Effective Demulsifier Research Articles

Development of a demulsifier and technological process study for the preparation of highly viscous heavy oils for refinement

One of the challenges in the petroleum industry is the production of highly viscous heavy oils, often accompanied by undesirable emulsion formation with very high aggregate stability. To prepare the crude oils for refinement, the oils must be destroyed. The destruction of aqueous emulsions containing highly viscous heavy oils is an intricate task owing to the comparatively small disparity in water and oil densities, as well as the high viscosity of the dispersive medium and its high content of mechanical impurities. The problem of the destruction of petroleum emulsions arises desperately during the desalination and dehydration of crude oils with a high content of emulsifiers (resins, asphalts, paraffin, etc.) The creation of a highly efficient demulsifier and the development of an optimal technological process for the preparation of highly emulsifying oils that are distinguished by the composition and quantity of emulsifiers of West Siberian oils, which are widely refined in Russia, are the ways to resolve this challenging and timely issue. This study focuses on the viscous heavy oil of the Verbliouje deposit in the Astrakhan region. It also explains the creation of an effective demulsifier for the destruction of petroleum emulsions characterized by a very high emulsifying power and the fundamental principles of the development of deep dehydration technology and desalination of such high-viscosity heavy oils.

Analytical evaluation of oil and water obtained from demulsification of crude oil using cashew (<i>Anacardium occidentale</i>) nutshell liquid

The physiochemical characteristics of oil and water obtained from the demusifier treatment of crude oil using equal concentrations of Cashew nutshell liquid (CSNL) and a commercial grade demulsifier (DX077) were evaluated. Results obtained shows that basic sediment and water (BSW) of the crude after treatment with CSNL and DXO77 were 17.5 and 17.9 % respectively which was 0.4% apart. The total oil and grease (TOG) and total petroleum hydrocarbon (TPH) of the produced water after treatment with CSNL were 24.4 and 21.7 mg/l respectively while results after treatment with DXO77 were 23.7 and 20.5 mg/l respectively. The TOG and TPH of the produced water after demulsifier treatment with CSNL and DX077 were within acceptable limit of < 30.0 mg/l as specified by Department of Petroleum Resources (DPR). Analyses of the same crude oil before demulsifier treatment gave a lower BSW of 9.50 % as well as an emulsion band of 16.2 % indicating improper oil/water separation. The TOG and TPH of the produced water before demulsifier treatment were 42.5 and 38.7 mg/l respectively which were above DPR specification. Disposal of produced water with high TOG and TPH into the environment can lead to the release of volatile organic compounds (VOCs) into the ecosystem resulting in environmental pollution as well as other health hazards. Results obtained also show that the water density, pH, electrical conductivity, salinity and chloride of the produced water after demulsifier treatment with CSNL and DX077 were within DPR specification. Reinjecting produced water with high salinity, chloride and conductivity into the reservoir can reduce oil recovery especially from sandstone and carbonate reservoirs. CSNL proved to be an effective demulsifier and is preferrable to the synthetic demulsifier (DX077) because it is more environmentally friendly owing to its green nature.

Recombinant strains expressing oxalate decarboxylase efficiently and environmental characteristics of their life cycle assessment

Oxalate decarboxylase has garnered significant attention due to its wide-ranging applications, particularly as an effective demulsifier for oil pollution remediation. However, the accumulation of oxalate decarboxylase by strain is insufficient, and the acquisition of necessary nutrients and energy for biosynthesis also poses challenges to the environment. Therefore, it is crucial to assess the strain's capacity and environmental burden in order to guide future developments and ensure sustainable scale-up. To enhance the protein yield of oxalate decarboxylase from Bacillus mojavensis XH1 (Bacm OxdC), a specialized biodemulsifier, our study investigated the properties of Bacm OxdC and improved its expression efficacy in Escherichia coli from an environmentally friendly perspective. By employing a promoter tandem strategy and optimizing the 5′ untranslated region, recombinant strains C3 and C5 were constructed, resulting in 1.22-fold and 6.90-fold increases in Bacm OxdC expression levels compared to the initial strain C1. The bioprocess of strain C5 achieved a life cycle assessment (LCA)-based environmental impact value of 322.75, representing the lowest environmental impact observed thus far. Improvement strategies included reducing protein purification steps and electricity consumption, which can further mitigate negative environmental impacts and carbon emissions. This study offers a technical strategy for large-scale production of oxalate decarboxylase while attaining green and low-carbon objectives for biological demulsifiers.

Разработка технологии регенерации некондиционных эмульсионных полуфабрикатов промышленных взрывчатых веществ

The research is aimed at improving the methods to produce and apply in the mining industry energy-intensive emulsions based on concentrated solutions of inorganic salts (nitrates), which are second-class dispersions of the "Water-inOil" type. Every year when mining useful minerals, surface and underground operations consume about 1.15 million tonnes of industrial emulsion explosives (IEE), the largest share of which are the so-called caseless pouring types. When the emulsion matrix is produced, it is possible that off-grade emulsion, i.e. emulsion that does not meet the requirements of the relevant normative and technical documentation, may also be generated. Tentatively, the volume of such production waste may reach 57.5 thousand tonnes per year. Therefore, the issues of reclaiming the off-grade emulsion semi-finished products of industrial explosives into initial products for their reuse is not only of scientific and technical interest, but also of great economic and ecological importance. The objective of this study, performed by employees of AZOTTECH LLC in cooperation with the D. I. Mendeleev Russian University of Chemical Technology, is the development of a method and industrial technology to recycle emulsion production wastes for re-use of the reclaimed materials in production. A chemical method of controlled emulsion destruction was obtained based on the results of the performed research activities. The most effective demulsifier available in the Russian market was selected, by means of which it was possible to separate the emulsion into immiscible phases containing the initial components. Samples of the stable emulsion matrix that match the requirements of the normative documents in terms of quality, were obtained using the oil phase reclaimed materials and the oxidant solution.

Demulsifier Performance Study: Relationship between Demulsifier Properties with Crude Characteristics

Due to the vast range of different types of crude oil characteristics which differ from region to region, wells and even day to day, developing and selecting effective demulsifiers for regional crude oils has been a time-consuming and tedious process. This experimental study defined a relationship between the crude characteristics of wax, asphaltene and crude API with relative solubility number (RSN) properties and chemistry groups of demulsifiers with their performances accordingly. Twenty-five different types of demulsifiers with RSN ranging from ten to twenty-three were tested using demulsifier bottle test. The demulsifiers comprise resin alkoxylate, modified polyol and polyimine derivative. Synthetic crude is used throughout the study with API of 27, 34 and 40. The wax and asphaltene contents of each crude API are varied. Based on the three chemistry groups, resin alkoxylate showed the best performance, while polyimine derivative-based demulsifiers had the poorest performance. The demulsifier with high RSN from 19 to 23 works best in resolving the emulsion compared to the low RSN demulsifiers. These findings provide valuable insights for the petroleum industry, offering guidance on demulsifier selection based on crude characteristics to optimize production, reduce operational costs, and effectively address emulsion-related challenges.

Synthesis and application of recyclable magnetic cellulose nanocrystals for effective demulsification of water in crude oil emulsions

The development of eco-friendly, efficient, and economical demulsifiers for the demulsification of water in crude oil emulsion is one of the important issues in the petroleum industry. Demulsifiers with suitable performance in several demulsification methods are good choices for effective and economical demulsification. In this study, recyclable magnetic cellulose nanocrystals have been synthesized from cotton by a simple method and used in the demulsification of water in crude oil emulsions. Chemical and magnetic demulsification by magnetic cellulose nanocrystals has been investigated. In addition, the effects of time, temperature, and demulsifier concentration on the demulsification efficiency have been evaluated. According to the results, this demulsifier can be used as an effective demulsifier for both chemical and magnetic demulsification and displayed a demulsification efficiency of 100 % at 50 °C without a magnet and 90 % at 20 °C with a magnet. The chemical demulsification efficiency of Fe3O4 nanoparticles was investigated and it showed lower DE compared to magnetic cellulose nanocrystals. The recyclability tests of the demulsifier indicated that magnetic cellulose nanocrystals can be used up to 4 times. Finally, the demulsification mechanism and interfacial tension measurements revealed that this demulsifier reduced the interfacial tension between water and crude oil and increased the water droplet sizes.

Demulsification of crude oil emulsions using a three-branched betaine type ionic liquid and its demulsification mechanism

In this work, a three-branched betaine type ionic liquid (TESA) with elevated interfacial activity was synthesized to separate water from crude oil emulsions at low temperature. The chemical structure, demulsification performance, and demulsification mechanism of TESA was investigated. The bottle tests exhibited that the dehydration efficiency was 100% with 150 mg/L of TESA for 40 min at 50 °C. TESA was effective in acidic, alkaline, and high salinity conditions. The dehydration efficiency of TESA was more than 95.63% with a wide pH range of 3–11. Furthermore, the dehydration efficiency was 100% with 50000 mg/L of salinity for 20 min at 50 °C. Encouragingly, the dehydration efficiency of TESA was better than that of commercial demulsifiers and reported work. The excellent dehydration efficiency of TESA was ascribed to the elevated interfacial activity, amphipathy, and strong interaction with asphaltenes. As a result, TESA improved the substitution of asphaltenes and considerably reduced interfacial tension, resulting in an unstable interfacial film and leading to demulsification. It indicated that TESA was an effective demulsifier, which promised application in the oil industry.

Development of the water-saving technology for refining high-viscosity watered petroleum in oilfield

The article presents research on demulsifiers for oil dehydration in order to increase the conservation of water resources by introducing an additional source. The laboratory experimental works on selection of highly effective demulsifier were carried out. The application of water-saving technology which provided the necessary technological and economic effect was proposed. The analysis of laboratory researches on improvement of the method of dehydration of high-viscosity watered oil showed that under optimally selected conditions, namely: concentration of 75 g/t, temperature of 70 degrees and long settling time, the most effective demulsifier from all the reagents used in the tests was the reagent number 2 which showed the lowest residual water content and satisfied the final criteria both in economic terms and in quality of separation of water from oil without changing its initial structure. The water extraction according to the improved oil dehydration technology increased from 10% to 60%.

Demulsification of water-in-oil emulsions stabilized with glycerol monostearate crystals

HypothesisColloidal particles can be used to generate water-in-oil (W/O) emulsions resistant against coalescence. Demulsification is possible with addition of low molecular weight surfactants to the emulsion continuous oil phase. Whether surfactants demulsify particle-stabilized W/O emulsions depends on their ability to modify the wettability of interfacially-bound particles. ExperimentalCrystals of glycerol monostearate (GMS) were prepared followed by water addition to generate GMS-stabilized W/O emulsions. The surfactants sorbitan monooleate (SMO), sorbitan monolaurate (SML), citric acid esters of monoglycerides (CITREM), sorbitan trioleate (STO), propylene glycol monolaurate (PgML), and polyglycerol polyricinoleate (PGPR) were added to the emulsion oil phase. Emulsion microstructure was characterized by light microscopy and cryo-scanning electron microscopy. Surfactant activity and crystal wetting were characterized by interfacial tension and three-phase contact angle measurements. Salt release from within the emulsions was used to assess demulsifier efficacy. FindingsEmulsions stabilized by platelet-like GMS crystals were generated. Of the six surfactants, SMO, SML, and CITREM were effective demulsifiers whereas STO, PgML, and PGPR were ineffective. The former three sufficiently modified the wettability of GMS crystals on the droplet surface, as they adsorbed to both the oil–water interface and GMS crystal surface. Emulsion destabilization was associated with faster NaCl release from the emulsion internal phase.

New Amphiphilic Ionic Liquids for the Demulsification of Water-in-Heavy Crude Oil Emulsion.

This work aimed to use abietic acid (AA), as a widely available natural product, as a precursor for the synthesis of two new amphiphilic ionic liquids (AILs) and apply them as effective demulsifiers for water-in-crude oil (W/O) emulsions. AA was esterified using tetraethylene glycol (TEG) in the presence of p-toluene sulfonic acid (PTSA) as a catalyst obtaining the corresponding ester (AATG). AATG was reacted with 1-vinylimidazole (VIM) throughout the Diels–Alder reaction, forming the corresponding adduct (ATI). Following this, ATI was quaternized using alkyl iodides, ethyl iodide (EI), and hexyl iodide (HI) to obtain the corresponding AILs, ATEI-IL, and ATHI-IL, respectively. The chemical structure, surface activity, thermal stability, and relative solubility number (RSN) were investigated using different techniques. The efficiency of ATEI-IL and ATHI-IL to demulsify W/O emulsions in different crude oil: brine volumetric ratios were evaluated. ATEI-IL and ATHI-IL achieved promising results as demulsifiers. Their demulsification efficiency increased as the brine ratios decreased where their efficiency reached 100% at the crude oil: brine ratio (90:10), even at low concentrations.

The Advantage Of Oil Content In Injection Water Determination Before Implementation Of Waterflood In Oilfield

Before implementation of water flooding in oilfield, it will be good to determine oil content in the injection water. The results of laboratory tests provide valuable and useful information, firstly, whether reverse demulsifier is required or not to reduce oil content in water. Secondly, the test results can select the effective reverse demulsifier. S1 and S2 injection water contain very low oil content, so it is not necessary to add reverse demulsifier in the both injection water. High oil content is obtained in S3 injection. The 50 mg/L DKM reverse demulsifier does not work effectively to reduce oil content in the S3 injection water. Whereas, the 50 mg/L Prolab reverse demulsifier is effective and able to reduce oil content sharply in the S3 injection water with 95.46 % efficiency.

A new image-based microfluidic method to test demulsifier enhancement of coalescence-rate, for water droplets in crude oil

The separation of water droplets from water-in-crude-oil emulsions is a vital process in the petroleum industry. Various components in crude oil, such as asphaltene, stabilize the water–oil interface, which inhibits the coalescence of water droplets. To enhance the oil–water separation, specific demulsifiers are often added to destabilize the emulsion and enhance the coalescence of the water droplets. In this work, we propose a new method to select an effective demulsifier and optimal concentration for a water-in-crude oil emulsion. This new experimental design involves an optical-access flow in a long 500 μm-square micro-fluidic channel, illuminated by a Near-Infrared laser and imaged with a B/W high-speed video camera. We can quantify the coalescence probability by using monodisperse droplets and identifying coalescence by their change in size. Coalescence probability is an indicator for selecting the optimal concentration and type of demulsifier.

Bio-based Products for Water-in-Crude Oil Emulsification/Demulsification Processes: An Update

There has been an increase in demand for green demulsifiers that will be as effective as the chemical demulsifiers but without the negative environmental effects. This demand has been partly addressed with the production of some bio-based demulsifiers. It is of importance to know the substances that act as emulsifiers in the production of crude oil and understand the mechanism of emulsification. This paper has reviewed emulsifiers and the mechanism of emulsification as well as bio-based demulsifiers and their mechanisms. This will enhance our knowledge on the type of compounds that can be used in the formation of effective demulsifiers. Innovation of these demulsifiers will enhance crude oil production and in the long run boost profitability and environmental sustainability. Currently, cashew nut shell liquid (CNSL) derivatives are in use for the formulation of effective green demulsifiers for water-in-crude oil emulsions.

Demulsification of water-in-crude oil emulsion driven by a carbonaceous demulsifier from natural rice husks

Removing emulsified water from a water-in-crude oil (W/O) emulsion is critically required prior to downstream processing in the petroleum industry. In this work, environmentally friendly and amphipathic rice husk carbon (RHC) demulsifier was prepared by a simple carbonization process in a muffle furnace using rice husks as starting materials. RHC was characterized by field-emission scanning electron microscope, energy dispersive spectrometer, Fourier transform infrared spectrometer, ultraviolet–visible spectrometer, powder X-ray diffraction, zeta potential and synchronal thermal analyzer. The factors such as dosage, temperature, settling time, pH value and salinity were systematically investigated. The results indicated that the dehydration efficiency (DE) reached as high as 96.99% with 600 mg/L of RHC for 80 min at 70 °C. RHC exhibited an optimal DE under neutral condition, but it was also effective under acidic and alkaline conditions. Also, it had an excellent salt tolerance. The possible demulsification mechanism was explored by interfacial properties, different treatment methods for RHC and microexamination. The demulsification of RHC is attributed to its high interfacial activity, oxygen-containing groups and content of silica. It indicates that RHC is an effective demulsifier for the treatment of the W/O emulsion.

Synthesis and Study of a New Type of Nonanionic Demulsifier for Chemical Flooding Emulsion Demulsification.

The application of chemical flooding improves the stability of the produced emulsion, which reduces the demulsification efficiency of conventional demulsifiers. To improve the demulsification effect, in this paper, a new multibranched nonanionic polyether demulsifier, FYJP, was prepared by grafting carboxylate based on a nonionic demulsifier. The FYJP demulsifier could generate an initiator through p-tert-butylphenol, triethylenetetramine, and methanol, which was polymerized with ethylene oxide (EO) and propylene oxide (PO) to produce a nonionic polyether demulsifier. Sodium chloroacetate was used to modify the polyether demulsifier to obtain a new type of nonanionic polyether demulsifier. The FYJP polyether demulsifier was characterized by the hydrophilic–lipophilic balance (HLB) value, relative solubility (RSN), and surface activity of the demulsifier, and the demulsification mechanism was analyzed by a microscopic demulsification process test, and the effect of demulsifier dosage on the demulsification effect was discussed. Meanwhile, a dehydration test was carried out. The experimental results showed that the highest dehydration rate of the demulsifier was 94.7% at 85 °C, 100 ppm demulsifier dosage, 50 mL of a W/O emulsion, and 120 min demulsification time. The abovementioned studies show that FYJP is an effective demulsifier for chemical flooding emulsions, and this work promises to provide a reference for future demulsifier research.

New Amphiphilic Tricationic Imidazolium and Pyridinium Ionic Liquids for Demulsification of Arabic Heavy Crude Oil Brine Emulsions.

Preparation of new green oilfield chemicals based on ionic liquids (ILs) having higher demulsification efficiency to solve the heavy crude oil brine water emulsions became a target in the petroleum research studies and industry. In the present work, the combination of pyridinium, imidazolium, and hydrophilic or hydrophobic moieties in the chemical structure of ILs has been investigated to improve the surface properties of ILs in both bulk solution and interfaces. Aminopyridine was quaternized with cetylbromide and condensed with glyoxal and 4-hydroxybenzaldehyde in acetic acid to prepare imidazolium–pyridinium bromide acetate ionic liquid (IPy-IL). The phenol group of IPy-IL was etherified with tetraethylene glycol to alter its amphiphilicity and synthesize new amphiphiles (AIPy-IL). Their chemical structure, thermal characteristics, and stabilities were characterized. Their aqueous solution performance in seawater was evaluated to investigate their surface activity, aggregation particle sizes, and surface charges. The demulsification performances of the prepared Arabic heavy crude oil seawater emulsions in the presence of different concentrations of IPy-IL and AIPy-IL were evaluated and proved by interfacial tension, particle size, and demulsification efficiencies at a temperature of 45 °C. The data concluded that AIPy-IL was an effective demulsifier for different crude oil seawater emulsion compositions at a low injection dose and temperature of 100 ppm and 45 °C, which were not report elsewhere.

Synthesis and application of geminal dicationic ionic liquids and poly (ionic liquids) combined imidazolium and pyridinium cations as demulsifiers for petroleum crude oil saline water emulsions

New geminal dicationic ionic liquids, ILs, containing both imidazolium and pyridinium cations were synthesized to apply as effective demulsifiers for stable sea water-in-heavy petroleum crude oil emulsions. In this respect, vinyl imidazolium and 4- amino-4-pyridyl diethoxylate (APE) or 4-pyridyl tetradecanamide were quaternized either with 1,4-dibromobutane or 1,12-dibromododecane to produce ILs monomers. Their vinyl group was polymerized via solution radical polymerization to produce geminal poly (ionic liquids), PILs, and their chemical structures were identified by nuclear magnetic resonance. The thermal stability and thermal characteristics of the prepared geminal dicationic imidazolium and pyridinium cations indicate that all prepared compounds behave as ILs and PILs having lower melting temperature below 100 °C and lower glass transition temperatures below 0 °C. The surface activity, micellization or aggregation, and adsorption at air/seawater or seawater/petroleum crude oil interfaces were investigated from surface and interfacial tension measurements. The interactions of the prepared ILs and PILs with asphaltenes were evaluated from particle sizes and zeta potentials. The demulsification of stable W/O emulsions at temperature of 60 °C using different concentrations of the prepared ILs and PILs confirm that the demulsification was carried out at lower injection dose (from 100 to 250 ppm) and shorter demulsification time (from 40 to 240 min).

Demulsification of a Nigerian crude emulsion using ethoxylated-resoles and their xylene modified blends

Demulsification is a method used to reduce or disrupt the water - crude oil emulsion system without uttering the initial composition of the crude oil. This process is done by the introduction of chemicals called demulsifiers, which break the emulsion into aqueous and organic phases. In this study, the demulsifier formulated was the base-catalyzed phenol-formaldehyde resin known as the resoles, with the ratios of phenol to formaldehyde, varied between 1.0:1.2 and 1.0:2.0. The different samples of resoles where then ethoxylated to make them more hydrophilic using different weights (10, 15 & 20 g) of polyethylene glycol (PEG). Screening of the ethoxylated demulsifiers was done using the established bottle test procedure, at 70 °C, the concentration of 50 ppm, and 20 minutes of residence or separation time, in order to select the most effective demulsifier, based on the amount of water removed from the emulsion. The best chemical-demulsifier produced was the ethoxylated resole, which was then blended with xylene at varying percentages (0, 20, 40, 50, and 80 % weight/weight) and was further screened, using the bottle test method. From the analysis, it was obtained that the most effective ethoxylate-xylene demulsifier blend was sample DR3, and made of formaldehyde to phenol ratio of 1.8:1, 20 g of PEG 400 blended with 20 % xylene. The demulsifier gave a water separation efficiency of 85.7 %, compared with the commercial demulsifier, which yielded 72.7 %. The result indicates the practical significance of solvent modified demulsifiers for separating crude oil emulsions in the petroleum industries.

A novel biodemulsifier of Bacillus mojavensis XH1 – Oxalate decarboxylase with the potential for demulsification of oilfield emulsion

In recent years, special attention has been devoted to biodemulsifiers as a new type of environment-friendly demulsifiers. A novel biodemulsifying oxalate decarboxylase (OxdC) secreted by Bacillus mojavensis XH1 is reported in the present study. A genome-wide comparison showed that strains with high demulsification efficiencies all possess alkane degradation genes. An analysis of the differentially expressed genes and proteins induced by different substrates showed that OxdC secreted by XH1 was an effective demulsifier. Moreover, the demulsification ability was verified by prokaryotic gene expression, knockout and complementation analyses. OxdC from XH1 exhibited a strong demulsification capacity and significantly outperformed the model protein Bacillus subtilis 168 OxdC (Yvrk), which shared a high amino acid similarity but showed limited demulsification ability. Based on a comparison of the structural characteristics, the hydrophobic amino acids on the surface of OxdC were identified as a key factor driving the favorable demulsification activity of XH1. The metabolic pathways of XH1 used liquid paraffin and glucose as substrates, illustrating that hydrocarbons are necessary for biodemulsifier secretion. The present study provides new insight into the application of OxdC as an additional genetic resource in biodemulsification.

Alginite rock as effective demulsifier to separate water from various crude oil emulsions

Due to environmental restriction laws in oil production and processing, there is a high demand for the oil industry to reduce the use of chemical demulsifiers and to employ safer, less toxic materials. The purpose of this research is to investigate whether Alginite, a naturally occurring and abundant oil-shale rock, can be utilised as an alternative, environmentally friendly and low-cost material to demulsify various water-in-crude oil emulsions (W/O). Three W/O emulsions were prepared using saline water with respectively light, medium and heavy crude oils. The properties of the crude oils were analysed and the effectiveness of Alginite to demulsify the corresponding W/O emulsions was investigated. The results confirm that naturally occuring Alginite exhibits exceptional water-removing capacity even from emulsions containing heavy crude oil, leaving only < 1.0 wt.-% water in the remaining demulsified oil, which satisfies the required specification for industrial applications. Alginite was shown to reduce viscosity and to deform the dispersed phase in W/O emulsions even in the absence of flow. The results of this work indicate that Alginite is of significant interest in petroleum research, in industrial oil processing as well as in environmental remediation.