Oxa-derivatized non-ionic demulsifying material, its preparation and use

Abstract

The present application relates to the technical field of demulsification, and provides an oxygen-hetero nonionic demulsification material, a preparation method and application thereof, the preparation method of the oxygen-hetero nonionic demulsification material comprises the following steps: (1) mixing a solution of a fatty alcohol nonionic polyether, a free radical initiator, an olefinic acid and an oil-soluble additive, and performing a polymerization reaction to obtain a first polymer; (2) performing a catalytic esterification reaction of an oxygen-rich organic acid and the first polymer to obtain an esterification reaction system, and after removing the solvent from the esterification reaction system, the oxygen-hetero nonionic demulsification material is obtained. The oxygen-hetero nonionic demulsification material is prepared by using the oxygen-rich organic acid and the oil-soluble additive as modification materials, the ability of the oxygen-hetero nonionic demulsification material to destroy the oil-water interface film is significantly improved, and the solubility of the oxygen-hetero nonionic demulsification material in the oil phase is improved, the demulsification effect of the oxygen-hetero nonionic demulsification material on the unconventional oil emulsion with stable nanometer and micro solid particles is excellent, and the application prospect is wide.

Description

Technical Field

[0001] The present invention relates to the technical field of demulsification, and in particular to an oxygen-hybridized nonionic demulsification material and a preparation method and application thereof. Background Art

[0002] With the continuous development of industrial technology, the world's demand for oil is increasing year by year. However, as conventional oil resources are becoming increasingly depleted, the exploitation of some important oil supplementary resources, such as oil sands, shale oil, tight oil, and extra heavy oil, has gradually entered the production process of the oil industry.

[0003] In the unconventional oil production process, a key issue that needs to be addressed is the demulsification of oil-water emulsion, because wherein there is the natural interfacial active substance that can stablize oil-water emulsion, such as asphaltenes, colloids, naphthenic acid etc., these are as natural emulsifiers, can form the interfacial film with certain mechanical strength, this interfacial film can be strongly adsorbed on the surface of water molecules so that oil-water two-phase exists with stable emulsified state form. In addition, the nano-micro solid particles that are inevitably introduced in the production process, such as silicon dioxide, calcium carbonate, clay etc., can act together with above natural emulsifier molecules, can significantly enhance the mechanical strength of oil-water interfacial film and the stability of emulsion, and greatly increase the difficulty of demulsification. The oil-water emulsions that these form not only bring great difficulty (corrosion equipment, make catalyst poisoning, increase transportation cost) to subsequent processing, and have a strong impact on the quality of oil product, therefore must carry out the demulsification dehydration of oil-water emulsion to reach the quality that improves oil, to reach the requirement of follow-up oil refining processing stage.

[0004] At present, conventional demulsifiers are mostly used to treat unconventional petroleum emulsions, such as SP169 (polyoxypropylene polyoxyethylene octadecyl alcohol ether block copolymer), AE1951 (polyethylene polyamine polyoxyethylene polyoxypropylene ether), AP2050 (fatty alcohol non-ionic polyether demulsifier), etc. Conventional demulsifiers have good demulsification effects on the interfacial film formed by interfacial active components such as asphaltene and colloid in crude oil. However, the structure of the interfacial film formed by the interaction between nano-solid particles in unconventional petroleum emulsions and the natural emulsifiers therein is very stable, and the applicability of conventional demulsifiers is poor, which is mainly reflected in the high demulsification temperature (above 80°C) and slow dehydration speed.

[0005] Chinese patent CN116023667A discloses a demulsifier containing a large number of tertiary amine groups. The synthesis process mainly involves first mixing N,N-dimethyl-1,3-propylenediamine, maleic anhydride, and an organic solvent for an acylation reaction to obtain a first intermediate. The first intermediate is then mixed with acrylic acid and a free radical initiator for a copolymerization reaction to obtain a second intermediate. The second intermediate is then mixed with a phenolic resin polyether for an esterification reaction to obtain the demulsifier. However, the demulsifier takes a long time to demulsify crude oil emulsions (>120 minutes) and cannot achieve complete dehydration. The demulsification rate is only between 85.7% and 97.1%. Moreover, the dehydration effect on emulsions containing nano-micro solid particles is unclear.

[0006] Chinese patent CN112915592A discloses a magnetic nano-emulsifier for demulsifying oil-water emulsions. The demulsifier is primarily prepared by reacting ferroferric oxide particles, an organic solvent, water, a silicon source, a silane coupling agent, and a hydroxyl-terminated polyether, followed by solid-liquid separation, washing, and drying. The organic groups and magnetic particles in the demulsifier act synergistically to shorten demulsification time, but the demulsifier does not achieve complete demulsification (90%) of the oil-water emulsion, and the dosage required (>3000 mg / L) is high, resulting in high economic costs.

[0007] In summary, it can be seen that it is still difficult to achieve complete demulsification of unconventional petroleum emulsions containing particles, and there is an urgent need to develop new demulsifiers or process optimization to achieve the demulsification effect. Summary of the Invention

[0008] To solve the above technical problems, the present invention provides an oxygen-hybridized nonionic demulsifier material, a preparation method thereof, and an application thereof. By constructing a phenyl group, an ester group, and an ether bond, and combining and designing the length and branching of the carbon chain, a structure shown in formula (1) is obtained, wherein the oxygen atom can help the demulsifier form more hydrogen bonds with the emulsified water droplets, and the phenyl group can improve the similar compatibility with asphaltene, thereby ultimately improving the demulsification effect.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides an oxygen-hybrid nonionic demulsifier material, wherein the oxygen-hybrid nonionic demulsifier material comprises a structure represented by formula (1):

[0011]

[0012] In formula (1), the value range of x is 40-60, the value range of y is 30-50, the value range of n is 10-20, the value range of x' is 20-30, and the value range of y' is 1-10.

[0013] Through multi-faceted research and design, the present invention has found that the oxygen-hybridized nonionic demulsifier material having the structure of formula (1) has an excellent demulsification effect on unconventional oil-water emulsions stabilized by micro-nano solid particles, wherein the phenyl group has a better miscibility with the condensed rings in asphaltene, and the high density of oxygen groups can enhance the multi-hydrogen bonding effect, thereby strengthening the interaction with asphaltene at the oil-water interface. In addition, the high content of oxygen groups has a stronger ability to reconstruct non-covalent bonds, which is more conducive to demulsification.

[0014] Furthermore, the present invention controls the value range of x to be 50-60. When the chain segments of x are too many, the hydrophilicity of the demulsifier molecule is too strong, and there is a problem of poor solubility in the oil phase. When the chain segments of x are too few, the hydrogen bonding ability of the demulsifier molecule and the water molecule is insufficient, and there is a problem of decreased demulsification ability. The value range of y is 30-40. When the chain segments of y are too many, the lipophilicity of the demulsifier molecule is too strong, and the hydrogen bonding ability with the water molecule is insufficient, and there is a problem of decreased demulsification ability. When the chain segments of y are too few, the lipophilicity of the demulsifier molecule is insufficient, and there is a problem of poor solubility in the oil phase. The value range of n is 10-20. When the chain segments of n are too many, the hydrophilicity of the demulsifier molecule is too strong. The water-based property is too strong, resulting in poor solubility in the oil phase. When the chain segments of n are too few, the hydrogen bonding ability between the demulsifier molecules and the water molecules is insufficient, resulting in a decrease in demulsification ability. The value range of x' is 20-30. When the chain segments of x' are too many, the hydrophilicity of the demulsifier molecules is too strong, resulting in poor solubility in the oil phase. When the chain segments of x' are too few, the hydrogen bonding ability between the demulsifier molecules and the water molecules is insufficient, resulting in a decrease in demulsification ability. The value range of y' is 1-10. When the chain segments of y' are too many, the lipophilicity of the demulsifier molecules is too strong, resulting in a decrease in water solubility. When the chain segments of y' are too few, the mutual solubility of the demulsifier molecules and the asphaltene condensed ring is insufficient.

[0015] wherein the value range of x is 50-60, for example, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59 or 60; the value range of y is 30-40, for example, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 or 40; the value range of n is 10-20, for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20; the value range of x' is 20-30, for example, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30; and the value range of y' is 1-10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0016] Therefore, the present invention selects the above-mentioned number of segments to achieve a better demulsification effect.

[0017] Preferably, the oxygen content in the oxygen-hybrid nonionic demulsifier is 30wt% to 40wt%, for example, it can be 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt% or 40wt%.

[0018] The present invention has no special restrictions on the preparation method of the oxygen-hybrid nonionic demulsifying material provided in the first aspect. It can be prepared by methods familiar to those skilled in the art. Preferably, it is prepared by the preparation method provided by the second aspect of the present invention, which has the advantages of simple process and better demulsification effect.

[0019] In a second aspect, the present invention provides a method for preparing the oxygen-hybrid nonionic demulsifier, the method comprising the following steps:

[0020] (1) mixing a solution of a fatty alcohol nonionic polyether, a free radical initiator, an olefinic acid, and an oil-soluble additive to carry out a polymerization reaction to obtain a first polymer;

[0021] (2) The oxygen-rich organic acid and the first polymer are subjected to a catalytic esterification reaction to obtain an esterification reaction system. After the solvent is removed from the esterification reaction system, the oxygen-hybridized nonionic demulsifier material is obtained.

[0022] The preparation method provided in the second aspect of the present invention first selects oxygen-rich organic acid and oil-soluble auxiliary agent as modifying substances, which can significantly improve the ability of the demulsifier to destroy the oil-water interface film and the solubility of the demulsifier in the oil phase; and the oxygen-rich organic acid can help the demulsifier to form more hydrogen bonds with the emulsified water droplets through its own oxygen atoms, thereby promoting demulsification, and the benzene ring and long alkyl chain in the oil-soluble auxiliary agent can promote the compatibility between the demulsifier and the oil phase; further, the oxygen-rich organic acid can undergo esterification and dehydration reaction with the fatty alcohol non-ionic polyether to generate more oxygen-rich groups, which is beneficial to improving the demulsification ability of the demulsifier.

[0023] Preferably, the solvent in the solution of the fatty alcohol nonionic polyether in step (1) is an organic solvent.

[0024] Preferably, the organic solvent includes an aromatic hydrocarbon organic solvent.

[0025] Preferably, the aromatic organic solvent includes any one of toluene, xylene, trimethylbenzene or ethylbenzene, or a combination of at least two thereof, wherein typical but non-limiting combinations are a combination of toluene and xylene, a combination of toluene and trimethylbenzene, a combination of trimethylbenzene and xylene, and a combination of ethylbenzene and xylene.

[0026] Preferably, the fatty alcohol nonionic polyether is a linear type, and preferably, the fatty alcohol nonionic polyether is formed by polymerization of ethylene oxide and propylene oxide using propylene glycol as an initiator.

[0027] Preferably, the molar ratio of ethylene oxide to propylene oxide is 1 to 2:1, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 or 2:1.

[0028] Preferably, the molecular weight of the fatty alcohol nonionic polyether is 3000-5000, for example, 3000, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 4000, 4200, 4500, 4800 or 5000.

[0029] Preferably, the molar ratio of the sum of propylene glycol, ethylene oxide and propylene oxide is 1 to 2:1, for example, it can be 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 or 2:1.

[0030] Preferably, the ratio of the fatty alcohol nonionic polyether single agent to the organic solvent is 1 to 60 g:100 mL, for example, it can be 1 g:100 mL, 8 g:100 mL, 15 g:100 mL, 21 g:100 mL, 28 g:100 mL, 34 g:100 mL, 41 g:100 mL, 47 g:100 mL, 54 g:100 mL or 60 g:100 mL, but is not limited to the listed values, and other values ​​not listed within this range are also applicable.

[0031] Preferably, the free radical initiator comprises any one of azobisisobutyronitrile, azobisisoheptanonitrile, benzoyl peroxide or dicumyl peroxide, or a combination of at least two thereof, wherein a typical but non-limiting combination is a combination of azobisisobutyronitrile and azobisisoheptanonitrile, a combination of benzoyl peroxide and azobisisoheptanonitrile, a combination of azobisisobutyronitrile and benzoyl peroxide, and a combination of dicumyl peroxide and azobisisoheptanonitrile.

[0032] Preferably, the free radical initiator accounts for 0.01 to 1 wt% of the mass of the fatty alcohol nonionic polyether, for example, it can be 0.01 wt%, 0.12 wt%, 0.23 wt%, 0.34 wt%, 0.45 wt%, 0.56 wt%, 0.67 wt%, 0.78 wt%, 0.89 wt% or 1 wt%, etc., but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0033] Preferably, the olefinic acid comprises an olefinic acid containing at least one carboxyl group and having 3 to 20 carbon atoms, for example, 3, 5, 7, 9, 11, 13, 15, 17, 19 or 20 carbon atoms, but is not limited to the listed values, and other values ​​not listed within this range are also applicable. Preferably, it comprises any one or a combination of at least two of 2-butenoic acid, oleic acid, acrylic acid or undecenoic acid, wherein typical but non-limiting combinations are a combination of 2-butenoic acid and oleic acid, a combination of acrylic acid and oleic acid, a combination of 2-butenoic acid and acrylic acid, and a combination of undecenoic acid and oleic acid.

[0034] Preferably, the olefinic acid accounts for 1 to 30 wt% of the mass of the fatty alcohol nonionic polyether, for example, it can be 1 wt%, 5 wt%, 8 wt%, 11 wt%, 14 wt%, 18 wt%, 21 wt%, 24 wt%, 27 wt% or 30 wt%, etc., but is not limited to the listed values, and other values ​​not listed within this range are also applicable.

[0035] The present invention further preferably controls the content of olefinic acid within the above range, which can better improve the solubility of the demulsifier in the oil phase and provide more hydrogen bonding sites, thereby achieving more excellent demulsification performance.

[0036] Preferably, the oil-soluble auxiliary agent includes any one or a combination of at least two of vinyltoluene, styrene propylene or styrene, wherein typical but non-limiting combinations are a combination of vinyltoluene and styrene propylene, a combination of styrene and styrene propylene, and a combination of vinyltoluene and styrene.

[0037] Preferably, the oil-soluble auxiliary agent accounts for 0.1 to 10 wt% of the mass of the fatty alcohol nonionic polyether, for example, it can be 0.1 wt%, 1.2 wt%, 2.3 wt%, 3.4 wt%, 4.5 wt%, 5.6 wt%, 6.7 wt%, 7.8 wt%, 8.9 wt% or 10 wt%, etc., but is not limited to the listed values, and other values ​​not listed within this range are also applicable.

[0038] The present invention further preferably controls the mass ratio of the oil-soluble additive to the fatty alcohol nonionic polyether within the above range, which can take into account the solubility of the demulsifier in both the oil phase and the water phase, thereby ultimately improving the demulsification performance.

[0039] Preferably, the polymerization reaction temperature is 60-100°C, for example, 60°C, 65°C, 69°C, 74°C, 78°C, 83°C, 87°C, 92°C, 96°C or 100°C, etc., but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0040] Preferably, the polymerization reaction duration is 2 to 8 hours, for example, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 6 hours, 7 hours or 8 hours.

[0041] Preferably, the oxygen-rich organic acid in step (2) comprises any one of lactic acid, citric acid or linoleic acid, or a combination of at least two thereof, wherein typical but non-limiting combinations are a combination of lactic acid and citric acid, a combination of linoleic acid and citric acid, and a combination of lactic acid and linoleic acid.

[0042] The present invention further prefers that the oxygen-rich organic acid is lactic acid, citric acid or linoleic acid. Compared with other organic acids, these acids can not only better form hydrogen bonding sites during the demulsification process, but also are well compatible with the oil phase, and have a better demulsification effect.

[0043] Preferably, the oxygen-rich organic acid accounts for 0.1 to 10 wt% of the mass of the fatty alcohol nonionic polyether, for example, it can be 0.1 wt%, 1.2 wt%, 2.3 wt%, 3.4 wt%, 4.5 wt%, 5.6 wt%, 6.7 wt%, 7.8 wt%, 8.9 wt% or 10 wt%, etc., but is not limited to the listed values, and other values ​​not listed within this range are also applicable.

[0044] The present invention further preferably controls the content of the oxygen-rich organic acid within the above range, which can better take into account the formation of hydrogen bonding sites of the demulsifier or the solubility of the demulsifier in the oil phase, and ultimately improve the demulsification effect of the demulsifier, and has broad application prospects.

[0045] Preferably, the temperature of the catalytic esterification reaction is 80-150°C, for example, 80°C, 88°C, 96°C, 104°C, 112°C, 119°C, 127°C, 135°C, 143°C or 150°C, but is not limited to the listed values, and other values ​​not listed within this range are also applicable.

[0046] Preferably, the catalytic esterification reaction is performed for 2 to 8 hours, for example, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 6 hours, 7 hours or 8 hours.

[0047] Preferably, the catalyst for catalyzing the esterification reaction is an organic catalyst.

[0048] Preferably, the organic catalyst comprises sulfonic acid and / or an organic acid salt.

[0049] Preferably, the sulfonic acid comprises an arylsulfonic acid, preferably any one or a combination of at least two of benzenesulfonic acid, p-toluenesulfonic acid, o-toluenesulfonic acid or m-toluenesulfonic acid, wherein typical but non-limiting combinations are a combination of benzenesulfonic acid and p-toluenesulfonic acid, a combination of o-toluenesulfonic acid and p-toluenesulfonic acid, a combination of benzenesulfonic acid and o-toluenesulfonic acid, and a combination of m-toluenesulfonic acid and o-toluenesulfonic acid.

[0050] Preferably, the organic acid salt comprises an acetate, preferably any one or a combination of at least two of zinc acetate, cobalt acetate or ferric acetate, wherein typical but non-limiting combinations are a combination of zinc acetate and cobalt acetate, and a combination of ferric acetate and cobalt acetate.

[0051] Preferably, the organic catalyst accounts for 0.01 to 1 wt% of the mass of the fatty alcohol nonionic polyether, for example, it can be 0.01 wt%, 0.12 wt%, 0.23 wt%, 0.34 wt%, 0.45 wt%, 0.56 wt%, 0.67 wt%, 0.78 wt%, 0.89 wt% or 1 wt%, etc., but is not limited to the listed values, and other values ​​not listed within this range are also applicable.

[0052] Preferably, said removing the solvent comprises drying.

[0053] Preferably, the drying temperature is 80-150°C, for example, 80°C, 88°C, 96°C, 104°C, 112°C, 119°C, 127°C, 135°C, 143°C or 150°C, but is not limited to the listed values. Other values ​​not listed within this range are also applicable. The pressure is -0.1MPa to -0.5MPa, for example, -0.1MPa, -0.15MPa, -0.2MPa, -0.25MPa, -0.3MPa, -0.35MPa, -0.4MPa, -0.45MPa or -0.5MPa, and the time is 20-120min, for example, 20min, 32min, 43min, 54min, 65min, 76min, 87min, 98min, 109min or 120min, but is not limited to the listed values. Other values ​​not listed within this range are also applicable.

[0054] In a third aspect, the present invention provides an application of the oxygen-hybrid nonionic demulsification material described in the first aspect or the oxygen-hybrid nonionic demulsification material prepared by the preparation method of the oxygen-hybrid nonionic demulsification material described in the second aspect, wherein the oxygen-hybrid nonionic demulsification material is used for demulsifying unconventional oil-water emulsions containing nano-micro solid particles.

[0055] The oxygen-hybridized nonionic demulsifying material provided by the present invention has an excellent demulsifying effect on unconventional oil-water emulsions containing nano-micro solid particles, which makes up for the problem of insufficient demulsification performance of such oil-water emulsions in the existing market.

[0056] Preferably, the particle size of the nano-micro solid particles in the unconventional oil-water emulsion containing nano-micro solid particles is 20 nm to 10 μm, for example, it can be 20 nm, 21 nm, 25 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 1 μm, 2 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm, etc.

[0057] The nano-micro solid particles of the present invention have a small particle size and therefore have extremely high stability at the oil-water interface, which increases the difficulty of oil-water demulsification.

[0058] Preferably, the unconventional oil-water emulsion containing nano-micro solid particles is a water-in-oil emulsion.

[0059] Preferably, the viscosity of the unconventional oil-water emulsion containing nano-micro solid particles is 50 to 500 mPa·s, for example, it can be 50 mPa·s, 100 mPa·s, 150 mPa·s, 200 mPa·s, 250 mPa·s, 300 mPa·s, 350 mPa·s, 400 mPa·s, 450 mPa·s or 500 mPa·s, etc.

[0060] Preferably, the asphaltene content in the unconventional oil-water emulsion containing nano-micro solid particles is 0.1-5wt%, for example, it can be 0.1wt%, 0.7wt%, 1.2wt%, 1.8wt%, 2.3wt%, 2.9wt%, 3.4wt%, 4wt%, 4.5wt% or 5wt%, etc.

[0061] Preferably, the water content in the unconventional oil-water emulsion containing nano-micro solid particles is 10 to 75 wt%, for example, it can be 10 wt%, 18 wt%, 25 wt%, 32 wt%, 39 wt%, 47 wt%, 54 wt%, 61 wt%, 68 wt% or 75 wt%, etc.

[0062] Preferably, the content of nano-micro solid particles in the unconventional oil-water emulsion containing nano-micro solid particles is 0.1-2 wt%, for example, it can be 0.1 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt% or 2 wt%, etc.

[0063] Preferably, the demulsification time is 30 min to 120 min, for example, it can be 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min or 120 min.

[0064] Preferably, the demulsification temperature is 40°C to 60°C, for example, 40°C, 43°C, 45°C, 47°C, 49°C, 52°C, 54°C, 56°C, 58°C or 60°C.

[0065] Preferably, the amount of the oxygen-hybridized nonionic demulsifying material added in the demulsifier is 100 mg / L to 1200 mg / L, for example, 100 mg / L, 220 mg / L, 345 mg / L, 460 mg / L, 580 mg / L, 710 mg / L, 830 mg / L, 950 mg / L, 1070 mg / L or 1200 mg / L, etc.

[0066] Compared with the prior art, the present invention has at least the following beneficial effects:

[0067] (1) The oxygen-hybridized nonionic demulsifier provided by the present invention can help the demulsifier form more hydrogen bonds with the emulsified water droplets through its own oxygen atoms, thereby promoting demulsification. In addition, the benzene ring and long alkyl chain can promote the compatibility between the demulsifier and the oil phase. The two synergistically enhance the destructive effect on the oil-water interface, ultimately having an excellent demulsification effect.

[0068] (2) The oxygen-hybrid nonionic demulsifier provided by the present invention generates more oxygen-rich groups by esterification and dehydration reaction between oxygen-rich organic acid and fatty alcohol nonionic polyether. The high-density oxygen groups can not only provide more hydrogen bonds, but also have stronger non-covalent bond reconstruction ability, which is beneficial to improving the demulsification ability of the oxygen-hybrid nonionic demulsifier;

[0069] (3) The oxygen-hybridized nonionic demulsifier provided by the present invention is used in unconventional oil-water emulsions stabilized by micro-nanoparticles. The demulsification time is as short as 45 minutes, the conditions are mild, generally within 60°C, and 100% complete demulsification can be achieved. The demulsification effect is excellent and the application prospects are broad. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] Figure 1 This is the H-NMR spectrum of the oxygen-hybridized nonionic demulsifier material prepared in Example 1 of the present invention.

[0071] Figure 2 This is the infrared spectrum of the oxygen-hybridized nonionic demulsifier material prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0072] For the convenience of understanding the present invention, the present invention is given below with examples. It should be understood by those skilled in the art that the examples are only for the purpose of helping to understand the present invention and should not be regarded as specific limitations of the present invention.

[0073] Example 1

[0074] This embodiment provides an oxygen-hybrid nonionic demulsification material, and the preparation method of the oxygen-hybrid nonionic demulsification material comprises the following steps:

[0075] (1) At room temperature, 10 g of a nonionic fatty alcohol polyether (brand 2040, molecular weight 4000) was added to a container equipped with a thermometer, a stirring component, and a reflux condensing component. The nonionic fatty alcohol polyether was formed by polymerization of ethylene oxide and propylene oxide in a ratio of 2:1 with propylene glycol as an initiator. 100 mL of xylene was then added and the nonionic fatty alcohol polyether was completely dissolved under stirring at 150 rpm. 2 g of acrylic acid, 1 g of styrene, and 0.02 g of benzoyl peroxide were then added. The temperature was gradually raised to 80° C., and a polymerization reaction was carried out for 2 hours to obtain a first polymer.

[0076] (2) Add 1 g of lactic acid and 0.04 g of p-toluenesulfonic acid to the first polymer, raise the system temperature to 130°C, and carry out a catalytic esterification reaction for 4 hours to obtain an esterification reaction system; then evaporate the xylene solvent in the esterification reaction system, and dry the obtained liquid in a vacuum drying oven at 80°C for 60 minutes to obtain an oxygen-hybridized nonionic demulsifier.

[0077] The equations in the preparation process of this embodiment are shown in the following equations (2) to (4):

[0078]

[0079] The oxygen-hybrid nonionic demulsifier prepared in this embodiment includes the structure described in formula (1):

[0080]

[0081] In formula (1), the value of x is 55, the value of y is 35, the value of n is 15, the value of x' is 25, and the value of y' is 8.

[0082] The nuclear magnetic hydrogen spectrum and infrared spectrum of the oxygen hybrid nonionic demulsifier prepared in this example are as follows: Figure 1 and Figure 2 As shown, from Figure 1 and Figure 2It can be seen that the oxygen hybrid nonionic demulsifier prepared in this embodiment has a carboxyl group. The absorption peak at 12.3 ppm in the nuclear magnetic spectrum indicates that a carboxyl group is introduced into the demulsifier, and the absorption peak at 7.1 ppm indicates that a phenyl group is introduced into the demulsifier. The infrared spectrum has an ester peak (1736 cm -1 ) and ether peak (1109cm -1 ), which shows that the oxygen-hybridized nonionic demulsifier in formula (1) was successfully synthesized.

[0083] Example 2

[0084] This embodiment provides an oxygen-hybrid nonionic demulsifier. The preparation method of the oxygen-hybrid nonionic demulsifier is the same as that of Example 1, except that 8 g of fatty alcohol nonionic polyether, 0.04 g of benzoyl peroxide, and 0.06 g of p-toluenesulfonic acid are added, the polymerization reaction time is 3 hours, and the esterification dehydration reaction time is 3 hours. The preparation method is not repeated here.

[0085] Example 3

[0086] This embodiment provides an oxygen-hybrid nonionic demulsifier. The preparation method of the oxygen-hybrid nonionic demulsifier is the same as that of Example 1, except that 6 g of fatty alcohol nonionic polyether, 0.06 g of benzoyl peroxide, and 0.04 g of p-toluenesulfonic acid are added, the polymerization reaction time is 4 hours, and the esterification dehydration reaction time is 5 hours. The preparation method is not repeated here.

[0087] Example 4

[0088] This embodiment provides an oxygen-hybrid nonionic demulsifier. The preparation method of the oxygen-hybrid nonionic demulsifier is the same as that of Example 1, except that 12 g of fatty alcohol nonionic polyether, 0.1 g of benzoyl peroxide, and 0.1 g of p-toluenesulfonic acid are added, the polymerization reaction time is 6 hours, and the esterification dehydration reaction time is 6 hours. The preparation method is not repeated here.

[0089] Example 5

[0090] This embodiment provides an oxygen-hybrid nonionic demulsifier. The preparation method of the oxygen-hybrid nonionic demulsifier is the same as that of Example 1, except that 20 g of fatty alcohol nonionic polyether, 5 g of acrylic acid, and 2 g of lactic acid are added. The preparation method will not be repeated here.

[0091] Example 6

[0092] This embodiment provides an oxygen-hybrid nonionic demulsifier. The preparation method of the oxygen-hybrid nonionic demulsifier is the same as that of Example 1, except that the olefinic acid is a mixture of acrylic acid and 2-butenoic acid, each with a mass of 1 g, the solvent is a mixed solvent of xylene and toluene, each with 50 mL, the free radical modifier is a mixture of azobisisobutyronitrile and benzoyl peroxide, with 0.01 g of each added, the polymerization reaction temperature is 90°C, and the esterification dehydration reaction temperature is 120°C. The rest is the same as that of Example 1 and will not be repeated here.

[0093] Example 7

[0094] This embodiment provides an oxygen-hybrid nonionic demulsifier. The preparation method of the oxygen-hybrid nonionic demulsifier is the same as that of Example 1, except that the olefinic acid is a mixture of oleic acid, acrylic acid, and 2-butenoic acid, each having a mass of 1.0 g, the oil-soluble additive is a mixture of styrene, propylene, and styrene, each having a mass of 0.5 g, the solvent is a mixed solvent of xylene and trimethylbenzene, each having a mass of 50 mL, and the organic acid catalyst is a mixture of benzenesulfonic acid, p-toluenesulfonic acid, and m-toluenesulfonic acid, each having a mass of 0.02 g. Detailed description is omitted here.

[0095] Example 8

[0096] This embodiment provides an oxygen-hybrid nonionic demulsifier. The preparation method of the oxygen-hybrid nonionic demulsifier is the same as that of Example 1, except that the olefinic acid is a mixture of oleic acid and acrylic acid, each having a mass of 1.0 g, the solvent is a mixed solvent of xylene, trimethylbenzene, and toluene, each having a mass of 30 mL, the oil-soluble auxiliary agent is a mixture of vinyltoluene and styrene, each having a mass of 0.5 g, the organic acid catalyst is a mixture of benzenesulfonic acid, p-toluenesulfonic acid, and m-toluenesulfonic acid, each of which is added at 0.02 g, and the free radical modifier is a mixture of azobisisobutyronitrile and benzoyl peroxide, each of which is added at 0.01 g. The rest is not repeated here.

[0097] Example 9

[0098] This embodiment provides an oxygen-hybrid nonionic demulsifier. The preparation method of the oxygen-hybrid nonionic demulsifier is the same as that of Example 1, except that the olefinic acid is a mixture of undecylenic acid, acrylic acid, and oleic acid, each having a mass of 0.5 g, the solvent is a mixed solvent of trimethylbenzene and toluene, each having a mass of 50 mL, the oil-soluble additive is a mixture of vinyltoluene and styrene, each having a mass of 0.5 g, the organic acid catalyst is a mixture of benzenesulfonic acid, p-toluenesulfonic acid, and m-toluenesulfonic acid, each having a mass of 0.03 g, and the free radical modifier is a mixture of azobisisobutyronitrile and azobisisoheptonitrile, each having a mass of 0.02 g. The details are not repeated here.

[0099] Example 10

[0100] This embodiment provides an oxygen-hybrid nonionic demulsifier. The preparation method of the oxygen-hybrid nonionic demulsifier is the same as that of Example 1, except that the olefinic acid is a mixture of oleic acid and undecylenic acid, each having a mass of 0.8 g, the solvent is a mixed solvent of xylene, trimethylbenzene, and toluene, each having a mass of 30 mL, the oil-soluble additive is a mixture of vinyltoluene, styrene, and styrene propene, each having a mass of 0.3 g, the organic acid catalyst is a mixture of p-toluenesulfonic acid and m-toluenesulfonic acid, each having a mass of 0.03 g, and the free radical modifier is a mixture of azobisisobutyronitrile and diisopropylbenzene peroxide, each having a mass of 0.02 g. The rest is the same as that of Example 1 and will not be repeated here.

[0101] Example 11

[0102] This embodiment provides an oxygen-hybrid nonionic demulsification material. Except for adding 4g of acrylic acid, the oxygen-hybrid nonionic demulsification material is the same as that of Example 1, which will not be described again.

[0103] Example 12

[0104] This embodiment provides an oxygen-hybrid nonionic demulsification material. The oxygen-hybrid nonionic demulsification material is the same as that of Example 1 except that 0.05 g of acrylic acid is added, and details thereof will not be repeated here.

[0105] Example 13

[0106] This embodiment provides an oxygen-hybrid nonionic demulsification material. The oxygen-hybrid nonionic demulsification material is the same as that of Example 1 except that 0.005 g of styrene is added, and details thereof will not be repeated here.

[0107] Example 14

[0108] This embodiment provides an oxygen-hybrid nonionic demulsification material. Except for adding 1.5 g of styrene, the oxygen-hybrid nonionic demulsification material is the same as that of Example 1, which will not be repeated here.

[0109] Example 15

[0110] This embodiment provides an oxygen-hybrid nonionic demulsification material. The oxygen-hybrid nonionic demulsification material is the same as that of Example 1 except that lactic acid is replaced by formic acid, and details thereof will not be repeated here.

[0111] Example 16

[0112] This embodiment provides an oxygen-hybrid nonionic demulsification material. The oxygen-hybrid nonionic demulsification material is the same as that of Example 1 except that 1.2 g of lactic acid is added, and details thereof will not be repeated here.

[0113] Example 17

[0114] This embodiment provides an oxygen-hybrid nonionic demulsification material. The oxygen-hybrid nonionic demulsification material is the same as that of Example 1 except that 0.005 g of lactic acid is added, and details thereof will not be repeated here.

[0115] Example 18

[0116] This embodiment provides an oxygen-hybrid nonionic demulsification material, and the preparation method of the oxygen-hybrid nonionic demulsification material comprises the following steps:

[0117] (1) At 40°C, 10 g of fatty alcohol nonionic polyether (brand 2040, molecular weight 5000, Nantong Derui Chemical Co., Ltd.) was added to a container equipped with a thermometer, a stirring component, and a reflux condensing component. The fatty alcohol nonionic polyether was formed by polymerization of ethylene oxide and propylene oxide in a ratio of 2:1 with propylene glycol as an initiator. Then, 110 mL of xylene was added and the fatty alcohol nonionic polyether was completely dissolved under stirring at 150 r / min. Then, 2.3 g of acrylic acid, 0.8 g of styrene, and 0.02 g of benzoyl peroxide were added, and the temperature was gradually raised to 60°C. The polymerization reaction was carried out for 4 hours to obtain a first polymer.

[0118] (2) Add 0.8 g of lactic acid and 0.03 g of p-toluenesulfonic acid to the first polymer, raise the system temperature to 150° C., and carry out a catalytic esterification reaction for 2 hours to obtain an esterification reaction system; then evaporate the xylene solvent in the esterification reaction system, and dry the obtained liquid in a vacuum drying oven at 75° C. for 80 minutes to obtain an oxygen-hybridized nonionic demulsifier.

[0119] Comparative Example 1

[0120] This comparative example provides a demulsifier, which is a commercially available demulsifier AP2040 (Nantong Derui Chemical Co., Ltd.).

[0121] Comparative Example 2

[0122] This comparative example provides a demulsifier, which is a commercially available demulsifier BP2050 (Nantong Derui Chemical Co., Ltd.).

[0123] Comparative Example 3

[0124] This comparative example provides a demulsifier, which is a commercially available demulsifier AE1951 (Nantong Derui Chemical Co., Ltd.).

[0125] Comparative Example 4

[0126] This comparative example provides a demulsifier, which is a commercially available demulsifier SP169 (Nantong Derui Chemical Co., Ltd.).

[0127] Comparative Example 5

[0128] This comparative example provides a demulsifier, which is the commercially available demulsifier OWT101 (Guangzhou Xiaozhong Environmental Protection Technology Co., Ltd.).

[0129] Comparative Example 6

[0130] This comparative example provides a demulsifier, which is the commercially available demulsifier OWT102 (Guangzhou Xiaozhong Environmental Protection Technology Co., Ltd.).

[0131] Comparative Example 7

[0132] This comparative example provides a demulsifier, which is the commercially available demulsifier OWT103 (Guangzhou Xiaozhong Environmental Protection Technology Co., Ltd.).

[0133] Comparative Example 8

[0134] This comparative example provides an oxygen-hybrid nonionic demulsification material. The oxygen-hybrid nonionic demulsification material is the same as Example 1 except that acrylic acid is replaced by acetic acid, and the rest is not repeated here.

[0135] Comparative Example 9

[0136] This comparative example provides an oxygen-hybrid nonionic demulsifier. The oxygen-hybrid nonionic demulsifier is the same as that in Example 1 except that styrene is replaced by ethylene, and details thereof will not be repeated here.

[0137] Comparative Example 10

[0138] This comparative example provides an oxygen-hybrid nonionic demulsification material. The oxygen-hybrid nonionic demulsification material is the same as Example 1 except that lactic acid is not added, and details thereof will not be repeated here.

[0139] Application Example 1

[0140] This application example provides an application of an oxygen-hybrid nonionic demulsifier material, and the application is carried out using the oxygen-hybrid nonionic demulsifier provided in Example 1. The specific steps include: a demulsification experiment of an unconventional petroleum emulsion stabilized by nano-micro solid particles (hereinafter referred to as "emulsion", with a viscosity of 150 mPa·s, an asphaltene content of 1 wt%, a water content of 30%, a nano-micro solid particle content of 1.5 wt%, and a particle size D50 of the nano-micro solid particles of 2 μm): the demulsifier prepared by Example 1 is added to an emulsion with a water content of 30% (volume fraction), the emulsion is pre-placed in a graduated stoppered measuring cylinder, the amount of demulsifier added is 800 ppm, and the stoppered measuring cylinder is then placed in a water bath at 60°C for demulsification to obtain separated oil phase and water phase.

[0141] Application Examples 2 to 17 and Comparative Application Examples 1 to 10

[0142] Application Examples 2 to 17 and Comparative Examples 1 to 10 provide an application of an oxygen-hybridized nonionic demulsifier. Except that the oxygen-hybridized nonionic demulsifiers in Examples 2 to 17 and Comparative Examples 1 to 10 are used respectively, and the amount of oxygen-hybridized nonionic demulsifier added in Application Example 4, Application Example 6, and Application Example 8 is 1000 ppm, and the amount of oxygen-hybridized nonionic demulsifier added in Application Example 10 is 1200 ppm, the rest are the same as Application Example 1 and will not be repeated here.

[0143] Application Example 18

[0144] This application example provides an application of an oxygen-hybrid nonionic demulsifier material, and the application is carried out using the oxygen-hybrid nonionic demulsifier provided in Example 18. The specific steps include: a demulsification experiment of an unconventional petroleum emulsion stabilized by nano-micro solid particles (hereinafter referred to as "emulsion", with a viscosity of 500 mPa·s, an asphaltene content of 2 wt%, a water content of 50%, a nano-micro solid particle content of 2 wt%, and a particle size D50 of the nano-micro solid particles of 500 nm): the demulsifier prepared by Example 1 is added to an emulsion with a water content of 50% (volume fraction), the emulsion is pre-placed in a graduated stoppered measuring cylinder, the amount of demulsifier added is 850 ppm, and the stoppered measuring cylinder is placed in a water bath at 50°C for demulsification to obtain separated oil phase and water phase.

[0145] The application of the oxygen-hybridized nonionic demulsifying materials provided in Application Examples 1 to 10 and Application Example 18 can achieve a demulsification efficiency of 100% within 45 minutes, and has broad application prospects.

[0146] Compared with Application Examples 11-12, Application Example 1 has too much or too little acrylic acid, which results in decreased solubility of the demulsifier in the oil phase or insufficient hydrogen bonding sites, resulting in decreased demulsification performance.

[0147] Compared with Application Examples 13-14, Application Example 1 has too much or too little acrylic acid, which results in a decrease in the solubility of the demulsifier in the oil phase or a decrease in the water solubility of the demulsifier, resulting in a decrease in the demulsification performance.

[0148] Compared with Application Examples 15 to 17, Application Example 1 uses formic acid, and the hydrogen bonding sites formed by the demulsifier are insufficient, resulting in a decrease in demulsification performance; in Application Examples 16 to 17, when more lactic acid is used, the solubility of the demulsifier in the oil phase is reduced, and when less lactic acid is used, the hydrogen bonding sites formed by the demulsifier are insufficient, ultimately leading to a decrease in demulsification performance.

[0149] When commercial demulsifiers were used in Comparative Examples 1 to 10 or a certain raw material of the demulsifier of the present invention was removed, the demulsification performance was significantly reduced compared with that of Application Example 1.

[0150] The demulsification efficiency in the present invention is calculated as the volume of separated water divided by the total volume of water in the emulsion. The test results of the above application examples and comparative examples are shown in Table 1.

[0151] Table 1

[0152]

[0153]

[0154] In summary, it can be seen that the new oxygen-hybrid nonionic demulsifier provided by the present invention has excellent demulsification performance. The demulsifier prepared by combining an oxygen-rich organic acid with an oil-soluble additive and a fatty alcohol nonionic polyether has better demulsification performance for unconventional petroleum emulsions stabilized by nanoparticles than the single polyether demulsifier. The effect of enhancing demulsification during the demulsification process is significant, and 100% demulsification efficiency can be achieved within 45 minutes.

[0155] The present invention uses the above-described embodiments to illustrate the detailed features of the present invention. However, the present invention is not limited to the above-described detailed features, which does not mean that the present invention must rely on the above-described detailed features to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacements for the selected technical features of the present invention, additions to auxiliary technical features, and selections of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A method for preparing an oxygen-hybrid nonionic demulsifier, characterized in that: The preparation method comprises the following steps: (1) A solution of a fatty alcohol nonionic polyether, a free radical initiator, an olefinic acid and an oil-soluble auxiliary agent are mixed to carry out a polymerization reaction to obtain a first polymer; the fatty alcohol nonionic polyether is a linear type, and the fatty alcohol nonionic polyether is formed by polymerization of ethylene oxide and propylene oxide with propylene glycol as an initiator; the olefinic acid accounts for 1 to 30 wt% of the mass of the fatty alcohol nonionic polyether; the oil-soluble auxiliary agent includes any one of vinyltoluene, styrene or propylene, or a combination of at least two thereof; the oil-soluble auxiliary agent accounts for 0.1 to 10 wt% of the mass of the fatty alcohol nonionic polyether; the olefinic acid includes an olefinic acid containing at least one carboxyl group and having 3 to 20 carbon atoms; (2) catalyzing an esterification reaction between an oxygen-rich organic acid and the first polymer to obtain an esterification reaction system, and removing the solvent from the esterification reaction system to obtain the oxygen-hybridized nonionic demulsifier material; The oxygen-rich organic acid includes any one of lactic acid, citric acid or linoleic acid, or a combination of at least two thereof; The oxygen-rich organic acid accounts for 0.1-10 wt % of the mass of the fatty alcohol nonionic polyether.

2. The preparation method according to claim 1, characterized in that The solvent in the solution of the fatty alcohol nonionic polyether in step (1) is an organic solvent.

3. The preparation method according to claim 2, characterized in that The organic solvent includes an aromatic hydrocarbon organic solvent.

4. The preparation method according to claim 3, characterized in that The aromatic hydrocarbon organic solvent includes any one of toluene, xylene, trimethylbenzene or ethylbenzene, or a combination of at least two of them.

5. The preparation method according to claim 1, characterized in that The molar ratio of the ethylene oxide to the propylene oxide is 1-2:

1.

6. The preparation method according to claim 1, characterized in that The molecular weight of the fatty alcohol nonionic polyether is 3000-5000.

7. The preparation method according to claim 1, characterized in that The molar ratio of the sum of the propylene glycol, ethylene oxide and propylene oxide is 0.01-0.0125:

1.

8. The preparation method according to claim 1, characterized in that The ratio of the fatty alcohol nonionic polyether to the organic solvent is 1-60 g:100 mL.

9. The preparation method according to claim 1, characterized in that The free radical initiator includes any one of azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide or dicumyl peroxide, or a combination of at least two thereof.

10. The preparation method according to claim 9, characterized in that The free radical initiator accounts for 0.01 to 1 wt % of the mass of the fatty alcohol nonionic polyether.

11. The preparation method according to claim 1, characterized in that The olefinic acid includes any one of 2-butenoic acid, oleic acid, acrylic acid or undecenoic acid, or a combination of at least two thereof.

12. The preparation method according to claim 1, characterized in that The polymerization reaction temperature is 60-100°C.

13. The preparation method according to claim 1, characterized in that The polymerization reaction time is 2 to 8 hours.

14. The preparation method according to claim 1, characterized in that The temperature of the catalytic esterification reaction is 80-150°C.

15. The preparation method according to claim 1, characterized in that The duration of the catalytic esterification reaction is 2 to 8 hours.

16. The preparation method according to claim 1, characterized in that The catalyst for catalyzing the esterification reaction is an organic catalyst.

17. The preparation method according to claim 16, characterized in that The organic catalyst includes sulfonic acid and / or organic acid salt.

18. The preparation method according to claim 17, characterized in that: The sulfonic acid includes arylsulfonic acid.

19. The preparation method according to claim 18, characterized in that The aryl sulfonic acid is any one of benzenesulfonic acid, p-toluenesulfonic acid, o-toluenesulfonic acid or m-toluenesulfonic acid, or a combination of at least two thereof.

20. The preparation method according to claim 17, characterized in that The organic acid salt includes acetate.

21. The preparation method according to claim 20, characterized in that The organic acid salt includes zinc acetate and / or iron acetate.

22. The preparation method according to claim 17, characterized in that The organic catalyst accounts for 0.01 to 1 wt % of the mass of the fatty alcohol nonionic polyether.

23. An oxygen-hybrid nonionic demulsifier material, characterized in that: The oxygen-hybrid nonionic demulsification material is prepared by the preparation method of the oxygen-hybrid nonionic demulsification material according to any one of claims 1 to 22.

24. Use of the oxygen-hybrid nonionic demulsification material according to claim 23 or the oxygen-hybrid nonionic demulsification material prepared by the preparation method of the oxygen-hybrid nonionic demulsification material according to any one of claims 1 to 22, characterized in that: The oxygen hybrid nonionic demulsifying material is used for demulsifying unconventional oil-water emulsions containing nano-micro solid particles.

25. The use according to claim 24, characterized in that The particle size of the nano-micro solid particles in the unconventional oil-water emulsion containing nano-micro solid particles is 20 nm to 10 μm.

26. The use according to claim 24, characterized in that The unconventional oil-water emulsion containing nano-micro solid particles is a water-in-oil emulsion.

27. The use according to claim 24, characterized in that The viscosity of the unconventional oil-water emulsion containing nano-micro solid particles is 50 mPa·s to 500 mPa·s.

28. The use according to claim 24, characterized in that The asphaltene content in the unconventional oil-water emulsion containing nano-micro solid particles is 0.1 wt% to 5 wt%.

29. The use according to claim 24, characterized in that The water content of the unconventional oil-water emulsion containing nano-micro solid particles is 10 wt % to 75 wt %.

30. The use according to claim 24, characterized in that The content of nano-micro solid particles in the unconventional oil-water emulsion containing nano-micro solid particles is 0.1 wt% to 2 wt%.

31. The use according to claim 24, characterized in that The time for demulsification is 30 min to 120 min.

32. The use according to claim 24, characterized in that The temperature of the demulsification is 40°C to 60°C.

33. The use according to claim 24, characterized in that The amount of the oxygen-hybridized nonionic demulsifying material added to the unconventional oil-water emulsion is 100 mg / L to 1200 mg / L.

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