CN116179236B - A demulsifier for treating crude oil emulsion layer - Google Patents
A demulsifier for treating crude oil emulsion layerInfo
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- CN116179236B CN116179236B CN202211497395.1A CN202211497395A CN116179236B CN 116179236 B CN116179236 B CN 116179236B CN 202211497395 A CN202211497395 A CN 202211497395A CN 116179236 B CN116179236 B CN 116179236B
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- phenolic resin
- demulsifier
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1033—Oil well production fluids
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a demulsifier for treating a crude oil emulsion layer, which comprises a component A, a component B, a component C and a component D, wherein the component A is a toluene diisonitrile ester modified phenolic resin based polyether solution, the component B is an acrylic acid modified phenolic resin based polyether solution, the component C is a high carbon alcohol polyether solution, the component D is a long chain alkyl dimethyl benzyl ammonium chloride solution, and the mass ratio of the component A to the component B to the component C to the component D is 30:30-50:1-10:5-15. The demulsifier has the advantages of high dehydration rate and low water content of the purified oil and is used for treating the crude oil emulsion layer.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a demulsifier for treating a crude oil emulsion layer.
Background
At present, most offshore oil fields in China enter the middle and later stages of development and production, the heavy trend of crude oil is obvious, the material composition in the oil-water interface of produced liquid is more complex, the oil-water separation difficulty is further increased, the problem of emulsion appears in a plurality of oil fields, namely, during the oil-water separation process, a certain amount of emulsion which cannot be broken by a conventional demulsifier appears on the oil-water interface of each level of separator (also called an intermediate layer, and if the intermediate layer cannot be treated, the intermediate layer becomes aged oil after entering an oil cargo tank). The emulsion which cannot be eliminated in the process is gradually accumulated, so that normal operation of equipment is influenced, the separation efficiency of oil and water is finally influenced, normal production of an oil field is influenced, and even the oil field has to be limited in production when serious. Moreover, when it accumulates to some extent, it will enter the water treatment system or cargo tank. If the crude oil enters a cargo oil tank, the water content of the externally-transported crude oil exceeds the standard, the price of the crude oil is reduced, and even the crude oil cannot be sold.
In general, there are two general categories of methods for treating emulsions in a process flow. The emulsion is reduced by adjusting the field production process, so that the influence of the emulsion on the whole process is reduced as much as possible, and the emulsion is reduced or even completely eliminated by adopting a chemical method, namely, by adopting a proper demulsifier and/or reverse demulsifier, a water purifying agent and the like, the stability of the emulsion is reduced thermodynamically, so that the quantity of the emulsion is reduced fundamentally, and the reduction or even complete disappearance of the emulsion is realized. However, because of the small space of the offshore oil field, the residence time of the produced liquid in the treatment equipment is short, and the conventional demulsifier optimization method cannot be fully suitable for the working condition of the offshore oil field.
Therefore, a demulsifier with a fast dehydration rate and low water content of the purified oil for treating an emulsion layer of crude oil becomes a key to solve the problem.
Disclosure of Invention
The invention combines the modified polyether with excellent dehydration performance to the water-in-oil emulsion, the polyether with excellent dehydration performance to the oil-in-water emulsion and the micromolecular cationic auxiliary agent to obtain the four-component crude oil demulsifier.
The invention aims to provide a demulsifier for treating an emulsion layer of crude oil, which has high dehydration rate and low water content of purified oil and can be used for treating the emulsion layer in a crude oil treatment process.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
A demulsifier for treating a crude oil emulsion layer is characterized by being prepared by mixing a component A, a component B, a component C and a component D, wherein the component A is toluene diisocyanate modified phenolic resin-based polyether solution, the component B is acrylic acid modified phenolic resin-based polyether solution, the component C is high-carbon alcohol polyether solution, the component D is long-chain alkyl dimethyl benzyl ammonium chloride solution, and the mass ratio of the component A to the component B to the component C to the component D is 30:30-50:1-10:5-15;
Wherein the toluene diisocyanate modified phenolic resin based polyether solution is one of a xylene solution of toluene diisocyanate modified bisphenol A phenolic resin polyoxypropylene polyoxyethylene ether, a xylene solution of toluene diisocyanate modified tertiary butyl phenolic resin polyoxypropylene polyoxyethylene ether and a xylene solution of toluene diisocyanate modified nonylphenol resin polyoxypropylene polyoxyethylene ether, the crosslinking degree is 0.5% -1.5%, and the content of effective matters is 50%;
The acrylic acid modified phenolic resin-based polyether solution is one of a xylene solution of acrylic acid modified bisphenol A phenolic resin polyoxypropylene polyoxyethylene ether, a xylene solution of acrylic acid modified tertiary butyl phenolic resin polyoxypropylene polyoxyethylene ether and a xylene solution of acrylic acid modified nonyl phenolic resin polyoxypropylene polyoxyethylene ether, the crosslinking degree is 5% -10%, and the content of effective matters is 50%;
the high-carbon alcohol polyether solution is a solution obtained by dissolving stearyl alcohol polyoxypropylene polyoxyethylene polyoxypropylene ether in a mixture of methanol and deionized water in a mass ratio of 8:2, and the content of effective matters is 50%;
The long-chain alkyl dimethyl benzyl ammonium chloride solution is obtained by dissolving octyl dimethyl benzyl ammonium chloride, decyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride and tetradecyl dimethyl benzyl ammonium chloride in a mixture of methanol and deionized water in a mass ratio of 1:1, and the effective matter content is 40%.
Preferably, the mass ratio of the component A, the component B, the component C and the component D is 30:40:5:10.
Preferably, the toluene diisocyanate modified phenolic resin based polyether solution is a xylene solution of toluene diisocyanate modified bisphenol A phenolic resin polyoxypropylene polyoxyethylene ether, and the crosslinking degree is 1%.
Preferably, the acrylic acid modified phenolic resin-based polyether solution is a xylene solution of acrylic acid modified nonylphenol-aldehyde resin polyoxypropylene polyoxyethylene ether, and the crosslinking degree is 10%.
Preferably, the long-chain alkyl dimethyl benzyl ammonium chloride solution is a solution obtained by dissolving dodecyl dimethyl benzyl ammonium chloride in a mixture of methanol and deionized water in a mass ratio of 1:1.
The invention has the advantages of high dehydration rate and low water content of the purified oil, and can be used for treating an emulsion layer in a crude oil treatment process.
Detailed Description
The invention is described in further detail to enable those skilled in the art to practice the same by reference to the specification.
Example 1
A demulsifier for treating a crude oil emulsion layer is prepared by mixing a component A, a component B, a component C and a component D, wherein the component A is a xylene solution of toluene diisocyanate modified bisphenol A phenolic resin polyoxypropylene polyoxyethylene ether, the component B is a xylene solution of acrylic acid modified nonylphenol phenolic resin polyoxypropylene polyoxyethylene ether, the component C is a solution obtained by dissolving stearyl alcohol polyoxypropylene polyoxyethylene polyoxypropylene ether in a mixture of methanol and deionized water in a mass ratio of 8:2, the component D is a solution obtained by dissolving dodecyl dimethyl benzyl ammonium chloride in a mixture of methanol and deionized water in a mass ratio of 1:1, and the mass ratio of the component A, the component B, the component C and the component D is 30:40:5:10.
The component A is formed by polymerizing bisphenol A phenolic resin, propylene oxide and ethylene oxide according to a mass ratio of 1:49:17, wherein a crosslinking agent toluene diisocyanate accounts for 1% of the mass of polyether, and the content of effective matters is 50%. The component B is formed by polymerizing the nonylphenol-formaldehyde resin, propylene oxide and ethylene oxide according to the mass ratio of 1:49:17, wherein the cross-linking agent acrylic acid accounts for 7% of the mass of the polyether, and the effective matter content is 50%. The content of the effective matters in the component C is 50 percent. The active content in component D was 40%.
Firstly, adding the component B into a three-neck flask with an electric stirring and thermometer, starting stirring, starting water bath heating, sequentially adding the component A, the component C and the component D when the temperature in the flask reaches 30 ℃, and stopping stirring and discharging after 10min to obtain the demulsifier for treating the crude oil emulsion layer.
Example 2
A demulsifier for treating a crude oil emulsion layer is prepared by mixing a component A, a component B, a component C and a component D, wherein the component A is a xylene solution of toluene diisocyanate modified bisphenol A phenolic resin polyoxypropylene polyoxyethylene ether, the component B is a xylene solution of acrylic acid modified tertiary butyl phenolic resin polyoxypropylene polyoxyethylene ether, the component C is a solution obtained by dissolving stearyl alcohol polyoxypropylene polyoxyethylene polyoxypropylene ether in a mixture of methanol and deionized water in a mass ratio of 8:2, the component D is a solution obtained by dissolving octyl dimethyl benzyl ammonium chloride in a mixture of methanol and deionized water in a mass ratio of 1:1, and the mass ratio of the component A, the component B, the component C and the component D is 30:50:10:10.
The component A is formed by polymerizing bisphenol A phenolic resin, propylene oxide and ethylene oxide according to a mass ratio of 1:49:17, wherein the cross-linking agent toluene diisocyanate accounts for 1.5% of the mass of polyether, and the content of effective matters is 50%. The components B are tertiary butyl phenolic resin, propylene oxide and ethylene oxide, wherein the mass ratio of the components B to the propylene oxide to the ethylene oxide is 1:39:13, the cross-linking agent acrylic acid accounts for 8% of the mass of polyether, and the content of effective matters is 50%. The content of the effective matters in the component C is 50 percent. The active content in component D was 40%.
Firstly, adding the component B into a three-neck flask with an electric stirring and thermometer, starting stirring, starting water bath heating, sequentially adding the component A, the component C and the component D when the temperature in the flask reaches 30 ℃, and stopping stirring and discharging after 10min to obtain the demulsifier for treating the crude oil emulsion layer.
Example 3
A demulsifier for treating a crude oil emulsion layer is prepared by mixing a component A, a component B, a component C and a component D, wherein the component A is a xylene solution of toluene diisocyanate modified nonylphenol aldehyde resin polyoxypropylene polyoxyethylene ether, the component B is a xylene solution of acrylic acid modified tert-butylphenol aldehyde resin polyoxypropylene polyoxyethylene ether, the component C is a solution obtained by dissolving stearyl alcohol polyoxypropylene polyoxyethylene polyoxypropylene ether in a mixture of methanol and deionized water in a mass ratio of 8:2, the component D is a solution obtained by dissolving tetradecyl dimethylbenzyl ammonium chloride in a mixture of methanol and deionized water in a mass ratio of 1:1, and the mass ratio of the component A, the component B, the component C and the component D is 30:30:1:5.
Wherein the component A is composed of the phenolic resin of the union group, propylene oxide and ethylene oxide according to the mass ratio of 1:49:17, and the toluene diisocyanate as a crosslinking agent accounts for 0.5% of the mass of the polyether, and the content of effective matters is 50%. The components B are tertiary butyl phenolic resin, propylene oxide and ethylene oxide, wherein the mass ratio of the components B to the propylene oxide to the ethylene oxide is 1:59:20, the cross-linking agent acrylic acid accounts for 5% of the mass of polyether, and the content of effective matters is 50%. The content of the effective matters in the component C is 50 percent. The active content in component D was 40%.
Firstly, adding the component B into a three-neck flask with an electric stirring and thermometer, starting stirring, starting water bath heating, sequentially adding the component A, the component C and the component D when the temperature in the flask reaches 30 ℃, and stopping stirring and discharging after 10min to obtain the demulsifier for treating the crude oil emulsion layer.
Example 4
A demulsifier for treating a crude oil emulsion layer is prepared by mixing a component A, a component B, a component C and a component D, wherein the component A is a xylene solution of toluene diisocyanate modified tertiary butyl phenol aldehyde resin polyoxypropylene polyoxyethylene ether, the component B is a xylene solution of acrylic acid modified bisphenol A phenol aldehyde resin polyoxypropylene polyoxyethylene ether, the component C is a solution obtained by dissolving stearyl alcohol polyoxypropylene polyoxyethylene polyoxypropylene ether in a mixture of methanol and deionized water in a mass ratio of 8:2, the component D is a solution obtained by dissolving decyl dimethyl benzyl ammonium chloride in a mixture of methanol and deionized water in a mass ratio of 1:1, and the mass ratio of the component A, the component B, the component C and the component D is 30:30:3:15.
Wherein the component A comprises tert-butyl phenol aldehyde resin, propylene oxide and ethylene oxide according to a mass ratio of 1:39:13, and the cross-linking agent toluene diisocyanate accounts for 1.5% of the mass of the polyether, and the effective matter content is 50%. The component B consists of bisphenol A phenolic resin, propylene oxide and ethylene oxide according to the mass ratio of 1:59:20, and the cross-linking agent acrylic acid accounts for 10% of the mass of polyether, and the effective matter content is 50%. The content of the effective matters in the component C is 50 percent. The active content in component D was 40%.
Firstly, adding the component B into a three-neck flask with an electric stirring and thermometer, starting stirring, starting water bath heating, sequentially adding the component A, the component C and the component D when the temperature in the flask reaches 30 ℃, and stopping stirring and discharging after 10min to obtain the demulsifier for treating the crude oil emulsion layer.
Data analysis
The demulsifier prepared by the invention has the use effect compared with the common demulsifier for oil fields under the equal effective concentration. Crude oil production liquid for comparison experiments is taken from different offshore oil fields in China.
1. The demulsifier prepared by the invention and the common demulsifier for oil fields are subjected to dehydration experiments under the condition of equal effective concentration, and table 1 is obtained.
Table 1 dehydration Effect of different Agents on heavy thickened oil emulsion
The oil sample source is 80mL mixing mode of 80mL sample volume of the primary separator of the Chengbei oilfield, the hand shaking 100 times of experiment temperature is 80 DEG C
2. The demulsifier prepared by the invention and the common demulsifier for oil fields are subjected to dehydration experiments under the condition of equal effective concentration to obtain the table 2.
TABLE 2 dewatering effects of different Agents on middle crude oil emulsions
Sample source BZ34-2/4 oilfield primary separator inlet sample volume 80mL mixing mode, hand shaking 100 times experiment temperature 65 DEG C
Therefore, the demulsifier for treating the crude oil emulsion layer prepared by the method has the advantages of high dehydration rate and low water content of purified oil, and can be used for treating the emulsion layer in a crude oil treatment flow.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (5)
1. A demulsifier for treating a crude oil emulsion layer is characterized by being prepared by mixing a component A, a component B, a component C and a component D, wherein the component A is toluene diisocyanate modified phenolic resin-based polyether solution, the component B is acrylic acid modified phenolic resin-based polyether solution, the component C is high-carbon alcohol polyether solution, the component D is long-chain alkyl dimethyl benzyl ammonium chloride solution, and the mass ratio of the component A to the component B to the component C to the component D is 30:30-50:1-10:5-15;
The toluene diisocyanate modified phenolic resin-based polyether solution is one of a xylene solution of toluene diisocyanate modified bisphenol A phenolic resin polyoxypropylene polyoxyethylene ether, a xylene solution of toluene diisocyanate modified tertiary butyl phenolic resin polyoxypropylene polyoxyethylene ether and a xylene solution of toluene diisocyanate modified nonylphenol resin polyoxypropylene polyoxyethylene ether, the crosslinking degree is 0.5% -1.5%, the content of effective matters is 50%, and the component A is formed by polymerizing toluene diisocyanate modified phenolic resin, propylene oxide and ethylene oxide according to a mass ratio of 1:39-49:13-17;
The acrylic acid modified phenolic resin-based polyether solution is one of a xylene solution of acrylic acid modified bisphenol A phenolic resin polyoxypropylene polyoxyethylene ether, a xylene solution of acrylic acid modified tertiary butyl phenolic resin polyoxypropylene polyoxyethylene ether and a xylene solution of acrylic acid modified nonylphenol resin polyoxypropylene polyoxyethylene ether, the crosslinking degree is 5% -10%, the content of effective matters is 50%, and the component B is formed by polymerizing acrylic acid modified phenolic resin, propylene oxide and ethylene oxide according to a mass ratio of 1:39-59:13-20;
the high-carbon alcohol polyether solution is a solution obtained by dissolving stearyl alcohol polyoxypropylene polyoxyethylene polyoxypropylene ether in a mixture of methanol and deionized water in a mass ratio of 8:2, and the content of effective matters is 50%;
The long-chain alkyl dimethyl benzyl ammonium chloride solution is obtained by dissolving octyl dimethyl benzyl ammonium chloride, decyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride or tetradecyl dimethyl benzyl ammonium chloride in a mixture of methanol and deionized water in a mass ratio of 1:1, and the effective matter content is 40%.
2. The demulsifier for treating an emulsion layer of crude oil according to claim 1, wherein the mass ratio of component A, component B, component C and component D is 30:40:5:10.
3. The demulsifier for treating an emulsified crude oil as set forth in claim 1, wherein the toluene diisocyanate-modified phenolic resin-based polyether solution is a xylene solution of toluene diisocyanate-modified bisphenol A phenolic resin polyoxypropylene polyoxyethylene ether having a crosslinking degree of 1%.
4. The demulsifier for treating an emulsified crude oil as set forth in claim 1, wherein the acrylic acid modified phenolic resin based polyether solution is a xylene solution of acrylic acid modified nonylphenol phenol resin polyoxypropylene polyoxyethylene ether having a degree of crosslinking of 10%.
5. The demulsifier for treating an emulsified crude oil as set forth in claim 1, wherein the long-chain alkyl dimethylbenzyl ammonium chloride solution is a solution obtained by dissolving dodecyldimethylbenzyl ammonium chloride in a mixture of methanol and deionized water in a mass ratio of 1:1.
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| CN202211497395.1A CN116179236B (en) | 2022-11-25 | 2022-11-25 | A demulsifier for treating crude oil emulsion layer |
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| CN202211497395.1A CN116179236B (en) | 2022-11-25 | 2022-11-25 | A demulsifier for treating crude oil emulsion layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102453497A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Demulsification method for hydrocarbon oil |
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| CN105440278B (en) * | 2015-12-31 | 2018-07-13 | 中国石油天然气股份有限公司 | A kind of demulsifier compound system and its preparation method and application |
| CN113684053B (en) * | 2021-10-25 | 2021-12-21 | 胜利油田海发环保化工有限责任公司 | Composite demulsifier and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102453497A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Demulsification method for hydrocarbon oil |
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