Catadiene process, Houdry

Butadiene and Isoprene. Butane may be transformed directly to 1,3-buta-diene on chromia-alumina (Houdry Catadiene process).144-146 172 The most significant condition is operation under subatmospheric pressure (0.1-0.4 atm), which provides an improved yield of 1,3-butadiene. Operating at about 600°C, the process produces a mixture of butenes and 1,3-butadiene. After the removal of the latter, the remaining butane-butenes mixture is mixed with fresh butane and recycled. Extensive coke formation requires regeneration of the catalyst after a few minutes of operation. 1,3-Butadiene yields up to 63% are obtained at a conversion level of 30 40%. 

The Houdry Catadiene process was used extensively for the production of butadiene, either by itself (n-butane to butadiene) or in conjunction with catalytic oxydehydrogenation of n-butene to butadiene. The latter was commercialized by the Petro-Tex Chemical Corp. and was called the Oxo-D process. A similar oxydehydrogenation approach for the production of butadiene was also adopted by Phillips Petroleum in their 0-X-D process. ... 

As deseribed earlier, the Houdry Catadiene process, the Houdry Catofln proeess, and other similar eyclical processes make use of parallel reactors that contain a shallow bed of chromia-alumina catalyst. Fig. 11 illustrates a schematic of such a process. 

It is well known that, in addition to butadiene from butane, the Houdry Catadiene process can produce propylene from propane. This process has been in successful operation to produce butadiene and butene... 

The major paper on the Houdry Catadiene process is that published by Hornaday, Ferrell, and Mills in 1961 (27). Their main concern is butadiene, but yield data are provided on dehydrogenation of other stocks, specifically, for present purposes, propane. 

Figure 6. The Houdry Catadiene process. Flow sheet for propane dehydrogenation.

In the late 1980s, the application of chromia-alumina catalysts was extended by Houdry to the dehydrogenation of propane to propylene and isobutane to isobutylene. The new process application called Catofin operates on the same cyclic principle as in the former Catadiene process. As of late 2000, a total of eight Catofin units existed for the production of isobutylene (including two converted older Catadiene units) with an aggregate capacity of about 2.8 million metric tons per annum (MTA) of isobutylene. In addition, two Catofin units were built for the production of propylene, but it is understood that only... 

Craig, R.G. Spence, D.C. Catalytic dehydrogenation of liquefied petroleum gas by the Houdry Catofin and Catadiene processes. In Handbook of Petroleum Refining Processes, Robert, A.M., Ed. McGraw-Hill, 1986 Section 4.1. 

Catadiene [Catalytic butadiene] Also spelled Catadien. A version of the Houdry process for converting mixtures of butane isomers into butadiene by dehydrogenation over an alumina/chromia catalyst. Another version converts propane to propylene. Rapid coking of the catalyst necessitates use of several reactors in parallel, so that reactivation can be carried out continuously. Developed by Houdiy and first operated at El Segundo, CA, in 1944. By 1993, 20 plants had been built worldwide. Now licensed by ABB Lummus Crest. 

The dehydrogenation process was first commercialized in the 1940 s (Houdry s CATADIENE). The initial catalyst used was chromia on alumina. Most commercial process still use this catalyst today. However, two recent processes use Pt on alumina catalyst (UOP s OLEFLEX) (Pujado, 1990) or other noble metals Phillip s STAR) (Brinkmeyer et al, 1983). 

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