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A series of novel amine triphenolate iron complexes were synthesized and characterized using UV, IR, elemental analysis, and high-resolution mass spectrometry. These complexes were applied to the ring-opening polymerization (ROP) of cyclohexene oxide (CHO), demonstrating excellent activity (TOF > 11050 h-1) in the absence of a co-catalyst. In addition, complex C1 maintained the dimer in the presence of the reaction substrate CHO, catalyzing the ring-opening polymerization of CHO to PCHO through bimetallic synergy. Furthermore, a two-component system consisting of iron complexes and TBAB displayed the ability to catalyze the reaction of CHO with CO2, resulting in the formation of cis-cyclic carbonate with high selectivity. Complex C4 exhibited the highest catalytic activity, achieving 80% conversion of CHO at a CHO/C4/TBAB molar ratio of 2000/1/8 and a CO2 pressure of 3 MPa for 16 h at 100 °C, while maintaining >99% selectivity of cis-cyclic carbonates, which demonstrated good conversion and selectivity.
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With increasing use of chemical oil displacement agents in tertiary recovery and the application of various demulsifiers for crude oil dehydration, a large amount of aging crude oil containing a high ratio of water is produced, and it is very difficult for processing and utilisation. In this article, we chose aging crude oil samples from a union station in an oilfield in China. Sample composition was analysed to demonstrate that the key of aging crude oil dehydration is the removal of solid impurities. Thus, an efficient method of combining heating and chemical treatments was developed to treat aging crude oil. It includes two steps: The first step is washing of aging crude oil with hot water with sodium dodecylbenzene sulfonate; the second step is chemical demulsification of the above mixture with hydrochloric acid and sodium chloride solution. The result showed that 2.9% of solid impurities and 29.2% of water were removed in the first step; 27.2% of oil, 24.3% of water, and 3.47% of solid impurities in the aging crude oil were recycled in the second step. A total 87.07% of aging crude oil could be solved with this method. The present two-step treatment method can ensure that the dehydration process runs normally and efficiently in the union station, making it a promising method in the recycling of aging crude oil.
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Calefação , Petróleo/análiseRESUMO
With the long-term water-flooding development of the reservoir, the non-homogeneity of the formation is increasing and the reservoir environment is deteriorating; the microspheres used for deep plugging have shown disadvantages, such as poor temperature and salt resistance and faster expansion. In this study, a polymeric microsphere was synthesized that is resistant to high temperature and high salt and can achieve slow expansion and slow release for deep migration. P(AA-AM-SA)@TiO2 polymer gel/inorganic nanoparticle microspheres were prepared by reversed-phase microemulsion polymerization using acrylamide (AM) and acrylic acid (AA) as monomers, 3-methacryloxypropyltrimethoxysilane (KH-570)-modified TiO2 as the inorganic core, and sodium alginate (SA) as a temperature-sensitive coating material. Through single-factor analysis of the polymerization process, the optimal synthesis conditions were determined as follows: the oil(Cyclohexane)-water volume ratio was 8:5, the emulsifier mass ratio (Span-80:Tween-80) was 3:1 (10 wt% of the total system amount), the stirring speed was 400 r/min, the reaction temperature was 60 °C, and the initiator (ammonium persulfate and sodium bisulfite) dosage was 0.6 wt%. The size of the dried polymer gel/inorganic nanoparticle microspheres prepared by the optimized synthesis conditions was 10~40 µm with uniform particle size. The observation of P(AA-AM-SA)@TiO2 microspheres reveals that the Ca elements are uniformly distributed on the microspheres, and FT-IR indicates that the synthesized product is the target product. TGA shows that the polymer gel/inorganic nanoparticle microspheres have better thermal stability after the addition of TiO2, with a larger mass loss at 390 °C, which can adapt to the medium-high permeability reservoir environment. The thermal and aqueous salinity resistance of the P(AA-AM-SA)@TiO2 microspheres was tested, and the cracking temperature of P(AA-AM-SA)@TiO2 microsphere temperature-sensitive material was 90 °C. It still has favorable water absorption and swelling performance under the sodium salt concentration of 2.5 × 104 mg/L and can tolerate calcium salt up to 2.0 × 104 mg/L. Plugging Performance Test results show that the microspheres have good injectability between the permeability of 1.23 and 2.35 µm2 and good plugging effect near the permeability of 2.20 µm2. At high temperature and high salinity, P(AA-AM-SA)@TiO2 microspheres have a remarkable effect on profile control and water shutoff, the plugging rate reaches 95.3%, and the oil recovery rate is increased by 12.89% compared with water flooding, achieving the effect of slow swelling and slow release.
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A pilot-scale airlift bioreactor (ALBR) system was built and operated continuously for refinery excess sludge (RES) reduction. Combined ALBR and function-enhanced microbes (composed of photosynthetic bacteria and yeast) were integrated into the system. The pilot-scale ALBR was operated for 62 days, and the start-up time was 7 d. Continuous operation showed that the sludge reduction efficiency was more than 56.22%, and the water quality of the effluent was satisfactory. This study focused on investigating the effects of hydraulic retention time (HRT) on the stability of the system and the effect of sludge reduction. Under different HRT conditions of 40, 26.7, 20, and 16 h, the sludge reduction rates reached 56.22%, 73.24%, 74.09%, and 69.64%, respectively. The removal rates of chemical oxygen demand (COD) and total nitrogen (TN) decreased with decreasing HRT, whereas the removal rate of NH4+-N increased. The removal rate of total phosphorus (TP) was approximately 30%. Results indicate that the ALBR and function-enhanced microbe system can reduce sludge and treat sewage simultaneously, and the effluent is up to the national emission standard. Addition of function-enhanced microbes can promote the degradation of petroleum hydrocarbon substances in the sludge, especially alkanes with low carbon numbers. This study suggests that the optimal HRT for the system is 16 h. The total operation cost of the ALBR combined with the function-enhanced microbe system can be reduced by 50% compared with the cost of direct treatment of the RES system.
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Esgotos , Eliminação de Resíduos Líquidos , Análise da Demanda Biológica de Oxigênio , Reatores Biológicos , Nitrogênio , FósforoRESUMO
Underwater superoleophobic coatings have attracted significant research attention for their excellent oil-repellent properties. However, the major challenge for current coatings is poor performance under harsh conditions, leading to limitations in terms of practical application. In this paper, we present a novel bioinspired poly(vinyl alcohol)/zeolite composite coating that can be fabricated through a facile approach. This composite coating shows outstanding underwater superoleophobicity to various oils, as well as good wax-prevention and self-cleaning performance. Furthermore, the excellent mechanical and chemical stabilities of the coating make it suitable for practical applications in harsh environments. This bioinspired multifunctional composite coating has promising prospects in the petroleum industry.
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A series of carboxybetaine surfactants, 2-((4-(alkoxy)-3,5-dimethylbenzyl)dimethyl-ammonio)acetate (C n OBCb, where n represents the hydrocarbon chain length of 12, 14, 16 and 18), were synthesized by an efficient and high-yield route for the first time. The surface activities and aggregation behavior of C n OBCb in aqueous solution were investigated by equilibrium surface tension, interfacial tension, steady-state fluorescence, dynamic light scattering (DLS), cryogenic transmission electron microscopy (cryo-TEM) and negative-staining transmission electron microscopy (TEM) measurements. In comparison with conventional N-alkylbetaine surfactants (C n Cb), the C n OBCb species, with a phenyl group introduced in the hydrophobic tail, exhibited excellent surface activities, including lower critical micelle concentration (cmc), lower surface tension and stronger adsorption tendency at an air/water interface. C n OBCb also displayed high efficiency in reducing the toluene/water interfacial tension, with C12OBCb achieving an ultralow interfacial tension (10-3 mN m-1) at concentrations from 0.2 to 1 mmol dm-3. The fluorescence intensity ratio and the scattering intensity in DLS measurements changed remarkably at concentrations around the cmc. Furthermore, the C n OBCb species spontaneously formed vesicles above the cmc in aqueous solution, and the size of the aggregates increased with increasing surfactant concentrations. Flooding experiments showed that C n OBCb could effectively improve oil recovery by 7.85-10.55%.
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The performance of a laboratory-scale, high-efficiency denitrification bioreactor (15L) using activated sludge immobilized by waterborne polyurethane in treating acrylonitrile wastewater with high concentration of nitrate nitrogen (249mg/L) was investigated. The bioreactor was operated at 30°C for 220days. Batch denitrification experiments showed that the optimal operation parameters were C/NO3--N molar ratio of 2.0 using sodium acetate as electron donor and carrier filling rate of 20% (V/V) in the bioreactor. Stable performance of denitrification was observed with a hydraulic retention time of 30 to 38h. A volumetric removal rate up to 2.1kgN/m3·d was achieved with a total nitrogen removal efficiency of 95%. Pyrosequencing results showed that Rhodocyclaceae and Pseudomonadaceae were the dominant bacterial families in the immobilized carrier and bioreactor effluent. The overall microbial diversity declined as denitrifiers gradually dominated and the relative abundance of other bacteria decreased along with testing time.
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Reatores Biológicos , Desnitrificação , Águas Residuárias , Acrilonitrila , Nitrogênio , Poliuretanos , EsgotosRESUMO
Heavy oil-produced water (HOPW) is a by-product during heavy oil exploitation and can cause serious environmental pollution if discharged without adequate treatment. Commercial biochemical treatment units are important parts of HOPW treatment processes, but many are not in stable operation because of the toxic and refractory substances, salt, present. Therefore, pilot-scale experiments were conducted to evaluate the performance of hydrolytic acidification-biological filter with airlift aeration (HA-BFAA), a novel HOPW treatment system. Four strains isolated from oily sludge were used for bioaugmentation to enhance the biodegradation of organic pollutants. The isolated bacteria were evaluated using 3-day biochemical oxygen demand, oil, dodecyl benzene sulfonic acid, and chemical oxygen demand (COD) removals as evaluation indices. Bioaugmentation enhanced the COD removal by 43.5 mg/L under a volume load of 0.249 kg COD/m(3) day and hydraulic retention time of 33.6 h. The effluent COD was 70.9 mg/L and the corresponding COD removal was 75.0 %. The optimum volumetric air-to-water ratio was below 10. The removal ratios of the total extractable organic pollutants, alkanes, and poly-aromatic hydrocarbons were 71.1, 94.4, and 94.0 %, respectively. Results demonstrated that HA-BFAA was an excellent HOPW treatment system.
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Reatores Biológicos/microbiologia , Indústria de Petróleo e Gás , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Bactérias Aeróbias/metabolismo , Biodegradação Ambiental , Análise da Demanda Biológica de Oxigênio , China , Desenho de Equipamento , Filtração , Hidrólise , Projetos Piloto , Esgotos/microbiologia , Poluentes Químicos da Água/metabolismoRESUMO
Biosurfactant producers are crucial for incremental oil production in microbial enhanced oil recovery (MEOR) processes. The isolation of biosurfactant-producing bacteria from oil reservoirs is important because they are considered suitable for the extreme conditions of the reservoir. In this work, a novel biosurfactant-producing strain Acinetobacter junii BD was isolated from a reservoir to reduce surface tension and emulsify crude oil. The biosurfactants produced by the strain were purified and then identified via electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS). The biosurfactants generated by the strain were concluded to be rhamnolipids, the dominant rhamnolipids were C26H48O9, C28H52O9, and C32H58O13. The optimal carbon source and nitrogen source for biomass and biosurfactant production were NaNO3 and soybean oil. The results showed that the content of acid components increased with the progress of crude oil biodegradation. A glass micromodel test demonstrated that the strain significantly increased oil recovery through interfacial tension reduction, wettability alteration and the mobility of microorganisms. In summary, the findings of this study indicate that the newly developed BD strain and its metabolites have great potential in MEOR.
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The community diversities of two oil reservoirs with low permeability of 1.81 × 10(-3) and 2.29 × 10(-3) µm(2) in Changqing, China, were investigated using a high throughput sequencing technique to analyze the influence of biostimulation with a nutrient activator on the bacterial communities. These two blocks differed significantly in salinity (average 17,500 vs 40,900 mg/L). A core simulation test was used to evaluate the effectiveness of indigenous microbial-enhanced oil recovery (MEOR). The results indicated that in the two high salinity oil reservoirs, one reservoir having relatively lower salinity level and a narrow salinity range had higher bacterial and phylogenetic diversity. The addition of the nutrient activator increased the diversity of the bacterial community structure and the diversity differences between the two blocks. The results of the core simulation test showed that the bacterial community in the reservoir with a salinity level of 17,500 mg/L did not show significant higher MEOR efficiency compared with the reservoir with 40,900 mg/L i.e. MEOR efficiency of 8.12% vs 6.56% (test p = 0.291 > 0.05). Therefore, salinity levels affected the bacterial diversities in the two low permeability oil blocks remarkably. But the influence of salinity for the MEOR recovery was slightly.
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Bactérias/classificação , Biodiversidade , Microbiologia Ambiental , Campos de Petróleo e Gás/microbiologia , Petróleo/microbiologia , Salinidade , Bactérias/genética , Biologia Computacional , Código de Barras de DNA Taxonômico , DNA Bacteriano , Microbiota , Filogenia , Análise de Sequência de DNARESUMO
The diversity of indigenous bacterial community and the functional species in the water samples from three production wells of a low permeability oil reservoir was investigated by high-throughput sequencing technology. The potential of application of indigenous bacteria for enhancing oil recovery was evaluated by examination of the effect of bacterial stimulation on the formation water-oil-rock surface interactions and micromodel test. The results showed that production well 88-122 had the most diverse bacterial community and functional species. The broth of indigenous bacteria stimulated by an organic nutrient activator at aerobic condition changed the wettability of the rock surface from oil-wet to water-wet. Micromodel test results showed that flooding using stimulated indigenous bacteria following water flooding improved oil recovery by 6.9% and 7.7% in fractured and unfractured micromodels, respectively. Therefore, the zone of low permeability reservoir has a great potential for indigenous microbial enhanced oil recovery.