Catalyst cobalt/zinc oxide

Cobalt/zinc oxide catalysts show low temperature activity for ethanol steam reforming even below 400 °C, along with low or no selectivity towards carbon monoxide, which has been reported by Uorca and coworkers [204,205]. However, residence time over the catalysts needs to be sufficiently low and the S/C ratio rather high to achieve this performance. 

Homs et al. reported that nickel supported on zinc oxide is not a favourable catalyst formulation for ethanol steam reforming, but the addition of nickel to a cobalt/zinc oxide catalyst promoted with sodium increased the catalytic activity [206]. At S/C 6.5 and only 300 °C reaction temperature, full ethanol conversion could be achieved without by-product formation, apart from methane. 

Natural gas contains both organic and inorganic sulfur compounds that must be removed to protect both the reforming and downstream methanol synthesis catalysts. Hydrodesulfurization across a cobalt or nickel molybdenum—zinc oxide fixed-bed sequence is the basis for an effective purification system. For high levels of sulfur, bulk removal in a Hquid absorption—stripping system followed by fixed-bed residual clean-up is more practical (see Sulfur REMOVAL AND RECOVERY). Chlorides and mercury may also be found in natural gas, particularly from offshore reservoirs. These poisons can be removed by activated alumina or carbon beds. 

Metals in the platinum family are recognized for their ability to promote combustion at lowtemperatures. Other catalysts include various oxides of copper, chromium, vanadium, nickel, and cobalt. These catalysts are subject to poisoning, particularly from halogens, halogen and sulfur compounds, zinc, arsenic, lead, mercury, and particulates. It is therefore important that catalyst surfaces be clean and active to ensure optimum performance. 

Ammonia production from natural gas includes the following processes desulfurization of the feedstock primary and secondary reforming carbon monoxide shift conversion and removal of carbon dioxide, which can be used for urea manufacture methanation and ammonia synthesis. Catalysts used in the process may include cobalt, molybdenum, nickel, iron oxide/chromium oxide, copper oxide/zinc oxide, and iron. 

A detailed study of the dehydrogenation of 10.1 l-dihydro-5//-benz[6,/]azcpinc (47) over metal oxides at 550 C revealed that cobalt(II) oxide, iron(III) oxide and manganese(III) oxide are effective catalysts (yields 30-40%), but formation of 5//-dibenz[7),/]azepinc (48) is accompanied by ring contraction of the dihydro compound to 9-methylacridine and acridine in 3-20 % yield.111 In contrast, tin(IV) oxide, zinc(II) oxide. chromium(III) oxide, cerium(IV) oxide and magnesium oxide arc less-effective catalysts (7-14% yield) but provide pure 5H-dibenz[b,/]azepine. On the basis of these results, optimum conditions (83 88% selectivity 94-98 % yield) for the formation of the dibenzazepine are proposed which employ a K2CO,/ Mn203/Sn02/Mg0 catalyst (1 7 3 10) at 550 C. 

Fischer-Tropsch A process for converting synthesis gas (a mixture of carbon monoxide and hydrogen) to liquid fuels. Modified versions were known as the Synol and Synthol processes. The process is operated under pressure at 200 to 350°C, over a catalyst. Several different catalyst systems have been used at different periods, notably iron-zinc oxide, nickel-thoria on kieselgtihr, cobalt-thoria on kieselgiihr, and cemented iron oxide. The main products are C5-Cn aliphatic hydrocarbons the aromatics content can be varied by varying the process conditions. The basic reaction was discovered in 1923 by F. Fischer and... 

Another difference between Co and Fe is their sensitivity towards impurities in the gas feed, such as H2S. In this respect, Fe-based catalysts have been shown to be more sulfur-resistance than their Co-based counterparts. This is also the reason why for Co F-T catalysts it is recommended to use a sulphur-free gas feed. For this purpose, a zinc oxide bed is included prior to the fixed bed reactor in the Shell plant in Malaysia to guarantee effective sulphur removal. Co and Fe F-T catalysts also differ in their stability. For instance, Co-based F-T systems are known to be more resistant towards oxidation and more stable against deactivation by water, an important by-product of the FTS reaction (reaction (1)). Nevertheless, the oxidation of cobalt with the product water has been postulated to be a major cause for deactivation of supported cobalt catalysts. Although, the oxidation of bulk metallic cobalt is (under realistic F-T conditions) not feasible, small cobalt nanoparticles could be prone to such reoxidation processes. 

Other organic sulphur compounds that are not easily removed by zinc oxide can be hydrogenated to H2S first by reacting with the hydrogen over a cobalt or nickel molybdenate catalyst. A conventional zinc oxide bed as described above can then remove the formed H2S. 

By far the most important synthesis gas reaction is its conversion into methanol, using copper/zinc oxide catalysts under relatively mild conditions (50 bar, 100-250°C). Methanol is further carbonylated to acetic acid (see Section 22-7), so that CH3C02H, methyl acetate, and acetic anhydride can all be made from simple CO and H2 feedstocks. Possible pathways to oxygenates in cobalt catalyzed reactions are shown in Fig. 22-6. 

In the steam-reforming process, any sulfur compounds present in the hydrocarbon feedstock have to be removed because the nickel-containing catalysts are sensitive to poisons. This is either achieved by hydrodesulfurization (see Hydrodesulfurization Hydrodenitrogenation), generally with a combination of cobalt-molybdenum and zinc oxide... 

Iron-chromium oxide catalysts, reduced with hydrogen-containing in the conversion plants, permit reactions temperatures of 350 to 380°C (high temperature conversion), the carbon monoxide content in the reaction gas is thereby reduced to ca. 3 to 4% by volume. Since, these catalysts are sensitive to impurities, cobalt- and molybdenum-(sulfide)-containing catalysts are used for gas mixtures with high sulfur contents. With copper oxide/zinc oxide catalysts the reaction proceeds at 200 to 250°C (low temperature conversion) and carbon monoxide contents of below 0.3% by volume are attained. This catalyst, in contrast to the iron oxide/chromium oxide high temperature conversion catalyst, is, however, very sensitive to sulfur compounds, which must be present in concentrations of less than 0.1 ppm. 

The selective production of methanol and of ethanol by carbon monoxide hydrogenation involving pyrolysed rhodium carbonyl clusters supported on basic or amphoteric oxides, respectively, has been discussed. The nature of the support clearly plays the major role in influencing the ratio of oxygenated products to hydrocarbon products, whereas the nuclearity and charge of the starting rhodium cluster compound are of minor importance. Ichikawa has now extended this work to a study of (CO 4- Hj) reactions in the presence of alkenes and to reactions over catalysts derived from platinum and iridium clusters. Rhodium, bimetallic Rh-Co, and cobalt carbonyl clusters supported on zinc oxide and other basic oxides are active catalysts for the hydro-formylation of ethene and propene at one atm and 90-180°C. Various rhodium carbonyl cluster precursors have been used catalytic activities at about 160vary in the order Rh4(CO)i2 > Rh6(CO)ig > [Rh7(CO)i6] >... 

The best catalyst was found to consist of zinc oxide and copper (or copper oxide) with an admixture of compounds of chromium. The success of the operation depended upon (a) the absence of alkali, which would cause decomposition of the methanol and the production of higher alcohols and oily products, and (b) the complete elimination of all metals except copper, aluminum and tin from those parts of the apparatus which come in contact with the reacting gases. Contact of carbon monoxide with iron, nickel, or cobalt had to be avoided since they formed volatile carbonyls winch deposited metal, by decomposition, on the active catalyst surface and thereby acted as poisons to destroy activity. 

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