Fixed catalysts

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). 

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. 

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. 

In the fixed catalyst method, the residence time in the reactor may be easily controlled to generate fibers of selected length and diameter, both dimensions which can vary over several orders of magnitude. Most of the physical properties which have been measured for VGCF have been made on this type of fiber. 

Applied Sciences, Inc. has, in the past few years, used the fixed catalyst fiber to fabricate and analyze VGCF-reinforced composites which could be candidate materials for thermal management substrates in high density, high power electronic devices and space power system radiator fins and high performance applications such as plasma facing components in experimental nuclear fusion reactors. These composites include carbon/carbon (CC) composites, polymer matrix composites, and metal matrix composites (MMC). Measurements have been made of thermal conductivity, coefficient of thermal expansion (CTE), tensile strength, and tensile modulus. Representative results are described below. 

Fig. 6. Micrograph of fixed catalyst VGCF showing the fibers are semi-aligned and semi-continuous.

The above data represent the first from composites fabricated with fixed catalyst VGCF. A review of the data leads to the conclusion that the thermal and electrical properties of this type of carbon fiber are perhaps the most likely to be exploited in the short term. While mechanical properties of the composites are not as attractive as the thermal and electrical, it may be noted that no effort has... 

Composites fabricated with fixed catalyst VGCF can be designed with fibers oriented in preferred directions to produce desired combinations of thermal conductivity and coefficient of thermal expansion. While such composites are not likely to be cost-competitive with metals in the near future, the ability to design for thermal conductivity in preferred directions, combined with lower density and lower coefficient of thermal expansion, could warrant the use of such VGCF composites in less price sensitive applications, such as electronics for aerospace vehicles. 

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). 

There is no separate shift conversion system and no recycle of product gas for temperature control (see Figure 1). Rather, this system is designed to operate adiabatically at elevated temperatures with sufficient steam addition to cause the shift reaction to occur over a nickel catalyst while avoiding carbon formation. The refractory lined reactors contain fixed catalyst beds and are of conventional design. The reactors can be of the minimum diameter for a given plant capacity since the process gas passes through once only with no recycle. Less steam is used than is conventional for shift conversion alone, and the catalyst is of standard ring size (% X %= in). 

Figure 9.28 shows the dependence of the catalytic rate of oxygen consumption, r0, on the oxygen partial pressure P02 at fixed pH2 under open-circuit conditions and for a potentiostatically fixed catalyst potential Urhe (=UWr). As also shown in Fig. 9.28, the open-circuit potential UrhE increases from 0.33 to 0.8 V as the Po Ph2 ratio increases from 0.2 to 3.6. 

Figure 9.28. Effect of P02 on the rate of O consumption (u.) and corresponding catalyst potential ( ), U°ile, under open-circuit conditions and on the rate of O consumption (A) and corresponding A0 value under closed-circuit conditions at fixed catalyst potential Urhe-1.05 V total molar flowrate fm=l.7 l0 4 mol/s.35 Reproduced by permission of The Electrochemical Society.

The ethylene selectivity (Fig. 5) and thus the ethylene yield depend strongly on the adsorbent mass (Fig. 5). For fixed catalyst mass, oxygen supply I/2F and methane conversion there is an optimal amount of adsorbent for maximizing ethylene selectivity and yield (Fig. 5). Excessive amounts of adsorbent cause quantitative trapping of ethane and thus a decrease in ethylene yield according to the above reaction network. This shows the important synergy between the catalytic and adsorbent units which significantly affects the product distribution and yield. 

Kirillov, V. A., and Stegasov, A. N., On the simulation of heterogeneous catalytic processes with phase transitions in fixed catalyst bed (in Russian). Teoreticheskiye osnoy khim-icheskoi teknhnologii 22,340-345 (1988). 

The combined diffusivity is, of course, defined as the ratio of the molar flux to the concentration gradient, irrespective of the mechanism of transport. The above equation was derived by separate groups working independently (8-10). It is important to recognize that the molar fluxes (Ni) are defined with respect to a fixed catalyst pellet rather than to a plane of no net transport. Only when there is equimolar counterdiffusion, do the two types of flux definitions become equivalent. For a more detailed discussion of this point, the interested readers should consult Bird, Stewart, and Lightfoot (11). When there is equimolal counterdiffusion NB = —NA and... 

Heterogeneous catalytic gas-phase reactions are most important in industrial processes, especially in petrochemistry and related fields, in which most petrochemical and chemical products are manufactured by this method. These reactions are currently being studied in many laboratories, and the results of this research can be also used for synthetic purposes. The reactions are usually performed [61] in a continuous system on a fixed catalyst bed (exceptionally a fluidized bed). 

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