CN110734543B - Naphthol modified phenolic resin and preparation method and application thereof - Google Patents
Naphthol modified phenolic resin and preparation method and application thereof Download PDFInfo
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- CN110734543B CN110734543B CN201911092430.XA CN201911092430A CN110734543B CN 110734543 B CN110734543 B CN 110734543B CN 201911092430 A CN201911092430 A CN 201911092430A CN 110734543 B CN110734543 B CN 110734543B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- 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 discloses naphthol modified phenolic resin and a preparation method and application thereof. The naphthol modified phenolic resin has a structure shown in a formula I
Description
Technical Field
The invention relates to the field of oil-water separation of coal coking and petrochemical industry, in particular to naphthol modified phenolic resin and a preparation method and application thereof.
Background
The coke-oven plant generally adopts the circulating ammonia water to cool the raw coke oven gas generated in the coking process, and a large amount of mixture of the ammonia water and the coal tar is generated at the moment. The ammonia water and the coal tar are fully mixed at a higher temperature, the raw gas carries some fine coal dust and coke dust particles, and the coal tar contains a large amount of asphaltene, so that the coal tar and the ammonia water form a stable emulsion. The ammonia water and the coal tar are separated, a mode of combining gravity settling and steam heating is generally adopted, and the content of the coal tar water is required to be reduced to below 4 percent after the coal tar is subjected to a mechanical clarifying tank.
The prior art discloses a polyether crude oil demulsifier taking linear alkyl phenolic resin as an initiator, which is developed mainly aiming at the aggravation of emulsification caused by the higher and higher blending ratio of the current inferior crude oil and is suitable for demulsification of thick oil.
Compared with heavy oil, the coal tar has higher asphaltene content, low paraffin content, more heteroatoms and higher demulsification difficulty. Therefore, when the crude oil demulsifier suitable for demulsifying the thickened oil is used for coal tar, the dehydration speed is low, and the dehydration amount is low. This is mainly due to the low affinity of the kerophilic medium chain alkyl groups for asphaltenes in coal tar, which has a very low paraffin content.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide a naphthol modified phenolic resin, a preparation method thereof, and an application thereof, wherein a polyether demulsifier is prepared by using the naphthol modified phenolic resin as an initiator to improve the acting force of the lipophilic group of the demulsifier and coal tar, and more aromatic ring structures can accelerate the demulsifier to diffuse to an oil-water interface.
In order to achieve the above object, one aspect of the present invention provides a naphthol modified phenolic resin having a structure represented by formula I
Wherein n is an integer of 0 to 9.
In order to achieve the above object, another aspect of the present invention provides a method for preparing naphthol modified phenolic resin, comprising the following steps:
mixing naphthol, phenol and aldehyde according to the ratio of (0.1-2): (5-10): (5-10) uniformly mixing at a rotating speed of 40-200r/mn, wherein the phenol can be cresol, xylenol, resorcinol, tert-butylphenol, bisphenol A and the like, then adding a catalyst under the condition of keeping the rotating speed, heating to 70-110 ℃ within 5-40 minutes, carrying out polycondensation reaction at constant temperature for 2-5 hours, and carrying out pressure reduction and dehydration after the reaction is finished.
Further, the catalyst is hydrochloric acid, oxalic acid, sulfuric acid, oxalic acid, benzenesulfonic acid, petroleum sulfonic acid, chloroacetic acid; the aldehyde is 35-50 wt% of formaldehyde solution or paraformaldehyde.
Further, when the aldehyde is formaldehyde solution, the method also comprises the step of pressure reduction dehydration after the reaction is finished.
In order to achieve the above object, the present invention provides a polyether demulsifier using naphthol modified phenolic resin as an initiator, wherein the formula of the polyether demulsifier is A- (PO)a-(EO)b-(PO)cWherein A is of formula I, PO is- (CH)2-O-CH2CH2) -, EO is- (O-CH)2CH2)-。
Further, wherein A/(PO)aThe mass ratio of (A) is 1/200-1/30, preferably 1/120; (PO)a/(EO)bThe mass ratio of (A) is 3-8, preferably 6; (PO)c/(PO)aThe mass ratio is 0-6, preferably 3.
Further, wherein the naphthol is 1-naphthol, 2-methyl-1-naphthol, 2-naphthol, 1-methyl-2-naphthol, or 6-ethyl-2-naphthol.
In order to achieve the above object, the present invention further provides a preparation method of the above polyether demulsifier, comprising the following steps:
weighing 1 part of phenolic resin, 30-200 parts of epoxypropane and 0.3-2 parts of potassium hydroxide solid, sequentially adding into a reaction kettle, closing a reaction kettle cover, and purging with nitrogen for 2-3 minutes; after the purging is finished, heating to 110-130 ℃ within 1-2 hours, and carrying out polymerization reaction for 1-2 hours at the temperature; after the reaction is finished, cooling the temperature to room temperature, adding 10-25 parts of ethylene oxide again, closing the reaction kettle cover, and purging with nitrogen for 2-3 minutes; after the purging is finished, heating to 110-130 ℃ within 1-2 hours, and reacting for 1-2 hours at the temperature; after the reaction is finished, the diblock polyether with an initiator-PO-EO structure is obtained.
Further, wherein the method further comprises: after the reaction generates the diblock polyether, adding propylene oxide, heating to 120-135 ℃ within 1-2 hours, and reacting for 0.5-1.5 hours at the temperature to obtain triblock polyether with an initiator-PO-EO-PO structure; the addition amount of the propylene oxide is less than 1200 parts.
Further wherein the nitrogen has a purity of 99.5%, 99.99%, or 99.999%.
The invention has the following beneficial effects:
according to the invention, the benzene ring content of the phenolic resin is increased through naphthol modification, the aromaticity of the demulsifier is improved, the demulsifier molecules can be favorably acted with the heavy oil or coal tar with high aromatic compound content, and the heavy oil or coal tar can be more quickly diffused to the surface of oil water, so that the demulsification capability of the demulsifier is improved. The demulsifier prepared by the invention is a clear water type demulsifier, and after the oil-water emulsion is separated, the water quality is clear, and the oil content and COD in the water are low. The demulsifier can also adjust the hydrophilic-lipophilic balance value of the demulsifier by changing the temperature and the addition amount of each reactant, and select the optimal proportion for different types of oil such as thickened oil or coal tar.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Materials, reagents and the like used in the following examples are commercially available.
Example 1
The embodiment provides a preparation method of a polyether demulsifier, which comprises the following steps:
(1) preparing a naphthol modified phenolic resin initiator: 5.4g of naphthol, 108g of phenol and 80g of 37 wt% aqueous formaldehyde solution are sequentially added into a three-necked flask, and uniformly mixed at a rotating speed of 80r/mn, then 1mL of 5M hydrochloric acid is added while the rotating speed is kept, the temperature is raised to 95 ℃ within 20 minutes, and the polycondensation reaction is carried out at the constant temperature for 3.5 hours. And after the reaction is finished, performing vacuum dehydration to obtain the naphthol modified phenolic resin.
(2) Sequentially adding 1.0g of naphthol modified phenolic resin, 102.0g of propylene oxide and 0.5g of potassium hydroxide serving as a catalyst into a high-pressure reaction kettle, closing a reaction kettle cover (screwing a bolt to seal the reaction kettle), and purging with nitrogen (the purity is 99.5%) for 2 minutes (so as to replace the air in the kettle for three times); after the purging is finished, the air inlet valve and the air outlet valve are closed, stirring and electric heating are started, the temperature in the reaction kettle is heated to 120 ℃ within 2 hours, and the polymerization reaction is carried out for 1 hour at the temperature. And stopping heating, cooling the temperature of the reaction kettle to room temperature, adding 34.0g of ethylene oxide into the reaction kettle again, closing the cover of the reaction kettle, purging with nitrogen for 2 minutes (for replacing air in the reaction kettle for three times), and heating to 120 ℃ within 1 hour after purging is finished, and continuing to react for 1 hour. After the reaction is finished, the naphthol modified phenolic resin diblock polyether demulsifier with an initiator-PO-EO structure is obtained.
Example 2
The embodiment provides a preparation method of a polyether demulsifier, which comprises the following steps:
(1) preparing a naphthol modified phenolic resin initiator: 10.8g of naphthol, 108g of cresol and 72g of 37 wt% aqueous formaldehyde solution are sequentially added into a three-necked flask, and are uniformly mixed at a rotating speed of 50r/mn, then 1mL of 5M hydrochloric acid is added under the rotating speed, the temperature is raised to 95 ℃ within 20 minutes, and the polycondensation reaction is carried out at the constant temperature for 3.5 hours. And after the reaction is finished, performing vacuum dehydration to obtain the naphthol modified phenolic resin.
(2) Adding 1.0g of naphthol modified phenolic resin, 102.0g of propylene oxide and 0.5g of potassium hydroxide serving as a catalyst into a high-pressure reaction kettle, closing a reaction kettle cover (screwing a bolt to seal the reaction kettle), and purging with nitrogen (the purity is 99.5%) for 2 minutes (so as to replace the air in the kettle for three times); after the purging is finished, the air inlet valve and the air outlet valve are closed, stirring and electric heating are started, the temperature in the reaction kettle is heated to 120 ℃ within 2 hours, and polymerization reaction is carried out for 1 hour at the temperature. Then, the heating was stopped, 34.0g of ethylene oxide was again added to the reaction vessel after the temperature of the reaction vessel was lowered to room temperature, the reaction vessel lid was closed and purged with nitrogen for 2 minutes (to displace the air in the reaction vessel three times), and the reaction was continued at this temperature for 1 hour. After the reaction is finished, the naphthol modified phenolic resin diblock polyether demulsifier with an initiator-PO-EO structure is obtained.
Example 3
The embodiment provides a preparation method of a polyether demulsifier, which comprises the following steps:
(1) preparing a naphthol modified phenolic resin initiator: adding 16.2g of naphthol, 108g of phenol and 80g of 37 wt% aqueous formaldehyde solution into a three-neck flask in sequence, uniformly mixing at a rotating speed of 100r/mn, adding 2g of oxalic acid while keeping the rotating speed, heating to 95 ℃ within 20 minutes, and carrying out polycondensation reaction at the constant temperature for 3.5 hours. And after the reaction is finished, performing vacuum dehydration to obtain the naphthol modified phenolic resin.
(2) Sequentially adding 1.0g of naphthol modified phenolic resin, 102.0g of propylene oxide and 0.5g of potassium hydroxide serving as a catalyst into a high-pressure reaction kettle, closing a reaction kettle cover (screwing a bolt to seal the reaction kettle), and purging with nitrogen (the purity is 99.99%) for 2 minutes (so as to replace the air in the kettle for three times); after the purging is finished, the air inlet valve and the air outlet valve are closed, stirring and electric heating are started, the temperature in the reaction kettle is heated to 120 ℃ within 2 hours, and the polymerization reaction is carried out for 1 hour at the temperature. And stopping heating, cooling the temperature of the reaction kettle to room temperature, adding 34.0g of ethylene oxide into the reaction kettle again, closing the cover of the reaction kettle, purging with nitrogen for 2 minutes (for replacing air in the reaction kettle for three times), and heating to 120 ℃ within 1 hour after purging is finished, and continuing to react for 1 hour. After the reaction is finished, the naphthol modified phenolic resin diblock polyether demulsifier with an initiator-PO-EO structure is obtained.
Example 4
The embodiment provides a preparation method of a polyether demulsifier, which comprises the following steps:
(1) preparing a naphthol modified phenolic resin initiator: 5.4g of naphthol, 122g of xylenol and 72g of 37 wt% aqueous formaldehyde solution are sequentially added into a three-necked flask, and uniformly mixed at a rotating speed of 150r/mn, then 1mL of 5M hydrochloric acid is added while the rotating speed is kept, the temperature is raised to 95 ℃ within 20 minutes, and the polycondensation reaction is carried out at the constant temperature for 3.5 hours. And after the reaction is finished, performing vacuum dehydration to obtain the naphthol modified phenolic resin.
(2) Sequentially adding 1.0g of naphthol modified phenolic resin, 60.0g of propylene oxide and 0.3g of potassium hydroxide serving as a catalyst into a high-pressure reaction kettle, closing a reaction kettle cover (screwing a bolt to seal the reaction kettle), and purging with nitrogen (the purity is 99.5%) for 2 minutes (so as to replace the air in the kettle for three times); after the purging is finished, the air inlet valve and the air outlet valve are closed, stirring and electric heating are started, the temperature in the reaction kettle is heated to 120 ℃ within 2 hours, and the polymerization reaction is carried out for 1 hour at the temperature. And then stopping heating, after the temperature of the reaction kettle is reduced to room temperature, adding 20.0g of ethylene oxide into the reaction kettle again, closing the cover of the reaction kettle, purging with nitrogen for 2 minutes (to replace air in the reaction kettle for three times), and after purging is finished, heating to 120 ℃ within 1 hour and continuing to react for 1 hour. After the reaction is finished, the naphthol modified phenolic resin diblock polyether demulsifier with an initiator-PO-EO structure is obtained.
Example 5
The embodiment provides a preparation method of a polyether demulsifier, which comprises the following steps:
(1) preparing a naphthol modified phenolic resin initiator: 10.8g of naphthol, 108g of phenol and 80g of 37 wt% aqueous formaldehyde solution are sequentially added into a three-necked flask, and uniformly mixed at a rotating speed of 100r/mn, then 1mL of 5M hydrochloric acid is added while the rotating speed is kept, the temperature is raised to 95 ℃ within 20 minutes, and the polycondensation reaction is carried out at the constant temperature for 3.5 hours. And after the reaction is finished, performing vacuum dehydration to obtain the naphthol modified phenolic resin.
(2) Sequentially adding 1.0g of naphthol modified phenolic resin, 153.0g of propylene oxide and 0.8g of potassium hydroxide serving as a catalyst into a high-pressure reaction kettle, closing a reaction kettle cover (screwing a bolt to seal the reaction kettle), and purging with nitrogen (the purity is 99.5%) for 2 minutes (so as to replace the air in the kettle for three times); after the purging is finished, the air inlet valve and the air outlet valve are closed, stirring and electric heating are started, the temperature in the reaction kettle is heated to 120 ℃ within 2 hours, and the polymerization reaction is carried out for 1 hour at the temperature. And stopping heating, cooling the temperature of the reaction kettle to room temperature, adding 51.0g of ethylene oxide into the reaction kettle again, closing the cover of the reaction kettle, purging with nitrogen for 2 minutes (for replacing air in the reaction kettle for three times), and heating to 120 ℃ within 1 hour after purging is finished, and continuing to react for 1 hour. After the reaction is finished, the naphthol modified phenolic resin diblock polyether demulsifier with an initiator-PO-EO structure is obtained.
Example 6
The embodiment provides a preparation method of a polyether demulsifier, which comprises the following steps:
(1) preparing a naphthol modified phenolic resin initiator: 5.4g of naphthol, 108g of phenol and 80g of 37 wt% aqueous formaldehyde solution were added to a three-necked flask in this order, and the mixture was uniformly mixed at a rotation speed of 80r/mn, and then 1mL of 5M aqueous hydrochloric acid was added while maintaining the rotation speed, and the temperature was raised to 95 ℃ within 20 minutes, at which temperature a polycondensation reaction was carried out for 3.5 hours at a constant temperature. And after the reaction is finished, performing vacuum dehydration to obtain the naphthol modified phenolic resin.
(2) Sequentially adding 1.0g of naphthol modified phenolic resin, 102.0g of propylene oxide and 0.5g of potassium hydroxide serving as a catalyst into a high-pressure reaction kettle, closing a reaction kettle cover (screwing a bolt to seal the reaction kettle), and purging with nitrogen (the purity is 99.5%) for 2 minutes (so as to replace the air in the kettle for three times); after the purging is finished, the air inlet valve and the air outlet valve are closed, stirring and electric heating are started, the temperature in the reaction kettle is heated to 120 ℃ within 2 hours, and the polymerization reaction is carried out for 1 hour at the temperature. And stopping heating, cooling the temperature of the reaction kettle to room temperature, adding 34.0g of ethylene oxide into the reaction kettle again, closing the cover of the reaction kettle, purging with nitrogen for 2 minutes (for replacing air in the reaction kettle for three times), and heating to 120 ℃ within 1 hour after purging is finished, and continuing to react for 1 hour. And then stopping heating, after the temperature of the reaction kettle is reduced to room temperature, adding 102.0g of propylene oxide into the reaction kettle again, closing the cover of the reaction kettle, purging with nitrogen for 2 minutes (to replace air in the reaction kettle for three times), and after purging is finished, heating to 120 ℃ within 1 hour and continuing to react for 1 hour. After the reaction is finished, the initiator
Naphthol modified phenolic resin triblock polyether demulsifier with-PO-EO-PO' structure.
Example 7
The embodiment provides a preparation method of a polyether demulsifier, which comprises the following steps:
(1) preparing a naphthol modified phenolic resin initiator: 5.4g of naphthol, 108g of phenol and 80g of 37 wt% aqueous formaldehyde solution are sequentially added into a three-necked flask, and uniformly mixed at a rotation speed of 200r/mn, then 1mL of 5M hydrochloric acid is added while maintaining the rotation speed, the temperature is raised to 95 ℃ within 20 minutes, and polycondensation reaction is carried out at the constant temperature for 3.5 hours. And after the reaction is finished, performing vacuum dehydration to obtain the naphthol modified phenolic resin.
(2) Sequentially adding 1.0g of naphthol modified phenolic resin, 60.0g of propylene oxide and 0.5g of potassium hydroxide serving as a catalyst into a high-pressure reaction kettle, closing a reaction kettle cover (screwing a bolt to seal the reaction kettle), and purging with nitrogen (the purity is 99.5%) for 2 minutes (so as to replace the air in the kettle for three times); after the purging is finished, the air inlet valve and the air outlet valve are closed, stirring and electric heating are started, the temperature in the reaction kettle is heated to 120 ℃ within 2 hours, and the polymerization reaction is carried out for 1 hour at the temperature. Then the heating is stopped, 20.0g of ethylene oxide is added into the reaction kettle again when the temperature of the reaction kettle is reduced to room temperature, the cover of the reaction kettle is closed and is purged by nitrogen for 2 minutes (to replace the air in the reaction kettle for three times), and after the purging is finished, the reaction kettle is heated to 120 ℃ within 2 hours, and the reaction is continued for 1 hour at the temperature. Then stopping heating, after the temperature of the reaction kettle is reduced to room temperature, adding 120.0g of propylene oxide into the reaction kettle again, closing the cover of the reaction kettle, purging with nitrogen for 2 minutes (to replace air in the reaction kettle for three times), heating to 120 ℃ within 2 hours after purging, and continuing to react for 1 hour at the temperature. After the reaction is finished, the naphthol modified phenolic resin triblock polyether demulsifier with the structure of initiator-PO-EO-PO is obtained.
Example 8
The embodiment provides a preparation method of a polyether demulsifier, which comprises the following steps:
(1) preparing a naphthol modified phenolic resin initiator: 10.8g of naphthol, 108g of phenol and 80g of 37 wt% aqueous formaldehyde solution are sequentially added into a three-necked flask, and uniformly mixed at a rotating speed of 100r/mn, then 1mL of 5M hydrochloric acid is added while the rotating speed is kept, the temperature is raised to 95 ℃ within 20 minutes, and the polycondensation reaction is carried out at the constant temperature for 3.5 hours. And after the reaction is finished, performing vacuum dehydration to obtain the naphthol modified phenolic resin.
(2) Sequentially adding 1.0g of naphthol modified phenolic resin, 60.0g of propylene oxide and 0.5g of potassium hydroxide serving as a catalyst into a high-pressure reaction kettle, closing a reaction kettle cover (screwing a bolt to seal the reaction kettle), and purging with nitrogen (the purity is 99.999%) for 2 minutes (so as to replace the air in the kettle for three times); after the purging is finished, the air inlet valve and the air outlet valve are closed, stirring and electric heating are started, the temperature in the reaction kettle is heated to 120 ℃ within 2 hours, and the polymerization reaction is carried out for 1 hour at the temperature. Then the heating is stopped, 20.0g of ethylene oxide is added into the reaction kettle again when the temperature of the reaction kettle is reduced to room temperature, the cover of the reaction kettle is closed and is purged by nitrogen for 2 minutes (to replace the air in the reaction kettle for three times), and after the purging is finished, the reaction kettle is heated to 120 ℃ within 2 hours, and the reaction is continued for 1 hour at the temperature. Then stopping heating, cooling the temperature of the reaction kettle to room temperature, adding 180.0g of propylene oxide into the reaction kettle again, closing the cover of the reaction kettle, purging with nitrogen for 2 minutes (to replace air in the kettle for three times), heating to 120 ℃ within 2 hours after purging, and continuing to react for 1 hour at the temperature. After the reaction is finished, the naphthol modified phenolic resin triblock polyether demulsifier with the structure of initiator-PO-EO-PO is obtained.
Example 9
The embodiment provides a preparation method of a polyether demulsifier, which comprises the following steps:
(1) preparing a naphthol modified phenolic resin initiator: 16.2g of naphthol, 108g of phenol and 80g of 37 wt% aqueous formaldehyde solution are sequentially added into a three-necked flask, and uniformly mixed at a rotating speed of 100r/mn, then 1mL of 5M hydrochloric acid is added while the rotating speed is kept, the temperature is raised to 95 ℃ within 20 minutes, and the polycondensation reaction is carried out at the constant temperature for 3.5 hours. And after the reaction is finished, performing vacuum dehydration to obtain the naphthol modified phenolic resin.
(2) Sequentially adding 1.0g of naphthol modified phenolic resin, 102.0g of propylene oxide and 0.7g of catalyst potassium hydroxide into a high-pressure reaction kettle, closing a reaction kettle cover (screwing a bolt to seal the reaction kettle cover), and purging with nitrogen (the purity is 99.99%) for 2 minutes (so as to replace the air in the kettle for three times); after the purging is finished, the air inlet valve and the air outlet valve are closed, stirring and electric heating are started, the temperature in the reaction kettle is heated to 120 ℃ within 2 hours, and the polymerization reaction is carried out for 1 hour at the temperature. Then the heating is stopped, 51.0g of ethylene oxide is added into the reaction kettle again when the temperature of the reaction kettle is reduced to room temperature, the cover of the reaction kettle is closed and is purged by nitrogen for 2 minutes (to replace the air in the reaction kettle for three times), and after the purging is finished, the reaction kettle is heated to 120 ℃ within 2 hours, and the reaction is continued for 1 hour at the temperature. Then the heating is stopped, 102.0g of propylene oxide is added into the reaction kettle again when the temperature of the reaction kettle is reduced to room temperature, the cover of the reaction kettle is closed and is purged by nitrogen for 2 minutes (to replace the air in the reaction kettle for three times), and after the purging is finished, the reaction kettle is heated to 120 ℃ within 2 hours, and the reaction is continued for 1 hour at the temperature. After the reaction is finished, the naphthol modified phenolic resin triblock polyether demulsifier with the structure of initiator-PO-EO-PO is obtained.
Example 10
The embodiment provides a preparation method of a polyether demulsifier, which comprises the following steps:
(1) preparing a naphthol modified phenolic resin initiator: 16.2g of naphthol, 108g of phenol and 80g of 37 wt% aqueous formaldehyde solution are sequentially added into a three-necked flask, and uniformly mixed at a rotating speed of 150r/mn, then 1mL of 5M hydrochloric acid is added while the rotating speed is kept, the temperature is raised to 95 ℃ within 20 minutes, and the polycondensation reaction is carried out at the constant temperature for 3.5 hours. And after the reaction is finished, performing vacuum dehydration to obtain the naphthol modified phenolic resin.
(2) Sequentially adding 1.0g of naphthol modified phenolic resin, 102.0g of propylene oxide and 0.7g of catalyst potassium hydroxide into a high-pressure reaction kettle, closing a reaction kettle cover (screwing a bolt to seal the reaction kettle), and purging with nitrogen (the purity is 99.5%) for 2 minutes (so as to replace the air in the kettle for three times); after the purging is finished, closing the air inlet valve and the air outlet valve, starting stirring and electric heating, heating to 120 ℃ within 2 hours in the reaction kettle, and carrying out polymerization reaction for 1 hour at the temperature. And stopping heating, cooling the temperature of the reaction kettle to room temperature, adding 51.0g of ethylene oxide into the reaction kettle again, closing the cover of the reaction kettle, purging with nitrogen for 2 minutes (for replacing air in the reaction kettle for three times), and heating to 120 ℃ within 2 hours to continue the reaction for 1 hour. And stopping heating, cooling the reaction kettle to room temperature, adding 153.0g of propylene oxide into the reaction kettle again, closing the cover of the reaction kettle, purging with nitrogen for 2 minutes (to replace air in the reaction kettle for three times), and heating to 120 ℃ within 2 hours to continue the reaction for 1 hour. After the reaction is finished, the initiator
Naphthol modified phenolic resin triblock polyether demulsifier with-PO-EO-PO' structure.
Demulsification effect experiment of demulsifier
Taking three demulsifiers for thick oil dehydration, namely a phenolic resin F3111, a phenolic amine resin TA1531 and a P0I2440 demulsifier provided by a demulsifier company in Shandong as examples, wherein the three demulsifiers are respectively numbered as 1#, 2#, and 3#, and performing a dehydration comparison experiment with the demulsifier (numbered as 4#) synthesized in the embodiment 8 of the invention, taking a high-temperature coal tar emulsion provided by a company in Ningxia as a dehydration test object, wherein the addition amount of the demulsifier is 50ppm, and the specific evaluation method refers to SY/T5281-2000 crude oil demulsifier service performance detection method bottle test method, and the experimental results are shown in Table 1.
TABLE 1
As can be seen from the above table 1, the initiator in the demulsifier has more aromatic ring structures and has stronger acting force with the coal tar macromolecule structure, so that the naphthol modified phenolic resin polyether demulsifier synthesized by the invention has better effect on dehydrating high-temperature coal tar compared with the commercial thick oil demulsifier.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (7)
1. The polyether demulsifier is characterized in that the polyether demulsifier takes naphthol modified phenolic resin as an initiator, and has a general formula of A- (PO)a-(EO)b-(PO)cWherein A is of formula I, PO is- (CH)2-O-CH2CH2) -, EO is- (O-CH)2CH2) -; the ratio of A/(PO)aThe mass ratio of (A) is 1/200-1/30; the (PO)a/(EO)bThe mass ratio of (A) to (B) is in the range of 3-8; the (PO)c/(PO)aThe mass ratio ranges from 0 to 6;
the naphthol modified phenolic resin has a structure shown in a formula I
Wherein n is an integer of 0 to 9.
2. The polyether demulsifier of claim 1, wherein the naphthol-modified phenolic resin is prepared by:
mixing naphthol, phenol and aldehyde according to the ratio of (0.1-2): (5-10): (6-10) uniformly mixing at a rotating speed of 40-200 r/min, adding a catalyst at the rotating speed for 5-40 minutes, heating to 70-110 ℃, carrying out polycondensation reaction at constant temperature for 2-5 hours, and carrying out pressure reduction and dehydration after the reaction is finished.
3. The polyether demulsifier of claim 2 wherein the catalyst is hydrochloric acid, sulfuric acid, oxalic acid, benzenesulfonic acid, petroleum sulfonic acid, chloroacetic acid; the aldehyde is 35-50 wt% of formaldehyde solution or paraformaldehyde.
4. The polyether demulsifier of claim 3, further comprising the step of dehydrating under reduced pressure after the reaction is complete, when the aldehyde is a formaldehyde solution.
5. A method for preparing the polyether demulsifier of any one of claims 1-4, comprising the steps of:
weighing 1 part of phenolic resin, 30-200 parts of epoxypropane and 0.3-2 parts of potassium hydroxide solid, sequentially adding into a reaction kettle, closing a reaction kettle cover, and purging with nitrogen for 2-3 minutes; after the purging is finished, heating to 110-130 ℃ within 1-2 hours, and carrying out polymerization reaction for 1-2 hours at the temperature; after the reaction is finished, cooling the temperature to room temperature, adding 10-25 parts of ethylene oxide again, closing the reaction kettle cover, and purging with nitrogen for 2-3 minutes; after the purging is finished, heating to 110-130 ℃ within 1-2 hours, and reacting for 1-2 hours at the temperature; after the reaction is finished, the diblock polyether with an initiator-PO-EO structure is obtained.
6. The method of claim 5, further comprising: after the reaction generates the diblock polyether, adding propylene oxide, heating to 120-135 ℃ within 1-2 hours, and reacting for 0.5-1.5 hours at the temperature to obtain triblock polyether with an initiator-PO-EO-PO structure; the addition amount of the propylene oxide is less than 1200 parts.
7. The method of claim 6, wherein the nitrogen gas has a purity of 99.5%, 99.99%, or 99.999%.
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|---|---|---|---|---|
| US5206333A (en) * | 1991-05-07 | 1993-04-27 | Hitachi Chemical Company, Ltd. | Method of producing a naphthol-modified phenolic resin of highly increased molecular weight |
| CN102245664A (en) * | 2008-12-12 | 2011-11-16 | 旭有机材工业株式会社 | Phenol resin for shell molding, process for production of the resin, resin-coated sand for shell molding, and molds obtained using same |
| JP2012111806A (en) * | 2010-11-22 | 2012-06-14 | Sumitomo Bakelite Co Ltd | Phenol resin composition for friction material, method for producing phenol resin for friction material and friction material |
| CN103396828A (en) * | 2013-07-26 | 2013-11-20 | 金浦新材料股份有限公司 | Polyether crude oil demulsifier using straight chain alkyl phenolic resin as initiator and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013046919A (en) * | 2011-08-29 | 2013-03-07 | Sumitomo Bakelite Co Ltd | Phenolic resin binder for shell mold and resin-coated sand for shell mold |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5206333A (en) * | 1991-05-07 | 1993-04-27 | Hitachi Chemical Company, Ltd. | Method of producing a naphthol-modified phenolic resin of highly increased molecular weight |
| CN102245664A (en) * | 2008-12-12 | 2011-11-16 | 旭有机材工业株式会社 | Phenol resin for shell molding, process for production of the resin, resin-coated sand for shell molding, and molds obtained using same |
| JP2012111806A (en) * | 2010-11-22 | 2012-06-14 | Sumitomo Bakelite Co Ltd | Phenol resin composition for friction material, method for producing phenol resin for friction material and friction material |
| CN103396828A (en) * | 2013-07-26 | 2013-11-20 | 金浦新材料股份有限公司 | Polyether crude oil demulsifier using straight chain alkyl phenolic resin as initiator and preparation method and application thereof |
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