CN111423903A - Novel preparation method of multi-branched cationic polyether reverse demulsifier and multi-branched cationic polyether reverse demulsifier - Google Patents

Novel preparation method of multi-branched cationic polyether reverse demulsifier and multi-branched cationic polyether reverse demulsifier Download PDF

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CN111423903A
CN111423903A CN202010319652.7A CN202010319652A CN111423903A CN 111423903 A CN111423903 A CN 111423903A CN 202010319652 A CN202010319652 A CN 202010319652A CN 111423903 A CN111423903 A CN 111423903A
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branched
polyether
reverse demulsifier
branched cationic
demulsifier
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张进
凌坤华
侯琳熙
范阳海
阮任杰
凌功明
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Jinhu Jinling New Material Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G33/00Dewatering or demulsification of hydrocarbon oils
    • C10G33/04Dewatering or demulsification of hydrocarbon oils with chemical means

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Abstract

The invention discloses a preparation method of a multi-branched cationic polyether reverse demulsifier, which comprises the steps of taking bisphenol A as a block polyether initiator, utilizing the o-hydrogen of phenolic hydroxyl group of the bisphenol A to generate a polyamine compound which takes the bisphenol A as a core and the vinylamine as a branch and the phenolic hydroxyl group as a leaf through aminomethylation reaction with formaldehyde and vinylamine, then carrying out ring-opening polymerization on the polyamine compound, epoxy compounds of propylene oxide and ethylene oxide to obtain multi-branched polyether, and further utilizing the tail end of the multi-branched cationic polyether reverse demulsifier to carry out modification with different cationic degrees to obtain the multi-branched cationic polyether reverse demulsifier; the multi-branched cationic polyether reverse demulsifier prepared by the invention has higher deoiling rate and demulsifying efficiency and better demulsifying capability, and can well make up for the functional defects of the traditional demulsifier; can effectively reduce the oil exploitation cost, save energy and reduce emission, and is beneficial to the development of the oil exploitation process.

Description

Novel preparation method of multi-branched cationic polyether reverse demulsifier and multi-branched cationic polyether reverse demulsifier
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a novel preparation method of a multi-branched cationic polyether reverse demulsifier and the multi-branched cationic polyether reverse demulsifier prepared by the method.
Background
With the continuous development and wide application of the petroleum industry, particularly tertiary oil recovery technology, the components of the crude oil produced liquid become more and more complex, and the water content is higher and higher. The difficulty of oil-water separation is increased, and the burden of equipment such as pumps, pipelines, storage tanks and the like in the transportation and refining processes is increased; therefore, before petroleum transportation and refining, demulsification and dehydration must be carried out. There are many ways of demulsifying, and the addition of a small amount of chemical agent, i.e., a demulsifier, is the fastest and most common way to achieve oil-water separation. For example, in patent CN109536201A, 200-400 parts of alkylphenol polyoxyethylene ether, 10-90 parts of chlorosulfonic acid, a proper amount of alkali liquor and bleaching powder are subjected to high-pressure stirring, deacidification and neutralization treatment to obtain the demulsifier with low temperature resistance, high starting speed in a low-temperature environment, good dehydration effect, thorough dehydration and clear and bright water quality. Similarly, patent CN110628012A discloses a preparation method of a demulsifier using fatty alcohol polyether as a matrix, which has high demulsification speed and simple preparation method. However, the above two patents do not evaluate the dehydration efficiency and the dehydration effect of crude oil with complex components, and the specific use effect is not clear.
In addition, along with the enhancement of the stability of the crude oil produced liquid, a large amount of mature and widely applied traditional polyether demulsifiers in China are difficult to meet the production requirements of efficient and rapid demulsification of oil fields due to low dehydration rate, low dehydration speed and the like. The reverse demulsifier is an effective demulsifier for treating complex crude oil produced liquid, and can well make up the functional defects of the traditional demulsifier. The demulsifier used for oil-in-water (O/W) emulsion can effectively improve the interfacial tension of water-in-oil (W/O) or oil-in-water (O/W) emulsion, so that colloidal particles in produced liquid lose stable repulsive force and attractive force, finally lose stability to form flocs, and further realize oil-water separation and separation of harmful impurities through chemical bridging to achieve the purpose of separating oil from water and other impurities. Therefore, developing a reverse demulsifier which can be different from the traditional demulsifier to improve the demulsification capability and efficiency of complex petroleum produced fluid and reduce the production cost is one of the technical problems which are urgently needed to be solved by the technical personnel in the field.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a novel multi-branched cationic polyether reverse demulsifier, and the multi-branched block polyether prepared by the preparation method has more complex and various structures, so that the multi-branched cationic polyether reverse demulsifier has stronger hydrophilic capacity, wettability and permeation effect, can quickly reach an oil-water interface, occupies a larger surface area than a linear molecule on the oil-water interface, and can replace more emulsifier molecules, thereby having higher deoiling rate; in addition, in the preparation process of the reverse demulsifier, tertiary amine groups contained in the polyether compound are utilized, the polyether compound is modified through a quaternization process, and the demulsification efficiency can be obviously improved due to the characteristic that quaternary ammonium salt can endow polyether cations.
The technical scheme provided by the invention is as follows:
a preparation method of a novel multi-branched cationic polyether reverse demulsifier comprises the following steps:
(1) uniformly mixing bisphenol A, diethylenetriamine and formaldehyde at room temperature, and performing reflux reaction under the action of a catalyst to obtain a branched polyamine compound;
(2) uniformly mixing the branched polyamine compound obtained in the step (1) with a catalyst, adding the mixture into a high-voltage covering type, sealing, heating and vacuumizing;
(3) adding a mixed system of propylene oxide and ethylene oxide into a high-voltage covering type to react, and carrying out post-treatment after the reaction is finished to obtain a multi-branched polyether compound;
(4) and (4) reacting the multi-branched polyether compound obtained in the step (3) with halogenated hydrocarbon to obtain the multi-branched cationic polyether reverse demulsifier.
Preferably, in the step (1), the mole fraction ratio of the bisphenol A, the diethylenetriamine, the catalyst and the formaldehyde is (10-30): (80-240): (10-50): (200-600) and the reaction time is 0.5-12 h.
Preferably, the catalyst is a base catalyst and a metal catalyst.
Preferably, in the step (2), the mole fraction ratio of the branched polyamine compound to the catalyst is (1-6): (1-6), and the temperature rise is 100-150 ℃.
Preferably, in the step (3), the mole fraction ratio of the propylene oxide to the ethylene oxide in the mixed system is (1-5): (1-5), the pressure of the reaction cover is 0.1-0.7 MPa, the reaction pressure is-0.2 MPa, and the reaction time is 2-12 h.
Preferably, in the step (4), the mole fraction ratio of the multi-branched polyether compound to the halogenated hydrocarbon is 1: (3-10) the reaction time is 4-8 h.
Preferably, the work-up in step (3) is distillation.
The invention also discloses a novel multi-branched cationic polyether reverse-phase demulsifier obtained by the preparation method.
Compared with the prior art, the invention has the following technical advantages:
(1) the invention takes bisphenol A as a block polyether initiator, and utilizes the phenolic hydroxyl group ortho-position hydrogen of the bisphenol A to react with formaldehyde and vinylamine through aminomethylation to generate a polyamine compound which takes bisphenol A as a core and vinylamine as a branch and phenolic hydroxyl group as a leaf, and the polyamine compound is subjected to ring-opening polymerization with an epoxy compound to prepare the multi-branched cationic polyether reverse-phase demulsifier; compared with straight-chain polyether, the multi-branched cationic polyether compound has higher demulsification capability, and the multi-branched cationic polyether reverse demulsifier has more complex and various structures (known from a synthetic route shown in figure 1 in the attached drawing of the specification) and high molecular weight, so that the multi-branched cationic polyether reverse demulsifier has stronger hydrophilic capability, wettability and permeation effect, can quickly reach an oil-water interface, realizes wider coverage on the oil-water interface, changes the polarity of the water surface, increases hydrophobicity, reduces surface tension, occupies a larger surface area on the oil-water interface than linear molecules, and can replace more emulsifier molecules, thereby having higher deoiling efficiency;
(2) and secondly, the polyether is endowed with the electric property of positive charge, so that the polyether is favorable for realizing efficient emulsion breaking by the charge neutralization principle. With the increase of the salinization degree of the quaternary ammonium, the higher the charge density, the stronger the electric neutralization effect between the quaternary ammonium and oil drops, and further the demulsification capability is stronger.
Because the small oil drops of the complex produced fluid are generally negatively charged, demulsification can be realized by the principle of charge neutralization, and the cationization degree of the polyether compound is often directly related to the final demulsification capacity and the demulsification efficiency of the demulsifier; the polyether compound contains a plurality of tertiary amine groups, so that the reverse demulsifier in the invention utilizes the tertiary amine groups contained in the polyether compound in the preparation process, modifies the tail end of the polyether compound by different cationization degrees through the quaternization process, endows the polyether with positive charge electric property, and is beneficial to realizing efficient demulsification through the charge neutralization principle. With the increase of the salinization degree of quaternary ammonium, the higher the charge density is, the stronger the electric neutralization effect between the quaternary ammonium and oil drops is, and further the demulsification capability is stronger;
(3) for the preparation of the multi-branched polyether compound, ring-opening polymerization of a polyamine compound, Propylene Oxide (PO) and Ethylene Oxide (EO) is required, the block ratio of the PO and the EO directly determines the water solubility and other various surface properties of the polyether compound, and the mol fraction ratio of the PO and the EO in the invention is (1-4): (1-4), the multi-branched cationic polyether reverse demulsifier formed by the method has more excellent demulsification performance, and compared with a system only adding single components of PO and EO, the PO and EO mixed system has the controllability of block proportion, so that the water solubility and the gradient change of demulsification efficiency can be ensured, and a theoretical basis is provided for obtaining a series of demulsifier products.
Drawings
FIG. 1 is a synthesis scheme of the multi-branched cationic polyether reverse demulsifier of the present invention.
Detailed Description
The invention will now be further described with reference to the accompanying drawings and specific embodiments.
Example 1
The invention discloses a preparation method of a novel multi-branched cationic polyether reverse demulsifier, which comprises the following steps:
(1) carrying out reflux reaction on bisphenol A, diethylenetriamine and formaldehyde for 1h according to a certain molar ratio under the action of an alkali catalyst, wherein the molar fraction ratio of the bisphenol A, the diethylenetriamine, the alkali catalyst and the formaldehyde is 1:8:1: 20.
(2) Adding the branched polyamine compound obtained in the step (1) and the base catalyst into a high-voltage covering type, sealing, heating and vacuumizing. The molar fraction ratio of the branched polyamine compound to the base catalyst was 1:1 and the temperature was 120 ℃.
(3) PO and EO are slowly and continuously added into the high-pressure covering type according to a certain proportion, the reaction is continuously carried out for 2 hours after the addition is finished, and the multi-branched polyether compound is obtained after the distillation. The mole fraction ratio of PO and EO was 1:1, the reaction lid pressure was 0.3 MPa, and the reaction pressure was-0.1 MPa.
(4) And (3) reacting the multi-branched polyether compound with different types of halogenated hydrocarbons for 4 hours to obtain the multi-branched cationic polyether reverse phase demulsifier, wherein the mol fraction ratio of the multi-branched polyether compound to the halogenated hydrocarbons is 1: 4.
Example 2
The invention discloses a preparation method of a novel multi-branched cationic polyether reverse demulsifier, which comprises the following steps:
(1) carrying out reflux reaction on bisphenol A, diethylenetriamine and formaldehyde for 5 hours according to a certain molar ratio under the action of an alkali catalyst, wherein the molar ratio of the bisphenol A to the diethylenetriamine to the alkali catalyst to the formaldehyde is 1:8:1: 20.
(2) Adding the branched polyamine compound obtained in the step (1) and the base catalyst into a high-voltage covering type, sealing, heating and vacuumizing. The molar fraction ratio of the branched polyamine compound to the base catalyst was 1:1 and the temperature was 120 ℃.
(3) PO and EO are slowly and continuously added into the high-pressure covering type according to a certain proportion, the reaction is continuously carried out for 4 hours after the addition is finished, and the multi-branched polyether compound is obtained after the distillation. The mole fraction ratio of PO and EO was 1:2, the reaction lid pressure was 0.3 MPa, and the reaction pressure was-0.1 MPa.
(4) And (3) reacting the multi-branched polyether compound with different types of halogenated hydrocarbons for 5 hours to obtain the multi-branched cationic polyether reverse demulsifier, wherein the mol fraction ratio of the multi-branched polyether compound to the halogenated hydrocarbons is 1: 4.
Example 3
The invention discloses a preparation method of a novel multi-branched cationic polyether reverse demulsifier, which comprises the following steps:
(1) carrying out reflux reaction on bisphenol A, diethylenetriamine and formaldehyde for 6 hours under the action of an alkali catalyst according to a certain molar ratio, wherein the molar ratio of the bisphenol A to the diethylenetriamine to the alkali catalyst to the formaldehyde is 1:8:1: 20.
(2) Adding the branched polyamine compound obtained in the step (1) and the base catalyst into a high-voltage covering type, sealing, heating and vacuumizing. The molar fraction ratio of the branched polyamine compound to the base catalyst was 1:1 and the temperature was 120 ℃.
(3) PO and EO are slowly and continuously added into the high-pressure covering type according to a certain proportion, the reaction is continuously carried out for 5 hours after the addition is finished, and the multi-branched polyether compound is obtained after the distillation. The mole fraction ratio of PO and EO was 2:3, the reaction lid pressure was 0.3 MPa, and the reaction pressure was-0.1 MPa.
(4) And (3) reacting the multi-branched polyether compound with different types of halogenated hydrocarbons for 6 hours to obtain the multi-branched cationic polyether reverse phase demulsifier, wherein the mol fraction ratio of the multi-branched polyether compound to the halogenated hydrocarbons is 1: 4.
Example 4
The invention discloses a preparation method of a novel multi-branched cationic polyether reverse demulsifier, which comprises the following steps:
(1) carrying out reflux reaction on bisphenol A, diethylenetriamine and formaldehyde for 7h under the action of an alkali catalyst according to a certain molar ratio, wherein the molar ratio of the bisphenol A to the diethylenetriamine to the alkali catalyst to the formaldehyde is 1:8:1: 20.
(2) Adding the branched polyamine compound obtained in the step (1) and the base catalyst into a high-voltage covering type, sealing, heating and vacuumizing. The molar fraction ratio of the branched polyamine compound to the base catalyst was 1:1 and the temperature was 120 ℃.
(3) PO and EO are slowly and continuously added into the high-pressure covering type according to a certain proportion, the reaction is continuously carried out for 6 hours after the addition is finished, and the multi-branched polyether compound is obtained after the distillation. The mole fraction ratio of PO and EO was 3:2, the reaction lid pressure was 0.3 MPa, and the reaction pressure was-0.1 MPa.
(4) And (3) reacting the multi-branched polyether compound with different types of halogenated hydrocarbons for 7 hours to obtain the multi-branched cationic polyether reverse phase demulsifier, wherein the mol fraction ratio of the multi-branched polyether compound to the halogenated hydrocarbons is 1: 4.
Example 5
The invention discloses a preparation method of a novel multi-branched cationic polyether reverse demulsifier, which comprises the following steps:
(1) carrying out reflux reaction on bisphenol A, diethylenetriamine and formaldehyde for 8h under the action of a metal catalyst according to a certain molar ratio, wherein the molar ratio of the bisphenol A to the diethylenetriamine to the alkali catalyst to the formaldehyde is 1:8:1: 20.
(2) Adding the branched polyamine compound obtained in the step (1) and the metal catalyst into a high-voltage covering type, sealing, heating and vacuumizing. The molar fraction ratio of the branched polyamine compound to the base catalyst was 1:1 and the temperature was 120 ℃.
(3) PO and EO are slowly and continuously added into the high-pressure covering type according to a certain proportion, the reaction is continuously carried out for 7 hours after the addition is finished, and the multi-branched polyether compound is obtained after the distillation. The mole fraction ratio of PO and EO was 1:1, the reaction lid pressure was 0.3 MPa, and the reaction pressure was-0.1 MPa.
(4) And (3) reacting the multi-branched polyether compound with different types of halogenated hydrocarbons for 8 hours to obtain the multi-branched cationic polyether reverse phase demulsifier, wherein the mol fraction ratio of the multi-branched polyether compound to the halogenated hydrocarbons is 1: 3.
Example 6
The invention discloses a preparation method of a novel multi-branched cationic polyether reverse demulsifier, which comprises the following steps:
(1) carrying out reflux reaction on bisphenol A, diethylenetriamine and formaldehyde for 9 hours under the action of a metal catalyst according to a certain molar ratio, wherein the molar ratio of the bisphenol A to the diethylenetriamine to the alkali catalyst to the formaldehyde is 1:8:1: 20.
(2) Adding the branched polyamine compound obtained in the step (1) and the metal catalyst into a high-voltage covering type, sealing, heating and vacuumizing. The molar fraction ratio of the branched polyamine compound to the base catalyst was 1:1 and the temperature was 120 ℃.
(3) PO and EO are slowly and continuously added into the high-pressure covering type according to a certain proportion, the reaction is continuously carried out for 9 hours after the addition is finished, and the multi-branched polyether compound is obtained after the distillation. The mole fraction ratio of PO and EO was 1:1, the reaction lid pressure was 0.3 MPa, and the reaction pressure was-0.1 MPa.
(4) And (3) reacting the multi-branched polyether compound with different types of halogenated hydrocarbons for 7 hours to obtain the multi-branched cationic polyether reverse demulsifier, wherein the mol fraction ratio of the multi-branched polyether compound to the halogenated hydrocarbons is 1: 5.
Example 7
The invention discloses a preparation method of a novel multi-branched cationic polyether reverse demulsifier, which comprises the following steps:
(1) carrying out reflux reaction on bisphenol A, diethylenetriamine and formaldehyde for 12h under the action of a metal catalyst according to a certain molar ratio, wherein the molar ratio of the bisphenol A to the diethylenetriamine to the base catalyst to the formaldehyde is 1:8:1: 20.
(2) Adding the branched polyamine compound obtained in the step (1) and the metal catalyst into a high-voltage covering type, sealing, heating and vacuumizing. The molar fraction ratio of the branched polyamine compound to the base catalyst was 1:1 and the temperature was 120 ℃.
(3) PO and EO are slowly and continuously added into the high-pressure covering type according to a certain proportion, the reaction is continuously carried out for 12 hours after the addition is finished, and the multi-branched polyether compound is obtained after the distillation. The mole fraction ratio of PO and EO was 1:1, the reaction lid pressure was 0.3 MPa, and the reaction pressure was-0.1 MPa.
(4) And (3) reacting the multi-branched polyether compound with different types of halogenated hydrocarbons for 8 hours to obtain the multi-branched cationic polyether reverse phase demulsifier, wherein the mol fraction ratio of the multi-branched polyether compound to the halogenated hydrocarbons is 1: 6.
Measurement of Performance
The dehydration rate, the oil-water interface condition, the surface tension and the like of the multi-branched cationic polyether reverse demulsifier obtained in the example 1 to 7 are measured, and the specific results are shown in tables 1 and 2;
table test performance results for reverse demulsifier at 150 deg.C
Figure 368130DEST_PATH_IMAGE002
Main performance index test result of reverse demulsifier at 245 ℃ in table
Figure DEST_PATH_IMAGE004
As can be seen from tables 1 and 2, as the parameters of dehydration ratio (%) at different times, oil content in aqueous phase (mg/L) and the like in comparative example 1, example 2, example 3 and example 4, it can be seen that the water solubility and surface property of the reverse demulsifier are improved with the increase of the block ratio of PO and EO, and the high-efficiency water-milk separation is realized, and the change of the block ratio plays a key role in the improvement of the surface property of the reverse demulsifier, and by adjusting the charging ratio of the different types of halogenated hydrocarbon and the multi-branched polyether compound, the critical micelle concentration (mg/L) and the surface tension (mN/m) in comparative example 1, example 2, example 3 and example 7 are controlled2) It can be seen that along with the continuous improvement of the multi-branching degree of the reverse demulsifier, the salinization degree of quaternary ammonium is increased, the charge density is increased, and the critical micelle concentration and the surface tension are correspondingly changed, so that the demulsification efficiency is improved. In general, the novel multi-branched cationic polyether reverse demulsifier prepared by the invention has excellent demulsification capability, stable physicochemical property and simple preparation, and is suitable for large-scale production and application.

Claims (8)

1. A preparation method of a novel multi-branched cationic polyether reverse demulsifier is characterized by comprising the following steps:
(1) uniformly mixing bisphenol A, diethylenetriamine and formaldehyde at room temperature, and performing reflux reaction under the action of a catalyst to obtain a branched polyamine compound;
(2) uniformly mixing the branched polyamine compound obtained in the step (1) with a catalyst, adding the mixture into a high-voltage covering type, sealing, heating and vacuumizing;
(3) adding a mixed system of propylene oxide and ethylene oxide into a high-voltage covering type to react, and carrying out post-treatment after the reaction is finished to obtain a multi-branched polyether compound;
(4) and (4) reacting the multi-branched polyether compound obtained in the step (3) with halogenated hydrocarbon to obtain the multi-branched cationic polyether reverse demulsifier.
2. The method for preparing the novel multi-branched cationic polyether reverse demulsifier according to claim 1, wherein the method comprises the following steps: in the step (1), the mole fraction ratio of bisphenol A, diethylenetriamine, catalyst and formaldehyde is (10-30): (80-240): (10-50): (200-600) and the reaction time is 0.5-12 h.
3. The method for preparing the novel multi-branched cationic polyether reverse demulsifier according to claim 1, wherein the method comprises the following steps: the catalyst is alkali catalyst and metal catalyst.
4. The method for preparing the novel multi-branched cationic polyether reverse demulsifier according to claim 1, wherein the method comprises the following steps: in the step (2), the mole fraction ratio of the branched polyamine compound to the catalyst is (1-6): (1-6), and the temperature rise is 100-150 ℃.
5. The method for preparing the novel multi-branched cationic polyether reverse demulsifier according to claim 1, wherein the method comprises the following steps: in the step (3), the mole fraction ratio of the epoxypropane to the epoxyethane in the mixed system is (1-5): (1-5), the pressure of the reaction cover is 0.1-0.7 MPa, the reaction pressure is-0.2 MPa, and the reaction time is 2-12 h.
6. The method for preparing the novel multi-branched cationic polyether reverse demulsifier according to claim 1, wherein the method comprises the following steps: in the step (4), the mole fraction ratio of the multi-branched polyether compound to the halogenated hydrocarbon is 1: (3-10) the reaction time is 4-8 h.
7. The method for preparing the novel multi-branched cationic polyether reverse demulsifier according to claim 1, wherein the method comprises the following steps: the post-treatment method in the step (3) is distillation.
8. A novel multi-branched cationic polyether reverse demulsifier obtained by the preparation method of claims 1-7.
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CN113429955A (en) * 2021-06-24 2021-09-24 中国矿业大学 Preparation of load type polyether polyquaternary ammonium salt reverse demulsifier and application of load type polyether polyquaternary ammonium salt reverse demulsifier in ternary combination flooding produced water treatment
CN113637497A (en) * 2021-08-27 2021-11-12 金湖金凌新材料科技有限公司 Preparation method of multi-branched cationic polyether microbial demulsifier

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CN113429955A (en) * 2021-06-24 2021-09-24 中国矿业大学 Preparation of load type polyether polyquaternary ammonium salt reverse demulsifier and application of load type polyether polyquaternary ammonium salt reverse demulsifier in ternary combination flooding produced water treatment
CN113429955B (en) * 2021-06-24 2022-03-11 中国矿业大学 Preparation of load type polyether polyquaternary ammonium salt reverse demulsifier and application of load type polyether polyquaternary ammonium salt reverse demulsifier in ternary combination flooding produced water treatment
CN113637497A (en) * 2021-08-27 2021-11-12 金湖金凌新材料科技有限公司 Preparation method of multi-branched cationic polyether microbial demulsifier

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