Iron-zinc oxide catalyst

This reaction is first conducted on a chromium-promoted iron oxide catalyst in the high temperature shift (HTS) reactor at about 370°C at the inlet. This catalyst is usually in the form of 6 x 6-mm or 9.5 x 9.5-mm tablets, SV about 4000 h . Converted gases are cooled outside of the HTS by producing steam or heating boiler feed water and are sent to the low temperature shift (LTS) converter at about 200—215°C to complete the water gas shift reaction. The LTS catalyst is a copper—zinc oxide catalyst supported on alumina. CO content of the effluent gas is usually 0.1—0.25% on a dry gas basis and has a 14°C approach to equihbrium, ie, an equihbrium temperature 14°C higher than actual, and SV about 4000 h . Operating at as low a temperature as possible is advantageous because of the more favorable equihbrium constants. The product gas from this section contains about 77% H2, 18% CO2, 0.30% CO, and 4.7% CH. ... 

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... 

F. Fischer and H. Tropsch, who first described the conversion of synthesis gas into hydrocarbons and oxygen-containing compounds ( oxygenates ) over heterogeneous transition metal catalysts such as iron/zinc oxide. This reaction was developed into a process for the conversion of coal into gasoline. At present such a process is economically feasible only where coal is plentiful and cheap while access to oil products is limited. Currently only South Africa operates plants using the Fischer-Tropsch process. 

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. 

With certain catalysts such as zinc oxide and finely divided iron it was found that the temperature at which reaction was made to occur was the controlling factor in determining the character of the product.108 Thus, with the zinc oxide catalyst only methane was obtained at 480° C., a mixture of 80 per cent methane and 20 per cent higher homologs at 380° C., and a mixture of 10 per cent methane and 90 per cent higher homologs at 300° C. This is not true of nickel catalysts as the hydrogenating activ-... 

Cobalt catalysts such as cobalt/manganese and cobalt/chromium show higher activity than iron/chromium catalysts at temperatures exceeding 300 °C and are highly sulfur tolerant [107]. However, their activity is certainly lower than that of the precious metal catalysts discussed below. Additionally, they are not suitable for low-temperature applications due to their low activity in this temperature range. Ruettinger et al. reported on proprietary base-metal water-gas shift catalyst development. The catalysts were claimed to have lower pyrophoricity than copper/zinc oxide catalysts, and to be stable towards air exposure at 150 ° C and even to liquid water [302]. 

In 1920s, the studies on the catalysts for ammonia sjmthesis were performed sporadically in BASF, instead, the company mainly focused on the organic synthesis under high pressm-es and the new fields in heterogeneous catalysis. Dm-ing the development of ammonia synthesis catalysts, researchers provided valuable information about the dm-ability, thermal stability, sensitivity to poisons, and in particular to the concept of promoter. Mittasch smnmarized the roles of various additives as shown in Fig. 1.9. The hypothesis of successful catalyst is multi-component system proposed by Mittasch was confirmed to be very successful. Iron-chromium catalysts for water gas shift reaction, zinc hromium catalystfor methanol synthesis, bismuth iron catalysts for ammonia oxidation and iron/zinc/alkali catalysts for coal hydrogenation were successively developed in BASF laboratories. 

The latter is carried out in two steps 1) with a cheap iron oxide catalyst and 2) with a more expensive supported copper-zinc oxide catalyst. After removal of the CO2 by pressure washing, residual traces of CO are hydrogenated in the methanation reaction, the reverse of the steam reforming (3.3), on a supported nickel catalyst. Nitrogen is obtained from the air. 

Methanol is prepared by the interaction of carbon monoxide and hydrogen. In older plants in which a promoted zinc oxide catalyst is utilized, reaction conditions are 300-400°C and about 30 MPa (300 atmospheres). In newer plants a copper-based catalyst is employed this allows the use of milder conditions, namely 200-300°C and 5-10 MPa (50-100 atmospheres). The methanol is condensed out and unreacted gases, with fresh make-up gas, recycled to the converters. In the second stage, methanol is oxidized to formaldehyde. In one process a mixture of methanol vapour and air is passed over a catalyst of molybdenum oxide promoted with iron at 350-450°C. The exit gases are scrubbed with water and the formaldehyde is isolated as an aqueous solution. 

Reforming is completed in a secondary reformer, where air is added both to elevate the temperature by partial combustion of the gas stream and to produce the 3 1 H2 N2 ratio downstream of the shift converter as is required for ammonia synthesis. The water gas shift converter then produces more H2 from carbon monoxide and water. A low temperature shift process using a zinc—chromium—copper oxide catalyst has replaced the earlier iron oxide-catalyzed high temperature system. The majority of the CO2 is then removed. 

Metal oxides, sulfides, and hydrides form a transition between acid/base and metal catalysts. They catalyze hydrogenation/dehydro-genation as well as many of the reactions catalyzed by acids, such as cracking and isomerization. Their oxidation activity is related to the possibility of two valence states which allow oxygen to be released and reabsorbed alternately. Common examples are oxides of cobalt, iron, zinc, and chromium and hydrides of precious metals that can release hydrogen readily. Sulfide catalysts are more resistant than metals to the formation of coke deposits and to poisoning by sulfur compounds their main application is in hydrodesulfurization. 

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. 

This was also accomplished with BaRu(0)2(OH)3. The same type of conversion, with lower yields (20-30%), has been achieved with the Gif system There are several variations. One consists of pyridine-acetic acid, with H2O2 as oxidizing agent and tris(picolinato)iron(III) as catalyst. Other Gif systems use O2 as oxidizing agent and zinc as a reductant. The selectivity of the Gif systems toward alkyl carbons is CH2 > CH > CH3, which is unusual, and shows that a simple free-radical mechanism (see p. 899) is not involved. ° Another reagent that can oxidize the CH2 of an alkane is methyl(trifluoromethyl)dioxirane, but this produces CH—OH more often than C=0 (see 14-4). ... 

Hitachi Cable Ltd. (35) has claimed that dehydrogenation catalysts, exemplified by chromium oxide—zinc oxide, iron oxide, zinc oxide, and aluminum oxide—manganese oxide inhibit drip and reduce flammability of a polyolefin mainly flame retarded with ATH or magnesium hydroxide. Proprietary grades of ATH and Mg(OH)2 are on the market which contain small amounts of other metal oxides to increase char, possibly by this mechanism. 

Catalysts, desiccants, and catalyst inerts. In 1988, the refinery began to recycle nonhazardous catalysts, desiccants, and catalyst fines. It recycles electrostatic precipitator fines, Claus catalyst, and catalyst support inerts for use in cement manufacture. Two other catalysts, zinc oxide and iron chromate from the hydrogen plant, are reprocessed at smelters to recover the metals. 

Strangely enough, a combination similar to the ammonia catalyst, iron oxide plus alumina, yielded particularly good results (32). Together with Ch. Beck, the author found that other combinations such as iron oxide with chromium oxide, zinc oxide with chromium oxide, lead oxide with uranium oxide, copper oxide with zirconium oxide, manganese oxide with chromium oxide, and similar multicomponent systems were quite effective catalysts for the same reaction (33). 

Desulfurization reactions in the 1,2-series are encountered among derivatives of both oxathiins and dithiins. 1,2-Oxathiin 2,2-dioxides extrude sulfur dioxide at elevated temperature over zinc oxide, iron or copper oxide to give the corresponding furan (66HC(21 -2)789) [cf. Section 2.26.3.1.2). Copper is a good catalyst for the extrusion of sulfur and sulfur dioxide from dibenzo[c,e3[l,2]dithiin (40) and its dioxide respectively to give dibenzothiophene (66HC(21-2)968). 

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