Emulsion gel demulsifier and preparation method thereof

Abstract

The invention belongs to the technical field of petrochemical industry, and relates to an emulsion gel demulsifier and a preparation method thereof. The preparation method of the emulsion gel demulsifier comprises the following steps: heating and carbonizing Tween 80, Span80, an alkyl glycoside surfactant and fatty alcohol-polyoxyethylene ether to obtain a component 1; the preparation method comprises the following steps: heating sorbitol, octadecanol and ZnO, adding alkali, blowing nitrogen, and vacuumizing; introducing ethylene oxide, heating, and introducing ethylene oxide until the reaction is complete to obtain a component 2; adding a catalyst into the resin, heating and vacuumizing, and adding epoxypropane to obtain a polyether epoxypropane block; adding a catalyst into the polyether epoxypropane block, and adding ethylene oxide to obtain a component 3; and mixing the components 1-3 with an organic solvent to obtain the emulsion gel demulsifier. According to the demulsifier composition, efficient demulsification of emulsion gel can be achieved through cooperation of multiple mechanisms, meanwhile, the requirement for low cost of industrial application is also met, and the demulsifier composition is suitable for the efficient demulsification process of emulsion gel in a special emulsion state formed on an offshore platform.

Description

Technical Field

[0001] The invention belongs to the technical field of petrochemical industry, and particularly relates to an emulsion gel demulsifier and a preparation method thereof. Background Art

[0002] Mainstream demulsifiers mainly break emulsions through displacement mechanism, solubilization mechanism, charge neutralization mechanism and flocculation mechanism, while most demulsifiers mainly act on the film-forming substances on the interface membrane, resulting in a loose adsorption layer and poor protection. Finally, oil and water settle due to density difference, and finally break the emulsion. At present, mainstream demulsifiers can solve most emulsion demulsification problems.

[0003] However, emulsion gel is a special emulsified state, in which a three-dimensional network structure is formed in the system, which binds water droplets and forms a semi-solid high-viscosity gel state. Due to the complex structure and high viscosity of crude oil emulsion gel, it is difficult for conventional demulsifier molecules to penetrate into the internal structure of the gel and effectively demulsify the emulsion gel. So far, there has been no report on an efficient demulsifier for emulsion gel. If an efficient demulsifier is developed for emulsion gel, it will have important application value. Summary of the invention

[0004] In view of the technical problem of difficulty in demulsifying emulsion gel, the present invention provides an emulsion gel demulsifier and a preparation method thereof.

[0005] Specifically, the present invention is achieved through the following technical solutions:

[0006] A method for preparing an emulsion gel demulsifier comprises:

[0007] (1) heating and carbonizing Tween 80, Span 80, an alkyl glycoside surfactant and fatty alcohol polyoxyethylene ether to obtain component 1;

[0008] (2) heating sorbitol, octadecyl alcohol and ZnO to react, then adding a base, blowing nitrogen into the system and evacuating to a first negative pressure; introducing ethylene oxide and raising the temperature, and when the system pressure is maintained at the first pressure, continuing to introduce a set experimental amount of ethylene oxide, and when the pressure reaches the first negative pressure, the reaction is complete to obtain component 2;

[0009] (3) adding a catalyst to the resin, heating and evacuating to a second negative pressure, raising the temperature, and intermittently adding propylene oxide to make the system pressure less than the second pressure. After the addition is completed, the reaction is continued until the pressure drops to the second negative pressure to obtain a polyether propylene oxide block;

[0010] (4) adding a catalyst to the polyether propylene oxide block, and continuing to increase the temperature and evacuate the block according to the method of step (3) and intermittently adding ethylene oxide to obtain component 3;

[0011] (5) Mixing the component 1, the component 2, and the component 3 with an organic solvent to obtain an emulsion gel demulsifier.

[0012] In the preparation method of the emulsion gel demulsifier, in step (1), the mass ratio of Tween 80, Span 80, alkyl glycoside surfactant and fatty alcohol polyoxyethylene ether is (1-1.2):(1-1.1):(1.8-2.0):(3-4).

[0013] In the preparation method of the emulsion gel demulsifier, the alkyl glycoside surfactant is a surfactant synthesized from glucose and fatty alcohol.

[0014] The preparation method of the emulsion gel demulsifier, the general formula of the fatty alcohol polyoxyethylene ether is RO (CH2CH2O) n H, where R is C 12 ~C 18 , n is 8 to 18.

[0015] In the above-mentioned method for preparing the emulsion gel demulsifier, in step (1), the heating temperature is 160 to 240° C., and the carbonization time is 12 to 24 hours.

[0016] In the preparation method of the emulsion gel demulsifier, in step (2), the molar ratio of the sorbitol to the octadecyl alcohol is 1:(1-1.2), and the ratio of the mass of the ethylene oxide to the total mass of the sorbitol and the octadecyl alcohol is (2-3):1.

[0017] In the above-mentioned method for preparing the emulsion gel demulsifier, in step (2), the first negative pressure is -0.01 to -0.02 MPa; and the first pressure is 0.25 to 0.35 MPa.

[0018] In the above-mentioned method for preparing the emulsion gel demulsifier, in step (3), the second negative pressure is -0.01 to -0.02 MPa; the heating temperature is 50 to 90°C, and the temperature after heating is 130±5°C; and the second pressure is 0.35 to 0.45 MPa.

[0019] In the above-mentioned method for preparing the emulsion gel demulsifier, in step (3), the resin is a phenolamine resin or a phenol-formaldehyde resin; and the catalyst is KOH.

[0020] In the above-mentioned method for preparing the emulsion gel demulsifier, in step (3) and step (4), the mass ratio of the resin, the propylene oxide and the ethylene oxide is 1:(40-80):(10-30).

[0021] In the preparation method of the emulsion gel demulsifier, the mass ratio of the component 1, the component 2 and the component 3 is: 1: (1.2-1.9): (0.1-0.2).

[0022] In the above-mentioned method for preparing the emulsion gel demulsifier, the organic solvent is one or two of isopropanol, xylene or methanol.

[0023] On the other hand, the present invention provides an emulsion gel demulsifier, which is obtained by the above-mentioned preparation method.

[0024] The technical solution of the present invention has the following beneficial effects:

[0025] The demulsifier combination of the present invention utilizes multiple mechanisms to achieve efficient demulsification of emulsion gels while also taking into account the low-cost requirements of industrial applications, and is suitable for the efficient demulsification process of emulsion gels in a special emulsified state formed on offshore platforms. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Various other advantages and benefits will become apparent to those of ordinary skill in the art by reading the following detailed description of the preferred embodiment.The drawings are only for the purpose of illustrating the preferred embodiments and are not to be construed as limiting the invention.

[0027] Figure 1 Comparative photos of the demulsification effects of different demulsifiers on emulsion gel;

[0028] Among them, from left to right are the demulsification effects of the demulsifiers prepared in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2 and Comparative Example 3 on emulsion gel. DETAILED DESCRIPTION

[0029] In order to fully understand the purpose, features and effects of the present invention, the present invention is described in detail through the following specific embodiments. Except for the following contents, the process method of the present invention adopts conventional methods or devices in the art. Unless otherwise specified, the following terms have the meanings commonly understood by those skilled in the art.

[0030] The terms "first", "second", etc. used herein do not indicate any order or importance, but are used to distinguish one element from another. When a numerical range is disclosed herein, the above range is considered continuous and includes the minimum and maximum values ​​of the range, and each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise indicated, all ranges disclosed herein should be understood to include any and all sub-ranges included therein.

[0031] The emulsion gel demulsifier provided by the present invention is composed of three components. Component 1 is a nano demulsifier with a polyhydroxy structure, which mainly enhances the solvation of asphaltene / colloid aggregates on the interface through hydrogen bond interaction. Component 2 has both long alkyl chains and polyoxyethylene chain structures, which interacts with wax crystals with high carbon numbers to change the wettability of its surface, destroy the three-dimensional network structure, and reduce the strength of the oil-water interface film. Component 3 is a common high-molecular-weight, high-surface-activity demulsifier, which enhances the flocculation ability of water droplets and improves the demulsification rate. The above-mentioned demulsifier combination performs its own functions, and the above-mentioned three mechanisms cooperate with each other to achieve efficient demulsification of emulsion gel, which cannot be achieved by a single component. At the same time, it also takes into account the low-cost requirements of industrial applications, and is suitable for the efficient demulsification process of emulsion gel in a special emulsified state formed on offshore platforms.

[0032] The components of the emulsion gel demulsifier of the present invention are introduced in detail below:

[0033] Component 1: Nano-emulsifier with polyhydroxy structure

[0034] The nano demulsifier with a polyhydroxy structure is a nanoparticle with a size of 1 to 10 nm, which is obtained by carbonizing Tween80, Span80, an alkyl glycoside surfactant and fatty alcohol polyoxyethylene ether at 160 to 240° C. for 12 to 24 hours.

[0035] Among them, Tween80, Span80 and alkyl glycoside surfactants provide polyhydroxy structures, and fatty alcohol polyoxyethylene ether provides alkyl hydrophobic tail chains, thereby regulating the hydrophilic-lipophilic balance of the final nano-emulsifier, improving the interfacial activity of the nano-emulsifier, and promoting the interaction between the nano-emulsifier and the colloid and asphaltene on the interfacial film. The above-mentioned nano-emulsifier will enhance the solvation of asphaltene / colloid aggregates through hydrogen bond interactions.

[0036] In some preferred embodiments, the mass ratio of Tween 80, Span 80, alkyl glycoside surfactant and fatty alcohol polyoxyethylene ether is (1-1.2):(1-1.1):(1.8-2.0):(3-4).

[0037] In some preferred embodiments, the alkyl glycoside surfactant is a surfactant synthesized from glucose and fatty alcohol, wherein the alkyl group of the fatty alcohol is C8-C16, and more preferably C12.

[0038] The alkyl glycoside surfactant is prepared by the following method: alkyl glycosides with different chain lengths are prepared by direct glycosidation method. Specific steps: weigh a certain amount of glucose, fatty alcohol (octanol, decanol, dodecanol, tetradecanol or hexadecanol) and p-toluenesulfonic acid (catalyst) and place them in a three-necked flask, wherein the molar ratio of glucose to fatty alcohol is 1:5, and the mass ratio of p-toluenesulfonic acid to glucose is 0.015:1. Heat to 115°C and reduce pressure to 10kPa to react for 2.5h. After the reaction is completed, adjust the pH to 8-9 with 20% NaOH solution, and then remove the unreacted alcohol by reduced pressure distillation to prepare alkyl glycosides with different chain lengths.

[0039] In some preferred embodiments, the fatty alcohol polyoxyethylene ether is an ether formed by condensation of polyethylene glycol and fatty alcohol, and the general formula of the fatty alcohol polyoxyethylene ether is RO(CH2CH2O): n H, wherein R is C12 to C18 (more preferably C18), and n is any integer between 8 and 18.

[0040] Wherein, the fatty alcohol polyoxyethylene ether is prepared by the following method:

[0041] Take 0.5g fatty alcohol initiator and a small amount of potassium hydroxide and add them to a high-temperature and high-pressure reactor. Use N2 to purge the gas in the reactor for 30 minutes and then stop. Use a vacuum pump to evacuate for 15 minutes until the pressure reaches -0.01MPa. Open the feed valve of ethylene oxide, pass ethylene oxide and heat it to 120℃. When the pressure reading decreases, continue to pass ethylene oxide into the reactor to maintain the pressure reading at around 0.25MPa. When the amount of ethylene oxide passed reaches the set experimental amount, close the feed valve of ethylene oxide and wait for the reaction in the reactor to continue until the reading on the pressure gauge of the reactor reaches -0.01MPa. It is considered that the reaction of the initiator and ethylene oxide in the reactor is complete, and the temperature is lowered and the reactor is opened to discharge the material.

[0042] Component 2: Compounds with both long alkyl chains and polyoxyethylene chains

[0043] Among them, component 2 is prepared by the following method: sorbitol, octadecyl alcohol and ZnO are heated to react, then a base is added, nitrogen is blown into the system and then evacuated to a first negative pressure; ethylene oxide is introduced and the temperature is increased, and when the system pressure is maintained at the first pressure, a set experimental amount of ethylene oxide is continued to be introduced, and when the pressure becomes the first negative pressure, the reaction is complete to obtain component 2.

[0044] In the present invention, after etherification reaction of sorbitol and octadecyl alcohol, they react with ethylene oxide, and the polyhydroxy structure of sorbitol can be utilized to form multiple hydrophilic tail chains of polyoxyethylene, which can effectively increase the wetting performance.

[0045] In some preferred embodiments, ZnO is a catalyst and is added in a catalytic amount.

[0046] In some preferred embodiments, the molar ratio of the sorbitol to the octadecyl alcohol is 1:(1-1.2) (more preferably 1:1), and the ratio of the mass of the ethylene oxide to the total mass of the sorbitol and the octadecyl alcohol is (2-3):1 (more preferably 2.5:1).

[0047] In some preferred embodiments, the first negative pressure is -0.01 to -0.02 MPa; the first pressure is 0.25 to 0.35 MPa.

[0048] In some preferred embodiments, the heating temperature of sorbitol, octadecyl alcohol and ZnO is 200-230° C., and the reaction time is 5-8 hours; after the ethylene oxide is introduced, the temperature is raised to 115-125° C.

[0049] In some preferred embodiments, the base is KOH.

[0050] In some preferred embodiments, the mass ratio of component 2 is 1.2 to 1.9 parts, based on 1 part by mass of component 1. When the mass ratio of component 2 is too much or too little, effective demulsification cannot be achieved.

[0051] Further preferably, based on 1 part by mass of component 1, the mass ratio of component 2 is 1.5 parts.

[0052] Component 3: Polyether demulsifier

[0053] Component 3 used in the present invention is a common polyether demulsifier, and the polyether demulsifier can be a diblock polyether demulsifier with high interfacial activity, and the preparation method is as follows:

[0054] Add a catalyst to the resin, heat and evacuate to a second negative pressure, increase the temperature, intermittently add propylene oxide to make the system pressure less than the second pressure, continue the reaction after the addition is completed until the pressure drops to the second negative pressure to obtain a polyether propylene oxide block; add a catalyst to the polyether propylene oxide block, continue to increase the temperature and evacuate according to the above method, and intermittently add ethylene oxide to obtain component 3.

[0055] Optionally, the resin is a phenolamine resin or a phenol-formaldehyde resin, which can be prepared by the following method: nonylphenol or cardanol, diethylenetriamine, tetraethylenepentamine or polyethylenepolyamine are added to a three-necked flask, placed in an oil bath, and formaldehyde solution is slowly added at a rate of 1 drop / s. After the addition is completed, the temperature is quickly raised to 65-85°C, and after reacting for 3-6 hours, xylene is added for high-temperature dehydration, and then the xylene is removed by reduced pressure distillation to finally obtain a reddish-brown viscous liquid, which is the phenolamine resin or the phenol-formaldehyde resin.

[0056] In some preferred embodiments, the second negative pressure is -0.01 to -0.02 MPa; the second pressure is 0.35 to 0.45 MPa.

[0057] In some preferred embodiments, the heating temperature is 50-90°C, and the temperature after heating is 130±5°C.

[0058] In some preferred embodiments, the catalyst is KOH.

[0059] In some preferred embodiments, the mass ratio of the resin, the propylene oxide and the ethylene oxide is 1:(40-80):(10-30), and more preferably 1:(50-60):(15-25).

[0060] In some preferred embodiments, the mass ratio of component 3 is 0.1 to 0.2 parts, based on 1 part by mass of component 1. When the mass ratio of component 3 is too much or too little, effective demulsification cannot be achieved.

[0061] Further preferably, based on 1 part by mass of component 1, the mass ratio of component 3 is 0.1 part.

[0062] Through practice, the emulsion gel demulsifier prepared according to the method of the present invention can not only realize the efficient demulsification of emulsion gel, but also take into account the low cost requirements of industrial applications, and is suitable for the efficient demulsification process of emulsion gel in a special emulsified state formed on offshore platforms.

[0063] Example

[0064] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions. The raw materials used in the following examples are all conventionally purchased.

[0065] Example 1

[0066] Weigh 2.0 g of Tween 80, 2.0 g of Span 80, 3.6 g of alkyl glycoside surfactant C12 and 6.0 g of fatty alcohol polyoxyethylene ether C18, place them in a reactor and carbonize them at 200° C. for 24 h to obtain component 1.

[0067] Weigh 2.5g of sorbitol and 2.5g of octadecyl alcohol, weigh 0.05g of ZnO as a catalyst, place the reaction at 200℃ for 6h, then add 0.05g of potassium hydroxide to the high-temperature and high-pressure reactor, use N2 to purge the gas in the reactor for 1min and stop, use a vacuum pump to evacuate for 15min until the pressure gauge reaches -0.01MPa. Open the feed valve of ethylene oxide, pass 12.5g of ethylene oxide and heat to 115℃, observe the pressure gauge drop, continue to pass ethylene oxide into the reactor to maintain the pressure gauge at 0.25MPa. When the amount of ethylene oxide passed reaches the set experimental amount, close the feed valve of ethylene oxide, wait for the reaction in the reactor to continue until the pressure gauge of the reactor shows -0.01MPa, it is considered that the initiator in the reactor and ethylene oxide react completely, cool down and open the reactor to discharge, and obtain component 2.

[0068] Weigh 1.5g of cardanol and 5g of diethylenetriamine in a three-necked flask, place it in an oil bath, slowly add 20mL of formaldehyde solution at a rate of 1 drop / s, and after the addition is completed, quickly heat it to 65°C, react for 4h, add xylene for high-temperature dehydration, and then remove xylene by vacuum distillation to finally obtain a reddish-brown viscous liquid, which is the phenolamine resin; weigh 1.0g of phenolamine resin and add it to a high-pressure reactor, add 0.01g of catalyst KOH, heat it to 80°C, use a vacuum pump to pump it to a gauge pressure of about -0.01MPa, and when the temperature rises to about 130°C, add 90g of propylene oxide, and the amount added keeps the reactor pressure less than 0.4MPa. After the addition is completed, continue the reaction until the pressure drops to -0.01MPa, and open the reactor to obtain a block polyether propylene oxide block. Weigh 90g of polyether propylene oxide block and add it to a high-pressure reactor, add 0.01g of catalyst KOH, raise the temperature to 120°C according to the above steps, intermittently add 90g of ethylene oxide, and add an amount to keep the reactor pressure less than 0.4MPa. When the pressure drops to -0.01MPa, open the reactor and discharge the material, which is component 3.

[0069] 10.0 g of component 1, 15.0 g of component 2 and 1.0 g of component 3 were weighed and directly mixed according to a certain mass, and 26 g of an organic solvent xylene was added to obtain an emulsion gel demulsifier.

[0070] Example 2

[0071] Weigh 2.0 g of Tween 80, 2.2 g of Span 80, 4.0 g of alkyl glycoside surfactant C16 and 7.0 g of fatty alcohol polyoxyethylene ether C16, place them in a reactor and carbonize them at 200° C. for 24 h to obtain component 1.

[0072] Weigh 2.0g sorbitol and 2.4g octadecyl alcohol, weigh 0.05g ZnO as a catalyst, place it at 200℃ for 6h, then add 0.05g potassium hydroxide to the high temperature and high pressure reactor, use N2 to purge the gas in the reactor for 1min and stop, use a vacuum pump to evacuate for 15min until the pressure gauge reaches -0.01MPa. Open the feed valve of ethylene oxide, pass 10.4g of ethylene oxide and heat to 115℃, observe the pressure gauge drop, continue to pass ethylene oxide into the reactor to maintain the pressure gauge at 0.25MPa. When the amount of ethylene oxide passed reaches the set experimental amount, close the feed valve of ethylene oxide, wait for the reaction in the reactor to continue until the pressure gauge of the reactor shows -0.01MPa, it is considered that the initiator in the reactor and ethylene oxide react completely, cool down and open the reactor to discharge, and obtain component 2.

[0073] Weigh 1.5g of cardanol and 5g of diethylenetriamine in a three-necked flask, place it in an oil bath, slowly add 20mL of formaldehyde solution at a rate of 1 drop / s, and after the addition is completed, quickly heat it to 65°C, react for 4h, add xylene for high-temperature dehydration, and then remove xylene by vacuum distillation to finally obtain a reddish-brown viscous liquid, which is the phenolamine resin; weigh 1.0g of phenolamine resin and add it to a high-pressure reactor, add 0.01g of catalyst KOH, heat it to 80°C, use a vacuum pump to pump it to a gauge pressure of about -0.01MPa, and when the temperature rises to about 130°C, add 60g of propylene oxide, and the amount added keeps the reactor pressure less than 0.4MPa. After the addition is completed, continue the reaction until the pressure drops to -0.01MPa, and open the reactor to obtain a block polyether propylene oxide block. Weigh 60g of polyether propylene oxide block and add it to a high-pressure reactor, add 0.01g of catalyst KOH, raise the temperature to 120°C according to the above steps, intermittently add 90g of ethylene oxide, and add an amount to keep the reactor pressure less than 0.4MPa. When the pressure drops to -0.01MPa, open the reactor and discharge the material, which is component 3.

[0074] 10 g of component 1, 12 g of component 2 and 0.2 g of component 3 were weighed and directly mixed according to a certain mass, and 27.6 g of an organic solvent xylene was added to obtain an emulsion gel demulsifier.

[0075] Example 3

[0076] Weigh 1.2 g Tween 80, 1.1 g Span 80, 2.0 g alkyl glycoside surfactants C12-14 and 3.8 g fatty alcohol polyoxyethylene ether C12, place them in a reactor and carbonize them at 200° C. for 24 h to obtain component 1.

[0077] Weigh 2.0g sorbitol and 2.4g octadecyl alcohol, weigh 0.05g ZnO as a catalyst, place it at 200℃ for 6h, then add 0.05g potassium hydroxide to the high temperature and high pressure reactor, use N2 to purge the gas in the reactor for 1min and stop, use a vacuum pump to evacuate for 15min until the pressure gauge reaches -0.01MPa. Open the feed valve of ethylene oxide, pass 11.0g of ethylene oxide and heat to 115℃, observe the pressure gauge drop, continue to pass ethylene oxide into the reactor to maintain the pressure gauge at 0.25MPa. When the amount of ethylene oxide passed reaches the set experimental amount, close the feed valve of ethylene oxide, wait for the reaction in the reactor to continue until the pressure gauge of the reactor shows -0.01MPa, it is considered that the initiator in the reactor and ethylene oxide react completely, cool down and open the reactor to discharge, and obtain component 2.

[0078] Weigh 1.5g of cardanol and 5g of diethylenetriamine in a three-necked flask, place it in an oil bath, slowly add 20mL of formaldehyde solution at a rate of 1 drop / s, and after the addition is completed, quickly heat it to 65°C, react for 4h, add xylene for high-temperature dehydration, and then remove xylene by vacuum distillation to finally obtain a reddish-brown viscous liquid, which is the phenolamine resin; weigh 1.0g of phenolamine resin and add it to a high-pressure reactor, add 0.01g of catalyst KOH, heat it to 80°C, use a vacuum pump to pump it to a gauge pressure of about -0.01MPa, and when the temperature rises to about 130°C, add 75g of propylene oxide, and the amount added keeps the reactor pressure less than 0.4MPa. After the addition is completed, continue the reaction until the pressure drops to -0.01MPa, and open the reactor to obtain a block polyether propylene oxide block. Weigh 60g of polyether propylene oxide block and add it to a high-pressure reactor, add 0.01g of catalyst KOH, raise the temperature to 120°C according to the above steps, intermittently add 90g of ethylene oxide, and add an amount to keep the reactor pressure less than 0.4MPa. When the pressure drops to -0.01MPa, open the reactor and discharge the material, which is component 3.

[0079] 10 g of component 1, 19 g of component 2 and 0.1 g of component 3 were weighed and directly mixed according to a certain mass, and 21.6 g of organic solvent xylene was added to obtain an emulsion gel demulsifier.

[0080] Comparative Example 1

[0081] Commercial demulsifier SP169 was purchased from Jingzhou Longhua Petrochemical Co., Ltd.

[0082] Comparative Example 2

[0083] A bisphenol A phenolic resin diblock polyether demulsifier was used as a comparison, in which the mass ratios of bisphenol A phenolic resin, propylene oxide and ethylene oxide were 1:99:99 respectively.

[0084] The specific experimental steps are as follows: add 2g of bisphenol A to a three-necked flask, place it in an oil bath, slowly add 15mL of formaldehyde solution at a rate of 1d / s, quickly heat to 75°C after the addition is completed, react for 4h, add 30mL of xylene for high-temperature dehydration, then remove xylene by vacuum distillation, and finally obtain a reddish-brown viscous liquid, which is bisphenol A phenolic resin; weigh 1g of bisphenol A phenolic resin and add it to a high-pressure reactor, add 0.01g of catalyst KOH, heat to 70°C, use a vacuum pump to pump to a gauge pressure of about -0.01MPa, and when the temperature rises to about 130±5°C, intermittently add 99g of propylene oxide, and the amount added keeps the reactor pressure less than 0.4MPa. After the addition is completed, continue the reaction until the pressure drops to -0.01MPa, and open the reactor to obtain a block polyether propylene oxide block. Weigh 99g of polyether propylene oxide block and add it to the autoclave, add 0.01g of catalyst KOH, raise the temperature to 120±5°C according to the above steps, add 99g of ethylene oxide, and add an amount to keep the pressure of the autoclave less than 0.4MPa.

[0085] Comparative Example 3

[0086] A polyethylene polyamine diblock polyether demulsifier was used as a comparison, in which the mass ratios of polyethylene polyamine, propylene oxide and ethylene oxide were 1:99:33 respectively.

[0087] The specific experimental steps are as follows: weigh 3g nonylphenol, add 5g polyethylene polyamine to a three-necked flask, place it in an oil bath, slowly add 20mL formaldehyde solution at a speed of 1d / s, quickly heat to 75℃ after the addition is completed, react for 4h, add 50mL xylene for high-temperature dehydration, then remove xylene by vacuum distillation, and finally obtain a reddish brown viscous liquid, which is polyethylene polyamine phenol amine resin; weigh 1g polyethylene polyamine phenol amine resin and add it to a high-pressure reactor, add 0.01g catalyst KOH, heat to 75℃, use a vacuum pump to pump to a gauge pressure of about -0.01MPa, and when the temperature rises to about 120±5℃, intermittently add 99g propylene oxide, and the amount added keeps the reactor pressure less than 0.4MPa. After the addition is completed, continue the reaction until the pressure drops to -0.01MPa, and open the reactor to obtain a block polyether propylene oxide block. Weigh 99g of polyether propylene oxide block and add it to the autoclave, add 0.01g of catalyst KOH, raise the temperature to 110±5°C according to the above steps, and add 33g of ethylene oxide intermittently, and the added amount keeps the pressure of the autoclave less than 0.4MPa.

[0088] Effect test

[0089] Referring to "SY-T 5281-2000 Crude Oil Demulsifier Performance Test Method (Bottle Test Method)", the demulsifier was added at a concentration of 100 mg / L to demulsify the emulsion gel. The specific steps are: accurately pour 100 mL of crude oil into a 100 mL colorimetric tube, heat it in a 50°C constant temperature water bath, then add 10 mg of demulsifier with a pipette, and use a constant temperature oscillator to oscillate at 100 rpm for 1 minute to mix the demulsifier and crude oil evenly, then place it in a 50°C constant temperature water bath to stand for demulsification, and read and record the volume of water removed at the specified time. The experimental results are shown in Table 1 and Figure 1 .

[0090] Table 1 Experimental results of emulsion gel high efficiency demulsifier

[0091]

[0092] The results of the demulsification experiment show that in the three experimental groups injected with ordinary demulsifiers, the crude oil had no water removed and the water content of the crude oil was 30%; the experimental group injected with emulsion gel high-efficiency demulsifier was able to remove water, and the water content of the crude oil after dehydration was only about 0.2%.

[0093] The present invention has been disclosed above with preferred embodiments, but those skilled in the art should understand that these embodiments are only used to describe the present invention and should not be understood as limiting the scope of the present invention. It should be noted that all changes and substitutions equivalent to these embodiments should be deemed to be included in the scope of the claims of the present invention. Therefore, the scope of protection of the present invention should be based on the scope defined in the claims.

Claims

1. A method for preparing an emulsion gel demulsifier, characterized in that: include: (1) heating and carbonizing Tween 80, Span 80, an alkyl glycoside surfactant and fatty alcohol polyoxyethylene ether to obtain component 1; (2) heating sorbitol, octadecyl alcohol and ZnO to react, then adding a base, blowing nitrogen into the system and evacuating to a first negative pressure; introducing ethylene oxide and raising the temperature, and when the system pressure is maintained at the first pressure, continuing to introduce a set experimental amount of ethylene oxide, and when the pressure reaches the first negative pressure, the reaction is complete to obtain component 2; (3) adding a catalyst to the resin, heating and evacuating to a second negative pressure, raising the temperature, and intermittently adding propylene oxide to make the system pressure less than the second pressure. After the addition is completed, the reaction is continued until the pressure drops to the second negative pressure to obtain a polyether propylene oxide block; (4) adding a catalyst to the polyether propylene oxide block, and continuing to increase the temperature and evacuate the block according to the method of step (3) and intermittently adding ethylene oxide to obtain component 3; (5) Mixing the component 1, the component 2, and the component 3 with an organic solvent to obtain an emulsion gel demulsifier.

2. The preparation method according to claim 1, characterized in that: In step (1), the mass ratio of Tween 80, Span 80, alkyl glycoside surfactant and fatty alcohol polyoxyethylene ether is (1-1.2):(1-1.1):(1.8-2.0):(3-4).

3. The preparation method according to claim 1, characterized in that: The alkyl glycoside surfactant is a surfactant synthesized from glucose and fatty alcohol.

4. The preparation method according to claim 1, characterized in that: The general formula of the fatty alcohol polyoxyethylene ether is RO(CH2CH2O) n H, where R is C 12 ~C 18 , n is 8 to 18.

5. The preparation method according to claim 1, characterized in that: In step (1), the heating temperature is 160 to 240° C., and the carbonization time is 12 to 24 hours.

6. The preparation method according to claim 1, characterized in that: In step (2), the molar ratio of the sorbitol to the octadecyl alcohol is 1:(1-1.2), and the ratio of the mass of the ethylene oxide to the total mass of the sorbitol and the octadecyl alcohol is (2-3):

1.

7. The preparation method according to claim 1, characterized in that: In step (2), the first negative pressure is -0.01 to -0.02 MPa; the first pressure is 0.25 to 0.35 MPa.

8. The preparation method according to claim 1, characterized in that: In step (3), the second negative pressure is -0.01 to -0.02 MPa; the heating temperature is 50 to 90°C, and the temperature after heating is 130±5°C; and the second pressure is 0.35 to 0.45 MPa.

9. The preparation method according to claim 1, characterized in that: In step (3), the resin is a phenolamine resin or a phenol-formaldehyde resin; and the catalyst is KOH.

10. The preparation method according to claim 1, characterized in that: In step (3) and step (4), the mass ratio of the resin, the propylene oxide and the ethylene oxide is 1:(40-80):(10-30).

11. The preparation method according to claim 1, characterized in that: The mass ratio of the component 1, the component 2 and the component 3 is: 1:(1.2-1.9):(0.1-0.2).

12. The preparation method according to claim 1, characterized in that: The organic solvent is one or two of isopropanol, xylene or methanol.

13. An emulsion gel demulsifier, characterized in that: The method is obtained by the preparation method according to any one of claims 1 to 12.

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