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: A fluidized catalytic cracking unit (FCCU) is one of the effective units in many refineries. Modeling and optimization of FCCU were done by many researchers in past decades, but in this research, comparison between post- and oxy-combustion was studied in the regenerator-FCCU. Therefore, a simplified mathematical model was derived by doing mass/heat balances around both reactor and regenerator. A state space analysis was employed to show effects of the flow rates variables such as air, feed, spent catalyst, regenerated catalyst and flue gas on the output variables. The main aim of studying dynamic responses is to figure out the most influencing variables that affect both reactor/regenerator temperatures; also, finding the upper/lower limits of the influencing variables to ensure that temperatures of the reactors and regenerator work within normal operating conditions. Therefore, those values will be used as side constraints in the optimization technique to find appropriate operating regimes. The objective functions were modeled to be maximizing the energy in the reactor while minimizing the energy consumption in the regenerator. In conclusion, an oxy-combustion process can be used instead of a post-combustion one.
Abstract: Catalysts play an important role in producing valuable fuel products in petroleum refining; but, due to feedstock’s impurities catalyst gets deactivated with carbon and metal deposition. The disposal of spent catalyst falls under the category of hazardous industrial waste that requires strict agreement with environmental regulations. The spent hydroprocessing catalyst contains Mo, V and Ni at high concentrations that have been found to be economically significant for recovery. Metal recovery process includes deoiling, decoking, grinding, dissolving and treatment with complexing leaching agent such as ethylene diamine tetra acetic acid (EDTA). The process conditions have been optimized as a function of time, temperature and EDTA concentration in presence of ultrasonic agitation. The results indicated that optimum condition established through this approach could recover 97%, 94% and 95% of the extracted Mo, V and Ni, respectively, while 95% EDTA was recovered after acid treatment.
Abstract: In recent years, different petrochemical complexes have been established to produce aromatic compounds. Among them, Nouri Petrochemical Complex (NPC) is the largest producer of aromatic raw materials in the world, and is located in south of Iran. Environmental concerns have been raised in this region due to generation of different types of solid waste generated in the process of aromatics production, and subsequently, industrial waste characterization has been thoroughly considered. The aim of this study is qualitative and quantitative characterization of industrial waste generated in the aromatics production process and determination of the best method for industrial waste management. For this purpose, all generated industrial waste during the production process was determined using a checklist. Four main industrial wastes were identified as follows: spent industrial soil, spent catalyst, spent molecular sieves and spent N-formyl morpholine (NFM) solvent. The amount of heavy metals and organic compounds in these wastes were further measured in order to identify the nature and toxicity of such a dangerous compound. Then industrial wastes were classified based on lab analysis results as well as using different international lists of hazardous waste identification such as EPA, UNEP and Basel Convention. Finally, the best method of waste disposal is selected based on environmental, economic and technical aspects.
Abstract: The effect of additional magnesium oxide (MgO) was
investigated by using the tungsten oxide supported on silica catalyst
(WOx/SiO2) physically mixed with MgO in a weight ratio 1:1. The
both fresh and spent catalysts were characterized by FT-Raman
spectrometer, UV-Vis spectrometer, X-Ray diffraction (XRD) and
temperature programmed oxidation (TPO). The results indicated that
the additional MgO could enhance the conversion of trans-2-butene
due to isomerization reaction. However, adding MgO would increase
the amount of coke deposit on the WOx/SiO2 catalyst. The TPO
profile presented two peaks when the WOx/SiO2 catalyst was
physically mixed with MgO. The further peak was suggested that
came from coke precursor could be produced by isomerization
reaction of undesired product. Then, the occurred coke precursor
could deposit and form coke on the acid catalyst.
Abstract: Co metal supported on SiO2 and Al2O3 catalysts with
a metal loading varied from 30 of 70 wt.% were evaluated for
decomposition of methane to COx free hydrogen and carbon
nanomaterials. The catalytic runs were carried out from 550-800oC
under atmospheric pressure using fixed bed vertical flow reactor. The
fresh and spent catalysts were characterized by BET surface area
analyzer, XRD, SEM, TEM and TG analysis. The data showed that
50% Co/Al2O3 catalyst exhibited remarkable higher activity at 800oC
with respect to H2 production compared to rest of the catalysts.
However, the catalytic activity and durability was greatly declined at
higher temperature. The main reason for the catalytic inhibition of Co
containing SiO2 catalysts is the higher reduction temperature of
Co2SiO4. TEM images illustrate that the carbon materials with
various morphologies, carbon nanofibers (CNFs), helical-shaped
CNFs and branched CNFs depending on the catalyst composition and
reaction temperature were obtained.
Abstract: Nanostructured catalysts were successfully prepared
by acidification of diatomite and regeneration of FCC spent catalysts.
The obtained samples were characterized by IR, XRD, SEM, EDX,
MAS-NMR (27Al and 29Si), NH3-TPD and tested in catalytic
pyrolysis of biomass (rice straw). The results showed that the similar
bio-oil yield of 41.4% can be obtained by pyrolysis with catalysts at
450oC as compared to that of the pyrolysis without catalyst at 550oC.
The bio-oil yield reached a maximum of 42.55% at the pyrolysis
temperature of 500oC with catalytic content of 20%. Moreover, by
catalytic pyrolysis, bio-oil quality was better as reflected in higher
ratio of H/C, lower ratio of O/C. This clearly indicated high
application potential of these new nanostructured catalysts in the
production of bio-oil with low oxygenated compounds.
Abstract: The present investigation deals with bioleaching of spent petroleum catalyst using At. ferrooxidans and At. thiooxidans. The spent catalyst used in the present study was pretreated with acetone to remove the oily hydrocarbons. FESEM and XPS analysis indicated the presence of metals in sulfide and oxide forms in spent catalyst. Both At. ferrooxidans and At. thiooxidans were found to be highly effective in producing the acid. Bioleaching with At. ferrooxidans and At. thiooxidans led to higher recovery of metals compare to control. During bioleaching similar recoveries of metals were obtained using At. ferrooxidans and At. thiooxidans. This might be due to the presence of metals as soluble oxides and sulphides in the spent catalyst. At the end of bioleaching, about 87-90% Ni, 34% Al, 65-73% Mo and 92-97% V were leached using above bacteria. It is elucidated that bioleaching with At. thiooxidans is comparatively more advantageous due to lower cost of sulphur.
Abstract: This study investigates the in-situ regeneration of deactivated Pt-Pd catalyst in a laboratory-scale catalysis reactor. Different regeneration conditions are tested and the activity and characteristics of regenerated catalysts are analyzed. Experimental results show that the conversion efficiencies of C3H6 by different regenerated Pt-Pd catalysts were significantly improved from 77%, 55% and 41% to 86%, 98% and 99%, respectively. The best regeneration conditions was 52ppm ozone, 500oC, and 10min. Regeneration temperature has more influences than ozone concentration and regeneration time. With the comparisons of characteristics of deactivated catalyst and regenerated catalyst, the major poison species (carbon, metals, chloride, and sulfate) on the spent catalysts can be effectively removed by ozone regeneration.
Abstract: Bioleaching of spent catalyst using moderate thermophilic chemolithotrophic acidophiles in growth medium without Fe source was investigated with two different pulp densities and three different size fractions. All the experiments were conducted on shake flasks at a temperature of 65 °C. The leaching yield of Ni and Al was found to be promising with very high leaching yield of 92-96% followed by Al as 41-76%, which means both Ni and Al leaching were favored by the moderate thermophilic bioleaching compared to the mesophilic bioleaching. The acid consumption was comparatively higher for the 10% pulp density experiments. Comparatively minimal difference in the leaching yield with different size fractions and different pulp densities show no requirement of grinding and using low pulp density less than 10%. This process would rather be economical as well as eco-friendly process for future optimization of the recovery of metal values from spent catalyst.
Abstract: In this study, the transesterification of palm oil with methanol for biodiesel production was studied by using CaO–ZnO as a heterogeneous base catalyst prepared by incipient-wetness impregnation (IWI) and co-precipitation (CP) methods. The reaction parameters considered were molar ratio of methanol to oil, amount of catalyst, reaction temperature, and reaction time. The optimum conditions–15:1 molar ratio of methanol to oil, a catalyst amount of 6 wt%, reaction temperature of 60 °C, and reaction time of 8 h–were observed. The effects of Ca loading, calcination temperature, and catalyst preparation on the catalytic performance were studied. The fresh and spent catalysts were characterized by several techniques, including XRD, TPR, and XRF.
Abstract: The recovery of metal values and safe disposal of
spent catalyst is gaining interest due to both its hazardous nature and
increased regulation associated with disposal methods. Prior to the
recovery of the valuable metals, removal of entrained deposits limit
the diffusion of lixiviate resulting in low recovery of metals must be
taken into consideration. Therefore, petroleum refinery spent catalyst
was subjected to acetone washing and roasting at 500oC. The treated
samples were investigated for metals bioleaching using
Acidithiobacillus ferrooxidans in batch reactors and the leaching
efficiencies were compared. It was found out that acetone washed
spent catalysts results in better metal recovery compare to roasted
spent. About 83% Ni, 20% Al, 50% Mo and 73% V were leached
using the acetone washed spent catalyst. In both the cases, Ni, V and
Mo was high compared to Al.
Abstract: In this study, the ability of Aspergillus niger and
Penicillium simplicissimum to extract heavy metals from a spent
refinery catalyst was investigated. For the first step, a spent
processing catalyst from one of the oil refineries in Iran was
physically and chemically characterized. Aspergillus niger and
Penicillium simplicissimum were used to mobilize Al/Co/Mo/Ni from
hazardous spent catalysts. The fungi were adapted to the mixture of
metals at 100-800 mg L-1 with increments in concentration of 100 mg
L-1. Bioleaching experiments were carried out in batch cultures. To
investigate the production of organic acids in sucrose medium,
analyses of the culture medium by HPLC were performed at specific
time intervals after inoculation. The results obtained from Inductive
coupled plasma-optical emission spectrometry (ICP-OES) showed
that after the one-step bioleaching process using Aspergillus niger,
maximum removal efficiencies of 27%, 66%, 62% and 38% were
achieved for Al, Co, Mo and Ni, respectively. However, the highest
removal efficiencies using Penicillium simplicissimum were of 32%,
67%, 65% and 38% for Al, Co, Mo and Ni, respectively
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.