CN111534323A - Demulsifier, preparation method and application thereof - Google Patents

Demulsifier, preparation method and application thereof Download PDF

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CN111534323A
CN111534323A CN202010455967.4A CN202010455967A CN111534323A CN 111534323 A CN111534323 A CN 111534323A CN 202010455967 A CN202010455967 A CN 202010455967A CN 111534323 A CN111534323 A CN 111534323A
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demulsifier
oil
preparation
esterification
reaction
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CN111534323B (en
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常大明
禹越海
王小勇
杨彬
张忠
陈荣凤
刘永存
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China Petroleum and Chemical Corp
Petroleum Engineering Technology Research Institute of Sinopec Henan Oilfield Branch Co
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Petroleum Engineering Technology Research Institute of Sinopec Henan Oilfield Branch Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals

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Abstract

The invention relates to a demulsifier, a preparation method and application thereof, and belongs to the technical field of petroleum processing. The preparation method of the demulsifier comprises the following steps: 1) carrying out esterification reaction on a compound shown as a formula I and a compound A under the action of an esterification catalyst to obtain an esterification product; the compound A is unsaturated carboxylic acid and/or unsaturated anhydride; 2) taking the esterification product as a polymerization monomer to carry out polymerization reaction of carbon-carbon double bonds, thus obtaining the product; the temperature of the polymerization reaction is 70-90 ℃, and the time is 0.5-1.5 h. The preparation method of the demulsifier improves the molecular weight of the product, and the prepared demulsifier has stronger surface activity and better oleophilic hydrophilicity, is simultaneously suitable for oil-water emulsions and aged crude oil, and is an efficient dehydration demulsifier for oil fields, which has the characteristics of high demulsification efficiency, low cost, small dosage, small side effect and the like.

Description

Demulsifier, preparation method and application thereof
Technical Field
The invention relates to a demulsifier, a preparation method and application thereof, and belongs to the technical field of petroleum processing.
Background
During the process of crude oil exploitation, oil-water emulsions with different emulsification degrees are often formed along with the generation of water, so that the load of storage, transportation and processing equipment is increased, the energy consumption is increased, and high-viscosity aging oil can be formed in a settling tank of a demulsification and dehydration system. The oil-water emulsion and the aged crude oil are difficult to demulsify and dewater, oil-water separation is difficult to complete by a simple gravity settling method, and the conventional heating and dosing treatment effects are also poor, and are mainly shown as follows: the oil-water separation speed is slow, the water content of the separated crude oil is high, the oil content of the separated sewage is high, a thicker emulsification transition layer is formed in a sewage settling tank, the crude oil output quality and the normal operation of a sewage treatment system are influenced, and the adverse effect on the oil field production is caused. The conventional demulsifier mainly comprises a polyether demulsifier, has low molecular weight, low dehydration speed and incomplete oil-water separation, and particularly has poor adaptability to aged crude oil.
Disclosure of Invention
The invention aims to provide a preparation method of a demulsifier with good demulsification and dehydration effects on oil-water emulsion and aged oil.
The invention also provides the demulsifier prepared by the preparation method.
The invention also provides an application of the demulsifier in demulsification of aged crude oil.
In order to realize the purpose, the preparation method of the demulsifier adopts the technical scheme that:
a preparation method of the demulsifier comprises the following steps:
1) carrying out esterification reaction on a compound shown as a formula I and a compound A under the action of an esterification catalyst to obtain an esterification product; the compound A is unsaturated carboxylic acid and/or unsaturated anhydride;
Figure BDA0002509242300000021
in the formula I, R1Is composed of
Figure BDA0002509242300000022
x is 2-5, and R is a hydroxyl-terminated polyether chain segment;
2) and (3) taking the esterification product as a polymerization monomer to carry out polymerization reaction of carbon-carbon double bonds, thus obtaining the product.
According to the preparation method of the demulsifier, the compound shown in the formula I is connected with polymerizable unsaturated double bonds through esterification reaction, and bonding among different molecules is realized through polymerization of carbon-carbon double bonds, so that the molecular weight of the product is improved. In the crude oil emulsion, the mechanical strength and the tightness of the oil-water interface film are the decisive factors of the stability of the crude oil emulsion, and the strength and the tightness of the oil-water interface film are mainly determined by the film-forming substances of the interface film. Natural surface active substances such as colloid, asphaltene, petroleum sulfonate and the like existing in crude oil are main film forming substances of an oil-water interface film, and are regularly and tightly arranged on an oil-water interface, so that the oil-water interface film has high strength, and crude oil emulsion has high stability and is difficult to demulsify and dewater. The demulsifier prepared by the invention belongs to modified polyether, not only has higher molecular weight, but also has a multi-branch structure, longer molecular chain segment, stronger surface activity and better oleophylic and hydrophilic properties, and replaces natural film-forming substances in part of original boundary films on an oil-water interface by interfacial adsorption to form a novel mixed interface film, and the film has smaller intermolecular force and greatly reduced film strength due to larger molecular volume, larger intermolecular gaps and loose arrangement among the molecules, thereby being more beneficial to demulsification and dehydration. The demulsifier is suitable for demulsification and dehydration of oil-water emulsion and aged crude oil, and has the characteristics of high demulsification efficiency, small dosage, low cost and the like.
Preferably, the polyether segment includes a hydrophobic segment and a hydrophilic segment. The hydrophilic chain segment is a polyethylene oxide chain segment, and the hydrophobic chain segment is a polypropylene oxide chain segment. The polyether chain segment simultaneously contains a polyethylene oxide chain segment (PEO chain segment) and a polypropylene oxide chain segment (PPO chain segment), so that the prepared demulsifier has oleophilic and hydrophilic properties, can quickly spread on an oil-water interface of an oil-water emulsion and partially replaces the original surface active substances. The demulsifying effect of the demulsifier is greatly related to the chain length of a PPO chain segment, the chain length of a PEO chain segment and the proportion of the PPO chain segment to the PEO chain segment in a molecule, which is mainly shown in that the length of the PPO chain segment, the length of the PEO chain segment and the proportion of the PPO chain segment to the PEO chain segment influence the hydrophilicity and lipophilicity of the demulsifier, the PEO chain segment extends into a water phase, the PPO chain segment is lipophilicity, and simultaneously, oxygen atoms of ether bonds in the PPO chain segment can be subjected to multi-point adsorption with water to form a loose and easily-cracked interface membrane, thereby. The PEO chain segment and the PPO chain segment are combined according to a proper proportion, so that the demulsifier which has certain solubility in both an oil phase and a water phase, high surface activity, low oil-water interfacial tension and high spreading capacity on an oil-water interfacial film can be obtained. In order to improve the stability of the demulsifier and achieve better demulsification effect, it is further preferable that R is- (C)3H6O)m(C2H4O)nH, m: n is 2-3.5: 1. Furthermore, m is 9 to 14, and n is 4 to 5.
Preferably, the esterification reaction is carried out at the temperature of 120-130 ℃ for 4-6 h.
The unsaturated carboxylic acid used in the preparation method of the invention contains olefinic carbon-carbon double bonds and carboxyl. Preferably, the unsaturated carboxylic acid is one or any combination of methacrylic acid, acrylic acid and maleic acid. The unsaturated anhydride is maleic anhydride.
Preferably, the mass ratio of the compound shown in the formula I to the compound A is 1: 3-8. The mass ratio of the compound I to the compound A in the control formula can ensure that the esterification reaction is completed as much as possible, and the unsaturated acid is properly excessive, so that the acidity of the final product can be increased, and the water solubility and the demulsification and dehydration effects of the final product can be improved.
Conventional esterification catalysts can be used in the preparation process of the present invention. Preferably, the esterification catalyst is one or any combination of p-toluenesulfonic acid, 4-dimethylaminopyridine, anhydrous sodium acetate, zinc oxide and tin oxide. The mass ratio of the esterification catalyst to the compound A is 1: 40-70.
Preferably, in step 2) of any of the above-mentioned production methods, the polymerization reaction is initiated by an initiator. The initiator is one or any combination of Benzoyl Peroxide (BPO), dilauroyl peroxide (LPO), tert-butyl peroxybenzoate (TBPB), dioctyl peroxydicarbonate (EHP), Azobisisobutyronitrile (AIBN) and Azobisisoheptonitrile (ABVN). The mass ratio of the initiator to the compound A for generating the esterification product is 1-10: 320. Further preferably, in the step 2), the mass ratio of the initiator to the compound a for generating the esterification product is 2-5: 320.
Preferably, in the step 2), the temperature of the polymerization reaction is 70-90 ℃ and the time is 0.5-1.5 h.
Preferably, the esterification reaction in step 1) is carried out under reflux in the absence of oxygen. The polymerization in step 2) is carried out in a solvent. The solvent is preferably toluene. The mass ratio of the solvent to the compound A is 1: 2.5-10, and more preferably 1: 5 to 7.
Preferably, R is- (C)3H6O)m(C2H4O)nWhen H, the compound shown in the formula I is prepared by a method comprising the following steps: under the alkaline condition, the ethylenediamine modified phenolic amine resin is taken as an initiator to sequentially carry out ring-opening polymerization reaction with propylene oxide and ethylene oxide, thus obtaining the epoxy resin.
Preferably, the ring-opening polymerization reaction is carried out at 125-145 ℃ and 0.3-0.4 MPa. The mass ratio of the propylene oxide to the ethylene oxide is 2-3.5: 1. The time for ring-opening polymerization reaction with the propylene oxide is 3-4 h. The time for ring-opening polymerization reaction with ethylene oxide is 3-4 h. In the preparation method of the compound shown in the formula I, the mass ratio of the ethylenediamine modified phenolic amine resin to the propylene oxide is 1: 70-100. The ring-opening polymerization reaction is carried out under the action of a catalyst. For example, the ring-opening polymerization may be carried out under the action of potassium hydroxide as a catalyst. The mass ratio of the potassium hydroxide to the ethylenediamine modified phenolic amine resin is 3: 6-8.
Preferably, the ethylenediamine modified phenolic amine resin is prepared by reacting ethylenediamine phenol, polyethylene polyamine and formaldehyde; the molar ratio of the ethylenediamine-formaldehyde to the polyethylene polyamine is 1: 8, and the molar ratio of the ethylenediamine-formaldehyde to the formaldehyde is 1: 8-8.2. Preferably, in the preparation method of the ethylenediamine modified phenolic amine resin, the reaction temperature is 90-120 ℃. Preferably, in the preparation method of the ethylenediamine modified phenolic amine resin, the reaction is carried out at 90-100 ℃ and then at 110-120 ℃. Preferably, in the preparation method of the ethylenediamine modified phenolic amine resin, the reaction time is 2.5-4 h. For example, the reaction can be carried out for 1 to 1.5 hours at 90 to 100 ℃ and then for 1.5 to 2.5 hours at 110 to 120 ℃.
Preferably, the polyethylene polyamine is one or any combination of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine.
Preferably, the preparation method of the ethylenediamine alkylphenol comprises the following steps:
i) under an alkaline condition, reacting formaldehyde with ethylenediamine at 70-90 ℃ to obtain ethylenediamine aldehyde; the molar ratio of formaldehyde to ethylenediamine is 4-4.5: 1;
ii) reacting the prepared ethylenediamine aldehyde with phenol at 80-100 ℃ under an acidic condition to obtain ethylenediamine aldehyde phenol; the molar ratio of phenol to ethylenediamine aldehyde is 4-4.5: 1.
In the step i), the reaction time is 1-3 h. In the step i), the pH value under the alkaline condition is 8-9.
In the step ii), the reaction time is 1-3 h. In the step ii), the pH value under the acidic condition is 3-5.
The demulsifier adopts the technical scheme that:
the demulsifier prepared by the preparation method of the demulsifier.
The demulsifier of the invention has better demulsification and dehydration effects on oil-water emulsions and aged crude oil, greatly shortens the dehydration period, obviously reduces the dehydration cost, ensures that the water content of the crude oil after dehydration is less than 1.0 percent, reaches the industry specified standard, and has the advantages of less dosage, low cost, outstanding demulsification effect and the like.
The application of the demulsifier in demulsification of aged crude oil adopts the technical scheme that:
the application of the demulsifier in demulsification of aged crude oil is disclosed.
When the demulsifier is used for demulsifying aged crude oil, the demulsifier has stronger surface activity, better oleophylic hydrophilicity and wetting permeability due to the unique multi-branch structure, longer molecular chain segment, higher molecular weight and a large amount of active groups, and molecules of the demulsifier can quickly reach an oil-water interface to form a mixed adsorption film. The high molecular weight polyether demulsifier of the present invention can also fully exert the bridging effect of macromolecules in the aged crude oil emulsion, and a plurality of active groups on the demulsifier molecules can attract and gather free liquid drops in the emulsion together to gradually agglomerate into large liquid drops so as to achieve the rapid separation of oil and water, thereby having good demulsification and dehydration effects on the aged crude oil.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Examples of preparation of demulsifiers
Example 1
The preparation method of the demulsifier of the embodiment comprises the following steps:
1) putting 350g of formaldehyde solution with the mass concentration of 37% into a three-necked bottle, dropwise adding 10% NaOH solution, adjusting the pH value to 8.5, heating to 50 ℃, stirring, dropwise adding 60g of ethylenediamine (the molar ratio of formaldehyde to ethylenediamine is 4.3: 1) into the three-necked bottle, heating to 80 ℃ for reaction for 2 hours after dropwise adding, cooling to 60 ℃, and performing vacuum drying to remove water and unreacted formaldehyde to obtain ethylenediamine aldehyde;
2) adding 396g of phenol into a three-necked bottle, dropwise adding an HCl solution with the mass concentration of 18%, adjusting the pH value to 4, heating to 70 ℃, dropwise adding all the ethylenediamine aldehyde prepared in the step 1) into the phenol (the molar ratio of the phenol to the ethylenediamine aldehyde is 4.2: 1), heating to 90 ℃ after dropwise adding, reacting for 2 hours, standing, layering, removing a water layer by using a separating funnel, and then performing vacuum drying to remove water and HCl to obtain a brown yellow viscous product ethylenediamine aldehyde;
3) 110g of ethylenediamine alkylphenol and 345g of tetraethylenepentamine are put into a three-neck flask (the molar ratio of the ethylenediamine alkylphenol to the tetraethylenepentamine is 1: 8) 151g of a 37% formaldehyde solution (molar ratio of ethylenediamine-phenol to formaldehyde 1: 8.2), slowly heating to 90 ℃ for reaction for 1h, and then heating to 120 ℃ for reaction for 2 h. Cooling, and drying the product in vacuum to obtain brown yellow viscous ethylenediamine modified phenolic amine resin;
4) adding 8g of ethylenediamine modified phenolic amine resin as an initiator and 3g of catalyst KOH into a high-pressure reaction kettle, sealing the kettle, testing the pressure, displacing air in the high-pressure kettle, a feeding kettle and a feeding pipe by using dry nitrogen, starting stirring, heating to 100 ℃, and starting a vacuum pump to vacuumize;
when the temperature rises to 120 ℃, stopping the vacuum pump, opening a feed valve, gradually pressing 580g of Propylene Oxide (PO) weighed in a storage tank into a reaction kettle by using nitrogen pressure, controlling the reaction temperature to 145 ℃ on the basis that the kettle pressure does not exceed 0.4MPa, reacting for 3 hours after the feeding is finished (the feeding time is about 1 hour), keeping the temperature to 145 ℃ and the pressure to 0.4MPa, cooling to 100 ℃, and reducing the pressure to normal pressure;
then adding 180g of Ethylene Oxide (EO) into a reaction kettle, controlling the reaction temperature to be 145 ℃ on the basis of the kettle pressure not exceeding 0.4MPa at the feeding speed, continuously keeping the temperature to be 145 ℃ and the pressure to be 0.4MPa after the feeding is finished (the feeding time is about 0.5h), reacting for 3h, cooling to normal temperature, reducing the pressure to be normal pressure, discharging, neutralizing a reaction product to be neutral by phosphoric acid to obtain the ethylenediamine modified phenol-amine resin two-block polyether, wherein the ethylenediamine modified phenol-amine resin two-block polyether has the following structure:
Figure BDA0002509242300000061
in the formula, R1Is composed of
Figure BDA0002509242300000062
R is- (C)3H6O)m(C2H4O)nH, m is 50, n is 20, m: n is 2.5: 1.
5) Adding 80g of ethylenediamine modified phenolic amine resin diblock polyether, 5g of p-toluenesulfonic acid, 320g of methacrylic acid and 50g of toluene into a four-neck flask with a reflux condenser, a stirrer and a thermometer of a water separator, introducing nitrogen to replace air, heating and stirring, and carrying out reflux reaction for 5 hours at 125 ℃;
then cooling to 60 ℃, adding 2g of Benzoyl Peroxide (BPO), heating to 85 ℃, continuing to react for 1h, then cooling to 30 ℃, and discharging to obtain the product.
The demulsifier prepared by the embodiment is a methacrylic acid modified efficient demulsifier.
Example 2
The preparation method of the demulsifier of the embodiment comprises the following steps:
1) ethylenediamine alkylphenol was prepared according to steps 1) to 2) of example 1; putting 55g of ethylenediamine-phenol and 172g of tetraethylenepentamine into a three-neck flask (the molar ratio of the ethylenediamine-phenol to the tetraethylenepentamine is 1: 8), dropwise adding 74g of formaldehyde solution with the mass concentration of 37% (the molar ratio of the ethylenediamine-phenol to the formaldehyde is 1: 8) at 60 ℃, slowly heating to 90 ℃ for reaction for 1h, then heating to 120 ℃ for reaction for 2h, cooling, and carrying out vacuum drying on the product to obtain brown yellow viscous ethylenediamine modified phenolic amine resin;
2) adding 6g of ethylenediamine modified phenolic amine resin as an initiator and 3g of catalyst KOH into a high-pressure reaction kettle, sealing the kettle, testing the pressure, displacing air in the high-pressure kettle, a feeding kettle and a feeding pipe by using dry nitrogen, starting stirring, heating to 100 ℃, and starting a vacuum pump to vacuumize;
when the temperature rises to 120 ℃, stopping the vacuum pump, opening a feed valve, gradually pressing 600g of weighed Propylene Oxide (PO) in the storage tank into the reaction kettle by using the nitrogen pressure, controlling the reaction temperature to 145 ℃ on the basis that the kettle pressure does not exceed 0.4MPa, continuously keeping the temperature to 145 ℃ and the pressure to 0.4MPa for reaction for 3 hours after the feeding is finished (the feeding time is about 1 hour), cooling to 100 ℃, and reducing the pressure to normal pressure;
then adding 220g of Ethylene Oxide (EO) into a reaction kettle, controlling the reaction temperature to be 145 ℃ on the basis of the kettle pressure not exceeding 0.4MPa at the feeding speed, continuously keeping the temperature to be 145 ℃ and the pressure to be 0.4MPa after the feeding is finished (the feeding time is about 0.5h), reacting for 3h, cooling to normal temperature, reducing the pressure to be normal pressure, discharging, neutralizing a reaction product to be neutral by phosphoric acid to obtain the ethylenediamine modified phenol-amine resin two-block polyether, wherein the ethylenediamine modified phenol-amine resin two-block polyether has the following structure:
Figure BDA0002509242300000071
in the formula, R1Is composed of
Figure BDA0002509242300000072
R is- (C)3H6O)m(C2H4O)nH, m is 69, n is 33, m: n is 2.1: 1.
3) Adding 80g of ethylenediamine modified phenolic amine resin diblock polyether, 6g of 4-dimethylaminopyridine, 400g of acrylic acid and 140g of toluene into a four-neck flask with a reflux condenser, a stirrer and a thermometer of a water separator, introducing nitrogen to replace air, heating and stirring, and carrying out reflux reaction for 4 hours at 130 ℃;
then cooling to 60 ℃, adding 3g of dilauroyl peroxide (LPO), heating to 90 ℃, continuing to react for 0.5h, then cooling to 30 ℃, and discharging to obtain the acrylic acid modified efficient demulsifier.
Example 3
The preparation method of the demulsifier of the embodiment comprises the following steps:
1) an ethylenediamine-modified phenol-amine resin diblock polyether was prepared according to steps 1) to 4) of example 1;
2) adding 80g of ethylenediamine modified phenolic amine resin diblock polyether, 9g of zinc acetate, 240g of acrylic acid, 160g of maleic anhydride and 40g of toluene into a four-neck flask with a reflux condenser, a stirrer and a thermometer of a water separator, introducing nitrogen to replace air, heating and stirring, and carrying out reflux reaction at 120 ℃ for 6 hours;
then cooling to 60 ℃, adding 4g of dioctyl peroxydicarbonate (EHP), heating to 70 ℃, continuing to react for 1.5h, then cooling to 30 ℃, and discharging to obtain the acrylic maleic anhydride modified efficient demulsifier.
Examples of demulsifiers
Example 4
The demulsifier of this embodiment is the demulsifier prepared by the preparation method of the demulsifier of the above embodiments 1-3, and is not described herein again.
Examples of the use of demulsifiers in demulsification of aged crude oils
Example 5
The application of the demulsifier in the demulsification of aged crude oil is the application of the demulsifier prepared by the preparation method of any one of the demulsifiers in the embodiments 1-3 in the demulsification of aged crude oil.
Experimental example 1
In the experimental example, the A-well platform oil-water emulsion is used as a test object, and the demulsifier is the ethylenediamine modified phenolic amine resin diblock polyether demulsifier prepared in example 1, so that the demulsification and dehydration effects are evaluated.
The evaluation method comprises the following steps: and (3) taking the crude oil emulsion which is not added with the chemicals from the well platform A, firstly carrying out water content measurement, and if the water content of the crude oil is lower than 30%, manually preparing the crude oil emulsion with the water content of 40%. Weighing a certain amount of crude oil sample and emulsion free sewage which are not added with drugs on site, preheating the oil sample and the sewage to 50 ℃, pouring the oil sample and the sewage into a stirring cup of a high-shear mixing emulsifying machine, stirring at 2000r/min for 8min to obtain 1000mL crude oil emulsion with water content of 40%, then respectively sampling 80mL of the mixture, adding the mixture into a test tube with a plug scale and a volume of 100mL and a division value of l mL, preheating in 55 deg.C constant temperature water bath for 15min, adding demulsifiers with different concentrations into the measuring cylinder with plug by pipette, screwing the bottle cap, oscillating up and down violently for 100 times in a manual mode, loosening the bottle cap after fully and uniformly mixing, and placing the measuring cylinder with the plug in a constant-temperature water bath again for standing and settling, respectively recording the dehydration amount at different time points, and observing the oil-water interface and the color condition of the removed sewage at 90min, wherein the results are shown in table 1.
TABLE 1 dehydration Effect of demulsifiers of different concentrations
Figure BDA0002509242300000091
As can be seen from table 1: when the temperature is 55 ℃ and the dosing concentration is 60mg/L, the dehydration rate of the crude oil reaches 96.8 percent, and the oil-water interface is uniform, so that the removed water quality is clear, and the demulsification and dehydration effects are good.
Experimental example 2
In the experimental example, the A-well platform oil-water emulsion is used as a test object, and the demulsifier is the ethylenediamine modified phenolic amine resin diblock polyether demulsifier prepared in the example 2, so that the demulsification and dehydration effects are evaluated.
The evaluation method comprises the following steps: the evaluation method and the test subjects of this example were the same as those of example 1, and the results are shown in Table 2.
TABLE 2 dehydration Effect of demulsifiers of different concentrations
Figure BDA0002509242300000092
Figure BDA0002509242300000101
As can be seen from table 2: when the temperature is 55 ℃ and the dosing concentration is 60mg/L, the dehydration rate of the crude oil reaches 96.8 percent, and the oil-water interface is uniform, so that the removed water quality is clear, and the demulsification and dehydration effects are good.
Experimental example 3
In the experimental example, the A-well platform oil-water emulsion is used as a test object, and the demulsifier is the ethylenediamine modified phenolic amine resin diblock polyether demulsifier prepared in example 3, so that the demulsification and dehydration effects are evaluated.
The evaluation method comprises the following steps: the evaluation method and the test subjects of this example were the same as those of example 1, and the results are shown in Table 3.
TABLE 3 dehydration Effect of demulsifiers of different concentrations
Figure BDA0002509242300000102
As can be seen from table 3: when the temperature is 55 ℃ and the dosing concentration is 60mg/L, the dehydration rate of the crude oil reaches 98.4 percent, and the oil-water interface is uniform, the removed water quality is clear, and the demulsification and dehydration effect is better.
Experimental example 4
In this experimental example, the aging oil in the crude oil settling tank of the a-well platform was used as a test object (the source was recovered ground oil, recovered sewage oil, emulsified oil formed in the operation process, and the like, and the comprehensive water content was 47%), and the demulsifier was the ethylenediamine modified phenolic amine resin two-block polyether demulsifier prepared in example 3, and the demulsification and dehydration effects were evaluated.
The evaluation method comprises the following steps: sampling 80mL of aging oil with a water content of 47% from a well platform A, adding the aging oil into a test tube with a plug scale and a volume of 100mL, dividing the volume into l mL, placing the test tube with the plug scale in a thermostatic water bath at the temperature of 55 ℃ for preheating for 15min, adding demulsifiers with different concentrations into the measuring tube with the plug by using pipette, screwing a bottle cap, oscillating the bottle cap manually and violently up and down for 100 times, loosening the bottle cap after fully and uniformly mixing, placing the measuring tube with the plug in the thermostatic water bath again for standing and settling, recording dehydration amounts at different time points, and observing oil-water interface and sewage color conditions after 90min, wherein the results are shown in Table 4.
TABLE 4 dehydration Effect of demulsifiers of different concentrations
Figure BDA0002509242300000111
As can be seen from table 4: when the temperature is 55 ℃ and the dosing concentration is 150mg/L, the dehydration rate of the crude oil reaches 97.1 percent, the oil-water interface is uniform, the removed water quality is clear, and the demulsification dehydration effect on the aging oil is better.
Experimental example 5
In the experimental example, a well platform oil-water emulsion A is used as a test object, demulsifiers are the ethylenediamine modified phenolic amine resin diblock polyether demulsifiers prepared in the examples 1, 2 and 3, and the demulsifier comparative examples are demulsifiers such as SP169, BP169, TA1031, AF3125 and RN-102 which are commonly used in oil fields, so that a comparative demulsification and demulsification effect evaluation experiment is performed. The evaluation method was the same as in Experimental example 1, and the results are shown in Table 5.
TABLE 5 comparison of demulsification effects of different demulsifiers at a dosing concentration of 60mg/L
Figure BDA0002509242300000112
Figure BDA0002509242300000121
As can be seen from table 5: when the temperature is 55 ℃ and the dosing concentration is 60mg/L, the demulsifiers are the ethylenediamine modified phenolic amine resin two-block polyether demulsifiers prepared in the embodiments 1, 2 and 3 respectively, the crude oil dehydration rates are respectively 96.8%, 96.8% and 97.1%, which are higher than those of the demulsifiers commonly used in the oil field at present, the oil-water interface is uniform, the water removal quality is clear, and the demulsifier has better demulsification and dehydration effects on crude oil emulsion of the oil field.
Experimental example 6
In the experimental example, the aging oil in the crude oil settling tank of the well platform a is used as a test object (the source is recovered ground oil, sewage recovered oil, emulsified oil formed in the operation process and the like, and the comprehensive water content is 47%), the demulsifiers are the ethylene diamine modified phenol-amine resin two-block polyether demulsifiers respectively prepared in the examples 1, 2 and 3, and the demulsifier comparative examples are demulsifiers commonly used in oil fields such as SP169, BP169, TA1031, AF3125, RN-102 and the like, so that comparative evaluation experiments on the demulsification and dehydration effects of the aging oil are performed.
The evaluation method comprises the following steps: sampling 80mL of aging oil with the water content of 47% from a well platform A, adding the aging oil into a test tube with a plug scale and a division value of l mL, wherein the test tube with the plug scale has a volume of 100mL, placing the test tube in a constant-temperature water bath at the temperature of 55 ℃ for preheating for 15min, adding demulsifiers with different types and concentrations into a measuring cylinder with the plug scale by using a pipette, screwing a bottle cap, oscillating the bottle cap manually and violently up and down for 100 times, loosening the bottle cap after fully and uniformly mixing, placing the measuring cylinder with the plug scale in the constant-temperature water bath again for standing and settling, recording the dehydration amount at different time points, observing the oil-water interface and the color condition of the separated sewage at 90 min.
TABLE 6 comparison of demulsification and dehydration effects of demulsifiers with different types and concentrations on aging oil
Figure BDA0002509242300000131
Figure BDA0002509242300000141
As can be seen from table 6: when the temperature is 55 ℃ and the dosing concentration is 150mg/L, the demulsifiers are the demulsifiers prepared in the examples 1, 2 and 3 respectively, the dehydration rate of crude oil is more than 95%, the oil-water interface is uniform, the removed water quality is clear, and the demulsifiers are obviously superior to other comparative demulsifiers, so that the demulsifiers prepared in the examples 1 to 3 have better demulsification and dehydration effects on aging oil.
From the experimental examples 1 to 6, the demulsifier disclosed by the invention has stronger demulsification and dehydration effects on oil-water emulsions and aged oil of an oil field, and the demulsifier has the advantages of clear quality of the dehydrated water, regular oil-water interface, lower dosage of the medicament and obviously better demulsification effects than a plurality of demulsifiers commonly used in the oil field at present.

Claims (10)

1. A preparation method of the demulsifier is characterized by comprising the following steps: the method comprises the following steps:
1) carrying out esterification reaction on a compound shown as a formula I and a compound A under the action of an esterification catalyst to obtain an esterification product; the compound A is unsaturated carboxylic acid and/or unsaturated anhydride;
Figure FDA0002509242290000011
in the formula I, R1Is composed of
Figure FDA0002509242290000012
x is 2-5, and R is a hydroxyl-terminated polyether chain segment;
2) and (3) taking the esterification product as a polymerization monomer to carry out polymerization reaction of carbon-carbon double bonds, thus obtaining the product.
2. The method for preparing the demulsifier according to claim 1, wherein the demulsifier comprises: the polyether segment includes a hydrophobic segment and a hydrophilic segment.
3. The method for preparing the demulsifier according to claim 1, wherein the demulsifier comprises: r is- (C)3H6O)m(C2H4O)nH, m is 9-14, n is 4-5, m: n is 2-3.5: 1.
4. The method for preparing the demulsifier according to claim 1, wherein the demulsifier comprises: the temperature of the esterification reaction is 120-130 ℃, and the time is 4-6 h.
5. The method for preparing the demulsifier according to claim 1, wherein the demulsifier comprises: the unsaturated carboxylic acid is one or any combination of methacrylic acid, acrylic acid and maleic acid; the unsaturated anhydride is maleic anhydride.
6. The method for preparing the demulsifier according to claim 1, wherein the demulsifier comprises: the mass ratio of the compound shown in the formula I to the compound A is 1: 3-8.
7. The method for preparing the demulsifier according to any one of claims 1 to 6, wherein the demulsifier comprises: in step 2), the polymerization is initiated by an initiator.
8. The method for preparing the demulsifier of claim 7, wherein: in the step 2), the temperature of the polymerization reaction is 70-90 ℃ and the time is 0.5-1.5 h.
9. The demulsifier prepared by the preparation method of the demulsifier of claim 1.
10. Use of the demulsifier of claim 9 in demulsification of aged crude oil.
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