Dehydrogenations applications

Yamashita, M., Kawamura, T., Suzuki, M., Saito, Y. 1991. Characteristics of suspended Ru/carbon catalyst for 2-propanol dehydrogenation applicable to chemical heat pump. Bull Chem Soc Jpn 64 272-278. 

The world propylene production capacity based on the use of catalytic dehydrogenation of propane has increased steadily over the past lOyr and is expected to grow even further under the right economic conditions relative to the availability and pricing of pro-pane. On the other hand, environmental concerns on the use of methyl-/ r/-butyl ether (MTBE), an oxygenated gasoline additive, are expected to adversely impact the future expansion of isobutane dehydrogenation applications. 

The commercial cost of Pd-Ag-supported membranes (mass production) is projected to be 1500 /m, and the catalyst cost for dehydrogenation applications is <100 /kg. The Pd-Ag membranes may provide fluxes (7ffj) as high as 0.5-2.5 mol/(m s) [16-18] and the DH reaction rates are in the range of 0.1-1 mol/(kg s). This estimation suggests that the membrane cost (when using mass production) will be comparable with the catalyst cost. 

Besides stmctural variety, chemical diversity has also increased. Pure silicon fonns of zeolite ZSM-5 and ZSM-11, designated silicalite-l [19] and silicahte-2 [20], have been synthesised. A number of other pure silicon analogues of zeolites, called porosils, are known [21]. Various chemical elements other than silicon or aluminium have been incoriDorated into zeolite lattice stmctures [22, 23]. Most important among those from an applications point of view are the incoriDoration of titanium, cobalt, and iron for oxidation catalysts, boron for acid strength variation, and gallium for dehydrogenation/aromatization reactions. In some cases it remains questionable, however, whether incoriDoration into the zeolite lattice stmcture has really occurred. 

The last example is an interesting application of the diene synthesis, for the adduct upon dehydrogenation (most simply by the action of oxygen upon its solution in alcoholic potash) yields 2 3-dimethylantbraquinone. 

The latest catalyst development is the contact DeH-9, which in terms of activity and stability is comparable with DeH-7 but with improved selectivity (fewer iso- and cycloparaffins and aromatics). This contact has been produced since 1990 and probably used commercially since 1992 [59]. In Table 7 the composition of the dehydrogenation products in relation to the catalyst and the application of the DeFine step is summarized. Table 8 shows the performance data for various catalysts [10] in relation to LAB production. 

As a new kind of carbon materials, carbon nanofilaments (tubes and fibers) have been studied in different fields [1]. But, until now far less work has been devoted to the catalytic application of carbon nanofilaments [2] and most researches in this field are focused on using them as catalyst supports. When most of the problems related to the synthesis of large amount of these nanostructures are solved or almost solved, a large field of research is expected to open to these materials [3]. In this paper, CNF is tested as a catalyst for oxidative dehydrogenation of propane (ODP), which is an attractive method to improve propene productivity [4]. The role of surface oxygen annplexes in catalyzing ODP is also addressed. 

Hydride species were also formed in the dehydrogenative coupling of hydrosilanes with DMF [45]. The catalytic system is applicable to tertiary silanes, which are known to be difficult to be converted into disiloxanes (Fig. 17). The catalytic reaction pathway involves the intermediacy of a hydrido(disilyl)iron complex... 

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]... 

Beside their use in equilibrium-restricted reactions, CMRs have been also proposed for very different applications [6], like selective oxidation and oxidative dehydrogenation of hydrocarbons they may also act as active contactor in gas or gas-liquid reactions. 

The Raney nickel is a very efficient catalyst for the dehydrogenation of 2-butanol into butanone (Scheme 45) with a good selectivity (90%). But, for industrial applications selectivities as high as 99% are required. This can be achieved by poisoning some sites by reaction with Bu4Sn (the best results are obtained with a Sn/Ni ratio of 0.02), which probably occurs first on the sites responsible for the side reactions. The consequence is a slight decrease of the catalytic activity and an increase of the selectivity in 2-butanone which can reach 99%. This catalyst, developed by IFF, has been used commercially in Japan for several years [180]. 

Dehydrogenation (the conversion of alicycllc or hydroaromatic compounds into their aromatic counterparts by removal of hydrogen and also, in some cases, of other atoms or groups) finds wide application in the determination of structure of natural products of complex hydroaromatic structure. Dehydrogenation is employed also for the s)mthesis of polycyclic hydrocarbons and their derivatives from the readily accessible synthetic hydroaromatic compounds. A very simple example is the formation of p-methylnaphthalene from a-tetra-lone (which is itself prepared from benzene—see Section IV, 143) ... 

Another recent patent (22) and related patent application (31) cover incorporation and use of many active metals into Si-TUD-1. Some active materials were incorporated simultaneously (e.g., NiW, NiMo, and Ga/Zn/Sn). The various catalysts have been used for many organic reactions [TUD-1 variants are shown in brackets] Alkylation of naphthalene with 1-hexadecene [Al-Si] Friedel-Crafts benzylation of benzene [Fe-Si, Ga-Si, Sn-Si and Ti-Si, see apphcation 2 above] oligomerization of 1-decene [Al-Si] selective oxidation of ethylbenzene to acetophenone [Cr-Si, Mo-Si] and selective oxidation of cyclohexanol to cyclohexanone [Mo-Si], A dehydrogenation process (32) has been described using an immobilized pincer catalyst on a TUD-1 substrate. Previously these catalysts were homogeneous, which often caused problems in separation and recycle. Several other reactions were described, including acylation, hydrogenation, and ammoxidation. 

These types of mechanisms would be generally applicable provided the required dehydrogenation is possible. 

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