CN-121991358-A - Fluorescent nano demulsifier and preparation method and application thereof

CN121991358ACN 121991358 ACN121991358 ACN 121991358ACN-121991358-A

Abstract

The invention discloses a fluorescent nanometer demulsifier and a preparation method and application thereof, wherein the method comprises the following steps of (1) preparing a modified nanometer material; and (2) dispersing the modified nano material in a solvent C, reacting with polystyrene maleic anhydride in the presence of a catalyst to obtain modified nano material grafted polystyrene maleic anhydride, dispersing the modified nano material grafted polystyrene maleic anhydride in a solvent D, then adding porphyrin-based polyamine resin into the solvent D for reaction, and obtaining the fluorescent nano demulsifier containing porphyrin fluorescent groups after the reaction is finished. The invention has the advantages of (1) good demulsification and oil removal functions, (2) capability of avoiding the generation of aged oil and oil sludge, (3) capability of observing the molecular motion process and the demulsification process of the fluorescent nano demulsifier, and (4) magnetism of the prepared fluorescent nano demulsifier when the nano particles are nano Fe 3 O 4 , and recycling under a magnetic field.

Inventors

SUN LIMEI
AN SHENFA
MENG YONG
Gong shanjun
LUAN ZHIYONG
LIU WENSHENG
FU FADONG
WANG YANG
MA JILIANG

Assignees

中国石油化工股份有限公司
中国石油化工股份有限公司胜利油田分公司

Dates

Publication Date: 20260508
Application Date: 20241104

Claims (20)

1. The fluorescent nanometer demulsifier is characterized in that the fluorescent nanometer demulsifier adopts polystyrene maleic anhydride as a bridging polymer, anhydride groups in the polystyrene maleic anhydride are respectively crosslinked with modified nanometer materials and porphyrin-based polyamine resin to obtain the fluorescent nanometer demulsifier containing porphyrin fluorescent groups, wherein: in the fluorescent nanometer demulsifier, the mass ratio of the groups from the polystyrene maleic anhydride, the modified nanomaterial and the porphyrin-based polyamine resin is 1 (0.1-1); The molecular weight range of the polystyrene maleic anhydride is 2000-100000; Taking the mass of the polystyrene maleic anhydride as a reference, wherein the content of the maleic anhydride is 5-50wt%; The modified nano material is one or more of modified nano TiO 2 , modified nano ZnO, modified nano SiO 2 , modified nano Fe 3 O 4 , modified graphene oxide and modified carbon nano tubes; the porphyrin-based polyamine resin is a compound shown in the following formula (I) or formula (II) or formula (III): Wherein 0<m is less than or equal to 3; R 1 、R 2 、R 3 is independently selected from one of H, cl, br, NO 2 、C n H 2n+1 or OC n H 2n+1 , wherein n=1 to 20.
2. The fluorescent nanoemulsion of claim 1, wherein the polystyrene maleic anhydride has a molecular weight in the range of 10000-50000, and/or And the content of the maleic anhydride is 10-40 wt% based on the mass of the polystyrene maleic anhydride.
3. The fluorescent nanoemulsifying agent of claim 1, wherein the porphyrin-based polyamine resin is a compound represented by the following formula (I) or formula (II) or formula (III): Wherein, m is more than or equal to 1 and less than or equal to 3;R 1 、R 2 、R 3 is respectively and independently selected from one of H, cl, br, NO 2 、C n H 2n+1 or OC n H 2n+1 , and n=1-10.
4. A method for preparing the fluorescent nanoemulsion according to any one of claims 1 to 3, comprising the following steps in parts by mass: (1) Carrying out modification reaction on the nano material and dopamine hydrochloride or tannic acid or silane coupling agent to obtain a modified nano material; (2) Dispersing the modified nano material in a solvent C, and reacting with polystyrene maleic anhydride in the presence of a catalyst p-toluenesulfonic acid or sulfuric acid to obtain modified nano material grafted polystyrene maleic anhydride; (3) Dispersing the modified nanomaterial grafted polystyrene maleic anhydride in a solvent D, then adding porphyrin-based polyamine resin into the solvent D for reaction, and obtaining the fluorescent nanometer demulsifier containing porphyrin fluorescent groups after the reaction is finished.
5. The method of claim 4, wherein the nanomaterial in step (1) is one or more of nano TiO 2 , nano ZnO, nano SiO 2 , nano Fe 3 O 4 , graphene oxide, and carbon nanotubes.
6. The method for preparing a fluorescent nanoemulsion as claimed in claim 5, wherein the nano Fe 3 O 4 is prepared by a solvothermal method, and comprises the following specific steps in parts by mass: 1 part of ferric trichloride hexahydrate, 1-5 parts of sodium acetate and 1-5 parts of polyethylene glycol are dissolved in a proper amount of solvent, are stirred uniformly and then are transferred into a polytetrafluoroethylene reaction kettle, are heated and reacted for at least 4 hours, preferably for 4-20 hours at a temperature of at least 120 ℃, so as to obtain a black product, are sequentially washed by ultrapure water and absolute ethyl alcohol for at least 3 times respectively, and are dried in vacuum for at least 3 hours, preferably for 3-12 hours at a temperature of at least 40 ℃, preferably at a temperature of 40-80 ℃, so as to obtain nano Fe 3 O 4 .
7. The method of claim 6, wherein the solvent is one or more of water, ethylene glycol, and propylene glycol, and/or The dosage of the solvent is 6-20 mL/g based on the dosage of ferric trichloride hexahydrate.
8. The method of preparing a fluorescent nanoemulsifier of claim 4, wherein the step of modifying the nanomaterial with dopamine hydrochloride in step (1) comprises the steps of: Taking dopamine hydrochloride and nano materials according to the mass ratio of 0.1-10:10, adding Tris-HCl solution with the mass of 2-20 times of the nano materials into a reactor, sealing, dispersing the nano materials in an ultrasonic oscillator for at least 0.5h, preferably 0.5-2 h by ultrasonic, then transferring to a constant-temperature water bath oscillator, oscillating at least 4h, preferably 4-24 h at a frequency of at least 100rpm, preferably 100-300 rpm, after the reaction is finished, centrifugally separating or filtering and separating, washing with ultrapure water and absolute ethyl alcohol for at least 3 times sequentially, and vacuum drying at least 12h at a temperature of at least 30 ℃, preferably 30-60 ℃ to obtain the polydopamine hydrochloride modified nano materials.
9. The method of preparing a fluorescent nanoemulsifying agent of claim 4, wherein the step of modifying the nanomaterial with tannic acid in step (1) comprises the steps of: taking tannic acid and nano materials according to the mass ratio of 0.1-10:10, adding a solvent A with the mass of 2-20 times of the nano materials into a reactor, sealing, ultrasonically dispersing the nano materials in an ultrasonic oscillator for at least 2h, then transferring to a constant-temperature water bath oscillator, oscillating at least at 100rpm, preferably at 100-300 rpm, for at least 4h, preferably at 4-24 h, centrifugally separating or filtering and separating after the reaction is finished, washing at least 3 times by using ultrapure water and absolute ethyl alcohol in sequence, and drying at least 12h under vacuum at least 30 ℃ preferably at 30-60 ℃ to obtain the tannic acid modified nano materials.
10. The method for preparing a fluorescent nanoemulsifier according to claim 9 wherein the solvent a is one or more of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, dioxane, dimethylsulfoxide, N-methylpyrrolidone.
11. The method for preparing a fluorescent nanoemulsion as claimed in claim 4, wherein the specific steps of the modification reaction of the nanomaterial and the silane coupling agent in the step (1) are as follows: And (3) taking a silane coupling agent and a nano material according to the mass ratio of 0.1-10:10, adding a solvent B with the mass of 2-20 times of that of the nano material into a reactor, dispersing the nano material in an ultrasonic oscillator for at least 0.5h, preferably 0.5-2 h by ultrasonic, transferring the nano material onto a constant-temperature magnetic stirrer, stirring and reacting for at least 2h, preferably 2-18 h at 30 ℃, preferably 30-100 ℃, centrifuging or filtering and separating after the reaction is finished, washing the nano material with ultrapure water and absolute ethyl alcohol for at least 3 times sequentially, and vacuum drying the nano material for at least 12h at least 30 ℃, preferably 30-60 ℃ to obtain the silane coupling agent modified nano material.
12. The method of claim 11, wherein the solvent B is one or more of methanol, ethanol, n-propanol, isopropanol, formic acid, acetic acid, and/or The silane coupling agent is one or more of 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane and diethylenetriamine propyl trimethoxy silane.
13. The method of preparing a fluorescent nanoemulsifier of claim 4, wherein the specific steps of step (2) are as follows: (21) Adding 0.1-1 part of modified nano material, 0.1-1 part of catalyst p-toluenesulfonic acid or sulfuric acid and 1 part of polystyrene maleic anhydride into a reactor, then adding 2-6 parts of solvent C, and dispersing the nano material in an ultrasonic oscillator for at least 0.5h, preferably 0.5-2 h to obtain a mixed solution; (22) Transferring the mixed solution to a constant-temperature magnetic stirrer, stirring and reacting at least 40 ℃, preferably 40-120 ℃ for at least 4 hours, preferably 4-24 hours, centrifugally separating or filtering and separating after the reaction is finished to obtain a solid product, washing the solid product with a solvent C for at least 3 times, washing with absolute ethyl alcohol for at least 2 times, and vacuum drying at least 60 ℃, preferably 60-80 ℃ for at least 12 hours to obtain the modified nanomaterial grafted polystyrene maleic anhydride.
14. The method for preparing a fluorescent nanoemulsifying agent according to claim 13, wherein the solvent C is one or more of toluene, xylene, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, N-methylpyrrolidone.
15. The method of preparing a fluorescent nanoemulsifier of claim 4, wherein the specific steps of step (3) are as follows: (31) Grafting polystyrene maleic anhydride and 0.1-1 part of porphyrin-based polyamine resin to the modified nano material obtained in the step (2) in a reactor, then adding a solvent D with the mass 2-10 times that of the porphyrin-based polyamine resin into the reactor, and performing ultrasonic dispersion in an ultrasonic oscillator for at least 0.5h, preferably 0.5-2 h to obtain a mixed solution; (32) Transferring the mixed solution to a constant temperature magnetic stirrer, stirring and reacting at least 40 ℃ and preferably 40-120 ℃ for at least 4 hours and preferably 4-24 hours, performing centrifugal separation or filtering separation after the reaction is finished to obtain a solid product, washing the solid for at least 3 times sequentially by using distilled water and absolute ethyl alcohol, and performing vacuum drying at least 60 ℃ and preferably 60-80 ℃ for at least 12 hours to obtain the fluorescent nano demulsifier containing the porphyrin fluorescent groups.
16. The method for preparing a fluorescent nanoemulsifying agent according to claim 15, wherein the solvent D is one or more of toluene, xylene, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, N-methylpyrrolidone.
17. The method for preparing a fluorescent nanoemulsifier according to claim 15 wherein the porphyrin-based polyamine resin is prepared by the following specific steps in parts by mole: 1 part of porphyrin containing hydroxyphenyl and 2-10 parts of polyamine are dissolved in an organic solvent with the mass of 2-10 times of that of the polyamine to obtain mixed solution, then the mixed solution is transferred to a reactor provided with a stirrer, a water separator and a dropping funnel, and the reactor is placed in a constant-temperature oil bath; Dissolving 2-50 parts of paraformaldehyde in an organic solvent with the mass being 1-5 times of that of the paraformaldehyde to obtain a paraformaldehyde organic solvent solution, transferring the paraformaldehyde organic solvent solution into a dropping funnel of the reactor, controlling the reaction temperature to be 90-150 ℃ to enable a reaction system to flow back, slowly dropwise adding the paraformaldehyde organic solvent solution into the reactor through the constant-pressure dropping funnel under the conditions of heating and stirring, reacting for at least 6 hours, preferably for 6-48 hours, stopping the reaction, and removing the solvent and unreacted formaldehyde by reduced pressure distillation to obtain the porphyrin-based polyamine resin.
18. The method of claim 17, wherein the organic solvent is one or more of benzene, toluene, and xylene, and/or The hydroxyphenyl-containing porphyrin has one of the following structures: wherein R 1 、R 2 、R 3 is independently selected from one of H, cl, br, NO 2 、C n H 2n+1 or OC n H 2n+1 , wherein n=1 to 20, and/or The polyamine is polyethylene polyamine, preferably one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
19. A fluorescent nanoemulsion prepared by the method of any one of claims 4-18.
20. Use of the fluorescent nanoemulsion of any one of claims 1-3, 19 as a demulsifier in the treatment of chemical flooding produced fluids.

Description

Fluorescent nano demulsifier and preparation method and application thereof Technical Field The invention relates to the field of oilfield chemistry, in particular to a fluorescent nano demulsifier and a preparation method and application thereof. Background With the sequential entry of the dominant oil field in China into the middle and later stages of exploitation, chemical flooding technology has been implemented and adopted on an industrial scale in order to improve the recovery ratio of crude oil. The chemical flooding which needs to be treated in China annually forms polymer-containing produced water of about 1 hundred million square. The polymer-containing produced water has complex composition, and contains emulsified crude oil, oil displacement surfactant and polymer, colloid and asphaltene in the crude oil, suspended matters, microorganisms and other complex oil-in-water emulsion, wherein the residual oil displacement surfactant and polymer, colloid and asphaltene in the crude oil and other components make the emulsion abnormally stable, and demulsification and oil-water separation difficult. One of the challenges facing the treatment of petroleum produced liquid in China is the problems of demulsification of produced water, oil-water separation and resource utilization. Traditionally, the treatment of oil-containing produced water has been by the addition of a produced water demulsifier. For example, chinese patent No. CN 108864421B discloses a multi-branched cationic polyether reverse demulsifier and its preparation method and application. The method firstly prepares hydroxymethyl BPA, then reacts with polyalkene amine to prepare the multi-branched BPA type phenolic amine resin, and the synthesis process of the phenolic amine resin effectively avoids side reaction of formaldehyde and vinylamine, and can lead ortho-position of phenolic hydroxyl to completely react. The BPA type phenolic amine resin is reacted with ethylene oxide to obtain a multi-branched polyether demulsifier, and the polyether reverse demulsifier is subjected to cationic modification by adopting quaternary ammonium salt and is applied to the treatment of oily sewage in oilfield produced liquid. 2022, Kou Zimin et al, on pages 1516-1519 of Liaoning chemical industry, disclose a synthesis and application performance study of a cationic-nonionic reverse demulsifier, which takes clear water type polyether, epichlorohydrin and trimethylamine as raw materials, synthesizes a reverse demulsifier BH-587, explores the influence of raw material proportion, reaction time and reaction temperature on product performance, and determines that the mole ratio of epichlorohydrin to trimethylamine is 1:1.4, the reaction temperature is 75 ℃, and the reaction time is 4h. The preparation method of the reverse demulsifier is simple, has excellent clear water effect and is worthy of popularization and application. However, cationic demulsifiers remove emulsified crude oil, negatively charged suspensions and other particulates from water by means of electro-neutralization-flocculation. Because the electric neutralization reaction and flocculation technology has no selectivity to negatively charged substances and particles in water, the electric neutralization reaction and flocculation technology not only reacts with negatively charged emulsified oil to flocculate, but also reacts with negatively charged particles such as suspended matters, residual oil displacement polymers in water and the like to form polymer-containing flocs mixed with crude oil and solid particles, namely oil sludge, so that pipelines are blocked, and the filter cannot normally operate and pollutes the environment. Meanwhile, a large amount of polymers in produced water cannot be effectively recycled, so that resource waste is caused, the cationic demulsifier is extremely inadaptable to chemical flooding produced water, and development of a nonionic reverse demulsifier capable of retaining the polymers is urgently needed. Demulsifiers, which act as a surfactant, are distributed at a concentration in oil and water. Along with the development of demulsifier technology, the molecular motion process of demulsifier molecules in an oil-water system is known, the distribution of demulsifiers in a production system is tracked to become a technical development trend, and a fluorescent demulsifier is generated, for example, a preparation method of a fluorescent visual magnetic MOFs demulsifier is disclosed in Chinese patent No. CN 110157471B. The preparation method of the fluorescence visualization magnetic MOFs demulsifier comprises the steps of taking three metal salts of iron, copper and zinc as precursors, taking trimesic acid as a ligand, doping non-noble metals such as nickel, manganese, cobalt and zirconium, preparing the magnetic MOFs material by a solvothermal method, reacting with the traditional polyether commodity demulsifier, taking three metal salts of iron, copper and zinc as p