CN113684054B - Demulsifier and preparation method thereof - Google Patents
Demulsifier and preparation method thereof Download PDFInfo
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- CN113684054B CN113684054B CN202111246905.3A CN202111246905A CN113684054B CN 113684054 B CN113684054 B CN 113684054B CN 202111246905 A CN202111246905 A CN 202111246905A CN 113684054 B CN113684054 B CN 113684054B
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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
Abstract
The invention belongs to the technical field of demulsifiers, and particularly relates to a demulsifier and a preparation method thereof. The demulsifier comprises, by mass, 20-25% of a silicone oil-modified phenolic amine resin polyether demulsifier, 30-35% of an acrylic acid-modified triblock phenolic amine resin polyether demulsifier, 5-8% of an ionic liquid, 0.5-0.7% of tetradecylamidopropyl hydroxypropyl sulfobetaine, 12-15% of diethylene glycol monobutyl ether and the balance of water. According to the demulsifier, bromo-1-octyl-2, 3-dimethyl imidazole is added as ionic liquid, so that the tension of an oil-water interface is reduced; the silicone oil modified phenolic amine resin polyether demulsifier and the acrylic acid modified triblock phenolic amine resin polyether demulsifier are used as main materials, the ionic liquid is used as an auxiliary material, and the raw materials are compounded for use, so that the synergistic effect is achieved, the crude oil dehydration is realized, and the characteristics of small using amount, low using temperature and high dehydration speed are realized.
Description
Technical Field
The invention belongs to the technical field of demulsifiers, and particularly relates to a demulsifier and a preparation method thereof.
Background
More than 80% of crude oil is produced with water of different degrees, the water content of some crude oil is even up to 90%, and if the crude oil is not dehydrated in time, the loads of a pump, a pipeline and a storage tank are increased, so that the corrosion and the scaling of a metal surface are caused; the discharged water also contains oil, which causes environmental pollution and crude oil waste. However, a large amount of chemical agents are added in the oil extraction process to cause certain difficulty in demulsification and dehydration of crude oil, so that the emulsion state of produced liquid is diversified, the phase state of the produced crude oil is not limited to W/O type, but also O/W type, W/O and O/W type emulsion are synthesized into an integrated multiple emulsion, the strength of an interface membrane is enhanced, and the demulsification difficulty is increased.
The crude oil demulsification is that the chemical action of the demulsifier is utilized to separate oil and water in emulsified oil-water mixed liquor, so that the purpose of crude oil dehydration is achieved, and the water standard of crude oil output is ensured. There are many methods for demulsifying crude oil, including a settling method, a heating method, an electric dehydration method, a chemical method, and the like, and a combination of two or more methods may be used. But the common chemical dehydration method is adopted, namely, the demulsifier is added into the crude oil emulsion to demulsify and dehydrate the crude oil at normal temperature or at elevated temperature.
In recent years, the conventional demulsifier is still adopted for crude oil dehydration, so that the dehydration temperature of crude oil is high. Currently, there are many different types of crude oil demulsifier synthesis techniques. But the prepared demulsifier has unsatisfactory flocculation capacity, coalescence capacity and dehydration effect and poor adaptability to crude oil products; the demulsifier for various oil fields is developed aiming at the physical properties of different crude oil, has strong pertinence, poor low-temperature dehydration effect on the crude oil, is not applicable and has poor comprehensive demulsification effect.
Disclosure of Invention
The purpose of the invention is: a demulsifier is provided. The demulsifier has low use temperature and wide application range; the invention also provides a preparation method thereof.
The demulsifier comprises, by mass, 20-25% of a silicone oil-modified phenolic amine resin polyether demulsifier, 30-35% of an acrylic acid-modified triblock phenolic amine resin polyether demulsifier, 5-8% of an ionic liquid, 0.5-0.7% of tetradecylamidopropyl hydroxypropyl sulfobetaine, 12-15% of diethylene glycol mono-n-butyl ether and the balance of water.
Preferably, the demulsifier provided by the invention comprises, by mass, 22% of a silicone oil-modified phenolic amine resin polyether demulsifier, 35% of an acrylic acid-modified triblock phenolic amine resin polyether demulsifier, 6% of an ionic liquid, 0.5% of tetradecylamidopropyl hydroxypropyl sulfobetaine, 14% of diethylene glycol mono-n-butyl ether and the balance of water.
Wherein:
the ionic liquid is bromo-1-octyl-2, 3-dimethyl imidazole.
Bromo-1-octyl-2, 3-dimethyl imidazole is added as ionic liquid, can reach an oil-water interface quickly, and reduces the tension of the oil-water interface.
The preparation method of the silicone oil modified phenol amine resin polyether demulsifier comprises the following steps:
(1) adding phenolic amine resin and an alkali catalyst into a high-pressure reaction kettle, stirring and heating to 90-95 ℃, vacuumizing and replacing with nitrogen, controlling the pressure to be-0.20-0.15 MPa, continuously heating to 125-0.15 MPa, introducing epoxypropane for reaction, keeping the pressure in the high-pressure reaction kettle to be 0.27-0.30 MPa, reacting for a period of time, introducing epoxyethane when the pressure is reduced to-0.20-0.15 MPa, keeping the pressure in the high-pressure reaction kettle to be 0.21-0.23MPa, keeping the reaction temperature to be 113-115 ℃, and finishing the reaction when the pressure is reduced to-0.20-0.15 MPa to prepare the diblock phenolic amine resin polyether;
(2) modification of silicone oils
And (3) dropwise adding methyl ethoxy silicone oil and oleic acid into the dehydrated diblock phenol-amine resin polyether, reacting at the temperature of 115-118 ℃ for 55-65min after the dropwise adding is finished, and then carrying out reduced pressure distillation reaction for 20-25min to prepare the silicone oil modified phenol-amine resin polyether demulsifier.
Wherein:
the preparation method of the phenolic amine resin in the step (1) comprises the following steps: dripping formaldehyde solution into a mixed system of 2, 2-bis (4-hydroxyphenyl) propane and diethylenetriamine, carrying out heat preservation reaction at 35-38 ℃ for 2.5-3h, then adding dimethylbenzene, heating to 100-105 ℃, carrying out high-temperature dehydration reaction for 3.5-4h, and removing dimethylbenzene to prepare the phenolic amine resin.
Wherein: the mass ratio of the 2, 2-bis (4-hydroxyphenyl) propane, the diethylenetriamine and the formaldehyde is 1:4-6: 4-6.
In the step (1), the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide is 100%, wherein: 3.5-5.5% of phenolic amine resin, 15-18% of ethylene oxide and 77-80% of propylene oxide.
The alkali catalyst in the step (1) is one or a mixture of more of potassium hydroxide, sodium hydroxide or sodium ethoxide; the mass of the added base catalyst accounts for 0.5 to 0.7 percent of the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide.
The dehydration treatment in the step (2) is to heat the diblock phenol amine resin to 100-105 ℃ and perform reduced pressure distillation dehydration treatment for 45-50 minutes.
The mass ratio of the diblock phenol amine resin polyether, the methyl ethoxy silicone oil and the oleic acid in the step (2) is 1:2.2-2.4: 0.05-0.07.
Through methyl ethoxy silicone oil modification, the molecular weight of the diblock polyether is increased, the surface tension of the prepared phenolic amine resin polyether demulsifier is reduced, and the hydrophobicity is improved.
The preparation method of the acrylic acid modified triblock phenol amine resin polyether demulsifier comprises the following steps:
(1) adding phenolic amine resin and an alkali catalyst into a high-pressure reaction kettle, stirring and heating to 90-95 ℃, vacuumizing and replacing with nitrogen, controlling the pressure to be-0.20-0.15 MPa, continuously heating to 125-0.15 MPa, introducing epoxypropane for reaction, keeping the pressure in the high-pressure reaction kettle to be 0.27-0.30 MPa, reacting for a period of time, introducing epoxyethane when the pressure is reduced to-0.20-0.15 MPa, keeping the pressure in the high-pressure reaction kettle to be 0.21-0.23MPa, keeping the reaction temperature to be 113-115 ℃, and finishing the reaction when the pressure is reduced to-0.20-0.15 MPa to prepare the diblock phenolic amine resin polyether;
(2) introducing propylene oxide to react for a period of time, keeping the pressure in the high-pressure reaction kettle at 0.27-0.30 MPa and the reaction temperature at 125-127 ℃, and after the reaction is finished when the pressure is reduced to-0.20 to-0.15 MPa, preparing the triblock phenol-amine resin polyether through post treatment;
(3) and (3) dissolving the triblock phenolic amine resin polyether prepared in the step (2) in a toluene solution, adding acrylic acid to perform esterification reaction by using dodecylbenzene sulfonic acid as a catalyst, adding azobisisobutyronitrile to perform polymerization reaction after the esterification reaction is finished, and performing post-treatment to prepare the acrylic acid modified triblock phenolic amine resin polyether.
Wherein:
the preparation method of the phenolic amine resin in the step (1) comprises the following steps: dripping formaldehyde solution into a mixed system of 2, 2-bis (4-hydroxyphenyl) propane and diethylenetriamine, carrying out heat preservation reaction at 35-38 ℃ for 2.5-3h, then adding dimethylbenzene, heating to 100-105 ℃, carrying out high-temperature dehydration reaction for 3.5-4h, and removing dimethylbenzene to prepare the phenolic amine resin.
Wherein: the mass ratio of the 2, 2-bis (4-hydroxyphenyl) propane, the diethylenetriamine and the formaldehyde is 1:4-6: 4-6.
In the step (1), the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide is 100%, wherein: 3.5-5.5% of phenolic amine resin, 15-18% of ethylene oxide and 77-80% of propylene oxide.
The alkali catalyst in the step (1) is one or a mixture of more of potassium hydroxide, sodium hydroxide or sodium ethoxide; the mass of the added base catalyst accounts for 0.5 to 0.7 percent of the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide.
The mass ratio of the propylene oxide added in the step (2) to the propylene oxide added in the step (1) is 3.0-3.3: 1.
The mass of the dodecylbenzene sulfonic acid in the step (3) accounts for 0.8-1.0% of the mass of the triblock phenol amine resin polyether; the mass of the acrylic acid accounts for 13-15% of that of the triblock phenol-amine resin polyether; the esterification reaction temperature is 150-155 ℃; the mass of the azodiisobutyronitrile accounts for 3.0-3.5% of that of the triblock phenolic amine resin polyether, the reaction temperature is 182 ℃ and 185 ℃, and the reaction time is 8.5-9 h.
The preparation method of the demulsifier comprises the following steps:
(1) uniformly mixing a silicone oil modified phenolic amine resin polyether demulsifier, an acrylic acid modified triblock phenolic amine resin polyether demulsifier, tetradecylamidopropyl hydroxypropyl sulphobetaine and water according to a certain mass ratio to obtain a first mixed solution;
(2) dissolving the ionic liquid in diethylene glycol mono-n-butyl ether, and stirring and mixing at 50-55 ℃ for 30-35min to obtain a second mixed solution;
(3) and (3) adding the second mixed solution prepared in the step (2) into the first mixed solution prepared in the step (1), and stirring at 40-45 ℃ for 25-30min to prepare the demulsifier.
Wherein:
the mixing temperature in the step (1) is 60-65 ℃, and the mixing time is 40-45 min.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the demulsifier, diethylene glycol mono-n-butyl ether has the properties of alcohol and ether, is a polar substance, can improve the polarity of an oil-water interface after being added, reduces the viscosity of an oil-water emulsion, and is beneficial to demulsification and dehydration after being compounded with ionic liquid and a plurality of demulsifiers.
(2) According to the demulsifier disclosed by the invention, bromo-1-octyl-2, 3-dimethylimidazole is added as ionic liquid, so that the demulsifier can quickly reach an oil-water interface and reduce the tension of the oil-water interface; the silicone oil modified phenol amine resin polyether demulsifier and the acrylic acid modified triblock phenol amine resin polyether demulsifier are used as main materials, the ionic liquid is used as an auxiliary material, the two modified polyether demulsifiers are used in a compounding way, the use temperature of the demulsifier is reduced by adding the silicone oil modified phenol amine resin polyether demulsifier, the acrylic acid modified triblock phenol amine resin polyether demulsifier has large molecular weight, large surface area and multiple active ends, and has good diffusion and permeation effects.
(3) According to the demulsifier, tetradecylamidopropyl hydroxypropyl sulphobetaine is added, and the demulsifier is compounded with a silicone oil modified phenolic amine resin polyether demulsifier and an acrylic acid modified triblock phenolic amine resin polyether demulsifier, so that the demulsifier has good low-temperature stability and thickening property, and the using effect of the modified polyether demulsifier is promoted.
(4) The preparation method of the demulsifier provided by the invention has mild operation conditions, is easy to realize industrialized popularization and production, and the prepared demulsifier has the advantages of wide application range, high oil-water separation rate and good comprehensive demulsification effect.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The demulsifier described in this example 1 comprises, by mass, 22% of a silicone oil-modified phenolic amine resin polyether demulsifier, 35% of an acrylic acid-modified triblock phenolic amine resin polyether demulsifier, 6% of an ionic liquid, 0.5% of tetradecylamidopropyl hydroxypropyl sulfobetaine, 14% of diethylene glycol mono n-butyl ether, and the balance water.
Wherein:
the ionic liquid is bromo-1-octyl-2, 3-dimethyl imidazole.
Bromo-1-octyl-2, 3-dimethyl imidazole is added as ionic liquid, can reach an oil-water interface quickly, and reduces the tension of the oil-water interface.
The preparation method of the silicone oil modified phenol amine resin polyether demulsifier comprises the following steps:
(1) adding phenolic amine resin and an alkali catalyst into a high-pressure reaction kettle, stirring and heating to 95 ℃, vacuumizing and replacing with nitrogen, controlling the pressure at-0.15 MPa, continuously heating to 127 ℃, introducing propylene oxide for reaction, keeping the pressure in the high-pressure reaction kettle at 0.30MPa, reacting for a period of time, introducing ethylene oxide when the pressure is reduced to-0.15 MPa, keeping the pressure in the high-pressure reaction kettle at 0.22MPa, keeping the reaction temperature at 115 ℃, and finishing the reaction when the pressure is reduced to-0.15 MPa to prepare diblock phenolic amine resin polyether;
(2) modification of silicone oils
And (3) dropwise adding methyl ethoxy silicone oil and oleic acid into the dehydrated diblock phenol-amine resin polyether, reacting at 115 ℃ for 60min after dropwise adding, and then carrying out reduced pressure distillation reaction for 25min to prepare the silicone oil modified phenol-amine resin polyether demulsifier.
Wherein:
the preparation method of the phenolic amine resin in the step (1) comprises the following steps: dripping formaldehyde solution into a mixed system of 2, 2-bis (4-hydroxyphenyl) propane and diethylenetriamine, keeping the temperature at 38 ℃ for reaction for 2.5h, then adding dimethylbenzene, heating to 100 ℃, carrying out high-temperature dehydration reaction for 3.5h, and removing the dimethylbenzene to prepare the phenolic amine resin.
Wherein: the mass ratio of the 2, 2-bis (4-hydroxyphenyl) propane, the diethylenetriamine and the formaldehyde is 1:5: 6.
In the step (1), the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide is 100%, wherein: 3.5 percent of phenolic amine resin, 16.5 percent of ethylene oxide and 80 percent of propylene oxide.
The alkali catalyst in the step (1) is potassium hydroxide; the mass of the added base catalyst accounts for 0.6 percent of the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide.
The dehydration treatment in the step (2) is to heat the diblock phenol amine resin to 100 ℃ and perform reduced pressure distillation dehydration treatment for 50 minutes.
The mass ratio of the diblock phenol amine resin polyether, the methyl ethoxy silicone oil and the oleic acid in the step (2) is 1:2.4: 0.06.
Through methyl ethoxy silicone oil modification, the molecular weight of the diblock polyether is increased, the surface tension of the prepared phenolic amine resin polyether demulsifier is reduced, and the hydrophobicity is improved.
The preparation method of the acrylic acid modified triblock phenol amine resin polyether demulsifier comprises the following steps:
(1) adding phenolic amine resin and an alkali catalyst into a high-pressure reaction kettle, stirring and heating to 95 ℃, vacuumizing and replacing with nitrogen, controlling the pressure at-0.15 MPa, continuously heating to 127 ℃, introducing propylene oxide for reaction, keeping the pressure in the high-pressure reaction kettle at 0.30MPa, reacting for a period of time, introducing ethylene oxide when the pressure is reduced to-0.15 MPa, keeping the pressure in the high-pressure reaction kettle at 0.22MPa, keeping the reaction temperature at 115 ℃, and finishing the reaction when the pressure is reduced to-0.15 MPa to prepare diblock phenolic amine resin polyether;
(2) introducing propylene oxide to react for a period of time, keeping the pressure in the high-pressure reaction kettle at 0.30MPa and the reaction temperature at 127 ℃, and performing post-treatment to obtain triblock phenol-amine resin polyether after the reaction is finished when the pressure is reduced to-0.15 MPa;
(3) and (3) dissolving the triblock phenolic amine resin polyether prepared in the step (2) in a toluene solution, adding acrylic acid to perform esterification reaction by using dodecylbenzene sulfonic acid as a catalyst, adding azobisisobutyronitrile to perform polymerization reaction after the esterification reaction is finished, and performing post-treatment to prepare the acrylic acid modified triblock phenolic amine resin polyether.
Wherein:
the preparation method of the phenolic amine resin in the step (1) comprises the following steps: dripping formaldehyde solution into a mixed system of 2, 2-bis (4-hydroxyphenyl) propane and diethylenetriamine, keeping the temperature at 38 ℃ for reaction for 2.5h, then adding dimethylbenzene, heating to 100 ℃, carrying out high-temperature dehydration reaction for 3.5h, and removing the dimethylbenzene to prepare the phenolic amine resin.
Wherein: the mass ratio of the 2, 2-bis (4-hydroxyphenyl) propane, the diethylenetriamine and the formaldehyde is 1:5: 6.
In the step (1), the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide is 100%, wherein: 3.5 percent of phenolic amine resin, 16.5 percent of ethylene oxide and 80 percent of propylene oxide.
The alkali catalyst in the step (1) is potassium hydroxide; the mass of the added base catalyst accounts for 0.6 percent of the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide.
The mass ratio of the propylene oxide added in the step (2) to the propylene oxide added in the step (1) is 3.2: 1.
The mass of the dodecylbenzene sulfonic acid in the step (3) accounts for 0.8 percent of the mass of the triblock phenol amine resin polyether; the mass of the acrylic acid accounts for 15 percent of the mass of the triblock phenol-amine resin polyether; the esterification reaction temperature is 155 ℃; the mass of the azodiisobutyronitrile accounts for 3.0 percent of the mass of the triblock phenolic amine resin polyether, the reaction temperature is 182 ℃, and the reaction time is 9 hours.
The preparation method of the demulsifier described in this example 1 comprises the following steps:
(1) uniformly mixing a silicone oil modified phenolic amine resin polyether demulsifier, an acrylic acid modified triblock phenolic amine resin polyether demulsifier, tetradecylamidopropyl hydroxypropyl sulphobetaine and water according to a certain mass ratio to obtain a first mixed solution;
(2) dissolving the ionic liquid in diethylene glycol mono-n-butyl ether, and stirring and mixing for 30min at 55 ℃ to obtain a second mixed solution;
(3) and (3) adding the second mixed solution prepared in the step (2) into the first mixed solution prepared in the step (1), and stirring at 40 ℃ for 30min to prepare the demulsifier.
Wherein:
the mixing temperature in the step (1) is 60 ℃, and the mixing time is 45 min.
Example 2
The demulsifier described in this example 2 is composed of, by mass, 20% of a silicone oil-modified phenolic amine resin polyether demulsifier, 33% of an acrylic acid-modified triblock phenolic amine resin polyether demulsifier, 5% of an ionic liquid, 0.6% of tetradecylamidopropyl hydroxypropyl sulfobetaine, 12% of diethylene glycol mono n-butyl ether, and the balance water.
Wherein:
the ionic liquid is bromo-1-octyl-2, 3-dimethyl imidazole.
Bromo-1-octyl-2, 3-dimethyl imidazole is added as ionic liquid, can reach an oil-water interface quickly, and reduces the tension of the oil-water interface.
The preparation method of the silicone oil modified phenol amine resin polyether demulsifier comprises the following steps:
(1) adding phenolic amine resin and an alkali catalyst into a high-pressure reaction kettle, stirring and heating to 90 ℃, vacuumizing and replacing with nitrogen, controlling the pressure at-0.20 MPa, continuously heating to 125 ℃, introducing propylene oxide for reaction, keeping the pressure in the high-pressure reaction kettle at 0.27MPa, reacting for a period of time, introducing ethylene oxide when the pressure is reduced to-0.20 MPa, keeping the pressure in the high-pressure reaction kettle at 0.21MPa, keeping the reaction temperature at 113 ℃, and finishing the reaction when the pressure is reduced to-0.20 MPa to prepare diblock phenolic amine resin polyether;
(2) modification of silicone oils
And (3) dropwise adding methyl ethoxy silicone oil and oleic acid into the dehydrated diblock phenol-amine resin polyether, reacting at 115 ℃ for 65min after dropwise adding, and then carrying out reduced pressure distillation reaction for 20min to prepare the silicone oil modified phenol-amine resin polyether demulsifier.
Wherein:
the preparation method of the phenolic amine resin in the step (1) comprises the following steps: dripping a formaldehyde solution into a mixed system of 2, 2-bis (4-hydroxyphenyl) propane and diethylenetriamine, keeping the temperature at 35 ℃ for reaction for 3h, then adding xylene, heating to 105 ℃, carrying out high-temperature dehydration reaction for 3.5h, and removing the xylene to prepare the phenolic amine resin.
Wherein: the mass ratio of the 2, 2-bis (4-hydroxyphenyl) propane, the diethylenetriamine and the formaldehyde is 1:4: 4.
In the step (1), the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide is 100%, wherein: the phenolic amine resin content is 4.5%, ethylene oxide content is 17.5%, and propylene oxide content is 78%.
The alkali catalyst in the step (1) is sodium hydroxide; the mass of the added base catalyst accounts for 0.5 percent of the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide.
The dehydration treatment in the step (2) is to heat the diblock phenol amine resin to 105 ℃ and perform distillation dehydration treatment under reduced pressure for 45 minutes.
The mass ratio of the diblock phenol amine resin polyether, the methyl ethoxy silicone oil and the oleic acid in the step (2) is 1:2.2: 0.05.
Through methyl ethoxy silicone oil modification, the molecular weight of the diblock polyether is increased, the surface tension of the prepared phenolic amine resin polyether demulsifier is reduced, and the hydrophobicity is improved.
The preparation method of the acrylic acid modified triblock phenol amine resin polyether demulsifier comprises the following steps:
(1) adding phenolic amine resin and an alkali catalyst into a high-pressure reaction kettle, stirring and heating to 90 ℃, vacuumizing and replacing with nitrogen, controlling the pressure at-0.20 MPa, continuously heating to 125 ℃, introducing propylene oxide for reaction, keeping the pressure in the high-pressure reaction kettle at 0.27MPa, reacting for a period of time, introducing ethylene oxide when the pressure is reduced to-0.20 MPa, keeping the pressure in the high-pressure reaction kettle at 0.21MPa, keeping the reaction temperature at 113 ℃, and finishing the reaction when the pressure is reduced to-0.20 MPa to prepare diblock phenolic amine resin polyether;
(2) introducing propylene oxide to react for a period of time, keeping the pressure in the high-pressure reaction kettle at 0.27MPa and the reaction temperature at 125 ℃, and performing post-treatment to obtain triblock phenol-amine resin polyether after the reaction is finished when the pressure is reduced to-0.20 MPa;
(3) and (3) dissolving the triblock phenolic amine resin polyether prepared in the step (2) in a toluene solution, adding acrylic acid to perform esterification reaction by using dodecylbenzene sulfonic acid as a catalyst, adding azobisisobutyronitrile to perform polymerization reaction after the esterification reaction is finished, and performing post-treatment to prepare the acrylic acid modified triblock phenolic amine resin polyether.
Wherein:
the preparation method of the phenolic amine resin in the step (1) comprises the following steps: dripping a formaldehyde solution into a mixed system of 2, 2-bis (4-hydroxyphenyl) propane and diethylenetriamine, keeping the temperature at 35 ℃ for reaction for 3h, then adding xylene, heating to 105 ℃, carrying out high-temperature dehydration reaction for 3.5h, and removing the xylene to prepare the phenolic amine resin.
Wherein: the mass ratio of the 2, 2-bis (4-hydroxyphenyl) propane, the diethylenetriamine and the formaldehyde is 1:4: 4.
In the step (1), the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide is 100%, wherein: the phenolic amine resin content is 4.5%, ethylene oxide content is 17.5%, and propylene oxide content is 78%.
The alkali catalyst in the step (1) is one or a mixture of more of potassium hydroxide, sodium hydroxide or sodium ethoxide; the mass of the added base catalyst accounts for 0.5 percent of the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide.
The mass ratio of the propylene oxide added in the step (2) to the propylene oxide added in the step (1) is 3.0: 1.
The mass of the dodecylbenzene sulfonic acid in the step (3) accounts for 0.9 percent of the mass of the triblock phenol amine resin polyether; the mass of the acrylic acid accounts for 13 percent of the mass of the triblock phenol-amine resin polyether; the esterification reaction temperature is 150 ℃; the mass of the azodiisobutyronitrile accounts for 3.2 percent of the mass of the triblock phenolic amine resin polyether, the reaction temperature is 185 ℃, and the reaction time is 8.5 hours.
The preparation method of the demulsifier described in this example 2 comprises the following steps:
(1) uniformly mixing a silicone oil modified phenolic amine resin polyether demulsifier, an acrylic acid modified triblock phenolic amine resin polyether demulsifier, tetradecylamidopropyl hydroxypropyl sulphobetaine and water according to a certain mass ratio to obtain a first mixed solution;
(2) dissolving the ionic liquid in diethylene glycol mono-n-butyl ether, and stirring and mixing at 50 ℃ for 35min to obtain a second mixed solution;
(3) and (3) adding the second mixed solution prepared in the step (2) into the first mixed solution prepared in the step (1), and stirring at 43 ℃ for 25min to prepare the demulsifier.
Wherein:
the mixing temperature in the step (1) is 62 ℃, and the mixing time is 42 min.
Example 3
The demulsifier described in this example 3 comprises, by mass, 25% of a silicone oil-modified phenolic amine resin polyether demulsifier, 30% of an acrylic acid-modified triblock phenolic amine resin polyether demulsifier, 8% of an ionic liquid, 0.7% of tetradecanamide propyl hydroxypropyl sulfobetaine, 15% of diethylene glycol mono-n-butyl ether, and the balance water.
Wherein:
the ionic liquid is bromo-1-octyl-2, 3-dimethyl imidazole.
Bromo-1-octyl-2, 3-dimethyl imidazole is added as ionic liquid, can reach an oil-water interface quickly, and reduces the tension of the oil-water interface.
The preparation method of the silicone oil modified phenol amine resin polyether demulsifier comprises the following steps:
(1) adding phenolic amine resin and an alkali catalyst into a high-pressure reaction kettle, stirring and heating to 92 ℃, vacuumizing and replacing with nitrogen, controlling the pressure at-0.20 MPa, continuously heating to 127 ℃, introducing propylene oxide for reaction, keeping the pressure in the high-pressure reaction kettle at 0.30MPa, reacting for a period of time, introducing ethylene oxide when the pressure is reduced to-0.20 MPa, keeping the pressure in the high-pressure reaction kettle at 0.23MPa, keeping the reaction temperature at 115 ℃, and finishing the reaction when the pressure is reduced to-0.20 MPa to prepare diblock phenolic amine resin polyether;
(2) modification of silicone oils
And (3) dropwise adding methyl ethoxy silicone oil and oleic acid into the dehydrated diblock phenol-amine resin polyether, reacting at 116 ℃ for 60min after dropwise adding is finished, and then carrying out reduced pressure distillation reaction for 22min to prepare the silicone oil modified phenol-amine resin polyether demulsifier.
Wherein:
the preparation method of the phenolic amine resin in the step (1) comprises the following steps: dripping formaldehyde solution into a mixed system of 2, 2-bis (4-hydroxyphenyl) propane and diethylenetriamine, keeping the temperature at 38 ℃ for reaction for 2.5h, then adding dimethylbenzene, heating to 100 ℃, carrying out high-temperature dehydration reaction for 4h, and removing the dimethylbenzene to prepare the phenolic amine resin.
Wherein: the mass ratio of the 2, 2-bis (4-hydroxyphenyl) propane, the diethylenetriamine and the formaldehyde is 1: 6: 5.
In the step (1), the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide is 100%, wherein: 5.5 percent of phenolic amine resin, 17.5 percent of ethylene oxide and 77 percent of propylene oxide.
The alkali catalyst in the step (1) is sodium ethoxide; the mass of the added base catalyst accounts for 0.7 percent of the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide.
The dehydration treatment in the step (2) is to heat the diblock phenol amine resin to 105 ℃ and perform distillation dehydration treatment under reduced pressure for 45 minutes.
The mass ratio of the diblock phenol amine resin polyether, the methyl ethoxy silicone oil and the oleic acid in the step (2) is 1:2.3: 0.07.
Through methyl ethoxy silicone oil modification, the molecular weight of the diblock polyether is increased, the surface tension of the prepared phenolic amine resin polyether demulsifier is reduced, and the hydrophobicity is improved.
The preparation method of the acrylic acid modified triblock phenol amine resin polyether demulsifier comprises the following steps:
(1) adding phenolic amine resin and an alkali catalyst into a high-pressure reaction kettle, stirring and heating to 92 ℃, vacuumizing and replacing with nitrogen, controlling the pressure at-0.20 MPa, continuously heating to 127 ℃, introducing propylene oxide for reaction, keeping the pressure in the high-pressure reaction kettle at 0.30MPa, reacting for a period of time, introducing ethylene oxide when the pressure is reduced to-0.20 MPa, keeping the pressure in the high-pressure reaction kettle at 0.23MPa, keeping the reaction temperature at 115 ℃, and finishing the reaction when the pressure is reduced to-0.20 MPa to prepare diblock phenolic amine resin polyether;
(2) introducing propylene oxide to react for a period of time, keeping the pressure in the high-pressure reaction kettle at 0.30MPa and the reaction temperature at 127 ℃, and performing post-treatment to obtain triblock phenol-amine resin polyether after the reaction is finished when the pressure is reduced to-0.20 MPa;
(3) and (3) dissolving the triblock phenolic amine resin polyether prepared in the step (2) in a toluene solution, adding acrylic acid to perform esterification reaction by using dodecylbenzene sulfonic acid as a catalyst, adding azobisisobutyronitrile to perform polymerization reaction after the esterification reaction is finished, and performing post-treatment to prepare the acrylic acid modified triblock phenolic amine resin polyether.
Wherein:
the preparation method of the phenolic amine resin in the step (1) comprises the following steps: dripping formaldehyde solution into a mixed system of 2, 2-bis (4-hydroxyphenyl) propane and diethylenetriamine, keeping the temperature at 38 ℃ for reaction for 2.5h, then adding dimethylbenzene, heating to 100 ℃, carrying out high-temperature dehydration reaction for 4h, and removing the dimethylbenzene to prepare the phenolic amine resin.
Wherein: the mass ratio of the 2, 2-bis (4-hydroxyphenyl) propane, the diethylenetriamine and the formaldehyde is 1: 6: 5.
In the step (1), the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide is 100%, wherein: 5.5 percent of phenolic amine resin, 17.5 percent of ethylene oxide and 77 percent of propylene oxide.
The alkali catalyst in the step (1) is sodium ethoxide; the mass of the added base catalyst accounts for 0.7 percent of the sum of the mass of the phenolic amine resin, the mass of the ethylene oxide and the mass of the propylene oxide.
The mass ratio of the propylene oxide added in the step (2) to the propylene oxide added in the step (1) is 3.2: 1.
The mass of the dodecylbenzene sulfonic acid in the step (3) accounts for 1.0 percent of the mass of the triblock phenol amine resin polyether; the mass of the acrylic acid accounts for 15 percent of the mass of the triblock phenol-amine resin polyether; the esterification reaction temperature is 155 ℃; the mass of the azodiisobutyronitrile accounts for 3.5 percent of that of the triblock phenolic amine resin polyether, the reaction temperature is 183 ℃, and the reaction time is 9 hours.
The preparation method of the demulsifier described in this embodiment 3 comprises the following steps:
(1) uniformly mixing a silicone oil modified phenolic amine resin polyether demulsifier, an acrylic acid modified triblock phenolic amine resin polyether demulsifier, tetradecylamidopropyl hydroxypropyl sulphobetaine and water according to a certain mass ratio to obtain a first mixed solution;
(2) dissolving the ionic liquid in diethylene glycol mono-n-butyl ether, and stirring and mixing for 35min at 55 ℃ to obtain a second mixed solution;
(3) and (3) adding the second mixed solution prepared in the step (2) into the first mixed solution prepared in the step (1), and stirring at 45 ℃ for 25min to prepare the demulsifier.
Wherein:
the mixing temperature in the step (1) is 62 ℃, and the mixing time is 40 min.
Comparative example 1
The preparation method of the demulsifier of the comparative example 1 is the same as that of the example 1, and the only difference is that the raw material composition is different, and the demulsifier of the comparative example 1 comprises, by mass, 22% of a silicone oil-modified phenolic amine resin polyether demulsifier, 35% of an acrylic acid-modified triblock phenolic amine resin polyether demulsifier, 14% of diethylene glycol mono-n-butyl ether and the balance of water.
Comparative example 2
The preparation method of the demulsifier of the comparative example 2 is the same as that of the example 1, and the only difference is that the raw material composition is different, and the demulsifier of the comparative example 2 comprises 57% of acrylic acid modified triblock phenolic amine resin polyether demulsifier, 6% of ionic liquid, 0.5% of tetradecylamidopropyl hydroxypropyl sulphobetaine, 14% of diethylene glycol mono-n-butyl ether and the balance of water by mass percent; the ionic liquid is bromo-1-octyl-2, 3-dimethyl imidazole.
Comparative example 3
The preparation method of the demulsifier of the comparative example 3 is the same as that of the example 1, and the only difference is that the raw materials have different compositions, and the demulsifier of the comparative example 3 comprises 57% of silicone oil modified phenolic amine resin polyether demulsifier, 6% of ionic liquid, 0.5% of tetradecylamidopropyl hydroxypropyl sulphobetaine, 14% of diethylene glycol mono-n-butyl ether and the balance of water by mass percent; the ionic liquid is bromo-1-octyl-2, 3-dimethyl imidazole.
The demulsifiers prepared in examples 1-3 and comparative examples 1-3 were tested for application properties, and the results are shown in table 1 below:
remarking:
1. the method for measuring the dehydration rate comprises the following steps:
(1) before the crude oil emulsion is used, the volume water content of the crude oil emulsion is firstly tested; (2) pouring the prepared crude oil emulsion into a measuring cylinder with a plug to reach the scale of 80 ml; (3) placing the crude oil emulsion into a constant-temperature water bath with the temperature lower than the preset dehydration temperature by 5 ℃, wherein the liquid level of the water bath is higher than that of the crude oil emulsion in the measuring cylinder with a plug, heating the constant-temperature water bath to be consistent with the actual operation temperature of a station, and keeping the constant temperature for 0.5 h; (4) adding 100mg/L of crude oil demulsifier solution prepared into the measuring cylinder with the plug by using a pipette; (5) turning the bottle cap, reversing the measuring cylinder with the plug for 5 times, slowly loosening the bottle cap, deflating, turning the bottle cap again, oscillating manually for 100 +/-10 times, wherein the amplitude is more than 10 cm, loosening the bottle cap after fully mixing uniformly, and placing the measuring cylinder with the plug in a constant-temperature water bath again for standing and settling; (6) the amount of water phase removed was recorded for 30 min.
2. Calculation of crude oil dehydration rate for 30 minutes:
S= V/( V0× WV) X is 100%; in the formula: s-dehydration rate of crude oil demulsifier,%; v, water yield of the crude oil emulsion after 30min sedimentation, mL; v0 -crude oil emulsion volume, mL; wVVolume water ratio of crude oil emulsion.
3. Water phase cleanliness: and (3) observing the color of the removed water phase when the mixture is settled for 30min, and judging the cleanliness of the water phase according to the following grades: level 1: clear water is removed and is transparent or milk white; and 2, stage: the dehydrated water is relatively clear and is light yellow; and 3, level: the dehydrated water is turbid, yellow and brown; 4, level: turbid, deep brown or black.
4. And (3) measuring the water content of the upper oil phase: and after 24h, a liquid extractor is used for inserting the middle position of the upper oil phase of the measuring cylinder with the plug after the dehydration rate measurement is finished, the middle position is fixed, an aurilave is inserted into a silica gel tube, about 10mL of crude oil is slightly sucked, and the fluctuation of an oil-water interface cannot be caused. Slowly moving the liquid taking device out of the measuring cylinder with the plug, firstly adding petroleum ether into the centrifugal tube to 50% of scales, then putting crude oil into the centrifugal tube to 100% of scales, shaking up and down, uniformly mixing, putting into a centrifugal machine, reading the scale value of outlet water in the centrifugal tube when the rotating speed of the centrifugal machine is 2000r/min and the centrifugal time is 10min, and measuring the water content of the crude oil according to GB/T8929.
Claims (6)
1. A demulsifier, characterized by: the emulsion comprises, by mass, 20-25% of silicone oil modified phenolic amine resin polyether demulsifier, 30-35% of acrylic acid modified triblock phenolic amine resin polyether demulsifier, 5-8% of ionic liquid, 0.5-0.7% of tetradecylamidopropyl hydroxypropyl sulfobetaine, 12-15% of diethylene glycol mono-n-butyl ether and the balance of water;
the ionic liquid is bromo-1-octyl-2, 3-dimethyl imidazole;
the preparation method of the silicone oil modified phenol amine resin polyether demulsifier comprises the following steps:
(1) adding phenolic amine resin and an alkali catalyst into a high-pressure reaction kettle, stirring and heating to 90-95 ℃, vacuumizing and replacing with nitrogen, controlling the pressure to be-0.20-0.15 MPa, continuously heating to 125-0.15 MPa, introducing epoxypropane for reaction, keeping the pressure in the high-pressure reaction kettle to be 0.27-0.30 MPa, reacting for a period of time, introducing epoxyethane when the pressure is reduced to-0.20-0.15 MPa, keeping the pressure in the high-pressure reaction kettle to be 0.21-0.23MPa, keeping the reaction temperature to be 113-115 ℃, and finishing the reaction when the pressure is reduced to-0.20-0.15 MPa to prepare the diblock phenolic amine resin polyether;
(2) modification of silicone oils
Dropwise adding methyl ethoxy silicone oil and oleic acid into the dehydrated diblock phenol-amine resin polyether, reacting at the temperature of 115-118 ℃ for 55-65min after the dropwise adding is finished, and then carrying out reduced pressure distillation reaction for 20-25min to prepare a silicone oil modified phenol-amine resin polyether demulsifier; wherein: the dehydration treatment is to heat the diblock phenol amine resin to 100-105 ℃ and carry out reduced pressure distillation dehydration treatment for 45-50 minutes;
the preparation method of the acrylic acid modified triblock phenol amine resin polyether demulsifier comprises the following steps:
(1) adding phenolic amine resin and an alkali catalyst into a high-pressure reaction kettle, stirring and heating to 90-95 ℃, vacuumizing and replacing with nitrogen, controlling the pressure to be-0.20-0.15 MPa, continuously heating to 125-0.15 MPa, introducing epoxypropane for reaction, keeping the pressure in the high-pressure reaction kettle to be 0.27-0.30 MPa, reacting for a period of time, introducing epoxyethane when the pressure is reduced to-0.20-0.15 MPa, keeping the pressure in the high-pressure reaction kettle to be 0.21-0.23MPa, keeping the reaction temperature to be 113-115 ℃, and finishing the reaction when the pressure is reduced to-0.20-0.15 MPa to prepare the diblock phenolic amine resin polyether;
(2) introducing propylene oxide to react for a period of time, keeping the pressure in the high-pressure reaction kettle at 0.27-0.30 MPa and the reaction temperature at 125-127 ℃, and completing the reaction when the pressure is reduced to-0.20-0.15 MPa to prepare the triblock phenol-amine resin polyether;
(3) dissolving the triblock phenol-amine resin polyether prepared in the step (2) in a toluene solution, adding acrylic acid to perform esterification reaction by using dodecylbenzene sulfonic acid as a catalyst, adding azobisisobutyronitrile to perform polymerization reaction after the esterification reaction is finished, and performing post-treatment to prepare acrylic acid modified triblock phenol-amine resin polyether;
wherein:
the diblock phenol amine resin polyether prepared in the step (1) of the preparation method of the silicone oil modified phenol amine resin polyether demulsifier is the same as the diblock phenol amine resin polyether prepared in the step (1) of the preparation method of the acrylic acid modified triblock phenol amine resin polyether demulsifier, wherein the step (1) of the diblock phenol amine resin polyether is as follows:
the preparation method of the phenolic amine resin comprises the following steps: dripping formaldehyde solution into a mixed system of 2, 2-bis (4-hydroxyphenyl) propane and diethylenetriamine, carrying out heat preservation reaction at 35-38 ℃ for 2.5-3h, then adding dimethylbenzene, heating to 100-105 ℃, carrying out high-temperature dehydration reaction for 3.5-4h, removing dimethylbenzene, and preparing the phenolic amine resin, wherein: the mass ratio of the 2, 2-bis (4-hydroxyphenyl) propane, the diethylenetriamine and the formaldehyde is 1:4-6: 4-6;
the mass sum of the phenolic amine resin, the ethylene oxide and the propylene oxide is 100%, wherein: 3.5 to 5.5 percent of phenolic amine resin, 15 to 18 percent of ethylene oxide and 77 to 80 percent of propylene oxide;
the alkali catalyst is one or a mixture of more of potassium hydroxide, sodium hydroxide or sodium ethoxide; the mass of the added base catalyst accounts for 0.5 to 0.7 percent of the mass sum of the phenolic amine resin, the ethylene oxide and the propylene oxide.
2. The demulsifier of claim 1, wherein: the emulsion comprises, by mass, 22% of silicone oil modified phenolic amine resin polyether demulsifier, 35% of acrylic acid modified triblock phenolic amine resin polyether demulsifier, 6% of ionic liquid, 0.5% of tetradecylamidopropyl hydroxypropyl sulphobetaine, 14% of diethylene glycol mono-n-butyl ether and the balance of water.
3. The demulsifier of claim 1, wherein: the preparation method of the silicone oil modified phenolic amine resin polyether demulsifier comprises the step (2) of mixing the diblock phenolic amine resin polyether, the methyl ethoxy silicone oil and the oleic acid in a mass ratio of 1:2.2-2.4: 0.05-0.07.
4. The demulsifier of claim 1, wherein: in the preparation method of the acrylic acid modified triblock phenol-amine resin polyether, the mass ratio of the propylene oxide added in the step (2) to the propylene oxide added in the step (1) is 3.0-3.3: 1;
the mass of the dodecylbenzene sulfonic acid in the step (3) accounts for 0.8-1.0% of the mass of the triblock phenol amine resin polyether; the mass of the acrylic acid accounts for 13-15% of that of the triblock phenol-amine resin polyether; the esterification reaction temperature is 150-155 ℃; the mass of the azodiisobutyronitrile accounts for 3.0-3.5% of that of the triblock phenolic amine resin polyether, the reaction temperature is 182 ℃ and 185 ℃, and the reaction time is 8.5-9 h.
5. A method of preparing the demulsifier of claim 1, comprising the steps of:
(1) uniformly mixing a silicone oil modified phenolic amine resin polyether demulsifier, an acrylic acid modified triblock phenolic amine resin polyether demulsifier, tetradecylamidopropyl hydroxypropyl sulphobetaine and water according to a certain mass ratio to obtain a first mixed solution;
(2) dissolving the ionic liquid in diethylene glycol mono-n-butyl ether, and stirring and mixing at 50-55 ℃ for 30-35min to obtain a second mixed solution;
(3) and (3) adding the second mixed solution prepared in the step (2) into the first mixed solution prepared in the step (1), and stirring at 40-45 ℃ for 25-30min to prepare the demulsifier.
6. The method for preparing the demulsifier of claim 5, which comprises the following steps: the mixing temperature in the step (1) is 60-65 ℃, and the mixing time is 40-45 min.
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| CN102993434A (en) * | 2012-12-28 | 2013-03-27 | 山东大学 | Preparation method of crude oil rapid demulsifying agent |
| CN107557055A (en) * | 2017-10-23 | 2018-01-09 | 天津正达科技有限责任公司 | A kind of preparation method of modified polyether crude oil rapid demulsifier |
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| CN102993434A (en) * | 2012-12-28 | 2013-03-27 | 山东大学 | Preparation method of crude oil rapid demulsifying agent |
| CN107557055A (en) * | 2017-10-23 | 2018-01-09 | 天津正达科技有限责任公司 | A kind of preparation method of modified polyether crude oil rapid demulsifier |
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