Catalyst preparation precursor formation

The SILP carbonylation catalyst was prepared by one-step impregnation of sihca support using a methanohc solution of the ionic liquid [BMIMjl and the dimer [Rh(CO)2l]2- The use of the dimeric precursor complex allowed formation of the catalyst anion [Rh(CO)2l2] directly during catalyst preparation without formation of contaminating byproducts in the ionic hquid catalyst solution. 

The reduction of the catalyst precursor with sodium formate resulted in a lower Pd dispersion than the catalyst prepared by hydrogen reduction, the particle size is much larger in the former catalyst. The mesoporous carbon supported Pd catalysts are near to those of Pd on titania with respect to their enantiodifferentiating ability. Besides the metal dispersion, the availability of the Pd surface in the pores for the large modifier molecules seems to be the determining factor of the enantioselectivity. 

Cr-ZSM-5 catalysts prepared by solid-state reaction from different chromium precursors (acetate, chloride, nitrate, sulphate and ammonium dichromate) were studied in the selective ammoxidation of ethylene to acetonitrile. Cr-ZSM-5 catalysts were characterized by chemical analysis, X-ray powder diffraction, FTIR (1500-400 cm 1), N2 physisorption (BET), 27A1 MAS NMR, UV-Visible spectroscopy, NH3-TPD and H2-TPR. For all samples, UV-Visible spectroscopy and H2-TPR results confirmed that both Cr(VI) ions and Cr(III) oxide coexist. TPD of ammonia showed that from the chromium incorporation, it results strong Lewis acid sites formation at the detriment of the initial Bronsted acid sites. The catalyst issued from chromium chloride showed higher activity and selectivity toward acetonitrile. This activity can be assigned to the nature of chromium species formed using this precursor. In general, C r6+ species seem to play a key role in the ammoxidation reaction but Cr203 oxide enhances the deep oxidation. 

Supported ruthenium catalysts prepared from Ru3(CO),2 have been used in CO hydrogenation because of the highly dispersed metallic phase achieved when this carbonyl-precursor is used [70,107-109]. However, under catalytic reaction conditions the loss of ruthenium from the support could take place, ft has been reported that at low temperatures it takes place through the formation of Ru(CO)s species, whereas at high temperature dodecarbonyl formation occurs [110]. Decarbonylation of the initial deposited carbonyl precursor under hydrogen could minimize this problem [107]. 

More recent research efforts have focused on the development of other possible catalysts such as promoted Raney copper,371,403 catalysts prepared from intermetal-lic precursors,362,371 386 404-406 and catalysts that tolerate high C02 content.407 Catalyst modifications allowed to shift the selectivity to the formation of higher alcohols.208,408 110 For example, in a process developed by IFP, a multicomponent oxide catalyst is applied with copper and chromium as the main components 410 By this method, 70-75% total alcohol selectivities and 30-50% of C2 and higher alcohol selectivities can be achieved at 12-18% conversion levels (260-320°C, 60-100 atm). 

As shown in Fig. 2, the catalytic activity of the zeolite prepared by the direct heating method for methanol conversion was higher than that of the zeolite crystallization for 25 days by the standard preparation method. However, deactivation of the catalyst by carbon deposit occurred early in the reaction, just as with the catalyst prepared by the standard method. Differences in crystallite morphology between those prepared by the standard method and the direct heating method would be attributed to the stage of the precursor formation. Therefore, after the precursor formation the rapid heating was adopted as described below. 

---