The asphaltene-rich alkaline-surfactant-polymer (ASP) flooding produced water has been identified with high interfacial stability and severe secondary emulsification, which poses great difficulties in its demulsification process. This leads to an urgent need to develop targeted and efficient demulsifiers. In this research, a novel polydopamine-polyquaternium modified Fe 3 O 4 (PQA-PDA@Fe 3 O 4 ) nanoparticle integrates the electrical neutralization, interfacial adsorption and magnetic aggregation functionalities was prepared to dispose this emulsion. Primarily, structural and surface properties of the PQA-PDA@Fe 3 O 4 demulsifier were systemically characterized by a series of analytical techniques, which presents its core-shell, hydrophilic and positively charged characters. When employing PQA-PDA@Fe 3 O 4 to treat the produced water that contained 500 mg/L emulsified oil, a demulsification efficiency of 90.5 % was achieved at 200 mg/L dosage. It was found that the PQA-PDA@Fe 3 O 4 nanoparticles could coalesce the fine oil droplets into large and dense aggregates, as demonstrated by the raised fractal dimension values. By monitoring the interfacial properties (interfacial tension, zeta potential and interfacial film elastic modulus) variations, the demulsification mechanism was further explored. The PQA-PDA@Fe 3 O 4 nanoparticle could spontaneously migrate to the oil/water interface and reassemble a loose interfacial film, thus leading the oil droplets destabilization and aggregation. Notably, the magnetic force between the PQA-PDA@Fe 3 O 4 nanoparticles significantly accelerates the oil droplets aggregation and inhibits the secondary emulsification process, so as to achieve the outstanding demulsification efficiency. Moreover, this PQA-PDA@Fe 3 O 4 nanoparticle exhibited acceptable magnetic recyclability. These results provided an effective and alternative protocol to demulsify the asphaltene-rich ASP flooding emulsions.
With the continuous improvement in oilfield development and the application of tertiary oil recovery technology, the water content of oilfield-produced fluids has gradually increased, and a large number of oilfield sewage with complex components has also been produced after oil–water separation, and effective treatment is urgently needed. ASP flooding sewage contains alkali, various surfactants, polymers, microemulsion oil droplets, and solid impurities, which are difficult to be effectively treated by traditional water treatment agents and methods. In this study, aminopropyl triethoxysilane (APTES) was used to modify the nano-Fe3O4 coated with tetraethyl silicate (TEOS). The product was used as the ferromagnetic nano-core for the iterative reaction of Michael addition and ester amidation to synthesize a magnetic hyperbranched polyamide amine, and its performance in the treatment of ASP flooding wastewater was evaluated experimentally. For the preparation of APTES-modified Fe3O4@SiO2 (FOSN) product, TEOS was coated over Fe3O4 in an ethanol aqueous solution environment and then APTES was added dropwise. The first-generation branched product (1-FSMN) was obtained by the reaction of FOSN and methyl acrylate graft product (FOSN-M) with ethylenediamine, and the highest yield was 93.7%. The highest yield of the second-generation branched product (2-FSMN) was 91.6%. In this study, a composite flooding wastewater sample from a block in the Bohai oilfield was taken. The suspended solids content was 143 mg/L, the oil content was 921.09 mg/L, the turbidity was 135 NTU, and the zeta potential was −47 mV. The third-generation hyperbranched polymer (3-FSMN) and its quaternary ammonium salt (3-FSMN-Q) performed best in the appropriate dosage range, with the highest oil removal rate of 97%, suspended solid removal rate of 90.3%, turbidity reduction rate of 86.6% and zeta potential reduction rate of 88%. For 3-FSMN and its quaternary ammonium salt, the gravity/magnetic PAC compound treatment experiment was carried out. In the settlement time of only 5 min, 3-FSMN/PAC and 3-FSMN-Q/PAC can achieve the maximum oil removal rate of 87.1% and suspended solids removal rate of 87.3% for polymer containing wastewater from ASP flooding, and 86.3 and 86.0% for 120 mg/L. Its treatment capacity was much better than that of common treatment agent combination (CPAM/PAC).
In this work, the effect of oil-displacing agent composition on oil/water interface stability of the asphaltene-rich alkali–surfactant–polymer (ASP) flooding-produced water was systematically investigated, especially from the perspective of the interaction between oil displacement agents and asphaltene at the oil/water interface. Primarily, adsorption behavior of the artificial and natural interfacial substances (oil displacement surfactant and asphaltenes) on the oil/water interface was investigated by molecular dynamics simulation. The oil displacement surfactant and asphaltenes formed a cross-linked and compact interfacial film structure, which significantly enhanced the interface stability; the more the oil displacement surfactants adsorbed on the interface, the more stable is the cross-linked structure formed between them and asphaltenes. Then, the interfacial property variations that are originating from the interactions differences between oil displacement agents and asphaltenes were monitored via interfacial tension, zeta potential, and interfacial film rheology tests. Moreover, the effect of oil displacement agent concentrations on the interfacial film thinning and rupture kinetic behavior was further investigated. Finally, cream experiments were conducted to verify the effect of oil displacement agent composition on the oil/water separation efficiencies of asphaltene-rich ASP flooding-produced water. When 5% asphaltenes was added, the creaming oil removal rate reduced from 90.0 to 85.3% at 19 h. The interactions between asphaltenes and oil displacement agents immensely enhance the oil/water interfacial film strength and impede the oil/water separation process.
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