Catalyst beds

Chemical reduction. The injection of ammonia reduces NO emissions by the reduction of NO , to nitrogen and water. Although it can be used at higher temperatures without a catalyst, the most commonly used method injects the ammonia into the flue gas upstream of a catalyst bed (typically vanadium and/or tin on a silica support). 

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). 

The preheated gases react exothermically over the first-stage catalyst with the peak temperature ia the range of 330—430°C, depending on conditions and catalyst selectivity. The conversion of propylene to waste gas (carbon dioxide and carbon monoxide) is more exothermic than its conversion to acroleia. At the end of the catalyst bed the temperature of the mixture drops toward that of the molten salt coolant. 

A typical catalyst bed is very shallow (10 to 50 mm) (76,77). In some plants the catalyst is contained in numerous small parallel reactors in others, catalyst-bed diameters up to 1.7 and 2.0 m (77,80) and capacities of up to 135,000 t/yr per reactor are reported (78). The silver catalyst has a useful life of three to eight months and can be recovered. It is easily poisoned by traces of transition group metals and by sulfur. 

Catalytic methanation processes include (/) fixed or fluidized catalyst-bed reactors where temperature rise is controlled by heat exchange or by direct cooling using product gas recycle (2) through wall-cooled reactor where temperature is controlled by heat removal through the walls of catalyst-filled tubes (J) tube-wall reactors where a nickel—aluminum alloy is flame-sprayed and treated to form a Raney-nickel catalyst bonded to the reactor tube heat-exchange surface and (4) slurry or Hquid-phase (oil) methanation. 

Figure 2 illustrates the three-step MIBK process employed by Hibernia Scholven (83). This process is designed to permit the intermediate recovery of refined diacetone alcohol and mesityl oxide. In the first step acetone and dilute sodium hydroxide are fed continuously to a reactor at low temperature and with a reactor residence time of approximately one hour. The product is then stabilized with phosphoric acid and stripped of unreacted acetone to yield a cmde diacetone alcohol stream. More phosphoric acid is then added, and the diacetone alcohol dehydrated to mesityl oxide in a distillation column. Mesityl oxide is recovered overhead in this column and fed to a further distillation column where residual acetone is removed and recycled to yield a tails stream containing 98—99% mesityl oxide. The mesityl oxide is then hydrogenated to MIBK in a reactive distillation conducted at atmospheric pressure and 110°C. Simultaneous hydrogenation and rectification are achieved in a column fitted with a palladium catalyst bed, and yields of mesityl oxide to MIBK exceeding 96% are obtained. 

In the vapor phase, acetone vapor is passed over a catalyst bed of magnesium aluminate (206), 2iac oxide—bismuth oxide (207), calcium oxide (208), lithium or 2iac-doped mixed magnesia—alumina (209), calcium on alumina (210), or basic mixed-metal oxide catalysts (211—214). Temperatures ranging... 

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. 

Distribution balls are frequently used on the top of each bed they are often employed to support the catalyst bed from below. The outlet of the reactor needs to include some type of collector in order to retain the catalyst and support balls while allowing the products to leave the reactor. 

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. 

At higher total flow rates, particularly when the Hquid is prone to foaming, the reactor is a pulsed column. This designation arises from the observation that the pressure drop within the catalyst bed cycles at a constant frequency as a result of Hquid temporarily blocking gas or vapor pathways. The pulsed column is not to be confused with the pulse reactor used to obtain kinetic data ia which a pulse of reactant is introduced into a tube containing a small amount of catalyst. 

Direct Process. Passing methyl chloride through a fluidized bed of copper and siUcon yields a mixture of chlorosilanes. The rate of methylchlorosilane (MCS) production and chemical selectivity, as determined by the ratio of dimethydichlorosilane to the other compounds formed, are significantly affected by trace elements in the catalyst bed very pure copper and siUcon gives poor yield and selectivity (22). 

Incieased catalyst-bed piessuie diop caused by dust fouling reduces production of acid and significantly increases energy consumption by the plant s blower. To avoid these problems, first converter-pass catalyst pellets are screened at every significant turnaround, typically every 12—24 months. 

Second-pass catalyst pellets need screening less frequendy because the first converter-pass catalyst bed acts as a filter for the rest of the converter. Typical screening losses range from 10—15% of the catalyst bed per screening. Screening losses depend on screen mesh size and catalyst hardness, as well as on screening rate. 

The Claus process is the most widely used to convert hydrogen sulfide to sulfur. The process, developed by C. F. Claus in 1883, was significantly modified in the late 1930s by I. G. Farbenindustrie AG, but did not become widely used until the 1950s. Figure 5 illustrates the basic process scheme. A Claus sulfur recovery unit consists of a combustion furnace, waste heat boiler, sulfur condenser, and a series of catalytic stages each of which employs reheat, catalyst bed, and sulfur condenser. Typically, two or three catalytic stages are employed. 

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 some liquid-phase processes, catalyst components are slowly leached from the catalyst bed and eventually the catalyst must be replaced. The feasibility of this type of process involves economics, ie, the costs of catalyst maintenance and keeping a unit out of service for catalyst replacement, and product quality and safety, ie, the effects of having catalyst components in the product and their ease of removal. 

Cost. The catalytically active component(s) in many supported catalysts are expensive metals. By using a catalyst in which the active component is but a very small fraction of the weight of the total catalyst, lower costs can be achieved. As an example, hydrogenation of an aromatic nucleus requires the use of rhenium, rhodium, or mthenium. This can be accomplished with as fittie as 0.5 wt % of the metal finely dispersed on alumina or activated carbon. Furthermore, it is almost always easier to recover the metal from a spent supported catalyst bed than to attempt to separate a finely divided metal from a liquid product stream. If recovery is efficient, the actual cost of the catalyst is the time value of the cost of the metal less processing expenses, assuming a nondeclining market value for the metal. Precious metals used in catalytic processes are often leased. 

---