Reactors catalyst deactivation

An indirect hydrogenation process that is still under development is catalytic gasification. In this process, a catalyst accelerates the gasification reactions, resulting in the formation of hydrogen and CO, at relatively low temperatures. This process also promotes catalytic formation of methane at the same low temperature within the same reactor. Catalyst deactivation and costs have been a major impediment to the commercialization of this process. 

The liquid phase Friedel-Crafts acylation of thioanisole with iso-butyric anhydride to produce 4-methyl thiobutyrophenone has been studied using supported silicotungstic acid catalysts. Reaction is rapid, giving the para-acylation product in high yield. Reactions have been performed in both batch slurry and trickle bed reactors. In both reactors catalyst deactivation due to strong adsorption of product was observed. 

Enhancement of reaction conversion by employing a permselective membrane often has the implication that, for a given conversion, it is possible to run the reaction at a lower temperature in the membrane reactor than in a conventional reactor. Catalyst deactivation due to coke formation generally becomes more severe as the reaction temperature increases. Therefore, the use of a membrane reactor to replace a conventional one should, in principle, reduce the propensity for coke formation because for the same conversion the membrane reactor configuration may be operated at a lower temperature than a conventional reactor. This is particularly true for such reactions as dehydrogenation. 

Exxon Donor Solvent Minerals in coal in liquefaction reactor CoO—M0O3/AI2O3 in separate hydrogenation reactor 450 140 Tetralin in liquefaction reactor. Recycled after hydrogenation in separate reactor Further hydrogenation of product liquids in separate reactor— catalyst deactivation slow. Typical product yields 0-3 to 0-4 te liquid/te coal feed... 

This was a Hquid-phase process which used what was described as siUceous zeoUtic catalysts. Hydrogen was not required in the process. Reactor pressure was 4.5 MPa and WHSV of 0.68 kg oil/h kg catalyst. The initial reactor temperature was 127°C and was raised as the catalyst deactivated to maintain toluene conversion. The catalyst was regenerated after the temperature reached about 315°C. Regeneration consisted of conventional controlled burning of the coke deposit. The catalyst life was reported to be at least 1.5 yr. 

The heat released from the CO—H2 reaction must be removed from the system to prevent excessive temperatures, catalyst deactivation by sintering, and carbon deposition. Several reactor configurations have been developed to achieve this (47). 

Catalyst Deactivation. Catalyst deactivation (45) by halogen degradation is a very difficult problem particularly for platinum (PGM) catalysts, which make up about 75% of the catalysts used for VOC destmction (10). The problem may weU He with the catalyst carrier or washcoat. Alumina, for example, a common washcoat, can react with a chlorinated hydrocarbon in a gas stream to form aluminum chloride which can then interact with the metal. Fluid-bed reactors have been used to offset catalyst deactivation but these are large and cosdy (45). 

Several processes based on non-precious metal also exist. Because of high catalyst deactivation rates with these catalyst systems, they all require some form of continuous regeneration. The Fluid Hydroforming process uses fluid solids techniques to move catalyst between reactor and regenerator TCR and Hyperforming use some form of a moving bed system. 

Similar approaches are applicable in the chemical industry. For example, maleic anhydride is manufactured by partial oxidation of benzene in a fixed catalyst bed tubular reactor. There is a potential for extremely high temperatures due to thermal runaway if feed ratios are not maintained within safe limits. Catalyst geometry, heat capacity, and partial catalyst deactivation have been used to create a self-regulatory mechanism to prevent excessive temperature (Raghaven, 1992). 

Four pilot plant experiments were conducted at 300 psig and up to 475°C maximum temperature in a 3.07-in. i.d. adiabatic hot gas recycle methanation reactor. Two catalysts were used parallel plates coated with Raney nickel and precipitated nickel pellets. Pressure drop across the parallel plates was about 1/15 that across the bed of pellets. Fresh feed gas containing 75% H2 and 24% CO was fed at up to 3000/hr space velocity. CO concentrations in the product gas ranged from less than 0.1% to 4%. Best performance was achieved with the Raney-nickel-coated plates which yielded 32 mscf CHh/lb Raney nickel during 2307 hrs of operation. Carbon and iron deposition and nickel carbide formation were suspected causes of catalyst deactivation. 

Do not infer from the above discussion that all the catalyst in a fixed bed ages at the same rate. This is not usually true. Instead, the time-dependent effectiveness factor will vary from point to point in the reactor. The deactivation rate constant kj) will be a function of temperature. It is usually fit to an Arrhenius temperature dependence. For chemical deactivation by chemisorption or coking, deactivation will normally be much higher at the inlet to the bed. In extreme cases, a sharp deactivation front will travel down the bed. Behind the front, the catalyst is deactivated so that there is little or no conversion. At the front, the conversion rises sharply and becomes nearly complete over a short distance. The catalyst ahead of the front does nothing, but remains active, until the front advances to it. When the front reaches the end of the bed, the entire catalyst charge is regenerated or replaced. 

An interesting way to retard catalyst deactivation is to expose the reaction mixture to ultrasound. Ultrasound treatment of the mixture creates local hot spots, which lead to the formation of cavitation bubbles. These cavitation bubbles bombard the solid, dirty surface leading to the removal of carbonaceous deposits [38]. The ultrasound source can be inside the reactor vessel (ultrasound stick) or ultrasound generators can be placed in contact with the wall of the reactor. Both designs work in practice, and the catalyst lifetime can be essentially prolonged, leading to process intensification. The effects of ultrasound are discussed in detail in a review article [39]. 

Sandelin, F., Salmi, T., and Murzin, D. (2006) Dynamic modelling of catalyst deactivation in fixed bed reactors skeletal isomerization of 1-pentene on ferrierite. Ind. Eng. Chem. Res., 45, 558-566. 

Furthermore, the application of the SOD membrane in a FT reaction has been investigated. The advantages of water removal in a FT reaction are threefold (i) reduction of H20-promoted catalyst deactivation, (ii) increased reactor productivity, and (iii) displaced water gas shift (WGS) equilibrium to enhance the conversion of CO2 to hydrocarbons [53]. Khajavi etal. report a mixture of H2O/H2 separation factors 10000 and water fluxes of 2.3 kg m h under... 

The selection of reactor type in the traditionally continuous bulk chemicals industry has always been dominated by considering the number and type of phases present, the relative importance of transport processes (both heat and mass transfer) and reaction kinetics plus the reaction network relating to required and undesired reactions and any aspects of catalyst deactivation. The opportunity for economic... 

One of the most studied applications of Catalytic Membrane Reactors (CMRs) is the dehydrogenation of alkanes. For this reaction, in conventional reactors and under classical conditions, the conversion is controlled by thermodynamics and high temperatures are required leading to a rapid catalyst deactivation and expensive operative costs In a CMR, the selective removal of hydrogen from the reaction zone through a permselective membrane will favour the conversion and then allow higher olefin yields when compared to conventional (nonmembrane) reactors [1-3]... 

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