Separation of Emulsified Oil from Oily Wastewater by Functionalized Multiwalled Carbon Nanotubes

Rapid separation of emulsified oil from oily wastewater is one of the most serious challenges faced in the petroleum industry. In this study, a rapid and efficient demulsifier, functionalized multiwalled carbon nanotubes (F-MWCNTs), was prepared and used to separate the emulsified oil from oily wastewater. Demulsification test showed that the oil removal efficiency could attain as high as 99.8% at an optimal condition within a few minutes. The micro-morphology of the oil–water mixture before and after demulsification was observed using a polarizing microscope. It was found that the fine oil droplets experienced a rapid coalescence to form oil phase floating on the water surface. Mechanism of the demulsification process was discussed. The introduction of the functional groups (such as ?OH and ?COOH) on the surfaces of F-MWCNTs enable them good amphiphilicity and therefore easily arriving at the oil/water interface to destroy the interfacial protective film mainly composed of asphaltenes and resins. The findings in this work showed that the F-MWCNT is an efficient nanomaterial to remove emulsified oil from the oily wastewater and might have wide application prospects in the petroleum industry.     

Synthesis and performances for treating oily wastewater of polyether copolymers based on polyethyleneimine

The demulsification of the oily wastewater generated in the oil recovery process is very important in the crude oil exploitation. In present work, 10 block copolymers based on polyethyleneimine were synthesized, and their performances for treating oily wastewater were studied. The evaluation of demulsification efficiency, the effects of temperature, and the dosage on the treatment of oily wastewater by prepared copolymers were also investigated. To explore the causes of the differences, the interface activity of prepared copolymer molecules at water‐oil interface was investigated by the interfacial tension, and a mechanism diagram of demulsification of wastewater by the prepared copolymers was proposed. The demulsification of wastewater could be divided into 3 processes that were (1) adsorption, (2) congestion, and (3) coalescence. The prepared copolymer molecule acted as a hand in the oily wastewater to achieve the demulsification.     

磁性可回收氟化石墨烯破乳材料的制备及乳液分离性能

以氟化石墨烯(FG)为原料, 首先制备了水合肼还原的具有一定亲水性的氟化石墨烯(HFG), 然后采用溶剂热法制备了可磁性分离的四氧化三铁负载的氟化石墨烯复合破乳材料(HFG-Fe₃O₄). 分别利用透射电子显微镜(TEM)、 扫描电子显微镜(SEM)、 傅里叶变换红外光谱仪(FTIR)、 X射线粉末衍射仪(XRD)和X射线光电子能谱仪(XPS)对HFG-Fe₃O₄的形貌、 结构和化学性质进行了表征. 最后研究了HFG-Fe₃O₄对含油废水的破乳性能, 探讨了影响其破乳性能的主要因素, 并对其破乳机理进行了分析. 结果表明: HFG-Fe₃O₄是一种表面负载有Fe₃O₄纳米颗粒的二维片状材料, 在最佳剂量为600 mg/L时对酸性和中性含油废水具有良好的破乳效果. 在酸性和中性条件下, 主要是利用HFG-Fe₃O₄与含油废水之间的静电吸引力以及HFG-Fe₃O₄与沥青质之间的π-π相互作用实现油-水分离. 但是, 在碱性条件下, HFG-Fe₃O₄与油滴之间的静电斥力将急剧增大, 最终导致破乳效率降低. 此外, 将磁性回收的HFG-Fe₃O₄循环利用4次后其乳液分离效率并没有明显下降, 表现出优异的循环稳定性.     

Screening and Demulsification Mechanism of Fluorinated Demulsifier Based on Molecular Dynamics Simulation

In order to solve the problem of demulsification difficulties in Liaohe Oilfield, 24 kinds of demulsifiers were screened by using the interface generation energy (IFE) module in the molecular dynamics simulation software Materials Studio to determine the ability of demulsifier molecules to reduce the total energy of the oil–water interface after entering the oil–water interface. Neural network analysis (NNA) and genetic function approximation (GFA) were used as technical means to predict the demulsification effect of the Liaohe crude oil demulsifier. The simulation results show that the SDJ9927 demulsifier with ethylene oxide (EO) and propylene oxide (PO) values of 21 (EO) and 44 (PO) reduced the total energy and interfacial tension of the oil–water interface to the greatest extent, and the interfacial formation energy reached −640.48 Kcal/mol. NNA predicted that the water removal amount of the SDJ9927 demulsifier was 7.21 mL, with an overall error of less than 1.83. GFA predicted that the water removal amount of the SDJ9927 demulsifier was 7.41mL, with an overall error of less than 0.9. The predicted results are consistent with the experimental screening results. SDJ9927 had the highest water removal rate and the best demulsification effect. NNA and GFA had high correlation coefficients, and their R²s were 0.802 and 0.861, respectively. The higher R² was, the more accurate the prediction accuracy was. Finally, the demulsification mechanism of the interfacial film breaking due to the collision of fluorinated polyether demulsifiers was studied. It was found that the carbon–fluorine chain had high surface activity and high stability, which could protect the carbon–carbon bond in the demulsifier molecules to ensure that there was no re-emulsion due to the stirring external force.     

Investigation of the Demulsification Efficiency of Some Ethoxylated Polyalkylphenol Formaldehydes Based on Locally Obtained Materials to Resolve Water-in-Oil Emulsions

Fourteen ethoxylated polyalkylphenol formaldehyde surfactants were prepared from locally sourced raw materials. These surfactants were used as demulsifiers to resolve asphltenic crude oil emulsions. Different factors affecting demulsification efficiency such as water:oil ratios, surfactant concentration, surfactant molecular weight, ethylene oxide content, alkyl chain length, and asphaltene content were investigated. From the data obtained it was found that the demulsification efficiency increases by increasing the concentration, alkyl chain length and water content in the emulsion. Also it was found that the increase of asphaltene content in the crude oil impeded the demulsification efficiency. The effect of molecular weight was studied and it was found that the demulsification efficiency was controlled by an optimum range of molecular weight between 3640 to 3810 for the family of demulsifiers studied. Regarding the effect of ethylene oxide content in the demulsifier structure, it was found that the maximum demulsification efficiency was obtaind at 40 units ethylene oxide. The maximum demulsification efficiency was obtained by TND5 (m.wt. = 3800, eo = 40 units). With this demulsifier 100% water separation was exhibited after 35 minutes at 150 ppm demulsifier concentration and 50% w/o emulsion. The surface, interfacial tension, and hydrophilic lipophilic balance (HLB) of the invistigated demulsifers were studied. The obtained results justified that they are strongly related to the demulsification effeciency.     

超支化聚酰胺-胺破乳剂的合成及应用

以N-丙烯酰-1,2-乙二胺盐酸盐(ADE)合成为基础,通过ADE的Michael加成反应制备阳离子超支化聚合物聚N-丙烯酰-1,2-乙二胺盐酸盐(HADE),并对其结构进行了表征。研究表明,50℃下,HADE破乳剂(质量浓度为200 mg/L)对含煤油质量分数5%的水包油(O/W)煤油乳液的除油率可高达95.6%,显示了产品在乳液破乳除油方面良好的发展前景。     

Synthesis and Preliminary Demulsification Efficiency Evaluation of New Demulsifiers Based on Fatty Oils

Three raw fatty oils were used as precursors for demulsifiers. The hydrolyzed form of each oil was adducted with maleic anhydride then modified by esterification with polyethylene glycols or ethyleneoxide-propyleneoxide block copolymers. The demulsfication efficiency, coalescence rate, some surface active, thermodynamic properties, and partition coefficient of a selected demulsifier were investigated. The best demulsifier shows 100% demulsification after 19 minutes at 300 ppm. A correlation between demulsification efficiency and rheological properties of the investigated demulsifier was investigated. Also, emulsification kinetics were followed by microscopic photography. A mechanism following coalescence and flocculation of water droplets is proposed.     

Nitrogen adsorption on fluorinated activated carbon fiber

Nitrogen adsorption isotherms for fluorinated activated carbon fiber (F-ACF) and fluorinated carbon black (F-CB) were measured at 77 K. Surface structures of F-ACF and F-CB were examined by _s -plot analysis using the adsorption data on the nonporous carbon black (CB) and F-CB. The surface energy of F-ACF was lower than that of ACF. The micropore structure of ACF was preserved even after fluorination, although the limiting adsorption amount and the micropore width decreased with fluorination.     

The Application and Research of Dispersing In Situ Nano-SiO2 in Polyether Demulsifier TA1031

In order to enlarge the application range of nanomaterial and improve the demulsification performance of macromolecule polyether demulsifier, the nano-SiO₂ was dispersed in situ in polyether demulsifier TA1031 to form a new high efficiency demulsifier. The new demulsifier was analyzed by FTIR, SEM, rotational viscometer, and interfacial tension meter. The result showed that dispersing nano-SiO₂ in crude oil demulsifier would greatly improve the demulsification performance of the original demulsifier. When the ratio of silicon dioxide and TA1031 is 1:10 (mass ratio), the demulsification performance of the new demulsifier was the best, and the dehydration rate of emulsion increased about by 20%. Also the time of demulification and dehydration would be greatly shortened, and the demusification mechanism was preliminary analyzed.     

Characterization and demulsification of produced liquid from weak base ASP flooding

Weak base alkali-surfactant-polymer (ASP) flooding technology has been applied in Daqing oilfield to enhance oil recovery. The effects of ASP on the characteristics of oil droplets in produced liquid were investigated. Surfactant can decrease interfacial tension (IFT) and zeta potential, making main contribution to the stability of oil droplets. Weak alkali (Na₂CO₃) can decrease IFT and polymer can decrease zeta potential, resulting in stable oil droplets in produced liquid. The produced liquid from weak base ASP flooding is easier to treat than that from strong base ASP flooding. A mixed demulsifier GFD410-8 was prepared and used to enhance oil–water separation in produced liquid. When the demulsifier dose of 50 mg/kg was used to demulsify the simulated produced liquid with the concentrations of alkali 2000 mg/kg, surfactant 600 mg/kg and polymer 600 mg/kg, water volume and water content after 30 min settling were less than 30% and 1000 mg/L, respectively. The demulsifier also greatly decreased water content in oil phase and oil concentration in water phase for actual produced liquid from oil well. The demulsification mechanism was also investigated in terms of IFT and zeta potential.     

Demulsification of water-in-oil emulsion by wetting coalescence materials in stirred- and packed-columns

Demulsification of emulsified water-in-oil droplets was developed using wetting coalescence materials. Demulsification tests were carried out using conventional stirred- and packed-columns. Of the four kinds of natural fibers and two kinds of inorganic materials tested, natural fiber A, selected from shaves of a wood showed the best performance in demulsification. The demulsification efficiency can exceed 97% when demulsification conditions are optimized. The packed-column showed much better performance both in terms of demulsification efficiency and repeated use of the recovered oil phase for extracting cadmium in a simulated wastewater. Operating variables that govern the demulsification efficiency were investigated.     

十八烷基超支化分子的结构表征与破乳性能

以甲醇为溶剂,用十八胺、丙烯酸甲酯和乙二胺为原料,通过迈克尔加成反应和酰胺化缩合反应,制备了1.0 G超支化分子;通过红外光谱、核磁共振手段对合成产品的结构进行了表征,且考察了十八烷基超支化分子对O/W型原油模拟乳液的破乳性能,并与传统的线性破乳剂SP-169进行了对比.结果表明:在温度为50℃、添加量为20 mg/L、破乳时间为120 min的条件下,其脱水率达到了76.2%,脱出水中的含油量为41.9 mg/L;而破乳剂SP-169在相同的条件下的脱水率为61.5%,脱出水中的含油量为52.4 mg/L.     

Synthesis and evaluation of some polymeric surfactants for treating crude oil—Part II. Destabilization of naturally occurring water‐in‐oil emulsions by polyalkylphenol formaldehyde amine resins

In the present work, three polymeric surfactants were prepared and used as demulsifiers; polyalkyl phenol formaldehyde monoethanol amine ethoxylate, eo, 136(D1), polyalkyl phenol formaldehyde diethanol amine ethoxylate, eo, 37(D2) and polyalkyl phenol formaldehyde triethanol amine ethoxylate, eo, 21.5(D3). Their demulsification potency in breaking water‐in‐crude oil emulsions was investigated. In this respect, two naturally occurring Egyptian water‐in‐oil (w/o) emulsions, one of them was waxy and the other was asphaltenic, were used in order to study the demulsification power of these compounds. The data revealed that, the resolution of water from waxy crude emulsion was easier than asphaltenic crude emulsion. The demulsification efficiency increases with increasing demulsifier concentration, contact time and temperature. The interfacial tension (IFT) at the crude oil–water interface was measured, it was found that the concentration of demulsifiers required to cause a minimum IFT are always less than these indicating a maximum demulsification efficiency. All the results were discussed in relation to emulsifier chemical structure and crude oil composition. Copyright © 2002 John Wiley & Sons, Ltd.     

新型高效原油破乳剂PNT-05的研制与应用

针对中原油田采油六厂二区原油破乳脱水过程中存在的脱水速度慢,乳化中间层厚等问题,通过分子结构设计手段,在非离子型破乳剂基础上,经酯化,在破乳剂分子中引入阳离子基团,合成出季胺盐阳离子型破乳剂PNT－05,利用季胺盐阳离子型破乳剂与助剂复配的方法室内解决了中原油田二区原油破乳脱水过程中顾在的问题,与油田现场用破乳剂相比,新的破乳剂体系脱水速度快,脱水效率高,使乳化中间层变薄或消失,同时探讨了季胺盐阳离子型破乳剂PNT－05的作用机制。     

Synthesis and evaluation of demulsifiers with polyethyleneimine as accepter for treating crude oil emulsions

Demulsifiers provide an important means of breaking water‐in‐crude oil, which are formed during crude oil exploitation. In present work, twenty polyether copolymers based on polyethyleneimine (PEI) were synthesized. The interfacial properties of the PEI polyethers at the water‐crude oil interface were described by interfacial tension (IFT) and interfacial dilational modulus. The effects of position isomerism, size of intermediate and ratio of ethylene oxide (EO)/propylene oxide (PO) on the demulsification efficiency of these polyethers were studied. The results show that different positions of the EO and PO in copolymers lead to huge difference in both interfacial properties and demulsification performance. Polymers with hydrophilic core and hydrophobic tails (Ex‐mn series) are not efficient on demulsification of water‐in‐oil emulsion whereas polymers with hydrophobic core and hydrophilic tails (Px‐mn series) are. Meanwhile, Px‐mn series show higher IFT and lower interfacial dilational modulus than Ex‐mn series. In the same series, the IFT and interfacial dilational modulus decrease with decreasing EO/PO ratio. In the series with best demulsification performance (P199‐mn series), 60 min water removal rates of the polymers increase with decreasing EO/PO ratio at 65°C. In other words, the longer the hydrophobic blocks of polymers, the stronger the demulsification capacity. The effect of concentration of demulsifier on the demulsification efficiency was also investigated. Copyright © 2015 John Wiley & Sons, Ltd.     

Interaction between polymer and anionic/nonionic surfactants and its mechanism of enhanced oil recovery

Various experimental methods were used to investigate interaction between polymer and anionic/nonionic surfactants and mechanisms of enhanced oil recovery by anionic/nonionic surfactants in the present paper. The complex surfactant molecules are adsorbed in the mixed micelles or aggregates formed by the hydrophobic association of hydrophobic groups of polymers, making the surfactant molecules at oil-water interface reduce and the value of interfacial tension between oil and water increase. A dense spatial network structure is formed by the interaction between the mixed aggregates and hydrophobic groups of the polymer molecular chains, making the hydrodynamic volume of the aggregates and the viscosity of the polymer solution increase. Because of the formation of the mixed adsorption layer at oil and water interface by synergistic effect, ultra-low interfacial tension (～2.0?×?10^?3 mN/m) can be achieved between the novel surfactant system and the oil samples in this paper. Because of hydrophobic interaction, wettability alteration of oil-wet surface was induced by the adsorption of the surfactant system on the solid surface. Moreover, the studied surfactant system had a certain degree of spontaneous emulsification ability (D50?=?25.04?µm) and was well emulsified with crude oil after the mechanical oscillation (D50?=?4.27?µm).     

Synthesis and characterization of lower generation broom molecules

Dendritic molecules with dodecyl groups as the hyperbranchs were synthesized in methanol by Michael addition with dodecylamine and methyl acrylate as raw materials. This new-type dendritic molecules were called vividly ＂broom molecules＂ in this report. The surface tension of the aqueous solution of broom molecule terminated amino group was measured by using the dropvolume method. The demulsification performance of the broom molecules for the oil/water （O/W） simulated crude oil emulsion was examined. The experimental results revealed that, as a new-type of surfactants, the broom molecules terminated amino groups showed demulsification for the O/W simulated crude oil emulsion. 2007 Jun Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All fights reserved.     

Demulsification of Heavy Oil-in-Water Emulsion by a Novel Janus Graphene Oxide Nanosheet: Experiments and Molecular Dynamic Simulations

Various nanoparticles have been applied as chemical demulsifiers to separate the crude-oil-in-water emulsion in the petroleum industry, including graphene oxide (GO). In this study, the Janus amphiphilic graphene oxide (JGO) was prepared by asymmetrical chemical modification on one side of the GO surface with n-octylamine. The JGO structure was verified by Fourier-transform infrared spectra (FTIR), transmission electron microscopy (TEM), and contact angle measurements. Compared with GO, JGO showed a superior ability to break the heavy oil-in-water emulsion with a demulsification efficiency reaching up to 98.25% at the optimal concentration (40 mg/L). The effects of pH and temperature on the JGO’s demulsification efficiency were also investigated. Based on the results of interfacial dilatational rheology measurement and molecular dynamic simulation, it was speculated that the intensive interaction between JGO and asphaltenes should be responsible for the excellent demulsification performance of JGO. This work not only provided a potential high-performance demulsifier for the separation of crude-oil-in-water emulsion, but also proposed novel insights to the mechanism of GO-based demulsifiers.     

Demulsification by increasing the gravitational force acting upon the dispersed phase owing to the adsorption/absorption of the magnetite particles

Demulsification using a magnetic demulsifier is commonly used to separate emulsions using an external magnetic field. However, this study presents a new demulsification method based on the increased weight of the dispersed phase due to the adsorption/absorption of the magnetite particles by the droplets. Micron-sized bare magnetite particles were used as the demulsifier in this method which does not necessarily need to apply a surface-active additive and the magnetic field for the demulsification. Magnetic responsivity of the demulsifier can only be used for the recovery of the demulsifier. The demulsification experiments were performed using the oil-in-water and water-in-oil emulsions. The effect of temperature, wettability, demulsifier dosage and activity, sedimentation rate and particles size were investigated. The results showed that the proposed method can remarkably improve the efficiency and speed of the demulsification, and has a great potential to be considered for the commercialization.     

Polyoxyethylenated bisphenol-A for breaking water-in-oil emulsions

Polyethylene glycol (PEG) of different molecular weights, namely, 600, 1000 and 4000 g/mol was reacted with bisphenol A to form compounds having different hydrophile–lipophile balances and hence different surface activities. The interfacial tension at the aqueous/benzene interface was determined. It was found that the concentrations of demulsifiers required to cause a minimum interfacial tension are always less than those inducing a maximum demulsification efficiency. The demulsification efficiency of the prepared surfactants in breaking synthetic water in benzene emulsions stabilized by petroleum asphaltenes was evaluated. The data revealed that the demulsification efficiency increases with increasing demulsifier concentration, contact time and hydrophilicity.