WO2024137277A1 - Copolymère séquencé désémulsifiant, procédé de formation d'un tel copolymère et procédé de désémulsification d'une émulsion de pétrole et d'eau - Google Patents

Copolymère séquencé désémulsifiant, procédé de formation d'un tel copolymère et procédé de désémulsification d'une émulsion de pétrole et d'eau Download PDF

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WO2024137277A1
WO2024137277A1 PCT/US2023/083534 US2023083534W WO2024137277A1 WO 2024137277 A1 WO2024137277 A1 WO 2024137277A1 US 2023083534 W US2023083534 W US 2023083534W WO 2024137277 A1 WO2024137277 A1 WO 2024137277A1
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Prior art keywords
demulsifying
block copolymer
oxide
water
alkylene
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PCT/US2023/083534
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English (en)
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Michael L. Tulchinsky
Tzu-Chi Kuo
Kathryn GRZESIAK
Roxanne M. Jenkins
Pramod AKHADE
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Dow Global Technologies Llc
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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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2627—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aromatic or arylaliphatic amine 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation

Definitions

  • Embodiments of the present disclosure are directed towards emulsions and specifically in reducing water in petroleum emulsions.
  • emulsions of petroleum and water are commonly formed, but are undesirable. Once formed, the emulsions can be stabilized by a variety of naturally occurring surface-active compounds found in petroleum such as surfactants and fine mineral particles.
  • An important step in addressing emulsions of petroleum and water is to break the interfacial film formed at the oil/water interface to enable the coalescence and separation of water from the petroleum. Separation of the petroleum from water and solids (e.g., from the dilbit) may be performed more efficiently by using additives to break the emulsion.
  • Known additives mostly belong to different classes of organic polymers, for example, ethylene oxide and propylene oxide copolymers, alkoxylated phenol formaldehyde resins, alkoxylated (poly)amines, or alkoxylated epoxy resins.
  • Current chemical treatments can reduce the water and solid contents in the petroleum to some degree, but there are still desires to remove more water and residuals to mitigate fouling and corrosion of process units. As such, there is a need to develop an efficient additive to further improve the reduction of water and minerals from such emulsions, including those formed from dilbit products.
  • the present disclosure provides for an efficient additive to improve the reduction of water and minerals from emulsions of petroleum and water, including those formed from dilbit products.
  • a demulsifying block copolymer that is the reaction product of an aniline derived starter containing an alkoxylation catalyst with a first alkylene oxide of butylene oxide to form an intermediate polymer, where the intermediate polymer is reacted with ethylene oxide in the presence of the alkoxylation catalyst to form an embodiment of the demulsifying block copolymer of the present disclosure.
  • Embodiments of the present disclosure further include a method of demulsifying an emulsion of petroleum and water that includes adding a demulsifying block copolymer to the emulsion of petroleum and water, where the demulsifying block copolymer comprises the reaction product of an aniline derived starter containing an alkoxylation catalyst with a first alkylene oxide selected from butylene oxide or propylene oxide to form an intermediate polymer; and the intermediate polymer with ethylene oxide in the presence of the alkoxylation catalyst to form the demulsifying block copolymer.
  • the method further includes allowing the emulsion having the demulsifying block copolymer to then separate into a petroleum phase and a water phase.
  • adding the demulsifying block copolymer to the emulsion can include adding 2 to 900 parts per million of the demulsifying block copolymer to the emulsion.
  • the aniline derived starter can have a structure of Formula I: where R
  • the aniline derived starter can be 0.3 to 2.2 weight percent of the total weight of the demulsifying block copolymer.
  • the aniline derived starter can be 4,4'-methylenebis(N,N-di(2- hy droxypropyl)aniline) .
  • the first alkylene oxide used to form the intermediate polymer is butylene oxide.
  • the weight ratio of the butylene oxide to the ethylene oxide in the demulsifying block copolymer can be from 1.2 to 2.7.
  • the weight average molecular weight of the demulsifying block copolymer can be in a range of 10,000 to 18,000 g/mol.
  • the first alkylene oxide used to form the intermediate polymer can be propylene oxide.
  • the weight ratio of the propylene oxide to the ethylene oxide in the demulsifying block copolymer is from 1.0 to 6.0.
  • the weight average molecular weight of the demulsifying block copolymer can be in a range of 7,000 to 15,000 g/mol.
  • the present disclosure provides for an efficient additive to improve the reduction of water and minerals from emulsions of petroleum and water, including those formed from dilbit products.
  • Embodiments of the present disclosure provide for the synthesis and use of a demulsifying block copolymer that enable significant water reduction in emulsions of petroleum and water.
  • the demulsifying block copolymer of the present disclosure employs an initiator containing aromatic moieties and primary amino groups to form an aniline derived starter, which in turn undergoes an alkoxylation reaction with either propylene oxide (PO) or butylene oxide (BO) to form an intermediate polymer, where the intermediate polymer undergoes alkoxylation with ethylene oxide (EO), as described herein, to form the demulsifying block copolymer of the present disclosure.
  • an initiator containing aromatic moieties and primary amino groups to form an aniline derived starter, which in turn undergoes an alkoxylation reaction with either propylene oxide (PO) or butylene oxide (BO) to form an intermediate polymer, where the intermediate polymer undergoes alkoxylation with ethylene oxide (EO), as described herein, to form the demulsifying block copolymer of the present disclosure.
  • PO propylene oxide
  • BO butylene oxide
  • EO ethylene oxide
  • the term “petroleum” includes unprocessed crude oil, crude oil emulsion, unprocessed bitumen, emulsion of refined crude oil, dilbit and dilbit products.
  • the terms emulsion or emulsions of petroleum and water can include a petroleum- in-water emulsion and/or a water-in-petroleum emulsion.
  • water can include, for example, a brine, a connate water, fresh water, surface water, well water, distilled water, carbonated water, engineered water, sea water and a combination thereof.
  • water will be used herein (unless clearly indicated otherwise), where it is understood that one or more of “brine,” “connate water,” “fresh water”, “surface water,” “well water”, “distilled water,” “carbonated water,” “engineered water” and/or “sea water” can be used interchangeably.
  • ethylene oxide” or “EO” is also known as oxirane and has the formula C2H4O.
  • propylene oxide” or “PO” includes 1,2-propylene oxide and 1,3-propylene oxide.
  • the propylene oxide or PO is 1,2-propylene oxide.
  • butylene oxide or “BO” includes ethyloxirane and 2,3-dimethyloxirane.
  • the butylene oxide or BO is ethyloxirane.
  • the demulsifying block copolymer of the present disclosure is the reaction product of an aniline derived starter containing an alkoxylation catalyst with a first alkylene oxide selected from butylene oxide or propylene oxide to form an intermediate polymer, where the intermediate polymer is reacted with ethylene oxide in the presence of the alkoxylation catalyst to form the demulsifying block copolymer of the present disclosure.
  • the demulsifying block copolymer of the present disclosure is the reaction product of an aniline derived starter containing the alkoxylation catalyst with the first alkylene oxide of butylene oxide to form the intermediate polymer, where the intermediate polymer is reacted with ethylene oxide in the presence of the alkoxylation catalyst to form the demulsifying block copolymer of the present disclosure.
  • the demulsifying block copolymer of the present disclosure is the reaction product of an aniline derived starter containing the alkoxylation catalyst with the first alkylene oxide of propylene oxide to form the intermediate polymer, where the intermediate polymer is reacted with ethylene oxide in the presence of the alkoxylation catalyst to form the demulsifying block copolymer of the present disclosure.
  • the aniline derived starter of the present disclosure can have a structure of Formula I: Formula I where R
  • R is a Cl to C3 alkylene or alkylidene
  • each R2 is a CO to C3 alkylene or alkylidene
  • R3 is a C2 or C3 alkylene.
  • each R2 is identical to the other R2 moiety in Formula I
  • each R3 is identical to the other R3 moieties in Formula I (e.g., the compound of Formula I is symmetrical). It is, however, possible that different R2 and/or R3 moieties are present in the aniline derived starter of Formula I e.g., the compound of Formula I is asymmetrical).
  • oligomers of Formula I e.g., two or more of the structure of Formula I
  • the aniline derived starter is 4,4'- methylenebis(N,N-di(2-hydroxypropyl)aniline of Formula II: Formula II where Rj is a Cl alkylene namely methylene; each R2 is not present (i.e., a CO alkyl) and R3 is a C3 alkylene namely 1,2-propylene.
  • Rj is a Cl alkylene namely methylene
  • each R2 is not present (i.e., a CO alkyl)
  • R3 is a C3 alkylene namely 1,2-propylene.
  • Other preferred formulae for the aniline derived starter of the present disclosure include those where R ⁇ is an ethylidene; each R2 is not present and R3 is a C4 alkylene namely 1,2-butylene.
  • the aniline derived starter of Formula I is formed from an initiator containing aromatic moieties and primary amino groups.
  • the initiator can have the structure of Formula III: Formula III where R
  • R is a Cl to C3 alkylene or alkylidene
  • each R2 is a CO to C3 alkylene or alkylidene.
  • each R2 is identical to the other R2 moiety in Formula I. It is, however, possible that different R2 moieties are present in the initiator of Formula III.
  • the initiator of Formula III is 4,4’-methylenedianiline (MDA), where Rj is methylene and each R2 is not present (z.e., a CO alkyl) and the primary amine moieties are in the para position relative to the position of the Rj group.
  • MDA 4,4’-methylenedianiline
  • Rj is methylene and each R2 is not present (z.e., a CO alkyl) and the primary amine moieties are in the para position relative to the position of the Rj group.
  • Other preferred initiators of Formula Ill include, but are not limited to, 4,4’-ethylidenedianiline, 3,3’-ethylidenedianiline and 4,4’- propylidenedianiline.
  • the initiator of Formula III undergoes an alkoxylation reaction with either propylene oxide (PO) or butylene oxide (BO) to form the aniline derived starter of Formula I.
  • the alkoxylation reaction to form the aniline derived starter is an autocatalytic reaction, as are known in the art.
  • the reaction mixture of the initiator of Formula III and either of PO or BO has a molar ratio of 1 :3 to 1 :5 (initiator to PO or BO).
  • the reaction mixture has a molar ratio of 1 :4 (initiator to PO or BO).
  • the alkoxylation reaction can take place at a reaction temperature of 80 °C to about 180 °C.
  • the alkoxylation reaction can take place at a reaction temperature of 100 °C to about 160 °C .
  • Reaction times for the alkoxylation reaction can be from 12 hours to 2 days. Those skilled in the art will be able to determine appropriate conditions with, at most, routine experimentation.
  • the aniline derived starter is then reacted under alkoxylation conditions in the presence of the alkoxylation catalyst and the first alkylene oxide selected from BO or PO to form an intermediate polymer.
  • the alkoxylation catalyst used for the alkoxylation reaction can be, for example, potassium hydroxide (KOH) or a double metal cyanide compound, as are known in the art.
  • KOH potassium hydroxide
  • aqueous KOH catalyst may be introduced and the water removed azeotropically to have the starter dry.
  • Various techniques may be used, including for instance the use of benzene and/or toluene followed by application of azeotropic distillation at ambient or reduced pressure, elevated temperature or both, employing nitrogen purge, or a combination of these.
  • the BO or PO are reacted with the aniline derived starter under alkoxylation conditions in the presence of a catalyst.
  • this reaction may be carried out at an elevated temperature or temperatures ranging from about 80 °C to about 180 °C. In other non-limiting embodiments, the temperature may range from about 100 °C to about 160 °C. Reaction times for the alkoxylation reaction can be from 2 hours to 4 days. Those skilled in the art will be able to determine appropriate conditions with, at most, routine experimentation.
  • the alkoxylation reaction is conducted in the presence of an effective amount of potassium hydroxide as catalyst.
  • the amount of the catalyst may, in some embodiments, range from about 0.1 wt.% to about 20 wt.% by weight, based on the total weight of the starter. In some embodiments, the amount may range from about 1 wt.% to 10 wt.%.
  • the starter containing the alkoxylation catalyst can be mixed with either BO or PO and the reaction continued until alkoxylation is completed to form the intermediate polymer.
  • the reaction may be subjected to digestion periods (e. , about 1-10 hours at about 100 °C to 160 °C), between butylene oxide, propylene oxide and ethylene oxide additions and/or after the butylene oxide, propylene oxide, and/or ethylene oxide addition.
  • the intermediate polymer may be discharged from the reactor without removal of the catalyst. If desired, the intermediate polymer may be treated to neutralize the catalyst
  • the intermediate polymer is then reacted with ethylene oxide (EO) in the presence of the alkoxylation catalyst, as described herein, to form an embodiment of the demulsifying block copolymer (Formula IV) of the present disclosure.
  • EO ethylene oxide
  • Rj, R2 and R3 are as previously discussed, where R4 is C3 or C4 alkyleneoxy group, R5 is C2 ethyleneoxy group, n is 5 to 50 and m is 4 to 70.
  • the first alkylene oxide used to form the intermediate polymer is BO (i.e., R4 is C4).
  • the weight ratio of the BO to the EO in the demulsifying block copolymer can be from 1.2 to 2.7.
  • the weight average molecular weight of the demulsifying block copolymer can be in a range of 10,000 to 18,000 g/mol.
  • n is 5 to 20 and m is 10 to 70.
  • the first alkylene oxide used to form the intermediate polymer is PO (i.e., R4 is C3).
  • the weight ratio of the PO to the EO in the demulsifying block copolymer can be from 1.0 to 6.0.
  • the weight average molecular weight of the demulsifying block copolymer can be in a range of 7,000 to 15,000 g/mol.
  • R4 is C3
  • n is 10 to 50
  • m is 4 to 40.
  • the initiator of Formula III can be 0.3 to 2.2 weight percent of the total weight of the demulsifying block copolymer.
  • Embodiments of the present disclosure also include a method of forming the demulsifying block copolymer of the present disclosure.
  • the aniline derived starter is reacted in the presence of the alkoxylation catalyst with the first alkylene oxide selected from butylene oxide or propylene oxide under alkoxylation conditions to form the intermediate polymer.
  • the intermediate polymer is reacted with ethylene oxide in the presence of the alkoxylation catalyst under alkoxylation conditions, as discussed herein, to form the demulsifying block copolymer of the present disclosure.
  • an initial step involves the autocatalytic propoxylation of 4,4’ -methylenedianiline (MDA) with PO to form an embodiment of Formula I, as discussed herein and as seen below, where R ⁇ is a Cl alkylene (methylene); each R2 is CO (i.e., not present) and R3 is a C3 alkylene (1,2-propylene).
  • MDA 4,4’ -methylenedianiline
  • R ⁇ is a Cl alkylene (methylene); each R2 is CO (i.e., not present) and R3 is a C3 alkylene (1,2-propylene).
  • the embodiment of Formula I is then alkoxylated with PO (or BO) in the presence of catalytic amounts of KOH after azeotropically distilling water off with toluene, as discussed herein.
  • the obtained PO- polymer (or BO-polymer) is then ethoxylated with EO, as discussed herein, to make an embodiment of the demulsifying block copolymer of the present disclosure.
  • This sequence of steps is depicted for the demulsifying block copolymer having the PO-EO copolymer moiety as follows:
  • the MDA can be present in 1.0 to 2.5 wt.% based on the total weight of the demulsifying block copolymer, while the PO to EO weight ratios can be in the approximate range from 2 to 5.
  • the gel permeation chromatography (GPC) based weight average molecular weights, M w can be in the range of 6,000 to 12,000 g/mol, with relative solubility numbers (RSN, described in the Examples section below) in the range of 10 to 15.
  • GPC gel permeation chromatography
  • RSN relative solubility numbers
  • the sequence of steps for the demulsifying block copolymer having the BO-EO copolymer moiety can be as follows:
  • the MDA can be present in 0.3 to 1.5 wt.% based on the total weight of the demulsifying block copolymer, while the BO to EO weight ratios can be in the approximate range from 2 to 1.
  • the gel permeation chromatography (GPC) based weight average molecular weights, Mw can be in the range of 8,000 to 20,000 g/mol, with RSN in the range of 10 to 15.
  • Embodiments of the present disclosure also include a method of demulsifying an emulsion of petroleum and water that includes adding the demulsifying block copolymer of the present disclosure to the emulsion and allowing the emulsion to separate into a petroleum phase and a water phase.
  • Using the demulsifying block copolymer of the present disclosure in demulsifying an emulsion of petroleum and water into a water phase and a petroleum phase may be carried out in a conventional manner.
  • demulsifying the emulsion of petroleum and water into the petroleum phase and the water phase and then separating and recovering the petroleum phase and water phase may be carried out by treating the emulsion with a demulsifying amount of the demulsifying block copolymer of the present disclosure.
  • Examples of demulsifying the emulsion of petroleum and water into the water phase and the petroleum phase can include adding 2 to 900 parts per million of the demulsifying block copolymer to the emulsion.
  • Other suitable amounts for demulsifying the emulsion of petroleum and water into the water phase and the petroleum phase can include adding 5 to 900 parts per million of the demulsifying block copolymer to the emulsion or adding 50 to 900 parts per million of the demulsifying block copolymer to the emulsion.
  • the demulsifying block copolymer of the present disclosure can help to destabilize the emulsion of petroleum and water so as to enhance water droplet coalescence.
  • a mixing process can be used with the emulsion of petroleum and water in breaking the emulsion with the demulsifying block copolymer of the present disclosure.
  • sufficient agitation can be used to allow the demulsifying block copolymer of the present disclosure to mix thoroughly with the emulsion of petroleum and water, followed by a period of flow inside a separator to promote gravity separation.
  • the process can also include a sufficient retention time in the separator(s) to allow the water droplets to settle.
  • the process may also require the addition of heat, electric grids, and coalescers to facilitate or completely resolve the emulsion.
  • the efficacy of the demulsifying block copolymer of the present disclosure can be dependent upon a number of factors such as the properties of the petroleum and/or the water of the emulsion, the mixer type, and the design and operating conditions of the demulsifying equipment.
  • the most effective conditions for the demulsification may be at least partially determined through the use of a bottle testing procedure, as is known.
  • demulsification can include, but are not limited to, temperature, pH, type of crude oil, brine composition, and droplet size and distribution.
  • An increase in temperature can result in a decrease in emulsion stability.
  • the pH of the emulsion of petroleum and water may also affect the performance of the demulsifying block copolymer of the present disclosure.
  • compositions including weight percent (wt.%) of 4,4’-methylenedianiline (MDA), BO, PO, and EO in the samples were determined by integration of r H NMR spectra (Varian 400-NMR spectrometer (400 MHz, 1 H) with an autosampler) of the materials in d- chloroform (CDCh).
  • GPC gel permeation chromatography
  • Agilent 1260 Infinity system equipped with a refractive index detector and columns with a linear MW operating range up to 30,000 g/mol, using Agilent EasiVial PS-L polystyrene standards.
  • GPC samples were prepared by weighing ⁇ 10 mg of each sample into pre-weighted vials, and the accurate weights were then recorded.
  • Tetrahydrofuran (THF) was added to prepare 1.0 mg/mL solutions. Samples were shaken to dissolve solids and filtered into vials for GPC.
  • RSN Relative solubility number
  • the reactions to form the demulsifying block copolymer MDA/PO/EO were carried out in a parallel pressure reactor (PPR®, Unchained Labs, formerly Symyx Technologies) setup containing 48 (6 x 8) reactors.
  • PPR® Parallel pressure reactor
  • Propylene oxide (PO) and ethylene oxide (EO) were delivered via a Teledyne ISCO syringe pump (Model 260D) equipped with a robotically controlled needle and compressed gas micro valve (Bio-Chem valve p/n 100T2-S493).
  • the layout for each of the used cells was designed using Library Studio®. A glass insert along with a removable PEEK stir paddle for each cell were dried in a vacuum oven at 125 °C.
  • Step 1 Initial Auto-Catalytic Reaction with PO
  • the MDA(PO)4 adduct with approximately four PO per each MDA as described above served as a starter for the subsequent alkoxylations.
  • the MDA(PO)4 adduct (10 g) was mixed with calculated amounts of 50 wt.% KOH solutions to make 20 wt.% KOH mixture relative to the MDA(P0)4 adduct. Then about 100-150 mL of toluene was added and water was removed azeotropically at 110 °C using a Dean-Stark trap. The remaining toluene was evaporated in vacuum.
  • the dry MDA(P0)4 adduct containing the KOH catalyst was weighed into glass inserts.
  • the glass inserts along with the stir paddles were loaded to the corresponding PPR wells and the reactors were sealed.
  • the cells were charged by robot with calculated amounts of PO.
  • the temperature was increased to 115 °C and reaction mixtures were stirred for 2 days after reaching the process temperature.
  • the pressure in the reactors gradually leveled off, indicating that the reactions were completed to produce MDA(PO)n intermediate.
  • the cells were cooled, vented and purged with nitrogen to remove any residual PO.
  • Laboratory scale dilbit was produced from oil sands obtained from various operators in Alberta, Canada. Approximately 1500 g of oil sands were used in a single batch and resulted in about 200-300 g extracted bitumen froth. First, the oil sand was placed in a heated vessel (58 °C). Approximately 3000 g of water containing 600 parts per million (ppm) KC1 was added to the oil sand while continuously stirring the mixture. The stir speeds varied at different times during the process to introduce large amounts of shear. While continuing to stir, nitrogen was bubbled up through the mixture to increase the separation of bitumen so that it rose to the top of the mixture as bitumen froth.
  • ppm parts per million
  • the process was stopped and the froth was scraped off the top of the vessel.
  • the collected bitumen froth was diluted with naphtha to produce dilbit using a ratio of 0.4 g naphtha per 1.0 g bitumen froth.
  • the efficiency of the demulsifying block copolymer MDA/PO/EO was evaluated using a high throughput bottle test method using a liquid handler. Each run contained 12 samples including controls. Dilbit was homogenized using an impeller attached to an overhead mixer (900 rpm for 10 min). Next the dilbit was mixed using a dual-axis speedmixer (FlakTek 2,000 rpm for 1.5 min, twice).
  • the dilbit was placed in a container on the deck of an 8-channel liquid handler, and the robot dispensed the dilbit into 12 vials (4 mL per vial).
  • Stock solutions of the demulsifying block copolymer MDA/PO/EO were formulated in a solvent mixture of 3 : 1 xylene: isopropanol, by mass.
  • the demulsifying block copolymer MDA/PO/EO concentration in the stock solutions was 0.6 wt.%.
  • the robot added 200 pL of the additive stock solutions into the vials to test the additives at 300 ppm with respect to the dilbit.
  • the samples were mixed at 3500 rpm for 1 minute using the dual-axis speed mixer, and then kept at 60 °C for 45 min.
  • the samples were then mixed again on the dual-axis speed mixer at 3500 rpm for 30 seconds (s). After that, they were centrifuged at 2000 rpm (470 g relative centrifuging acceleration) for 5 min, and then about 150 mg from each vial at a fixed depth (about 1/3 of the same volume from the top) was withdrawn via syringe for Karl Fischer analysis.
  • the water contents of the samples were measured using a Metrohm oven Karl Fischer Titrator with an autosampler, which heats the sample to 120 °C to remove all the water from the sample.
  • CE A-C were prepared in a manner similar to EX 1-10 as discussed above, but the tested demulsifying compositions of the comparative examples had chemical properties that fell outside of those for the demulsifying block copolymer MDA/PO/EO, where the differences are noted in Table 2.
  • CE D CE D tested the performance of the commercially available benchmark additive, which is an amine-initiated polyol block copolymer with an approximate average molecular weight of 4,500 daltons sold under the tradename DemtrolTM.
  • the benchmark additive which contained a different amine initiator and a lower average MW than the demulsifying block copolymer of the present disclosure showed lower performance at 300 ppm than the demulsifying block copolymer of the present disclosure as seen in Table 2.
  • Step 1 identical to EX 1-10.
  • Step 2 MDA-(PO)4 Adduct Reaction with BO.
  • the MDA-(P0)4 adduct with approximately four PO per each MDA as described above served as a starter for the subsequent alkoxylations.
  • the MDA-(PO)q adduct (10 g) was mixed with calculated amounts of 50 wt.% KOH solutions to make 20 wt.% KOH mixture relative to the MDA-(PO)4 adduct. Then about 100-150 mL of toluene was added and water was removed azeotropically at 110 °C using a Dean-Stark trap. The remaining toluene was evaporated in vacuum.
  • the dry MDA-(P0)4 adduct containing the KOH catalyst was weighed into glass inserts.
  • the glass inserts along with the stir paddles were loaded to the corresponding PPR wells and the reactors were sealed.
  • the cells were charged by robot with calculated amounts of BO.
  • the temperature was increased to 115 °C and reaction mixtures were stirred for 2 days after reaching the process temperature.
  • the pressure in the reactors gradually leveled off, indicating that the reactions were completed to form MDA(PO)4(BO)n.
  • the cells were cooled, vented and purged with nitrogen to remove residual BO.
  • the efficiency of the demulsifying block copolymer MDA/PO/BO/EO was tested as described above for the demulsifying block copolymer MDA/PO/EO.
  • the results on remaining water in the samples are normalized with the control (containing no additive) and are presented in Table 3 as relative percent water. Lower relative water percentages correspond to the better performance of the additive.
  • CE E-F were prepared in a manner similar to EX 11-14 as discussed above, but the tested demulsifying compositions of the comparative examples had chemical properties that fell outside of those for the demulsifying block copolymer MDA/PO/BO/EO, where the differences are noted in Table 3.
  • CE G tested the performance of the commercially available benchmark additive, which is an amine-initiated polyol block copolymer with an approximate average molecular weight of 4,500 daltons sold under the tradename DemtrolTM
  • the benchmark additive which contained a different amine initiator and a lower average MW than the demulsifying block copolymer of the present disclosure showed lower performance at 300 ppm than the demulsifying block copolymer of the present disclosure as seen in Table 3.
  • Examples 15 and 16 are large scale synthesis of the demulsifying block copolymer MDA-(PO)4(BO)m(EO)n, while EX 17 is a large scale synthesis of the demulsifying block copolymer MDA-(PO)4(EO)n.
  • Step 1 The initial auto-catalytic reaction with PO was carried out similar to the step 1 procedure in EX 1-10 to give the MDA(P0)4 adduct.
  • Step 2 MDA(P0)4 adduct reactions with BO.
  • the MDA(P0)4 adduct (10 g) was mixed with calculated amounts of 50 wt.% KOH solutions to make 20 wt.% KOH mixture relative to the MDA(P0)4 adduct. Then about 100-150 mb of toluene was added and water was removed azeotropically at 110 °C using a Dean-Stark trap. The remaining toluene was evaporated in vacuum.
  • the dry MDA(P0)4 adduct containing the KOH catalyst (0.135 g) was weighed into 48 glass inserts. The glass inserts along with the stir paddles were loaded to the corresponding PPR wells and the reactors were sealed. The 24 cells in the top half of the plate were charged manually with 3.99 mL of BO and the 24 cells in the bottom half of the plate were charged with 3.56 mL of BO. The temperature was increased to 115 °C and reaction mixtures were stirred for 2 days after reaching the process temperature to produce the MDA(P0)4(B0)m intermediates. The pressure in the reactors gradually leveled off, indicating that the reactions were completed forming the MDA(P0)4(B0)m intermediates. The cells were cooled, vented and purged with nitrogen to remove any residual BO.
  • Step 3 MDA(P0)4(B0)m intermediates reaction with EO.
  • 1.28 mL of EO were introduced by robot at 50 °C to the top half of the plate and 1.68 mL of EO were added to the bottom half of the plate.
  • the temperature was increased to 130 °C and the reactors were stirred for 4 hours to produce the demulsifying block copolymer MDA-(P0)4(B0)m(E0)n.
  • the pressure curves were consistent with the reaction completion.
  • Step 1 The initial auto-catalytic reaction with PO was carried out similar to the step 1 procedure in EX 1-10 to give the MDA(P0)4 adduct.
  • Step 2 MDA(P0)4 adduct reactions with PO.
  • the MDA(P0)4 adduct (10 g) was mixed with calculated amounts of 50 wt.% KOH solutions to make 20 wt.% KOH mixture relative to the MDA(P0)4 adduct. Then about 100-150 mL of toluene was added and water was removed azeotropically at 110 °C using a Dean-Stark trap. The remaining toluene was evaporated in vacuum.
  • the dry MDA(P0)4 adduct containing the KOH catalyst (0.135 g) was weighed into 32 glass inserts.
  • the glass inserts along with the stir paddles were loaded to the corresponding PPR wells and the reactors were sealed.
  • the 32 cells on the plate were charged manually with 4.39 mL of PO each.
  • the temperature was increased to 115 °C and reaction mixtures were stirred for 2 days after reaching the process temperature to produce the MDA(PO)q intermediates.
  • the pressure in the reactors gradually leveled off, indicating that the reactions were completed forming the MDA(PO)q intermediates.
  • the cells were cooled, vented and purged with nitrogen to remove any residual PO.
  • Step 3 MDA(PO)q intermediates reaction with EO.
  • 0.84 mL of EO were introduced by robot at 50 °C.
  • the temperature was increased to 130°C and the reactors were stirred for 4 hours to produce the demulsifying block copolymer MDA-(PO)q(EO)n.
  • the pressure curves were consistent with the reaction completion.
  • small samples of the demulsifying block copolymer MDA-(PO)q(EO)n were taken from each reactor for GPC analyses.
  • CE H is a polyol block copolymer which contains a different amine initiator and a lower average MW than the present Examples.
  • CE l is a field demulsifier formulation that contains EO/PO block copolymer and alkylphenol formaldehyde resin alkoxylate intermediate.
  • CE J is a knockout drop demulsifier.
  • Crude Oil A and CE I Crude Oil emulsion and incumbent CE I from Canada.
  • Crude Oil B Emulsion from drilled cutting cleaning process.
  • Crude Oil C Crude oil emulsion from Russia.
  • Demulsifying block copolymer evaluation for Crude Oil A at 50, 100, and 200 ppm The efficiency of the demulsifying block copolymers of the present disclosure was evaluated using a standard bottle test method for Crude Oil A at 50, 100, and 200 ppm.
  • the demulsifying block copolymers were heated at 50 °C for 30 min. in a water bath. Then, stock solutions of each demulsifying block copolymer were formulated in a solvent mixture of 3 : 1 toluene: isopropanol, by mass.
  • the demulsifying block copolymer concentration in the stock solutions was 10 wt.%.
  • Prescription bottles were charged with 100 mL of crude oil emulsion.
  • the additive stock solutions were dosed into the bottles to test the additives at 50, 100, and 200 ppm (based on actives) with respect to the crude oil.
  • Free water drop amount of water (mL) that separated in the bottle after heating at 50
  • Dry oil from top amount of dry oil (mL) that separated in the bottle after heating at 50 °C after 30 min. A larger number indicates faster drying performance.
  • BS basic sediments
  • % water (W) the percentage of water separated in the graduated tube after centrifugation. A smaller number indicates better performance.
  • EX 15 offered better properties in emulsion breaking and oil drying as compared to CE H-J. When compared with the CE H, the EX 15 showed superior performance at 100 ppm. Approximately 54.5% less BS&W and 70% improved dry oil volume were observed for EX 15 as compared to the CE H, indicating EX 15 exhibits faster oil drying properties at the higher dosage.
  • EX 15 showed excellent oil drying properties and exhibited better performance than both CE H and CE I and the blank.
  • the data shows the product yields 99.5% less BS&W than both CE H and CE I and the blank, indicating less water was present in the oil for the sample dosed with EX 15.
  • EX 16 showed superior performance at 100 ppm and 200 ppm: -99.5% less BS&W and -140% improved dry oil volume, indicating EX 16 has faster oil drying properties as compared to CE H.
  • increasing EX 15 dosage offered better properties in emulsion breaking and oil drying.
  • EX 15 showed excellent oil drying properties at 200 ppm and showed superior performance as compared to CE I and CE J and blank sample.
  • EX 15 shows 99.5% less BS&W as compared to CE I and CE J and blank sample, which indicates more water was removed from the oil.

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Abstract

La présente divulgation concerne un copolymère séquencé désémulsifiant qui est le produit de réaction d'un initiateur dérivé d'aniline en présence d'un catalyseur d'alcoxylation avec un premier oxyde d'alkylène choisi parmi l'oxyde de butylène ou l'oxyde de propylène pour former un polymère intermédiaire, le polymère intermédiaire étant mis à réagir avec de l'oxyde d'éthylène en présence du catalyseur d'alcoxylation pour former le copolymère séquencé désémulsifiant.
PCT/US2023/083534 2022-12-21 2023-12-12 Copolymère séquencé désémulsifiant, procédé de formation d'un tel copolymère et procédé de désémulsification d'une émulsion de pétrole et d'eau WO2024137277A1 (fr)

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