CN117025251A - Oil-soluble demulsifier for middle east oilfield crude oil and preparation method thereof - Google Patents
Oil-soluble demulsifier for middle east oilfield crude oil and preparation method thereof Download PDFInfo
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- CN117025251A CN117025251A CN202310928626.8A CN202310928626A CN117025251A CN 117025251 A CN117025251 A CN 117025251A CN 202310928626 A CN202310928626 A CN 202310928626A CN 117025251 A CN117025251 A CN 117025251A
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- 239000010779 crude oil Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- -1 butyl phenolic resin Chemical compound 0.000 claims abstract description 90
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 69
- 229920000570 polyether Polymers 0.000 claims abstract description 69
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000005011 phenolic resin Substances 0.000 claims abstract description 52
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 239000003921 oil Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000013329 compounding Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 64
- 238000010438 heat treatment Methods 0.000 claims description 30
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 22
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 16
- 239000008098 formaldehyde solution Substances 0.000 claims description 16
- 238000009489 vacuum treatment Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 1
- 230000018044 dehydration Effects 0.000 abstract description 12
- 238000006297 dehydration reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 238000010612 desalination reaction Methods 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 4
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- 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
- C08G65/2618—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 nitrogen
- C08G65/2621—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 nitrogen containing amine groups
- C08G65/2627—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 nitrogen containing amine groups containing aromatic or arylaliphatic amine groups
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
Abstract
The invention discloses an oil-soluble demulsifier for crude oil of a Zhongdong oilfield and a preparation method thereof, wherein the demulsifier is formed by compounding butyl phenolic resin block polyether and bisphenol A phenolic amine resin block polyether, and the mass ratio of the butyl phenolic resin block polyether to the bisphenol A phenolic amine resin block polyether is 50-70:30-50. The oil-soluble demulsifier for the crude oil of the middle east oilfield has good demulsification and desalination effects, and can shorten the treatment time and reduce the salt content after desalination. The water content of crude oil such as Ai Hadai oil field after dehydration can reach more than 99%.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to an oil-soluble demulsifier for crude oil of a Zhongdong oilfield and a preparation method thereof.
Background
Along with the continuous expansion of development scale of foreign oil fields, the oil products comprise various oil products such as light oil, medium oil, heavy oil and the like, the components of crude oil are more and more complex, emulsion breaking is difficult, and the water content of the crude oil is continuously increased.
Chinese patent application CN105440278A discloses a demulsifier compound system, and preparation method and application thereof, wherein the preparation method mainly comprises: a) Adding a para-tertiary butyl phenol aldehyde polyether demulsifier and a propylene glycol polyether demulsifier into a reaction container, and raising the temperature in the reaction container to 60-100 ℃: then acrylic acid is dripped into the reaction vessel, and the reaction is carried out for 0.5 to 2 hours after the dripping is finished; b) And (3) dropwise adding toluene diisocyanate into the reaction container, and reacting for 0.2-2h after the dropwise adding is finished to obtain the modified para-tert-butylphenol aldehyde polyether demulsifier. However, the demulsifier prepared by the method is mainly aimed at crude oil produced in domestic oil fields, and the crude oil imported in the middle east has poor effect, so that a more suitable demulsifier is still required to be developed for the crude oil imported in the middle east.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of an oil-soluble demulsifier for crude oil of a Zhongdong oilfield, and the demulsifier has good demulsification and desalination effects, and can shorten the treatment time and reduce the salt content after desalination. The demulsifier is a compound of butyl phenolic resin block polyether and bisphenol A phenolic amine resin block polyether.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the oil-soluble demulsifier for the crude oil of the middle east oilfield is prepared by compounding butyl phenolic resin block polyether and bisphenol A phenolic amine resin block polyether, wherein the mass ratio of the butyl phenolic resin block polyether to the bisphenol A phenolic amine resin block polyether is 50-70:30-50.
Preferably, the butyl phenolic resin block polyether is prepared by reacting the following raw materials in parts by weight: 20-40 parts of butyl phenolic resin initiator, 30-45 parts of propylene oxide and 25-45 parts of ethylene oxide.
Preferably, the bisphenol A phenolic amine resin block polyether is prepared by reacting the following raw materials in parts by weight: 0.3 to 1 part of bisphenol A phenolic amine resin initiator, 60 to 75 parts of propylene oxide and 25 to 40 parts of ethylene oxide.
Preferably, the butyl phenolic resin block polyether is prepared as follows:
adding a butyl phenolic resin initiator into a high-pressure reaction kettle, adding a catalyst 1, heating, controlling the temperature to be 90-120 ℃, keeping the vacuum degree to be more than or equal to 0.09Mpa, carrying out vacuum treatment for 30 minutes, closing a vacuum pump, continuously heating to 130 ℃, adding propylene oxide until the pressure in the reaction system is 0.01-0.4 Mpa, then carrying out heat preservation reaction until the pressure in the reaction system is-0.04 Mpa, then cooling to about 100 ℃, carrying out vacuum treatment for 30 minutes, closing the vacuum pump, adding ethylene oxide until the pressure in the reaction system is 0.01-0.4 Mpa, carrying out heat preservation reaction to-0.04 Mpa, then cooling to about 100 ℃, keeping the vacuum degree to be more than or equal to 0.09Mpa, carrying out vacuum treatment for 30 minutes, cooling to 80 ℃, adding a neutralizing agent, neutralizing and discharging to obtain the butyl phenolic resin segmented polyether.
Preferably, the vacuum treatment temperature is 90-110 ℃, and the thermal insulation reaction temperature of the propylene oxide is 135-145 ℃; the temperature of the ethylene oxide thermal insulation reaction is 120-130 ℃.
Preferably, the catalyst 1 is one or two of potassium hydroxide and sodium hydroxide; the neutralizer is acetic acid; the mass ratio of the butyl phenolic resin block polyether to the catalyst 1 to the neutralizer is 1000:3.5-4.0:3.2-4.2.
Preferably, the bisphenol a phenolic amine resin block polyether is prepared as follows:
putting bisphenol A phenolic amine resin initiator into a high-pressure reaction kettle, adding a catalyst 2, heating, controlling the temperature to be 90-120 ℃, keeping the vacuum degree to be more than or equal to 0.09Mpa, carrying out vacuum treatment for 30 minutes, closing a vacuum pump, continuously heating to 130 ℃, adding propylene oxide until the pressure in a reaction system is 0.01-0.4 MPa, and then carrying out heat preservation reaction until the pressure in the reaction system is-0.04 MPa; cooling to about 100 ℃, vacuum-treating for 30 minutes, closing a vacuum pump, adding ethylene oxide until the pressure in a reaction system is 0.01-0.4 MPa, carrying out heat preservation reaction until the pressure is-0.04 MPa, cooling to about 100 ℃, keeping the vacuum degree not less than 0.09MPa, vacuum-treating for 30 minutes, cooling to 80 ℃, adding a neutralizing agent, and neutralizing and discharging to obtain the bisphenol A phenolic amine resin block polyether.
Preferably, the vacuum treatment temperature is 90-110 ℃, and the thermal insulation reaction temperature of the propylene oxide is 135-145 ℃; the temperature of the ethylene oxide thermal insulation reaction is 120-130 ℃.
Preferably, the catalyst 2 is one or two of potassium hydroxide and sodium hydroxide; the neutralizer is acetic acid; the mass ratio of the bisphenol A phenolic amine resin block polyether to the catalyst 2 to the neutralizer is 1000:3.5-4.0:3.2-4.2.
Preferably, the butyl phenol resin initiator is synthesized by the following method:
adding p-tert-butylphenol into a reaction container, heating and melting, and adding formaldehyde solution and a catalyst 3; stirring, heating to reflux temperature, maintaining the temperature, keeping the temperature for 2h, stopping heating and stirring, cooling the intermediate to about 60deg.C, adding xylene, heating, distilling under reduced pressure, removing xylene and water, cooling, and discharging.
Preferably, the heating and melting temperature of the p-tertiary butyl phenol is 80-90 ℃; the reflux reaction temperature is 110 ℃, and the reaction is carried out for 2 hours; the temperature of the reduced pressure distillation is 150-160 ℃.
Preferably, the formaldehyde solution is an aqueous formaldehyde solution with a solubility of 36.5% (mass ratio); the catalyst 3 is one or two of potassium hydroxide and sodium hydroxide.
Preferably, the mass ratio of the p-tert-butylphenol to the formaldehyde solution to the dimethylbenzene to the catalyst 3 is as follows: 55-60:30-35:5-10:0.3-0.4.
Preferably, the oil head (hydrophobic block portion) of the butyl phenolic resin block polyether is 25% to 40% of the total mass of the butyl phenolic resin block polyether.
Preferably, the bisphenol a phenolic amine resin initiator is synthesized by the following method:
adding bisphenol A and polyethylene polyamine into a reaction vessel, heating until materials are completely dissolved, stirring for 0.5 hour, dropwise adding formaldehyde solution, carrying out reflux reaction, cooling after the reaction is completed, adding dimethylbenzene, heating, carrying out reduced pressure distillation, removing dimethylbenzene and water in a system, cooling, and discharging to obtain the bisphenol A phenolic amine resin initiator.
Preferably, the temperature at which the heated material of bisphenol A is fully dissolved is 60-70 ℃; the reflux reaction temperature is 110 ℃, and the reaction is carried out for 2 hours; the temperature of reduced pressure distillation is 150-160 ℃; the solubility of the formaldehyde solution is 36.5% (mass ratio), the temperature is reduced to 40-50 ℃, and formaldehyde is added dropwise.
Preferably, the mass ratio of the para-bisphenol A to the polyethylene polyamine to the formaldehyde solution to the dimethylbenzene is as follows: 8-15:38-50:12-18:15-25.
According to another aspect of the present invention, the present invention provides a method for preparing an oil-soluble demulsifier for middle east oilfield crude oil, comprising mixing and compounding the butyl phenolic resin block polyether and bisphenol A phenolic amine resin block polyether in a ratio, wherein
The mass ratio of the butyl phenolic resin block polyether to the bisphenol A phenolic amine resin block polyether is 50-70:30-50.
Advantageous effects
The oil-soluble demulsifier for the crude oil of the Zhongdong oilfield, disclosed by the invention, has good demulsification and desalination effects, and can shorten the treatment time and reduce the salt content after desalination. The water content of crude oil such as Ai Hadai oil field after dehydration can reach more than 99%.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description, it is to be understood that the terms used in this specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description set forth herein is merely a preferred example for the purpose of illustration and is not intended to limit the scope of the invention, so that it should be understood that other equivalents or modifications may be made thereto without departing from the spirit and scope of the invention.
Compared with the common demulsifier in China, the butyl phenolic resin disclosed by the invention has the advantages that the phenolic ratio can be changed as required, the molecular structure of the demulsifier is adjusted, the p-tert-butyl phenol has two active points, the positioning effect of the hydroxyl group on the p-tert-butyl group is good, the oil solubility is good, the proportion of the butyl phenolic resin block polyether oil head can reach more than 30%, the synthesized demulsifier is good in oil solubility, the sufficient expansion of the demulsifier at the emulsion oil-water interface can be ensured, the spreading area is large, the collision probability of the demulsifier on dispersed water drops is improved, and the dehydration rate is improved. The bisphenol A phenolic resin block polyether has the advantages of high molecular weight, slow dehydration and strong deep dehydration capability, and the butyl phenolic resin block polyether and the bisphenol A phenolic resin block polyether are matched for use, so that the advantages of high dehydration speed and strong desalting capability of the butyl phenolic resin block polyether can be exerted, and the advantage of strong deep dehydration capability of the bisphenol A phenolic resin block polyether can be exerted by adjusting the proportion. The compounded demulsifier has the advantages of high dehydration speed, high dehydration rate and low residual water, and meets the field use requirement.
The oil-soluble demulsifier of the middle east oilfield crude oil is formed by compounding butyl phenolic resin block polyether and bisphenol A phenolic amine resin block polyether, wherein the mass ratio of the butyl phenolic resin block polyether to the bisphenol A phenolic amine resin block polyether is 50-70:30-50.
The butyl phenolic resin block polyether is prepared by reacting the following raw materials in parts by weight: 20-40 parts of butyl phenolic resin initiator, 30-45 parts of propylene oxide and 25-45 parts of ethylene oxide. The proportion of the butyl phenolic resin block polyether oil head can reach more than 30%, the synthesized demulsifier has good oil solubility, the demulsifier can be ensured to be fully stretched at an emulsion oil-water interface, the spreading area is large, the collision probability of the demulsifier on dispersed water drops is improved, and the dehydration rate is improved. If the ratio of the initiator is too low or too high, the demulsification effect is reduced to various degrees, and the butyl phenolic resin initiator is kept in the above range, the latest technical effect can be obtained.
Preferably, the bisphenol A phenolic amine resin block polyether is prepared by reacting the following raw materials in parts by weight: 0.3 to 1 part of bisphenol A phenolic amine resin initiator, 60 to 75 parts of propylene oxide and 25 to 40 parts of ethylene oxide. When bisphenol A phenolic amine resin block polyether is synthesized according to the proportion, the bisphenol A phenolic amine resin block polyether has a better synergistic effect with butyl phenolic resin block polyether, the demulsification capability of a demulsifier is improved, and if an initiator or epoxide is not in the range, the effect is not ideal.
All features or conditions defined herein in terms of numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values within the range, particularly integer values. For example, a range description of "1 to 8" should be taken as having specifically disclosed all sub-ranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., particularly sub-ranges defined by all integer values, and should be taken as having specifically disclosed individual values such as 1, 2, 3, 4, 5, 6, 7, 8, etc. within the range. The foregoing explanation applies to all matters of the invention throughout its entirety unless indicated otherwise, whether or not the scope is broad.
If an amount or other numerical value or parameter is expressed as a range, preferred range, or a series of upper and lower limits, then it is understood that any range, whether or not separately disclosed, from any pair of the upper or preferred value for that range and the lower or preferred value for that range is specifically disclosed herein. Furthermore, where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
In this context, numerical values should be understood to have the accuracy of the numerical significance of the numerical values provided that the objectives of the present invention are achieved. For example, the number 40.0 is understood to cover a range from 39.50 to 40.49.
Meanwhile, in the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene conversion molecular weights analyzed by Gel Permeation Chromatography (GPC), and the molecular weight distribution can be calculated from the ratio. Mw/Mn.
The following examples are merely illustrative of embodiments of the present invention and are not intended to limit the invention in any way, and those skilled in the art will appreciate that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1
(1) Synthesis of butyl phenol resin initiator
180g of p-tert-butylphenol is added into a 500ml four-necked flask, heated and melted until the materials are transparent, and 98.95g of formaldehyde solution (the mass percentage concentration is 36.5%) and 1.05g of KOH are added; stirring and heating to reflux temperature of 110 ℃, maintaining the temperature for reaction for 2 hours, stopping heating and stirring, adding 25g of dimethylbenzene when the intermediate is cooled to about 60 ℃, slowly heating to 150-160 ℃, performing reduced pressure distillation, removing dimethylbenzene and water in the system, cooling and discharging after the quality requirement is met, and obtaining the butyl phenolic resin initiator.
(2) Synthesis of bisphenol A phenolic amine resin initiator
Adding 46g of bisphenol A and 175g of polyethylene polyamine into a 500ml four-mouth bottle, heating until the materials are completely dissolved, stirring for 0.5 hour, cooling to 35-40 ℃, dropwise adding 64g of formaldehyde solution (the mass percentage concentration is 36.5%), carrying out reflux reaction at 110 ℃, cooling after the reaction is finished, adding 90g of dimethylbenzene, heating to 150-160 ℃, carrying out reduced pressure distillation, removing dimethylbenzene and water in a system, cooling, and discharging to obtain the bisphenol A phenolic amine resin initiator.
(3) Synthesis of butyl phenolic resin block polyether
Adding 320g of butyl phenolic resin initiator into a high-pressure reaction kettle, adding 3.51g of KOH, stirring, heating to 100 ℃, controlling the temperature to 90-110 ℃, keeping the vacuum degree equal to or higher than 0.09Mpa, vacuum treating for 30min, closing a vacuum pump, continuously heating to 130 ℃, starting a propylene oxide feeding valve (368 g of propylene oxide feeding amount), controlling the temperature to 135-145 ℃, reacting the pressure of a system to 0.2-0.4 MPa, after feeding, performing heat preservation reaction until the pressure of the reaction system is minus 0.04Mpa, cooling to 100 ℃, controlling the temperature to 90-110 ℃, keeping the vacuum degree equal to or higher than 0.09Mpa, vacuum treating for 30min, after vacuum treatment is finished, closing a vacuum pump, starting an ethylene oxide feeding valve (288 g of ethylene oxide feeding amount), after feeding is finished, performing heat preservation reaction to minus 0.04Mpa, cooling to 100 ℃, controlling the temperature to 90-110 ℃, keeping the vacuum degree equal to or higher than 0.09Mpa, vacuum treating for 30min, cooling to 80 ℃, adding acetic acid to 3.70g, cooling, and discharging to obtain butyl phenolic resin segmented polyether.
(4) Synthesis of bisphenol A phenolic amine resin block polyether
2.3g bisphenol A phenolic amine resin initiator is put into a high-pressure reaction kettle, 2.31g KOH is added, stirring and heating are carried out to 100 ℃, the temperature is controlled to 90-110 ℃, the vacuum degree is kept to be more than or equal to 0.09Mpa, vacuum treatment is carried out for 30min, a vacuum pump is closed, the temperature is continuously increased to 130 ℃, a propylene oxide feeding valve (427.8 g of propylene oxide feeding quantity) is opened, the temperature is controlled to 135-145 ℃, the reaction pressure is 0.2-0.4 MPa, after the feeding is finished, the reaction is carried out to-0.04 Mpa, the temperature is reduced to 100 ℃, the temperature is controlled to 90-110 ℃, the vacuum degree is kept to be more than or equal to 0.09Mpa, the vacuum treatment is carried out for 30min, the temperature is reduced to 80 ℃, acetic acid is added to 2.47g, the temperature is reduced, and the material is discharged, so that bisphenol A phenolic amine resin block polyether is obtained.
(5) Compound of oil-soluble demulsifier A for middle east oil field
And mixing and compounding the prepared butyl phenolic resin block polyether and bisphenol A phenolic amine resin block polyether according to a mass ratio of 65:35 to obtain the demulsifier A.
(6) Compound of oil-soluble demulsifier B for middle east oil field
And mixing and compounding the prepared butyl phenolic resin block polyether and bisphenol A phenolic amine resin block polyether according to the mass ratio of 60:40 to obtain the demulsifier B.
Example 2 demulsifier indoor evaluation experiment
Bottle test demulsification experiments were performed on Ai Hadai oil field produced fluid.
The demulsification experiment refers to SY/T5281-2000 crude oil demulsifier service performance detection method (bottle test method) of the oil and gas industry standard of the people's republic of China, and crude oil water content determination refers to GB/T8929-2006 crude oil water content determination distillation method of the oil and gas industry standard of the people's republic of China.
Ai Hadai oilfield produced fluid from a certain block: the water content is about 13%, the salt content is 17500mg/L, the crude oil API density is 20-22, the wax content is about 3%, and the colloid and asphaltene content is 4.38%.
The oil-soluble demulsifier A, B of the middle east oil field synthesized in the above example 1 was compared with a foreign demulsifier and a common demulsifier, and the experimental results are shown in table 1.
Table 1.70 ℃ demulsification experiment for Ai Hadai oil field produced liquid
Analysis of results: the novel synthetic demulsifier A has better demulsification effect compared with other demulsifiers under the condition that the dosage of the crude oil is 120ppm and the demulsification temperature is 70 ℃, the dehydration rate is better than that of other agents, the dehydration rate is more than 99%, and the sewage is separated.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. The oil-soluble demulsifier for the crude oil of the middle east oilfield is prepared by compounding butyl phenolic resin block polyether and bisphenol A phenolic amine resin block polyether, wherein the mass ratio of the butyl phenolic resin block polyether to the bisphenol A phenolic amine resin block polyether is 50-70:30-50.
2. The oil-soluble demulsifier of crude oil in the middle east oilfield of claim 1, wherein the butyl phenolic resin block polyether is prepared by reacting the following raw materials in parts by weight: 20-40 parts of butyl phenolic resin initiator, 30-45 parts of propylene oxide and 25-45 parts of ethylene oxide.
3. The oil-soluble demulsifier for crude oil in the middle east oilfield of claim 1, wherein the bisphenol a phenolic amine resin block polyether is prepared by reacting the following raw materials in parts by weight: 0.3 to 1 part of bisphenol A phenolic amine resin initiator, 60 to 75 parts of propylene oxide and 25 to 40 parts of ethylene oxide.
4. The oil demulsifier for middle east oilfield crude oil of claim 1, wherein the butyl phenolic resin block polyether is prepared as follows:
adding a butyl phenolic resin initiator into a high-pressure reaction kettle, adding a catalyst 1, heating, controlling the temperature to be 90-120 ℃, keeping the vacuum degree to be more than or equal to 0.09Mpa, carrying out vacuum treatment for 30 minutes, closing a vacuum pump, continuously heating to 120 ℃, adding propylene oxide until the pressure in the reaction system is 0.01-0.4 Mpa, then carrying out heat preservation reaction until the pressure in the reaction system is-0.04 Mpa, then cooling to about 100 ℃, carrying out vacuum treatment for 30 minutes, closing the vacuum pump, adding ethylene oxide until the pressure in the reaction system is 0.01-0.4 Mpa, carrying out heat preservation reaction to-0.04 Mpa, then cooling to about 100 ℃, keeping the vacuum degree to be more than or equal to 0.09Mpa, carrying out vacuum treatment for 30 minutes, cooling to 80 ℃, adding a neutralizing agent, neutralizing and discharging to obtain the butyl phenolic resin segmented polyether;
preferably, the vacuum treatment temperature is 90-110 ℃, and the thermal insulation reaction temperature of the propylene oxide is 135-145 ℃; the temperature of the ethylene oxide thermal insulation reaction is 120-130 ℃;
preferably, the catalyst 1 is one or two of potassium hydroxide and sodium hydroxide; the neutralizer is acetic acid; the mass ratio of the butyl phenolic resin block polyether to the catalyst 1 to the neutralizer is 1000:3.5-4.0:3.2-4.2.
5. The oil-soluble demulsifier for crude oil in the middle east oilfield of claim 1, wherein the bisphenol a phenolic amine resin block polyether is prepared by:
putting bisphenol A phenolic amine resin initiator into a high-pressure reaction kettle, adding a catalyst 2, heating, controlling the temperature to be 90-120 ℃, keeping the vacuum degree to be more than or equal to 0.09Mpa, carrying out vacuum treatment for 30 minutes, closing a vacuum pump, continuously heating to 130 ℃, adding propylene oxide until the pressure in a reaction system is 0.01-0.4 MPa, and then carrying out heat preservation reaction until the pressure in the reaction system is-0.04 MPa; cooling to about 100 ℃, vacuum-treating for 30 minutes, closing a vacuum pump, adding ethylene oxide until the pressure in a reaction system is 0.01-0.4 MPa, carrying out heat preservation reaction until the pressure is-0.04 MPa, cooling to about 100 ℃, keeping the vacuum degree not less than 0.09MPa, vacuum-treating for 30 minutes, cooling to 80 ℃, adding a neutralizing agent, and neutralizing and discharging to obtain the bisphenol A phenolic amine resin block polyether;
preferably, the vacuum treatment temperature is 90-110 ℃, and the thermal insulation reaction temperature of the propylene oxide is 135-145 ℃; the temperature of the ethylene oxide thermal insulation reaction is 120-130 ℃;
preferably, the catalyst 2 is one or two of potassium hydroxide and sodium hydroxide; the neutralizer is acetic acid; the mass ratio of the bisphenol A phenolic amine resin block polyether to the catalyst 2 to the neutralizer is 1000:3.5-4.0:3.2-4.2.
6. The oil demulsifier for middle east oilfield crude oil of claim 1, wherein the butyl phenolic resin starter is synthesized by the following method:
adding p-tert-butylphenol into a reaction container, heating and melting, and adding formaldehyde solution and a catalyst 3; stirring, heating to reflux temperature, maintaining the temperature, keeping the temperature for 2h, stopping heating and stirring, cooling the intermediate to about 60deg.C, adding xylene, heating, performing reduced pressure distillation, removing xylene and water, cooling, and discharging;
preferably, the heating and melting temperature of the p-tertiary butyl phenol is 80-90 ℃; the reflux reaction temperature is 110 ℃, and the reaction is carried out for 2 hours; the temperature of reduced pressure distillation is 150-160 ℃;
preferably, the formaldehyde solution is an aqueous formaldehyde solution with a solubility of 36.5% (mass ratio); the catalyst 3 is one or two of potassium hydroxide and sodium hydroxide;
preferably, the mass ratio of the p-tert-butylphenol to the formaldehyde solution to the dimethylbenzene to the catalyst 3 is as follows: 55-60:30-35:5-10:0.3-0.4;
preferably, the oil head (hydrophobic block portion) of the butyl phenolic resin block polyether is 25% to 40% of the total mass of the butyl phenolic resin block polyether.
7. The oil-soluble demulsifier for crude oil in the middle east oilfield of claim 1, wherein the bisphenol a phenolic amine resin initiator is synthesized by the following method:
adding bisphenol A and polyethylene polyamine into a reaction vessel, heating until materials are completely dissolved, stirring for 0.5 hour, dropwise adding formaldehyde solution, carrying out reflux reaction, cooling after the reaction is completed, adding dimethylbenzene, heating, carrying out reduced pressure distillation, removing dimethylbenzene and water in a system, cooling, and discharging to obtain the bisphenol A phenolic amine resin initiator;
preferably, the temperature at which the heated material of bisphenol A is fully dissolved is 60-70 ℃; the reflux reaction temperature is 110 ℃, and the reaction is carried out for 2 hours; the temperature of reduced pressure distillation is 150-160 ℃; the solubility of the formaldehyde solution is 36.5 percent (mass ratio), the temperature is reduced to 40-50 ℃, and formaldehyde is added dropwise;
preferably, the mass ratio of the para-bisphenol A to the polyethylene polyamine to the formaldehyde solution to the dimethylbenzene is as follows: 8-15:38-50:12-18:15-25.
8. The preparation method of the oil-soluble demulsifier of the middle east oilfield crude oil comprises the step of mixing and compounding the butyl phenolic resin block polyether and the bisphenol A phenolic resin block polyether according to a proportion, wherein the mass ratio of the butyl phenolic resin block polyether to the bisphenol A phenolic resin block polyether is 50-70:30-50.
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