Demulsification system, metal ion scavenger and preparation method thereof

Abstract

The invention discloses a metal ion scavenger, the general structural formula of which is: a preparation method of the metal ion scavenger, comprising: (1) pretreatment; (2) dissolving vinyl triethoxysilane or vinyl trimethoxysilane or vinyl tris (β-methoxyethoxy) silane to prepare a solution; (3) adding vermiculite powder to the solution, stirring, filtering and drying to obtain vermiculite powder; (4) adding sodium 2-alkyl carbeneate to a reaction vessel, adding distilled water, hexadecyl ammonium chloride and acrylamide, heating, cold water reflux, stirring, dissolving, adding urea peroxide, reflux reaction, filtering and drying to obtain a solid product; (5) mixing and dissolving the solid product, 2,4-dihydroxybenzophenone and an organic solvent, adding vermiculite powder, shaking, filtering and obtaining a solid product, and irradiating the solid product under an ultraviolet lamp to obtain the metal ion scavenger. A demulsification system comprises 5% to 10% of the above-mentioned metal ion scavenger.

Description

Technical Field

[0001] The invention belongs to the field of crude oil processing, and in particular relates to a demulsification system, a metal ion scavenger and a preparation method thereof. Background Art

[0002] After crude oil (water content less than 1.5%) enters the refinery, it is first desalted and dehydrated by settling in the crude oil tank. During this process, whether to add a demulsifier depends on the difficulty of dehydration. After the crude oil is desalted and dehydrated, it enters the electric desalting system. During the electric desalting process, a certain proportion of fresh water is injected, and demulsifiers, decalcifying agents, etc. are added for further desalting and dehydration.

[0003] Normally, qualified oil products fed into the electric desalting and dehydration system complete the desalting process normally. However, the properties of the crude oil exported from a certain oilfield fluctuate. Every second half of the year, some oil products frequently experience strong emulsion stability, making demulsification and dehydration difficult. This results in the electric desalting and dehydration system not functioning properly.

[0004] The current primary response to these issues is to increase the water cutoff in the electro-desalter and reduce water injection to prevent water carryover into the primary distillation tower, impacting product quality. However, this leads to the following problems: 1. Crude oil desalting and dehydration performance deteriorates significantly, leading to corrosion, catalyst deactivation, and scaling of hydrogenation heat exchangers in subsequent equipment. 2. Increasing the water cutoff increases the amount of oil carried over from the saline wastewater. Simultaneously, the difference in specific gravity and viscosity between oil and water reduces heat transfer efficiency, resulting in higher temperatures at the outlet of the saline wastewater. 3. Solid particle deposition in the crude oil significantly reduces the heat transfer efficiency of the cooling equipment, severely impacting the normal operation of the refinery. Summary of the Invention

[0005] Purpose of the invention: In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is to disclose a demulsification system, a metal ion scavenger and a preparation method thereof. The demulsification system disclosed in the present invention has a high demulsification and dehydration rate, which overcomes the problem of low demulsification and dehydration rate of conventional demulsifiers.

[0006] Technical solution: Metal ion capture agent, the general structural formula of which is:

[0007]

[0008] Wherein, Z refers to vermiculite, R1 is a C8-C18 straight-chain alkane group or a branched-chain alkyl group, wherein the branch of the branched-chain alkyl group is a C1-C6 alkane group or a phenyl group.

[0009] The preparation method of the metal ion scavenger comprises the following steps, calculated by weight:

[0010] (1) Pretreatment

[0011] The vermiculite powder is soaked in a weakly acidic aqueous solution with a pH value of 2 to 6 for at least 30 minutes to remove soluble ash components, and then the vermiculite powder is washed with clean water until neutral, and then soaked, rinsed, and filtered with deionized water for at least 5 times, and vacuum-dried at low temperature to obtain pretreated vermiculite powder;

[0012] (2) dissolving vinyltriethoxysilane or vinyltrimethoxysilane or vinyltri(β-methoxyethoxy)silane in an alcohol-water mixture to prepare 100 parts of a solution having a mass concentration of 0.5 to 2.5%;

[0013] (3) adding 5 to 20 parts of the vermiculite powder obtained in step (1) to the solution obtained in step (2), stirring and shaking at a low speed of 25 to 40° C. for 6 to 12 hours, filtering off the liquid, and drying to obtain vermiculite powder;

[0014] (4) adding 14.2 to 45 parts of sodium 2-alkylcarbenoate to a reaction vessel, adding 90 to 120 parts of distilled water, and then adding 1 to 5 parts of hexadecyl ammonium chloride and 8 to 10 parts of acrylamide, heating to 60 to 80°C and maintaining, reflux with cold water, stirring, and dissolving. After complete dissolution, adding 0.2 to 2 parts of urea peroxide, reflux reaction for 8 to 24 hours to obtain a reaction solution, filtering the reaction solution, taking a solid product and drying it to obtain a dried solid product;

[0015] (5) 40 to 60 parts of the solid product obtained in step (4), 0.5 to 5 parts of 2,4-dihydroxybenzophenone, and 80 to 120 parts of an organic solvent are mixed and fully dissolved, and then 5 to 20 parts of the vermiculite powder obtained in step (3) are added, and the mixture is slowly shaken for 4 to 6 hours, and then the liquid is removed by filtration to obtain a solid product. The solid product is placed under an ultraviolet lamp and irradiated for 30 to 120 minutes to obtain a metal ion capture agent.

[0016] Furthermore, the vermiculite powder in step (1) is micro-nano vermiculite powder.

[0017] Furthermore, the vermiculite powder in step (1) has a particle size of 10 nm to 50 μm.

[0018] Furthermore, in the alcohol-water mixture in step (2), alcohol accounts for 70-80% of the total mass.

[0019] Furthermore, the alcohol in the alcohol-water mixture in step (2) is at least one of methanol, ethanol, and isopropanol.

[0020] Furthermore, in step (4), the general formula of sodium 2-alkyl carbeneate is:

[0021] in:

[0022] R1 is a C8-C18 straight-chain alkyl group or a branched-chain alkyl group, wherein the branch of the branched-chain alkyl group is a C1-C6 alkyl group or a phenyl group.

[0023] Furthermore, the organic solvent in step (5) is one of petroleum ether, ethanol, and isopropanol.

[0024] The demulsification system includes 5% to 10% of the above-mentioned metal ion scavenger in terms of mass percentage.

[0025] Furthermore, it also includes 20% to 30% of organosilicon modified polyether demulsifier, 8% to 12% of low molecular alcohol polyether, 10% to 20% of OP-10, 2% to 5% of cationic surfactant and 1% to 5% of alcohol, and the balance is water.

[0026] Furthermore, the alcohol is one of ethanol, propanol, isopropanol and methanol, preferably ethanol.

[0027] Furthermore, the organosilicon-modified polyether demulsifier is diethylenetriamine organosilicon-modified polyoxypropylene polyoxyethylene ether, diethylenetriamine organosilicon-modified polyoxypropylene polyoxyethylene polyoxypropylene ether, diethylenetriamine organosilicon-modified polyoxyethylene polyoxypropylene polyoxyethylene ether, triethylenetetramine organosilicon-modified polyoxypropylene polyoxyethylene ether, triethylenetetramine organosilicon-modified polyoxypropylene polyoxyethylene polyoxypropylene ether, triethylenetetramine organosilicon-modified polyoxyethylene polyoxypropylene Polyoxyethylene ether, one or more of tetraethylenepentamine-based silicone-modified polyoxypropylenepolyoxyethylene ether, tetraethylenepentamine-based silicone-modified polyoxypropylenepolyoxyethylenepolyoxypropylene ether, tetraethylenepentamine-based silicone-modified polyoxyethylenepolyoxypropylenepolyoxyethylene ether, pentaethylenehexamine-based silicone-modified polyoxypropylenepolyoxyethylene ether, pentaethylenehexamine-based silicone-modified polyoxypropylenepolyoxyethylenepolyoxypropylene ether, and pentaethylenehexamine-based silicone-modified polyoxyethylenepolyoxypropylenepolyoxyethylene ether.

[0028] Furthermore, the low molecular weight alcohol polyether is one or more of ethylene glycol polyoxypropylene polyoxyethylene ether, ethylene glycol polyoxypropylene polyoxyethylene polyoxypropylene ether, ethylene glycol polyoxyethylene polyoxypropylene polyoxyethylene ether, propanol polyoxypropylene polyoxyethylene ether, propanol polyoxypropylene polyoxyethylene polyoxypropylene ether, propanol polyoxypropylene polyoxyethylene polyoxypropylene ether, isopropyl alcohol polyoxypropylene polyoxyethylene ether, isopropyl alcohol polyoxypropylene polyoxyethylene polyoxypropylene ether, isopropyl alcohol polyoxypropylene polyoxyethylene polyoxypropylene ether, propylene glycol polyoxypropylene polyoxyethylene ether, propylene glycol polyoxypropylene polyoxyethylene polyoxypropylene ether, propylene glycol polyoxyethylene polyoxypropylene polyoxyethylene ether, glycerol polyoxypropylene polyoxyethylene ether, glycerol polyoxypropylene polyoxyethylene polyoxypropylene ether, and glycerol polyoxyethylene polyoxypropylene polyoxyethylene ether.

[0029] Furthermore, the cationic surfactant is a monoalkyl quaternary ammonium salt and / or a dialkyl quaternary ammonium salt, wherein:

[0030] Monoalkyl quaternary ammonium salts include dodecyltrimethyl quaternary ammonium salt, tridecyltrimethyl quaternary ammonium salt, and tetradecyltrimethyl quaternary ammonium salt;

[0031] The general formula of dialkyl quaternary ammonium salt is as follows:

[0032]

[0033] Wherein: X is one of Br, Cl, and I, preferably Cl;

[0034] x, y, and z are all integers, and 1≤x≤16, 2≤y≤16, and 1≤z≤16;

[0035] If x<8, and z<8, then y>8;

[0036] If x≥8 and z≥8, then y≤8.

[0037] The method of using the present invention:

[0038] 1. Measure the carbon atom distribution of the crude oil to be demulsified, select a multifunctional metal ion scavenger that matches the carbon atom distribution of the crude oil, and then add it at the required concentration.

[0039] 2. Before entering vacuum distillation, crude oil must first undergo two dehydration steps: one is sedimentation dehydration in a settling tank, and the other is dehydration in an electric dehydration desalination device. The demulsifier in this invention can be added directly to the crude oil settling tube for use, or it can be directly added to the electric dehydration desalination process to improve the demulsification and dehydration efficiency of crude oil.

[0040] 3. The demulsifier of the present invention can be used directly, or the metal ion scavenger of the present invention can be directly added according to the on-site conditions.

[0041] The reason why metal ion scavengers can improve the demulsification effect:

[0042] Refineries' difficult-to-demulsify crude oils contain high levels of iron, nickel, calcium, and sodium (see Table 1). Laboratory validation has shown that metal ions such as iron, nickel, and calcium are key factors contributing to the difficulty in emulsifying and dehydrating crude oil, while sodium ions have no effect. This is because iron, nickel, and calcium, combined with petroleum sulfonates in the crude oil, form high-valent surfactants, further stabilizing the water-in-oil emulsion. The refinery's existing demulsifiers were no longer suitable for the incoming oil, leading to operational failure of the electrical desalting and dehydration unit.

[0043] Table 1 Comparison of Cations of Crude Oils with Difficulty in Demulsification in a Refinery (mg / kg)

[0044]

[0045] The metal ion scavenger of the present invention rapidly breaks the emulsion and dehydrates the emulsion through the following actions: 1. The scavenger has both long hydrophobic carbon chains and hydrophilic groups, which can be rapidly adsorbed and distributed on the oil-water interface of the emulsion droplets, destroying the stable structure of the interfacial membrane of the emulsion droplets; 2. The cationic charge on the scavenger rapidly interacts with the negative charge on the phenylcyclic acid group, forcing the iron, nickel, vanadium and calcium metal ions to be released and quickly surrounded and complexed by the scavenger.

[0046] Effect of the invention: The demulsification system, metal ion scavenger and preparation method disclosed in the present invention have the following advantages:

[0047] Beneficial effects:

[0048] 1. The refinery crude oil demulsification and dehydration rate is greatly improved, the water content of the crude oil is reduced to below 0.5% before entering the atmospheric and vacuum unit, the salt content is effectively controlled, the corrosion problem of the unit is greatly reduced, the catalyst activity retention rate is above 98%, and the scaling problem of the heat exchanger can be well solved;

[0049] 2. As the crude oil demulsification and dehydration rate is increased to the qualified range, the electric desalting and dehydration device can be cut off normally. The oil content in the saline wastewater is greatly reduced, the sludge adsorbed on the heat exchanger is greatly reduced, the heat exchange efficiency of the heat exchanger is maintained at more than 95%, and the temperature of the saline wastewater out of the device returns to normal;

[0050] 3. The solid particles in the crude oil were removed along with the water phase during demulsification and dehydration, which greatly reduced their deposition on the cold exchange equipment. The heat exchange efficiency of the cold exchange equipment increased by 62%, and the refinery resumed normal operation. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 Schematic diagram of the effect of metal ion scavenger concentration on demulsification and dehydration effect. DETAILED DESCRIPTION

[0052] The specific embodiments of the present invention are described in detail below.

[0053] Example 1

[0054] Metal ion scavenger, its general structural formula is:

[0055]

[0056] Wherein, Z refers to vermiculite, and R1 is an n-octadecane group.

[0057] Example 2

[0058] Metal ion scavenger, its general structural formula is:

[0059]

[0060] Wherein, Z refers to vermiculite, and R1 is n-octyl.

[0061] Example 3

[0062] Metal ion scavenger, its general structural formula is:

[0063]

[0064] Wherein, Z refers to vermiculite, and R1 is an isoheptyl group (ie, R1 is a C7 branched alkyl group, wherein the branch of the branched alkyl group is a methyl group at position 2).

[0065] Example 4

[0066] Metal ion scavenger, its general structural formula is:

[0067]

[0068] Wherein, Z refers to vermiculite, and R1 is 2-hexyl-dodecyl (R1 is a C12 branched alkyl group, wherein the branch of the branched alkyl group is a straight-chain hexyl group at position 2).

[0069] Example 5

[0070] Metal ion scavenger, its general structural formula is:

[0071]

[0072] Wherein, Z refers to vermiculite, and R1 is 2-phenyl-decyl (R1 is a C10 branched alkyl group, wherein the branch of the branched alkyl group is a phenyl group at position 2).

[0073] Example 6

[0074] The preparation method of the metal ion scavenger comprises the following steps, calculated by weight:

[0075] (1) Pretreatment

[0076] The vermiculite powder was soaked in a weakly acidic aqueous solution with a pH value of 2 for 30 minutes to remove soluble ash components, and then the vermiculite powder was washed with clean water until neutral, and then soaked, rinsed, and filtered with deionized water for 5 times, and vacuum-dried at low temperature to obtain the pretreated vermiculite powder;

[0077] (2) dissolving vinyltriethoxysilane in an alcohol-water mixture to prepare 100 parts of a solution with a mass concentration of 0.5%;

[0078] (3) adding 10 parts of the vermiculite powder obtained in step (1) to the solution obtained in step (2), shaking at a low speed with stirring at 25° C. for 6 h, removing the liquid by suction filtration, and obtaining vermiculite powder after drying;

[0079] (4) 14.2 parts of sodium 2-alkylcarbenoate were added to a reaction vessel, 90 parts of distilled water were added, and then 1.5 parts of hexadecyl ammonium chloride and 8.2 parts of acrylamide were added thereto, and the mixture was heated to 60°C and maintained, refluxed with cold water, stirred and dissolved, and after complete dissolution, 0.2 parts of urea peroxide were added, and the mixture was refluxed for 8 hours to obtain a reaction solution, the reaction solution was filtered, and a solid product was taken and dried to obtain a dried solid product;

[0080] (5) After 40 parts of the solid product obtained in step (4), 2.5 parts of 2,4-dihydroxybenzophenone, and 80 parts of an organic solvent are mixed and fully dissolved, 5 parts of the vermiculite powder obtained in step (3) are added, and the mixture is slowly shaken for 4 hours. After the liquid is removed by filtration, a solid product is obtained. The solid product is placed under an ultraviolet lamp and irradiated for 30 minutes to obtain a metal ion capture agent.

[0081] Furthermore, the vermiculite powder in step (1) is micro-nano vermiculite powder.

[0082] Furthermore, the vermiculite powder in step (1) has a particle size of 10 nm.

[0083] Furthermore, in the alcohol-water mixture in step (2), alcohol accounts for 75% of the total mass.

[0084] Furthermore, the alcohol in the alcohol-water mixture in step (2) is ethanol.

[0085] Furthermore, the structural formula of sodium 2-alkyl carbeneate in step (4) is:

[0086] in:

[0087] R1 is n-octadecyl.

[0088] Furthermore, the organic solvent in step (5) is petroleum ether.

[0089] Example 7

[0090] The preparation method of the metal ion scavenger comprises the following steps, calculated by weight:

[0091] (1) Pretreatment

[0092] The vermiculite powder was soaked in a weakly acidic aqueous solution with a pH value of 3 for 45 minutes to remove soluble ash components, and then the vermiculite powder was washed with clean water until neutral, and then soaked, rinsed, and filtered with deionized water for 6 times, and vacuum-dried at low temperature to obtain the pretreated vermiculite powder;

[0093] (2) dissolving vinyltrimethoxysilane in a mixture of alcohol and water to prepare 100 parts of a solution with a mass concentration of 2%;

[0094] (3) adding 15 parts of the vermiculite powder obtained in step (1) to the solution obtained in step (2), shaking at a low speed with stirring at 40° C. for 12 h, removing the liquid by suction filtration, and obtaining vermiculite powder after drying;

[0095] (4) Add 33.1 parts of sodium 2-pentadecyl-9-arylcarbenate to a reaction vessel, add 90 parts of distilled water, and then add 2 parts of hexadecyl ammonium chloride and 8 parts of acrylamide. Heat to 70°C and maintain, reflux with cold water, stir and dissolve. After complete dissolution, add 0.5 parts of urea peroxide, reflux for 8 hours to obtain a reaction solution, filter the reaction solution, take a solid product and dry it to obtain a dried solid product.

[0096] (5) After 45 parts of the solid product obtained in step (4), 3 parts of 2,4-dihydroxybenzophenone, and 80 parts of an organic solvent are mixed and fully dissolved, 8 parts of the vermiculite powder obtained in step (3) are added, and the mixture is slowly shaken for 4 to 6 hours, and then the liquid is removed by filtration to obtain a solid product. The solid product is placed under an ultraviolet lamp and irradiated for 90 minutes to obtain a metal ion capture agent.

[0097] Furthermore, the vermiculite powder in step (1) is micro-nano vermiculite powder.

[0098] Furthermore, the vermiculite powder in step (1) has a particle size of 50 μm.

[0099] Furthermore, in the alcohol-water mixture in step (2), alcohol accounts for 75% of the total mass.

[0100] Furthermore, the alcohol in the alcohol-water mixture in step (2) is isopropanol.

[0101] Furthermore, the structural formula of sodium 2-dodecyl-9-arylcarbenoate in step (4) is:

[0102] in:

[0103] R1 is a C18 branched alkyl group, wherein the branch of the branched alkyl group is a phenyl group at position 9.

[0104] Furthermore, the organic solvent in step (5) is petroleum ether.

[0105] Example 8

[0106] The preparation method of the metal ion scavenger comprises the following steps, calculated by weight:

[0107] (1) Pretreatment

[0108] The vermiculite powder was soaked in a weakly acidic aqueous solution with a pH value of 4 for 60 minutes to remove soluble ash components, and then the vermiculite powder was washed with clean water until neutral, and then soaked, rinsed, and filtered with deionized water for 7 times, and vacuum-dried at low temperature to obtain the pretreated vermiculite powder;

[0109] (2) dissolving vinyl tris(β-methoxyethoxy)silane in an alcohol-water mixture to prepare 100 parts of a solution with a mass concentration of 2%;

[0110] (3) adding 10 parts of the vermiculite powder obtained in step (1) to the solution obtained in step (2), shaking at a low speed with stirring at 35° C. for 8 h, removing the liquid by suction filtration, and obtaining vermiculite powder after drying;

[0111] (4) 31.1 parts of sodium 2-heptadecanyl-5-methylcarbenoate were added to a reaction vessel, 100 parts of distilled water were added, and then 4 parts of hexadecyl ammonium chloride and 9 parts of acrylamide were added thereto. The mixture was heated to 70°C and maintained, refluxed with cold water, stirred and dissolved. After complete dissolution, 1.5 parts of urea peroxide were added, and the mixture was refluxed for 12 hours to obtain a reaction solution. The reaction solution was filtered, and a solid product was taken and dried to obtain a dried solid product.

[0112] (5) 50 parts of the solid product obtained in step (4), 4 parts of 2,4-dihydroxybenzophenone, and 100 parts of an organic solvent were mixed and fully dissolved, and then 15 parts of the vermiculite powder obtained in step (3) were added, and the mixture was slowly shaken for 5 hours. After that, the liquid was removed by filtration to obtain a solid product. The solid product was placed under an ultraviolet lamp and irradiated for 80 minutes to obtain a metal ion capture agent.

[0113] Furthermore, the vermiculite powder in step (1) is micro-nano vermiculite powder.

[0114] Furthermore, the vermiculite powder in step (1) has a particle size of 10 μm.

[0115] Furthermore, in the alcohol-water mixture in step (2), alcohol accounts for 75% of the total mass.

[0116] Furthermore, the alcohol in the alcohol-water mixture in step (2) is isopropanol.

[0117] Furthermore, the structural formula of sodium 2-heptadecyl-5-methylcarbenoate in step (4) is:

[0118] in:

[0119] R1 is a C18 branched alkyl group, wherein the branch of the branched alkyl group is a methyl group.

[0120] Furthermore, the organic solvent in step (5) is ethanol.

[0121] Example 9

[0122] The preparation method of the metal ion scavenger comprises the following steps, calculated by weight:

[0123] (1) Pretreatment

[0124] The vermiculite powder was soaked in a weakly acidic aqueous solution with a pH value of 2 for 30 minutes to remove soluble ash components, and then the vermiculite powder was washed with clean water until neutral, and then soaked, rinsed, and filtered with deionized water for 5 times, and vacuum-dried at low temperature to obtain the pretreated vermiculite powder;

[0125] (2) dissolving vinyltriethoxysilane in an alcohol-water mixture to prepare 100 parts of a solution with a mass concentration of 0.5%;

[0126] (3) adding 5 parts of the vermiculite powder obtained in step (1) to the solution obtained in step (2), shaking at low speed with stirring at 25° C. for 2 h, removing the liquid by suction filtration, and obtaining vermiculite powder after drying;

[0127] (4) Add 14.2 parts of sodium 2-dodecyl-8-phenyl-carbenoate to a reaction vessel, add 90 parts of distilled water, and then add 1 part of hexadecyl ammonium chloride and 8 parts of acrylamide. Heat to 60°C and maintain, reflux with cold water, stir and dissolve. After complete dissolution, add 0.2 parts of urea peroxide, reflux for 8 to 24 hours to obtain a reaction solution, filter the reaction solution, take a solid product and dry it to obtain a dried solid product.

[0128] (5) After 40 parts of the solid product obtained in step (4), 0.5 parts of 2,4-dihydroxybenzophenone, and 80 parts of an organic solvent are mixed and fully dissolved, 5 parts of the vermiculite powder obtained in step (3) are added, and the mixture is slowly shaken for 4 hours. After the liquid is removed by filtration, a solid product is obtained. The solid product is placed under an ultraviolet lamp and irradiated for 30 minutes to obtain a metal ion capture agent.

[0129] Furthermore, the vermiculite powder in step (1) is micro-nano vermiculite powder.

[0130] Furthermore, the vermiculite powder in step (1) has a particle size of 20 nm.

[0131] Furthermore, in the alcohol-water mixture in step (2), alcohol accounts for 70% of the total mass.

[0132] Furthermore, the alcohol in the alcohol-water mixture in step (2) is methanol.

[0133] Furthermore, the structural formula of sodium 2-dodecyl-8-phenyl-carbenoate in step (4) is:

[0134] in:

[0135] R1 is a C18 branched alkyl group, wherein the branch of the branched alkyl group is a phenyl group.

[0136] Furthermore, the organic solvent in step (5) is isopropanol.

[0137] Example 10

[0138] The preparation method of the metal ion scavenger comprises the following steps, calculated by weight:

[0139] (1) Pretreatment

[0140] The vermiculite powder was soaked in a weakly acidic aqueous solution with a pH value of 6 for 120 minutes to remove soluble ash components, and then the vermiculite powder was washed with clean water until neutral, and then soaked, rinsed, and filtered 10 times with deionized water, and dried under vacuum at low temperature to obtain the pretreated vermiculite powder;

[0141] (2) dissolving vinyltrimethoxysilane in an alcohol-water mixture to prepare 100 parts of a solution with a mass concentration of 2.5%;

[0142] (3) adding 20 parts of the vermiculite powder obtained in step (1) to the solution obtained in step (2), shaking at a low speed with stirring at 40° C. for 6 h, removing the liquid by suction filtration, and obtaining vermiculite powder after drying;

[0143] (4) Add 45 parts of sodium 2-tetradecenoate to a reaction vessel, add 120 parts of distilled water, and then add 5 parts of hexadecyl ammonium chloride and 10 parts of acrylamide. Heat to 80°C and maintain, reflux with cold water, stir and dissolve. After complete dissolution, add 2 parts of urea peroxide, reflux for 24 hours to obtain a reaction solution, filter the reaction solution, take a solid product and dry it to obtain a dried solid product.

[0144] (5) 60 parts of the solid product obtained in step (4), 5 parts of 2,4-dihydroxybenzophenone, and 120 parts of an organic solvent were mixed and fully dissolved, and then 20 parts of the vermiculite powder obtained in step (3) were added. The mixture was slowly shaken for 6 hours, and then the liquid was removed by filtration to obtain a solid product. The solid product was placed under an ultraviolet lamp and irradiated for 120 minutes to obtain a metal ion capture agent.

[0145] Furthermore, the vermiculite powder in step (1) is micro-nano vermiculite powder.

[0146] Furthermore, the vermiculite powder in step (1) has a particle size of 10 μm.

[0147] Furthermore, in the alcohol-water mixture in step (2), alcohol accounts for 80% of the total mass.

[0148] Furthermore, the alcohol in the alcohol-water mixture in step (2) is isopropanol.

[0149] Furthermore, the structural formula of sodium 2-tetradecenoate in step (4) is:

[0150] in:

[0151] R1 is a C14 straight-chain alkane group.

[0152] Furthermore, the organic solvent in step (5) is isopropanol.

[0153] Example 11

[0154] The demulsification system includes 10% of the metal ion scavenger prepared in Example 6 in terms of mass percentage.

[0155] Furthermore, the invention further comprises 30% of an organosilicon-modified polyether demulsifier, 12% of a low-molecular alcohol polyether, 20% of OP-10, 5% of a cationic surfactant and 5% of alcohol, and the balance is water.

[0156] Furthermore, the alcohol is ethanol.

[0157] Furthermore, the organosilicon-modified polyether demulsifier is diethylenetriamine-based organosilicon-modified polyoxypropylene polyoxyethylene ether.

[0158] Furthermore, the low molecular alcohol polyether is ethylene glycol polyoxypropylene polyoxyethylene ether.

[0159] Furthermore, the cationic surfactant is a monoalkyl quaternary ammonium salt, wherein:

[0160] The monoalkyl quaternary ammonium salt is dodecyltrimethyl quaternary ammonium salt.

[0161] Example 12

[0162] The demulsification system includes 5% of the metal ion scavenger prepared in Example 7 in terms of mass percentage.

[0163] Furthermore, the invention further comprises 20% of an organosilicon-modified polyether demulsifier, 8% of a low-molecular alcohol polyether, 10% of OP-10, 2% of a cationic surfactant and 1% of alcohol, and the balance is water.

[0164] Furthermore, the alcohol is propanol.

[0165] Furthermore, the organosilicon-modified polyether demulsifier is diethylenetriamine-based organosilicon-modified polyoxypropylene polyoxyethylene polyoxypropylene ether.

[0166] Furthermore, the low molecular alcohol polyether is ethylene glycol polyoxypropylene polyoxyethylene polyoxypropylene ether.

[0167] Furthermore, the cationic surfactant is a mixture of equal masses of monoalkyl quaternary ammonium salt and dialkyl quaternary ammonium salt, wherein:

[0168] The monoalkyl quaternary ammonium salt is dodecyltrimethyl quaternary ammonium salt;

[0169] The general formula of dialkyl quaternary ammonium salt is as follows:

[0170]

[0171] Wherein: X is Br;

[0172] x, y, and z are all integers, and x=2, y=10, and z=4.

[0173] Example 13

[0174] The demulsification system includes 5% to 10% of the metal ion scavenger prepared in Example 8 in terms of mass percentage.

[0175] Furthermore, the invention further comprises 25% of an organosilicon-modified polyether demulsifier, 10% of a low-molecular alcohol polyether, 15% of OP-10, 3% of a cationic surfactant and 3% of alcohol, and the balance is water.

[0176] Furthermore, the alcohol is isopropyl alcohol.

[0177] Furthermore, the organosilicon-modified polyether demulsifier is diethylenetriamine-based organosilicon-modified polyoxypropylene polyoxyethylene polyoxypropylene ether.

[0178] Furthermore, the low molecular alcohol polyether is ethylene glycol polyoxyethylene polyoxypropylene polyoxyethylene ether.

[0179] Furthermore, the cationic surfactant is a mixture of equal masses of monoalkyl quaternary ammonium salt and dialkyl quaternary ammonium salt, wherein:

[0180] The monoalkyl quaternary ammonium salt is tridecyltrimethyl quaternary ammonium salt;

[0181] The general formula of dialkyl quaternary ammonium salt is as follows:

[0182]

[0183] Wherein: X is Cl;

[0184] x, y, and z are all integers, x=12, y=4, z=10.

[0185] Example 14

[0186] The demulsification system includes 5% of the metal ion scavenger prepared in Example 9 in terms of mass percentage.

[0187] Furthermore, the invention further comprises 30% of an organosilicon-modified polyether demulsifier, 8% of a low-molecular alcohol polyether, 20% of OP-10, 5% of a cationic surfactant and 1% of alcohol, and the balance is water.

[0188] Furthermore, the alcohol is methanol.

[0189] Furthermore, the organosilicon-modified polyether demulsifier is triethylenetetramine-based organosilicon-modified polyoxypropylene polyoxyethylene ether.

[0190] Furthermore, the low molecular weight alcohol polyether is propylene glycol polyoxyethylene ether.

[0191] Furthermore, the cationic surfactant is a dialkyl quaternary ammonium salt, wherein:

[0192] The general formula of dialkyl quaternary ammonium salt is as follows:

[0193]

[0194] Where: X is 1;

[0195] x, y, and z are all integers, and x=8, y=8, and z=8.

[0196] Example 15

[0197] The demulsification system includes 10% of the metal ion scavenger prepared in Example 10, calculated by mass percentage.

[0198] Furthermore, the invention further comprises 30% of an organosilicon-modified polyether demulsifier, 10% of a low-molecular alcohol polyether, 15% of OP-10, 3% of a cationic surfactant and 2% of alcohol, and the balance is water.

[0199] Furthermore, the alcohol is ethanol.

[0200] Furthermore, the organosilicon-modified polyether demulsifier is pentaethylenehexamine-based organosilicon-modified polyoxyethylene polyoxypropylene polyoxyethylene ether.

[0201] Furthermore, the low molecular alcohol polyether is glycerol polyoxyethylene polyoxypropylene polyoxyethylene ether.

[0202] Furthermore, the cationic surfactant is a dialkyl quaternary ammonium salt, wherein:

[0203] The general formula of dialkyl quaternary ammonium salt is as follows:

[0204]

[0205] Wherein: X is Cl;

[0206] x, y, and z are all integers, and x=16, y=2, and z=16.

[0207] Examples 16-17

[0208] It is roughly the same as Example 11, except that the monoalkyl quaternary ammonium salt is different:

[0209]

[0210]

[0211] Examples 18-30

[0212] The method is similar to Example 11, except that the silicone-modified polyether demulsifier is different.

[0213]

[0214]

[0215] Examples 31-46

[0216] It is roughly the same as Example 11, the only difference being the low molecular weight alcohol polyether:

[0217]

[0218]

[0219] Performance testing:

[0220] 1. Evaluation of demulsification and dehydration effects of different demulsifiers (systems)

[0221] The carbon number distribution of oil from a refinery was determined to be primarily C12, C13, C14, C15, and C16. Multifunctional metal ion scavengers prepared from sodium carbenates having the corresponding carbon number were added to the demulsification systems of Examples 11 to 15, respectively. The demulsification and dehydration effects are shown in Table 2. The results in Table 2 indicate that the demulsification system of the present invention has a higher demulsification and dehydration rate than both the refinery's current demulsifiers and the comparative demulsifiers. The multifunctional metal ion exhibits excellent demulsification capabilities in various demulsifier formulations, demonstrating strong universality.

[0222] Table 2 Comparison of dehydration rates of difficult-to-demulsify crude oil in a refinery

[0223] Demulsifier type Dosage concentration, ppm Indoor dehydration rate% Refinery demulsifiers 10 17.1 Comparison of demulsifiers 10 15.7 Demulsification system of Example 11 10 41.2 Demulsification system of Example 12 10 40.5 Demulsification system of Example 13 10 39.7 Demulsification system of Example 14 10 42.6 Demulsification system of Example 15 10 38.6

[0224] 2. Effect of multifunctional metal ion scavenger concentration on demulsification and dehydration effect

[0225] The dehydration effect of the demulsifier was evaluated by changing the concentration of the multifunctional metal ion scavenger in the demulsifier. The results are as follows: Figure 1 As shown. Figure 1 Researchers found that increasing the concentration of a multifunctional metal ion scavenger initially increased crude oil dehydration, then decreased slightly. This is attributed to the fact that increasing the concentration of the multifunctional metal ion scavenger gradually increased the number of metal ions captured, significantly reducing their impact on the stability of the crude oil emulsion interfacial film. However, when the optimal dosage was exceeded, the active groups in the multifunctional metal ion scavenger actually helped stabilize the emulsion interfacial film, resulting in a decrease in the demulsification rate. Therefore, the optimal addition concentration of this multifunctional metal ion is 5%-10%.

[0226] 3. Field Application - Application Effect of the Demulsification System Disclosed in Example 11 in a Settling Tank

[0227] After 65 hours of settling in a settling tank, crude oil from a certain refinery (Shengli export crude oil) had a crude oil dehydration rate of only 13.4%, nearly double the normal value of 31.0%. After this problem occurred, the demulsifier system prepared in Example 11 of the present invention was replaced with an unchanged dosage of 10 mg / L. After 20 hours of continued settling, the dehydration rate reached 29.5%, essentially reaching the normal level. Adding the demulsifier of the present invention as soon as the oil began to settle resulted in a dehydration rate of 38.1%, far higher than the normal level.

[0228] 4. Field Application - Application Effect of the Demulsification System Prepared in Example 13 in an Electrodesorption Device

[0229] The oil from a certain refinery (Shengli crude oil) was severely emulsified and difficult to dehydrate. The electro-demulsifier operated poorly and the current suddenly increased. Immediately after the problem occurred, the demulsifier prepared in Example 13 of the present invention was replaced at the same dosage concentration of 8 mg / L. After 46 minutes, the current decreased and stabilized. After stabilization, the demulsifier of the present invention was continued, and the electro-demulsifier operated normally.

[0230] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the above embodiments, and various modifications can be made within the scope of knowledge possessed by those skilled in the art without departing from the spirit of the present invention.

Claims

1. A metal ion scavenger, characterized in that Its general structural formula is: Wherein, Z refers to vermiculite, R1 is a C8-C18 straight-chain alkane group or a branched-chain alkyl group, wherein the branch of the branched-chain alkyl group is a C1-C6 alkane group or a phenyl group.

2. A method for preparing a metal ion scavenger, characterized in that: Calculated by mass, comprising the following steps: (1) Pretreatment The vermiculite powder is soaked in a weakly acidic aqueous solution with a pH value of 2 to 6 for at least 30 minutes to remove soluble ash components, and then the vermiculite powder is washed with clean water until neutral, and then soaked, rinsed, and filtered with deionized water for at least 5 times, and vacuum-dried at low temperature to obtain pretreated vermiculite powder; (2) dissolving vinyltriethoxysilane or vinyltrimethoxysilane or vinyltri(β-methoxyethoxy)silane in an alcohol-water mixture to prepare 100 parts of a solution having a mass concentration of 0.5 to 2.5%; (3) adding 5 to 20 parts of the vermiculite powder obtained in step (1) to the solution obtained in step (2), stirring and shaking at a low speed of 25 to 40° C. for 6 to 12 hours, filtering off the liquid, and drying to obtain vermiculite powder; (4) adding 14.2 to 45 parts of sodium 2-alkylcarbenoate to a reaction vessel, adding 90 to 120 parts of distilled water, and then adding 1 to 5 parts of hexadecyl ammonium chloride and 8 to 10 parts of acrylamide, heating to 60 to 80°C and maintaining, reflux with cold water, stirring, and dissolving. After complete dissolution, adding 0.2 to 2 parts of urea peroxide, reflux reaction for 8 to 24 hours to obtain a reaction solution, filtering the reaction solution, taking a solid product and drying it to obtain a dried solid product; (5) 40 to 60 parts of the solid product obtained in step (4), 0.5 to 5 parts of 2,4-dihydroxybenzophenone, and 80 to 120 parts of an organic solvent are mixed and fully dissolved and mixed, and then 5 to 20 parts of the vermiculite powder obtained in step (3) are added, and the mixture is slowly shaken for 4 to 6 hours, and then the liquid is removed by suction filtration to obtain a solid product, and the solid product is placed under an ultraviolet lamp and irradiated for 30 to 120 minutes to obtain a metal ion capture agent, wherein: The general formula of sodium 2-alkyl carbeneate in step (4) is: in: R1 is a C8-C18 straight-chain alkyl group or a branched-chain alkyl group, wherein the branch of the branched-chain alkyl group is a C1-C6 alkyl group or a phenyl group.

3. The method for preparing the metal ion scavenger according to claim 2, wherein The vermiculite powder in step (1) is micro-nano vermiculite powder.

4. The method for preparing the metal ion scavenger according to claim 3, wherein The particle size of the vermiculite powder in step (1) is 10 nm to 50 μm.

5. The method for preparing the metal ion scavenger according to claim 2, wherein In the alcohol-water mixture in step (2), alcohol accounts for 70-80% of the total mass.

6. The method for preparing the metal ion scavenger according to claim 2, wherein: The alcohol in the alcohol-water mixture in step (2) is at least one of methanol, ethanol and isopropanol.

7. The method for preparing a metal ion scavenger according to claim 2, wherein: The organic solvent in step (5) is one of petroleum ether, ethanol and isopropanol.

8. Demulsification system, characterized in that: Calculated by mass percentage, the metal ion capture agent prepared by the preparation method according to any one of claims 2 to 6 comprises 5% to 10%.

9. The demulsification system according to claim 8, characterized in that The invention also comprises 20% to 30% of organosilicon modified polyether demulsifier, 8% to 12% of low molecular alcohol polyether, 10% to 20% of OP-10, 2% to 5% of cationic surfactant and 1% to 5% of alcohol, and the balance is water.

10. The demulsification system according to claim 9, characterized in that The alcohol in the 1% to 5% alcohol is one of ethanol, propanol, isopropanol and methanol.

11. The demulsification system according to claim 10, characterized in that The alcohol in the 1% to 5% alcohol is ethanol.

12. The demulsification system according to claim 9, characterized in that The organosilicon-modified polyether demulsifier is diethylenetriamine-based organosilicon-modified polyoxypropylene polyoxyethylene ether, diethylenetriamine-based organosilicon-modified polyoxypropylene polyoxyethylene polyoxypropylene ether, diethylenetriamine-based organosilicon-modified polyoxyethylene polyoxypropylene polyoxyethylene ether, triethylenetetramine-based organosilicon-modified polyoxypropylene polyoxyethylene polyoxyethylene ether, triethylenetetramine-based organosilicon-modified polyoxypropylene polyoxyethylene polyoxypropylene ether, triethylenetetramine-based organosilicon-modified polyoxyethylene polyoxypropylene polyoxyethylene Ether, tetraethylene pentamine-based silicone modified polyoxypropylene polyoxyethylene ether, tetraethylene pentamine-based silicone modified polyoxypropylene polyoxyethylene polyoxypropylene ether, tetraethylene pentamine-based silicone modified polyoxyethylene polyoxypropylene polyoxyethylene ether, pentaethylene hexamine-based silicone modified polyoxypropylene polyoxyethylene ether, pentaethylene hexamine-based silicone modified polyoxypropylene polyoxyethylene polyoxypropylene ether, one or more of pentaethylene hexamine-based silicone modified polyoxyethylene polyoxypropylene polyoxyethylene ether.

13. The demulsification system according to claim 9, characterized in that The low molecular alcohol polyether is one or more of ethylene glycol polyoxypropylene polyoxyethylene ether, ethylene glycol polyoxypropylene polyoxyethylene polyoxypropylene ether, ethylene glycol polyoxyethylene polyoxypropylene polyoxyethylene ether, propanol polyoxypropylene polyoxyethylene ether, propanol polyoxypropylene polyoxyethylene polyoxypropylene ether, propanol polyoxypropylene polyoxyethylene polyoxypropylene ether, isopropyl alcohol polyoxypropylene polyoxyethylene ether, isopropyl alcohol polyoxypropylene polyoxyethylene polyoxypropylene ether, isopropyl alcohol polyoxypropylene polyoxyethylene polyoxypropylene ether, propylene glycol polyoxypropylene polyoxyethylene ether, propylene glycol polyoxypropylene polyoxyethylene polyoxypropylene ether, propylene glycol polyoxyethylene polyoxypropylene polyoxyethylene ether, glycerol polyoxypropylene polyoxyethylene ether, glycerol polyoxypropylene polyoxyethylene polyoxypropylene ether, and glycerol polyoxyethylene polyoxypropylene polyoxyethylene ether.

14. The demulsification system according to claim 9, characterized in that The cationic surfactant is a monoalkyl quaternary ammonium salt and / or a dialkyl quaternary ammonium salt, wherein: Monoalkyl quaternary ammonium salts include dodecyltrimethyl quaternary ammonium salt, tridecyltrimethyl quaternary ammonium salt, and tetradecyltrimethyl quaternary ammonium salt; The general formula of dialkyl quaternary ammonium salt is as follows: Wherein: X is one of Br, Cl, and I; x, y, and z are all integers, and 1≤x≤16, 2≤y≤16, and 1≤z≤16; If x < 8 and z < 8 then y > 8; If x≥8 and z≥8, then y≤8.

15. The demulsification system according to claim 14, characterized in that The cationic surfactant is a monoalkyl quaternary ammonium salt and / or a dialkyl quaternary ammonium salt, wherein: Monoalkyl quaternary ammonium salts include dodecyltrimethyl quaternary ammonium salt, tridecyltrimethyl quaternary ammonium salt, and tetradecyltrimethyl quaternary ammonium salt; The general formula of dialkyl quaternary ammonium salt is as follows: Wherein: X is Cl; x, y, and z are all integers, and 1≤x≤16, 2≤y≤16, and 1≤z≤16; If x < 8 and z < 8 then y > 8; If x≥8 and z≥8, then y≤8.

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