A Model of Catalytic Cracking: Catalyst Deactivation Induced by Feedstock and Process Variables

Changes in the quality of the feedstocks generated by involving various petroleum fractions in catalytic cracking significantly affect catalyst deactivation, which stems from coke formed on the catalyst surface. By conducting experimental studies on feedstocks and catalysts, as well as using industrial data, we studied how the content of saturates, aromatics and resins (SAR) in feedstock and the main process variables, including temperature, consumptions of the feedstock, catalyst and slops, influence the formation of catalytic coke. We also determined catalyst deactivation patterns using TG-DTA, N2 adsorption and TPD, which were further used as a basis for a kinetic model of catalytic cracking. This model helps predict the changes in reactions rates caused by coke formation and, also, evaluates quantitatively how group characteristics of the feedstock, the catalyst-to-oil ratio and slop flow influence the coke content on the catalyst and the degree of catalyst deactivation. We defined that a total loss of acidity changes from 8.6 to 30.4 wt% for spent catalysts, and this depends on SAR content in feedstock and process variables. The results show that despite enriching the feedstock by saturates, the highest coke yields (4.6–5.2 wt%) may be produced due to the high content of resins (2.1–3.5 wt%).

Studies on the Formation of Catalytically Active PGM Nanoparticles from Model Solutions as a Basis for the Recycling of Spent Catalysts

The paper presents basic studies on the precipitation of platinum, palladium, rhodium, and ruthenium nanoparticles from model acidic solutions using sodium borohydride, ascorbic acid, and sodium formate as reducing agents and polyvinylpyrrolidone as a stabilizing agent. The size of the obtained PGM particles after precipitation with NaBH4 solution does not exceed 55 nm. NaBH4 is an efficient reducer; the precipitation yields for Pt, Pd, Ru, Rh are 75, 90, 65 and 85%, respectively. By precipitation with ascorbic acid, it is possible to efficiently separate Pt, Rh, and Ru from Pd from the two-component mixtures. The obtained Pt, Pd, and Rh precipitates have the catalytic ability of the catalytic reaction of p-nitrophenol to p-aminophenol. The morphological characteristic of the PGM precipitates was analyzed by AFM, SEM-EDS, and TEM.

Study of Nickel Extraction Process from Spent Catalysts with Hydrochloric Acid Solution: Effect of Temperature and Kinetics Study

As one of the hazardous and toxic solid wastes, spent catalysts need to be treated before the waste is discharged into the environment. One of the substances that need to be removed from the spent catalysts is the heavy metal ions and/or compounds contained therein. The method that can be applied is the extraction method using an acid solvent. In this study, the extraction process was carried out on spent catalysts samples from PT. Petrokimia Gresik. The focus of the study is on nickel extraction by varying the temperature in the range of 30–85 oC. A 1 M hydrochloric acid (HCl) solution was used as a solvent while the extraction process was 120 minutes. The experimental results show that the maximum nickel recovery of 14.70% can be achieved at a temperature of 85 oC. Kinetic studies were carried out using two kinetic models. The results of both models evaluation on the research data show that the lump model gives better results than the shrinking core model. The average error percentage of the lump model is smaller than the shrinking core model. It indicates that the extraction process was controlled by the diffusion step through the ash layer in the solid and chemical reactions simultaneously.

Hydrometallurgical process development to recycle valuable metals from spent SCR deNOX catalyst

Spent catalyst, containing vanadium and tungsten oxide in a TiO2 glass fiber matrix, pose a risk of environmental contamination due to the high toxicity of its metal oxides if leached into the soil when disposed in landfills. Due to the increasing demand of metals and the continuous depletion of primary resources there is an growing necessity for recycling and reprocessing of spent catalysts and other secondary metal sources for environmental and economical reasons. Study of spent SCR catalyst soda roasting process with dissolved NaOH compared with the usual NaOH dry roasting and its influence in the subsequent water leaching. After optimization, the ideal parameters are roasting using a 0.4 ratio of NaOH/spent SCR catalyst in solution for 2 h at 973 K and de-ionized water leaching for 30 min, at 298 K with a pulp density of 30%. The research results show an important reduction of the roasting temperature and leaching time during the processing of spent SCR catalyst obtaining a 95.4% W and 80.2% V leaching efficiency liquor. Silicon compounds are one of the main impurities leached alongside the valuable metals and in this work, the silicon compounds leached are reduced significantly with the aim of avoiding the de-silication post-processing of the leach liquor. The main advantage of the proposed process is the increase of the leaching efficiency of vanadium and tungsten with a minimization of silicon impurities in a shorter time regardless of the leaching temperature.

Recovery of cobalt and molybdenum from spent catalyst using citric acid

Valuable metals play essential roles in various industrial sectors, such as petroleum, petrochemical, and steel industries. Potential secondary resources of these metals can be obtained from spent catalysts, which are a solid waste of the chemical and oil industries. Spent catalysts contain valuable metal compounds such as nickel (Ni), vanadium (V), cobalt (Co), molybdenum (Mo), rhodium (Rh), platinum (Pt), alumina (Al), etc. In this research, the recovery of cobalt and molybdenum from the spent catalyst of Pertamina Refinery Unit IV, Cilacap, Indonesia, was leaching using citric acid. Samples of spent catalyst were analyzed using EDXRF prior to the leaching process. Citric acid at various concentrations of 1.0, 1.5 and 2 M was used as a leaching agent. The leaching experiment was carried out for 300 minutes and sampling was undertaken at 1, 3, 5, 15, 30, 90 and 300 minutes. Each sample was separated between solid and liquid phases using a centrifuge at 400 rpm for 10 minutes. For analysis, 2 ml of the liquid phase was taken and the cobalt and molybdenum concentrations were analyzed using ICP-OES. It was found that at higher the citric acid concentration and temperature, the recovery of cobalt and molybdenum was also higher. The best leaching condition is obtained at a citric acid concentration of 2 M and 60ºC, where recovery of cobalt and molybdenum were 17.35% and 2.27%, respectively.

CATALYST PROCESSING AND RECYCLING

Discussed auto catalysts contain interesting quantities of platinum noble metals, palladium and rhodium according to the type of auto catalyst, thereby becoming a possible source of these metal aims to acquaint themselves with catalysts in general, their history and last but not least the possibilities of processing and obtaining noble metals for further use. The article deals with knowledge at the theoretical level of use of methods in processing depleted catalysts. It is pyrometallurgical and hydrometallurgical methods. The platinum group metals (PGMs) palladium, platinum, and rhodium represent the key materials for automotive exhaust gas treatment. Since there are currently no adequate alternatives, the importance of these metals for the automotive industry is steadily rising. The high value of PGMs in spent catalysts justifies their recycling. The state-of the-art technology is to melt the ceramic carrier and collect the precious fraction in a liquid metal bath. As the feed material has quite high melting points, huge amounts of energy are required for this process. Hydrometallurgical treatments of the spent catalysts offer the possibility to recycle the PGMs with less energy and time demands. Moreover, automotive catalysts contain further valuable materials to improve the exhaust gas treatment. These compounds, like cerium oxide, cannot be recovered in pyrometallurgical processes.

Towards Understanding the Cathode Process Mechanism and Kinetics in Molten LiF–AlF3 during the Treatment of Spent Pt/Al2O3 Catalysts

Electrochemical decomposition of spent catalyst dissolved in molten salts is a promising approach for the extraction of precious metals from them. This article reports the results of the study of aluminum electrowinning from the xLiF–(1-x)AlF3 melt (x = 0.64; 0.85) containing 0–5 wt.% of spent petroleum Pt/γ-Al2O3 catalyst on a tungsten electrode at 740–800 °C through cyclic voltammetry and chronoamperometry. The results evidence that the aluminum reduction in the LiF–AlF3 melts is a diffusion-controlled two-step process. Both one-electron and two-electron steps occur simultaneously at close (or same) potentials, which affect the cyclic voltammograms. The diffusion coefficients of electroactive species for the one-electron process were (2.20–6.50)∙10−6 cm2·s–1, and for the two-electron process, they were (0.15–2.20)−6 cm2·s−1. The numbers of electrons found from the chronoamperometry data were in the range from 1.06 to 1.90, indicating the variations of the partial current densities of the one- and two-electron processes. The 64LiF–36AlF3 melt with about 2.5 wt.% of the spent catalysts seems a better electrolyte for the catalyst treatment in terms of cathodic process and alumina solubility, and the range of temperatures from 780 to 800 °C is applicable. The mechanism of aluminum reduction from the studied melts seems complicated and deserves further study to find the optimal process parameters for aluminum reduction during the spent catalyst treatment and the primary metal production as well.

Extraction of the Rare Element Vanadium from Vanadium-Containing Materials by Chlorination Method: A Critical Review

Vanadium as a rare element has a wide range of applications in iron and steel production, vanadium flow batteries, catalysts, etc. In 2018, the world’s total vanadium output calculated in the form of metal vanadium was 91,844 t. The raw materials for the production of vanadium products mainly include vanadium-titanium magnetite, vanadium slag, stone coal, petroleum coke, fly ash, and spent catalysts, etc. Chlorinated metallurgy has a wide range of applications in the treatment of ore, slag, solid wastes, etc. Chlorinating agent plays an important role in chlorination metallurgy, which is divided into solid (NaCl, KCl, CaCl2, AlCl3, FeCl2, FeCl3, MgCl2, NH4Cl, NaClO, and NaClO3) and gas (Cl2, HCl, and CCl4). The chlorination of vanadium oxides (V2O3 and V2O5) by different chlorinating agents was investigated from the thermodynamics. Meanwhile, this paper summarizes the research progress of chlorination in the treatment of vanadium-containing materials. This paper has important reference significance for further adopting the chlorination method to treat vanadium-containing raw materials.