Fluorided catalyst, first development

Detal [Detergent alkylation] A process for making detergent alkylate, i.e., alkyl aromatic hydrocarbons such as linear alkyl benzenes, as intermediates for the manufacture of detergents, by reacting C10-C13 olefins with benzene in a fixed bed of an acid catalyst. Developed by UOP and CEPSA as a replacement for their Detergent Alkylate process, which uses liquid hydrogen fluoride as the catalyst. Demonstrated in a pilot plant in 1991 and first commercialized in Canada in 1996. Offered by UOP. 

The first process developed employed an amorphous catalyst reputedly with high fluoride levels to increase acidity and bring about partial hydroisomerization. Since wax conversion was incomplete, the final step was solvent dewaxing to remove unconverted wax and complete achievement of the target pour point. A preliminary hydrotreatment step was used to remove sulfur and nitrogen. 

Among these families of solid bases, we have particularly developed three new types of catalysts derived from these "classical" solid bases. The first two ones (MgLa mixed oxides and alkali fluorides supported on a alumina) were applied to fine chemistry [11-16] while in the third case (supported CuO) we studied the role of the basic strength of this oxidant on the selective adsorption of NO in the NOx trap technology [17]. In each case, we found a fundamental effect of the active species dispersion on the catalyst basic strength and reactivity. 

The double bonds in the CPs (5) always react to some extent with sulfuric acid (or HF) to produce CP sulfates (or fluorides). The importance of CPs in the overall reaction sequence is indicated by the following information First, fresh sulfuric acid is a poor catalyst until a small amount of CPs is obtained (6). The best quality alkylates are produced with sulfuric acids containing 3-6% polymers (7,8). Although less information has been published when HFs are used as catalysts, the level of CPs in HF is also important. Phillips Petroleum Company (9) has developed a near-infrared technique to monitor the CP [or acid-soluble oil (ASO)] content of their HF phase. They report that in a refinery, the HF contained 10% by weight CPs but the acidity was about 84 85%. Since the HF contains about 0.2% water, about 4% was unreported. It is mainly alkyl fluorides. 

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