Diesel Oil Removal by Froth Flotation Under Low Interfacial Tension Conditions I: Foam Characteristics,and Equilibration Time

Abstract

Froth flotation is a surfactant‐based separation process which is suitable for treating dilute wastewaters. To achieve high performance for the froth flotation operation, the combination of an ultra‐low interfacial tension (IFT) between excess oil and excess water phases, high foam production rates, and high stability of the foam produced, must be attained. To obtain the ultra‐low interfacial tensions, a Winsor Type III or middle phase microemulsion has to be formed. In this study, branched alcohol propoxylate sulfate sodium salt with 14–15 carbon number and 4 PO groups (Alfoterra 145–4PO) was used to form microemulsions with diesel oil. From the results of this work, an increase in surfactant concentration decreased the IFT, and increased foam stability. To obtain the minimum IFT in the region of a Winsor Type III microemulsion, the addition of 5 wt.% NaCl was needed. However, this optimum salinity does not result in effective froth flotation due to poor foam characteristics. The results indicate that both the IFT and the foam characteristics should be optimized to achieve high efficiency of oil removal in a froth flotation operation. Unlike the previously‐studied ethylbenzene system, agitation of the solution before introduction into the flotation column yielded the lowest diesel oil removal efficiency because of the poor foam characteristics compared to either unagitated systems or systems allowed to equilibrate for one month.     

Removal of motor oil by continuous multistage froth flotation: Effect of operational parameters

A continuous multistage froth flotation column was employed to remove motor oil from water at a low concentration (500 mg/L) using an extended surfactant – branched alcohol propoxylate sulphate sodium salt (C_14-15–8PO–SO₄–Na) – as a frother. The highest separation efficiency (97% motor oil removal with the enrichment ratio of 16 for motor oil) was obtained at a foam height of 60 cm, an air flow rate of 40 L/min, a feed flow rate of 60 mL/min, a surfactant concentration of 0.3% (w/v), and an NaCl concentration of 1.5% (w/v). The process performance increased with increasing tray number but beyond 4 trays, the system could only offer lower concentrations of motor oil and surfactant in the effluent.     

Surfactant (in situ)–Surfactant (Synthetic) Interaction in Na2CO3/Surfactant/Acidic Oil Systems for Enhanced Oil Recovery: Its Contribution to Dynamic Interfacial Tension Behavior

The effect of synthetic surfactant molecular structure on the dynamic interfacial tension (DIFT) behavior in Na₂CO₃/surfactant/crude oil was investigated. Three surfactants, a nonionic (iC₁₇(EO)₁₃), an alcohol propoxy sulfate (C_14–15(PO)₈SO₄), and sodium dodecyl sulfate (SDS) were considered in this study. Sodium tripolyphosphate (STPP) was added to ensure complete compatibility between brine and Na₂CO₃. In Na₂CO₃/iC₁₇(EO)₁₃/oil and Na₂CO₃/C_14–15(PO)₈SO₄/oil systems, a strong synergistic effect for lowering the dynamic interfacial tension was observed, in which the dynamic IFT are initially reduced to ultralow transient minima in the range 1.1 × 10^?3–6.6 × 10^?3 mNm^?1 followed by an increment to a practically similar equilibrium value of 0.22 mNm^?1 independent of Na₂CO₃ concentration (for iC₁₇(EO)₁₃) and to decreasing equilibrium values with increasing alkali concentrations (for C_14–15(PO)₈SO₄). The observed difference in the equilibrium IFT for the two systems suggest that in both systems, the mixed interfacial film is efficient in reducing the dynamic interfacial tension to ultralow transient minima (～10^?3 mNm^?1) but the mixed film soap‐iC₁₇(EO)₁₃ is much less efficient than the mixed film soap‐C_14–15(PO)₈SO₄ in resisting soap diffusion from the interface to the bulk phases. In both systems, the synergism was attributed, in part, to the intermolecular and intramolecular ion–dipole interactions between the soap molecules and the synthetic surfactant as well as to some shielding effect of the electrostatic repulsion between the carboxylate groups by the nearby ethylene oxide (13 EO) and propylene oxide (8 PO) groups in the mixed interfacial monolayer. SDS surfactant showed a much lower synergism relative to iC₁₇(EO)₁₃ and C_14–15(PO)₈SO₄, probably due to the absence of ion–dipole interactions and shielding effect in the mixed interfacial layer at the oil–water interface.     

Synergistic Effects between Anionic and Sulfobetaine Surfactants for Stabilization of Foams Tolerant to Crude Oil in Foam Flooding

In foam flooding, foams stabilized by conventional surfactants are usually unstable in contacting with crude oil, which behaves as a strong defoaming agent. In this article, synergistic effects between different surfactants were utilized to improve foam stability against crude oil. Targeted to reservoir conditions of Daqing crude oil field, China (45 °C, salinity of 6778 mg L⁻¹, pH = 8–9), foams stabilized by typical anionic surfactants fatty alcohol polyoxyethylene ether sulfate (AES) and sodium dodecyl sulfate (SDS) show low composite foam index (200–500 L s) and low oil tolerance index (0.1–0.2). However, the foam stability can be significantly improved by mixing the anionic surfactant with a sulfobetaine surfactant, which behaves as a foam stabilizer increasing the half-life of foams, and those with longer alkyl chain behave better. As an example, by mixing AES and SDS with hexadecyl dimethyl hydroxypropyl sulfobetaine (C₁₆HSB) at a molar fraction of 0.2 (referring to total surfactant, not including water), the maximum composite foaming index and oil tolerance index can be increased to 3000/5000 L s and 1.0/4.0, respectively, at a total concentration between 3 and 5 mM. The attractive interaction between the different surfactants in a mixed monolayer as reflected by the negative β^s parameter is responsible for the enhancement of the foam stabilization, which resulted in lower interfacial tensions and therefore negative enter (E), spreading (S), and bridging (B) coefficients of the oil. The oil is then emulsified as tiny droplets dispersed in lamellae, giving very stable pseudoemulsion films inhibiting rupture of the bubble films. This made it possible to utilize typical conventional anionic surfactants as foaming agents in foam flooding.     

Formulation of ultralow interfacial tension systems using extended surfactants

Inspired by the concept of lipophilic and hydrophilic linkers, extended surfactants have been proposed as highly desirable candidates for the formulation of microemulsions with high solubilization capacity and ultralow interfacial tension (IFT), especially for triglyceride oils. The defining characteristic of an extended surfactant is the presence of one or more intermediate-polarity groups between the hydrophilic head and the hydrophobic tail. Currently only limited information exists on extended surfactants; such knowledge is especially relevant for cleaning and separation applications where the cost of the surfactant and environmental regulations prohibit the use of concentrated surfactant solutions. In this work, we examine surfactant formulations for a wide range of oils using dilute solutions of the extended surfactant classes sodium alkyl polypropyleneoxide sulfate (R-(PO) _x −SO₄Na), and sodium alkyl polypropyleneoxide-polyethyleneoxide sulfate (R-(PO) _y -(EO) _z −SO₄Na). The IFT of these systems was measured as a function of electrolyte and surfactant concentration for polar and nonpolar oils. The results show that these extended surfactant systems have low critical micelle concentrations (CMC) and critical microemulsion concentrations (CμC) compared with other surfactants. We also found that the unique structure of these extended surfactants allows them to achieve ultralow IFT with a wide range of oils, including highly hydrophobic oils (e.g., hexadecane), triolein, and vegetable oils, using only ppm levels of these extended surfactants. It was also found that the introduction of additional PO and EO groups in the extended surfactant yielded lower IFT and lower optimum salinity, both of which are desirable in most formulations. Based on the optimum formulation conditions, it was found that the triolein sample used in these experiments behaved as a very polar oil, and all other vegetable oils displayed very hydrophobic behavior. This unexpected triolein behavior is suspected to be due to uncharacterized impurities in the triolein sample, and will be further evaluated in future research.     

Short-time tracer dispersion in a two-dimensional rising froth

Experimental results on the dispersion of a fluorescein tracer in a rising froth of water/glycerol mixture with SDS as the frother are described. These experiments illuminate the physical phenomena that are important to the application of washwater in flotation processes. Two-dimensional numerical solutions of foam drainage in rising systems are also presented at values of background liquid hold-up relevant to the flotation process. It is shown that, at short times, the dominant mechanism for tracer dispersion is due to liquid drainage in the froth rather than due to packed-bed type behaviour as liquid percolates through a network of Plateau borders in between the bubbles. Two foam drainage models, channel-dominated drainage and node-dominated drainage, have been previously described in the literature. It is shown that neither can adequately predict the phenomena of tracer dispersion in a rising froth. The reality appears to lie somewhere in between the two extremes. However, it has been observed that channel-dominated behaviour is approached as liquid disperses and local volumetric liquid hold-up decreases. Finally experimental results are presented for a tracer of very concentrated fluorescein solution that show dispersion behaviour quite unlike that described by the two established foam drainage models.     

Dialkyl Sulfobetaine Surfactants Derived from Guerbet Alcohol Polyoxypropylene–Polyoxyethylene Ethers for SP Flooding of High Temperature and High Salinity Reservoirs

Dialkyl hydroxypropyl sulfobetaine (HSB) surfactants, C₁₆GA-(PO)₅-(EO)₃-HSB and C₂₄GA-(PO)₁₀-(EO)₁₀-HSB, were synthesized from Guerbet alcohols (GA) polyoxypropylene–polyoxyethylene (PO-EO) ethers and their behaviors in surfactant-polymer (SP) flooding of high temperature and high salinity reservoirs were examined and compared with their anionic hydroxypropyl sulfonate (HS) counterparts, C₁₆GA-(PO)₅-(EO)₃-HS and C₂₄GA-(PO)₁₀-(EO)₁₀-HS. The PO-EO chain embedded improves their aqueous solubility, and the sulfobetaines show better salt resistance than sulfonates. For a reservoir condition of total salinity 19,640 mg L⁻¹ and 60–80°C, C₁₆GA-(PO)₅-(EO)₃-HSB alone can reduce crude oil/connate water interfacial tension (IFT) to ultralow at 0.25–5 mM, which can be further widened to 0.1–5 mM by mixing with dodecylhexyl (C₁₂₊₆) glyceryl ether hydroxypropyl sulfobetaine (C₁₂₊₆GE-HSB), a slightly hydrophobic surfactant. C₂₄GA-(PO)₁₀-(EO)₁₀-HSB is more hydrophobic for the specified reservoir condition, however, by mixing with hexadecyl dimethyl hydroxypropyl sulfobetaine (C₁₆HSB), a hydrophilic surfactant, ultralow IFT can also be achieved at a total concentration of 0.25–5 mM. The anionic counterparts can also reduce IFT to ultralow by mixing with C₁₂₊₆GE-HSB and C₁₆HSB, respectively. Moreover, the optimum binary mixture, C₁₆GA-(PO)₅-(EO)₃-HSB/C₁₂₊₆GE-HSB at a molar fraction ratio of 0.6/0.4, can keep the negatively charged solid surface water-wet (θ_w = 12–23°) in a wide concentration range, and can still achieve ultralow IFT after stored at 90°C for 90 days (initially 5 mM), which overall are favor of improving oil displacement efficiency at high temperature and high salinity reservoir conditions.     

One-step synthesis of mesoporous sulfated zirconia nanoparticles with anionic template

Mesoporous sulfated zirconia nanoparticles (MSZNP) with high surface area have been synthesized by using sodium dodecyl sulfate (C₁₂H₂₅OSO₃Na, SDS), both as a template and a sulfating agent via one-step route. On the basis of FT-IR, EDS together with NH₃-TPD analyses, the SO ₄ ^2? anion, originated from the hydrophilic head of SDS, can be incorporated into ZrO₂ to form MSZNP with super-acidity. The phase transition of ZrO₂ from tetragonal to monoclinic phase was effectively inhibited by the presence of SO ₄ ^2? , and the formation mechanism was illustrated in detail. MSZNP₍₅₅₀₎ achieved far higher activity than CSZ₍₅₅₀₎ in transesterification of soybean oil with methanol due to the synergistic effect of strong acidity, high BET surface area and the formation of mesostructure.     

Microemulsion Formation and Detergency with Oily Soil: V. Effects of Water Hardness and Builder

In this study, the impact of water hardness and builder on the phase diagrams of motor oil microemulsions and the detergency of oil removal from a polyester/cotton blend was investigated. Water hardness and builder were found to have insignificant effects on the microemulsion phase diagram with motor oil. A mixed surfactant system of two parts C_14–15(PO)₃SO₄Na, and 98 parts C_12–14H_25–29O(EO)₅H of the total actives at 4% salinity was used to study the effect of water hardness and builders sodium tripolyphosphate (STPP) or ethylenediaminetetraacetic acid (EDTA) on detergency at 30 °C at a total active concentration of 0.3%. This formulation is in the Winsor Type III microemulsion regime. The microemulsion-based formulation resulted in better detergency than a leading commercial liquid laundry detergent at all concentrations up to 0.5% actives. The microemulsion-based formulation showed a plateau in detergency at >80% oil removal above 0.1% actives. The total oil removal decreased with increasing water hardness while the interfacial tension increased. When hard water was used in laundering, the total oil removal improved with increasing concentrations of STPP or EDTA up to stoichiometric levels, with STPP being slightly more effective than EDTA on a molar basis. Even high builder concentration could not improve hard water detergency to that of soft water. A significant fraction of oil removal occurred in the rinse steps vs. the wash step. Increasing water hardness reduced this fractional oil removal in the rinse steps, but it was still over half of total oil removal at 1,000 ppm water hardness.

Effects of Surfactant Headgroups on Oil-in-Water Emulsion Droplet Formation: An Experimental and Simulation Study

Nonpolar oils such as kerosene and diesel oil are common collectors in coal flotation. Surfactants are usually added to the pulp to emulsify the oil collectors. The present study used dodecane as the oil collector and anionic sodium dodecyl sulfonate (SDS) and nonionic tetraethylene glycol monododecyl ether (C₁₂EO) with different headgroups and identical chain alkyls to investigate the effect of the surfactant headgroups on oil-in-water emulsion droplet formation. The morphology and stability of dodecane emulsions were determined experimentally. Density functional theory (DFT) and molecular dynamics (MD) simulations were used to explain the microscopic mechanism. The results of DFT indicated a larger interaction between SDS and the water molecules than that between C₁₂EO and water molecules. The results obtained by MD suggested that the SDS headgroup exhibited a loose arrangement and a relatively large gap size, thereby weakening the interaction between SDS and water molecules at the dodecane/water interface. In contrast, the headgroups of C₁₂EO were bent and interwoven with others to form a tight reticulation at the interface. According to the simulation results, the ability of the surfactant to form dodecane-in-water emulsion droplets depends on the arrangement of the surfactants at the oil–water interface rather than on the interaction strength between the headgroups of the surfactants and water molecules. The presented microscopic mechanism of the surfactant headgroup formation of oil-in-water emulsion droplets offers surfactant selection and design references.     

Effect of oil viscosity on recovery processes in relation to foam flooding

Laboratory experiments were conducted to determine the effect of oil viscosity on the oil-recovery efficiency in porous media. The pure surfactants (i.e., sodium dodecyl sulfate and various alkyl alcohols) were selected to correlate the molecular and surface properties of foaming solutions with viscosity, and the recovery of oil. Oil-displacement efficiency was measured by water, surfactant-solution and foam-flooding processes, which included 2 types of foams (i.e., air foam and steam foam). A significant increase in heavy-oil recovery was observed by steam foam flooding compared with that by air foam flooding, whereas for light oils, the steam foam and air foam produced about the same oil recovery. An attempt was made to correlate the chain-length compatibility with the surface properties of the foaming agents and oil-recovery efficiency in porous media. For mixed foaming systems (C₁₂ SO₄ Na + C_n H_2n+1 OH), a minimum in surface tension, a maximum in surface viscosity, a minimum in bubble size and a maximum in oil recovery were observed when both components of the foaming system had the same chain length. These results were explained on the basis of thermal motions (i.e., vibrational, rotational and oscillational) and the molecular packing of surfactants at the gas-liquid interface. The effects of chain-length compatibility and the surface properties of mixed surfactants are relevant to the design of surfactant formulations for oil recovery under given reservoir conditions.     

Influence of Hydrocarbon Chain Branching on Foam Properties of Olefin Sulfonate with FoamScan

The influence of surfactant structure on foam properties of internal olefin sulfonate (IOS) and alpha olefin sulfonate (AOS) in aqueous solutions was estimated from measurements of the foamability, foam stability, and foam morphology, as obtained from conductivity and image analyses techniques. It was found that the foamability and foam stability of C_16–18 AOS are higher compared to that of C_16–18 IOS, indicating that hydrocarbon chain branching decreases the foamability and foam stability. The foamability and foam stability are enhanced with increasing surfactant concentration, which increases the adsorbed quantity of surfactant molecules at the air–water interface. The influence of hydrocarbon chain branching on foam morphology was also investigated. It was found that foam cells produced by branched chain C_16–18 IOS are larger than the foam cells generated by straight chain C_16–18 AOS.     

Distribution of clay minerals in the process streams produced by the extraction of bitumen from Athabasca oil sands

This study investigates the affinity of clay minerals in oil sands for the water‐continuous tailings and hydrocarbon‐continuous froth streams produced from the extraction of bitumen from oil sands. Clay minerals in oil sands processing impact bitumen flotation in separation vessels, emulsion formation during froth treatment, and fine tailings behaviour. X‐ray diffraction of oriented clay slides and random powder samples were used to quantify the clay minerals in the oil sands ore and process streams. Particle size distribution and clay activity balances were also conducted around the extraction process. The degree of partitioning during the conditioning and flotation stages in a batch extractor was determined by the surface properties of the clay minerals present. The water‐continuous tailings stream was further separated into fine and coarse tailings fractions through sedimentation. The bulk of the clay minerals reported to the fine tailings stream. Illite and mixed layered illite‐smectite partitioned less to the hydrocarbon‐continuous froth than kaolinite. Also, the illite‐smectite in the froth stream appeared to be different from the illite‐smectite in the water continuous streams.     

Combustion characteristics of fatty acid methyl esters derived from recycled cooking oil

The goal of this study is to find out the exhaust emissions differences produced by different kinds of fatty acid methyl esters (FAME) derived from used cooking oils and animal fats, as well as the importance of the purification step in exhaust emissions production. A total of 120 L of waste vegetable oil and 30 L of waste frying oil were collected and converted into three batches of FAME. There were two batches of FAME produced from waste vegetable oil (B01 and B02), and one batch of FAME produced by mixing 2% of waste frying oil with waste vegetable oil (B03). The FAMEs used in this study had higher density, kinematic viscosity, and flash point, but a lower gross heating value, when compared to the premium diesel. The B01 engine produced higher CO formation and the diesel-fuelled engine produced higher CO than the B02 and B03 did for engine speeds higher than 1400 rpm. Most of the FAME fuels produced higher CO₂ than the diesel fuel did. The FAME fuels emitted higher NO_x and PM, but lower SO₂, than the diesel fuel. C_nH_2n+2, diphenyl sulfone (C₁₂H₁₀O₂S), and diethyl phthalate (C₁₂H₁₄O₄) can be selected as the character index for the combustion of FAME.     

Removal of Cu(II) from Aqueous Solutions by the Foam Separation Techniques of Precipitate and Adsorbing Colloid Flotation

Abstract

Experimental investigations on the removal of Cu(II) from aqueous solution were carried out through two foam separation techniques: precipitate flotation and adsorbing colloid flotation with Fe(III). The optimum pH for good removal was found to be about 9 for the former and about 7 for the latter. The effects of surfactant (sodium lauryl sulfate), foreign ions (Na⁺, Ca²⁺, NO^? ₃, and SO^2- ₄), and Al(III) addition on the efficiency of Cu(II) removal are discussed.     

Removal of trace Cu from aqueous solution by foam fractionation

A system for removal of Cu²⁺ from aqueous solution by foam fractionation is proposed. The effects of pH, gas flow rate, surfactant concentration and froth/solution ratio on the removal rate and the enrichment ratio were studied to optimize the conditions. The results show that the removal rate increased with gas flow rate decreased, surfactant concentration increased and the froth/solution ratio increased, and was higher at pH4.0-5.0 than at other pH value. The optimum separation conditions were pH5.0, 200 mL/min of gas flow rate, 0.15 g/L of surfactant concentration and 1.1 of froth/solution ratio. Under the optimum conditions, the removal rate was 97.2% and the enrichment was 53.0.     

Study on the Adaptability of Alkanolamide (LDEA) Lowering Oil/Water Interfacial Tension to Different Crude Oils

In order to investigate the high interfacial activity and fair oil phase adaptability of alkanolamide, “1:1” type lauric acid diethanolamide impurities (LDEA) were synthesized and purified by the column chromatography method to obtain dodecanoic acid diethanolamide (C₁₂DEA), ester mixture, etc. The exact structures of these compounds were further confirmed by IR, gas chromatogrph with mass spectroscopy (GC–MS), and NMR. The influence of each component on the interfacial tension of oil/water (IFT) was studied by systematic quantitative analysis. The results showed that (i) the strength of each system to reduce oil/water IFT is C₁₂DEA /DEA ≈ LDEA > C₁₂DEA/DEA/ESTER > C₁₂DEA/NaOH > C₁₂DEA > C₁₂DEA/ESTER > DEA. This indicates that LDEA contributes to the reduction of the oil/water IFT and the enhanced adaptability of crude oil in this order: DEA > > ESTER; (ii) when the IFT of the LDEA/DEA system reached an ultralow value, the minimum content of DEA in the system was 1%, and the maximum ester content was less than 5% when the LDEA/DEA/ESTER system reached the ultralow IFT; (iii) the possible mechanism of effect of LDEA components on the IFT and oil phase adaptability was proposed as the synergistic process among the hydrogen bonding, alkali effect, and interface self-assembly of molecules in the interfacial layer. The contribution of these three factors were hydrogen bonding > alkali effect > interface self-assembly.     

The effect of different flotation operating parameters on the froth properties and their relation to clean coal ash content

Froth properties and their relation to the concentrate grade play an important role in monitoring flotation running conditions and predicting flotation concentrate quality. In this paper, the correlation between the froth properties and clean coal ash content was investigated under complicated conditions where the frother dosage, gas velocity, and froth height were changed together. For the froth properties under study, their degree of correlation with clean coal ash content decreased in the order of homogeneity, water recovery, gray value, and froth velocity. The coefficient of determination (R²) of the fitting relationship between homogeneity and clean coal ash content was as high as 0.9028, because homogeneity has a close correlation with the foam structure and foam destabilization behaviors.     

Surfactant-Based Oil Extraction of Corn Germ

An aqueous surfactant-based extraction system was developed for the extraction of corn oil from corn germ with anionic extended surfactants. The surfactants used in this study were sodium linear-alkyl polypropoxylated polyethoxylated sulfates (C_12,14–P₁₀–E₂–SO₄Na and C₁₀–P₁₈–E₂–SO₄Na). Interfacial tension, critical microemulsion concentration (CμC), and optimum salinity values of the extended surfactants with corn oil were determined. In the extraction process, the ground corn germ was shaken with predetermined surfactant and salt concentrations at room temperature for 45 min. About 83%, the sum of total free oil and total oil-in-water emulsion, of the corn oil was extracted from the corn germ using a formulation of 0.4% C_12,14–P₁₀–E₂–SO₄Na and 1% NaCl. A solid/liquid ratio of 1/10 performed best for efficient oil recovery. The chemical compositions of the extracted corn oils were found to be similar to that of hexane extracted corn oil.     

Development of a vision‐based online soft sensor for oil sands flotation using support vector regression and its application in the dynamic monitoring of bitumen extraction

Extraction from oil sands is a crucial step in the industrial recovery of bitumen. It is challenging to obtain online measurements of process outputs such as bitumen grade and recovery. Online measurements are a prerequisite for innovating better process control solutions for process efficiency and cost reduction. We have developed a soft sensor to provide online measurements of bitumen grade and recovery in a flotation‐based oil sand extraction process. Continuous froth images were captured using a VisioFroth camera system on a batch flotation unit. A support vector regression (SVR) model with a Gaussian kernel was constructed to develop a soft sensor for bitumen grade and recovery using froth image features as the inputs. The model was trained and validated for batch flotation of different grades of oil sands ore at industry‐relevant process conditions. A Dean‐Stark analyzer was used to obtain offline grade and recovery measurements that were used to calibrate the soft sensor. Mean squared errors (MSE) of 62 and 74 were achieved for grade (%) and recovery (%), respectively, and this was obtained using 5‐fold cross validation. The developed soft sensor model has been applied successfully in the real‐time dynamic monitoring of flotation grade and recovery for different grades of ore and operating conditions.