improving and accelerating the separation of the phases.

[0007] For this purpose, various surfactant compositions have been developed and used over the past few decades. Among the surfactants used to break emulsions, the most important are alkylene oxide derivatives of phenolic resins. More recently, resins derived from cardanol have appeared on the market. For the purposes of the present invention, alkylene means a divalent hydrocarbon group.

[0008] Cardanol is a bio-sourced phenolic derivative, obtained from the anacardic acid present in the fruit of the cashew tree. In addition to the advantage of accessing a bio-sourced raw material, the use of cardanol also makes it possible to enhance the non-edible part of the cashew fruit, the edible part: the cashew nut, being widely exploited.

[0009] Document US5460750 describes a surfactant composition for demulsifying crude oil emulsions comprising alkoxylated resins based on cardanol, p-nonylphenol and formaldehyde.

[0010] However, it turns out that p-nonylphenol is a toxic, bioaccumulative and relatively persistent component. Consequently, high-performance demulsifiers are being sought which do not use this reagent.

[0011] It is known from the scientific publication Journal of Petrochemical Universities, Vol. 24 (5), (October 2011), pages 34-37 by Wang, the use of alkoxylated resins based on formocardanol, comprising OP (propoxy) and OE (ethoxy) units and polyamines as demulsifiers in the petroleum field.

[0012] It is also known from the scientific publication of FX Feitosa et al. (Fuel, 245, (2009), pages 21-28), the use of resins based on alkoxylated formocardanol, comprising EO units, as a demulsifier in the petroleum field. This study concerns dehydrogenated derivatives of cardanol.

[0013] However, demulsifying agents that are ever more efficient and easier to synthesize are being sought.

[0014] It has now been surprisingly discovered that compositions comprising a mixture of alkoxylated cardanol and alkoxylated formocardanol resin, in a specific ratio, make it possible to demulsify an oil production fluid more quickly, i.e. lead to an improvement in the separation of the oil and water phases present in the fluid. This separation takes place much more quickly.

[0015] Other objectives, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and the examples which follow. In what follows, and unless otherwise indicated, the limits of a range of values ​​are included in this range, in particular in the expressions "between... and..." and "ranging from... to...".

[0016] Thus, the invention relates to the use of a composition comprising: - one or more resins obtained from alkoxylated formocardanol comprising from 2 to 200 alkoxylated units per phenolic unit and - one or more alkoxylated cardanol compounds comprising from 2 to 200 alkoxylated units per phenolic unit, the mass ratio between said alkoxylated resin(s) and said alkoxylated cardanol compound(s) being between 1:1 and 50:1, preferably between 2:1 and 30:1, more preferably between 3:1 and 25:1, to demulsify fluids from oil production, particularly hydrocarbons.

[0017] The invention also relates to a process for demulsifying fluids, and in particular hydrocarbons, resulting from oil production, comprising a step adding the aforementioned composition to the fluid to be treated.

[0018] Use

[0019] The invention relates to the use of a composition comprising: - one or more resins obtained from alkoxylated formocardanol comprising from 2 to 200 alkoxylated units per phenolic unit and - one or more alkoxylated cardanol compounds comprising from 2 to 200 alkoxylated units per phenolic unit, the mass ratio between said alkoxylated resin(s) and said alkoxylated cardanol compound(s) are between 1:1 and 50:1, preferably between 2:1 and 30:1, more preferably between 3:1 and 25:1.

[0020] Cardanol

[0021] Cardanol is a constituent of the oil obtained from the shell of the cashew nut, the main constituent of which is the compound of the following formula (I): in which X denotes a C15 hydrocarbon chain containing 1 to 3 double bonds. This compound is described in the scientific publication by R. Ikeda et al., Macromol. Rapid Commun., 21, 496-499 (2000) or in A. Mahannar, Journal of Applied Polymer Science, 61, 2107-2111 (1996).

[0022] Cardanol is also commercially available, sold for example under the name Cardolite NX-2026 by the company Cardolite.

[0023] The cardanol present in the composition according to the invention is an alkoxylated cardanol. It is therefore a cardanol, the hydroxyl function of which has undergone an alkoxylation step. The alkoxylated cardanol compound(s), also referred to as “alkoxylated cardanols” hereinafter and usable in the process according to the invention, comprise from 2 to 200 alkoxylated units per phenolic unit, preferably 2 to 150 alkoxylated units per phenolic unit, more preferably from 2 to 100 alkoxylated units.

[0024] Advantageously, the alkoxylated units carried by the alkoxylated cardanol(s) are of formula -(RO)-, where the group R is a linear or branched alkylene group, C1-C6, preferably C2-C4. Preferably, the alkoxylated units are chosen from ethoxy groups denoted OE, propoxy denoted OP, butoxy denoted OB and mixtures thereof. The alkoxylated cardanol may thus comprise the following sequences: OP-OE, OE-OP-OE, OP-OE-OP, OE-OB, OB-OE, OB-OP, OP-OB, OE-OP-OB, OE-OB-OP, OP-OE-OB, OP-OE-OB, OB-OE-OP, OB-OP-OE, each alkoxy unit: OE, OP or OB comprising one or more identical monomers. The alkoxylated chains (i.e. the chains of alkoxyl groups) of the alkoxylated cardanol are terminated by the hydrogen atom or by a group R”, R” being a linear or branched alkyl group, C1-C36, preferably C1-C24, more preferably C1-C18, and even more preferably C2-C12. Preferably, the alkoxyl chains are terminated by the hydrogen atom.

[0025] Preferably, the alkoxylated cardanol according to the invention is not hydrogenated.

[0026] Preferably, the alkoxylated cardanol present in the composition according to the invention has a mixture of ethoxy units and propoxy units.

[0027] Preferably, the alkoxylated cardanol(s) present in the composition according to the invention comprise from 2 to 100 ethoxy and / or propoxy units.

[0028] Formocardanol resins

[0029] Formocardanol resins are resins well known to those skilled in the art. The methods for synthesizing these resins are for example described in document US20040050752.

[0030] For the purposes of the present invention, these formocardanol resins are then alkoxylated according to conventional synthesis routes.

[0031] Such alkoxylated formocardanol resins are well known to those skilled in the art and are commercially available or easily prepared using known procedures. Particularly preferred for the purposes of the invention are alkoxylated formocardanol resins which are bio-sourced and which comprise a content of atoms derived from biomass greater than 30%, as indicated above, and preferably greater than 40%, contents measured according to standard NF EN 16785-1 of January 2016.

[0032] The alkoxylated formocardanol resin(s) present in the composition according to the invention comprise from 2 to 200 alkoxyl units per phenolic unit, preferably from 2 to 150 alkoxyl units per phenolic unit, even more preferably from 2 to 100 alkoxyl units.

[0033] Advantageously, the alkoxyl units carried by the alkoxylated formocardanol resin are of formula -(R'O)-, where the R' group is a linear or branched alkylene group, C1-C6, preferably C2-C4. Preferably, the alkoxyl units are chosen from ethoxy groups denoted OE, propoxy denoted OP, butoxy denoted OB and their mixture. The alkoxylated formocardanol resin can thus comprise the following sequences: OP-OE, OE-OP-OE, OP-OE-OP, OE-OB, OB-OE, OB-OP, OP-OB, OE-OP-OB, OE-OB-OP, OP-OE-OB, OP-OB-OE, OB-OE-OP, OB-OP-OE, each alkoxy unit: OE, OP or OB comprising one or more identical monomers. The alkoxyl chains (i.e. the sequences of alkoxyl groups) of the alkoxylated formocardanol resin are terminated by the hydrogen atom or by a group R”, R” being a linear or branched alkyl group, C1-C36, preferably C1-C24, more preferably primarily in C1-C18, and even more preferably in C2-C12. Preferably, the alkoxylated chains are terminated by the hydrogen atom.

[0034] Preferably, the alkoxylated formocardanol resins present in the composition according to the invention comprise a mixture of ethoxy units and propoxy units.

[0035] Preferably, the alkoxylated formocardanol resins present in the composition according to the invention comprise from 2 to 100 ethoxy and / or propoxy units.

[0036] The molar mass of the non-alkoxylated formocardanol resin, i.e. the molar mass of the resin before its alkoxylation, is advantageously characterized by being between 600 g.mol1 and 200,000 g.mol ', preferably from 700 g.mol1 to 100,000 g.mol ', preferably from 900 g.mol1 to 50,000 g.mol *, more preferably from 1,000 g.mol1 to 20,000 g.mol *.

[0037] The composition according to the invention may further comprise one or more organic solvents in a content of between 1% and 98% by weight relative to the total weight of the composition, preferably between 5% and 70% by weight, more preferably between 10% and 60% by weight.

[0038] Preferably, the organic solvent is chosen from aromatic or aliphatic hydrocarbons, linear or branched, cyclic or acyclic, saturated or unsaturated, but also from glycols, glycolesters, esters, ketones, alcohols, water, as well as from mixtures of two or more of them.

[0039] More particularly, the organic solvent is chosen from methanol, ethanol, isopropanol, propanol, and advantageously from n-propanol, butanol, and more advantageously from tert-butanol, pentanol, glycerol, amyl alcohol, benzyl alcohol, phenol, benzene, toluene, xylene, kerosene, and organic solvents marketed under the brands SOLVESSO™, CAROMAX®, SOLVAREX®, SHELLSOL®, SOLVESSO™ 100 (supplier EXXON MOBIL), SOLVESSO™ 150 (supplier EXXON MOBIL), SOLVESSO™ 200 ND (supplier EXXON MOBIL), CAROMAX® 18 (supplier Petrochem Carless Limited); ShellSol® A100 (supplier Shell Chemicals Europe BV), SOLVAREX® 9 A (Supplier Total Fluides), CAROMAX® 20LN (supplier HALTERMANN CARLESS), ShellSol® A150 ND (Shell Chemicals), CAROMAX® 28 LN (PETROCHEM CARLESS).

[0040] The composition according to the invention may comprise other compounds known as demulsifiers, such as polyalkoxylated block copolymers and their ester derivatives, alkoxylated alkylphenol-aldehyde resins, polyol polyalkoxylates, glycidyl ether polyalkoxylates, amphoteric acrylic acid copolymers, diallyldimethylammonium halides, polyalkyl thiooxides, poly-(1-acryloyl-4-methylpiperazine), polyalkoxylated glycerol and its ester derivatives, polyalkoxylated diethanol and its ester derivatives, polyalkoxylated triethanol and its derivatives esters, polyalkoxylated polyamines and associated cationic polymers, polyurethanes and their polyalkoxylated derivatives, hyperbranched polymers, vinyl polymers, polysilicones, dithiocarbamates, polyetheramines, sulfonated polystyrenes, cationic surfactants, anionic surfactants, amphoteric surfactants, non-ionic surfactants, ionic liquids and mixtures thereof.

[0041] According to a preferred embodiment, the useful composition comprises: - one or more resins obtained from alkoxylated formocardanol comprising from 2 to 100 ethoxy and / or propoxy units per phenolic unit and - one or more alkoxylated cardanol compounds comprising from 2 to 100 ethoxy and / or propoxy units per phenolic unit, the mass ratio between said alkoxylated resin(s) and said alkoxylated cardanol compound(s) is between 2:1 and 30:1, the resin(s) obtained from formocardanol having a molar mass ranging from 700 g.mol1 to 100,000 g.mol *.

[0042] Method

[0043] The invention also relates to a process for demulsifying fluids in the form of an emulsion, and in particular hydrocarbons from oil production, comprising a step of adding a composition as defined above.

[0044] Preferably, the composition is injected downhole, at the wellhead, upstream or at the water / hydrocarbon fluid separation installations. The composition according to the invention can be injected into the fluid via so-called umbilical pipes or via so-called "gas lift" pipes.

[0045] The composition according to the invention can be introduced into the fluid to be treated continuously, discontinuously, temporarily, in one or more times.

[0046] The composition may be introduced into the production fluid in a content of between 1 ppm by weight and 50,000 ppm by weight, or between 0.0001% and 5% by weight, preferably between 5 ppm by weight and 20,000 ppm by weight, more preferably between 8 ppm and 10,000 ppm by weight, and more particularly between 10 ppm by weight and 1,000 ppm by weight relative to the oil phase of the fluid.

[0047] It is possible to inject the composition according to the invention at the same time as other chemical additives such as corrosion inhibitors, anti-asphaltenes, anti-paraffins, pour point reducers (in English "pour point near are"), anti-foam, anti-hydrates (kinetic inhibitor, thermodynamic inhibitor, anti-caking agents), drag reducer (in English "drag reducer"), de-oilers, scavenger, mineral deposit inhibitors, asphaltene or paraffin dispersants.

[0048] The invention will be better understood in light of the following examples, given for illustrative purposes only and which are not intended to restrict the scope of the invention, defined by the appended claims. EXAMPLES

[0049] Table 1 describes the products tested. FCR 1, FCR 2 and FRC 3 are alkoxylated formocardanol resins. These resins have molar masses of approximately 1300 g.mol1 or 2000 g.mol1 before alkoxylation. CDL 1, CDL 2, CDL 3 and CDL 4 are alkoxylated compounds of cardanol. [Tables 1] Number of EO units Number of OP units FCR 1 Alkoxylated formocardanol resin with a molar mass of 2000 g.mol1 before alkoxylation 8 5 FCR 2 Alkoxylated formocardanol resin with a molar mass of 1300 g.mol1 before alkoxylation 8 - FCR 3 Alkoxylated formocardanol resin with a molar mass of 1300 g.mol1 before alkoxylation 6 1.5 CDL 1 Alkoxylated cardanol 8 5 CDL 2 Alkoxylated cardanol 6 1.5 CDL 3 Alkoxylated cardanol 30 - CDL 4 Alkoxylated cardanol 60 -

[0050] The following compositions are prepared. The contents are given as a percentage by weight relative to the total weight of the composition.

[0051] Compositions 1, 2, 5 and 6 are comparative compositions. Composition 1 comprises alkoxylated formocardanol resins as the sole active compound. Composition 2 comprises a mixture of ethoxylated formocardanol resins and alkoxylated cardanols, the mass ratio of which is below the claimed ratio. Compositions 5 and 6 comprise ethoxylated cardanol as the sole active compound.

[0052] Compositions 3 and 4 are according to the invention. [Tables 2] 1 Comp 2 Comp 3 Inv 4 Inv 5 Comp 6 Comp FCR 1 25.00 25.00 25.00 - - - FCR2 8.00 8.00 8.00 - - - CDL 1 - 37.00 8.60 - - - FCR 3 - - - 45.00 - - CLD2 - - - 4.50 40.00 - CLD3 - - - 5.00 - - CLD4 - - - 5.00 - 40.00 Solvent1 67.00 32.00 58.40 40.50 60.00 60.00 FCR / CDL ratio - 0.89:1 3.84:1 3.10:1 - - 1 aromatic solvent in CIO sold under the trade name Solvesso™ 150 by the company ExxonMobil. Evaluation of the compositions:

[0053] The effectiveness of the compositions is determined by measuring the separation of water from the crude oil emulsion as a function of time. The emulsion used contains 45% water. For this, 100 mL of emulsion is added to the graduated conical glass tubes. In each tube, 100 ppm of composition is introduced with a micropipette and then the tubes are shaken on an oscillating table for 2 minutes (150 oscillations per minute). The tubes are then placed in a water bath thermostatically controlled at 50°C. The separation of water is observed.

[0054] The crude oil used has an API density of 37.6° API and a Wax Apparent Temperature (WAT) of 34.5°C. The water used is synthetic water with 150 gL 1 of sodium chloride (NaCl) and a pH equal to 5.5. Results :

[0055] The results of the work are presented in Table 3 below: [Tables 3] volume of separated water (%) 1 comp 2 comp 3 inv 4 inv 5 comp 6 comp 0 min 0 0 0 0 0 0 5 min 8 6 23 13 0 0 10 min 17 10 36 20 0 0 20 min 31 25 45 34 1 3 30 min 36 28 45 40 2 5

[0056] The results show that compositions 3 and 4 can break the emulsion more quickly than comparative compositions 1, 2, 5 and 6.

Claims

Claims

1. Use of a composition comprising: - one or more alkoxylated formocardanol resins comprising from 2 to 200 alkoxylated units per phenolic unit, - one or more alkoxylated cardanol compounds comprising from 2 to 200 alkoxylated units per phenolic unit, the mass ratio between said alkoxylated resin(s) and said alkoxylated cardanol compound(s) being between 1:1 and 50:1, preferably between 2:1 and 30:1, more preferably between 3:1 and 25:1, for demulsifying fluids from oil production, and in particular hydrocarbons.

2. Use according to claim 1, characterized in that the molar mass of the non-alkoxylated formocardanol resin is between 600 g.mol1 and 200,000 g.mol *, preferably from 700 g.mol1 to 100,000 g.mol *, preferably from 900 g.mol1 to 50,000 g.mol *, more preferably 1000 g.mol1 to 20,000 g.mol *.

3. Use according to claim 1 or 2, characterized in that the composition comprises one or more organic solvents in a content of between 1% and 98% by weight relative to the total weight of the composition, preferably between 5% to 70% by weight, more preferably between 10% and 60% by weight.

4. Use according to any one of the preceding claims, characterized in that the resin(s) obtained from alkoxylated formocardanol comprise from 2 to 150 alkoxylated units per phenolic unit, preferably from 2 to 100 alkoxylated units.

5. Use according to any one of the preceding claims, characterized in that the alkoxylated units present in the resin(s) obtained from formocardanol are of formula -(R'O)- where the group R' is a linear or branched alkylene group, C1-C6, preferably C2-C4, and the chains of alkoxylated units (alkoxylated chains) are terminated by the hydrogen atom or a group R” which is a linear or branched alkyl group, C1-C36, preferably C1-C24, more preferably C1-C8, and even more preferably C2-C12.

6. Use according to claim 5, characterized in that the alkoxylated units are chosen from ethoxy, propoxy, butoxy groups and their mixtures.

7. Use according to any one of claims 1 to 6, characterized in that the alkoxylated cardanol(s) comprise from 2 to 150 alkoxyl units per phenolic unit, preferably from 2 to 100 alkoxyl units.

8. Use according to any one of claims 1 to 7, characterized in that the alkoxyl units present in the alkoxylated cardanol compound(s) are of formula -(R'O)- where the R' group is a linear or branched C1-C6, preferably C2-C4, alkylene group and the chains of alkoxyl units (alkoxyl chains) are terminated by the hydrogen atom or a R” group which is a linear or branched C1-C36, preferably C1-C24, more preferably C1-C18, and even more preferably C2-C12, alkyl group.

9. Use according to claim 8, characterized in that the alkoxyl units are chosen from ethoxy (OE), propoxy (OP), butoxy (OB) groups and their mixtures.

10. Process for demulsifying fluids in emulsion form, and in particular hydrocarbons, resulting from oil production, comprising a step of adding a composition as defined in claims 1 to 9.

11. Method according to claim 10, in which the composition is added in a content of between 1 ppm by weight and 50,000 ppm by weight, or between 0.0001% and 5% by weight, preferably between 5 ppm by weight and 20,000 ppm by weight, more preferably between 8 ppm and 10,000 ppm by weight, and more particularly between 10 ppm by weight and 1,000 ppm by weight relative to the oil phase of the fluid.

12. A method according to claim 10 or claim 11, wherein the composition is introduced into the production fluid continuously, discontinuously, or temporarily, in one or more times.