High-pressure carbon monoxide decomposition

CNTs can be made by means of arc-discharge, laser ablation, high pressure carbon monoxide decomposition (HiPCO), and chemical vapor decomposition (CVD) processes. The HiPCO process delivers high quality SWCNTs but the upscaling is difficult. Arc-discharge, laser ablation and CVD systems are currently used to produce SWCNTs as well as MWCNTs in laboratory scales. However, until now only CVD processes have been upscaled successfully to produce MWCNTs in commercially relevant amounts. For this purpose the synthesis is usually performed in fluidized beds [10-12]. Currently (2011), industrial grades of MWCNTs can be purchased for less than 130 USD/kg. 

Other procedures for the synthesis of CNTs use a gas phase for introducing the catalyst, in which both the catalyst and the hydrocarbon gas are fed into a furnace, followed by a catalytic reaction in the gas phase. The method is suitable for large-scale synthesis, because nanotubes are free from catalytic supports and the reaction can be operated continuously. A high-pressure carbon monoxide reaction method, in which the CO gas reacts with iron pentacarbonyl to form SWNTs, has been developed [38]. SWNTs have been synthesized from a mixture of benzene and ferrocene in a hydrogen gas flow [55]. In both methods, catalyst nanoparticles are formed through thermal decomposition of organometallic compounds, such as iron pentacarbonyl and ferrocene. 

While both SWNT and MWNT existed in small quantities from the first wood fires at the dawn of Earth s history, their discovery and methods of preparation are only recent, as described above. Briefly, some synthetic methods include nickel catalyzed pyrolysis of methane at bOO C (64) for MWNT, and the so-called HiPCO (high pressure carbon monoxide) process for SWNT.This latter involves thermal decomposition of iron pentacarbonyl in a flow of CO at 800-1200°C (65). 

A high carbon monoxide pressure ( 5 atmos.) favours the formation of the butane. Possible mechanisms for its formation include homolytic cleavage of the benzyl-cobalt tetracarbonyl complex and recombination of the radicals to generate 2,3-diphenylbutane and dicobalt octacarbonyl, or a base-catalysed decomposition of the benzylcobalt tetracarbonyl complex (Scheme 8.4). The ethylbenzene and styrene could arise from the phenylethyl radical, or from the n-styrene hydridocobalt tricarbonyl complex. 

The insertion of CO is in many instances thermodynamically unfavourable the thermodynamically most favourable product in hydroformylation and carbonylation reactions of the present type is always the formation of low or high-molecular weight alkanes or alkenes, if chain termination occurs via (3-hydride elimination). The decomposition of 3-pentanone into butane and carbon monoxide shows the thermodynamic data for this reaction under standard conditions. Higher pressures of CO will push the equilibrium somewhat to the left. 

Finely divided nickel combines with carbon monoxide to form zero valent nickel tetracarbonyl, Ni(CO)4. The reaction occurs at 50°C and one atmosphere, although it is usually carried out at 200°C under high CO pressure between 100 to 400 atm for high yield of carbonyl, and to prevent product decomposition. Carbon monoxide at ordinary pressure may be passed over freshly reduced metal to form the tetracarbonyl. 

Nickel tetracarbonyl is a highly toxic volatile colorless liquid that is shipped in cylinders pressurized with carbon monoxide.8 Its vapor is about six times as dense as air. Purification of nickel by the Mond process is based on the decomposition of Ni(CO)4, the reverse of Eq. 15.3. The yellow-red iron pentacarbonyl slowly decomposes in air and is sensitive to light and heal. In feet. Fe-jfCOJy, an orange solid, is prepared by photolysis of Fe(CO). ... 

Most gases do not affect refractory bricks. Under high pressure hydrogen gas can reduce silicon dioxide. At appr. 400-800 °C, carbon monoxide is converted into carbon and carbon dioxide. The carbon is deposited on the brick and this may lead to brick s compression. However, a solution has been found. The decomposition of carbon monoxide appeared to be stimulated by certain iron compounds. By firing the bricks at a sufficiently high temperature, you can convert these iron compounds into iron silicates which do not act as catalysts. 

Bibbo, G.S., Benson, P.M. and Pantano, C.G., (1991), Effect of carbon monoxide partial pressure on the high-temperature decomposition of Nicalon fibre , J. Mater. Sci., 26(18), 5075-5080. 

In spite of its instability in the liquid state, cobalt hydrocarbonyl can be carried from one vessel to another as a vapor highly diluted with carbon monoxide or any other inert gas at room temperature and pressure. A semiquantitative study of the rate of decomposition in both the vapor state and in hexane solution indicates that the half-life is dependent on the initial concentration (Sternberg, Wender, Friedel, and Orchin, 29). It can be absorbed in water at 0° and behaves as a strong mineral acid. The ionization provides a cobalt carbonyl anion ... 

The reaction also takes place within two days at room temperature, under high pressure, to give the two uncontaminated products [2193]. In contrast, the photochemical decomposition (253.7 nm) of SFgOF in the presence of carbon monoxide gave mainly COj and SFg, but a small amount of COFj was found to be one of the by-products of the reaction [641 aa]. 

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