Characterization of C80 Naphthenic Acid and Its Calcium Naphthenate

A C80 naphthenic acid (tetraacid) and its calcium naphthenate have been characterized with respect to their interfacial properties at both the oil/water and the air/water interfaces as well as their thermal properties. Naphthenic acids in crude oils may give rise to different problems in oil production including naphthenate deposition and formation of stable emulsions. This may lead to severe disturbances of regularity and shut‐in in the oil production. The interfacial activity and film properties of the compounds were examined by the oscillating drop method. The calcium naphthenate film was primarily elastic and solid‐like. Measurements on the acid gave similar results, an elastic, solid‐like film was formed, but the effect was less pronounced than for the calcium naphthenate. Langmuir‐Blodgett films of the acid and its naphthenate were deposited on conducting substrates and subsequently analyzed by scanning electron microscopy, SEM. It was found that the pure acid formed crystalline structures in the interfacial film on compression. The calcium naphthenate, on the other hand, form a continuous amorphous film on the substrate.     

Model compounds for C80 isoprenoid tetraacids: Part II. Interfacial reactions, physicochemical properties and comparison with indigenous tetraacids

Novel model compounds are desired to study properties of a narrow group of tetrameric acids from crude oil mainly responsible for naphthenate deposition. It is important to make a comparison to find to what degree the model compounds can reflect the properties of the indigenous tetraacids and where there are deviations, before using the model compounds in naphthenate research. A comparison between two synthesised model compounds and indigenous tetraacids has been carried out regarding physicochemical properties including thermal solid state properties, critical micelle concentrations, monolayer properties and interfacial reactions. Of the two studied model compounds, one was observed to form the same cross-linked network with Ca²⁺, a typical feature of the indigenous tetraacids. Interfacial reactions using the pendant drop technique also showed that four different divalent cations could all form this network with the model tetraacid. The film formation was however dependent on the ratio M²⁺/TA. The main deviations were in the solid state, where the model compounds showed crystalline transitions, contrary to the indigenous tetraacids. We conclude that the two different model compounds mimic the indigenous tetraacids well with respect to several of their properties and are suitable for use in naphthenate research.     

Inhibition of Calcium Naphthenate. Experimental Methods to Study the Effect of Commercially Available Naphthenate Inhibitors

In this study, different methods have been developed for studying naphthenate inhibitors. One first method is based on interfacial activity of systems with naphthenic acids, inhibitors, and calcium viewing reaction mechanisms at interfaces of the inhibitors. A second method is based on gravimetrical determination of interfacial layer in a two phase system and gives a thermodynamic approach to naphthenate formation, and a third method utilizes a ultraviolet-active model tetraacid to directly determine the depletion in bulk phase concentration during a two-phase reaction. The results indicate that inhibitors may act through several mechanisms, and depending on the total system different mechanisms may have the highest efficiency also by combining several mechanisms.     

Methods to Study Naphthenate Formation in w/o Emulsions by the Use of a Tetraacid Model Compound

Precipitation of naphthenate salts is normally a problem in the processing of acidic crude oils. In this study, the goal was to find suitable methods to investigate the interfacial reaction between tetraacid and calcium under emulsified conditions. Two different systems have been studied depending on composition and applied shear. The influence of inhibitors has been investigated and the same inhibitor was found to be the most effective one regardless of the system. Depletion of tetraacid in the oil phase was analyzed with UV-vis and HPLC. Interfacial area and droplet size in the emulsions were measured with fluorescence microscope and pulse-field gradient NMR. Since this reaction takes place over the interface, the investigation clearly documents, the importance of the total interfacial area of the emulsified system.     

Interactions between synthetic and indigenous naphthenic acids and divalent cations across oil–water interfaces: effects of addition of oil-soluble non-ionic surfactants

Interactions between naphthenic acids and divalent metal cations across model oil–alkaline water interfaces were investigated by correlating changes in dynamic interfacial tension (IFT), to plausible reaction mechanisms. The measurements were carried out by using a CAM 200 optical instrument, which is based on the pendant drop technique. The naphthenic acids used were synthesised model compounds as well as commercial acid mixtures from crude distillation and extracted acid fractions from a North Sea crude oil. The divalent cations involved Ca²⁺, Mg²⁺, Sr²⁺, and Ba²⁺, which are all common in co-produced formation water and naphthenate deposits. The results show that the dynamic IFT strongly depends on naphthenic acid structure, type of divalent cation, and the concentration of the compounds as well as the pH of the aqueous phase. Introducing divalent cations to systems involving saturated naphthenic acids caused mostly a permanent lowering of the IFT. The decline in IFT is due to electrostatic attraction forces across the interface between the cations in the aqueous phase and the carboxylic-groups at the o/w interface, which cause a higher interfacial density of naphthenic acid monomers. The permanent lowering in IFT is likely due to formation of positively charged monoacid complexes, which possess high interfacial activity. On the other hand, in the case of the aromatic model compounds, the cations affected the IFT differently. This is mainly discussed in light of degree of cation hydration and steric conditions. Various oil-soluble non-ionic surfactant mixtures were also introduced to systems involving a model naphthenic acid and Ca²⁺ in order to investigate how the interfacial competition affected the local interactions. Based on the behaviour of dynamic IFT, probable inhibition mechanisms are discussed.Electronic Supplementary Material Supplementary material is available for this article at     

Structure and Orientation of Tetracarboxylic Acids at Oil–Water Interfaces

Fouling caused by tetracarboxylic acids in transport and separation process chains involving petroemulsions occurs when the interfacial concentration of tetraacids becomes large enough for calcium ions in the water phase to “crosslink” the adsorbed tetraacid molecules and form a precipitate. At present, the structure and orientation of tetraacid molecules at oil–water interfaces, which influences the precipitation behavior, has not been studied in detail. In this work, molecular dynamics simulations of indigenous and synthetic tetracarboxylic acid compounds are presented to describe the structure and spatial orientation of tetraacid molecules at oil–water interfaces. Molecular distributions relative to the oil–water dividing surface along with the length and orientation angle distributions of the acidic arm groups are presented. The probability distributions determined here that describe the tetraacids at an oil–water interface can be employed to reconstruct the density of carboxylic acid groups at the oil–water interface. The interfacial carboxylic acid density can be employed to determine the fraction of adsorbed tetraacid molecules that are “crosslinked” with calcium ions based on the distances between carboxylic acid groups. The simulations presented also form a basis to calculate interfacial molecular areas and virial coefficients to employ in molecular mixed monolayer adsorption isotherms.     

Effect of Aqueous Phase pH on the Dynamic Interfacial Tension of Acidic Crude Oils and Myristic Acid in Dodecane

The time dependence of the interfacial tension between water–acidic crude oil and water–synthetic oil was investigated for aqueous phase pHs ranging from 2 to 9 using the du Noüy ring method at 20°C. Myristic acid in dodecane was selected as a model (synthetic oil) for acidic crude oil containing indigenous surfactants, and the similarities and differences between the dynamic interfacial tension behaviours of the natural and synthetic crude oil systems were compared. The initial interfacial tension and the relaxation of the interfacial tension are sensitive to the aqueous phase pH for both systems. The adsorption kinetics of the indigenous surfactants and myristic acid could be well fitted with the monoexponential model, and the time constants obtained in this manner indicates that reorganization of the indigenous surfactants and myristic acid at the w/o interface are pH dependent. The experimental results also indicate that indigenous surfactants in acidic crude oil and myristic acid in dodecane have similar film formation behaviours at the w/o interface for the range of pHs investigated.     

Isolation and Characterization of Naphthenic Acids from a Metal Naphthenate Deposit: Molecular Properties at Oil‐Water and Air‐Water Interfaces

Naphthenic acids from a West African metal naphthenate deposit have been isolated and characterized by infrared (IR), nuclear magnetic resonance (NMR), and Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR MS). The sample has been shown to comprise a narrow group of 4‐protic naphthenic acids of molecular weight ～1230 Da. The determined mass of 1230.0627 Da suggests a compound with the elemental composition C₈₀H₁₄₂O₈. The NMR data show no sign of carbon‐carbon multiple bonds. Hence, the elemental composition indicates the presence of six saturated hydrocarbon rings. The naphthenic acids have proved to be highly oil‐water (o/w) interfacially active. On elevation of the pH from 5.6 to 9.0, interfacial activity increases gradually due to a higher degree of dissociation of the carboxylic groups. At pH 9.0, the interfacial tension (IFT) between water and toluene‐hexadecane (1–9 vol.) is lowered by ～40 mN/m at concentrations of only 0.0050–0.010 mM naphthenic acid. The time rate of decrease of the IFT (dγ/dt) is also concentration‐dependent, and a well‐defined IFT is attained at long observation periods.

The C₈₀ naphthenic acids form relatively unstable Langmuir monolayers. The stability decreases further with increasing pH as more monomers become dissociated and dissolve into the aqueous phase. The stability is altered upon addition of calcium ions into the subphase due to formation of calcium naphthenate at the surface. In the undissociated state, the acids have a molecular area of ～160 Å²/molecule in the noninteracting region. The high area reflects an extended molecular structure comprising four carboxylic head groups, which are likely to be separated by hydrocarbon chains.     

Near-IR spectroscopy as a method for studying the formation of calcium naphthenate

A method for studying the precipitation of calcium naphthenate particles by means of near-IR spectroscopy is presented. Naphthenic or fatty acids were dissolved in water at high pH (11.2–11.5). Upon addition of a Ca²⁺ solution the nucleation period and particle growth were monitored. The near-IR spectra experience a baseline elevation owing to the formation and growth of calcium naphthenate particles. The resulting change in optical density over time is discussed on the basis of supersaturation, particle sizes, agglomeration, Ca²⁺-to-carboxylic acid ratio and nucleation process. Solubility products, defined as the ion concentration products where no particle growth was detected, were estimated for the calcium soaps. The method showed some quantitative limitations since the particle sizes changed with supersaturation. Smaller particles will have less influence on the optical density and the larger particle will dominate the resulting scattering contribution. However, it is obvious that the method has qualitative value, for example, to study the efficiency of different calcium naphthenate inhibitors.     

Influence of Interaction Between Heavy Oil Components and Petroleum Sulfonate on the Oil–Water Interfacial Tension

The purpose of this study is to obtain the interaction between heavy oil components and petroleum sulfonate (NPS). In this article, the effects of pH, NaCl concentration, and NPS on the oil–water interfacial tension (IFT) of Gudao crude oil and its polar components were investigated. The results show that the NPS concentration corresponding to turning point of IFT is 0.001 g·mL^?1. This is lower than the CMC of NPS (0.0015 g·mL^?1) as there is a positive synergetic effect between NPS and the active substances of crude and its components, and the strength of their interaction depends on the interfacial activity of crude components. In simulated system of crude and polar components with 0.1 wt% NPS, at basic condition, the acidic substances in the polar components create naphthenates (the component whose acid number is higher creates more naphthenates), leading to lower IFT, so the interaction between heavy oil components and NPS is stronger in the basic condition. Proper concentration of NaCl in the stimulated systems improved the hydrophile-lipophile balance of emulsifier (NPS), accelerated the well-regulated adsorption of NPS in oil–water interface, and increased the interfacial activity of NPS, the interaction between heavy oil components and NPS was also enhanced.     

Stability of water/crude oil emulsions based on interfacial dilatational rheology

The dilatational viscoelasticity behaviors of water/oil interfaces formed with a crude oil and its distilled fractions diluted in cyclohexane were investigated by means of an oscillating drop tensiometer. The rheological study of the w/o interfaces at different frequencies has shown that the stable w/o emulsions systematically correspond to interfaces which present the rheological characteristics of a 2D gel near its gelation point. The stability of emulsions was found to increase with both the gel strength and the glass transition temperature of the gel. As expected, the indigenous natural surfactants responsible for the formation of the interfacial critical gel have been identified as the heaviest amphiphilic components present in the crude oil; i.e., asphaltenes and resins. Nevertheless, we have shown that such a gel can also form in the absence of asphaltene in the oil phase.     

Adsorption of octanoic acid at the water/oil interface

Fats are widely present in a large variety of food and represent the main source of energy for the body. In the current study we investigate the behaviour of fatty acids at liquid–liquid interfaces, mimicking some steps of the very complex digestion process. Octanoic acid is used as an example of middle chain fatty acids. For the oil phase we choose sunflower oil as an industrial product and hexane as pure oil.The influence of the fatty acid concentration and the pH of the aqueous phase on the interfacial tension is determined by profile analyse tensiometry (PAT), which allows to examine the way of adsorption and transition of the fatty acids from one phase to the other. Predominantly, the pH affects the dissociation and thereby the strength of the hydrophilic character of the fatty acid. The adsorption behaviour indicates the different interfacial activity of the studied octanoic acid.     

Oil-Water Partitioning of a Synthetic Tetracarboxylic Acid as a Function of pH

The oil-water partitioning of a synthetic tetraacid acting as a model compound for indigenous C₈₀-C₈₂ ARN acids has been studied as a function of pH, ionic strength and type of monovalent counterion. Experimental data obtained with ultraviolet-visible and HPLC/UV analyses have been fitted to thermodynamic models based on one, two or four dissociation steps to obtain o/w partition coefficients (K _wo ) of the fully protonated acid between chloroform and aqueous solutions, and its apparent acidity constant(s), pK _a. As the study is conducted above the CMC of the tetraacid, in general high apparent acidity constants were obtained in the range from 6 to 8 resulting from micellization equilibria. K _wo values were obtained in the range from 10^?3 to 10^?4, and decreasing with increasing salinity. At 50 mM K⁺, no conclusions could be made regarding the number of distinguishable dissociation steps, while at higher ionic strength (184 mM and 452 mM K⁺) and at 184 mM Na⁺ a model with two dissociation steps provided good fits to the experimental data. The first step was found to be given by a pK _a ≈ 6.6–6.8 and the second dissociation step at pK _a values ≈ 7.8–8.3. The two-step mechanism supports previous results obtained by potentiometric titrations. No significant difference in the o/w behavior was observed when changing the counterion from potassium to sodium. The main partitioning of the tetraacid in the aqueous phase occurred above pH 8, where the fully deprotonated acid was formed.     

The chemistry of tetrameric acids in petroleum

This article reviews the properties of a novel class of molecules: the tetrameric acids. These molecules have brought a large interest in petroleum science since the discovery of the family of molecules named ARN in 2004. ARN, which is naturally present in oil, is responsible, by reaction with calcium ion, of the formation of calcium naphthenate deposits; organic deposits that cause irregularities in crude oil production and processing. In order to study the properties of ARN, a model tetrameric acid molecule mimicking some of its properties named BP-10 has been developed in 2008 by Nordgård and Sjöblom and has been extensively used since then.     

Interfacial dilational rheology properties of films formed at the oil/water interface by reaction between tetrameric acid and calcium ion

This article aims to determine the applicability of interfacial dilational rheology to study the formation of viscoelastic film at the oil/water interface by reaction between tetrameric acids ARN and calcium ions, and to determine the influence of asphaltenes and naphthenic acids (NA) on this film. It was first found that the formation of viscoelastic film by reaction between ARN and calcium ions is easily observed by dilational rheology: Significantly high values of E′ (130?mN/m) were measured for this system at low ARN concentration (10?µM). These values are at least 5 to 10 times higher than values obtained for ARN without Ca²⁺ or other crude oil components such as asphaltenes and naphthenic acids.

The influence of asphaltenes and NA on the viscoelastic film formation has been studied. When asphaltenes or NA are present, the interfacial viscoelastic film is weakened: There is a gradual decrease of E′ and E″ when the asphaltenes or NA concentration increases. These two components can therefore inhibit the ARN/Ca²⁺ film formation. This decrease is similar to the one previously observed by shear rheology. Several explanations are proposed.     

用红外光谱法测定环烷酸纯度的研究

环烷酸是一类带有碳环结构的一元羧酸,是以各种不同分子量的一元羧酸的混合物存在于石油中．将石油各馏分精炼过程的碱洗废液,经过酸处理,就制得工业环烷酸．工业环烷酸中环烷酸含量是环烷酸最重要的一个理化指标,在红外光谱上,环烷酸的羧基在1700cm^-1附近有一极强的特征吸收峰,并且吸收不受样品中其它组分的干扰．因此,红外光谱是快速准确测定工业环烷酸中环烷酸含量较为理想的方法．     

Interfacial Tension Measurements Between Oil Fractions of a Crude Oil and Aqueous Solutions with Different Ionic Composition and pH

Dynamic and equilibrium interfacial tensions between crude oil fractions and aqueous solutions of various compositions and pH were measured. The basic oil components seemed to determine the interfacial tensions at pH 2, while the non-dissociated and dissociated acidic components governed the interfacial tension at the natural pH and pH 9, respectively. The ionic composition of the aqueous phase influenced the degree of dissociation of the acidic components at pH 9: Na⁺ ions in the aqueous phase promoted dissociation of the interfacial acidic components (compared to pure water), while Ca²⁺ ions resulted in complexation with the dissociated acids and most likely formation of stable interfacial films. The amount of Ca²⁺ determined which of these phenomena that dominated when both ions were present in sea water solutions. Generally, the interfacial tensions of the oil fractions were lower when measured against the high salinity aqueous solutions than against the corresponding low salinity solutions.      

Studies of synergism for lowering dynamic interfacial tension in sodium alpha-(n-alkyl) naphthalene sulfonate/alkali/acidic oil systems

Alkylnaphthalene sulfonates with high purity were selected as model components to research synergism for lowering interfacial tension (IFT) in surfactant/alkali/acidic oil systems. The dynamic IFTs between alkylnaphthalene sulfonates with different alkyl chain length and n-decane, oleic acid model oil, or Shengli crude oil were measured. The results showed that the alkylnaphthalene sulfonates with different alkyl chain lengths had different synergism with different acidic components and their ionized acids under the same conditions. The synergism for lowering dynamic IFT in alkylnaphthalene sulfonate/alkali/acidic oil systems was controlled by alkylnaphthalene sulfonate concentration, alkyl chain length, alkali concentration, alkali type, and oleic acid concentration: optimal physicochemical conditions were necessary to the best synergism. This indicates that the synergism among added surfactant acidic components in crude oil and their ionized acids is controlled by the ratio of their interfacial concentrations.     

过饱和度、反应物化学计量比及离子强度对草酸钙晶体生长的影响

肾结石是一种普遍的疾病,全球的发病率约为10%,且其复发率高。2003年欧洲的一项统计表明,尿石患者第一次复发率为40%[1]。草酸钙(CaOxa)是肾结石的主要成分,其体外模拟引起了人们广泛的关注[2,3]。然而,普通溶液体系的模拟环境不能充分反映尿石的形成环境,用类似细胞膜的有序分     

Monitoring of calcium stearate formation by thermogravimetry

Naphthenates are produced when naphthenic acids present in crude oil are mixed with brine. They deposit at oil/water interface and are insoluble in either of the phases causing a large problem to the oil industry. Generally, naphthenates precipitate jointly with others compounds such as sulfates and carbonates. This fact makes difficult their characterization. In this study, calcium stearate formation from stearic acid was investigated, under different conditions, as a previous model to understanding of calcium naphthenate precipitation. Medium reactions distinct were studied and the results indicated that the ethanol medium was the most efficient for the formation of solids because in this only case, the stearic acid was completely converted into stearate. Monitoring of the conversion was performed by thermogravimetry in spite of this technique not be typical in salts characterization. Nevertheless, the thermogravimetric analysis showed that is possible to identify differences between an organic acid, a salt of this acid and an inorganic salt, in the same sample. Infrared spectra was used in order to confirm the results obtained by thermogravimetry. However, this technique showed less efficiency and sensibility.