Catalyst bed reactions

The main catalyst bed reaction is the same as in conventional acidmaking, i.e.  

Industrially, up to 20% of the SO3 produced by Reaction (1.1) reacts to form H2S04(g) before it leaves the last catalyst bed. 

Wet sulfuric acid process SO2 oxidation catalyst is similar to dry sulfuric acid catalyst (Chapter 8). However, its substrate is stronger so that it can withstand the softening effect of H20(g) (Degerman et al., 2008, Haldor Topsoe, 2008). 

The gas leaving Fig. 25.1 s last catalyst bed is prepared for H2S04(f) condensation by  

The last process in the catalytic converter is cooling of the oxidized gas below the last catalyst bed (Fig. 25.1). This cooling promotes Reaction (25.1) so that a substantial part of the gas s SO3 can react to H2S04(g) before it enters the H2S04(f) condenser. 

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Oxidation of o-xylene over V20s/Si02 [6]. The rate enhancement was because of a temperature gradient of approx. 100 K in the catalyst bed. Reaction conditions a flow fixed-bed multi-mode reactor. 

Flow condition Ctube/shell) Thermal condition Catalyst bed Reaction (s) Reference... 

When designing WGSR (Chen et al, 2008), it is known that a proper selection on certain parameters is of the most importance because the reaction result depends strongly on the combination of these parameters. Typically, the important parameters include the catalyst type, residence time of reactants in a catalyst bed, reaction temperature and feeding reactants ratio or CO/ steam ratio. 

The reaction of adipic acid with ammonia in either Hquid or vapor phase produces adipamide as an intermediate which is subsequentiy dehydrated to adiponitrile. The most widely used catalysts are based on phosphoms-containing compounds, but boron compounds and siHca gel also have been patented for this use (52—56). Vapor-phase processes involve the use of fixed catalyst beds whereas, in Hquid—gas processes, the catalyst is added to the feed. The reaction temperature of the Hquid-phase processes is ca 300°C and most vapor-phase processes mn at 350—400°C. Both operate at atmospheric pressure. Yields of adipic acid to adiponitrile are as high as 95% (57). 

Fluidized-bed reaction systems are not normally shut down for changing catalyst. Fresh catalyst is periodically added to manage catalyst activity and particle size distribution. The ALMA process includes faciUties for adding back both catalyst fines and fresh catalyst to the reactor. 

Quench Converter. The quench converter (Fig. 7a) was the basis for the initial ICl low pressure methanol flow sheet. A portion of the mixed synthesis and recycle gas bypasses the loop interchanger, which provides the quench fractions for the iatermediate catalyst beds. The remaining feed gas is heated to the inlet temperature of the first bed. Because the beds are adiabatic, the feed gas temperature increases as the exothermic synthesis reactions proceed. The injection of quench gas between the beds serves to cool the reacting mixture and add more reactants prior to entering the next catalyst bed. Quench converters typically contain three to six catalyst beds with a gas distributor in between each bed for injecting the quench gas. A variety of gas mixing and distribution devices are employed which characterize the proprietary converter designs. 

Tube-Cooled Converter. The tube-cooled converter functions as an interchanger, consisting of a tube-filled vessel with catalyst on the shell side (Fig. 7c). The combined synthesis and recycle gas enters the bottom of the reactor tubes, where it is heated by the reaction taking place in the surrounding catalyst bed. The gas turns at the top of the tubes and passes down through the catalyst bed. The principal advantage of this converter is in... 

Oxidation. Naphthalene may be oxidized direcdy to 1-naphthalenol (1-naphthol [90-15-3]) and 1,4-naphthoquinone, but yields are not good. Further oxidation beyond 1,4-naphthoquinone [130-15-4] results in the formation of ortho- h. h5 ic acid [88-99-3], which can be dehydrated to form phthaUc anhydride [85-44-9]. The vapor-phase reaction of naphthalene over a catalyst based on vanadium pentoxide is the commercial route used throughout the world. In the United States, the one phthaUc anhydride plant currently operating on naphthalene feedstock utilizes a fixed catalyst bed. The fiuid-bed process plants have all been shut down, and the preferred route used in the world is the fixed-bed process. 

The catalyst is employed in bead, pellet, or microspherical form and can be used as a fixed bed, moving bed, or fluid bed. The fixed-bed process was the first process used commercially and employs a static bed of catalyst in several reactors, which allows a continuous flow of feedstock to be maintained. The cycle of operations consists of (/) the flow of feedstock through the catalyst bed (2) the discontinuance of feedstock flow and removal of coke from the catalyst by burning and (J) the insertion of the reactor back on-stream. The moving-bed process uses a reaction vessel, in which cracking takes place, and a kiln, in which the spent catalyst is regenerated and catalyst movement between the vessels is provided by various means. 

Alcohol Amination. There are many similarities in the process technologies for Methods 1 and 2. In both, an alcohol reacts with ammonia over a fixed catalyst bed at elevated temperature. The reaction section consists of feed systems, vapori2ers, and/or preheaters which pass a Hquid or gaseous feed mixture over the catalyst bed in the desired ratio, temperature, and pressure. Possible amination catalysts for each method are as foUows. 

Trickle bed reaction of diol (12) using amine solvents (41) has been found effective for producing PDCHA, and heavy hydrocarbon codistiUation may be used to enhance diamine purification from contaminant monoamines (42). Continuous flow amination of the cycloaUphatic diol in a Hquid ammonia mixed feed gives >90% yields of cycloaUphatic diamine over reduced Co /Ni/Cu catalyst on phosphoric acid-treated alumina at 220°C with to yield a system pressure of 30 MPa (4350 psi) (43). 

Process Description. Reactors used in the vapor-phase synthesis of thiophene and aLkylthiophenes are all multitubular, fixed-bed catalytic reactors operating at atmospheric pressure, or up to 10 kPa and with hot-air circulation on the shell, or salt bath heating, maintaining reaction temperatures in the range of 400—500°C. The feedstocks, in the appropriate molar ratio, are vaporized and passed through the catalyst bed. Condensation gives the cmde product mixture noncondensable vapors are vented to the incinerator. 

In a typical oxychlorination reaction, preheated gas streams at temperatures of 180—200°C are fed onto a fixed- or fiuidized-catalyst bed containing 2—10% copper impregnated on an activated alumina. The reaction occurs during a 15—22 s residence time on the catalyst bed at a temperature of 230—315°C. Typical yields to 1,2-dichloroethane range from 92—97%. 

Oxychlorination of Ethylene or Dichloroethane. Ethylene or dichloroethane can be chlorinated to a mixture of tetrachoroethylene and trichloroethylene in the presence of oxygen and catalysts. The reaction is carried out in a fluidized-bed reactor at 425°C and 138—207 kPa (20—30 psi). The most common catalysts ate mixtures of potassium and cupric chlorides. Conversion to chlotocatbons ranges from 85—90%, with 10—15% lost as carbon monoxide and carbon dioxide (24). Temperature control is critical. Below 425°C, tetrachloroethane becomes the dominant product, 57.3 wt % of cmde product at 330°C (30). Above 480°C, excessive burning and decomposition reactions occur. Product ratios can be controlled but less readily than in the chlorination process. Reaction vessels must be constmcted of corrosion-resistant alloys. 

The various reaction rate properties of the different solvents influence the design of a catalytic reactor. Eor example, for a specific catalyst bed design, an effluent stream containing a preponderance of monohydric alcohols, aromatic hydrocarbons, or propjiene requires a lower catalyst operating temperature than that required for solvents such as isophorone and short-chain acetates. 

Some modes of heat transfer to stirred tank reacdors are shown in Fig. 23-1 and to packed bed reactors in Fig. 23-2. Temperature and composition profiles of some processes are shown in Fig. 23-3. Operating data, catalysts, and reaction times are stated for a number of industrial reaction processes in Table 23-1. 

NO -laden fumes are preheated by effluent from the catalyst vessel in the feed/effluent heat exchanger and then heated by a gas- or oil-fired heater to over 600° F. A controlled quantity of ammonia is injected into the gas stream before it is passed through a metal oxide, zeolite, or promoted zeolite catalyst bed. The NO is reduced to nitrogen and water in the presence or ammonia in accordance with the following exothermic reactions ... 

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