Life cycle of hydroprocessing catalysts and total catalyst management

Hydroprocessing catalysts based on Ni, Co, Mo and W are used in various refinery processing applications where several deactivation mechanisms become of importance (coke formation, active phase sintering, metals deposition, poisoning) in the catalyst's life cycle. The life cycle of commercial hydroprocessing catalysts is very complex and includes the catalyst production, sulfidation, use, oxidative regeneration followed by re-sulfidation and reuse or, if reuse is not possible, recycling or disposal. To understand the changes in catalyst properties taking place during a life cycle, the catalyst quality in the different stages can be best monitored by using advanced analytical techniques. The catalyst's life cycle is further complicated by numerous technical, environmental and organizational issues involved. In principle, different companies can be involved in each of the life cycle steps. Leading catalyst manufacturers, together with specialized firms, offer refineries a total catalyst management concept, starting with the purchase of the fresh catalyst and ending with its final recycling or disposal. Total catalyst management includes a broad range of services, ensuring optimal timing during the change-out process, reliable, smooth and safe operations, minimal downtime and maximum catalyst and unit performance.     

Hydroprocessing peculiarities of Fischer–Tropsch syncrude

When catalysts developed for crude oil hydroprocessing are used for syncrude, there are syncrude-specific peculiarities to consider. These relate to differences in the nature and abundance of heteroatoms, olefins, metal species, waxes and aqueous products. Some important aspects are (a) heat release during naphtha and distillate hydroprocessing is very high, but wax hydrocracking is almost isothermal; (b) syncrude is sulphur-free and the use of sulphided base-metal hydroprocessing catalysts require the addition of sulphur-containing compounds to the syncrude; (c) oxygenates strongly adsorb on some catalytic surfaces to affect catalytic behaviour; (d) carbonyl–carboxylic acid interconversion and water produced by hydrodeoxygenation (HDO) may result in catalyst degradation by acid and hydrothermal attack; (e) carboxylic acids in syncrude result in equipment corrosion and catalyst leaching; (f) metal carboxylates are the main metal-containing species in syncrude and are not removed by hydrodemetallation (HDM) catalysis, but by thermal decomposition.     

Hydroprocesssing of light gas oil — rape oil mixtures

Two series of experiments of hydroprocessing of light gas oil - rape oil mixtures were carried out. The reactor feed was composed of raw material: first series — 10 wt.% rape oil and 90 wt.% of diesel oil; second series — 20 wt.% rape oil and 80 wt.% of diesel oil.     

Hydroprocessing of Bio-Oils and Oxygenates to Hydrocarbons. Understanding the Reaction Routes

To produce diesel fuel from renewable organic material such as vegetable oils, it has for a number of years been known that triglycerides can be hydrogenated into linear alkanes in a refinery hydrotreating unit over conventional sulfided hydrodesulfurization catalysts. A number of new reactions occur in the hydrotreater, when a biological component is introduced, and experiments were conducted to obtain a more detailed understanding of these mechanisms. The reaction pathways were studied both in model compound tests and in real feed tests with mixtures of straight-run gas oil and rapeseed oil. In both sets of experiments, the hydrogenation of the oxygen containing compounds was observed to proceed either via a hydrodeoxygenation (HDO) route or via a decarboxylation route. The detailed pathway of the HDO route was further illuminated by studying the hydroprocessing of methyl laurate into n-dodecane. The observed reaction intermediates did not support a simple stepwise hydrogenation of the aldehyde formed after hydrogenation of the connecting oxygen in the ester. Instead, it is proposed that the aldehyde formed is enolized before further hydrogenation. The existence of an enol intermediate was further corroborated by the observation that a ketone lacking α-hydrogen (that cannot be directly enolized) had a much lower reactivity than a corresponding ketone with α-hydrogen. In real feed tests, the complete conversion of rapeseed oil into linear alkanes at mild hydrotreating conditions was demonstrated. From the gas and liquid yields, the relative rates of HDO and decarboxylation were calculated in good agreement with the observed distribution of the n-C₁₇/n-C₁₈ and n-C₂₁/n-C₂₂ formed. The hydrogen consumption associated with each route is deduced, and it was shown that hydrogen consumed in the water-gas-shift and methanization reactions may add significant hydrogen consumption to the decarboxylation route. The products formed exhibited high cetane values and low densities. The challenges of introducing triglycerides in conventional hydrotreating units are discussed. It is concluded that hydrotreating offers a robust and flexible process for converting a wide variety of alternative feedstocks into a green diesel fuel that is directly compatible with existing fuel infrastructure and engine technology.     

On the importance of calculating fresh-basis catalyst composition from spent catalyst analysis

The importance of expressing composition of used catalysts in fresh basis is highlighted in this work. Since catalysts are subject to changes during processing, e.g. coking and metal deposition, their composition varies depending on their state (fresh, spent, regenerated) and to properly determine catalyst life, composition needs to be changed to fresh-basis. Previous works are commented to demonstrate the current confusion existing in the literature when reporting metal content of used catalyst, and a simple approach is developed to change catalyst metal composition to fresh-basis.     

Experimental study on two-stage catalytic hydroprocessing of middle-temperature coal tar to clean liquid fuels

Special Mo–Co/γ-Al₂O₃ and W–Ni/γ-Al₂O₃ catalysts with different metal loadings were prepared applying new synthesis technologies that combine ultrasonic-assisted impregnation and temperature-programming methods. Clean liquid oil was obtained from middle-temperature coal tar via hydrogenation in two-stage fixed beds filled with the laboratory made catalysts. The Mo–Co/γ-Al₂O₃ catalyst with 12.59 wt.% Mo and 3.37 wt.% Co loadings, and the W–Ni/γ-Al₂O₃ catalyst with 15.75 wt.% W and 2.47 wt.% Ni loadings were selected. The effects of pressure and liquid hourly space velocity on hydrogenation performance were investigated while other experimental conditions remained constant. Gasoline (?180 °C) and diesel (180–360 °C) fractions were separated from the oil product and analyzed. The two-stage reacting system was capable of removing nitrogen and sulfur from 1.69 and 0.98 wt.% in the feed to less than 10 ppm and 100 ppm, respectively in the products. The results indicated that the raw coal tar could be considerably upgraded through catalytic hydroprocessing and high-quality fuels were obtained.     

MODELLING OF AXIALLY DISPERSED NON-ISOTHERMAL TUBULAR REACTORS FOR HYDROPROCESSING OF SOLID-LIQUID MIXTURES

A mathematical model for hydroprocessing of coal-oil slurries in non-isothermal, axially dispersed tubular reactors is developed and numerically solved, considering a five component-six reaction model representing the chemistry of the process, and, dispersive, corrective and interfacial mass and energy transfers. Several simulation results are presented.     

国产INCOLOY825高压空冷器的设计制造

国内自行设计制造的INCOLOY 825高压空冷器已应用在齐鲁石化公司胜利炼油厂1.5Mt/a(150万吨/年)渣油加氢脱硫(VRDS)装置中.与装置中原有的反应产物空冷器相比,空冷器翅片管以IN-COLOY 825合金为基管,增强了设备的防腐蚀性,延长了装置的运行周期并提高了操作可靠性.     

MODELING OF HYDROPROCESSING REACTIONS

Langmuir-Hinshelwood-Hougen-Watson rate expressions are developed for the hydroprocessing of quinoline, naphthalene and dibenzothiophene based on batch reactor data at 350^°C and at 500 psig. Based on competitive adsorption, the kinetics are extended to binary mixtures of quinoline/naphtha-lene and quinoline/dibenzothiophene. In doing so, the differences in hydrogenation and hydro-genolysis sites are taken into consideration. In all cases, the agreement between the predicted and experimental results are good