Studies on recycling and utilization of spent catalysts: Preparation
of active hydrodemetallization catalyst compositions from
spent residue hydroprocessing catalysts
Spent catalysts form a major source of solid wastes in the petroleum re\ufb01ning industries. Due to environmental concerns, increasing emphasis has been placed on the development of recycling processes for the waste catalyst materials as much as possible. In the present study the potential reuse of spent catalysts in the preparation of active new catalysts for residual oil hydrotreating was examined. A series of catalysts were prepared by mixing and extruding spent residue hydroprocessing catalysts that contained C, V, Mo, Ni and Al2O3with boehmite in different proportions. All prepared catalysts were characterized by chemical analysis and by surface area, pore volume, pore size and crushing strength measurements. The hydrodesulfurization (HDS) and hydrodemetallization (HDM) activities of the catalysts were evaluated by testing in a high pressure \ufb01xed-bed microreactor unit using Kuwait atmospheric residue as feed. A commercial HDM catalyst was also tested under similar operating conditions and their HDS and HDM activities were compared with that of the prepared catalysts. The results revealed that catalyst prepared with addition of up to 40 wt% spent catalyst to boehmite had fairly high surface area and pore volume together with large pores. The catalyst prepared by mixing and extruding about 40 wt% spent catalyst with boehmite was relatively more active for promoting HDM and HDS reactions than a reference commercial HDM catalyst. The formation of some kind of new active sites from the metals (V, Mo and Ni) present in the spent catalyst is suggested to be responsible for the high HDM activity of the prepared catalyst.
Large quantities of catalysts are used in the petroleum re\ufb01ning industry for the puri\ufb01cation and upgrading of various petroleum streams and residues. The catalysts deactivate with time and when the activity of the catalyst declines below the acceptable level, it is usually regenerated and reused. But, regeneration is not always possible[1,2] and after a few cycles of regeneration and reuse, the catalyst activity may decrease to very low levels and further regeneration may not be economically feasible. The spent catalysts are discarded as solid wastes[3,4]. The quantity of spent catalysts discharged from different processing units depends largely on the amount of fresh catalysts used, their life and on the amount of the
deposits formed on them during use in the reactors. In most re\ufb01neries, a major portion of the spent catalyst waste comes from the residue hydrotreating and hydroprocessing units. This is because the catalysts used in these processes deactivate rapidly by coke and metal (V and Ni) deposits, and have a short life[5\u20137]. Furthermore, technology for regeneration and reactivation of the catalysts deactivated by metal fouling is not available to the re\ufb01ners.
The volume of spent hydroprocessing catalysts discarded as solid wastes has increased signi\ufb01cantly in recent years due to a steady increase in the processing of heavier feedstocks containing higher sulfur, nitrogen and metal (V and Ni) contents together with a rapid growth in diesel hydrotreating capacity to meet the increasing demand for low sulfur fuels. At the same time, environmental laws concerning spent catalyst disposal have become increasingly more severe in recent years. Spent hydroprocessing catalysts have been classi\ufb01ed as hazardous wastes by the Environmental Protection Agency
in the USA[8,9]. The most important hazardous characteristic of spent hydroprocessing catalysts is their toxic nature. Chemicals such as V, Ni, Mo and Co present in the catalyst can be leached by water after disposal and pollute the environment.
The hazardous nature of the spent catalysts is attracting the attention of environmental authorities in many countries and the re\ufb01ners are experiencing pressures from environmental authorities for safe handling of spent catalysts. Several alternative methods such as disposal in land\ufb01lls, reclamation of metals, regeneration/rejuvenation and reuse, and utilization as raw materials to produce other useful products are available to the re\ufb01ners to deal with the spent catalyst problem[3,4,10\u2013
In recent years, increasing emphasis has been placed on the development of processes for recycling the waste catalyst materials as much as possible. Utilization of spent catalysts as raw materials in the production of other valuable products is an attractive option for recycling spent catalysts from environ- mental and economical points of view. Spent \ufb02uid catalytic cracking (FCC) catalysts have been successfully used in cement production[13,14]. Recently, a process for making highly stabilized non-leachable ceramic materials from spent catalysts has been reported by Sun et al.. A few studies on the preparation of active catalysts from spent catalysts for various applications have been reported in the literature. Lee et al. reported that active reforming catalysts can be prepared using the V, Ni and Mo containing extract obtained by leaching spent catalysts with citric acid. Furimsky found that spent Co\u2013 Mo/Al2O3and Ni\u2013Mo/Al2O3catalysts, after regeneration, can catalyze the decomposition of H2S. In a recent patented process, Choi et al. used spent hydroprocessing catalysts to prepare active catalysts for reduction of nitrogen oxides. The use of spent catalysts in preparation of active hydrotreating catalysts, have been reported in a few earlier studies[19,20]. However, the spent catalysts used in these earlier works were from petroleum distillates hydrotreating units and contained Mo, Co and Al2O3without V and Ni.
Spent catalyst handling and utilization has been the subject of some investigation in our laboratory. In most of the previous studies, rejuvenation of spent residue hydroprocessing catalysts for reuse was addressed[21\u201327]. In the present work, utilization of spent residue hydroprocessing catalysts contain- ing high levels of V and coke together with Mo, Ni and Al2O3in the preparation of active hydrodemetallization (HDM) catalysts has been considered. HDM catalysts are used in the front end reactors of petroleum residue hydrotreating processes to remove the metals such as V and Ni that are present in the residual oil. The catalyst usually possesses high activity for promoting HDM reactions together with some activity for sulfur removal by hydrodesulfurization (HDS) reaction. The catalysts were prepared by mixing and extruding the spent catalyst powder with boehmite in different percentages, and the effect of mix ratio between spent catalyst and boehmite on the key catalyst properties such as surface area, pore volume, pore size distribution and the metals (V, Mo and Ni) content of the
prepared catalyst samples was examined. The HDM and HDS activities of the catalysts were tested in a high pressure \ufb01xed- bed microreactor unit using Kuwait atmospheric residue as feed and compared with that of a commercial HDM catalyst.
catalyst extrudates from spent catalyst\u2013boehmite mix in the present work are shown inFig. 1. Boehmite used in the catalyst preparation experiments were obtained from Sasol, Germany. Spent catalyst was obtained from Kuwait National Petroleum Company (KNPC). The spent catalyst was \ufb01rst washed with naphtha and then extracted with toluene in a soxhlet apparatus to remove the residual oil. The oil free-spent catalyst was ground to \ufb01ne powder in a grinding machine (Christison Particle Technologies Ltd., Model KM 100) and then sieved using a sieve shaker (Endecotts, model OCT Digital 4587-01) with appropriate sieves obtain particle sizes in the range 25\u2013 90mm similar to that of the boehmite powder. The chemical and physical properties of the oil-free spent catalyst powder were analyzed by various techniques. The characteristic of the spent catalyst are shown inTable 1.
A laboratory kneading and extrusion machine (Type: LUK 2.5 AS) manufactured by Werner and P\ufb02eiderer Gmbh & Co., Germany, was used for the preparation of catalyst extrudates from spent catalyst\u2013boehmite mixtures. It contained a mixing chamber, two blades for mixing, and a drive unit with two three- phase motors and gears, and a discharge screw.
experiment. Then 185 ml of dilute nitric acid (e.g., 2%), as a peptizing reagent, was added in drops at a constant rate to the boehmite powder, and the two were mixed and kneaded. The blades in the mixing chamber were counter rotating and turned at different speeds. They were designed and arranged for intensive mixing and kneading of the boehmite with the nitric acid to form a good, extrudable paste. At the end of the mixing and kneading time (20\u201330 min), the product was extruded by means of the discharge screw through a die containing several holes (1.5 mm in diameter) to form catalyst extrudates. The extrudates were dried at 1108C in an oven for 24 h. The dried extrudates were calcined at 3708C for 2 h, 4508C for 3 h and 5008C for 2 h. After calcinations the prepared extrudates were cooled in desiccators and characterized.
The concentrations of V, Mo, and Ni in the spent catalyst and in the prepared catalyst samples were determined by inductively coupled plasma atomic emission spectroscopy (Varian Liberty II ICP-AES). A scanning electron microprobe X-ray analyzer (model: EPMA JXA 8600MX) from Joel was used for measuring the distribution pro\ufb01les of the metals across the catalyst pellets. Surface areas of the catalysts were determined by BET method using an autosorb adsorption unit manufactured by Quantachrome Corporation, USA. A mercury porosimeter (Quantachrome Poremaster-60) was used for pore volume and pore size distribution determination in catalyst samples. The method involves intrusion of mercury into the pores at high pressures of up to 60,000 psi. A side crushing strength measuring apparatus designed and manufactured by AKZO Nobel (Model No. 120794-108) was used to determine the side crushing strength of the catalyst pellets.
Hydrotreating activities of the prepared catalysts were tested in a high pressure \ufb01xed bed microreactor unit using Kuwait atmospheric residue as feed. The feedstock contained 4.3 wt% sulfur, 0.27 wt% nitrogen, 69 ppm vanadium, 21 ppm nickel, 3.6 wt% asphaltenes and 12.4 wt% CCR. Thirty millilitres of the catalyst diluted with an equal amount of carborundum was used for each run. The catalysts were presul\ufb01ded using 1% CS2 in straight run gas oil by a standard procedure, before introducing the feed. After presul\ufb01ding, the test conditions were adjusted to desired operating temperature, pressure, hydrogen to oil ratio and liquid hourly space velocity (LHSV).
For each run, product samples were collected every 24 h for analysis of S and metals (Ni, V) content. Sulfur content was determined using an Oxford Model 3000 XRF instrument. The concentrations of V and Ni in the oil were determined without ashing using a Varian Liberty Series II, ICP spectrophotometer.
The catalyst extrudates prepared with the addition of spent catalyst to boehmite in different proportions were subjected to chemical analysis to determine the concentration of Mo, Ni and V in them. The results are plotted inFig. 2. It is seen that the concentration of the metals in the prepared catalysts increases linearly with increasing percentage of spent catalyst in the mix. A larger increase is noticed for V than the other metals. A catalyst prepared from a mix containing 20% spent catalyst and 80% boehmite contains 1.84% V, 0.91% Mo and 0.77% Ni. Increasing the amount of spent catalyst in the mix from 20 to 40% increases the V content to 3.8% whereas, the Mo and Ni concentrations increase to 1.85% and 1.47%, respectively. These results are consistent with the higher concentration of V than Mo and Ni in spent catalyst (Table 1).
The distribution pro\ufb01les of vanadium, and nickel within the pellets of spent catalyst and in the extrudates prepared by mixing different percentages of spent catalyst with boehmite are shown inFig. 3a and b. It is seen that in the spent catalyst vanadium concentration is more near the outer edges than at the center of the pellet. Nickel distribution in the spent catalyst is more uniform than that of vanadium. In the prepared catalyst extrudates high edge concentration of vanadium is not seen, and
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