Dithiooxamide-Immobilized Microalgal Residue for the Selective Recovery of Pd(II) and Pt(IV)

Microalgal residue was chemically modified by immobilizing a functional group of dithiooxamide to prepare a novel type of adsorbent. This adsorbent exhibited high adsorption affinity and selectivity for Pd(II) and Pt(IV) whereas the adsorption of coexisting base metal ions was negligible. From the adsorption isotherms, this adsorbent was found to exhibit remarkably high adsorption capacity. The thermodynamic parameters indicated that the adsorption is governed by an endothermic reaction. The effective separation of Pd(II) and Pt(IV) from Cu(II) was confirmed also by a dynamic adsorption test. The effectiveness of elution of adsorbed Pd(II) and Pt(IV) was 85% and 96%, respectively.     

Separation of Palladium(II) and Platinum(IV) by Bulk Liquid Membranes during Electrodialysis

Abstract

The process of PdCl₄ ^2? and PtCl₆ ^2? separation extracting from binary hydrochloric mixtures as well as palladium(II) extraction from individual solutions by bulk liquid membranes containing diphenylthiourea and di‐o‐tolylthiourea in 1,2‐dichloroethane is studied at galvanostatic electrodialysis. The effects of the current density, the composition of the liquid membrane and of aqueous solutions on the rate of the metal transport are determined. It is shown that an effective separation of Pt(IV) from Pd(II) is achieved in the presence of an excess of the carrier. Maximum separation factor β_Pt/Pd of 380 is obtained in 1 hour of electrodialysis under optimal conditions. The transport of platinum(IV) is supposed to occur in the form of ionic associates (PdL₄Cl)₂PtCl₆. Platinum(IV) concentration and composition of the strip solution do not exert a considerable influence on the separation factor.     

Recovery of Platinum and Palladium from Spent Automobile Catalyst by Solvent-Impregnated Resins

ABSTRACT

Separation of platinum and palladium, using solvent-impregnated resin (SIR) impregnating di-hexylamine (DHA), di-n-octylamine (DOA), or di-hexyl sulfide (DHS), coated by polyvinyl alcohol crosslinked by glutaraldehyde, was investigated. Coating of the SIR successfully suppressed leakage of the extractant during adsorption. The coated SIR was applied to chromatographic recovery of the two metals and quantitative adsorption–elution was performed via the frontal analysis mode. The adsorption of Pt and Pd was achieved, while adsorption of the co-existing metals in the leaching solution was suppressed. Separation of Pt and Pd was achieved by employing sequential chromatography system together with the quantitative elution of Pt from DHA-SIR with the mixture of 0.5 mol/L thiourea and 0.5 mol/L HCl and that of Pd from DHS-SIR with the mixture of 0.1 mol/L thiourea and 0.5 mol/L HCl solution. Finally, elementary Pt was then obtained from the eluent of sequential chromatography system by simultaneous precipitation and reduction of Pt with sodium borohydride with 99.2% purity.     

Selective Recovery of Palladium (II) from Metallurgical Wastewater Using Thiadiazole-Based Chloromethyl Polystyrene-Modified Adsorbent

Selective adsorption of palladium from metallurgical wastewater containing Pt (IV), Rh (III), Ca²⁺, Cu²⁺, Fe³⁺, Ni²⁺, Pb²⁺, V³⁺, and Ti⁴⁺ has tremendous economic and environmental benefits. In this paper, a novel thiadiazole-based chloromethyl polystyrene-modified adsorbent, viz. 2, 5-bis-polystyrene-1,3,4-thiadiazole (PS-DMTD), was synthesized using chloromethyl polystyrene as the backbone. The experimental results show that PS-DMTD can selectively separate Pd (II) from metallurgical wastewater in a one-step adsorption process. The calculated saturation adsorption capacity of PS-DMTD for Pd (II) was 176.3 mg/g at 25 °C. The separation factors of β_{Pd (II)/M}ⁿ⁺ (Mⁿ⁺: Pt (IV), Rh (III), Ca²⁺, Cu²⁺, Fe³⁺, Ni²⁺, Pb²⁺, V³⁺, and Ti⁴⁺) were all higher than 1 × 10⁴. FT-IR, XPS, and single-crystal X-ray diffraction showed that the adsorption of Pd (II) to PS-DMTD was primarily through a coordination mechanism. Density functional theory (DFT) calculations revealed that the other base metal ions could not coordinate with the PS-DMTD. Pt (IV) could not be adsorbed to PS-DMTD due to its strong chlorophilicity. Furthermore, Rh (III) existed as a polyhydrate, which inhibited Rh (III) diffusion toward the positively charged absorption sites on the PS-DMTD. These results highlight that PS-DMTD has broad application prospects in the recovery of Pd (II) from metallurgical wastewater.     

废催化剂选择法浸渣中提取钯新工艺

在含钯废催化剂的选择溶解法废弃渣中，仍然残留10~100 g/t的Pd，本文分析了可能存在的5个动力学因素(重新吸附、自发扩散、水解、取代、包裹)，提出并实验证明采用弱碱性溶液和强配位剂转型是很有效的. 对于磨细至–150目的样品，钯含量由51.6 g/t降低至1.2 g/t，对于同品位球形颗粒料，槽浸渣钯含量降低至3.0 g/t，浸出率分别达97.7%和94.2%；活性炭(AC)直接吸附浸液中的钯，富氧焚烧载钯AC后，采用氨络合法可制得纯度>99.95%的钯粉. 此工艺具有设备要求低、流程简单、金属回收率高等特点     

Highly Efficient Alkyne Hydroarylation with Chelating Dicarbene Palladium(II) and Platinum(II) Complexes

1 We report on a novel reaction protocol for the coupling of arenes with alkynes (the Fujiwara reaction), yielding products of formal trans‐hydroarylation of the triple bond. The protocol makes use of a chelating N‐heterocyclic dicarbene palladium(II) complex as catalyst and allows us to perform the reaction in a few hours with only 0.1 mol % catalyst yielding the trans‐hydroarylation product in high yields and with excellent selectivity. We discuss the applicability of this reaction protocol, which appears at present quite general with respect to the alkyne, albeit limited to electron‐rich arenes. We also present the results of catalyst optimisation with respect to the nature of the nitrogen substituents in the carbene units, of the bridging group between the carbene units and of the coordinated anionic ligands. Finally, we also discuss the catalytic performance of a related chelating dicarbene complex of platinum(II).     

Antiandrogen and Antimicrobial Aspects of Coordination Compounds of Palladium(II), Platinum(II) and Lead(II)

Synthesis, characterization and antimicrobial activities of an interesting class of biologically potent macrocyclic complexes have been carried out. All the complexes have been evaluated for their antimicrobial effects on different species of pathogenic fungi and bacteria. The testicular sperm density, testicular sperm morphology, sperm motility, density of cauda epididymal spermatozoa and fertility in mating trails and biochemical parameters of reproductive organs have been examined and discussed. The resulting biologically active [M(MaL(n))(R(2))]Cl(2) and [Pb(MaL(n))(R(2))X(2)] (where, M = Pd(II) or Pt(II) and X = Cl or NO(3)) type of complexes have been synthesized by the reactions of macrocyclic ligands (MaL(n)) with metal salts and different diamines in 1:1:1 molar ratio in methanol. Initially the complexes were characterized by elemental analyses, molecular weight determinations and conductivity measurements. The mode of bonding was established on the basis of IR, (1)H NMR, (13)C NMR, (195)Pt NMR, (207)Pb NMR, XRD and electronic spectral studies. The macrocyclic ligand coordinates through the four azomethine nitrogen atoms which are bridged by benzil moieties. IR spectra suggest that the pyridine nitrogen is not coordinating. The palladium and platinum complexes exhibit tetracoordinated square-planar geometry, whereas a hexacoordinated octahedral geometry is suggested for lead complexes.     

Thermodynamic and sorption behavior of U(VI) and Th(IV) on unsaturated polyester–styrene polymeric beads

The sorption behavior of Th(IV) and U(VI) species on two batch molds of radiation‐induced polymerized unsaturated polyester beads containing 40 wt % styrene was investigated. The distribution coefficients of both ions on the polymeric sorbents were evaluated at 30°C using 10^?4 M solution and found to be 271.9 and 469.8 mL/g on the first mold and 296 and 1189.2 mL/g on the second mold for Th(VI) and U(IV), respectively. Testing the sorption data using different theories provided evidence that the sorption data accurately fit the Langmuir, Freundlich, and D‐R isotherms, indicating chemisorption occurred and that E, the mean sorption energy of thorium and uranium on the different molds of unsaturated polyester–styrene, was between 8.304 and 13.92 kJ/mol, reflecting the nature of the ion exchange. The thermodynamics of sorption were considered in order to evaluate ΔH, ΔS, and ΔG. The data showed that the sorption process was spontaneous and exothermic. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4098–4106, 2006     

Adsorptive Removal of Pb(II) and Cu(II) Ions from Aqueous Solutions by Cross-Linked Chitosan-Polyphosphate-Epichlorohydrin Beads

In this study, the cross-linked chitosan-polyphosphate-epichlorohydrin (CCPE) beads were prepared by cross-linking chitosan with both polyphosphate and epichlorohydrin and used as bioadsorbent for the removal of Pb(II) and Cu(II) ions from aqueous solutions. The effects of the dosage of CCPE beads, solution pH, initial metal ion concentration, contact time, and temperature were investigated. Then, three important factors were selected to optimize the removal processes by the orthogonal test. The results show that CCPE beads can effectively remove the Pb(II) and Cu(II) ions from aqueous solutions, and the maximum percentage removals for Pb(II) and Cu(II) ions are 99.7% and 91.2%, respectively. The data show also that the removal processes for both Pb(II) and Cu(II) ions fit best the pseudo-second order kinetic model. Moreover, the decrease of the adsorption ability of CCPE beads is less than 10% after reuse for 9 times, which suggests that CCPE beads have good reusability.     

Effective and Selective Recovery of Precious Metals by Thiourea Modified Magnetic Nanoparticles

Adsorption of precious metals in acidic aqueous solutions using thiourea modified magnetic magnetite nanoparticle (MNP-Tu) was examined. The MNP-Tu was synthesized, characterized and examined as a reusable adsorbent for the recovery of precious metals. The adsorption kinetics were well fitted with pseudo second-order equation while the adsorption isotherms were fitted with both Langmuir and Freundlich equations. The maximum adsorption capacity of precious metals for MNP-Tu determined by Langmuir model was 43.34, 118.46 and 111.58 mg/g for Pt(IV), Au(III) and Pd(II), respectively at pH 2 and 25 °C. MNP-Tu has high adsorption selectivity towards precious metals even in the presence of competing ions (Cu(II)) at high concentrations. In addition, the MNP-Tu can be regenerated using an aqueous solution containing 0.7 M thiourea and 2% HCl where precious metals can be recovered in a concentrated form. It was found that the MNP-Tu undergoing seven consecutive adsorption-desorption cycles still retained the original adsorption capacity of precious metals. A reductive adsorption resulting in the formation of elemental gold and palladium at the surface of MNP-Tu was observed.     

Fertility Inhibitor Heterobimetallic Complexes of Platinum(II) and Palladium(II): Synthetic, Spectroscopic and Antimicrobial Aspects

Synthetic, spectroscopic and antimicrobial aspects of some fertility inhibitor heterobimetallic complexes have been carried out. These heterobimetallic chelates [M(C(5)H(5)N(3))(2)M(2)'(R)(4)]Cl(2) (M = Pd or Pt and M' = Si, Sn, Ti and Zr) have been successfully synthesinzed via the reaction of M(C(5)H(7)N(3))(2)Cl(2) with group four or fourteen dichlorides in 1:2 stoichiometric proportions. The products were characterized by elemental analyses, molecular weight determinations, magnetic susceptibility measurements, conductance, and IR multinuclear NMR and electronic spectral studies. A square planar geometry has been suggested for all the complexes with the help of spectral data. Conductivity data strongly suggest that chlorine atoms are ionic in nature due to which complexes behave as electrolytes. All the complexes have been evaluated for their antmicrobial effects on different species of pathogenic fungi and bacteria. The testicular sperm density, testicular sperm morphology, sperm motility, density of cauda epididymal spermatozoa and fertility in mating trails and biochemical parameters of reproductive organs have been examined and discussed.     

Adsorptive Removal of Thiophene from Benzene by NaY Zeolite Ion-Exchanged with Ce(IV)

The commercial NaY zeolite with the Si/Al ratio of 5:1 was selected and modified for researching the adsorptive removal of thiophene from benzene. The zeolite was ion-exchanged in Ce(NO₃)₃ solution and then calcined in muffle to prepare the CeY sorbent. The results show that it is a suitable method to prepare the sorbent removing thiophene from benzene that NaY zeolite is ion-exchanged by cerium in Ce(NO₃)₃ solution. The desulfurization efficiency of CeY sorbent increases obviously comparing with NaY zeolite. The effects of the calcination temperature, calcination time, concentration of Ce(NO₃)₃ solution, ion-exchange time, and ion-exchange times on the desulfurization capacity of CeY sorbent were also studied. The results show that the optimal CeY sorbent can be obtained when NaY zeolite is ion-exchanged in 0.5 mol/L Ce(NO₃)₃ solution at 100°C for 4 h, calcined at 700°C for 2 h, and repeated the above steps two times. The results of XRD and BET characterization indicate that those preparation conditions mainly influence on the crystallinity, specific surface area of CeY sorbent. The best CeY sorbent can remove thiophene to 136.8 mg/L from 550.0 mg/L in thiophene-benzene solution at ambient temperature and pressure with the agent-liquid ratio of 1:16 (g/mL).     

Quaternary Amine Modified Persimmon Tannin Gel: An Efficient Adsorbent for the Recovery of Precious Metals from Hydrochloric Acid Media

Persimmon tannin was chemically modified to prepare a quaternary amine type of adsorption gel, named as quaternary amine modified persimmon tannin (QAPT) gel. The QAPT gel has been used to investigate the adsorption behaviors for Au(III), Pd(II), and Pt(IV) from HCl media. It was found that the gel exhibited good selectivity towards precious metals over a wide concentration range of HCl. However, it exhibited poor affinity towards base metals such as Cu(II), Fe(III), Ni(II), and Zn(II). The adsorption isotherms of the gel for precious metal ions were described by the Langmuir model. The maximum adsorption capacities for Au(III), Pd(II), and Pt(IV) were evaluated as 4.16, 0.84, and 0.52 mmol g^?1, respectively. Although the anion exchange is the main mechanism for the adsorption of anionic species of Au(III), Pt(IV), and Pd(II), adsorption of Au(III) is followed by subsequent reduction, which results in the extraordinary high adsorption capacity for Au(III). Adsorption behavior of QATP gel for Au(III) was also compared to that of the persimmon tannin, the feed material.     

The adsorption behavior of Cu(II), Pb(II), and Co(II) of ethylene vinyl acetate‐clinoptilolite nanocomposites

In this study, ethylene vinyl acetate (EVA) was mixed with clinoptilolite (C), a natural zeolite, to prepare EVA‐C nanocomposites. The films were characterized by SEM‐EDS, XRD, and FT‐IR, and heavy metal removal was studied using the batch technique. The effects of the initial pH value and concentration of solutions, contact time, and filler dosage on the adsorption capacity of the composites were investigated. To study the influence of pretreatment on the filler, clinoptilolite was activated using KCl, NaCl, and HCl. Adsorption results show that equilibrium was reached after 24 h, and that sorption reached its maximum at pH values between 5 and 7. The selectivity trend was observed to be Pb > Cu > Co, which was consistent for both single and mixed metal‐ion solutions. Pretreatment significantly increased adsorption capacity of the composite, but was dependent on the conditioning reagent. Nanocomposites filled with HCl‐activated particles demonstrated a high adsorption capacity of between 70 and 80% for all three metals, while KCl‐activated particles were the least efficient with a maximum adsorption capacity of 69% for Pb(II), 54% for Cu(II) and 48% for Co(II). The adsorption data were then fitted to both Langmuir and Freundlich isotherms over the entire concentration range, and the Langmuir isotherm showed a better fit of the experimental sorption data than the Freundlich isotherm. The results obtained show that this simple methodology which can be up‐scaled has great potential for the preparation of a wide variety of similar particle‐filled adsorbent nanocomposites in other environmental remediation applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Lewis Acid Behavior of Cationic Complexes of Palladium(II) and Platinum(II): Some Examples of Catalytic Applications

The behavior of a variety of cationic diphosphine complexes of Pd(II) and Pt(II) as Lewis acid catalysts is reviewed. The reactions considered are the Baeyer–Villiger oxidation of ketones, the acetalization of aldehydes and ketones and the Diels–Alder reaction in both their regular and enantioselective version.     

Removal Characteristics of Cd(II), Cu(II), Pb(II), and Zn(II) by Natural Mongolian Zeolite through Batch and Column Experiments

The removal characteristics of Cd(II), Cu(II), Pb(II), and Zn(II) from model aqueous solutions by 5 natural Mongolian zeolites were investigated. The adsorption of metals on zeolites reached a plateau value within 6 h. The adsorption kinetic data were fitted with adsorption kinetic models. The equilibrium adsorption capacity of the zeolites was measured and fitted using Langmuir and Freundlich isotherm models. The order of adsorption capacity of zeolite was Pb(II) > Zn(II) > Cu(II) > Cd(II). The maximum adsorption capacity of natural zeolite depends on its cation exchange capacity and pH. The leaching properties of metals were simulated using four leaching solutions. The results show that natural zeolite can be used as an adsorbent for metal ions from aqueous solutions or as a stabilizer for metal-contaminated soils.     

Kinetic and Equilibrium Modeling of Pb(II) and Co(II) Sorption onto Rose Waste Biomass

Abstract

An attempt was made to assess the biosorption potential of rose waste biomass for the removal of Pb(II) and Co(II) ions from synthetic effluents. Biosorption of heavy metal ions (>90%) reached equilibrium in 30 min. Maximum removal of Pb(II) and Co(II) occurred at pH 5 and 6 respectively. The biosorbent dose for efficient uptake of Pb(II) and Co(II) was 0.5 g/L for both metals. The biosorbent size affected the Pb(II) and Co(II) biosorption rate and capacity. Rose waste biomass was found effective for Pb(II) and Co(II) removal from synthetic effluents in the concentration range 10–640 mg/L. Equilibrium sorption studies showed that the extent of Pb(II) and Co(II) uptake by the rose waste biomass was better described by the Langmuir isotherm in comparison to the Freundlich model. The uptake capacities of the two metal ions were 156 and 27.15 mg/g for Pb(II) and Co(II) respectively.