Studies on the feasibility of electrochemical recovery of palladium from high-level liquid waste

The electrochemical behavior of palladium (II) in nitric acid medium has been studied at platinum and stainless steel electrodes by cyclic voltammetry. The cyclic voltammogram consisted of a surge in cathodic current occurring at platinum electrode at a potential of −0.1 V (vs. Pd), which culminates in a peak at −0.3 V was due to the reduction of Pd(II) to Pd. This was accompanied by a broad scant anodic peak at 0.25 V during scan reversal. Reduction of Pd(II) was irreversible and the diffusion coefficient was found to be 2.35 × 10⁻⁸ cm²/s at 298 K. At stainless steel electrode, a surge in the cathodic current occurring at −0.4 V (vs. Pd) was due to palladium deposition, which was immediately followed by a steep increase in cathodic current at −0.66 V due to H⁺ reduction. Electrolysis of palladium nitrate from 1 M to 4 M nitric acid medium at stainless steel electrode resulted in complete recovery of palladium with reasonably high Faradaic efficiency depending upon nitric acid concentration. However, the recovery and Faradaic efficiency were significantly lowered (to 40%) in the case of electrolysis from simulated high-level liquid waste due to other interfering competitive reactions.     

Hydrogen permeation in high strength steel under load in aqueous environment

Abstract

The hydrogen assisted cracking problem is one of the major causes of the failure occurring in the high strength steel structures used in various industries. In aqueous environment, hydrogen is generated by the hydrogen reduction reaction on the steel surface. With depletion of the high quality resources in oil and gas industry, the hydrogen assisted cracking problem becomes severe in sour environment, which contains high amount of H₂S. Understanding on the hydrogen permeation behaviour is crucial to deal properly with the hydrogen related problems since they are primarily determined by the hydrogen uptake and transport in the steel. The Devanathan–Stachurski method is widely used to evaluate electrochemically the hydrogen permeation behaviour. This method has been successfully used for the steel with no load. Under loading condition, this electrochemical test method has been modified to accommodate the externally applied load. However, the data require careful examination to validate the technical importance because of the stability and homogeneity of palladium layer coated on the steel surface under load. In this paper, the hydrogen permeation test method under loading condition will be reviewed for the high strength steels used in oil and gas industry. The factors affecting the hydrogen permeation in the high strength steel will be discussed in terms of the applied stress level and the sulphide film forming on the steel surface in sour environment.     

Hydrogenation of 2-Butyn-1,4-diol in the Presence of Functional Crosslinked Resin Supported Pd Catalyst. The Role of Polymer Properties in Activity/Selectivity Pattern

Functional gel type resins of various crosslinking degrees (3–20%) with C=O and carboxylic groups were used as the supports for Pd catalysts (0.5–2 wt% Pd). The role of polymer properties was studied in the hydrogenation of 2-Butyne-1,4-diol (B3-D) to alkene (B2-D) and alkane (B1-D). Hydrogenation was studied at atmospheric pressure of hydrogen using THF, H₂O and THF + H₂O mixtures as the solvents. Systematic studies were carried out to determine the role of the type of solvent, crosslinking degree of polymer, the content of Pd in catalysts, initial B3-D concentration and the procedure of catalyst reduction in activity/selectivity behaviour of catalysts. Swelling degree of polymer matrix under the catalytic run exhibits crucial role in the activity and selectivity to alkene, B2-D. In the presence of highly expanded catalyst (THF solvent, 3% crosslinking degree, 1 wt% Pd) the alkyne, B3-D, is hydrogenated to alkene, B2-D, with selectivity ca. 85% up to high B3-D conversion (90%). The suppression of alkene to alkane hydrogenation in the stage of B3-D is ascribed to high ability of Pd centres in the Pd/OFP catalysts to strong adsorption of alkyne substrate. It may also be related to steric hindrances of polymer in the vicinity of active Pd centres. At small content of added water (5% by vol.) to THF the catalysts offer very attractive performance in terms of activity and 98% selectivity to alkene. Water facilitates interactions of B3-D with functional groups of polymer that leads to better expansion of polymer matrix and more effective suppression of alkene hydrogenation in the alkyne stage.     

Oxide (CeO2, NiO, Co3O4 and Mn3O4)-promoted Pd/C electrocatalysts for alcohol electrooxidation in alkaline media

This study investigated Pt/C, Pd/C and oxide (CeO₂, NiO, Co₃O₄ and Mn₃O₄)-promoted Pd/C for electrooxidation reactions of methanol, ethanol, ethylene glycol and glycerol in alkaline media. The results show that Pd/C electrocatalysts alone have low activity and very poor stability for the alcohol electrooxidation. However, addition of oxides like CeO₂, NiO, Co₃O₄ and Mn₃O₄ significantly promotes catalytic activity and stability of the Pd/C electrocatalysts for the alcohol electrooxidation. The Pd-Co₃O₄ (2:1, w:w)/C shows the highest activity for the electrooxidation of methanol, EG and glycerol while the most active catalyst for the ethanol electrooxidation is Pd-NiO (6:1, w:w)/C. On the other hand, Pd-Mn₃O₄/C shows significantly better performance stability than other oxide-promoted Pd/C for the alcohol electrooxidation. The poor stability of the Pd-Co₃O₄/C electrocatalysts is most likely related to the limited solubility of cobalt oxides in alkaline solutions.     

Autothermal reforming of methane to syngas with palladium catalysts and an electric metal monolith heater

The autothermal reforming of methane to syngas for use in the Fischer-Tropsch synthesis was studied in this work over PdO containing various combinations of CeO₂, BaO or SrO in a washcoated form on a metallic monolith at atmospheric pressure. This study focused on the autothermal operation of the system, in which an electric heater inside the reactor was used only to reach the ignition temperature, and thereafter the autothermal reaction successfully sustained itself without any external heat source. It was concluded from the experiments that the PdO/Al₂O₃ catalyst was better than the others, except for PdO-CeO₂-BaO-SrO/Al₂O₃, which showed similar performance in terms of the CH₄ conversion and H₂+CO selectivity, while affording a higher H₂/CO ratio (close to ca. 3) than the PdO/Al₂O₃ catalyst did (close to ca. 2). The gas hourly space velocity and O₂/CH₄ ratio governed the methane conversion, while the H₂O/CH₄ ratio controlled the H₂/CO ratio. A methane conversion of ∼87%, H₂+CO selectivity of ∼94%, H₂/CO ratio of ∼2.9, and M factor ∼2.15 were obtained under the conditions of a gas hourly space velocity (GHSV) of 120,000 h⁻¹, O₂/CH₄=0.6 and H₂O/CH₄=0.5.     

Temperature programmed desorption of oxygen from Pd films interfaced with Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-doped ZrO<Subscript>2</Subscript>

The origin of the effect of non-faradaic electrochemical modification of catalytic activity (NEMCA) or Electrochemical Promotion was investigated via temperature-programmed-desorption (TPD) of oxygen, from polycrystalline Pd films deposited on 8 mol%Y₂O₃–stabilized–ZrO₂ (YSZ), an O²⁻ conductor, under high-vacuum conditions and temperatures between 50 and 250 °C. Oxygen was adsorbed both via the gas phase and electrochemically, as O²⁻, via electrical current application between the Pd catalyst film and a Au counter electrode. Gaseous oxygen adsorption gives two adsorbed atomic oxygen species desorbing at about 300 °C (state β₁) and 340–500 °C (state β₂). The creation of the low temperature peak is favored at high exposure times (exposure >1 kL) and low adsorption temperatures (T_ads < 200 °C). The decrease of the open circuit potential (or catalyst work function) during the adsorption at high exposure times, indicates the formation of subsurface oxygen species which desorbs at higher temperatures (above 450 °C). The desorption peak of this subsurface oxygen is not clear due to the wide peaks of the TPD spectra. The TPD spectra after electrochemical O²⁻ pumping to the Pd catalyst film show two peaks (at 350 and 430 °C) corresponding to spillover O_ads and according to the reaction:

New polymerization of dienes and related monomers catalyzed by late transition metal complexes

This article reviews recent studies on the polymerization of 1,6-heptadienes and 2-aryl- and 2-alkoxy-1-methylenecyclopropanes catalyzed by Co, Fe, and Pd complexes. Co and Fe complexes with bis(imino)pyridine ligands catalyze the cyclopolymerization of 1,6-heptadiene in the presence of MMAO to produce the polymer, which contains five-membered rings in the monomer units. The polymers with cis- or trans-five-membered rings are obtained selectively, depending on the complex used in the polymerization. The catalyst, prepared from the Co complex having a bis(imino)pyridine ligand and MMAO, promotes the polymerization of 2-aryl-1-methylenecyclopropanes without ring-opening. The reaction under ethylene atmosphere produces alternating copolymer of the two monomers to yield the polymers composed of the C4 repeating unit with a 1,1-cyclopropanediyl group. The alternating copolymer of ethylene and 7-methylenebicyclo[4.1.0]heptane undergoes thermal rearrangement to afford the polymer with CC double bond in main chain. A radical pathway is proposed. Dinuclear π-allylpalladium complexes with bridging Cl ligands initiate living polymerization of 2-alkoxy-1-methylenecyclopropanes, which accompanies ring-opening of the monomer, to afford the polymers composed of the C₃ repeating units having alkoxy and vinylidene groups. A cyclic dinuclear π-allylpalladium complex reacts with 2-alkoxy-1-methylenecyclopropane in the presence of pyridine to produce the living polymer with macrocyclic structures. Block copolymerization of the two monomers that contain OR or O(CH₂CH₂O)R as the substituents on the three-membered ring, results in the polymers with hydrophobic and hydrophilic segments.     

Hydrogen production from allothermal biomass gasification by means of palladium membranes

One of the most promising technologies for the production of hydrogen is the use of a Palladium Membrane in order to separate hydrogen from a gas mixture coming from the allothermal biomass gasification process. At the TU München, an innovative allothermal gasifier called Biomass Heat Pipe Reformer (BioHPR) has been developed. This gasifier produces a hydrogen rich gas which can be further used for energy production. A Palladium Membrane can be installed in the gasifier in order to gain pure hydrogen from this gas mixture. This gas can be then used in applications which demand high purified hydrogen like for example Polymer Electrolyte Membrane Fuel Cells (PEMFC). The present paper describes the aforementioned gasification technology combined with a palladium filter and investigates the results from the simulation of these systems.     

Advanced technology catalytic combustor for high temperature ground power gas turbine applications

We report results from a lean burn ultra-low emission catalytic combustor. In a sub-scale rig, atmospheric testing with methane demonstrated NO_x<3, CO<5, and UHC<1 ppm, with stable combustion at inlet temperatures of 400–500°C (750–1020°F) and combustor discharge temperatures of 1150–1540°C (2100–2800°F). Catalyst temperatures were held well below metal substrate material limits, while combustor discharge temperatures of up to 1540°C (2800°F) were achieved.     

Solute concentrations and stresses in nanograined H–Pd solid solution

In the present work, we applied the Gibbs-approach-based adsorption isotherm for nanograined polycrystals to H–Pd solid solutions. Using the published experimental data of lattice strain and sample strain of the nanograined Pd, with an average grain size of 10 nm and in thermodynamic equilibrium with an H₂ partial pressure, we determined H concentrations and stresses, as a function of the H₂ partial pressure, in both grains and grain boundaries. More importantly, we determined the intrinsic properties of grain boundaries, such as the grain boundary bulk modulus, the grain boundary excess thickness, and the difference in chemical potential between grains and grain boundaries. With the determined intrinsic properties, the Gibbs-approach-based adsorption isotherm predicted the segregation of H in grain boundaries of nanograined Pd with an average grain size of 5 nm. The predication was verified by other reported experimental data.