Abstract: Spent catalysts are considered as hazardous residues of major concern, mainly due to the simultaneous presence of several metals in elevated concentrations. Although hydrometallurgical, pyrometallurgical and chelating agent methods are available to remove and recover some metals contained in spent catalysts; these procedures generate potentially hazardous wastes and the emission of harmful gases. Thus, biotechnological treatments are currently gaining importance to avoid the negative impacts of chemical technologies. To this end, diverse microorganisms have been used to assess the removal of metals from spent catalysts, comprising bacteria, archaea and fungi, whose resistance and metal uptake capabilities differ depending on the microorganism tested. Acidophilic sulfur oxidizing bacteria have been used to investigate the biotreatment and extraction of valuable metals from spent catalysts, namely Acidithiobacillus thiooxidans and Acidithiobacillus ferroxidans, as they present the ability to produce leaching agents such as sulfuric acid and sulfur oxidation intermediates. In the present work, the ability of A. thiooxidans DSM 26636 for the bioleaching of metals contained in five different spent catalysts was assessed by growing the culture in modified Starkey mineral medium (with elemental sulfur at 1%, w/v), and 1% (w/v) pulp density of each residue for up to 21 days at 30 °C and 150 rpm. Sulfur-oxidizing activity was periodically evaluated by determining sulfate concentration in the supernatants according to the NMX-k-436-1977 method. The production of sulfuric acid was assessed in the supernatants as well, by a titration procedure using NaOH 0.5 M with bromothymol blue as acid-base indicator, and by measuring pH using a digital potentiometer. On the other hand, Inductively Coupled Plasma - Optical Emission Spectrometry was used to analyze metal removal from the five different spent catalysts by A. thiooxidans DSM 26636. Results obtained show that, as could be expected, sulfuric acid production is directly related to the diminish of pH, and also to highest metal removal efficiencies. It was observed that Al and Fe are recurrently removed from refinery spent catalysts regardless of their origin and previous usage, although these removals may vary from 9.5 ± 2.2 to 439 ± 3.9 mg/kg for Al, and from 7.13 ± 0.31 to 368.4 ± 47.8 mg/kg for Fe, depending on the spent catalyst proven. Besides, bioleaching of metals like Mg, Ni, and Si was also obtained from automotive spent catalysts, which removals were of up to 66 ± 2.2, 6.2±0.07, and 100±2.4, respectively. Hence, the data presented here exhibit the potential of A. thiooxidans DSM 26636 for the simultaneous bioleaching of metals contained in spent catalysts from diverse provenance.
Abstract: 36 strains of sulfur-oxidizing bacteria were isolated in
Southern Kazakhstan soda-saline soils and identified. Screening of
strains according bio-oxidation (destruction thiosulfate to sulfate) and
enzymatic (Thiosulfate dehydrogenises and thiosulfate reductase)
activity was conducted. There were selected modes of aeration and
culture conditions (pH, temperature), which provide optimum harvest
cells. These strains can be used in bio-melioration technology.
Abstract: Selective oxidation of H2S to elemental sulfur in a
fixed bed reactor over newly synthesized alumina nanocatalysts was
physio-chemically investigated and results compared with a
commercial Claus catalyst. Amongst these new materials, Al2O3-
supported sodium oxide prepared with wet chemical technique and
Al2O3 nanocatalyst prepared with spray pyrolysis method were the
most active catalysts for selective oxidation of H2S to elemental
sulfur. Other prepared nanocatalysts were quickly deactivated,
mainly due to the interaction with H2S and conversion into sulfides.
Abstract: In this research a mathematical model for direct
oxidization of hydrogen sulfide into elemental sulfur in a fluidized
bed reactor with external circulation was developed. As the catalyst
is deactivated in the fluidized bed, it might be placed in a reduction
tank in order to remove sulfur through heating above its dew point.
The reactor model demonstrated via MATLAB software. It was
shown that variations of H2S conversion as well as; products formed
were reasonable in comparison with corresponding results of a fixed
bed reactor. Through analyzing results of this model, it became
possible to propose the main optimized operating conditions for the
process considered. These conditions included; the temperature range
of 100-130ºC and utilizing the catalyst as much as possible providing
the highest bed density respect to dimensions of bed, economical
aspects that the bed ever remained in fluidized mode. A high active
and stable catalyst under the optimum conditions exhibited 100%
conversion in a fluidized bed reactor.
Abstract: The modified Claus process is the major technology
for the recovery of elemental sulfur from hydrogen sulfide. The
chemical reactions that can occur in the reaction furnace are
numerous and many byproducts such as carbon disulfide and carbon
carbonyl sulfide are produced. These compounds can often contribute
from 20 to 50% of the pollutants and therefore, should be hydrolyzed
in the catalytic converter. The inlet temperature of the first catalytic
reactor should be maintained over than 250 °C, to hydrolyze COS
and CS2. In this paper, the various configurations for the first
converter reheating of sulfur recovery unit are investigated. As a
result, the performance of each method is presented for a typical
clause unit. The results show that the hot gas method seems to be
better than the other methods.
Abstract: Spent petroleum catalyst from Korean petrochemical
industry contains trace amount of metals such as Ni, V and Mo.
Therefore an attempt was made to recover those trace metal using
bioleaching process. Different leaching parameters such as Fe(II)
concentration, pulp density, pH, temperature and particle size of
spent catalyst particle were studied to evaluate their effects on the
leaching efficiency. All the three metal ions like Ni, V and Mo
followed dual kinetics, i.e., initial faster followed by slower rate. The
percentage of leaching efficiency of Ni and V were higher than Mo.
The leaching process followed a diffusion controlled model and the
product layer was observed to be impervious due to formation of
ammonium jarosite (NH4)Fe3(SO4)2(OH)6. In addition, the lower
leaching efficiency of Mo was observed due to a hydrophobic coating
of elemental sulfur over Mo matrix in the spent catalyst.