Predictive methods for density and refractive index of naphthenic lubricating oils during solvent extraction process

Lubricating oils are usually produced by solvent extraction to separate aromatics in order to achieve the desired specifications and better quality products.Among the different properties of lubricating oils,density and refractive index are some of the most important properties which can both be used for petroleum fluid characterization.Predictions of density and refractive index for naphthenic oils during solvent extraction by DMSO obtained by the pseudo-component approach and the quadratic correlation were both examined.The pseudo-component approach is a method to predict density and refractive index from composition while the latter merely relates density to refractive index.Results indicated that the predictions yielded by the pseudo-component method were in good agreement with experimental data for naphthenic oils.And the use of a function of refractive index(FRI_(20))as a pseudo-component property remarkably improved n_(20)predictions for the naphthenic mixtures.However,the density and refractive index predictions obtained by the quadratic correlation exhibited significantly higher de-viations for naphthenic oils than those for paraffinic oils.Thus a new modified correlation of the same functional form was proposed for naphthenic oils.The modification significantly improved predictions for naphthenic oils,which presented similar accuracy as the pseudo-component approach.And the previous correlation was still used for paraffinic oils.Additionally,effect of temperature on density and refractive index of naphthenic oils was examined.Results showed that the modified quadratic correlation was accurate for describing the relationship between density and refractive index of naphthenic oils at 20-90℃.The temperature dependence of density and refractive index for the raffinates and the extracts could be accurately described by the thermal coefficients for saturates and aromatics,respectively.Regarding the refractive index variation of the extracts with temperature,the empirical equation was proved to be a better option compared with the method using the thermal coefficient for aromatics.

Simulation of Solvent Extraction for Naphthenic Lubricating Base Oils

Solvent extraction is the process of separating aromatics from vacuum distillates for the production oflubricating base oils. In this study, the authors use dimethyl sulfoxide (DMSO) instead of furfural as solvent, in light of itshigher selectivity, to obtain extracts with a high aromatic content for naphthenic lubricating base oils. We systematicallyinvestigated effects of the solvent-to-oil (S/O) ratio and extraction temperature on the yield of the extract, efficiency ofaromatic removal, and composition of the extracts and raffinates. The results showed that the aromatic content of extractsfor naphthenic oils could reach a high value of about 80%. The solvent maintained a high selectivity for aromatics fornaphthenic oils even under a high S/O ratio and a high extraction temperature. Moreover, the efficiency of aromatic removalfor naphthenic lubricating base oils could be enhanced by increasing either the S/O ratio or the extraction temperature,although these measures had limited effects in practice. Following this, we used the non-random two-liquid (NRTL) modelbased on the pseudo-component approach to simulate the liquid-liquid equilibrium of the system of DMSO + naphtheniclubricating base oils, and determined the parameters of binary interaction through regression based on the data on phaseequilibrium. The modeling results showed that the predicted yield, content of the solvent, and composition of the raffinatesand extracts were in good agreement with those obtained in the experiments. This validates the reliability of the model usedto represent the DMSO + naphthenic lubricating base oil system. Both the experimental data and the method of simulationreported here can help optimize the extraction of naphthenic lubricating base oils, and provide a better understanding of thecorresponding process.

Separation of nickel, cobalt and copper by solvent extraction with P204

Nickel, cobalt and copper were separated by solvent extraction with P204. The experimental results show that [Co(NH 3) 6] 3+ is an inert complex in extraction kinetics, therefore cobalt can be separated from nickel and copper by non equilibrium solvent extraction. Under the conditions of temperature 25?℃, contact time of two phases 10?min, phase ratio 1∶1, aqueous pH 10.10 and concentration of P204 20%, [Co(NH 3) 6] 3+ is hardly extracted by P204, while the percentage extractions of nickel and copper are 79.3% and 93.9% respectively. Nickel and copper are separated by equilibrium solvent extraction with P204. Under the conditions of temperature 25?℃, contact time of two phases 1?min, phase ratio 1∶1, equilibrium pH 4.01 and concentration of P204 20%, the separation factor of copper and nickel is 216.

Extracting vanadium from stone-coal by oxygen pressure acid leaching and solvent extraction

Vanadium extraction from stone-coal was investigated by oxygen pressure acid leaching and solvent extraction.The mineralogy of the stone-coal from Tongren City of Guizhou Province,China,was investigated by various determination methods. The effects of leaching time,leaching temperature,leaching agent concentration,leaching L/S ratio,granularity of material,additive consumption were investigated based on the mineralogy.The results show that under the conditions of leaching time of 3-4 h, temperature of 150℃,sulfuric acid consumption of 25%?30%,ratio of liquid to solid of 1.2:1,the granularity less than 0.074 mm, additive consumption of 3%-5%,and oxygen pressure of 1.2 MPa,and the vanadium leaching rate can be more than 92%by the method of two-step pressurized acid leaching.The powdery V2O5 product with 99.52%in V2O5 content is obtained by the flowsheet of acid recovery,removing iron by reduction process,solvent extraction,precipitating vanadium with ammonium water,and pyrolysis from the stone-coal oxygen pressure acid-leaching solution.The total recovery efficiency of vanadium is above 85%,which is more than 20%higher than that obtained in the conventional process.Furthermore,the new process does not cause air pollution since no HCl or Cl2 is released by calcination of the raw material.

Selective separation of Cu(Ⅱ),Zn(Ⅱ),and Cd(Ⅱ)by solvent extraction

An experimental investigation was presented on the separation of Cu（Ⅱ）, Zn（Ⅱ）, and Cd（Ⅱ） from a rich sulfate leachate of zinc slag by solvent extraction. The results of orthogonal experiments indicate that LIX 984N is highly selective and very efficient in the extraction of Cu（Ⅱ）, and the analysis of variance indicates that the sequence of parameters according to their influence on the separation efficiency is phase ratio 〉 LIX 984N concentration 〉 pH value 〉 extraction time. The optimal condition for copper extraction is obtained as 25% of LIX 984N concentration, 7 rain of extraction time, 3：2 of phase ratio O/A, and pH = 1.7. The separation of Zn（Ⅱ） and Cd（Ⅱ） was performed after the copper extraction from the raffinate. Comparative analysis of the separation with di-2-ethylhexyl phosphoric acid （D2EHPA）, D2EHPA-tributyl- phosophate （TBP） synergistic extracting system, and 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester （HEHEHP） was made at pH = 2.0. It is demonstrated that the extraction efficiency with D2EHPA is improved after being saponified by sodium hydroxide, and D2EHPA-TBP synergistic extracting, as well as HEHEHP, has a superior selectivity to Zn（Ⅱ） over Cd（Ⅱ）.

Solvent extraction of vanadium from sulfuric acid solution

The behaviour of vanadium（V） extracted from sulfuric acid solution was investigated using Cyanex 923 as an extractant. The effects of the concentration of Cyanex 923 and the pH of the solution were studied. The extraction of vanadium（V） increases with the increase of Cyanex 923 concentration and shaking time. Cyanex 923 can extract vanadium（V） from sulfuric acid solution at low pH conditions, and the best pH conditions for extraction of vanadium（V） are at pH 1.0-2.0. The species extracted into the organic phase is VO2HSO4 with one molecule of Cyanex 923. Equilibrium studies were used to assess the extraction efficiency of vanadium（V） recovery from the sulfuric acid solution.

Process development for the direct solvent extraction of nickel and cobalt from nitrate solution:aluminum,cobalt,and nickel separation using Cyanex 272

A direct solvent extraction（DSX） process for purifying nickel and cobalt from the nitric acid leach solution of nickel laterite ores was conceived and experimentally probed. The proposed process consists of two solvent extraction（SX） steps but with only one extractant - bis（2,4,4-trimethylpentyl）phosphinic acid（Cyanex？ 272） - used in both steps. The first extraction step involved the removal of aluminum and zinc, whereas the second extraction step involved the separation of cobalt along with manganese from nickel. The experimental results showed essentially quantitative removal of aluminum（〉97%） and zinc（〉99%） in a single extraction stage using 20vol% Cyanex 272 at pH 2.1. Some cobalt（32%） and manganese（55%） were co-extracted but were easily scrubbed out completely from the loaded organic phase using dilute sulfuric acid at pH ≤ 1.38. Cobalt and manganese in the first extraction raffinate were extracted completely in four extraction stages at staggered pH values of 4.0, 4.4, 4.5, and 4.0 in the first, second, third, and fourth stages, respectively, using also 20vol% Cyanex 272. A small amount of nickel（up to 6.6%） was co-extracted but was easily scrubbed out completely with dilute sulfuric acid at pH 2.0. A flow diagram showing the input and output conditions and the metals separated under the deduced optimum conditions is presented.

Influences of solid particles on the formation of the third phase crud during solvent extraction

The influences of solid particles in leach solution on the formation of the third phase crud during solvent extraction of copper were studied. Analyzed from the point of view of pH value and surface tension, the study results showed that the solid particle is one of the most important contributors for the formation of the third phase crud. During solvent extraction, if the pH value was greater than 2.30, the number of solid particles in the mother solution increased, in which case the possibility of forming the third phase crud could also increase, and the interface tension value might grow in pace with the quantity of the third phase crud.

Separation of middle rare earths by solvent extraction using 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester as an extractant

The extraction of the trivalent middle rare earths from chloride media by kerosene solutions of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester as an extractant was studied. The separation factors between the elements using solution simulating wastes from NiMH spent batteries have been evaluated: the order of the extractive ability of extractant can be confirmed in Tb>Gd>Eu>Sm.

Application of hydrophobic ionic liquid [Bmmim][PF6] in solvent extraction for oily sludge

In this study, an ionic liquid(IL), 1-butyl-2,3-dimmmethylimidazolium hexafluorophosphate([Bmmim][PF6]),was used in combination with a composite solvent of methyl acetate and n-heptane to enhance the oil extraction from oily sludge. The oil recovery increased by approximately 15% compared with that of solvent extraction without [Bmmim][PF6] at the optimal ratios of IL to sludge and solvents to sludge, which were at 2:5(M/M) and 4:1(V/M), respectively. The saturate, aromatic, resin and asphaltene(SARA) analysis revealed that the recovery of resins and asphaltenes was increased by 14% and 38%, respectively, in the solvent extraction with the addition of [Bmmim][PF6]. [Bmmim][PF6] maintained a good performance after its reuse four times. The addition of[Bmmim][PF6] changed the adhesion forces between oil and soil. The IL-assisted solvent extraction procedure followed the pseudo second-order kinetic model, while the unassisted solvent extraction procedure followed the pseudo first-order kinetic model. The results also demonstrated that [Bmmim][PF6] decreased the solvent consumption by approximately 60% each time. Additionally, [Bmmim][PF6] can be easily separated. The results suggested that enhancing the solvent extraction with this IL is a promising way to recover oil from oily sludge with a higher oil recovery rate and lower organic solvent consumption than those with the unassisted solvent extraction method.

Prediction of Density and Refractive Index of Lubricating Oils during Secondary Solvent Extraction Process by Furfural

To meet the requirements for high aromatic content and low polycyclic aromatic(PCA)concentration,eco-friendly aromatic-rich rubber extender oils are usually produced by two-stage solvent extraction processes with furfural.Among the different properties of rubber processing oils,density and refractive index are some of the most important properties related to their final quality.Two types of methods,including a pseudo-component approach by using mixing rules and several correlations,were used for calculation of density and refractive index at 20℃ of paraffinic furfural-extract oils and their secondary raffinates.Results indicated that similar accuracy was obtained for predicting the density and the refractive index of furfural+furfural-extract paraffinic oil systems.However,the quadratic correlation presents its advantage over the pseudo-component approach when the composition of oils is not available.Moreover,the quadratic correlation was also used for naphthenic lubricating oils during two-stage solvent extraction processes.The predictions showed much larger discrepancies with respect to experimental values than those of paraffinic lubricating oils,which indicated that the quadratic correlation was more suitable for paraffinic oils with a CN value of below 37%.

Recovery of oxalic acid from mother-liquor containing hydrochloric acid and cobalt by solvent extraction with P350

The solvent of P350 was applied to extract and separate the oxalic acid from the mother-liquor originated from the precipitation of cobalt by oxalic acid,and its extraction mechanism was deduced.Some factors,including the concentration of P350, the concentration of hydrochloric acid and the concentration of oxalic acid were investigated to determine the best distribution coefficient of the oxalic acid.In the case of phase ratio(O/A)at 2.0,the extraction of the oxalic acid was more than 95%and its concentration in the extraction raffinate was lower than 0.004 0 mol/L after six-stage counter-current extraction.While the phase ratio(O/A)of the stripping was at 1.0,the recovery of oxalic acid attained more than 95%after ten-stage counter-current stripping.

Nickel solvent extraction from cold purification filter cakes of Angouran mine concentrate using LIX984N

Cold purification filter cakes generated in the hydrometallurgical processing of Angouran mine zinc concentrate commonly contain significant amounts of Zn, Cd, and Ni ions and thus are valuable resources for metal recovery. In this research, a nickel containing solution that was obtained from sulfuric acid leaching of the filter cake following cadmium and zinc removal was subjected to solvent extraction experiments using 10vol%LIX984N diluted in kerosene. Under optimum experimental conditions （pH 5.3, volume ratio of organic/aqueous （O：A） = 2：1, and contact time -5 min）, more than 97.1% of nickel was extracted. Nickel was stripped from the loaded organic by contacting with a 200 g/L sulfuric acid solution, from which 77.7% of nickel was recovered in a single contact at the optimum conditions （pH 1-1.5, O：A =5：1, and contact time =15 min）.

Rapid determination of volatile constituents in safflower from Xinjiang and Henan by ultrasonic-assisted solvent extraction and GC-MS

The total volatile components were extracted from safflower by ultrasonic-assisted solvent extraction （USE） and their chemical constituents were analyzed by gas chromatographymass spectrometry （GC-MS） to provide scientific basis for the quality control of safflower. Five different solvents （diethyl ether, ethanol, ethyl acetate, dichloromethane and acetone） were used and compared in terms of number of volatile components extracted and the peak areas of these components in TIC. The results showed that USE could be used as an efficient and rapid method for extracting the volatile components from safflower. It also could be found that the number of components in the TIC of ethyl acetate extract was more than that in the TIC of other solvent ones. Meanwhile, the volatile components of safflower from Xinjiang Autonomous Region and Henan Province of China were different in chemical components and relative contents. It could be concluded that both the extraction solvents and geographical origin of safflower are responsible for these differences. The experimental results also indicated that USE/GC-MS is a simple, rapid and effective method to analyze the volatile oil components of safflower.

Separation of tungsten and molybdenum with solvent extraction using functionalized ionic liquid tricaprylmethylammonium bis(2,4,4-trimethylpentyl)phosphinate

Functionalized ionic liquids(FILs)as extractants were employed for the separation of tungsten and molybdenum from a sulfate solution for the first time.The effects of initial pH,extractant concentration,metal concentrations in the feed were comprehensively investigated.The results showed that tricaprylmethylammonium bis(2,4,4-trimethylpentyl)phosphinate([A336][Cyanex272])could selectively extract W over Mo at an initial pH value of 5.5;the best separation factorβ_(W/Mo) of 25.61 was obtained for a solution with low metal concentrations(WO3:2.49 g/L,Mo:1.04 g/L).The[A336][Cyanex272]system performed effectively for solutions of different W/Mo molar ratios and different metal ion concentrations in the feed.The chemical reaction between[A336][Cyanex272]and W followed the ion association mechanism,which was further proved by the Fourier-transform infrared(FTIR)spectra of loaded[A336][Cyanex272]and the free extractant.The stripping experiments indicated that 95.48%W and 100.00%Mo were stripped using a 0.20 mol/L sodium hydroxide solution.Finally,the selective extractions of W and Mo from two synthetic solutions of different high metal concentrations were obtained;the separation factorβW/Mo reached 23.24 and 17.59 for the first and second solutions,respectively.The results suggest the feasibility of[A336][Cyanex272]as an extractant for the separation of tungsten and molybdenum.

Enrichment of copper and recycling of cyanide from copper–cyanide waste by solvent extraction

The enrichment of copper from copper–cyanide wastewater by solvent extraction was investigated using a quaternary ammonium salt as an extractant. The influences of important parameters, e.g., organic-phase components, aqueous pH values, temperature, inorganic anion impurities, CN/Cu molar ratio, and stripping reagents, were examined systematically, and the optimal conditions were determined. The results indicated that copper was effectively concentrated from low-concentration solutions using Aliquat 336 and that the extraction efficiency increased linearly with increasing temperature. The aqueous pH value and concentrations of inorganic anion impurities only weakly affected the extraction process when varied in appropriate ranges. The CN/Cu molar ratio affected the extraction efficiency by changing the distribution of copper–cyanide complexes. The difference in gold leaching efficiency between using raffinate and fresh water was negligible.

Solvent extraction equilibrium of dysprosium(Ⅲ) from nitric acid solutions with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester

In view of the importance of solvent extraction of rare earth metals with the acidic organophosphorous reagent,the development of a chemically based model applicable to high concentration is desired.In the present study,the equilibrium distribution of dysprosium(Ⅲ)between an aqueous nitric acid solution and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (PC88A)was measured in the range of an initial aqueous dysprosium(Ⅲ)concentration from 1.0×10-3to 1.0×10-1kmol/m 3and PC88A concentration from 0.16 to 0.65 kmol/m3in Shellsol D70 as the diluent.The obtained data were analyzed using the chemically based model in order to correlate the equilibrium distribution ratios.In this model,dysprosium(Ⅲ)was assumed to be extracted with the PC88A dimer as a 1:3 complex,the activities were considered for the aqueous species,and the effective concentration of the PC88A dimer was calculated using Alstad's empirical equation.As a result,the apparent extraction equilibrium constant was determined to be 253(kmol·m- 3)-2with an excellent correlation between the experiment and calculation results in the wide range of the logarithm of the distribution ratio from-2 to 3.5.In conclusion,the methodology in this model would be effective for quantitative description of solvent extraction behavior of general rare earth elements as well as dysprosium.

Separation of cobalt and nickel by non-equilibrium solvent extraction

The separation of cobalt and nickel in the ammoniacal sulfate solution by non equilibrium solvent extraction with a phosphate (P303) as extractant was studied. In the experiment, the effects of equilibrium pH value in aqueous phase, contact time of the two phases, the air blowing time for feed liquor in the open beaker on percentage extraction of cobalt and nickel and percentage reextraction of nickel from the loaded organic phase with dilute H 2SO 4. etc were studied. The results showed that: Co(Ⅱ) can be oxidized to Co(Ⅲ) ammino complex by adding (NH 4) 2S 2O 8 or blowing air to the aqueous phase, and Co(Ⅲ) ammino complex is a kind of kinetically inert complex. Its extractive speed is very slow, while the nickel′s is much faster than that of cobalt. By controlling the contact time of the two phases, nickel can be separated from cobalt by non equilibrium solvent extraction. Then nickel was reextracted from the loaded organic phase with dilute H 2SO 4.

Synthesis of amorphous manganese borohydride in the(NaBH_4–MnCl_2) system, its hydrogen generation properties and crystalline transformation during solvent extraction

The mixture of(2NaBH4+ MnCl2) was ball milled in a magneto-mill. No gas release was detected. The XRD patterns of the ball milled mixture exhibit only the Bragg diffraction peaks of the Na Cl-type salt which on the basis of the present X-ray diffraction results and the literature is likely to be a solid solution Na(Cl)x(BH4)(1-x), possessing a cubic Na Cl-type crystalline structure. No presence of any crystalline hydride was detected by powder X-ray diffraction which clearly shows that NaBH4in the initial mixture must have reacted with MnCl2forming a Na Cl-type by-product and another hydride that does not exhibit X-ray Bragg diffraction peaks. Mass spectrometry(MS) of gas released from the ball milled mixture during combined MS/thermogravimetric analysis(TGA)/differential scanning calorimetry(DSC) experiments, confirms mainly hydrogen(H2) with a small quantity of diborane gas, B2H6. The Fourier transform infra-red(FT-IR) spectrum of the ball milled(2NaBH4+ MnCl2) is quite similar to the FT-IR spectrum of crystalline manganese borohydride, c-Mn(BH4)2, synthesized by ball milling, which strongly suggests that the amorphous hydride mechano-chemically synthesized during ball milling could be an amorphous manganese borohydride. Remarkably, the process of solvent filtration and extraction at 42 °C, resulted in the transformation of mechano-chemically synthesized amorphous manganese borohydride to a nanostructured,crystalline, c-Mn(BH4)2hydride.

Solid-liquid solvent extraction of metal ions

An overview of extraction of some trace metal ions using molten solvent (lowmelting substance) during last two decades is presented. The development of this technique since itsinception is briefly traced. The comparison of extraction efficiency, thermodynamics and kineticsmainly involving extraction of rare earth ions between molten solvent extraction at high temperatureand usual liquid-liquid extraction at room temperature are discussed in detail. The variousparameters obtained from the previous and present studies such as equilibrium extraction constantK_(ex), pH_(1/2), thermodynamic and kinetic data are displayed in tabular form. Finally, the currentdemands, disadvantages and future prospects are also evaluated.