CN107162154B - Ternary combination flooding produced water load type reverse demulsifier and preparation method thereof - Google Patents
Ternary combination flooding produced water load type reverse demulsifier and preparation method thereof Download PDFInfo
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- CN107162154B CN107162154B CN201710436917.XA CN201710436917A CN107162154B CN 107162154 B CN107162154 B CN 107162154B CN 201710436917 A CN201710436917 A CN 201710436917A CN 107162154 B CN107162154 B CN 107162154B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/682—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of chemical compounds for dispersing an oily layer on water
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
Abstract
Ternary combination flooding produced waterA load type reverse demulsifier and a preparation method thereof, belonging to an oily sewage demulsifier and a preparation method thereof. Firstly, synthesizing a basic skeleton of a reverse demulsifier through hydrosilylation, then carrying out epoxy ring-opening reaction on polyquaternium and co-modified silicone oil to synthesize a polyether polyquaternium reverse demulsifier, and then adopting a silane coupling agent KH-570 to react with hydrated silicon dioxide (SiO)2·nH2O) surface is subjected to hydrophobic modification, and finally the polyether polyquaternium reverse demulsifier and the modified hydrated silicon dioxide are subjected to surface grafting polymerization reaction to prepare the load type reverse demulsifier. The load type reverse demulsifier performs the demulsification by replacing and neutralizing the interfacial film charge with the polyether polyquaternium reverse demulsifier loaded on the modified hydrated silicon dioxide carrier particles, and oil drops are quickly adsorbed by the carrier particles and are settled and separated after demulsification and destabilization, thereby completing the demulsification and adsorption processes. The provided load type reverse demulsifier has the characteristics of high deoiling rate, small using amount, high oil-water separation speed, easy separation and the like.
Description
Technical Field
The invention relates to an oil-containing sewage demulsifier and a preparation method thereof, in particular to a ternary combination flooding produced water load type reverse demulsifier and a preparation method thereof.
Background
The treatment of the produced water of the oil field is an important guarantee for the continuous stability and high yield of the oil field and the ecological environment protection. The oil exploitation is carried out by three stages of primary oil recovery, secondary oil recovery and tertiary oil recovery, and the recovery ratio of the three stages is respectively 10-15%, 30-50% and 50-70%. At present, each main oil field in China enters a middle and later high water content exploitation stage, the oil exploitation amount needs to be continuously increased for stabilizing the yield, the yield of produced water is continuously increased, and about 10 hundred million m of oil is required to be treated every year in China3Oil field produced water. Therefore, the treatment of the sewage produced by the oil field is an important subject facing the development of the oil field in the mine field and the protection of the ecological environment.
The treatment of the three-element composite flooding produced water becomes one of the technical bottlenecks of the popularization of the three-element composite flooding technology. The ternary combination flooding is a tertiary oil recovery technology for injecting three chemical agent mixed solutions of alkali, surfactant and polymer, improves the recovery ratio by more than 20 percent compared with the common water flooding, and plays an important role in maintaining the stable yield of the oil field in the later period in China. The ternary combination flooding produced water has complex water quality, has the characteristics of high mineralization, high oil-containing emulsification degree, high interfacial film strength, high small-particle-size suspension, high small oil drop particle size content, high viscosity, low interfacial tension and the like, has stable phase state and high oil-water separation difficulty, and limits the popularization of the ternary combination flooding oil extraction technology.
The demulsification and destabilization of the emulsion are key links for improving the treatment efficiency of the ternary combination flooding produced water. The surfactant contained in the ternary combination flooding produced water reduces the oil-water interfacial tension and the Zeta potential, increases the interfacial elasticity of oil drops, and makes the oil drops difficult to destabilize and coalesce. The polymer increases the produced water viscosity, increases the negative charge density and interfacial elasticity. The alkali can react with acidic substances in the crude oil to generate certain surface active substances, so that the negative charge density of the surface of oil drops is increased, and the stability of the oil drops is enhanced. The key of the ternary combination flooding produced water treatment is to change the surface property of oil drops to break emulsion and destabilize the oil drops, and small oil drops can be combined into large oil drops to accelerate the oil-water separation speed.
Conventional demulsification methods are classified into physical methods (gravity settling method, filtration method, centrifugation method, air flotation demulsification, membrane method, microwave demulsification, electric field demulsification and the like), chemical methods (demulsification agents) and biological methods. Chemical emulsion breaking is a new film formed by selecting a surfactant which strongly adsorbs at the oil-water interface to replace the emulsifier which forms a strong film in the emulsion. The new interfacial film is thin and the strength of the film is significantly reduced to break the emulsion. The chemical demulsification method has high efficiency and strong practicability, and is widely applied in actual production.
At present, the reverse demulsifiers used for O/W type emulsion demulsification at home and abroad mainly comprise three categories of low molecular electrolytes, alcohols, surfactants and high molecular polymers. The demulsification effect of the electrolyte and the alcohol is limited, the addition amount is large, secondary pollution is easy to form, and the electrolyte and the alcohol are eliminated. The surfactant demulsifiers mainly include cationic, anionic and nonionic demulsifiers. The cationic surfactant is mainly quaternary ammonium salt, the anionic surfactant is mainly dithiocarbamate, and the nonionic surfactant is mainly polyamine. The high molecular polymer reverse demulsifier comprises polyether type, polyquaternary ammonium salt, polysiloxane and the like. The polyquaternary ammonium salt demulsifier has the advantages of good water solubility, high diffusion speed and the like. The polysiloxane has the advantages of high chemical stability, low surface tension, strong hydrophobicity and good interface diffusivity in O/W type emulsion. In recent years, the research of demulsifiers has been greatly advanced, for example, US5045212 discloses a reverse demulsifier compounded by an organic cation demulsifier and an inorganic salt demulsifier, EP0331323a2 discloses an amine polymer demulsifier suitable for crude oil exploitation, CN201310534158 discloses a magnetic reverse demulsifier suitable for oil-containing sewage treatment in the process of oil exploitation, CN200810115284 uses polyamide-amine quaternary ammonium salt and linear quaternary ammonium salt (LPQA) to be mixed to obtain a star-shaped polyquaternary ammonium salt reverse demulsifier, and the reverse demulsifier prepared by CN201210035036 consists of cationic polyamide-amine, polyepichlorohydrin quaternary ammonium salt and polyacryloyloxyethyl trimethyl ammonium chloride. But the ternary combination flooding produced water has fine oil drop grain size, high oil-containing emulsification degree, high interfacial film strength and large demulsification difficulty. The ternary complex flooding produced water demulsification system is a complex system in which a demulsification agent and an emulsifier coexist, the demulsification process and the emulsification process coexist, and the demulsification process is reversible, so that a novel efficient demulsification agent suitable for the ternary complex flooding produced water demulsification needs to be further developed.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a ternary combination flooding produced water load type reverse demulsifier and a preparation method thereof, and solves the problem that ternary combination flooding produced water is difficult to demulsify.
The technical scheme is as follows: the purpose of the invention is realized as follows: the demulsifier for the ternary combination flooding produced water comprises: a load type reverse demulsifier and a preparation method thereof.
The load type reverse demulsifier has the following structural formula:
wherein x is1＝1～30；x2＝1～30；x3＝1～20；y＝1～50；a＝7～19；b＝1～19；m＝9～10；n＝1～3。
The preparation method of the load type reverse demulsifier comprises the following steps: firstly, a reverse phase demulsifier basic skeleton is synthesized through hydrosilylation reaction, and then the poly quaternary ammonium salt and the co-modified silicone oil are subjected to epoxy ring-opening reaction to synthesize polyether poly quaternary ammonium salt reverse phaseDemulsifier, silane coupling agent KH-570 and hydrated silicon dioxide (SiO)2·nH2O) surface is subjected to hydrophobic modification, and finally the polyether polyquaternium reverse demulsifier and the modified hydrated silicon dioxide are subjected to surface grafting polymerization reaction to prepare the load type reverse demulsifier.
The method comprises the following specific steps:
1) basic skeleton synthesis of reverse demulsifier molecules
Mixing epoxy ether, methyl ether and hydrogen-containing silicone oil, adding chloroplatinic acid as a catalyst, stirring for 20-30 min, placing in a microwave reactor, reacting for 10-40 min under the microwave power of 100-500W, fully dissolving a reaction product by using n-hexane, separating an undissolved product, performing rotary evaporation to remove a small amount of solvent, and performing vacuum drying at 60 ℃ for 24h to obtain an epoxy ether methyl ether co-modified silicone oil intermediate;
2) polyquaternary ammonium salt synthesis
Sequentially adding dibutylamine and an organic amine cross-linking agent into a reactor with a condensing device, introducing nitrogen and stirring, slowly adding epoxy chloropropane at 10-30 ℃, heating to 40-80 ℃ after adding, continuously stirring for reacting for 3-8 h, cooling to obtain a yellow viscous liquid product, fully washing the reaction product with 1:1 anhydrous ethanol-acetone, then performing rotary evaporation to remove the solvent, and performing vacuum drying at 70 ℃ for 24h to obtain a product polyquaternary ammonium salt;
3) synthesis of polyether polyquaternary ammonium salt type reverse demulsifier
Sequentially adding polyquaternium and an alcohol solvent into a reactor with a condensing device, introducing nitrogen and stirring, adding co-modified silicone oil at 25-45 ℃, stirring and reacting for 3-7 h, cooling, washing a product with a 1:1 anhydrous ethanol-acetone solution for multiple times, removing the solvent by rotary evaporation, and drying in vacuum for 24h to obtain the polyether polyquaternium PPA;
4) hydrophobic modification of carrier hydrated silica
Fully mixing hydrated silicon dioxide and a silane coupling agent, adding the mixture into an alcohol solvent, stirring for 20-30 min, adding a catalyst methanesulfonic acid, stirring and refluxing for 16-32 h at 35-60 ℃, washing a product with ethanol for 3-5 times after the reaction is finished, and performing vacuum drying for 12-14 h at 70-90 ℃ to obtain hydrophobically modified hydrated silicon dioxide;
5) synthesis of load type reverse demulsifier
Adding hydrophobic modified hydrated silicon dioxide, polyether polyquaternium PPA and an alcohol solvent into a reactor with a heat exchange device, introducing nitrogen and stirring, adding a catalyst chloroplatinic acid after 5min, stirring and refluxing for 6-10 h at 30-50 ℃, washing with isopropanol and ethanol for multiple times after the reaction is finished, and drying for 24h at 120 ℃ to obtain a final product SiO2@PPA。
The epoxy ether added in the preparation step 1) is allyl polyoxyethylene polyoxypropylene epoxy ether-1, EO: PO 10:1, allyl polyoxyethylene polyoxypropylene epoxy ether-2, EO: PO 3: 1; the methyl ether is allyl polyoxyethylene polyoxypropylene methyl ether-1, EO is PO 1:1, allyl polyoxyethylene polyoxypropylene methyl ether-2, EO is PO 7: 1; the hydrogen-containing silicone oil comprises 0.1 to 0.25 percent of hydrogen by mass percent; the molar ratio of the epoxy ether to the methyl ether is 1: 5-5: 1, the molar ratio of the silicon-hydrogen bond to the carbon-carbon double bond is 1: 1.0-1: 1.2, and the dosage of the catalyst chloroplatinic acid is 10-50 mu g/g.
The mol ratio of the epoxy chloropropane to the dibutylamine in the preparation step 2) is 1: 0.9-1: 1.4; the organic amine crosslinking agent is ethylenediamine, n-butylamine and polyethylene polyamine, and the adding amount of the organic amine is 1-15% of the mass percentage of the reaction mass.
The alcohol solvent in the preparation step 3) is methanol, ethanol or isopropanol; the mass ratio of the polyquaternium to the co-modified silicone oil to the alcohol solvent is 0.8-1.2: 0.5-2.5: 15-30.
The silane coupling agent in the preparation step 4) is 3-methacryloxypropyltrimethoxysilane; the alcohol solvent is methanol, ethanol or isopropanol, and the mass ratio of the alcohol solvent to water to methane sulfonic acid is 1:1: 0.03-0.07; the particle size distribution range of the hydrated silicon dioxide particles is 10-100 mu m, and the mass ratio of the hydrated silicon dioxide to the silane coupling agent is 0.8-1.2: 2.0-10.0.
The alcohol solvent in the preparation step 5) is methanol, ethanol or isopropanol; the mass ratio of the hydrophobically modified silicon dioxide to the polyether polyquaternium PPA to the alcohol solvent is 0.6-0.8: 0.8-1.2: 2.0-3.0; the dosage of the catalyst chloroplatinic acid is 40-80 mu g/g.
The invention has the beneficial effects that due to the adoption of the scheme, the load type reverse demulsifier and the preparation method thereof bond the polyether polyquaternium reverse demulsifier PPA to the porous modified hydrated silicon dioxide (SiO) with large specific surface area by adopting the surface grafting polymerization method2·nH2O) surface, preparing the load type polyether polyquaternium reverse demulsifier. The loaded reverse demulsifier has the demulsification function of destroying the original oil-water interface film by replacing the displacement demulsification function and the interfacial film charge demulsification function through the polyether polyquaternium reverse demulsifier loaded on the modified hydrated silicon dioxide carrier particles, and demulsification is realized by replacing the displacement demulsification function and the interfacial film charge neutralizing function through the polyether polyquaternium reverse demulsifier; the demulsified and destabilized oil drops can be quickly adsorbed by the carrier particles of the supported reverse demulsifier, and the oil drops are quickly adsorbed by the carrier particles and are subjected to sedimentation separation after demulsification and destabilization to complete the demulsification and adsorption processes.
The load type reverse demulsifier provided by the invention has double effects of demulsification and adsorption. The polyether polyquaternium reverse demulsifier loaded on the loaded reverse demulsifier carrier particle breaks the emulsion by replacing displacement demulsification and neutralizing interfacial film charge demulsification through the polyether polyquaternium reverse demulsifier, has the characteristic of reducing the content of organic matters in water, is suitable for demulsification treatment of oil-containing sewage, particularly ternary complex flooding produced water, oil drops after demulsification can be quickly adsorbed by the carrier particle, can enable micro-fine-particle-grade oil drops after demulsification to be subjected to reversible emulsification, and has the characteristic of easy separation and recovery of the carrier particle. The problem of difficult demulsification of the produced water of the ASP flooding is solved, and the purpose of the invention is achieved.
The advantages are that: the load type reverse demulsifier has the advantages of high deoiling rate, small using amount, high oil-water separation speed and easy separation, ensures demulsification and destabilization of the ternary complex flooding produced water, accelerates the oil-water separation speed, and is applied to the field of treatment of oil-containing sewage in oil exploitation.
Description of the drawings:
FIG. 1 is a schematic diagram of the demulsification and adsorption synergy of the load-type reverse demulsifier of the invention.
FIG. 2 is a comparison graph of infrared spectra of hydrogen-containing silicone oil and co-modified silicone oil obtained in example 2 of the present invention.
FIG. 3 is a comparison graph of the IR spectra of a polyquaternium prepared in example 2 of the present invention and a polyether polyquaternium.
FIG. 4 is a comparison graph of IR spectra of hydrated silica, hydrophobically modified silica prepared and a supported reverse demulsifier according to example 2 of the present invention.
FIG. 5 is an XPS spectrum analysis of the loaded reverse demulsifier of example 2 of the invention.
FIG. 6 is a comparative graph of the effects of treating ternary combination flooding produced water in example 1 of the present invention.
FIG. 7 is a graph comparing the effects of treating ASP flooding produced water in example 4 of the present invention.
Detailed Description
The invention comprises the following steps: a load type reverse demulsifier and a preparation method thereof.
The load type reverse demulsifier has the following structural formula:
wherein x is1＝1～30；x2＝1～30；x3＝1～20；y＝1～50；a＝7～19；b＝1～19；m＝9～10；n＝1～3。
The load type reverse demulsifier and the preparation method thereof are as follows: firstly, synthesizing a basic skeleton of a reverse demulsifier through hydrosilylation, then carrying out epoxy ring-opening reaction on polyquaternium and co-modified silicone oil to synthesize a polyether polyquaternium reverse demulsifier, and then adopting a silane coupling agent KH-570 to react with hydrated silicon dioxide (SiO)2·nH2O) surface is subjected to hydrophobic modification, and finally the polyether polyquaternium reverse demulsifier and the modified hydrated silicon dioxide are subjected to surface grafting polymerization reaction to prepare the load type reverse demulsifier.
The method comprises the following specific steps:
1) basic skeleton synthesis of reverse demulsifier molecules
Mixing epoxy ether, methyl ether and hydrogen-containing silicone oil, adding chloroplatinic acid as a catalyst, stirring for 20-30 min, placing in a microwave reactor, reacting for 10-40 min under the microwave power of 100-500W, fully dissolving a reaction product by using n-hexane, separating an undissolved product, performing rotary evaporation to remove a small amount of solvent, and performing vacuum drying at 60 ℃ for 24h to obtain an epoxy ether methyl ether co-modified silicone oil intermediate;
2) polyquaternary ammonium salt synthesis
Sequentially adding dibutylamine and an organic amine cross-linking agent into a reactor with a condensing device, introducing nitrogen and stirring, slowly adding epoxy chloropropane at 10-30 ℃, heating to 40-80 ℃ after adding, continuously stirring for reacting for 3-8 h, cooling to obtain a yellow viscous liquid product, fully washing the reaction product with 1:1 anhydrous ethanol-acetone, then performing rotary evaporation to remove the solvent, and performing vacuum drying at 70 ℃ for 24h to obtain a product polyquaternary ammonium salt;
3) synthesis of polyether polyquaternary ammonium salt type reverse demulsifier
Sequentially adding polyquaternium and an alcohol solvent into a reactor with a condensing device, introducing nitrogen and stirring, adding co-modified silicone oil at 25-45 ℃, stirring and reacting for 3-7 h, cooling, washing a product with a 1:1 anhydrous ethanol-acetone solution for multiple times, removing the solvent by rotary evaporation, and drying in vacuum for 24h to obtain the polyether polyquaternium PPA;
4) hydrophobic modification of carrier hydrated silica
Fully mixing hydrated silicon dioxide and a silane coupling agent, adding the mixture into an alcohol solvent, stirring for 20-30 min, adding a catalyst methanesulfonic acid, stirring and refluxing for 16-32 h at 35-60 ℃, washing a product with ethanol for 3-5 times after the reaction is finished, and performing vacuum drying for 12-14 h at 70-90 ℃ to obtain hydrophobically modified hydrated silicon dioxide;
5) synthesis of load type reverse demulsifier
Adding hydrophobic modified hydrated silicon dioxide, polyether polyquaternium PPA and alcohol solvent into a reactor with a heat exchange device, introducing nitrogen and stirring, and adding catalyst chloroplatinum after 5minAcid is stirred and refluxed for 6 to 10 hours at the temperature of between 30 and 50 ℃, after the reaction is finished, isopropanol and ethanol are used for washing for many times, and then the mixture is dried for 24 hours at the temperature of 120 ℃, thus obtaining the final product SiO2@PPA。
The epoxy ether added in the preparation step 1) is allyl polyoxyethylene polyoxypropylene epoxy ether-1, the domestic commercial product is DEG-501, the EO: PO ═ 10:1 and allyl polyoxyethylene polyoxypropylene epoxy ether-2, the domestic commercial product is DEG-502, and the EO: PO ═ 3: 1; the added methyl ether is allyl polyoxyethylene polyoxypropylene methyl ether-1, the domestic trade mark is DEM-2002, EO: PO is 1:1, and allyl polyoxyethylene polyoxypropylene methyl ether-2; the domestic commodity brand is DEM-402EO, wherein PO is 7: 1; the hydrogen-containing silicone oil comprises 0.1 to 0.25 percent of hydrogen by mass percent; the molar ratio of the epoxy ether to the methyl ether is 1: 5-5: 1, the molar ratio of the silicon-hydrogen bond to the carbon-carbon double bond is 1: 1.0-1: 1.2, and the dosage of the catalyst chloroplatinic acid is 10-50 mu g/g.
The mol ratio of the epoxy chloropropane to the dibutylamine in the preparation step 2) is 1: 0.9-1: 1.4; the organic amine crosslinking agent is ethylenediamine, n-butylamine and polyethylene polyamine, and the adding amount of the organic amine is 1-15% of the mass percentage of the reaction mass.
The alcohol solvent in the preparation step 3) is methanol, ethanol or isopropanol; the mass ratio of the polyquaternium to the co-modified silicone oil to the alcohol solvent is 0.8-1.2: 0.5-2.5: 15-30.
The silane coupling agent in the preparation step 4) is 3-methacryloxypropyltrimethoxysilane with the domestic trade mark of KH-570; the alcohol solvent is methanol, ethanol or isopropanol, and the mass ratio of the alcohol solvent to water to methane sulfonic acid is 1:1: 0.03-0.07; the particle size distribution range of the hydrated silicon dioxide particles is 10-100 mu m, and the mass ratio of the hydrated silicon dioxide to the silane coupling agent is 0.8-1.2: 2.0-10.0.
The alcohol solvent in the preparation step 5) is methanol, ethanol or isopropanol; the mass ratio of the hydrophobically modified silicon dioxide to the polyether polyquaternium PPA to the alcohol solvent is 0.6-0.8: 0.8-1.2: 2.0-3.0; the dosage of the catalyst chloroplatinic acid is 40-80 mu g/g.
The loaded reverse demulsifier is added into the oil-containing sewage, and the polyether polyquaternium reverse demulsifier loaded on the modified hydrated silicon dioxide carrier particles replaces displacement demulsification and neutralizes interfacial film charges to achieve the demulsification effect. After the oil drops are demulsified and destabilized, the oil drops can be quickly adsorbed by carrier particles and are settled and separated, thereby completing the demulsification and adsorption processes.
The technical solution and technical effects of the present invention will be further described below by specific examples.
Example 1: mixing epoxy ether-29.3 g, methyl ether-14.6 g and hydrogen-containing silicone oil 10.0g, adding 500mg/L of chloroplatinic acid catalyst 2.3mL, stirring for 20min, placing in a microwave reactor, reacting for 30min under the microwave power of 300W, fully dissolving the reaction product with n-hexane, separating undissolved product, removing a small amount of solvent by rotary evaporation, and drying in vacuum at 60 ℃ for 24h to obtain the co-modified silicone oil intermediate. Adding 19.0g of dibutylamine and 1.3g of a polyvinyl polyamine crosslinking agent into a reactor with a heat exchange device in sequence, introducing nitrogen and stirring, adding 10.3g of epoxy chloropropane at 30 ℃, heating to 60 ℃ after the addition is finished, continuing stirring for reaction for 6h, cooling to obtain a yellow viscous liquid product, fully washing the product with 1:1 absolute ethyl alcohol-acetone, performing rotary evaporation to remove the solvent, and performing vacuum drying at 70 ℃ for 24h to obtain the polyquaternium; sequentially adding 8.33g of polyquaternium and 15.0g of isopropanol into a reactor with a heat exchange device, introducing nitrogen and stirring, adding 8.3g of co-modified silicone oil at 35 ℃, stirring and reacting for 5 hours, cooling a product, washing the product with a 1:1 anhydrous ethanol-acetone solution for three times, removing a solvent by rotary evaporation, and drying in vacuum for 24 hours to obtain the polyether polyquaternium reverse demulsifier (PPA). In 100mL of ASP flooding produced water, wherein the alkali content is 700mg/L, the surfactant content is 300mg/L, the polymer content is 500mg/L, 50mg/LPPA is added and mixed uniformly, oscillation is carried out for 1h at 30 ℃, the oil-containing sewage treated by the PPA reverse demulsifier has clear oil-water interface, and the deoiling rate is 83.4%.
FIG. 1 is a comparison graph of the effects of treating ASP flooding produced water. Wherein, the graph a is the water sample extracted by the ASP flooding with the oil concentration of 500mg/L, and the graph b is the water sample treated by the PPA demulsifier.
Example 2:mixing 212.4 g of epoxy ether, 14.2 g of methyl ether and 15.0g of hydrogen-containing silicone oil, adding 2.6mL of chloroplatinic acid serving as a 500mg/L catalyst, stirring for 20min, placing in a microwave reactor, reacting for 20min under the microwave power of 200W, fully dissolving a reaction product by using n-hexane, separating an undissolved product, performing rotary evaporation to remove a small amount of solvent, and performing vacuum drying at 60 ℃ for 24h to obtain a co-modified silicone oil intermediate. Adding 19.0g of dibutylamine and 0.3g of a polyvinyl polyamine crosslinking agent into a reactor with a heat exchange device in sequence, introducing nitrogen and stirring, adding 10.3g of epoxy chloropropane at the temperature of 30 ℃, heating to 1h to 60 ℃ after the addition is finished, continuously stirring for reaction for 6h, cooling to obtain a yellow viscous liquid product, fully washing the product with 1:1 absolute ethyl alcohol-acetone, removing the solvent by rotary evaporation, and performing vacuum drying at 70 ℃ for 24h to obtain polyquaternium; sequentially adding 8.33g of polyquaternium and 15.0g of isopropanol into a reactor with a heat exchange device, introducing nitrogen and stirring, adding 10g of co-modified silicone oil at 35 ℃, stirring for reaction for 5h, cooling, washing the product with a 1:1 anhydrous ethanol-acetone solution for three times, performing rotary evaporation to remove the solvent, and performing vacuum drying for 24h to obtain the polyether polyquaternium reverse demulsifier (PPA). Fully mixing 10.0g of hydrated silicon dioxide particles with the particle size distribution range of 50-100 mu m and 20.0g of silane coupling agent, adding the mixture into 100g of ethanol-water mixed solvent, stirring for 20min, adding 0.5g of methane sulfonic acid serving as a catalyst, and stirring and refluxing for 24h at 50 ℃. After the reaction is finished, washing the product with ethanol for 3 times, and then drying in vacuum at 70 ℃ for 12 hours to obtain the hydrophobic modified hydrated silicon dioxide. 6g of hydrophobic modified hydrated silica, 8.9g of PPA and 20.0g of isopropanol are added into a reactor with a heat exchange device, nitrogen is introduced and stirred, 4.2mL of 500mg/L catalyst chloroplatinic acid is added after 5min, and stirring and refluxing are carried out for 8h at 40 ℃. After the reaction is finished, cleaning the product with isopropanol for 2 times, then washing with ethanol for 1 time, and drying at 120 ℃ for 24 hours to obtain the final product SiO2@ PPA. 2.0g/LSiO is added into 100mL of three-element composite flooding produced water (wherein the alkali content is 700mg/L, the surfactant content is 300mg/L, and the polymer content is 500mg/L)2@ PPA was mixed well and shaken at 30 ℃ for 1 h. The oily sewage treated by the load type reverse demulsifier has clear oil-water interface, clear water color and deoiling rate of 92.3 percent.
Example 3: mixing epoxy ether-15.6 g, methyl ether-116.3 g and hydrogen-containing silicone oil 20.0g, adding 500mg/L of chloroplatinic acid catalyst 3.4mL, stirring for 20min, placing in a microwave reactor, reacting for 20min under the microwave power of 200W, fully dissolving the reaction product with n-hexane, separating undissolved product, removing a small amount of solvent by rotary evaporation, and drying in vacuum at 60 ℃ for 24h to obtain the co-modified silicone oil intermediate. Adding 15.0g of dibutylamine and 1.1g of ethylenediamine crosslinking agent into a reactor with a heat exchange device in sequence, introducing nitrogen and stirring, adding 10.3g of epoxy chloropropane at 30 ℃, heating to 60 ℃ after the addition is finished, continuing stirring for reaction for 6h, cooling to obtain a yellow viscous liquid product, fully washing the product with 1:1 absolute ethyl alcohol-acetone, removing the solvent by rotary evaporation, and performing vacuum drying at 70 ℃ for 24h to obtain the polyquaternary ammonium salt. Sequentially adding 8.33g of polyquaternium and 15.0g of isopropanol into a reactor with a heat exchange device, introducing nitrogen and stirring, adding 10g of co-modified silicone oil at 35 ℃, stirring for reaction for 5 hours, cooling, washing the product with a 1:1 anhydrous ethanol-acetone solution for three times, performing rotary evaporation to remove the solvent, and performing vacuum drying for 24 hours to obtain the polyether polyquaternium reverse demulsifier (PPA). Fully mixing 10.0g of hydrated silica particles with the particle size distribution range of 50-100 mu m and 20.0g of silane coupling agent, adding the mixture into 100g of ethanol-water mixed solvent, stirring for 20min, adding 0.5g of methane sulfonic acid serving as a catalyst, and stirring and refluxing for 24h at 50 ℃. After the reaction is finished, washing the product with ethanol for 3 times, and then drying in vacuum at 70 ℃ for 12 hours to obtain the hydrophobic modified hydrated silicon dioxide. 6g of hydrophobic modified hydrated silica, 8.9g of PPA and 20.0g of isopropanol are added into a reactor with a heat exchange device, nitrogen is introduced and stirred, 4.2mL of 500mg/L catalyst chloroplatinic acid is added after 5min, and stirring and refluxing are carried out for 8h at 40 ℃. After the reaction is finished, cleaning the product with isopropanol for 2 times, then washing with ethanol for 1 time, and drying at 120 ℃ for 24 hours to obtain the final product SiO2@ PPA. 2.0g/LSiO is added into 100mL of three-element composite flooding produced water (wherein the alkali content is 700mg/L, the surfactant content is 300mg/L, and the polymer content is 500mg/L)2@ PPA was mixed well and shaken at 30 ℃ for 1 h. The oily sewage treated by the load type reverse demulsifier has clear oil-water interface, clear water color and 90.6 percent deoiling rate.
Example 4: mixing 212.4 g of epoxy ether, 14.2 g of methyl ether and 15.0g of hydrogen-containing silicone oil, adding 2.6mL of chloroplatinic acid serving as a 500mg/L catalyst, stirring for 20min, placing in a microwave reactor, reacting for 20min under the microwave power of 200W, fully dissolving a reaction product by using n-hexane, separating an undissolved product, performing rotary evaporation to remove a small amount of solvent, and performing vacuum drying at 60 ℃ for 24h to obtain a co-modified silicone oil intermediate. Adding 19.0g of dibutylamine and 0.3g of a polyvinyl polyamine crosslinking agent into a reactor with a heat exchange device in sequence, introducing nitrogen and stirring, adding 10.3g of epoxy chloropropane at 30 ℃, heating to 1h to 60 ℃ after the addition is finished, continuously stirring for reaction for 6h, cooling to obtain yellow viscous liquid, fully washing the product with 1:1 anhydrous ethanol-acetone, removing the solvent by rotary evaporation, and performing vacuum drying at 70 ℃ for 24h to obtain the polyquaternium. Sequentially adding 8.33g of polyquaternium and 15.0g of isopropanol into a reactor with a heat exchange device, introducing nitrogen and stirring, adding 10g of co-modified silicone oil at 35 ℃, stirring for reaction for 5 hours, cooling, washing the product with a 1:1 anhydrous ethanol-acetone solution for three times, performing rotary evaporation to remove the solvent, and performing vacuum drying for 24 hours to obtain the polyether polyquaternium reverse demulsifier (PPA). Fully mixing 10.0g of hydrated silicon dioxide particles with the particle size distribution range of 10-50 mu m and 20.0g of silane coupling agent, adding the mixture into 100g of ethanol-water mixed solvent, stirring for 20min, adding 0.5g of methane sulfonic acid serving as a catalyst, and stirring and refluxing for 24h at 40 ℃. After the reaction is finished, washing the product with ethanol for 3 times, and then drying in vacuum at 70 ℃ for 12 hours to obtain the hydrophobic modified hydrated silicon dioxide. 6g of hydrophobic modified hydrated silica, 8.9g of PPA and 20.0g of isopropanol are added into a reactor with a heat exchange device, nitrogen is introduced and stirred, 4.2mL of 500mg/L catalyst chloroplatinic acid is added after 5min, and stirring and refluxing are carried out for 8h at 40 ℃. After the reaction is finished, cleaning the product with isopropanol for 2 times, then washing with ethanol for 1 time, and drying at 120 ℃ for 24 hours to obtain the final product SiO2@ PPA. 1.5g/LSiO is added into 100mL of three-element composite flooding produced water (wherein the alkali content is 700mg/L, the surfactant content is 300mg/L, and the polymer content is 500mg/L)2@ PPA was mixed well and shaken at 30 ℃ for 1 h. The oily sewage treated by the load type reverse demulsifier has clear oil-water interface, clear water color and deoiling rate of 91.6 percent.
FIG. 7 is a comparison graph of the effects of treating ASP flooding produced water. Wherein the left figure is the water sample extracted by the ASP flooding with the oil concentration of 500mg/L, and the right figure is the water sample extracted by the ASP flooding2@ PPA treated water samples.
Example 5: mixing 18.4 g of epoxy ether, 28.6 g of methyl ether and 13.0g of hydrogen-containing silicone oil, adding 2.6mL of chloroplatinic acid serving as a 500mg/L catalyst, stirring for 20min, placing in a microwave reactor, reacting for 20min under the microwave power of 200W, fully dissolving a reaction product by using n-hexane, separating an undissolved product, performing rotary evaporation to remove a small amount of solvent, and performing vacuum drying at 60 ℃ for 24h to obtain a co-modified silicone oil intermediate. Adding 19.0g of dibutylamine and 0.5g of dibutylamine crosslinking agent into a reactor with a heat exchange device in sequence, introducing nitrogen and stirring, adding 10.3g of epoxy chloropropane at 30 ℃, heating to 60 ℃ after the addition is finished, continuing stirring for reaction for 6h, cooling to obtain a yellow viscous liquid product, fully washing the product with 1:1 absolute ethyl alcohol-acetone, removing the solvent by rotary evaporation, and performing vacuum drying at 70 ℃ for 24h to obtain the polyquaternary ammonium salt; sequentially adding 8.33g of polyquaternium and 15.0g of isopropanol into a reactor with a heat exchange device, introducing nitrogen and stirring, adding 10g of co-modified silicone oil at 35 ℃, stirring for reaction for 5 hours, cooling, washing the product with a 1:1 anhydrous ethanol-acetone solution for three times, performing rotary evaporation to remove the solvent, and performing vacuum drying for 24 hours to obtain the polyether polyquaternium reverse demulsifier (PPA). Fully mixing 10.0g of hydrated silicon dioxide particles with the particle size distribution range of 10-50 mu m and 20.0g of silane coupling agent, adding the mixture into 100g of ethanol-water mixed solvent, stirring for 20min, adding 0.5g of methane sulfonic acid serving as a catalyst, and stirring and refluxing for 24h at 50 ℃. After the reaction is finished, the product is washed by ethanol for 3 times and then is dried in vacuum at 70 ℃ for 12 hours, and the hydrophobic modified hydrated silicon dioxide is obtained. 6g of hydrophobic modified hydrated silica, 8.9g of PPA and 20.0g of isopropanol are added into a reactor with a heat exchange device, nitrogen is introduced and stirred, 4.2mL of 500mg/L catalyst chloroplatinic acid is added after 5min, and stirring and refluxing are carried out for 8h at 40 ℃. After the reaction is finished, cleaning the product with isopropanol for 2 times, then washing with ethanol for 1 time, and drying at 120 ℃ for 24 hours to obtain the final product SiO2@ PPA. In 100mL of three-component combination flooding produced water (wherein the alkali content is 700mg/L,Surfactant content of 300mg/L and polymer content of 500mg/L) was added to 1.5g/LSiO2@ PPA was mixed well and shaken at 30 ℃ for 1 h. The oily sewage treated by the load type reverse demulsifier has clear oil-water interface, clear water color and deoiling rate of 89.8 percent.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (8)
1. The utility model provides a three-element combination flooding produced water load type reverse demulsifier which characterized by: the structural formula of the load type reverse demulsifier is as follows:
wherein x is1＝1～30；x2＝1～30；x3＝1～20；y＝1～50；a＝7～19；b＝1～19；m＝9～10；n＝1～3。
2. The preparation method of the ternary combination flooding produced water loaded reverse demulsifier of claim 1 is characterized in that: the preparation method of the load type reverse demulsifier comprises the following steps: firstly, synthesizing a basic skeleton of a reverse demulsifier through hydrosilylation, then carrying out epoxy ring-opening reaction on polyquaternium and co-modified silicone oil to synthesize a polyether polyquaternium reverse demulsifier, and then adopting a silane coupling agent KH-570 to react with hydrated silicon dioxide (SiO)2·nH2O) surface is subjected to hydrophobic modification, and finally the polyether polyquaternium reverse demulsifier and the modified hydrated silicon dioxide are subjected to surface grafting polymerization reaction to prepare the load type reverse demulsifier.
3. The preparation method of the ASP flooding produced water loaded reverse demulsifier according to claim 2, which is characterized in that: the method comprises the following specific steps:
1) basic skeleton synthesis of reverse demulsifier molecules
Mixing epoxy ether, methyl ether and hydrogen-containing silicone oil, adding chloroplatinic acid as a catalyst, stirring for 20-30 min, placing in a microwave reactor, reacting for 10-40 min under the microwave power of 100-500W, fully dissolving a reaction product by using n-hexane, separating an undissolved product, performing rotary evaporation to remove a small amount of solvent, and performing vacuum drying at 60 ℃ for 24h to obtain an epoxy ether methyl ether co-modified silicone oil intermediate;
2) polyquaternary ammonium salt synthesis
Sequentially adding dibutylamine and an organic amine cross-linking agent into a reactor with a condensing device, introducing nitrogen and stirring, slowly adding epoxy chloropropane at 10-30 ℃, heating to 40-80 ℃ after adding, continuously stirring for reacting for 3-8 h, cooling to obtain a yellow viscous liquid product, fully washing the reaction product with 1:1 anhydrous ethanol-acetone, then performing rotary evaporation to remove the solvent, and performing vacuum drying at 70 ℃ for 24h to obtain a product polyquaternary ammonium salt;
3) synthesis of polyether polyquaternary ammonium salt type reverse demulsifier
Sequentially adding polyquaternium and an alcohol solvent into a reactor with a condensing device, introducing nitrogen and stirring, adding co-modified silicone oil at 25-45 ℃, stirring and reacting for 3-7 h, cooling, washing a product with a 1:1 anhydrous ethanol-acetone solution for multiple times, removing the solvent by rotary evaporation, and drying in vacuum for 24h to obtain the polyether polyquaternium PPA;
4) hydrophobic modification of carrier hydrated silica
Fully mixing hydrated silicon dioxide and a silane coupling agent, adding the mixture into an alcohol solvent, stirring for 20-30 min, adding a catalyst methanesulfonic acid, stirring and refluxing for 16-32 h at 35-60 ℃, washing a product with ethanol for 3-5 times after the reaction is finished, and performing vacuum drying for 12-14 h at 70-90 ℃ to obtain hydrophobically modified hydrated silicon dioxide;
5) synthesis of load type reverse demulsifier
Adding hydrophobic modified hydrated silicon dioxide, polyether polyquaternium PPA and an alcohol solvent into a reactor with a heat exchange device, introducing nitrogen and stirring, adding a catalyst chloroplatinic acid after 5min, stirring and refluxing for 6-10 h at 30-50 ℃, washing with isopropanol and ethanol for multiple times after the reaction is finished, and then at 120 DEG CDrying for 24 hours to obtain the final product SiO2@PPA。
4. The preparation method of the ASP flooding produced water loaded reverse demulsifier according to claim 3, which is characterized in that: the epoxy ether added in the preparation step 1) is allyl polyoxyethylene polyoxypropylene epoxy ether-1, EO: PO 10:1, allyl polyoxyethylene polyoxypropylene epoxy ether-2, EO: PO 3: 1; the methyl ether is allyl polyoxyethylene polyoxypropylene methyl ether-1, EO is PO 1:1, allyl polyoxyethylene polyoxypropylene methyl ether-2, EO is PO 7: 1; the hydrogen-containing silicone oil comprises 0.1 to 0.25 percent of hydrogen by mass percent; the molar ratio of the epoxy ether to the methyl ether is 1: 5-5: 1, the molar ratio of the silicon-hydrogen bond to the carbon-carbon double bond is 1: 1.0-1: 1.2, and the dosage of the catalyst chloroplatinic acid is 10-50 mu g/g.
5. The preparation method of the ASP flooding produced water loaded reverse demulsifier according to claim 3, which is characterized in that: the mol ratio of the epoxy chloropropane to the dibutylamine in the preparation step 2) is 1: 0.9-1: 1.4; the organic amine crosslinking agent is ethylenediamine, n-butylamine and polyethylene polyamine, and the adding amount of the organic amine is 1-15% of the mass percentage of the reaction mass.
6. The preparation method of the ASP flooding produced water loaded reverse demulsifier according to claim 3, which is characterized in that: the alcohol solvent in the preparation step 3) is methanol, ethanol or isopropanol; the mass ratio of the polyquaternium to the co-modified silicone oil to the alcohol solvent is 0.8-1.2: 0.5-2.5: 15-30.
7. The preparation method of the ASP flooding produced water loaded reverse demulsifier according to claim 3, which is characterized in that: the silane coupling agent in the preparation step 4) is 3-methacryloxypropyltrimethoxysilane; the alcohol solvent is methanol, ethanol or isopropanol, and the mass ratio of the alcohol solvent to water to methane sulfonic acid is 1:1: 0.03-0.07; the particle size distribution range of the hydrated silicon dioxide particles is 10-100 mu m, and the mass ratio of the hydrated silicon dioxide to the silane coupling agent is 0.8-1.2: 2.0-10.0.
8. The preparation method of the ASP flooding produced water loaded reverse demulsifier according to claim 3, which is characterized in that: the alcohol solvent in the preparation step 5) is methanol, ethanol or isopropanol; the mass ratio of the hydrophobically modified silicon dioxide to the polyether polyquaternium PPA to the alcohol solvent is 0.6-0.8: 0.8-1.2: 2.0-3.0; the dosage of the catalyst chloroplatinic acid is 40-80 mu g/g.
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| CN109054888B (en) * | 2018-07-26 | 2021-01-01 | 中国石油天然气集团有限公司 | Demulsifier and preparation method thereof |
| CN110041474B (en) * | 2019-04-15 | 2021-11-30 | 中国海洋石油集团有限公司 | Organic/inorganic hybrid cation reverse demulsifier and preparation method and application thereof |
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| CN111302436A (en) * | 2020-03-02 | 2020-06-19 | 东南大学 | Preparation method of adsorption type demulsifier for oil-water separation of cleaning waste liquid |
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| 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 |
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