SOLVENT EXTRACTION OF Au(III), Pd(II) AND Pt(lV) WITH SULFUR-CONTAINING METHYLPHOSPHONATES AND β-KETOPHOSPHONATE

Three sulfur-containing methylphosphonates, dibutyl propylthiomethylphosphonate, (C₄H₈O)₂P(0)CH₂SC₃H₇,(DBPTMP),dibutyl propylsulfinylmethylphosphonate, (C₄H₉0)₂P(0)CH₂S(0)C₃H₇, (DBPSiMP) and dibutyl propylsulf onylmethylphosphonate, (C₄H₈O)₂P(0)CH₂S(0) C₃H₇ (DBPSiMP) were synthesized. The extraction of gold(III), palladium(II) and platinum(IV) from HCl media with the synthesized compounds and dibutyl 2-keto-3-methylbutyl-phosphonate, (C₄H₈O)₂P(0)CH₂C (0) CH(CH₃) CH₃, (DBKPP) was investigated at various mixing times and acidities. DBPTMP and DBPSiMP were found to provide nearly quantitative extraction of Au(III) and Pd(II) with short equilibration times for Pd(II) extraction. DBKPP was selective for Au(TII) over Pt(IV) and Pd(II) at high acidity. The behavior of these extractants was also examined in comparison with the corresponding monofunctional extractants, dibutyl butylphosphonate(DB‘BP’), tributyl-phosphate(TBP), dioctylsulphide(DOS) and dioctyl-sulphoxide(DOSO).     

PURIFICATION OF BILIRUBIN AND MICRO-PARTICLE FORMATION WITH SUPERCRITICAL FLUID ANTI-SOLVENT PRECIPITATION

1 INTRODUCTIONA supercritical fluid is one existing at temperatures and pressures above its criticalpoint values(T_c,p_c) [1].Supercritical fluid has unconventional thermophysical prop-erties,exhibiting higher density,greater compressibility,lower viscosity between the gasand liquid extremes.Its solute binary diffusion coefficient is considerably higher thanthat in liquids[2-4].Supercritical fluid extraction(SFE)has been suggested as a viablealternative to other separation technologies.     

SYNERGISM IN THE EXTRACTION OF ZINC(II)AND CADMIUM(II) WITH SOME LOWER FATTY ACIDS IN THE PRESENCE OF AMINES AND THEIR SEPARATIONS∗

Abstract

Synergism in the extraction of Zn(Il) and Cd(II)with chloroform solution of propionic, butyric and valeric acids in the presence of n-butylamine, dibutylamine, tributylamine, β-picoline, pyridine and quinoline is reported The effect of various parameters affecting extractions has been investigated The compositions of synergistic adduct extracted into the organic phase have been proposed on the basis of slope analysis method. In general the species have been represented as MA2.2HA.B (aliphatic amine system and MA₂.2HA.2B (heterocyclic amine system), where M = zn(Il)/CdII), HA = acid and B = amine. On the basis of extraction constant (K_ex) values the relative effectiveness of different amines as synergists has been compared. Based on the extraction data some separations of metal ions have also been reported with fairly high separation factor (β).     

α-HYDROXYCARBOXYLIC ACID AS ADDUCT FORMING LIGAND FOR EXTRACTION OF LANTHANIDE(III)

Lanthanide(lII) chelates with 1,1,1 -trif luoro-5,5-dimethyl-2,4-hexanedione form adducts with benzilic acid, an a-hydroxycar-boxylic acid, in chloroform. The order of. the adduct formation constants in magnitude is: La^m> Eu^m> Yb^m although it is known that the stability constant of lanthanide(III) complexes with α-hydroxycarboxylic acids in aqueous solutions increases with increasing atomic number.     

MECHANISMS OF OXIDATIVE DEGRADATION OF CARBOHYDRATES DURING OXYGEN DELIGNIFICATION. II. REACTION OF PHOTOCHEMICALLY GENERATED HYDROXYL RADICALS WITH METHYL β-CELLOBIOSIDE

ABSTRACT

Near infrared spectrometry and multivariate data analysis were applied to predict the chemical composition and physico–chemical characteristics of eucalypt unbleached kraft pulps obtained at different laboratory pulping conditions. Viscosity, degree of polymerization (DP), kappa, brightness and contents of glucan, xylan, uronic acids, and lignin were the modeled variables using diffuse reflectance near infrared spectra obtained on pulp handsheets and the partial least squares (PLS) method. Models with two to four PLS components and good predictive ability were established after first derivative spectra pre-processing and application of cross-validation methodology. The predictive models can reduce the time consuming traditional analyses in the pulping industry laboratories, and also lead to a better process monitoring for suitable applications.     

STUDIES ON ALKYLATION OF BENZENE WITH PROPYLENE OVER βZEOLITE (Ⅱ) SIMULATION OF REACTOR

通过对FX-01沸石催化剂上苯与丙烯的烷基化反应中试工况进行模拟,判识了合适的外扩散传质关联式,并计算出外扩散传质阻力,得出了反应过程的控制步骤。固定床鼓泡反应器中烷基化反应过程阻力的大小顺序为:气液膜阻力>液固膜阻力>内扩散阻力与化学反应阻力之和。     

SANS STUDY OF AGGREGATION OF THE COMPLEXES FORMED BY SELECTED METAL CATIONS AND P,P'-DI(2-ETHYLHEXYL) ETHANE- AND BUTANE-DIPHOSPHONIC ACIDS∗

ABSTRACT

The aggregation of several metal complexes formed during solvent extraction with P,P'-di(2-ethylhexyl) ethanediphosphonic acid, H₂DEH[EDP], and by P,P'-di(2-ethylhexyl) butanediphosphorac acid, H₂DEH[BuDP], in deuterated toluene, has been investigated by small angle neutron scattering (SANS). With H₂DEH[EDP], the extraction of Ca(II), La(IH) and U(VT) does not disrupt the cyclic hexameric structure of the ligand in solution. Fe(III) and Th(IV) complexes of H₂DEH[EDP], on the other hand, exhibit a very modest tendency to aggregate but only at very high metal loading in the organic phase. With H₂DEH[BuDP], the extraction of Ca(H), La(III), U(VI) and Th(IV) is not accompanied by significant aggregation of the metal complexes The Fe(HI)-H₂DEH[BuDP] complexes, however, form long cylindrical aggregates similar to those previously observed with P,P'di(2-ethylhexyl) methanediphosphonic acid, H₂DEH[MDP]. The aggregation behavior of the various metal-extractant species is discussed in light of the information obtained from earlier solvent extraction, vapor pressure osmometry, and infrared spectroscopy studies.     

PREPARATION AND ADSORPTION PROPERTIES OF THE POLYSTYRENE RESIN HAVING DIETHYLENETRIAMINE-N,N′- BIS(METHYLENEPHOSPHONATE) GROUP

Styrene-divinylbenzene copolymer beads containing diethylenetriamine-N,N′-bis(methylenephosphonate) group have been synthesized. The adsorption properties, of the present resin for some trivalent and bivalent metal ions have been examined. The selectivity sequence of the present resin at pH lower than 2.0 is as follows: Ga(III)> A1(III)> Sm(III)>Cu(II)>Co(II)>Zn(II)>Ca(II). The present resin reveals remarkable selectivity for the trivalent metal ions. The selective concentration of In(III) Ga(III) and Sm(III) from an acidic aqueous solution has been demonstrated by using a column of the present resin.     

SIMPLIFIED FRAMEWORK FOR DESCRIPTION OF MIXING WITH CHEMICAL REACTIONS (Ⅰ) PHYSICAL PICTURE OF MICRO- AND MACROMIXING

1 INTRODUCTION When a fluid is injected into a turbulence field to mix with another fluid,twohomogenization processes take place simultaneously:micromixing(on the molecularscale)and macromixing(on the mixer scale).For micromixing,three successive stages arerecognized at high Schmidt number(1)turbulent dispersion,in which the original ma-terial lumps are dispersed by turbulence into discrete elements with smallest eddy sizeλ_k;(2)viscous deformation,in which the size of the elements is further reduced     

LIQUID-LIQUID EXTRACTION OF Pa(V) AND Zr(IV) BY MIXTURES OF A β-DIKETOHE AND A SULPHOXIDE FROM HTDROCHLORIC ACID MEDIA

The species involved in the solvent extraction of zirconium(IV) from hydrochloric acid medium by mixtures of thenoyltrifluoroacetone (HTTA) and dipentyl sulphoxlde (DPSO) in benzene as the diluent seems to be Zr(OH) ₂(TTA)₂(DPSO). Extraction of protactinium(V) by mixtures of HTTA and DPSO exhibits synergism but the extent of synergism is not very appreciable.     

SOLVENT EXTRACTION OF ANTIMONY (III), BISMUTH (HI), LEAD (II) AND TIN (IV) WITH BIS(2,4,4-TRIMETHYLPENTYL)PHOSPHINODITHIOIC ACID (CYANEX 301®)

The solvent extraction of antimony (in), bismuth (111), lead (II) and tin (IV) from aqueous hydrochloric acid solutions by bis(2,4,4-trimethylpentyl) phosphinodithioic acid (Cyanex 301® denoted HL) in kerosene + 10 % v/v n-decanol was investigated. Lead (II), tin (IV), bismuth (III) and antimony (III) are efficiently extracted by Cyanex 301® up to about 5, 6, 9 and 11 mol.L^1? HCl, respectively. The corresponding extracted species were identified as PbL₂, SnCl₂L₂, BiL₃ and SMvj. However, it was observed that Sn (IV) can be moderately extracted from the aqueous phase by the mere mixture of kerosene and n-decanol above 9 mol.L^1?HCl. In all cases, extraction equilibrium was reached within a few minutes. Finally, a thermodynamic modelling of the extraction system was developed in the particular case of lead (II).     

EXTRACTION OF NEPTUNIUM AND PLUTONIUM NITRATES WITH n-OCTYL(PHENYL)-N,N-DIISOBUTYL-CARBAMOYLMETHYLPHOSPHINE OXIDE∗

Distribution equilibria of Np and Pu in various valence states and stripping of Np(V) were studied in a system involving 0.20 M n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide + 1.2 M tributyl phosphate in dodecane as a solvent. Np(V) is weakly extractable at <2 M nitric acid but more effectively extractable at >3 M nitric acid, due to the disproportionation of Np(V) to Np(IV) and Np(VI). Addition of nitrous acid to solutions containing Np(V) increases the over-all extractabllity of Np, due to its partial oxidation to Np(VI). This is also the case In the presence of oxalic acid, both at room temperature and at 40^°C. Both Np(IV) and Np(VI) are highly extractable, but the reduction of Np(V,VI) to Np(IV) is slow even with a reductant as strong as sodium formaldehyde sulfoxylate. Pu(IV) is highly extractable and its reduction to Pu(III) with sulfoxylate Is incomplete in the two-phase system if the aqueous phase contains >0.5 M nitric acid. Extracted Np(VI) can be stripped by reduction to Np(V). The stripping rate is, however, slow with nitrous acid as the reductant at low nitric acid concentration. The reduction of Np(VI) by hydrogen peroxide is fast, but is followed by further reduction to Np(IV). Sulfurous acid reduces Np(VI) rapidly and, if no iron is present, only to Np(V), but Fe(II) induces further reduction to Np(IV).     

EFFECT OF CHAIN LENGTH OF ALKANE-1-HYDROXY-1, 1′-METHYLDIPHOSPHONIC ACIDS ON THE IRON (III) LIQUID–LIQUID EXTRACTION

ABSTRACT

(1-Hydroxy-1-phosphonohexadecyl) phosphonic acid (HPHPA) and (1-hydroxy-1-phosphonododecyl) phosphonic acid (HPDPA) were prepared by reaction of phosphorus trichloride with palmitic and lauric acids, respectively. After purification, these products were characterized by elemental microanalysis and by IR, ¹H, ³¹P?NMR spectroscopies. In this paper, we propose a tentative assignment for the shifts of those two ligands and their specific complexes with iron (III). A spectroscopic analysis has showed that coordination of iron (III) takes place via oxygen atoms. We also measured the extraction of Fe⁺³ by HPHPA and HPDPA from [CCl₄-Octanol (v/v: 90%/10%)] solutions. The complexes formed in the organic phase may be Fe[C₁₁ H₂₃C(OH)(PO₃H)₂]Cl, 3H₂O with HPDPA and Fe[C₁₅H₃₁C(OH) (PO₃H)₂]Cl, 3H₂O with HPHPA, respectively. HPHPA as ligand exhibits a stronger extracting power for Fe³⁺ and has a more hydrophobic character than HPDPA.     

AGGREGATION OF P,P' -DI( 2-ETHYLHEXYL) METHANEDIPHOSPHONIC ACID AND ITS Fe(III) COMPLEXES ∗

ABSTRACT

The aggregation of P,P' -di( 2-ethylhexyl) methanediphosphonic acid, H2DEH[ MDP] dissolved in deuterated toluene has been investigated by small angle neutron scattering ( SANS) The title compound was shown to exist in solution as a dimer under all conditions. Dimer formation is independent of the acidity of the aqueous solution with which the organic solution is pre-equilibrated. Solutions of H₂ DEH[ MDP] containing increasing amounts of Fe( lll) extracted from aqueous solutions in the acidity range from 0.1 to 5 M were also investigated. The SANS results confirm the tendency of H2DEH[ MDP] -Fe( III) species in aromatic diluents to form rod-like aggregates characteristic by a constant cross section and a length which increases with increasing amounts of metal in the organic phase. Particle growth is independent of the acidity of the aqueous solutions from which the metal is extracted. These results are important for understanding the chemistry underlying the solvent extraction behavior H₂DEH[ MDP] and its practical application in separation procedures.     

THE SYNTHESIS AND ACTINIDE AND LANTHANIDE COMPLEXATION OF“ SOFT” DONOR LIGANDS: COMPARISON BETWEEN 4-BENZOYL-2,4-DIHYDRO-5-METHYL-2-PHENYL-3H-PYRAZOL-3-THIONE ( HBMPPT) AND 4-THIOBENZOYL-2,4-DIHYDRO-5-METHYL-2-PHENYL-3H-PYRAZOL-3-ONE ( HTBMPP) WITH TRI-n-OCTYLPHOSPHINE OXIDE (TOPO) SYNERGIST FOR Am( III) AND Eu( III) EXTRACTION

A comparison study between two “ soft” donor ligand isomers, 4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione ( HBMPPT) and 4-thiobenzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one ( HTBMPP), both with tri-n-octylphosphine oxide ( TOPO) synergist in toluene, is reported for the extraction of Am( III) and Eu(UI). The more stable ligand, HBMPPT, gave no detectable extraction, but when HBMPPT and TOPO were combined, substantial extraction occurred with selectivity for Am( UI) over Eu( III) in three acid systems HC1, HCIO4, and HNO3. A maximum separation factor ( SF = DAm/ DEu) of 125 was obtained at pH 3.0 for the HBMPPT/ TOPO/ HCIO4 system. The other less stable ligand isomer, HTBMPP, did extract Am( m) to a small extent but combination with TOPO greatly enhanced the extraction. A maximum SF of 15 at pH 3.0 was observed for the HTBMPP/ TOPO/ HCIO4 system. Comparison of HBMPPT/ TOPO among the acids studied indicated different extraction mechanisms in the linear region in each system for Eu( ID) extraction, whereas the Am( m) extraction mechanism remained nearly constant and the same as Eu( m) in chloride media. The large difference in the selectivity and extraction behavior between the two ligands appears to be related to charge density distribution on the donor heteroatoms     

JOURNAL OF CHEMICAL INDUSTSY AND ENGINEERING(CHINA)

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COBALT–NICKEL SEPARATION: THE EXTRACTION OF COBALT(II) AND NICKEL(II) WITH BIS(2-ETHYLHEXYL) PHOSPHINIC ACID (PIA-8) IN TOLUENE

The extraction behaviour of cobalt(II) and nickel(II) from sulfate solutions with bis(2-ethylhexyl) phosphinic acid (PIA-8) in toluene has been studied. Quantitative extraction of Co(II) was observed at pH 5.0–5.9 while that of Ni(II) at pH 6.8–7.0 with 0.03 M PIA-8 in toluene. The difference in pH_0.5 for Co(II) and Ni(II) was 1.9. The stoichiometry of the extracted species were determined by slope analysis method. The extraction reaction proceeds by cation exchange mechanism and the extracted species were Co · R₂(HR)₂ and Ni · R₂ · 2(HR)₂. Temperature dependance of the extraction equilibrium constants were determined to estimate the apparent thermodynamic functions (ΔG, ΔS and ΔH). The method was used for separation of cobalt(II) and nickel(II). Cobalt(II) was separated from nickel even at 1:20 (Co:Ni) ratio. The separation of cobalt(II) from nickel(II) was favoured with the increase in temperature.     

STUDIES ON ULTRASONIC DEGRADATION AND BLOCK COPOLYMERIZATION OF POLYACRYLAMIDE AND POLY(ETHYLENE OXIDE)

The kinetics of ultrasonic degradation of aqueous solution of polyacrylamide(PAM)and poly(ethyleneoxide)(PEO)as well as ultrasonic block copolymerization of aqueous solution of the mixture of PAM/PEOwere studied respectively.The degradation reaction of PEO follows a linear relationship between(P_1-P_∞)~(-1)and irradiation time,while that of PAM follows a linear relationship between(P_1-P_∞)~(-1/2)and irradiation time.The structure of the copolymer was identified by IR,NMR and DTA,and the copolymer prepared is a blockone.The copolymer formed by irradiating 1% aqueous solution of PEO/PAM mixture(1:1)for a period of40min.at 18.2 kHz with a sonic intensity corresponding to 2.OA input current on the reversed main circuitamounts to 61.8%.