Identification of Crude Oil Components Responsible for Foaming

1985 ◽  
Vol 25 (02) ◽  
pp. 171-175 ◽  
Author(s):  
I.C. Callaghan ◽  
A.L. McKechnie ◽  
J.E. Ray ◽  
J.C. Wainwright

Abstract The foaming characteristics of a number of crude oils from a variety of sources were determined by Bikerman's pneumatic method. Extraction of these crudes with both pneumatic method. Extraction of these crudes with both alkali and acid indicated that the crude oil components responsible for the foam stability were removed by the alkali extraction. Further examination of the alkali extract revealed that after neutralization it was the chloroform soluble part of this extract (0.02% wt% of the whole crude) that was responsible for the foaming properties of the crudes investigated. This latter point was confirmed by demonstrating that the surface rheological properties of one of the extracted crudes could be restored by adding back the chloroform-soluble portion of the neutralized alkali extract. Analysis of this extract indicated that the foam-stabilizing materials were short-chain carboxylic acids and phenols of molecular weight -400. In principle, such analytical information could be used to identify principle, such analytical information could be used to identify crude oils likely to present severe foaming problems in the field. Such information could enable the process engineer to take appropriate corrective measures early in the life of a new field, thus avoiding the need for high capital expenditure at a later stage. Introduction Crude oil foams can pose major problems for operators of gas/oil separation plants, causing a loss of crude in the separated gas stream and consequent loss of revenue and possible damage to downstream compressors. Thus, an possible damage to downstream compressors. Thus, an understanding of the factors controlling crude oil foam stability is highly desirable, since it should lead to better methods of foam prediction and control. With this end in mind, we have attempted to identify those crude oil components responsible for foam stabilization. This paper outlines our findings to date and attempts to demonstrate that a similar suite of compounds is responsible for the stabilization of a wide range of crude oil foams. Experimental Materials Crude Oils. Chemical-free samples of 16 different stock-tank crude oils were obtained from a variety of sources (see Table 1). Particular care was taken to ensure that these samples were stored under nitrogen to prevent oxidation of the crudes. prevent oxidation of the crudes. Reagents used were cyclohexane, spectroscopic grade (from BDH); chloroform, general purpose reagent grade (from BDH); diethyl ether, general purpose reagent grade (from BDH); sodium hydroxide pellets, technical grade (from BDH); and SIL-PREP reagent: Applied Science Laboratories Ltd. All solvents were distilled before use, and only an 80% heart cut was taken. Techniques Foaminess Index Measurements. The foaming column used in this work consisted of a graduated glass tube approximately 30 cm [12 in.] in length with two fine sintered glass disks placed 1 cm [0.4 in.] apart, situated at the base of the tube just above the gas inlet. The gas used to create the foam is admitted to the column by way of a pressure reduction and flow meter assembly (see Ref. 1). The measurements were initiated by pipetting an aliquot of crude oil, just sufficient to cover the upper sintered disk, into the foaming column. The oil was allowed to spread over the sintered disk. Compressed air (or natural gas), flowing at a constant rate (40 cm3/sec [40 mL/min]), then was admitted to the column by way of the sintered disk and the crude oil was taken up into the froth. The bubbling was continued for 5 minutes after all the liquid had been taken up into the foam. When a homogeneous foam had been achieved, the height of the upper foam/gas interface was recorded. Three runs were performed on each crude oil studied. The foaminess index performed on each crude oil studied. The foaminess index (E) of each of the stripped and complete stock-tank crude oils then was determined by Bikerman's method. (1) where V, is the constant foam volume at time t and V is the volume of gas injected during time t. Extraction of Crude Oil Surfactants. Treatment with dilute aqueous sodium hydroxide solution was found to be the best means of extracting the acidic components in the crude oils. The oils were dissolved in cyclohexane to give 10% vol/vol solutions, thereby reducing viscosity and thus facilitating rapid phase separation. Despite this precaution some oil still was removed with the aqueous precaution some oil still was removed with the aqueous phase, which necessitated thorough back extraction with phase, which necessitated thorough back extraction with fresh solvent to ensure the selectivity of the separation. The sodium salts in the aqueous extract then were converted back to the free acids by treatment with excess mineral acid. The concentrate obtained was derived for analysis by combined gas chromatography/mass spectrometry (GC/MS). SPEJ P. 171

1975 ◽  
Vol 15 (03) ◽  
pp. 197-202 ◽  
Author(s):  
Harley Y. Jenning

Abstract This paper presents the results of a study of caustic solution-crude oil interfacial tension measurements on 164 crude oils from 78 fields. Of these crude oils 131 showed marked surface activity against caustic solutions. Surface activity of crude oil against caustic solution correlates with the acid number, gravity, and viscosity. Almost all crude oils with gravities of 20 degrees API or lower produced a caustic solution-crude oil interfacial produced a caustic solution-crude oil interfacial tension less than 0.01 dyne/cm. Of the interfacially active samples, 90 percent reached maximum measurable surface activity at a caustic concentration of close to 0.1 percent by weight. The dissolved solids content of the water bas a marked influence on the surface activity. Sodium chloride in solution reduces the caustic concentration required to give maximum surface activity. Conversely, calcium chloride in solution suppresses surface activity. Introduction The oil-production technology literature contains a number of papers that indicate that the addition of sodium hydroxide to the flood water beneficially affects oil recovery. Although the proposed recovery mechanisms differ in detail, a variable common to almost all is the interfacial tension between caustic solutions and crude oil. A study of the factors influencing caustic solution-crude oil interfacial tensions is fundamental to an understanding of the proposed mechanisms and their optimum utilization. proposed mechanisms and their optimum utilization. We have obtained interfacial tensions against caustic solutions of 164 crudes. These crudes come from all major oil-producing areas in the free world. In addition to determining the correlation of interfacial tension with crude oil properties of acid number, gravity, and viscosity, we have also determined the effect of certain dissolved solids in the water. We define acid number as the number of milligrams of potassium hydroxide required to neutralize the acid in one gram of sample. The interfacial tension data were obtained by the pendent-drop method. pendent-drop method. EXPERIMENTAL PROCEDURE The caustic solutions used in this study were prepared by adding reagent-grade sodium hydroxide prepared by adding reagent-grade sodium hydroxide to laboratory distilled water. Our standard solutions were made from a 50 percent by weight reagent-grade sodium hydroxide solution. For convenience in relating our laboratory data to possible field application, the data were recorded and plotted in terms of weight percent sodium hydroxide. The pH of the caustic solutions was determined experimentally using a Coming expanded-scale pH meter; and the densities of the caustic solutions were measured experimentally using a Chainomatic Westphal balance. CRUDE OILS The crude oils were protected from the atmosphere and were collected in carefully cleaned glass or, when practicable, in plastic-lined containers. The crude oil samples were free of chemical additives, such as emulsion breakers and corrosion inhibitors. If the oil contained suspended solid material it was dehydrated and filtered. The densities were determined by the Westphal balance; and the viscosities were determined as a function of temperature using a glass capillary viscometer. APPARATUS AND EXPERIMENTAL PROCEDURE The interfacial tension measurements described in this study were made by the pendent-drop method. The pendent-drop method is based on the formation of a drop of liquid on a tip, the drop being slightly smaller than that which will spontaneously detach itself from the tip. The profile of this drop is magnified by projection and can be recorded on a photosensitive emulsion. The interfacial tension is photosensitive emulsion. The interfacial tension is calculated from the dimensions of the drop profile, a knowledge of be densities of the liquid forming. the drop, and the bulk phase surrounding the drop. All interfacial tensions described in this paper were recorded at a temperature of 74 degrees F and at an interface age of 10 seconds. Most systems were studied as a function of temperature; but temperature was found to be a second-order effect, so we selected 74 degrees F in order that all correlations would be at constant temperature. We selected 10 seconds because a study of the time variable showed that most of the decay of interfacial tension with time in these systems had occurred by the end of 10 seconds. SPEJ P. 197


2010 ◽  
Vol 24 (12) ◽  
pp. 6483-6488 ◽  
Author(s):  
Victor V. Likhatsky ◽  
Rustem Z. Syunyaev

1981 ◽  
Vol 21 (04) ◽  
pp. 493-499 ◽  
Author(s):  
J.H. Runnels ◽  
C.J. Engel

Abstract An procedure is given for separating surfactant precursors that occur in some crude oils. The effect of the precursors on the properties of the oils are described also. The separations were made by silica gel chromatography on crude oil from which the asphaltenes had been removed. The effect of the precursors on the properties of the crude was evaluated by blending the surfactant precursors into the original oil, a modified oil, or a hydrocarbon solvent such as benzene. Precursors activated and converted to surface active materials by a strong base such as sodium hydroxide are effective in reducing the interfacial tension between the oil and aqueous phase. Occurrence of precursors in crude oils is essential for improved oil recovery by the causticflood process. The procedure for separating the precursors should provide a viable means for evaluating the applicability of a causticflood tertiary oil recovery process to a particular crude or reservoir. Introduction Tertiary oil recovery by the causticflood process is inherently dependent on naturally occurring surfactant precursors in the crude. The surfactant precursors react with the caustic (base) in the floodwater to form surface active compounds that reduce the interfacial tension between the crude and aqueous phase, alter the wettability of the mineral surfaces, or reduce rigid film formation at the crude/aqueous interface. In laboratory oil-recovery tests, these mechanisms stimulate oil production characterized by increased production at caustic breakthrough and a high oil/water ratio after breakthrough. An early effort to identify the surfactant precursors in a Rio Bravo (CA) crude concluded that the surfactant precursors were related closely to the asphaltene and resin fractions of the crude. Subsequent studies using an Eichlingen Niedersachen (West German) crude and a Ventura (CA) crude concluded that the surfactant precursors were acids and phenols, respectively. The extensive work of Seifert established that the surfactant precursors of a Ventura crude were carboxylic acids and that the phenolic components of the crude were interfacially inactive. The purpose of our study was to develop a simple and practical method of separating surfactant precursors from crude oil and to evaluate their effect on the interfacial tension, acid number, and other properties of the crude. The separation technique was developed using Smackover Nacatoch crude and the surfactant precursors evaluated were obtained from the same crude. Description of Smackover Nacatoch Crude The Smackover reservoir is located in southern Arkansas, and the Nacatoch pay zone is the shallowest of five pay zones. The crude has an API gravity of 21 degrees, a viscosity of 160 cp at room temperature, and is produced from an unconsolidated sand formation about 2,000 ft deep. Preliminary studies showed that the interfacial tension between the crude and an aqueous phase was reduced from about 12 to 0.02 dyne/cm when the pH of the aqueous phase was increased from 7.0 to 12.5 with sodium hydroxide. The significant reduction in interfacial tension at higher pH's indicated that the crude contained a relatively high concentration of surfactant precursors that were converted to surface active materials by sodium hydroxide. SPEJ P. 493^


2018 ◽  
Vol 5 (1) ◽  
pp. 43-54
Author(s):  
Suresh Aluvihara ◽  
Jagath K Premachandra

Corrosion is a severe matter regarding the most of metal using industries such as the crude oil refining. The formation of the oxides, sulfides or hydroxides on the surface of metal due to the chemical reaction between metals and surrounding is the corrosion that  highly depended on the corrosive properties of crude oil as well as the chemical composition of ferrous metals since it was expected to investigate the effect of Murban and Das blend crude oils on the rate of corrosion of seven different ferrous metals which are used in the crude oil refining industry and investigate the change in hardness of metals. The sulfur content, acidity and salt content of each crude oil were determined. A series of similar pieces of seven different types of ferrous metals were immersed in each crude oil separately and their rates of corrosion were determined by using their relative weight loss after 15, 30 and 45 days. The corroded metal surfaces were observed under the microscope. The hardness of each metal piece was tested before the immersion in crude oil and after the corrosion with the aid of Vicker’s hardness tester. The metallic concentrations of each crude oil sample were tested using atomic absorption spectroscopy (AAS). The Das blend crude oil contained higher sulfur content and acidity than Murban crude oil. Carbon steel metal pieces showed the highest corrosion rates whereas the stainless steel metal pieces showed the least corrosion rates in both crude oils since that found significant Fe and Cu concentrations from some of crude oil samples. The mild steel and the Monel showed relatively intermediate corrosion rates compared to the other types of ferrous metal pieces in both crude oils. There was a slight decrease in the initial hardness of all the ferrous metal pieces due to corrosion.


Resources ◽  
2021 ◽  
Vol 10 (8) ◽  
pp. 75
Author(s):  
Ivelina K. Shishkova ◽  
Dicho S. Stratiev ◽  
Mariana P. Tavlieva ◽  
Rosen K. Dinkov ◽  
Dobromir Yordanov ◽  
...  

Thirty crude oils, belonging to light, medium, heavy, and extra heavy, light sulfur, and high sulfur have been characterized and compatibility indices defined. Nine crude oil compatibility indices have been employed to evaluate the compatibility of crude blends from the thirty individual crude oils. Intercriteria analysis revealed the relations between the different compatibility indices, and the different petroleum properties. Tetra-plot was employed to model crude blend compatibility. The ratio of solubility blending number to insolubility number was found to best describe the desalting efficiency, and therefore could be considered as the compatible index that best models the crude oil blend compatibility. Density of crude oil and the n-heptane dilution test seem to be sufficient to model, and predict the compatibility of crude blends.


Chemosphere ◽  
2021 ◽  
pp. 131563
Author(s):  
Laurens van Gelderen ◽  
Kristoffer Gulmark Poulsen ◽  
Jan H. Christensen ◽  
Grunde Jomaas

2001 ◽  
Vol 4 (06) ◽  
pp. 455-466 ◽  
Author(s):  
A. Graue ◽  
T. Bognø ◽  
B.A. Baldwin ◽  
E.A. Spinler

Summary Iterative comparison between experimental work and numerical simulations has been used to predict oil-recovery mechanisms in fractured chalk as a function of wettability. Selective and reproducible alteration of wettability by aging in crude oil at an elevated temperature produced chalk blocks that were strongly water-wet and moderately water-wet, but with identical mineralogy and pore geometry. Large scale, nuclear-tracer, 2D-imaging experiments monitored the waterflooding of these blocks of chalk, first whole, then fractured. This data provided in-situ fluid saturations for validating numerical simulations and evaluating capillary pressure- and relative permeability-input data used in the simulations. Capillary pressure and relative permeabilities at each wettability condition were measured experimentally and used as input for the simulations. Optimization of either Pc-data or kr-curves gave indications of the validity of these input data. History matching both the production profile and the in-situ saturation distribution development gave higher confidence in the simulations than matching production profiles only. Introduction Laboratory waterflood experiments, with larger blocks of fractured chalk where the advancing waterfront has been imaged by a nuclear tracer technique, showed that changing the wettability conditions from strongly water-wet to moderately water-wet had minor impact on the the oil-production profiles.1–3 The in-situ saturation development, however, was significantly different, indicating differences in oil-recovery mechanisms.4 The main objective for the current experiments was to determine the oil-recovery mechanisms at different wettability conditions. We have reported earlier on a technique that reproducibly alters wettability in outcrop chalk by aging the rock material in stock-tank crude oil at an elevated temperature for a selected period of time.5 After applying this aging technique to several blocks of chalk, we imaged waterfloods on blocks of outcrop chalk at different wettability conditions, first as a whole block, then when the blocks were fractured and reassembled. Earlier work reported experiments using an embedded fracture network,4,6,7 while this work also studied an interconnected fracture network. A secondary objective of these experiments was to validate a full-field numerical simulator for prediction of the oil production and the in-situ saturation dynamics for the waterfloods. In this process, the validity of the experimentally measured capillary pressure and relative permeability data, used as input for the simulator, has been tested at strongly water-wet and moderately water-wet conditions. Optimization of either Pc data or kr curves for the chalk matrix in the numerical simulations of the whole blocks at different wettabilities gave indications of the data's validity. History matching both the production profile and the in-situ saturation distribution development gave higher confidence in the simulations of the fractured blocks, in which only the fracture representation was a variable. Experimental Rock Material and Preparation. Two chalk blocks, CHP8 and CHP9, approximately 20×12×5 cm thick, were obtained from large pieces of Rørdal outcrop chalk from the Portland quarry near Ålborg, Denmark. The blocks were cut to size with a band saw and used without cleaning. Local air permeability was measured at each intersection of a 1×1-cm grid on both sides of the blocks with a minipermeameter. The measurements indicated homogeneous blocks on a centimeter scale. This chalk material had never been contacted by oil and was strongly water-wet. The blocks were dried in a 90°C oven for 3 days. End pieces were mounted on each block, and the whole assembly was epoxy coated. Each end piece contained three fittings so that entering and exiting fluids were evenly distributed with respect to height. The blocks were vacuum evacuated and saturated with brine containing 5 wt% NaCl+3.8 wt% CaCl2. Fluid data are found in Table 1. Porosity was determined from weight measurements, and the permeability was measured across the epoxy-coated blocks, at 2×10–3 µm2 and 4×10–3 µm2, for CHP8 and CHP9, respectively (see block data in Table 2). Immobile water saturations of 27 to 35% pore volume (PV) were established for both blocks by oilflooding. To obtain uniform initial water saturation, Swi, oil was injected alternately at both ends. Oilfloods of the epoxy-coated block, CHP8, were carried out with stock-tank crude oil in a heated pressure vessel at 90°C with a maximum differential pressure of 135 kPa/cm. CHP9 was oilflooded with decane at room temperature. Wettability Alteration. Selective and reproducible alteration of wettability, by aging in crude oil at elevated temperatures, produced a moderately water-wet chalk block, CHP8, with similar mineralogy and pore geometry to the untreated strongly water-wet chalk block CHP9. Block CHP8 was aged in crude oil at 90°C for 83 days at an immobile water saturation of 28% PV. A North Sea crude oil, filtered at 90°C through a chalk core, was used to oilflood the block and to determine the aging process. Two twin samples drilled from the same chunk of chalk as the cut block were treated similar to the block. An Amott-Harvey test was performed on these samples to indicate the wettability conditions after aging.8 After the waterfloods were terminated, four core plugs were drilled out of each block, and wettability measurements were conducted with the Amott-Harvey test. Because of possible wax problems with the North Sea crude oil used for aging, decane was used as the oil phase during the waterfloods, which were performed at room temperature. After the aging was completed for CHP8, the crude oil was flushed out with decahydronaphthalene (decalin), which again was flushed out with n-decane, all at 90°C. Decalin was used as a buffer between the decane and the crude oil to avoid asphalthene precipitation, which may occur when decane contacts the crude oil.


1998 ◽  
Vol 19 (1) ◽  
pp. 93-126 ◽  
Author(s):  
Trond Friisø ◽  
Yannick Schildberg ◽  
Odile Rambeau ◽  
Tore Tjomsland ◽  
Harald Førdedal ◽  
...  

Energies ◽  
2018 ◽  
Vol 11 (10) ◽  
pp. 2766 ◽  
Author(s):  
Jandyson Santos ◽  
Alberto Wisniewski Jr. ◽  
Marcos Eberlin ◽  
Wolfgang Schrader

Different ionization techniques based on different principles have been applied for the direct mass spectrometric (MS) analysis of crude oils providing composition profiles. Such profiles have been used to infer a number of crude oil properties. We have tested the ability of two major atmospheric pressure ionization techniques, electrospray ionization (ESI(±)) and atmospheric pressure photoionization (APPI(+)), in conjunction with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The ultrahigh resolution and accuracy measurements of FT-ICR MS allow for the correlation of mass spectrometric (MS) data with crude oil American Petroleum Institute (API) gravities, which is a major quality parameter used to guide crude oil refining, and represents a value of the density of a crude oil. The double bond equivalent (DBE) distribution as a function of the classes of constituents, as well as the carbon numbers as measured by the carbon number distributions, were examined to correlate the API gravities of heavy, medium, and light crude oils with molecular FT-ICR MS data. An aromaticity tendency was found to directly correlate the FT-ICR MS data with API gravities, regardless of the ionization technique used. This means that an analysis on the molecular level can explain the differences between a heavy and a light crude oil on the basis of the aromaticity of the compounds in different classes. This tendency of FT-ICR MS with all three techniques, namely, ESI(+), ESI(−), and APPI(+), indicates that the molecular composition of the constituents of crude oils is directly associated with API gravity.


Author(s):  
Jing Wen ◽  
Chun Li ◽  
Jinlai Feng ◽  
Chunlei Dai ◽  
Jungang Li ◽  
...  
Keyword(s):  

Sign in / Sign up

Export Citation Format

Share Document