CN113429955A - 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 - Google Patents
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 Download PDFInfo
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Abstract
The invention discloses a preparation method of a load type polyether polyquaternary ammonium salt reverse demulsifier and application thereof in treating ternary combination flooding produced water. Firstly, polyether polyquaternium is synthesized through ring-opening addition reaction, and then the polyether polyquaternium is introduced to the surface of a porous metal organic frame with large specific surface area through a surface grafting method, so that the load type polyether polyquaternium reverse demulsifier with high interfacial activity and high deoiling property is constructed. The load type reverse demulsifier prepared by the invention has the functions of demulsification and adsorption, the polyether polyquaternary ammonium salt is demulsified by displacement and electric neutralization, and after the demulsification is finished, the carrier can quickly adsorb oil drops and is separated by gravity settling, so that the purpose of oil-water separation is achieved. Finally, the oil-carrying carrier is regenerated by a solvent method, crude oil is recovered, and the treated water meets the reinjection requirement and can be directly recycled, so that the treatment efficiency of the ASP flooding produced water is effectively improved. The preparation method has the advantages of simple equipment, convenient operation, refined steps and strong practicability.
Description
Technical Field
The invention belongs to the technical field of oily sewage treatment, relates to preparation and application of a reverse demulsifier, and particularly relates to preparation of a load type polyether polyquaternary ammonium salt reverse demulsifier and application of the load type polyether polyquaternary ammonium salt reverse demulsifier in ternary combination flooding produced water treatment.
Background
The ternary combination flooding is a tertiary oil recovery technology for injecting a mixed solution of three chemical agents of alkali, a surfactant and a polymer, and the recovery ratio is improved by more than 20 percent compared with that of the common water flooding. With the popularization and application of the ASP flooding oil extraction technology, a large amount of produced water is generated. The ternary combination flooding produced water is an O/W type emulsification system, has complex water quality, high oil-containing emulsification degree, high viscosity, high interfacial film strength, fine oil drop particle size (less than 10 mu m), low interfacial tension, stable phase state and high oil-water separation difficulty, and can damage water injection equipment and block pipelines if the reinjection standard cannot be met after the treatment or the treatment, and the water body can be polluted and the ecological balance can be damaged due to the direct discharge.
The conventional demulsification methods comprise a gravity settling method, a dissolved air flotation method, a biological treatment method, an electrochemical method, a coagulation-flocculation method, a membrane treatment method and the like, but the conventional demulsification methods have the defects of low removal efficiency, overlong treatment period, large investment on infrastructure and equipment, wide occupied area, easiness in causing secondary pollution and the like generally, and are not suitable for treating the oilfield produced water with high emulsified oil content, oil drop particle size of less than 10 mu m and large water yield. The chemical demulsification method has high efficiency and strong practicability, and a surfactant which can be strongly adsorbed on an oil-water interface is selected to replace an emulsifier which generates a firm film in an emulsion to generate a new film, so that the demulsification is realized due to the obvious reduction of the strength of the film. At present, the conventional reverse demulsifiers mainly comprise polyether, polysiloxane, polyquaternary ammonium salt and the like, and the reverse demulsifiers are already applied on site. Li Sanxi et al [ Fine petrochemical, 2015,32,25] uses an ethylene oxide/propylene oxide block unsaturated polyether as raw material, uses Benzoyl Peroxide (BPD) as initiator, xylene as solvent, uses acrylic acid to make chain extension, and adds hydrochloric acid as catalyst to further esterify and synthesize a comb-type polyether demulsifier. Asis k. et al [ Journal of Applied Polymer Science,2014,131,1366] use polypropylene glycol and xylene as solvents, polyether and xylene of different polarity are fully reacted in a high pressure homogeneous reactor to prepare polyether demulsifier. In patent CN101357992A, firstly, a linear polyquaternium is prepared by ring-opening polymerization of organic amines such as secondary amine and tertiary amine and epichlorohydrin, and then a star polyquaternium cationic reverse demulsifier is prepared by taking dendritic polyamide-amine as a cross-linking agent. The prepared demulsifier and the conventional demulsifier have the following problems after demulsification: the micro-fine fraction oil drops are difficult to coalesce, and the demulsifier and the oil displacement surfactant (alkali, surfactant and polymer) generate competitive adsorption on the surface of the oil drops to have a secondary emulsification phenomenon, so that the demulsification and emulsification processes of the ASP flooding produced water system coexist and are reversible, and the demulsification difficulty is further increased. Therefore, the development of a novel efficient demulsifier for treating the ASP flooding produced water is urgently needed.
Disclosure of Invention
The invention aims to provide a preparation method of a load type polyether polyquaternium reverse demulsifier.
The invention also aims to provide the application of the reverse demulsifier prepared by the preparation method in the treatment of the three-element composite flooding produced water.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
on one hand, the invention provides a preparation method of a load type polyether polyquaternium reverse demulsifier, which comprises the following steps:
firstly, preparing polyether polyquaternium: carrying out ring-opening addition reaction on di-n-butylamine and epoxy chloropropane to synthesize polyquaternium, and carrying out ring-opening addition reaction on the synthesized polyquaternium and glycerol ether again to synthesize polyether polyquaternium;
step two, preparation of UiO-66: synthesizing a metal organic framework UiO-66 by a solvothermal method by taking terephthalic acid as an organic ligand and zirconium tetrachloride as a zirconium source;
step three, preparation of the load type polyether polyquaternary ammonium salt reverse demulsifier: polyether polyquaternium is introduced to the surface of the UiO-66 carrier by adopting a surface grafting method to obtain the load type polyether polyquaternium reverse demulsifier.
Preferably, the preparation method of the polyether polyquaternium comprises the following specific steps: uniformly mixing di-n-butylamine and an organic amine cross-linking agent in proportion, stirring at a constant temperature of 20-30 ℃ for 1-2 hours in an inert atmosphere, then slowly dropwise adding epoxy chloropropane, slowly increasing the temperature to 60-80 ℃ in the dropwise adding process, and continuously reacting at a constant temperature for 3-7 hours after the dropwise adding is finished; after the reaction is finished, adjusting the pH value to be 5, adding an absolute ethyl alcohol-acetone mixed solution with the volume ratio of 1:1, and fully washing to obtain yellow viscous liquid polyquaternium; and adding the polyquaternium into an alcohol solvent, slowly dropwise adding glycerol ether at room temperature, heating to 60-70 ℃ after dropwise adding, keeping the temperature for reacting for 4-7 h, adding an absolute ethyl alcohol-acetone mixed solution with the volume ratio of 1:1 after the reaction is finished, fully washing, and drying in vacuum to semi-solid brown yellow to obtain the polyether polyquaternium demulsifier.
Preferably, the mass ratio of the di-n-butylamine to the epoxy chloropropane is 1.75: 1-1.4: 1; the glycerol ether is allyl polyethylene glycol glycidyl ether; the mass ratio of the polyquaternium to the glycerol ether is 4: 5-4: 9.
Preferably, the organic amine crosslinking agent is one of ethylenediamine, n-butylamine and polyethylene polyamine.
Preferably, the alcohol solvent is one of methanol, ethanol or isopropanol.
Preferably, the preparation method of the UiO-66 specifically comprises the following steps: weighing a proper amount of zirconium tetrachloride, placing the zirconium tetrachloride in a reaction kettle, adding N, N-dimethylformamide and concentrated hydrochloric acid, performing ultrasonic dispersion, then weighing a proper amount of terephthalic acid, placing the terephthalic acid in the solution, performing ultrasonic dispersion, then placing the reaction kettle in an electric heating forced air drying box, reacting for 12-18 h at 80-90 ℃, taking out, washing for 7-8 times with absolute ethyl alcohol, and performing vacuum drying to obtain UiO-66.
Preferably, the molar ratio of the zirconium tetrachloride to the terephthalic acid is 1: 1-1: 2; the volume ratio of the N, N-dimethylformamide to the concentrated hydrochloric acid is 10: 1-12: 1.
Preferably, the preparation method of the load type polyether polyquaternium reverse demulsifier comprises the following specific steps: respectively weighing a proper amount of polyether polyquaternium and UiO-66, weighing a certain volume of isopropanol, adding the isopropanol into a reactor, stirring for 5-10 min in an inert atmosphere, adding a catalyst chloroplatinic acid, stirring at 70-80 ℃ for reaction for 6-10 h, and drying to obtain the product of polyether polyquaternium loaded UiO-66, namely PPA @ UiO-66.
Preferably, the mass ratio of the polyether polyquaternium to the UiO-66 is 2: 1-2.5: 1; the concentration of the chloroplatinic acid is 30-50 mu g/g.
On the other hand, the invention also provides the application of the load type polyether polyquaternium reverse demulsifier prepared by the preparation method in the treatment of the ternary combination flooding produced water.
The method comprises the following specific steps: adding the loaded reverse-phase demulsifier solid powder into the ASP flooding produced water in an adding amount of 0.3-0.5 g/L, oscillating and adsorbing at a constant temperature of 20-40 ℃ and 150r/min for 50-80 min, and then standing and settling for 50-60 min.
In addition, the invention also provides a regeneration process of the oil carrying carrier.
The method for recovering the oil-carrying carrier particles by adopting a solvent regeneration method comprises the following specific steps: transferring the dried oil-carrying particles into a filter paper cylinder, putting the filter paper cylinder into a Soxhlet extractor, extracting petroleum ether from the upper end of an extraction condensing pipe of the extractor to 2/3 of the volume in the bottle, controlling the heating reflux temperature to be 83 ℃ (the boiling range of the petroleum ether is 60-90 ℃), keeping the petroleum ether in a slightly boiling state and continuously refluxing and extracting for 4 hours, and finally taking out the carrier particles and putting the carrier particles into a vacuum drying oven for vacuum drying for 12 hours at 100 ℃.
The load type polyether polyquaternium reverse demulsifier has demulsification and adsorption effects, and the polyether polyquaternium has positive charges, has strong affinity with an oil-water interface membrane, can be strongly adsorbed on an oil-water interface, replaces the original surfactant, reduces the interfacial tension of the surface of oil drops, and thins the interface membrane; in addition, positive charges on the surface of the polyether polyquaternium can neutralize negative charges of an interfacial film and reduce repulsive force among oil drops, so that the polyether polyquaternium has the effect of demulsification and destabilization. After demulsification is finished, oil drops can be quickly adsorbed and captured by the carrier particles UiO-66, and the carrier particles adsorbed with the oil drops are separated by gravity settling, so that the purpose of oil-water separation is achieved. Finally, the oil-carrying carrier is regenerated by a solvent method, crude oil is recovered, and the treated water meets the reinjection requirement and can be directly recycled, so that the treatment efficiency of the ASP flooding produced water is effectively improved.
The invention adopts a metal organic framework material UiO-66 with ultra-large specific surface area, ultra-high porosity and delicate pore structure as an adsorbent, and introduces polyether polyquaternium to the surface of a UiO-66 carrier by adopting a surface grafting method to obtain the load type polyether polyquaternium reverse demulsifier. The process is simple and convenient to operate, the investment is low, the treatment efficiency is high, and the separated emulsified oil can be recycled and can be reused as a renewable resource.
Drawings
FIG. 1 is a microscopic image of UiO-66 and PPA @ UiO-66 prepared in example 1 of the present invention, observed under a scanning electron microscope. Wherein: (a) is UiO-66; (b) is PPA @ UiO-66.
FIG. 2 is a graph of nitrogen sorption-desorption curves for UiO-66(a) and PPA @ UiO-66(b) prepared in inventive example 1.
Fig. 3(a) is a graph showing the change in the emulsified oil removal rate with the change in contact time according to example 2 of the present invention.
FIG. 3(b) is a graph showing the change in the equilibrium adsorption amount of the emulsified oil according to example 2 of the present invention with the change in the contact time.
FIG. 4 is a photograph showing the removal efficiency of emulsified oil according to example 2 of the present invention as a function of contact time.
FIG. 5 is an adsorption equilibrium isotherm of emulsified oil of example 3 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1: preparation of PPA @ UiO-66 reverse demulsifier
(1) Preparation of polyether polyquaternium
16.8g of di-n-butylamine and 1.0g of polyethylene polyamine, which were weighed, were added to a beaker, and transferred to a 250mL three-necked flask after being mixed uniformly. The three-neck flask is provided with a reflux condensing device and a constant-pressure dropping funnel, 9.6g of epoxy chloropropane is accurately weighed and placed in the constant-pressure dropping funnel, the three-neck flask is placed on a constant-temperature magnetic stirring water bath kettle, nitrogen is introduced to discharge air in a reaction system, air is prevented from entering in subsequent reaction, and constant-temperature water bath is carried out for 1h at the temperature of 30 ℃ at a proper stirring speed. Slowly dripping epichlorohydrin into the flask at the dripping speed of 1mL/10min, slowly raising the temperature to 70 ℃ in the dripping process, and continuously reacting for 4 hours at constant temperature after the dripping is finished. After the reaction was completed, the pH was adjusted to 5, and 20mL of an absolute ethanol-acetone solution at a volume ratio of 1:1 was added thereto, and the mixture was sufficiently washed to obtain a yellow viscous liquid polyquaternium. And then 9.8g of the polyquaternium obtained in the first step and 10g of isopropanol as a solvent are weighed and placed in a three-neck flask, 12.4g of allyl polyethylene glycol glycidyl ether is weighed and placed in a constant pressure dropping funnel, the glycerol ether is slowly dropped into the three-neck flask, after the dropping is finished, the temperature is raised to 60 ℃ for reaction, the temperature is kept for reaction for 5 hours, then 20mL of absolute ethyl alcohol-acetone solution with the volume ratio of 1:1 is added for full washing, and the mixture is dried in vacuum to be semi-solid brown yellow, so that the polyether polyquaternium demulsifier is obtained.
The chemical equation is as follows:
(2) preparation of UiO-66
Weighing 0.123g of zirconium tetrachloride, placing the zirconium tetrachloride in a reaction kettle, adding 10mL of DMMF and 1mL of concentrated hydrochloric acid, performing ultrasonic dispersion, weighing 0.125g of terephthalic acid, placing the terephthalic acid in the solution, performing ultrasonic dispersion, placing the reaction kettle in an electric heating forced air drying oven, reacting for 12h at 80 ℃, taking out, washing for 7-8 times with absolute ethyl alcohol, and performing vacuum drying for 12h at 100 ℃ to obtain UiO-66.
(3) Preparation of load type polyether polyquaternary ammonium salt reverse demulsifier
Accurately weighing the polyether polyquaternium obtained in the second step and the UiO-66 obtained in the third step according to the mass ratio of 2:1, measuring a certain volume of isopropanol, adding the isopropanol into a three-neck flask, stirring for 5min in an inert atmosphere, adding a catalyst chloroplatinic acid, wherein the concentration of the chloroplatinic acid is 40 mu g/g, adjusting the temperature to 70 ℃, stirring and reacting for 6h in a constant-temperature magnetic stirrer, and vacuum drying for 12h to obtain the product of the polyether polyquaternium loaded UiO-66, namely PPA @ UiO-66.
The chemical equation is as follows:
FIG. 1 shows the micro-topography of UiO-66(a) and PPA @ UiO-66(b) observed under a scanning electron microscope. UiO-66 can be seen as spherical particles with a size of about 100nm, with no change in crystal particle morphology and size after loading.
FIG. 2 shows the nitrogen desorption curves for UiO-66 and PPA @ UiO-66. As can be seen, the adsorption-desorption curves are I-type adsorption isotherms, and the BET specific surface areas of UiO-66 and PPA @ UiO-66 are 722.08m2/g、623.47m2The BET specific surface area after loading is reduced because the surface of UiO-66 is wrapped by polyether polyquaternium demulsifier chain, and partial pore channels on the surface are blocked.
The simulated ASP flooding produced water used in the following examples is prepared according to the Water quality index of ASP flooding produced water in Daqing oilfield:
preparing mineralized water: the total mineralization degree of the mineralized water is 3729.7mg/L, wherein the concentration of sodium chloride is 1167.2mg/L, the concentration of sodium bicarbonate is 2442.9mg/L, the concentration of sodium sulfate is 6.8mg/L, the concentration of calcium chloride is 59.7mg/L, the concentration of magnesium chloride hexahydrate is 53.1mg/L, a proper amount of five inorganic salts are respectively weighed and dissolved in a certain amount of deionized water, finally, the volume is determined by a volumetric flask, and the mineralized water is well prepared by shaking up;
preparing an oil drop mother solution: adding surfactant sodium dodecyl benzene sulfonate and polymer polyacrylamide into mineralized water to prepare a solution with the concentrations of both the polymer and the surfactant being 1000 mg/L. Adding the solution and crude oil in a ratio of 1:1 into a wide-mouth bottle, then carrying out constant-temperature water bath at 45 ℃ for 60min to disperse the surface of the oil, and emulsifying for 15min by using a high-shear dispersion emulsifying homogenizer to prepare oil drop mother liquor with the oil content of 50%;
preparing simulated produced water: preparing solutions with the concentration of sodium hydroxide, the concentration of sodium dodecyl benzene sulfonate and the concentration of polyacrylamide being 700mg/L, 300mg/L and 500mg/L respectively by using mineralized water as a solvent, weighing 0.4g of oil drop mother liquor, adding the oil drop mother liquor into the solutions, carrying out constant-temperature water bath for 20min, and waiting until the oil drop mother liquor is dispersed. Emulsifying for 20min by using a high-shear dispersion emulsifying homogenizer, standing for 1-2 h, and removing floating oil on the solution by using absorbent cotton to obtain stable ternary combination flooding produced water to prepare simulated produced water, wherein the oil content of the ternary combination flooding produced water is about 250-400 mg/L.
Example 2: application of PPA @ UiO-66 reverse demulsifier in treating ternary combination flooding produced water
Taking 7 parts of simulated ASP flooding produced water, wherein each part is 50mL, the initial concentration of emulsified oil is 260mg/L, the temperature is 20 ℃, and the oscillation frequency is 150 r/min.
Adding equivalent PPA @ UiO-66 into each part of simulated ASP produced water according to the adding amount of 0.4g/L, oscillating at constant temperature of 20 ℃ and 150r/min, respectively taking out a group of water samples when the contact time is 5, 10, 15, 20, 30, 50 and 60min, standing, settling and layering for about 50min, collecting supernatant, adding 10mL of middle-layer liquid into a separating funnel by using a pipette, transferring 10mL of petroleum ether for full extraction, and standing for 15min to separate into a petroleum ether phase and a water phase. And (3) transferring the petroleum ether phase into a cuvette, measuring the absorbance of the petroleum ether phase at the wavelength of 258nm by using an ultraviolet spectrophotometer, determining the oil content according to a standard curve, and determining the concentration of the residual emulsified oil. Calculating the equilibrium adsorption quantity qeInvestigation of contact time on Carrier particle qeThe influence of (c).
qeThe calculation formula is as follows:
in the formula, qe-equilibrium adsorption capacity, mg/g; v-simulated water sample volume, L; c0-simulating the initial oil concentration of the water sample, mg/L; ce-residual oil concentration in the water sample after adsorption equilibration, mg/L; m-addition of adsorbent, g.
The results show that: the emulsified oil removal efficiency increased with longer contact time as shown in figure 3 a. Equilibrium adsorption capacity qeThe adsorption reached essentially equilibrium state after a rapid increase and then gradually stabilized, when the contact time was 50min, as shown in fig. 3 b. In the initial stage, the carrier particles are in a range of 0-30 minA large number of adsorption active sites exist on the surface, the oil concentration in the water sample is higher, the driving force of the adsorption process is larger, the adsorption rate is higher, and q iseIncreasing; as the adsorption sites are occupied by oil droplets, the adsorption driving force decreases, qeIncrease slowly until adsorption equilibrium. Fig. 4 is a digital photograph of the emulsified oil removal efficiency as a function of contact time, which visually demonstrates a dynamic adsorption process. The load type reverse demulsifier is an effective demulsifier for removing emulsified oil in the simulated ASP flooding produced water, and has the functions of demulsification and adsorption.
Example 3: application of PPA @ UiO-66 reverse demulsifier in treating ternary combination flooding produced water
Taking 15 parts of simulated ASP flooding produced water, wherein each part is 50mL, dividing the produced water into three groups, each group comprises 5 parts, the initial concentration of emulsified oil is 75-450 mg/L, the temperature is 20 ℃, 30 ℃ and 40 ℃, the contact time is 50min, and the oscillation frequency is 150 r/min.
Selecting the PPA @ UiO-66 dosage of 0.4g/L at the temperature of 20 ℃, 30 ℃ and 40 ℃, oscillating in a water bath for 50min under the condition of 150r/min, standing and settling for about 50min, collecting supernatant, and determining the concentration of the residual emulsified oil. And (3) under the condition that the initial oil concentration is 75-450 mg/L, examining the influence of the adsorption temperature on the oil removal rate and the adsorption quantity.
The results show that: as shown in FIG. 5, the equilibrium adsorption capacity of PPA @ UiO-66 increased with increasing initial oil concentration under the same temperature conditions. In addition, the equilibrium adsorption capacity of PPA @ UiO-66 increases with the increase of temperature, and the fact that the emulsified oil is adsorbed from the simulated ASD flooding water by using the reverse demulsifier can be inferred to be an endothermic process, and the increase of temperature is helpful for the adsorption process.
Example 4: regeneration of oil-carrying vehicles
The method for recovering the oil-carrying carrier particles by adopting a solvent regeneration method comprises the following specific steps: transferring the dried oil-carrying particles into a filter paper cylinder, putting the filter paper cylinder into a Soxhlet extractor, extracting petroleum ether from the upper end of an extraction condensing pipe of the extractor to 2/3 of the volume in the bottle, controlling the heating reflux temperature to be 83 ℃ (the boiling range of the petroleum ether is 60-90 ℃), keeping the petroleum ether in a slightly boiling state and continuously refluxing and extracting for 4 hours, and finally taking out the carrier particles and putting the carrier particles into a vacuum drying oven for vacuum drying for 12 hours at 100 ℃.
Claims (11)
1. The preparation method of the load type polyether polyquaternium reverse demulsifier is characterized by comprising the following steps:
firstly, preparing polyether polyquaternium: carrying out ring-opening addition reaction on di-n-butylamine and epoxy chloropropane to synthesize polyquaternium, and carrying out ring-opening addition reaction on the synthesized polyquaternium and glycerol ether again to synthesize polyether polyquaternium;
step two, preparation of UiO-66: synthesizing a metal organic framework UiO-66 by a solvothermal method by taking terephthalic acid as an organic ligand and zirconium tetrachloride as a zirconium source;
step three, preparation of the load type polyether polyquaternary ammonium salt reverse demulsifier: polyether polyquaternium is introduced to the surface of the UiO-66 carrier by adopting a surface grafting method to obtain the load type polyether polyquaternium reverse demulsifier.
2. The preparation method of the load type polyether polyquaternium reverse demulsifier according to claim 1, wherein the preparation method of the polyether polyquaternium comprises the following specific steps: uniformly mixing di-n-butylamine and an organic amine cross-linking agent in proportion, stirring at a constant temperature of 20-30 ℃ for 1-2 hours in an inert atmosphere, then slowly dropwise adding epoxy chloropropane, slowly increasing the temperature to 60-80 ℃ in the dropwise adding process, and continuously reacting at a constant temperature for 3-7 hours after the dropwise adding is finished; after the reaction is finished, adjusting the pH value to be 5, adding an absolute ethyl alcohol-acetone mixed solution with the volume ratio of 1:1, and fully washing to obtain yellow viscous liquid polyquaternium; and adding the polyquaternium into an alcohol solvent, slowly dropwise adding glycerol ether at room temperature, heating to 60-70 ℃ after dropwise adding, keeping the temperature for reacting for 4-7 h, adding an anhydrous ethanol: alcohol-acetone mixed solution with a volume ratio of 1:1 after the reaction is finished, fully washing, and drying in vacuum to semi-solid brown yellow to obtain the polyether polyquaternium demulsifier.
3. The preparation method of the supported polyether polyquaternium reverse demulsifier according to claim 2, wherein the mass ratio of di-n-butylamine to epichlorohydrin is 1.75: 1-1.4: 1; the glycerol ether is allyl polyethylene glycol glycidyl ether; the mass ratio of the polyquaternium to the glycerol ether is 4: 5-4: 9.
4. The method for preparing the loaded polyether polyquaternium reverse demulsifier according to claim 2, wherein the organic amine crosslinking agent is one of ethylenediamine, n-butylamine and polyethylene polyamine.
5. The method for preparing the loaded polyether polyquaternium reverse demulsifier according to claim 2, wherein the alcohol solvent is one of methanol, ethanol or isopropanol.
6. The preparation method of the supported polyether polyquaternium reverse demulsifier according to claim 1, wherein the preparation of the UiO-66 specifically comprises the following steps: weighing a proper amount of zirconium tetrachloride, placing the zirconium tetrachloride in a reaction kettle, adding N, N-dimethylformamide and concentrated hydrochloric acid, performing ultrasonic dispersion, then weighing a proper amount of terephthalic acid, placing the terephthalic acid in the solution, performing ultrasonic dispersion, then placing the reaction kettle in an electric heating forced air drying box, reacting for 12-18 h at 80-90 ℃, taking out, washing for 7-8 times with absolute ethyl alcohol, and performing vacuum drying to obtain UiO-66.
7. The preparation method of the supported polyether polyquaternium reverse demulsifier according to claim 6, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid is 1: 1-1: 2; the volume ratio of the N, N-dimethylformamide to the concentrated hydrochloric acid is 10: 1-12: 1.
8. The preparation method of the load type polyether polyquaternium reverse demulsifier according to claim 1, wherein the preparation method of the load type polyether polyquaternium reverse demulsifier comprises the following specific steps: respectively weighing a proper amount of polyether polyquaternium and UiO-66, weighing a certain volume of isopropanol, adding the isopropanol into a reactor, stirring for 5-10 min in an inert atmosphere, adding a catalyst chloroplatinic acid, stirring at 70-80 ℃ for reaction for 6-10 h, and drying to obtain the product of polyether polyquaternium loaded UiO-66, namely PPA @ UiO-66.
9. The preparation method of the load type polyether polyquaternium reverse demulsifier according to claim 8, wherein the mass ratio of the polyether polyquaternium to the UiO-66 is 2: 1-2.5: 1; the concentration of the chloroplatinic acid is 30-50 mu g/g.
10. The application of the load type polyether polyquaternium reverse demulsifier prepared by the preparation method of any one of claims 1 to 9 in the treatment of the three-component combination flooding produced water.
11. The application of claim 10, comprising the following steps:
adding the loaded reverse-phase demulsifier solid powder into the ASP flooding produced water in an adding amount of 0.3-0.5 g/L, oscillating and adsorbing at a constant temperature of 20-40 ℃ and 150r/min for 50-80 min, and then standing and settling for 50-60 min.
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