Reductions of carbon oxides

Although other experimental evidence also exists for a formate to methoxy mechanism, Baiker argues that formate intermediates are not involved in the reduction of carbon oxides to methanol on Zr02-based catalysts.8,35,624 Rather, formates are intermediates in methanation (see Section 3.2.1). 

Examination of the catalog shelf-list section for titles in the field of hydrogenation reveals a number of texts in this field—e.g., Hydrogenation of Organic Substances by C. Ellis, and The Fischer-Tropsch and Related Syntheses by H. A. Storch et al. Ellis book. Chapter 55, Reduction of Carbon Oxides, is specific to the problem in question. All the other texts listed in this section should, of course, be examined also, well as the Kirk-Othmer, Ullmann, and Thorpe encyclopedias, and the books on catalysis. 

Non-catalytic reactions are very non-efficient imder the conditions of an electrode process because the direct one-electron reduction of this molecule to CO2 needs the potential about -2 V. The catalysts, viz., Re(bipy)(CO)3Cl and [Re(bipy)2(CO)2] complexes and Ni " and Co " derivatives, allow the reduction of carbon oxide to CO and H2 imder much milder conditions. 

Toda , formaldehyde is manufactured principally from methanol limited amoimts are also produced by the oxidation of natural gas and the lower petroleum hydrocarbons. Although other methods of preparation im oh ing the hydrogenation of carbon oxides, the pyrolytic decomposixion of foiTuates, etc., ha e been patented, they do not appear to have achieved commercial importance. In connection with the reduction of carbon oxides, Xeu ton and Dodg determined the equilibriiun constant for the reaction,... 

Consider the reduction of zinc oxide, by carbon monoxide. The equations are ... 

Hence for the reduction of zinc oxide by carbon monoxide we have. 

The conventional electrochemical reduction of carbon dioxide tends to give formic acid as the major product, which can be obtained with a 90% current efficiency using, for example, indium, tin, or mercury cathodes. Being able to convert CO2 initially to formates or formaldehyde is in itself significant. In our direct oxidation liquid feed fuel cell, varied oxygenates such as formaldehyde, formic acid and methyl formate, dimethoxymethane, trimethoxymethane, trioxane, and dimethyl carbonate are all useful fuels. At the same time, they can also be readily reduced further to methyl alcohol by varied chemical or enzymatic processes. 

The Iron Bla.stFurna.ee, The reduction of iron oxides by carbon in the iron (qv) blast furnace is the most important of all extractive processes, and the cornerstone of all industrial economies. Better understanding of the reactions taking place within the furnace has made possible a more efficient operation through better preparation of the burden, higher blast temperature, and sometimes increased pressure. Furnace capacity has doubled since the 1800s, whereas coke consumption has been reduced by about half The ratio of coke to iron produced on a per weight basis is ca 0.5 to 1. 

The dissolution of carbon in molten iron in the lower part of the furnace, leads to the reduction of manganese oxide (eq. 15) and some sihea (eq. 14), both in the slag, whereby the subsequent dissolution of these metals occurs in the molten iron. 

Zinc is produced by reduction of 2inc oxide, usually a calcine obtained by roasting 2inc sulfide concentrates. Carbon is used in the absence of air at 1200—1300°C, well above the boiling point of the metal (906°C). 

Tantalum. Numerous methods developed to extract tantalum metal from compounds included the reduction of the oxide with carbon or calcium the reduction of the pentachloride with magnesium, sodium, or hydrogen and the thermal dissociation of the pentachloride (30). The only processes that ever achieved commercial significance are the electrochemical reduction of tantalum pentoxide in molten K TaF /KF/KCl mixtures and the reduction of K TaF with sodium. 

Vanadium metal can be prepared either by the reduction of vanadium chloride with hydrogen or magnesium or by the reduction of vanadium oxide with calcium, aluminum, or carbon. The oldest and most commonly used method for producing vanadium metal on a commercial scale is the reduction of V20 with calcium. Recently, a two-step process involving the alurninotherniic reduction of vanadium oxide combined with electron-beam melting has been developed. This method makes possible the production of a purer grade of vanadium metal, ie, of the quaUty required for nuclear reactors (qv). 

Preparation. Boron carbide is most commonly produced by the reduction of boric oxide with carbon in an electric furnace between 1400 and 2300°C. In the presence of carbon, magnesium reduces boric oxide to boron carbide at 1400—1800°C. The reaction is best carried out in a hydrogen atmosphere in a carbon tube furnace. By-product magnesium compounds are removed by acid treatment. 

Carbides of the Actinides, Uranium, and Thorium. The carbides of uranium and thorium are used as nuclear fuels and breeder materials for gas-cooled, graphite-moderated reactors (see Nuclearreactors). The actinide carbides are prepared by the reaction of metal or metal hydride powders with carbon or preferably by the reduction of the oxides uranium dioxide [1344-57-6] UO2 tduranium octaoxide [1344-59-8], U Og, or thorium... 

Catalytic Pyrolysis. This should not be confused with fluid catalytic cracking, which is used in petroleum refining (see Catalysts, regeneration). Catalytic pyrolysis is aimed at producing primarily ethylene. There are many patents and research articles covering the last 20 years (84—89). Catalytic research until 1988 has been summarized (86). Almost all catalysts produce higher amounts of CO and CO2 than normally obtained with conventional pyrolysis. This indicates that the water gas reaction is also very active with these catalysts, and usually this leads to some deterioration of the olefin yield. Significant amounts of coke have been found in these catalysts, and thus there is a further reduction in olefin yield with on-stream time. Most of these catalysts are based on low surface area alumina catalysts (86). A notable exception is the catalyst developed in the former USSR (89). This catalyst primarily contains vanadium as the active material on pumice (89), and is claimed to produce low levels of carbon oxides. 

Carbotbermic Reactions Some apparently solid/solid reactions with carbon apparently take place through intermediate CO and CO2. The reduction of iron oxides has the mechanism... 

Stable oxides, such as those of clrromium, vanadium and titanium cannot be reduced to the metal by carbon and tire production of these metals, which have melting points above 2000 K, would lead to a refractoty solid containing carbon. The co-reduction of the oxides widr iron oxide leads to the formation of lower melting products, the feno-alloys, and tlris process is successfully used in industrial production. Since these metals form such stable oxides and carbides, tire process based on carbon reduction in a blast furnace would appear to be unsatisfactory, unless a product samrated with carbon is acceptable. This could not be decarburized by oxygen blowing without significairt re-oxidation of the refractory metal. 

These formerly involved the use of banks of externally heated, horizontal retorts, operated on a batch basis. They were replaced by continuously operated vertical retorts, in some cases electrically heated. Unfortunately none of these processes has the thermal efficiency of a blast furnace process (p. 1072) in which the combustion of the fuel for heating takes place in the same chamber as the reduction of the oxide. The inescapable problem posed by zinc is that the reduction of ZnO by carbon is not spontaneous below the boiling point of Zn (a problem not encountered in the smelting of Fe, Cu or Pb, for instance), and the subsequent cooling to condense the vapour is liable, in the presence of the combustion products, to result in the reoxidation of the metal ... 

From the results of other authors should be mentioned the observation of a similar effect, e.g. in the oxidation of olefins on nickel oxide (118), where the retardation of the reaction of 1-butene by cis-2-butene was greater than the effect of 1-butene on the reaction of m-2-butene the ratio of the adsorption coefficients Kcia h/Kwas 1.45. In a study on hydrogenation over C03O4 it was reported (109) that the reactivities of ethylene and propylene were nearly the same (1.17 in favor of propylene), when measured separately, whereas the ratio of adsorption coefficients was 8.4 in favor of ethylene. This led in the competitive arrangement to preferential hydrogenation of ethylene. A similar phenomenon occurs in the catalytic reduction of nitric oxide and sulfur dioxide by carbon monoxide (120a). 

Purification, Opening, and Size Reduction of Carbon Nanotubes by Oxidative Treatments... 

Sol-gel technique has also been applied to modify the anode/electrolyte interface for SOFC running on hydrocarbon fuel [16]. ANiA SZ cermet anode was modified by coating with SDC sol within the pores of the anode. The surface modification of Ni/YSZ anode resulted in an increase of structural stability and enlargement of the TPB area, which can serve as a catalytic reaction site for oxidation of carbon or carbon monoxide. Consequently, the SDC coating on the pores of anode leads to higher stability of the cell in long-term operation due to the reduction of carbon deposition and nickel sintering. 

Although this chemistry is complex, the basic process is reduction of iron oxide by carbon in an atmosphere depleted of oxygen. Archaeologists have found ancient smelters in Africa (in what is now Tanzania) that exploited this chemistry to produce iron in prehistoric times. Early African peoples lined a hole with a fuel of termite residues and added iron ore. Chamed reeds and charcoal provided the reducing substance. Finally, a chimney of mud was added. When this furnace was fired, a pool of iron collected in the bottom. 

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