Demulsifying block copolymers, methods for forming such copolymers and methods of demulsifying emulsions of petroleum and water

Abstract

The present disclosure relates to a demulsified block copolymer which is the reaction product of an aniline-derived starter with a first alkylene oxide selected from butylene oxide or propylene oxide in the presence of an alkoxylation catalyst to form an intermediate polymer, wherein the intermediate polymer is reacted with ethylene oxide in the presence of the alkoxylation catalyst to form the demulsified block copolymer.

Description

Technical Field

[0001] Embodiments of the present disclosure relate to emulsions and, in particular, to reducing water in petroleum emulsions. Background Art

[0002] In the extraction, transportation, and refining of various forms of petroleum, such as diluted bitumen (“dilbit”), emulsions of petroleum and water are often formed, which is undesirable. Once formed, the emulsions can be stabilized by various naturally occurring surface-active compounds found in petroleum, such as surfactants and fine mineral particles.

[0003] An important step in resolving petroleum and water emulsions is to disrupt the interfacial film formed at the oil / water interface so that water can coalesce and separate from the petroleum. By using additives to disrupt the emulsion, the separation of petroleum from water and solids (e.g., from dilbit) can be performed more effectively. Most known additives belong to different classes of organic polymers, such as 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 solids content in petroleum to some extent, but there is still a desire to remove more water and residues to mitigate fouling and corrosion of process units. Therefore, there is a need to develop effective additives to further improve the reduction of water and minerals from such emulsions, including those formed from dilbit products. Summary of the Invention

[0004] The present disclosure provides effective additives to improve the reduction of water and minerals from emulsions of petroleum and water, including those formed from dilbit products. With respect to the present disclosure, a demulsifying block copolymer is provided, which is the reaction product of an aniline-derived initiator containing an alkoxylation catalyst and a first alkylene oxide of epoxybutane to form an intermediate polymer, wherein the intermediate polymer reacts with ethylene oxide in the presence of an alkoxylation catalyst to form an embodiment of the demulsifying block copolymer of the present disclosure.

[0005] Embodiments of the present disclosure also include a method for demulsifying an emulsion of petroleum and water, the method comprising adding a demulsifying block copolymer to the emulsion of petroleum and water, wherein the demulsifying block copolymer comprises the reaction product of: an aniline-derived initiator containing an alkoxylation catalyst and a first alkylene oxide selected from epoxybutane or propylene oxide to form an intermediate polymer; and the intermediate polymer and ethylene oxide in the presence of an alkoxylation catalyst to form a demulsifying block copolymer. The method further comprises allowing the emulsion having the demulsifying block copolymer to then separate into a petroleum phase and a water phase. For various embodiments, adding the demulsifying block copolymer to the emulsion may comprise adding from 2 million parts to 900 million parts of the demulsifying block copolymer to the emulsion.

[0006] For various embodiments, the aniline-derived initiator can have the structure of Formula I:

[0007]

[0008] wherein R1 is a C1-C3 alkylene or alkylidene; each R2 is a C0-C3 alkylene or alkylidene; and R3 is a C2 or C3 alkylene. For various embodiments, the aniline-derived initiator can be from 0.3 wt% to 2.2 wt% of the total weight of the demulsifying block copolymer. For various embodiments, the aniline-derived initiator can be 4,4'-methylenebis(N,N-bis(2-hydroxypropyl)aniline).

[0009] For various embodiments of the demulsifying block copolymer, the first alkylene oxide used to form the intermediate polymer is butylene oxide. For these various embodiments, the weight ratio of butylene oxide to ethylene oxide in the demulsifying block copolymer can be from 1.2 to 2.7. Further, for these embodiments, the weight-average molecular weight of the demulsifying block copolymer can be in the range of 10,000 g / mol to 18,000 g / mol.

[0010] In an alternative embodiment of the demulsifying block copolymer, the first alkylene oxide used to form the intermediate polymer can be propylene oxide. For these various embodiments, the weight ratio of propylene oxide to ethylene oxide in the demulsifying block copolymer is from 1.0 to 6.0. Further, for these embodiments, the weight-average molecular weight of the demulsifying block copolymer can be in the range of 7,000 g / mol to 15,000 g / mol. DETAILED DESCRIPTION

[0011] The present disclosure provides effective additives for improving the reduction of water and minerals from emulsions of oil and water, including those formed from diluted bitumen products. Embodiments of the present disclosure provide the synthesis and use of demulsifying block copolymers capable of significantly reducing water in emulsions of oil and water. The demulsifying block copolymers of the present disclosure employ an initiator containing an aromatic moiety and a primary amino group to form an aniline-derived initiator, which in turn undergoes alkoxylation with propylene oxide (PO) or butylene oxide (BO) to form an intermediate polymer, wherein the intermediate polymer undergoes alkoxylation with ethylene oxide (EO), as described herein, to form the demulsifying block copolymers of the present disclosure.

[0012] As used herein, the term "petroleum" includes unprocessed crude oil, crude oil emulsions, unprocessed asphalt, emulsions of refined crude oil, dilbit, and dilbit products. As used herein, one or more emulsions of petroleum and water can include water-in-petroleum emulsions and / or petroleum-in-water emulsions. As used herein, the term "water" can include, for example, brine, connate water, fresh water, surface water, well water, distilled water, carbonated water, engineered water, seawater, and combinations thereof. For the sake of brevity, the word "water" will be used herein (unless otherwise expressly stated), with the understanding that one or more of "brine", "connate water", "fresh water", "surface water", "well water", "distilled water", "carbonated water", "engineered water", and / or "seawater" can be used interchangeably. As used herein, "ethylene oxide" or "EO" is also known as oxirane and has the formula C2H4O. As used herein, "propylene oxide" or "PO" includes 1,2-propylene oxide and 1,3-propylene oxide. Preferably, propylene oxide or PO is 1,2-propylene oxide. As used herein, "butylene oxide" or "BO" includes ethyl oxirane and 2,3-dimethyloxirane. Preferably, butylene oxide or BO is ethyl oxirane.

[0013] For various embodiments, the demulsifying block copolymer of the present disclosure is the reaction product of an aniline-derived initiator containing an alkoxylation catalyst and a first alkylene oxide selected from butylene oxide or propylene oxide to form an intermediate polymer, wherein the intermediate polymer is reacted with ethylene oxide in the presence of an alkoxylation catalyst to form the demulsifying block copolymer of the present disclosure. In a more specific embodiment, the demulsifying block copolymer of the present disclosure is the reaction product of an aniline-derived initiator containing an alkoxylation catalyst and butylene oxide as the first alkylene oxide to form an intermediate polymer, wherein the intermediate polymer is reacted with ethylene oxide in the presence of an alkoxylation catalyst to form the demulsifying block copolymer of the present disclosure. In another embodiment, the demulsifying block copolymer of the present disclosure is the reaction product of an aniline-derived initiator containing an alkoxylation catalyst and propylene oxide as the first alkylene oxide to form an intermediate polymer, wherein the intermediate polymer is reacted with ethylene oxide in the presence of an alkoxylation catalyst to form the demulsifying block copolymer of the present disclosure.

[0014] For various embodiments, the aniline-derived initiator of the present disclosure can have the structure of Formula I:

[0015]

[0016] wherein R1 is a C1-C3 alkylene or alkylidene group; each R2 is a C0-C3 alkylene or alkylidene group; and R3 is a C2 or C3 alkylene group. Preferably, each R2 is the same as the other R2 moieties in Formula I, and each R3 is the same as the other R3 moieties in Formula I (e.g., the compounds of Formula I are symmetric). However, different R2 and / or R3 moieties may be present in the aniline-derived starting materials of Formula I (e.g., the compounds of Formula I are asymmetric). For various embodiments, oligomers of Formula I (e.g., two or more structures of Formula I linked together) can also be used in the embodiments provided herein.

[0017] For various embodiments, a preferred aniline-derived starting material is 4,4'-methylenebis(N,N-di(2-hydroxypropyl)aniline) of Formula II:

[0018]

[0019] wherein R1 is a C1 alkylene group, i.e., a methylene group; each R2 is absent (i.e., a C0 alkyl group) and R3 is a C3 alkylene group, i.e., 1,2-propylene. Other preferred formulas of the aniline-derived starting materials of the present disclosure include those wherein R1 is an ethylene group; each R2 is absent and R3 is a C4 alkylene group, i.e., 1,2-butylene.

[0020] For various embodiments, the aniline-derived starting materials of Formula I are formed from an initiator containing an aromatic moiety and a primary amino group. For example, the initiator can have the structure of Formula III:

[0021]

[0022] wherein R1 is a C1-C3 alkylene or alkylidene group, and each R2 is a C0-C3 alkylene or alkylidene group. Preferably, each R2 is the same as another R2 moiety in Formula I. However, different R2 moieties may be present in the initiator of Formula III. Preferably, the initiator of Formula III is 4,4'-methylenedianiline (MDA), wherein R1 is a methylene group and each R2 is absent (i.e., a C0 alkyl group) and the position of the primary amine moiety relative to the R1 group is para. Other preferred initiators of Formula III include, but are not limited to, 4,4'-ethylenedianiline, 3,3'-ethylenedianiline, and 4,4'-propylenedianiline.

[0023] For various embodiments, the initiator of formula III undergoes an alkoxylation reaction with propylene oxide (PO) or butylene oxide (BO) to form an aniline-derived starter of formula I. For various embodiments, the alkoxylation reaction to form the aniline-derived starter is a self-catalytic reaction, as known in the art. In forming the aniline-derived starter, the reaction mixture of the initiator of formula III with PO or BO has a molar ratio of 1:3 to 1:5 (initiator to PO or BO). Preferably, the reaction mixture has a molar ratio of 1:4 (initiator to PO or BO). For various embodiments, the alkoxylation reaction can be carried out at a reaction temperature of 80 °C to about 180 °C. Preferably, the alkoxylation reaction can be carried out at a reaction temperature of 100 °C to about 160 °C. The reaction time of the alkoxylation reaction can be from 12 hours to 2 days. Those skilled in the art can determine the appropriate conditions at most through routine experiments.

[0024] For various embodiments, the aniline-derived starter is then reacted with a first epoxide selected from BO or PO in the presence of an alkoxylation catalyst under alkoxylation conditions to form an intermediate polymer. The alkoxylation catalyst for the alkoxylation reaction can be, for example, potassium hydroxide (KOH) or a double metal cyanide, as known in the art. Before the alkoxylation reaction, an aqueous KOH catalyst can be introduced and water can be removed by azeotropic distillation to dry the starter. Various techniques can be used, including, for example, using benzene and / or toluene, followed by azeotropic distillation under ambient pressure or reduced pressure, elevated temperature, or both, employing nitrogen purging, or a combination of these.

[0025] BO or PO is reacted with the aniline-derived starter in the presence of a catalyst under alkoxylation conditions. In non-limiting examples illustrating suitable alkoxylation conditions, this reaction can be carried out at an elevated temperature or at a temperature in the range of about 80 °C to about 180 °C. In other non-limiting examples, the temperature can be in the range of about 100 °C to about 160 °C. The reaction time of the alkoxylation reaction can be from 2 hours to 4 days. Those skilled in the art can determine the appropriate conditions at most through routine experiments.

[0026] Preferably, the alkoxylation reaction is carried out in the presence of an effective amount of potassium hydroxide as a catalyst. In some embodiments, the amount of the catalyst can be in the range of about 0.1 wt% to about 20 wt% by weight based on the total weight of the starter. In some embodiments, the amount can be in the range of about 1 wt% to about 10 wt%.

[0027] In a typical illustrative method, a starting material containing an alkoxylation catalyst can be mixed with BO or PO, and the reaction can be continued until alkoxylation is complete to form an intermediate polymer. The reaction can undergo a digestion period (e.g., about 1 hour to 10 hours at about 100 °C to 160 °C) between and / or after the addition of butylene oxide, propylene oxide, and ethylene oxide.

[0028] After the alkoxylation reaction, the intermediate polymer can be discharged from the reactor without removing the catalyst. If desired, the intermediate polymer can be treated to neutralize the catalyst.

[0029] For various embodiments, the intermediate polymer is then reacted with ethylene oxide (EO) in the presence of an alkoxylation catalyst as described herein to form embodiments of the demulsifying block copolymer (Formula IV) of the present disclosure.

[0030]

[0031] Wherein R1, R2, and R3 are as previously discussed, wherein R4 is a C3 or C4 alkyleneoxy, R5 is a C2 ethyleneoxy, n is from 5 to 50 and m is from 4 to 70. For various embodiments of the demulsifying block copolymer, the first alkylene oxide used to form the intermediate polymer is BO (i.e., R4 is C4). For these various embodiments, the weight ratio of BO to EO in the demulsifying block copolymer can be from 1.2 to 2.7. Additionally, for these embodiments, the weight-average molecular weight of the demulsifying block copolymer can be in the range of 10,000 g / mol to 18,000 g / mol. For embodiments of the present invention (i.e., R4 is C4), n is from 5 to 20 and m is from 10 to 70. In other various embodiments of the demulsifying block copolymer, the first alkylene oxide used to form the intermediate polymer is PO (i.e., R4 is C3). For these various embodiments, the weight ratio of PO to EO in the demulsifying block copolymer can be from 1.0 to 6.0. Additionally, for these embodiments, the weight-average molecular weight of the demulsifying block copolymer can be in the range of 7,000 g / mol to 15,000 g / mol. For embodiments of the present invention (i.e., R4 is C3), n is from 10 to 50 and m is from 4 to 40. For the various embodiments provided herein, the initiator of Formula III can be from 0.3 wt% to 2.2 wt% of the total weight of the demulsifying block copolymer.

[0032] Embodiments of the present disclosure also include a method of forming the demulsifying block copolymer of the present disclosure. As discussed herein, an aniline-derived starting material is reacted with a first alkylene oxide selected from butylene oxide or propylene oxide in the presence of an alkoxylation catalyst under alkoxylation conditions to form an intermediate polymer. Next, the intermediate polymer is reacted with ethylene oxide in the presence of an alkoxylation catalyst under alkoxylation conditions, as discussed herein, to form the demulsifying block copolymer of the present disclosure.

[0033] An example of forming the demulsifying block copolymer of the present disclosure is outlined below. In a first example, the starting step involves the autocatalytic propoxylation of 4,4'-methylenedianiline (MDA) with PO to form an embodiment of Formula I, as discussed herein and shown below, where R1 is a C1 alkylene group (methylene); each R2 is C0 (i.e., absent) and R3 is a C3 alkylene group (1,2-propylene). As discussed herein, after azeotropically distilling off water with toluene, the embodiment of Formula I shown below is then alkoxylated with PO (or BO) in the presence of a catalytic amount of KOH. As discussed herein, the obtained PO-polymer (or BO-polymer) is then ethoxylated with EO to produce an embodiment of the demulsifying block copolymer of the present disclosure. For a demulsifying block copolymer having a PO-EO copolymer portion, the step sequence is described as follows:

[0034] Synthesis of MDA / PO / EO Demulsifying Block Copolymer

[0035]

[0036] For the synthesis of the MDA / PO / EO demulsifying block copolymer, based on the total weight of the demulsifying block copolymer, MDA can be present in an amount of 1.0 wt% to 2.5 wt%, while the weight ratio of PO to EO can be in the approximate range of 2 to 5. Based on gel permeation chromatography (GPC), the weight-average molecular weight M w can be in the range of 6,000 to 12,000 g / mol, and the relative solubility number (RSN, described in the Examples section below) is in the range of 10 to 15. The demulsifying block copolymer meeting the above requirements can effectively remove water from diluted bitumen and conventional crude oil water emulsions, having significantly better performance than the benchmark at the same dosage rate.

[0037] The step sequence of a demulsifying block copolymer having a BO-EO copolymer portion can be as follows:

[0038] Synthesis of MDA / PO / BO / EO Demulsifying Block Copolymer

[0039]

[0040] For the synthesis of the MDA / PO / BO / EO demulsifying block copolymer, based on the total weight of the demulsifying block copolymer, MDA can be present in an amount of 0.3 wt% to 1.5 wt%, and the weight ratio of BO to EO can be in the approximate range of 2 to 1. Based on the weight-average molecular weight M w as determined by gel permeation chromatography (GPC) can be in the range of 8,000 to 20,000 g / mol, where the RSN is in the range of 10 to 15. The demulsifying block copolymer that meets the above requirements can effectively remove water from diluted bitumen and conventional crude oil water emulsions and has significantly better performance than the benchmark at the same dosage rate.

[0041] Embodiments of the present disclosure also include a method for demulsifying an emulsion of oil and water, the method comprising adding the demulsifying block copolymer of the present disclosure to the emulsion and separating the emulsion into an oil phase and a water phase. The use of the demulsifying block copolymer of the present disclosure in demulsifying an emulsion of oil and water into a water phase and an oil phase can be carried out in a conventional manner. For example, demulsifying an emulsion of oil and water into an oil phase and a water phase and then separating and recovering the oil phase and the water phase can be carried out by treating the emulsion with a demulsifying amount of the demulsifying block copolymer of the present disclosure. Examples of demulsifying an emulsion of oil and water into a water phase and an oil phase can include adding from 2 million parts to 900 million parts of the demulsifying block copolymer to the emulsion. Other suitable amounts for demulsifying an emulsion of oil and water into a water phase and an oil phase can include adding from 5 million parts to 900 million parts of the demulsifying block copolymer to the emulsion or adding from 50 million parts to 900 million parts of the demulsifying block copolymer to the emulsion. Once formed, the water phase is separated from the oil phase. Once separated, either the water phase and / or the oil phase can be recovered for further processing.

[0042] For various embodiments, the demulsifying block copolymer of the present disclosure can contribute to destabilizing an emulsion of oil and water, thereby enhancing water droplet coalescence. In breaking the emulsion with the demulsifying block copolymer of the present disclosure, a mixing method can be used for the emulsion of oil and water. For example, sufficient stirring can be used to fully mix the demulsifying block copolymer with the emulsion of oil and water, followed by flowing for a period of time in a separator to promote gravity separation. The method can also include retaining in the separator for a sufficient time to allow the water droplets to settle. The method can also require adding heat, an electric grid, and a coalescing agent to promote or fully break the emulsion.

[0043] As understood, the efficacy of the demulsifying block copolymer of the present disclosure can depend on many factors, such as the properties of the oil and / or water of the emulsion, the type of mixer, and the design and operating conditions of the demulsifying equipment. The most effective conditions for demulsification can be determined at least in part by using known bottle test procedures.

[0044] Other factors that can affect demulsification can include, but are not limited to, temperature, pH, crude oil type, brine composition, and droplet size and distribution. An increase in temperature can lead to a decrease in emulsion stability. The pH of an oil and water emulsion can also affect the performance of the demulsifying block copolymers of the present disclosure.

[0045] The following examples are provided to describe the preferred embodiments and utilities of the present invention and are not meant to limit the present invention unless otherwise stated in the appended claims.

[0046] Examples

[0047] The examples below are provided for illustration only and are not intended to limit or restrict the embodiments in any way. In the examples (EX) and comparative examples (CE) of the present invention, various terms and names of materials were used, and these terms and names include, for example, the following:

[0048] Table 1. Materials

[0049]

[0050] Testing and Equipment

[0051] Molecular composition, including the weight percentages (wt%) of 4,4'-methylenedianiline (MDA), BO, PO, and EO in the sample, was determined by the integration of the 1 1H NMR spectrum (Varian 400-NMR spectrometer with autosampler (400 MHz, 1 1H)) of the material in d-chloroform (CDCl3).

[0052] Molecular weight was determined using gel permeation chromatography (GPC, 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 approximately 10 mg of each sample into a pre-weighed vial and then recording the exact weight. Tetrahydrofuran (THF) was added to prepare a 1.0 mg / mL solution. The sample was vibrated to dissolve the solid and filtered into a vial for GPC. Analysis was performed on an Agilent 1260 Infinity equipped with 1 PLgel 3 μm × 50 mm × 7.5 mm guard column and 2 PLgel 3 μm × 50 mm × 7.5 m mixed E columns (maintained at 35 °C). The sample was eluted with THF at a flow rate of 1.77 mL / min and RID was used as the detector. The weight-average molecular weight (M w w), number-average molecular weight (M n) and polydispersity index (PDI = M w / M n ).

[0053] The relative solubility number (RSN) of EX and CE was measured using the following literature procedure, which is incorporated herein by reference. Toluene-ethylene glycol dimethyl ether (EGDE) with a volume ratio of 2.6:97.4 was used as the RSN solvent to determine the RSN of EX and CE. In this method, 0.1 gram (g) of the additive was dissolved in 3 milliliters (mL) of the RSN solvent, and then the resulting solution was titrated with deionized (DI) water until a visible and persistent turbidity appeared. The volume of DI water used as the titrant (in milliliters) divided by the weight of the additive (in grams) was recorded as the RSN value. Details of the initial method can be found in Wu, J.; Xu, Y.; Dabros, T.; Hamza, H. “Development of a method for measurement of relative solubility of nonionic surfactants”, Colloids Surf., A 2004, 232, 229 - 237, which is incorporated herein by reference.

[0054] Examples (Ex) 1 to Example 10

[0055] Synthesis of Demulsifier Block Copolymer MDA / PO / EO

[0056] The reaction to form the demulsifying block copolymer MDA / PO / EO was carried out in a parallel pressure reactor ( Unchained Labs, formerly Symyx Technologies) with 48 (6×8) reactors. Propylene oxide (PO) and ethylene oxide (EO) were delivered via a Teledyne ISCO syringe pump (model 260D) equipped with a robot-controlled needle and a compressed gas micro-valve (Bio-Chem valve p / n 100T2-S493). The layout of each cell used was designed using Library Design. The glass inserts and removable PEEK stirrers for each cell were dried in a vacuum oven at 125 °C.

[0057] Step 1: Initial Autocatalytic Reaction with PO

[0058] 4,4'-Methylenedianiline (MDA) (1.98 g; 0.01 mol) was manually added to the glass insert under nitrogen. Since the capacity of each PPR reactor does not exceed 6 mL, the same amount of components was used in all 8 PPR reactors of each module to make a larger amount of MDA / PO starter. The glass insert and the stirring blade were loaded together into the corresponding PPR reactor hole, and the PPR reactor was sealed. An amount of 2.32 g (2.80 mL; 0.04 mol) of PO was added to the cell. The temperature was raised to 140 °C, and the reaction mixture was stirred for 24 hours after the process temperature was reached. The pressure profile indicated the completion of the reaction, producing the MDA(PO)4 adduct. The cell was vented and purged with nitrogen to remove residual PO. After cooling and venting, a sample of the MDA(PO)4 adduct was taken for NMR analysis.

[0059] Step 2: Reaction of MDA(PO)4 with PO

[0060] The MDA(PO)4 adduct with approximately four POs per MDA as described above was used as a starter for subsequent alkoxylation. The MDA(PO)4 adduct (10 g) was mixed with a calculated amount of 50 wt% KOH solution to make a 20 wt% KOH mixture relative to the MDA(PO)4 adduct. Then approximately 100 mL to 150 mL of toluene was added, and water was removed azeotropically at 110 °C using a Dean-Stark trap. The remaining toluene was evaporated under vacuum. The dry MDA(PO)4 adduct containing the KOH catalyst was weighed into the glass insert. The glass insert and the stirring paddle were loaded together into the corresponding PPR hole, and the reactor was sealed. A calculated amount of PO was added to the cell by a robot. The temperature was raised to 115 °C, and the reaction mixture was stirred for 2 days after the process temperature was reached. The pressure in the reactor gradually leveled off, indicating the completion of the reaction, producing the MDA(PO)n intermediate. The cell was cooled, vented, and purged with nitrogen to remove any residual PO.

[0061] Step 3: Intermediate Reaction of MDA(PO)n with EO

[0062] A calculated amount of EO was introduced into the obtained MDA(PO)n intermediate by a robot at 50 °C, then the temperature was raised to 130 °C and the reactor was stirred for 4 hours. The pressure curve was consistent with the completion of the reaction. After cooling and venting the system as described above, small samples of the resulting demulsifying block copolymer MDA / PO / EO of the present disclosure were taken from each reactor for NMR and GPC analysis.

[0063] This synthesis produced samples with different compositions and different PO / EO monomer ratios. The data are listed in Table 2.

[0064] Evaluation of Demulsifying Block Copolymer MDA / PO / EO Block Copolymer for Dehydration of Diluted Asphalt (Diluted Asphalt)

[0065] Laboratory-scale diluted bitumen was produced from oil sands obtained from different operators in Alberta, Canada. Approximately 1500 g of oil sands were used in a single batch, and approximately 200 g to 300 g of extracted bitumen foam were produced. First, the oil sands were placed in a heating container (58 °C). Approximately 3000 g of water containing 600 parts per million (ppm) of KCl was added to the oil sands while continuously stirring the mixture. The stirring speed was changed at different times during the process to introduce substantial shear. While continuing to stir, nitrogen was bubbled through the mixture to enhance the separation of bitumen such that the bitumen rose to the top of the mixture as bitumen foam. After 20 minutes (min), the process was stopped and the foam was scraped off from the top of the container. The collected bitumen foam was diluted with naphtha at a ratio of 0.4 g of naphtha / 1.0 g of bitumen foam to produce diluted bitumen.

[0066] The efficiency of the demulsifying block copolymer MDA / PO / EO was evaluated using a high-throughput vial test method with a liquid handler. Each run included 12 samples, including a control. The diluted bitumen was homogenized (900 rpm, 10 minutes) using an impeller attached to an overhead mixer. Next, the diluted bitumen was mixed using a biaxial high-speed mixer (FlakTek 2,000 rpm, 1.5 minutes, twice). Then the diluted bitumen was placed in a container on the platform of an 8-channel liquid handler, and the robot dispensed the diluted bitumen into 12 vials (4 mL each). A stock solution of the demulsifying block copolymer MDA / PO / EO was prepared in a solvent mixture of xylene:isopropanol at a mass ratio of 3:1. The concentration of the demulsifying block copolymer MDA / PO / EO in the stock solution was 0.6 wt%. Subsequently, the robot added 200 μL of the additive stock solution to the vials to test the additive at 300 ppm relative to the diluted bitumen. The samples were mixed at 3500 rpm for 1 minute using a biaxial speed mixer and then held at 60 °C for 45 minutes. Then the samples were mixed again at 3500 rpm for 30 seconds on the biaxial speed mixer. After that, the samples were centrifuged at 2000 rpm (470 g relative centrifugal acceleration) for 5 minutes, and then approximately 150 mg was taken from each vial at a fixed depth (approximately 1 / 3 of the same volume from the top) via a syringe for Karl Fischer analysis. The water content of the samples was measured using a Metrohm oven Karl Fischer titrator with an autosampler, which heated the samples to 120 °C to remove all water from the samples.

[0067] The results of the water remaining in the samples were normalized with respect to the control (without additive) and expressed as relative water percentages in Table 2. Lower relative water percentages corresponded to better performance of the additive.

[0068] Comparative Examples (CE) A to Comparative Example D

[0069] Comparative Examples A to Comparative Example C

[0070] CE A to CE C were prepared in a manner similar to EX 1 to EX 10 described above, but the test demulsifying compositions of the comparative examples had chemical properties outside those of the demulsifying block copolymer MDA / PO / EO, where the differences are noted in Table 2.

[0071] CE D

[0072] CE D tested the performance of a commercially available reference additive, which is an amine-initiated polyol block copolymer with an approximate average molecular weight of 4,500 daltons sold under the trade name Demtrol TM As seen in Table 2, the reference additive containing different amine initiators and a lower average MW than the demulsifying block copolymers of the present disclosure showed lower performance at 300 ppm than the demulsifying block copolymers of the present disclosure.

[0073] Table 2 - Composition, Relative Solubility Number, MW and Performance Results of Demulsifying Block Copolymer MDA / PO / EO at 300 ppm Additive 。

[0074] % water measured by “a” divided by control water % × 100%; b xylene / isopropanol (3:1). PDI - polydispersity index (Mw / Mn).

[0075]

[0076]

[0077] Examples (Ex) 11 to Example 14

[0078] Synthesis of Demulsifier Block Copolymer MDA / PO / BO / EO

[0079] The reaction was carried out as described above for EX 1 to EX 10, except for the following changes.

[0080] Step 1: Same as EX 1 to EX 10 。

[0081] Step 2: Adduct Reaction of MDA-(PO)4 with BO

[0082] As described above, each MDA has an MDA-(PO)4 adduct with about four POs as the starting material for subsequent alkoxylation. The MDA(PO)4 adduct (10 g) is mixed with a calculated amount of 50 wt% KOH solution to make a 20 wt% KOH mixture relative to the MDA(PO)4 adduct. Then about 100 mL to 150 mL of toluene is added, and water is removed azeotropically at 110 °C using a Dean-Stark water separator. The remaining toluene is evaporated under vacuum. The dry MDA-(PO)4 adduct containing the KOH catalyst is weighed into a glass insert. The glass insert and the stirrer paddle are loaded together into the corresponding PPR hole, and the reactor is sealed. A calculated amount of BO is added to the cell by a robot. The temperature is raised to 115 °C, and the reaction mixture is stirred for 2 days after the process temperature is reached. The pressure in the reactor gradually levels off, indicating that the reaction is complete to form MDA(PO)4(BO)n. The cell is cooled, vented, and purged with nitrogen to remove the residual BO.

[0083] Step 3: Reaction of MDA(PO)4(BO)n with EO

[0084] EO is introduced together with MDA(PO)4(BO)n at 50 °C, then the temperature is raised to 130 °C and the reactor is stirred for 4 hours. The pressure curve is consistent with the completion of the reaction to form the demulsifying block copolymer MDA / PO / BO / EO. After cooling and venting the system as described above, small samples of the demulsifying block copolymer MDA / PO / BO / EO are taken from each reactor for NMR and GPC analysis.

[0085] This synthesis produces demulsifying block copolymers MDA / PO / BO / EO with different compositions and different BO / EO monomer ratios. The data are listed in Table 3.

[0086] Evaluation of Demulsifying Block Copolymer MDA / PO / BO / EO for Diluted Asphalt Dehydration

[0087] The efficiency of the demulsifying block copolymer MDA / PO / BO / EO is tested as described above for the demulsifying block copolymer MDA / PO / EO. The results of the remaining water in the samples are normalized with respect to the control (without additive) and expressed as relative water percentages in Table 3. Lower relative water percentages correspond to better performance of the additive.

[0088] Comparative Examples (CE) E to Comparative Example G

[0089] CE E to CE F are prepared in a manner similar to EX 11 to EX 14 described above, but the tested demulsifying compositions of the comparative examples have chemical properties outside those of the demulsifying block copolymer MDA / PO / BO / EO, with the differences noted in Table 3.

[0090] CE G tested the performance of a commercially available reference additive, which is an amine-initiated polyol block copolymer with an approximate average molecular weight of 4,500 Daltons sold under the trade name Demtrol. As seen in Table 3, the reference additives containing different amine initiators and having a lower average MW than the demulsifying block copolymers of the present disclosure showed lower performance at 300 ppm than the demulsifying block copolymers of the present disclosure. TM The average of two measurements of “a” divided by the control × 100%; b xylene / isopropanol (3:1).

[0091] Table 3. Composition, Phase Relative Solubility Number, MW and Performance Results of the Invention Samples of Demulsifying Block Copolymer MDA / PO / BO / EO at 300 ppm Additive

[0092]

[0093] “a” twice measurement average divided by control × 100%; b xylene / isopropanol (3:1).

[0094] Examples (Ex) 15 to Example 17

[0095] Example 15 and Example 16 are large-scale syntheses 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.

[0096] The reaction was carried out in a Symyx setup containing a plate with 48 (6×8) reactors. 24 reactors contained the same components and conditions to make a large sample of Example 15, and the other 24 reactors were similarly used to make a large sample of Example 16. Similarly, 24 reactors containing the same components and conditions were also prepared to make a large sample for EX 17. Propylene oxide (PO), butylene oxide (BO), and ethylene oxide (EO) were delivered via an ISCO syringe pump equipped with a robot-controlled needle and a compressed gas micro-valve. The layout of each pool used was designed using Library. The glass inserts and removable PEEK stirrers for each pool were dried in a vacuum oven at 125 °C. The glass inserts and removable PEEK stirrers for each pool were dried in a vacuum oven at 125 °C.

[0097] EX 15 and EX 16

[0098] Step 1: The initial autocatalytic reaction with PO was carried out similar to the procedure in Step 1 of EX 1 to EX 10 to obtain the MDA(PO)4 adduct.

[0099] ​Step 2: Adduct reaction of MDA(PO)4 with BO. As described above, each MDA having about four POs, the MDA-(PO)4 adduct is used as the starting material for subsequent alkoxylation. The MDA(PO)4 adduct (10 g) is mixed with a calculated amount of 50 wt% KOH solution to make a 20 wt% KOH mixture relative to the MDA(PO)4 adduct. Then about 100 mL to 150 mL of toluene is added, and water is removed azeotropically at 110 °C using a Dean-Stark water separator. The remaining toluene is evaporated under vacuum. The dried MDA(PO)4 adduct (0.135 g) containing the KOH catalyst is weighed into 48 glass inserts. The glass inserts and the stirrers are loaded together into the corresponding PPR holes, and the reactor is sealed. 3.99 mL of BO is manually added to 24 cells in the upper half of the plate, and 3.56 mL of BO is added to 24 cells in the lower half of the plate. The temperature is raised to 115 °C, and after reaching the process temperature, the reaction mixture is stirred for 2 days to produce the MDA(PO)4(BO)m intermediate. The pressure in the reactor gradually levels off, indicating that the reaction is complete and the MDA(PO)4(BO)m intermediate is formed. The cells are cooled, vented, and purged with nitrogen to remove any residual BO.

[0100] Step 3: Reaction of the MDA(PO)4(BO)m intermediate with EO. To each of the obtained MDA(PO)4(BO)m intermediates, 1.28 ml of EO is introduced into the upper half of the plate at 50 °C by a robot, and 1.68 ml of EO is added to the lower half of the plate. Then the temperature is raised to 130 °C and the reactor is stirred for 4 hours to produce the demulsifying block copolymer MDA-(PO)4(BO)m(EO)n. The pressure curve is consistent with the completion of the reaction. After cooling and venting the system as described above, small samples of the demulsifying block copolymer MDA-(PO)4(BO)m(EO)n are taken from each reactor for GPC analysis. Samples of reagents with similar GPC and pressure data having the same starting amounts are combined to produce two large samples EX 15 (86 g) and EX 16 (84 g), and these two large samples are analyzed by 1H NMR and GPC in d6-acetone. The compositional data and MW of the large-scale demulsifying block copolymer MDA-(PO)4(BO)m(EO)n samples of the present invention produced in a parallel pressure reactor are listed in Table 4.

[0101] EX 17

[0102] Step 1: The initial autocatalytic reaction with PO is carried out in a procedure similar to that of Step 1 in EX 1 to EX 10 to obtain the MDA(PO)4 adduct.

[0103] Step 2: Adduct reaction of MDA(PO)4 with PO. As described above, the MDA-(PO)4 adduct with each MDA having about four POs is used as the starting material for subsequent alkoxylation. Mix the MDA(PO)4 adduct (10 g) with a calculated amount of 50 wt% KOH solution to make a 20 wt% KOH mixture relative to the MDA(PO)4 adduct. Then add about 100 mL to 150 mL of toluene, and remove water azeotropically at 110 °C using a Dean-Stark water separator. Evaporate the remaining toluene under vacuum. Weigh the dry MDA(PO)4 adduct (0.135 g) containing the KOH catalyst into 32 glass inserts. Load the glass inserts and the stirrer paddle into the corresponding PPR holes, and seal the reactor. Manually add 4.39 mL of PO to each of the 32 wells on the plate. Raise the temperature to 115 °C, and stir the reaction mixture for 2 days after reaching the process temperature to produce the MDA(PO)q intermediate. The pressure in the reactor gradually levels off, indicating that the reaction is complete and the MDA(PO)q intermediate is formed. Cool the wells, vent, and purge with nitrogen to remove any residual PO.

[0104] Step 3: Reaction of the MDA(PO)q intermediate with EO. Introduce 0.84 mL of EO into each well having the obtained MDA(PO)q intermediate by a robot at 50 °C. Then raise the temperature to 130 °C and stir the reactor for 4 hours to produce the demulsifying block copolymer MDA-(PO)q(EO)n. The pressure curve is consistent with the completion of the reaction. After cooling and venting the system as described above, remove a small sample of the demulsifying block copolymer MDA-(PO)q(EO)n from each reactor for GPC analysis. Combine the samples of reagents having similar GPC and pressure data with the same starting amounts to produce a large sample EX 17 (about 98 g), and analyze this large sample by 1 1H NMR and GPC in d6-acetone. The compositional data and MW of the large-scale demulsifying block copolymer MDA-(PO)q(EO)n samples of the present invention produced in a parallel pressure reactor are listed in Table 4.

[0105] Table 4. Composition and MW of EX 15 to EX 17

[0106] Weight % MDA Weight % PO Weight % EO Weight % BO Mn Mw PD EX 15 2.01％ 4.75％ 27.00％ 66.24％ 13622 13965 1.03 EX 16 1.79％ 5.60％ 32.32％ 60.28％ 13445 13778 1.02 EX 17 1.27％ 83.88％ 14.84％ 0 13088 13757 1.05

[0107] Comparative Examples (CE) H to Comparative Example J

[0108] Evaluate the performance of a commercially available reference additive (CE H) and two existing additives (CE I to CE J). CE H is a polyol block copolymer containing different amine initiators and having a lower average MW than in this example. CE I is a field demulsifier formulation containing an EO / PO block copolymer and an alkylphenol formaldehyde resin alkoxylate intermediate. CE J is a knockout droplet demulsifier.

[0109] The sources of the crude oils used for the performance tests are as follows.

[0110] Crude oil A and CE I: Crude oil emulsion from Canada and existing CE I.

[0111] Crude oil B: Emulsion from the borehole cuttings cleaning process.

[0112] Crude oil C: Crude oil emulsion from Russia.

[0113] Examples (Ex) 15 to Example 16

[0114] Evaluate the demulsifying block copolymer for crude oil A at 50 ppm, 100 ppm, and 200 ppm. Evaluate the efficiency of the demulsifying block copolymer of the present disclosure at 50 ppm, 100 ppm, and 200 ppm using the standard bottle test method for crude oil A. Heat the demulsifying block copolymer in a water bath at 50 °C for 30 minutes. Then, prepare a stock solution of each demulsifying block copolymer in a solvent mixture of toluene:isopropanol in a mass ratio of 3:1. The concentration of the demulsifying block copolymer in the stock solution is 10 wt%. Add 100 mL of the crude oil emulsion to a prescription bottle. Subsequently, meteringly add the additive stock solution to the bottle to test the additive at 50 ppm, 100 ppm, and 200 ppm (based on the active substance) relative to the crude oil. Then place the bottle in a pre-heated water bath at 50 °C for 45 minutes. After 45 minutes, remove the bottle from the water bath and shake it vigorously for 30 seconds, and then place it back in the 50 °C water bath for 30 minutes. Record the visual observation of free water droplets at t = 0 minutes, 10 minutes, and 30 minutes, and record the dry oil layer from the top of each sample. After 30 minutes, withdraw a sample from the 75 mL mark of the top liquid layer of each sample and add it to a standard centrifuge tube to the 50% mark. Then add toluene to fill the centrifuge tube to the 100% mark. Shake the centrifuge tube, and then place it in a centrifuge unit and centrifuge at 1200 rpm for 5 minutes. After completion, record the measurements of basic sediment and free water. The following parameters are reported in Table 5.

[0115] Free water droplets: The amount (mL) of water separated in the bottle after heating for a specified time at 50 °C. The larger the value, the faster the drying performance.

[0116] Drying oil from the top: The amount (mL) of drying oil separated in the bottle after heating at 50 °C for 30 minutes. A larger value indicates faster drying performance.

[0117] % Basic sediment (BS): The percentage of basic sediment separated in the graduated tube after centrifugation. A smaller value indicates better performance.

[0118] % Water (W): The percentage of water separated in the graduated tube after centrifugation. A smaller value indicates better performance.

[0119] Table 5. Performance Results of EX15 and EX 16 Screened in Crude Oil A at 50 ppm, 100 ppm and 200 ppm

[0120]

[0121] Discussion on Performance Results of EX 15 Screened in Crude Oil A

[0122] When compared with the CE H sample, at 50 ppm, the results of the drying oil, basic sediment, and water (BS and W) on the top are relatively similar. However, compared with CE H to CE J, increasing the dosage concentration of EX 15 provides better properties in terms of demulsification and oil drying. When compared with CE H, EX 15 shows excellent performance at 100 ppm. Compared with CE H, a reduction of approximately 54.5% in BS and W and an improvement of 70% in the volume of drying oil are observed for EX 15, indicating that EX 15 exhibits faster oil drying properties at higher dosages.

[0123] At 200 ppm, EX 15 shows excellent oil drying properties and performs better than both CE H and CE I as well as the blank. The data shows that the product produces 99.5% less BS and W than both CE H and CE I as well as the blank, indicating less water in the oil for the samples with metered addition of EX 15.

[0124] Discussion on Performance Results of EX 16 Screened in Crude Oil A

[0125] When compared with CE H, the results of the drying oil, BS, and W on the top were relatively similar at 50 ppm. However, increasing the dosage of EX16 provided better properties in terms of demulsification and oil drying. Compared with CEI and CE J, EX 16 showed excellent oil drying properties at 100 ppm and exhibited better performance. Compared with CE I, CE J, and the blank sample, a significant reduction in BS and W (99.5%) was observed for the samples with metered addition of EX 16, indicating less water present. When compared with CE H, EX16 showed excellent performance at 100 ppm and 200 ppm: reducing BS and W by approximately 99.5% and improving the drying oil volume by approximately 140%, indicating that EX 16 has faster oil drying properties compared to CE H.

[0126] Discussion on Performance Results of EX 15 to EX 16 Screened in Crude Oil B

[0127] As described in the evaluation of EX 15 and EX 16 for crude oil A, similar test methods were used to evaluate EX15 and EX 16 for crude oil B, except that the extraction samples were taken after heating for 3 hours instead of 30 minutes.

[0128] Table 6. Performance Results of EX 15 and EX 16 Screened in Crude Oil B at 50 ppm, 100 ppm and 200 ppm Additive Results

[0129]

[0130] Discussion on Performance Results of EX 15 Screened in Crude Oil B

[0131] When compared with CE H to CE J, the results of the drying oil, BS, and W on the top were relatively similar at 50 ppm and 100 ppm. However, increasing the dosage of EX 15 provided better properties in terms of demulsification and oil drying. Compared with CE I, CE J, and the blank sample, Example 15 showed excellent oil drying properties at 200 ppm and exhibited excellent performance. Compared with CE I, CEJ, and the blank sample, EX 15 showed a 99.5% reduction in BS and W, indicating that more water was removed from the oil.

[0132] Discussion on Performance Results of EX 16 Screened in Crude Oil B

[0133] When compared with CE H to CE J, the results of the drying oil, BS, and W on the top were relatively similar at 50 ppm and 100 ppm. However, increasing the dosage of EX 16 provided better properties in terms of demulsification and oil drying. Compared with CE I, CE J, and the blank sample, Example 16 showed excellent oil drying properties at 100 ppm and exhibited excellent performance. The data showed a 99.5% reduction in BS and W, indicating that more water was removed from the oil by EX 16.

[0134] Performance Evaluation of EX17 for Crude Oil C at 300 ppm, 600 ppm and 900 ppm

[0135] Using a similar test method as described for the evaluation of EX 15 and EX 16 screened in crude oil A, except that EX 17 was dosed at 300 ppm, 600 ppm and 900 ppm (based on active substance) and the bottles were heated at 45 °C for 45 minutes. The results are provided in Table 7.

[0136] Table 7. Performance results at 300 ppm, 600 ppm and 900 ppm EX 17 screened in crude oil C

[0137]

[0138] Discussion on Performance Results of EX 17 Screened in Crude Oil

[0139] Compared to CE I, CE J and the blank sample, EX 17 showed excellent water droplet properties at 300 ppm and 600 ppm, as confirmed by the free water droplets at 0 minutes, 10 minutes and 30 minutes. When compared to CE I, CE J and the blank, EX 17 showed excellent performance at 300 ppm: a 79.8% reduction in BS and W and a 28% reduction in water droplets, indicating faster oil drying properties.

Claims

1. A demulsifying block copolymer, the demulsifying block copolymer comprising the reaction product of: An aniline-derived starter containing an alkoxylation catalyst and a first alkylene oxide of butylene oxide to form an intermediate polymer; and The intermediate polymer and ethylene oxide in the presence of the alkoxylation catalyst to form the demulsifying block copolymer.

2. The demulsifying block copolymer according to claim 1, wherein the aniline-derived starter has the structure of formula I: Wherein R1 is a C1-C3 alkylene or alkylidene group; each R2 is a C0-C3 alkylene or alkylidene group; and R3 is a C2 or C3 alkylene group.

3. The demulsifying block copolymer according to any one of claims 1 to 2, wherein the aniline-derived starter is 4,4'-methylenebis(N,N-bis(2-hydroxypropyl)aniline).

4. The demulsifying block copolymer according to claim 1, wherein the weight ratio of butylene oxide to ethylene oxide in the demulsifying block copolymer is 1.2 to 2.

7.

5. The demulsifying block copolymer according to claim 1, wherein the weight-average molecular weight of the demulsifying block copolymer is in the range of 10,000 g / mol to 18,000 g / mol.

6. The demulsifying block copolymer according to any one of claims 1 to 5, wherein the aniline-derived starter is 0.3% to 2.2% by weight of the total weight of the demulsifying block copolymer.

7. A method for forming the demulsifying block copolymer according to any one of claims 1 to 6, the method comprising: Reacting the aniline-derived starter with the first alkylene oxide of butylene oxide in the presence of the alkoxylation catalyst to form the intermediate polymer; And Reacting the intermediate polymer with ethylene oxide in the presence of the alkoxylation catalyst to form the demulsifying block copolymer.

8. A method for demulsifying an emulsion of oil and water, the method comprising: Adding a demulsifying block copolymer to the emulsion of oil and water, wherein the demulsifying block copolymer comprises the reaction product of: An aniline-derived starter containing an alkoxylation catalyst and a first alkylene oxide selected from butylene oxide or propylene oxide to form an intermediate polymer; and The intermediate polymer and ethylene oxide in the presence of the alkoxylation catalyst to form the demulsifying block copolymer; and Separating the emulsion into an oil phase and a water phase.

9. The method according to claim 8, wherein adding the demulsifying block copolymer to the emulsion comprises adding 2 to 900 parts per million of the demulsifying block copolymer to the emulsion.

10. The method according to any one of claims 8 to 9, wherein the aniline-derived starter has the structure of formula I: Wherein R1 is a C1-C3 alkylene or alkylidene group; each R2 is a C0-C3 alkylene or alkylidene group; and R3 is a C2 or C3 alkylene group.

11. The method according to any one of claims 8 to 10, wherein the aniline-derived starter is 4,4'-methylenebis(N,N-bis(2-hydroxypropyl)aniline).

12. The method according to any one of claims 8 to 11, wherein the first alkylene oxide is butylene oxide; or wherein the first alkylene oxide is butylene oxide, and the weight ratio of butylene oxide to ethylene oxide in the demulsifying block copolymer is from 1.2 to 2.7; or wherein the first alkylene oxide is butylene oxide, and the weight-average molecular weight of the demulsifying block copolymer is in the range of 10,000 g / mol to 18,000 g / mol.

13. The method according to any one of claims 8 to 11, wherein the first alkylene oxide is propylene oxide; or wherein the first alkylene oxide is propylene oxide, and the weight ratio of propylene oxide to ethylene oxide in the demulsifying block copolymer is from 1.0 to 6.0; or wherein the first alkylene oxide is propylene oxide, and the weight-average molecular weight of the demulsifying block copolymer is in the range of 7,000 g / mol to 15,000 g / mol.

14. The method according to any one of claims 8 to 13, wherein the aniline-derived starting material is from 0.3% by weight to 2.2% by weight of the total weight of the demulsifying block copolymer.

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