Reviews of Metallurgical Technology to Recovery Platinum Group Metals from Secondary Resource in China

China is extremely poor in mineral resources of Platinum Group Metals (PGMs), productive output of PGMs from mineral resource is 2.5 tons per year. At the same time, China is the biggest PGMs consumption country in the world, the mineral resource of PGMs is critical shortage, it shows the importance of recycling the secondary resource of PGMs. Sino-Platinum Metals Resource (Yimen) Co., Ltd. is the leader in recycling of PGMs from secondary resource, and has made outstanding contributions to China PGMs secondary resources recycling. This article elucidates the current situation of secondary resources recovery and development of metallurgical technology for PGMs.

Platinum Group Metals New Material

Platinum group metals (PGM) include six elements, namely Pt, Pd, Rh, Ir, Os and Ru. PGM and their alloys are the important fundamental materials for modern industry and national defense construction, they have special physical and chemical properties, widely used in metallurgy, chemical, electric, electronic, information, energy, environmental protection, aviation, aerospace, navigation and other high technology industry. Platinum group metals and their alloys, which have good plasticity and processability, can be processed to electrical contact materials, resistance materials, solder, electronic paste, temperature-measurement materials, elastic materials, magnetic materials and high temperature structural materials.

Slag design and optimization for iron capturing platinum group metals from alumina-based spent catalysts

Production of petrochemical catalysts accounts for one of the largest shares of platinum group metals(PGMs) consumption;thus,recycling of spent petrochemical catalysts holds great economic value.Conventionally,PGMs are recovered through hydrometallurgical processes which have a low recovery efficiency and produce a large amount of waste.In this regard,this paper proposed a method to use iron-capturing PGMs based on CaO-Al_(2)O_(3)-Na_(2)O slag.This method avoided the formation of Fe-Si alloy and achieved efficient enrichment of PGMs.The droplet force model showed that the recovery efficiency of PGMs could be improved if the slag had low density and low viscosity.Based on this result,FactSage software optimized the composition of slag.Furthermore,the effect of B_(2)O_(3) on the 1400 ℃ liquidus of CaO-Al_(2)O_(3)-Na_(2)O_(3)-B_(2)O_(3) phase diagram was revealed.Moreover,it was found that the recovery efficiency of PGMs exceeded 99% under the following optimized conditions:basicity of 1.0,20 wt%Na_(2)O,15 wt% B_(2)O_(3),15 wt% Fe,3 wt% C and a temperature range of 1400-1500℃.The thermodynamic model revealed the mechanism of iron capture.Different chemical bonds prevented the formation of bonds between the alloy and slag,resulting in the separation of the slag from the alloy.PGMs particles and iron microspheres had significant surface Gibbs free energy.Only when iron microspheres and PGMs particles collided and fused with each other to reduce their surface area could the Gibbs free energy of the system be reduced.

Versatile application of wet-oxidation for ambient CO abatement over Fe(OH)_x supported subnanometer platinum group metal catalysts

The efficient and stable abatement of CO pollutant under ambient conditions is of great significance;however,it remains a formidable challenge.Herein,we report the versatile application of wet oxidation over Fe(OH)x supported subnanometer Pt group metal(PGM)catalysts for the complete removal of CO under ambient temperature and humidity conditions.Typically,the 1.8 wt%Rh/Fe(OH)x catalyst exhibited better durability during a^1400 min run for wet oxidation than for dry CO oxidation.Multiple characterization results including HR-TEM,H2-TPR,and in-situ DRIFTS suggested that Fe(OH)x,with good reducibility,promoted by the subnanometer Rh clusters,provided sites for the adsorption and reaction of O2 and H2 O to form OH species.Subsequently,these OH species reacted with the adsorbed CO on Rh sites with a considerably lower activation energy(9 kJ mol^-1)than that of dissociated 0 species(22 kJ mol^-1),thus rationalizing the outstanding performance of Rh/Fe(OH)x for wet oxidation.Extended experiments with other PGMs revealed a good generality for the application of wet oxidation in the efficient abatement of CO under humid conditions with Fe(OH)x as the support.

Oxygen pressure leaching-flotation joint process for Jinbaoshan platinum group minerals

An oxygen pressure leaching-flotation joint process was proposed to treat Jinbaoshan platinum group minerals to produce a desired concentrate. The result demonstrates that leaching parameters which include particle size, stirring speed, liquid-solid ratio, and the dosage of calcium lignosulfonate, simultaneously affect the leaching rates of base metals and the recovery of platinum group metals (PGMs). The complete dissolution of base metals sulfides leads to a reduction in the amount of flotation carrier for enriching PGMs, decreasing the recovery of PGMs. The optimum leaching conditions are determined as follows: liquid-solid ratio of 10 mL/g, 73% occupancy of ore particle size below 0.043 mm, stirring speed of 400 r/min, and 0.6 g dosage of calcium lignosulfonate. Under optimal conditions, the leaching rates of Cu, Ni and Fe are 87.6%, 87.6% and 90.3%, respectively. The grade of PGMs enriched in the flotation concentrate is 420 g/t through the flotation technology.

Recent progress in CO oxidation over Pt-group-metal catalysts at low temperatures

CO oxidation is probably the most studied reaction in heterogeneous catalysis.This reaction has become a hot topic with the discovery of nanogold catalysts,which are active at low temperatures（at or below room temperature）.Au catalysts are the benchmark for judging the activities of other metals in CO oxidation.Pt-group metals（PGMs） that give comparable performances are of particular interest.In this mini-review,we summarize the advances in various PGM（Pt,Pd,Ir,Rh,Ru）catalysts that have high catalytic activities in low-temperature CO oxidation arising from reducible supports or the presence of OH species.The effects of the size of the metal species and the importance of the interface between the metal and the reducible support are covered and discussed in terms of their promotional role in CO oxidation at low temperatures.

Solar-assisted selective separation and recovery of precious group metals from deactivated air purification catalysts

The mitigation of environmental and energy crises could be advanced by reclaiming platinum group precious metals(PGMs) from decommissioned air purification catalysts. However, the complexity of catalyst composition and the high chemical inertness of PGMs significantly impede this process. Consequently,recovering PGMs from used industrial catalysts is crucial and challenging. This study delves into an environmentally friendly approach to selectively recover PGMs from commercial air purifiers using photocatalytic redox technology. Our investigation focuses on devising a comprehensive strategy for treating three-way catalysts employed in automotive exhaust treatment. By meticulously pretreating and modifying reaction conditions, we achieved noteworthy results, completely dissolving and separating rhodium(Rh), palladium(Pd), and platinum(Pt) within a 12-h time frame. Importantly, the solubility selectivity persists despite the remarkably similar physicochemical properties of Rh, Pd, and Pt. To bolster the environmental sustainability of our method, we harness sunlight as the energy source to activate the photocatalysts, facilitating the complete dissolution of precious metals under natural light irradiation. This ecofriendly recovery approach demonstrated on commercial air purifiers, exhibits promise for broader application to a diverse range of deactivated air purification catalysts, potentially enabling implementation on a large scale.

Separation of Pd and Pt from highly acidic leach liquor of spent automobile catalysts with monothio-Cyanex 272 and trioctylamine

Platinum group metals(PGMs),especially Pd,Pt,and Rh,have drawn great attention due to their unique features.Direct separation of Pd and Pt from highly acidic automobile catalyst leach liquors is disturbed by various factors.This work investigates the effect of various parameters including the acidity,extractant concentration,phase ratio A/O,and diluents on the Pd and Pt extraction and their stripping behaviors.The results show that the Pd and Pt are successfully separated from simulated leach liquor of spent automobile catalysts with monothioCyanex 272 and trioctylamine(TOA).Monothio-Cyanex 272 shows strong extractability and specific selectivity for Pd,and only one single stage is needed to recover more than 99.9% of Pd,leaving behind all the Pt,Rh,and base metals of Fe,Mg,Ce,Ni,Cu,and Co in the raffinate.The loaded Pd is efficiently stripped by acidic thiourea solutions.TOA shows strong extractability for Pt and Fe at acidity of 6 mol·L^(–1) HCl.More than 99.9% of Pt and all of the Fe are extracted into the organic phase after two stages of countercurrent extraction.Diluted HCl easily scrubs the loaded base metals(Fe,Cu,and Co).The loaded Pt is efficiently stripped by 1.0 mol·L^(–1) thiourea and 0.05–0.1 mol·L^(–1) Na OH solutions.Monothio-Cyanex 272 and TOA can realize the separation of Pd and Pt from highly acidic leach liquor of spent automobile catalysts.

Study on the Recovery of Rhodium from Spent Organic Rhodium Catalysts of Acetic Acid Industry Using Pyrometallurgical Process

A new process recycling rhodium from organic waste containing rhodium in acetic acid industry is developed. Use the special affinity of base metal sulfides (FeS, Ni2S3 , CuS, etc.) on platinum group metals, adopting high nickel matte trapping-aluminothermic activation method to recovery rhodium from incinerator residue of organic rhodium waste. The method is shorter process, lower equipment requirement, and the higher activity of rhodium black. In pyrometallurgy enrichment process,the recovery rate of rhodium reached 94.65%, the full flow of rhodium recovery rate was 92.04%.

The pilot test of Pt-Pd and Pt-Rh feeds extracted and separated with a new sulfoxide extractant

Platinum, palladium and rhodium of the raw feeds extracted and separated with a new sulfoxide extractant （MSO） were studied in the paper. The pilot test results showed that the percentage extractions are more than 99% for platinum and palladium in Pt-Pd feed, and the percentage strippings are 100% and 99.2% with HCl and ammonia, respectively. The ratio of palladium to platinum is 0.0016 in stripping platinum solution, and the ratio of platinum to palladium is 0.0020 in stripping palladium solution. The percentage extraction of platinum is 99% in Pt-Rh feed, and the percentage stripping is 100%. The ratio of rhodium to platinum is 0.0002 in stripping platinum solution. Therefore, platinum, palladium, and rhodium feeds are separated effectively with MSO.

Study on the Leaching of Pt, Pd and Rh from Spent Auto-catalysts in Various Acidities

Auto-catalysts were the largest consumers of platinum group metals and the most important secondary resources, recovery of PGMs from spent auto-catalysts by leaching with various acidities were investigated. The leaching thermodynamics of PGMs at 363 K was first discussed. At 363 K the higher the acidities of HCl, the higher the leaching recoveries of PGMs, and the sequence of leaching recovery was Pd>Pt>Rh. When H2SO4 used alone, the leaching recoveries of PGMs was low, when the acidity of H2SO4 increasing, the leaching recovery of Rh kept stable.

The Values ＆ Benefits of Umicore＇s Process Excellence Model

We will highlight the values Umicore's unique Process Excellence Model is based upon and how these do correlate with the overall culture of Umicore. Besides, we are going to explain about the benefits for the target industries that come along with our approach. Here, we will not mainly focus on the usually mentioned cost saving potential, but how also other aspects do create substantial value for the industries.

Density functional theory study of structural,electronic,and thermal properties of Pt,Pd,Rh,Ir,Os and PtPdX(X=Ir,Os,and Rh)alloys

The structural, electronic, mechanical, and thermal properties of Pt, Pd, Rh, Ir, Os metals and their alloys PtPdX （X = Ir, Os and Rh） are studied systematically using ab initio density functional theory. The groundstate properties such as lattice constant and bulk modulus are calculated to find the equilibrium atomic position for stable alloys. The electronic band structure and density of states are calculated to study the electronic behavior of metals on making their alloys. The electronic properties substantiate the metallic behavior for all studied materials. The firstprinciples density functional perturbation theory as implemented in quasi-harmonic approximation is used for the calculations of thermal properties. We have calculated the thermal properties such as the Debye temperature, vibrational energy, entropy and constant-volume specific heat. The calculated properties are compared with the previously reported experimental and theoretical data for metals and are found to be in good agreement. Calculated results for alloys could not be compared because there is no data available in the literature with such alloy composition.

Recovery of platinum from spent automotive catalyst based on hydrometallurgy

Platinum(Pt)is a critical raw material for automotive catalytic converters due to its high-temperature stability,corrosion resistance and catalytic activity,whereas its limited primary resources and uneven distribution make it hard to meet the growing demand of platinum.Spent automotive catalyst(SAC)is currently the most important secondary resource of platinum,of which the platinum content is much higher than that of the primary platinum resources.The recovery process of platinum from spent automobile catalyst mainly consists of pretreatment followed by enrichment and refining,involving pyro-and hydrometallurgical techniques,among which enrichment and refining processes are extremely important for platinum recovery from spent automobile catalyst.This paper provides an overview of the technologies for platinum recovery from spent automotive catalyst.The emphasis is placed on the processes of enrichment and refining based on hydrometallurgical techniques.Future directions of research and development of platinum recovery from spent automobile catalyst are also proposed.

RESEARCH ON REFRACTORY SUPERALLOYS IN THE HTM 21 PROJECT

It was proposed that a new class of alloys based on platinum group metals (PGMs) were called refractory superalloys. These refractory superalloys have an fcc and L12 coherent two-phase structure (similar to that of Ni-based superalloys), high melting temperatures and good potential as structural materials used at temperatures up to 1800 ℃. Our recent results on the microstruc-ture evolution, deformation and fracture behavior of some of these refracotry superalloys, especial Ir- and Rh-base refractory superalloys were reported.

Low-content and highly effective zoned Rh and Pd three-way catalysts for gasoline particulate filter potentially meeting Euro 7

The next-generation Euro 7 standard proposed much lower pollutant limits from gasoline vehicles,specifically for CO and NO_(x),which would be challenging for the three-way catalysts(TWCs)utilized commercially to eliminate these pollutants.TWCs with reductive(Rh)and oxidative(Pd)active components on gasoline particulate filters(TWC on GPF)play importantly auxiliary roles in the remediation of CO and NO_(x)downstream the close coupled TWCs to meet their emission targets.Here,a low-content Rh-based TWC(0.17 wt%)zoned with a less expensive Pd-based TWC(0.29 wt%)for GPF applications(cGPF)is reported using improved colloidal deposition method.The supporting of Rh on Y-stabilized ZrO_(2)rather than on CeO_(2)-ZrO_(2)inhibits the formation of inactive Ce rhodate species,while Pd on CeO_(2)-ZrO_(2)not only guarantees the high oxygen storage capacity(OSC)but also enhances catalytic activity.The layout of the front one-fifth in volume being 0.29 wt%Pd on Ce_(0.43)Zr_(0.5)7O_(2)and the rear four-fifths being 0.17 wt%Rh on Zr_(0.85)Y_(0.15)O_(2)prevents the possible alloying of Rh with Pd.The highly effective zoned Rh and Pd TWCs show synergistic three-way activity before and after severe hydrothermal aging at 1000℃with 10%water for24 h,which could be potential choices for close coupled GPF application to satisfy the upcoming stringent emission standards,such as Euro 7 and China 6b.

Metal separations of interest to the Chinese metallurgical industry

IBC Advanced Technologies’ Molecular Recognition Technology(MRT) SuperLig products selectively and rapidly bind with target species enabling their selective removal from solutions.The MRT process can produce a high purity separation product of maximum added value at a competitive cost.SuperLig products have high selectivity for many target species which can include metal ions,anions,and neutral molecules.In operation,the SuperLig product is first placed in a packed column.A solution containing a mixture of the target species and other chemical species is then passed through the column.The target species is removed selectively by the SuperLig product,the column is washed to remove residual feed solution,and the target species is recovered by a minimal quantity of eluent.The result is a pure and concentrated species that can be kept for its value or disposed of safely.The process is environmentally and ecologically friendly with no organic solvents being used.This paper provides a review of some examples of applications of MRT to separations of interest to the Chinese metallurgical industry.Included are several applications of MRT,including Pd separations from Pt metal refinery streams and low-grade spent catalyst wastes,Rh recovery from spent auto catalyst and other feeds,Re removal from selected impurity ions,Cd removal from Co electrolyte,Bi removal from Cu electrolyte,In and Ge separations from difficult matrices,and removal of bivalent first transition series and other metal ions from acid mine drainage(Berkeley Pit,Montana).Finally,the potential application of MRT to separations involving the recovery of rare earth metals and Li from low-level waste solutions and end-of-life products is discussed.