Separation of fuel additives based on mechanism analysis and thermodynamic phase behavior

tert-butanol and ethyl acetate,as fuel additives and oxygenated fuels,can improve fuels quality and reduce exhaust emissions.Therefore,the recovery of these compounds from azeotropic systems is of great significance.Ionic liquids(ILs)are promising green solvents for separating azeotropic systems.In this study,an efficient extraction strategy based on 1-butyl-3-methylimidazolium acetate([Bmim][AC])is proposed.The mechanism by which ILs enable the separation of binary alcohol-ester azeotropes was revealed by evaluating the lowest conformational energy through combining an independent gradient model based on the Hirshfeld partition(IGMH)and frontier molecular orbitals,to preliminarily screen the extractants.The range of extractants was further reduced by a vapor–liquid phase equilibrium(VLE)experiment,and a modeling method for separating the alcohol–ester system and recovering the solvent using[Bmim][AC]and 1-ethyl-3-methyl-3-imidazolium acetate([Emim][AC])is established.Under the optimal operating conditions,the use of[Bmim][AC]can reduce the total annual cost(TAC)per year by 17.78%,and the emissions of CO_(2),SO_(2),and NO can be reduced by 10.86%.In this study,a comprehensive method for screening extractants is proposed,and the simulation process is optimized in combination with the economic and environmental impact.The results have important guiding significance for realizing efficient,energy-saving,and green azeotropic separation systems in industry.

Separation and analysis of six fractions in low temperature coal tar by column chromatography

The low temperature coal tar(CT)is taken as the raw material,and the extraction and column chromatography are used for detailed and accurate characterization in this paper.The n-heptane soluble fraction(CT-HS)and insoluble fraction(CT-HI)were obtained by n-heptane Soxhlet extraction.The extraction rate of CT-HS reached 92.79%(mass),which indicated that there are few heavy compounds in it.Further,different solvents(methylbenzene,benzene,ethyl acetate,methylbenzene-ethanol)were used to elute CT-HS by chromatographic column to obtain five fractions(saturates,aromatics,heteroatoms,phenolics and resins,named CT-SA,CT-AR,CT-HE,CT-PH,CT-RE,respectively).The yields of CTSA,CT-AR,CT-HE,CT-PH,CT-RE are 42.12%,10.43%,2.19%,9.50%and 6.63%(mass),respectively.Gas chromatography-mass spectrometry analysis of eluting components show that alkanes are the main components in CT,followed by polycyclic aromatics,and the corresponding fractions are CT-SA and CT-AR,respectively.The relative content of aliphatics in CT-SA is 76.93%,and the relative content of aromatics in CT-AR is 75.05%.This separation technology effectively separates and enriches different components in CT,and the activation energy required for the pyrolysis process of a single eluting fraction is lower than that of CT,which is expected to provide an important reference for the separation,analysis and conversion of complex oil products such as coal-oil co-processing products,coal tar and other complex heavy carbon oil products.

Precursor solution prepared by evaporation deamination complex method for solvent separation of Mo and W by H_2O_2-complexation

An novel method on preparation of precursor solution for solvent separation of molybdenum （Mo） and tungsten （W） by hydrogen peroxide （H2O2）-complexation from the ammonium tungstate solution containing high Mo was studied. The precursor solution was obtained via evaporation deamination and H202-complex transformation processes. Then it was extracted with a mixture extractant of tri-alkyl phosphine oxide （TRPO） and tributyl phosphate （TBP） to separate Mo and W. The results indicated that the evaporation deamination complex method reduced the acid consumption by more than 90% in comparison with the traditional directly acid regulation complex method. The transformation rates of W and Mo were higher than 95% and the decomposition rate of H202 was less than 15% at a 1.8-1.9 times H202 dosage, 45-50 ℃, initial pH of 1.80-1.90, and transformation volume ratio of 100% for 60 min in the H2O2-complexation transformation process. The minimum extraction rate of W was 2%, the maximum extraction rate of Mo was 82.6% and the highest separation coefficient was 76.7 in a single-stage extraction.

A novel hydrothermal method for zinc extraction and separation from zinc ferrite and electric arc furnace dust

A novel hydrothermal process was developed to extract zinc from pure zinc ferrite（ZnFe2O4） nanopowder and zinc-containing electric arc furnace（EAF） dust using hexahydrated ferric chloride（FeCl3-6H2O） as a decomposing agent.The effects of solid FeCl3-6H2O to ZnFe2O4 ratio by mass（RF/Z）,hydrothermal reaction temperature,and time on zinc extraction were systematically investigated.In the results,when the hydrothermal reaction is conducted at 150℃ for 2 h with RF/Z of 15：20,the efficiency of zinc extraction from ZnFe2O4 reaches97.2%,and the concentration of ferric ions（Fe^3＋） in the leaching solution is nearly zero,indicating a high selectivity for zinc.In addition,the zinc extraction efficiency from the EAF dust reaches 94.5%in the case of the hydrothermal reaction performed at 200℃ for 10 h with the solid FeCl3-6H2O to EAF dust ratio by mass（RF/EAF dust） of 15：10.Zinc and iron separation is achieved by adjusting the pH value of the leaching solution according to the different precipitation pH values of metal hydroxides.

Extraction Separation of Scandium，Iron and Lutetium with Isopropyl Phosphonic Acid Mono（1－hexyl－4－ethyl）OctylEster

The extraction and stripping of scandium from its sulfate solutions by isopropyl phosphonic acid mono (1-hexyl-4-ethyl) octyl ester (PT-2, HL) diluted with n-hexane are reported. A high efficiency of separation between scandium, iron and lutetium can be achieved by controlling aqueous acidity. Different mechanisms of Sc3+ with PT-2 in various acid range have been proposed.At lower aqueous acidity, it is a cation exchange reaction, while at higher acidity. a solvation reaction was ascertained. Its IR and NMR spectra have been discussed. The effect of temperature on extraction of Sc3+ was observed and thermodynamic functions were calculated.

Mathematical Simulation of Nd and Sm Extract Separation in （Nd，Sm）Cl_3－HCL－HEHEHP－Kerosene System

A number of epuilibrium data of single stage in the system (Nd-SM)Cl_3-HCl-H_2O-1mol/L HEHEHP-kerosence was determined On the basis of epuilibrium data, two mathematical describing extract epui-librium of Nd and Sm were developed.The models cover wide available ranges (the total RE concentration inepuilibrated apueous phase is 0. 07～0. 77 mol/L and the acidity is 0. 11～0. 48 mol/L; the mole fraction ofMd or Sm is 0. 020～0. 998) with small average relative errors(The model of Nd is 6. 11 % and the model ofSm is 3. 07 %, respectively ) With the developed models, the extract behaviors of Nd and sM, such as thedistribution of rare earth concentrations in both phase, the effects of acidity, RE concentration, mole fractionof RE in aqueous phase on the RE concentration in organic phase, were researched The separation circuits be-tween Nd and Sm simulated and performed by the experiments in laboratory. The purities obtained prod-uct of Nd_2O_3O_3 as well as Sm_2O_3 were higher than 99%.Two calculation programs were written in BASIC language. One of them is used for publishing epuilibri-um model and another is used for simulation of fractional solvent extraction. The amulation results obtainedmay serve as a reference for designing solvent extraction process.

STUDY ON THE SEPARATION AND EXTRACTION MECHANISM OF RARE EARTH ELEMENTS BY MEANS OF REVERSED-PHASE PAPER CHROMATOGRAPHY

Reversed-phase paper chromatography technique is used for study on the extraction mechanism and sep- aration of rare earth elements.As the stationary phase,chromatographic paper strips are impregnated with a solution of monomyristyl phosphoric acid (MPA) in chloroform.Mineral acids are used as developers. The effect of concentration of acids and/or salts upon R_f has been investigated.According to the re- sults of R_f values for a given rare earth element in various acids,the order of extraction ability is HCl>HNO_3>H_2SO_4.A tetrad effect is clearly observed.for the R_f value of rare earth elements.The effects of other parameters on the R_f value,such as the quantities of extractant retained by the paper and the temperature are also examined.Based on the determination of the molar ratio of MPA to rare earth elements and the number of H^+ ions released in extraction reaction,a reasonable mechanism is proposed.The mutual separation of heavy rare earth elements will be better than that of the light rare earth group because of the larger separation coefficient of the former.A mixture of Ho-Er-Tm-Lu is successfully separated by the present method.

Breakthrough in the China's Separation Technology for Extraction of Rare Earth Elements

Separation technology of rare earth elements （REEs）, as the critical step in the separation process, had long been fraught with technical difficulty. A research project conducted by Baotou Shibo Rare Earth Extraction ＆ Equipment Co. Ltd., Baotou REE Research Institute, and Baotou Steel ＆ REE Group Hi-Tech Co. Ltd （Inner Mongolia）, has successfully solved the problem using a centrifugal extractor and advanced techniques to achieve a key breakthrough.

Application of ionic liquids in hydrometallurgy of nonferrous metals

Ionic liquids as green solvents have shown important application in the extraction and separation of nonferrous metals.The new application perspective,the important fundamental and the applied studies of the extraction and separation of nonferrous metals in ionic liquids,including the dissolution and corrosion of metal and metal oxide,hydrometallurgy of chalcopyrite and metallic oxidized ore,and extraction and separation of metal ions,are introduced.

Extraction of Tetracycline via Ionic Liquid Two-phase System

A new method to extract and separate tetracycline（TC） in a new aqueous tyro-phase system（ATPS） consisting of hydrophilic [Bmim]BF4 and NaH2PO4 was investigated. The effects of the amount of salt, ionic liquid as well as tetracycline on extraction efficiency were studied systematically. The results show that ionic liquid-ATPS exhibited the highest extraction efficiency higher than 90%. When the concentration of NaH2PO4 was 33.3%--38.5% （mass fraction）, the amounts of ionic liquid and TC were 1.0--2.0 mL and 1.8 mL, respectively, and ionic liquid could be re-used.

Application of Multi－objective Optimization Method to Extracton Separtion Process

A multi-objective decision procedure was proposed to select the optimal precase parameters of extractionseporating zirconium and hafnium from sulphuric acid solution with Alamine-336 as an extractant in this pa-per.Adaptive Random Search(ARS) algorithm was adopted for optimizing calculation. The results obtainedshow that the multi-objective decision method is much better than sangle-objecive decision method.

Chemical Compositions of Stemmacantha carthamoides Root

[Objectives] Chemical compositions of S. carthamoides root were isolated and identified. [Methods]Solvent extraction,repeated silica gel column chromatography,ODS column chromatography,preparative liquid chromatography and recrystallization were used for separation and purification,and chemical structure of compound was identified via its physical-chemical properties and spectral analysis data.[Results] Eight compounds were obtained from methanol extract of S. carthamoides root: 24-ethyl-20-oxhydryl ecdysone( 1),β-ecdysterone( 2),Ajugasterone C( 3),3,4-DHBA( 4),3-methoxy-quercetin( 5),( 7 S,8 S)-syringoylglycerol( 6),( E)-3,7-dimethyl-1-O-[α-L-arabinofuranosyl-( 1→6)-β-D-glucopyranosy1]-oct-2-en-7-ol( 7),Polypodine B( 8). [Conclusions] Compounds 6 and 7 were firstly isolated from the plant.

Strategies for improving extraction capacity through preorganization structure:A novel 5,6-bicyclicmalonamide extractant(THPPD)

Rational design of extractant structure to improve the extraction and separation capacity of rare earth elements(REEs)is a long-standing challenge.Herein,a new strategy was proposed to improve the stability of the chelating structure formed by malonamide and REEs.The stability of the chelating structure is greatly improved by using a double-ring framework structure which makes the two carbonyl groups of malonamide unable to rotate freely and both of them point to the metal ion position.Three benzyl groups were used to construct the hydrophobicity of the extractant and the organic shell of the extracted species.Tribenzylhexahydro-pyrrolo-pyridine-dione(THPPD)was designed and synthesized.The structure reduces the energy consumed by rotating carbonyl group in the coordination with metal ions and then improves the extraction ability of extractant.The crystal structure was preorganized as expected,with the two carbonyls pointing in a favorable coordination direction to the structural complement of the metal ion.The extraction behaviors of REEs with THPPD in a nitric acid medium were studied.Compared with N,N’-dibenzyl-N,N’-dimethylmalonamide(DBDM-MA)with a chain structure,the extraction capacity of THPPD is 360 times higher than that of DBDM-MA at 5.0 mol/L sodium nitrate.Furthermore,the binding energy and Gibbs free energy were investigated by density functional theory(DFT)in conjunction with the B3LYP.The theoretical results show that THPPD has more effective interaction with Pr(NO_(3))3 than DBDM-MA.The construction of chelating groups conformation is a worthy direction to improve the coordination ability and even selectivity of extractant.

A review on yttrium solvent extraction chemistry and separation process

This paper reviewed various systems such as neutral phosphorus and acid phosphorus, carboxylic acid and amine extractant for solvent extraction chemistry of yttrium, including thermodynamics, kinetics and yttrium extracting separation process containing the development course and new separation process.

Extraction and separation of heavy rare earths from chloride medium byα-aminophosphonic acid HEHAPP

The extraction and separation of heavy rare earths（REs） using newly synthesized a-aminophosphonic acid extractant 2-ethylhexyl-3-（2-ethylhexylamino）pentan-3-yl phosphonic acid（HEHAPP, HA） in nheptane were investigated from chloride medium. The extraction stoichiometries of lanthanum, gadolinium, yttrium and lutetium are determined to be REA3 by the slope analysis method. The favorable separation factors of adjacent heavy REs（Ⅲ）,i.e. β（Y/Ho）, β（Er/Y）,β（Tm/Er）,β（Yb/Tm） and β（Lu/Yb）, are determined to be1.87,1.36, 3.21,3.22 and 1.93, respectively, when extracted from a binary system at proper condition. The loading capacities of HA for Ho, Er, Yb and Lu increase in the order Ho 〈 Er 〈 Yb 〈 Lu with the values being 0.201, 0.205, 0.216 and 0.229 mol/L, respectively. So HA would be a potential extractant for the separation of heavy REs（Ⅲ）. Among inorganic acids such as H2 SO4, HNO3 and HCl, HCl is tested to be the most effective stripping agent.

Recent advances of rhenium separation and enrichment in China： Industrial processes and laboratory trials

China is a major producer of rhenium, which is widely used in aerospace technologies （as superalloy） and petrochemical industries （as catalyst）. There is a gap between the demand and fact for the enrichment of rhenium, due to its rather small content （10-9） in the earth＇s crust. Also, there is no available single occurrence of mineral rhenium. Instead, the rhenium is associated with either molybdenum or copper （of up to 0.2% in content） as a by-product in metallurgical industry. This makes the separation of rhenium from the major mineral metals a challenge. The recent progresses in the separation and enrichment of rhenium were reviewed in this paper, especially, the advances in China. The details of varied separation methods used either in laboratories or factories, such as ion-exchange, solvent extraction, separation utilizing extractive resins, liquid membrane, or novel materials, etc., were elaborated. Comparison of the different methods was disclosed and an outlook on the rhenium chemistry and industry in the future was brought forward.

Studies on the separation treatment of high-level liquid waste by bisamide podand(Ⅰ):Extraction and separation of An(Ⅲ)from Ln(Ⅲ)

A process for actinide(Ⅲ)and lanthanum(Ⅲ)extraction separation from high-level liquid waste(HLLW)was proposed,with N,N,N’,N’-tetraoctyl diglycolamide(TODGA)as the extractant,tri-n–butyl phosphate(TBP)as the phase modifier and 2,6-bis[1-(propan-1-ol)-1,2,3-triazol-4-yl]pyridine(PyTri-Diol or PTD)as hydrophilic stripping agent.This‘hot test’was successfully carried out,achieving 99.92%removal of americium-241(^(241)Am)with a separation factor SF(Eu/Am)of 3.8×10^(3)in the actinide(Ⅲ)product solution.The results show that bisamide podand extractants can effectively realize the extraction and separation of actinide(Ⅲ)and lanthanum(Ⅲ)from Chinese commercial HLLW and thus have a bright practical application potential for the treatment of commercial HLLW.

Study on preparation and application of novel saponification agent for organic phase of rare earths extraction

In view of the problem of ammonia-nitrogen wastewater pollution in rare earths extraction and separation, the novel saponification agent of organic phase, which is magnesium bicarbonate solution, was prepared with the natural rich and cheap dolomite as raw material through carbonation process. The behavior and purification of main impurities ions in the carbonation process as well as the application effect of the novel saponification agent in the extraction and separation was researched. The results showed that the concentration of Fe, A1, Si im- purities ions was.less than 5 ppm in the saponification agent through the development of effective removal technology, respectively. When the novel saponification agent was used in the extraction and separation, magnesium utilization rate was more than 95%, and rare earths extrac- tion rate above 99.5% has achieved. Therefore, the technology could replace ammonia-water to saponify the organic phase in rare earth ex- traction and separation process.

Review of harmless treatment of municipal solid waste incineration fly ash

Incineration is widely adopted in municipal solid waste management,which produces large amounts of municipal solid waste incineration(MSWI)fly ash.The harmless treatment of MSWI fly ash requires the appropriate disposal of heavy metals and dioxins that are enriched in fly ash.This review summarizes recently developed harmless disposal methods for MSWI fly ash including solidification/stabilization,thermal treatment,and separation/extraction.In addition,we discuss heavy metal and dioxin fixation,and the removal capacity of fly ash via solidification/stabilization(including cement solidification,chemical stabilization,hydrothermal processes,and mechano-chemical methods),thermal treatment(including sintering,fuel-burning,or electric melting/vitrification),and separation/extraction(including water-washing,chemical reagent leaching,biological leaching,electrodialysis separation,chemical reagent extraction,and nanomaterials extraction).The advantages and disadvantages of different harmless treatment methods are compared and future research prospects and suggestions are summarized.This review provides general guidelines for the harmless treatment of MSWI fly ash in the future.

Recovery of natural active molecules using aqueous two-phase systems comprising of ionic liquids/deep eutectic solvents

Due to environmental protection requirements,extraction of bioactive compounds from plant materials using environment-friendly green solvents has always been a research hotspot.And great efforts of scholars have been made in this direction,as well as environment-friendly solvents have been used to develop many innovative extraction techniques.Ionic liquids(ILs)and deep eutectic solvents(DESs)are two kinds of typical designable green solvents,which are potential replacements for traditional volatile organic solvents used for extracting.Under the substances action of inorganic salts or polymers,ILs/DESs can form an aqueous two-phase system(ATPS),which has obvious advantages for separating natural products.This paper discussed the phase separation principle of ILs/DESs-based ATPSs and reviewed the applications in the extraction of natural active molecules in recent years,as well as to promote the development of separation of the active constituents in Chinese materia medica.