Forms of Carbons Deposits

Forms of Carbon Deposits.—Ross in the earlier review referred to the more-reactive Dent carbon without considering its nature. One type of carbon deposited on Ni catalysts takes the form of filaments, the formation of which was explained by Trimm and co-workers in terms of dissolution of carbon in Ni, followed by diffusion through the Ni and reprecipitation at a grain boundary between the Ni particle and the surface. They found that because the Ni surface was disrupted in this way, its activity for reforming propylene was increased at 

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Whatever the exact form of carbon deposition may be, it must be recognized and taken into account in future calculations. The deposited material is called Dent carbon, and equilibrium constants based on its free energy are included in Figure 1. The deposition of carbon as Dent carbon was confirmed qualitatively by Pursley et al. (4). In other recently reported equilibrium calculations (5, 6, 7), it was assumed that... 

The overall cycling rates of carbon have always depended upon geothermal forces that cause volcanic CO2 exhalation and carbonate uplift, independently of life processes. The hydrosphere s carbonate buffer system kept the oceans at near saturation, with respect to CaC03, at all times (Holland, 1972). Rates of deposition and accumulation of carbonate rocks per unit of geological time have also been within the range of fluctuation observed for the Phanerozoic (Garrels et al., 1976). The form of carbonate deposits, however, was certainly different in the Precambrian from those of today, i.e. it was a predominantly chemical precipitate, rather than biogenic skeletal carbonate (Monty, 1973). 

The initial activity/selectivity of the catalyst was investigated at 773 K and 873 K by pulsing aliquots of propane over a freshly reduced catalyst at each temperature. The pulses are equivalent to one second of continuous flow at the relevant space velocity. Hence the results shown in Table 1 represent the activity/selectivity of the catalyst in its first five seconds of life. Interestingly the amoimt of propene produced does not increase significantly on increasing the temperature from 773 K to 873 K, yet the conversion increases from 30% to 92%. Much of the increase in conversion is taken up by the catalyst in the form of carbon deposition. 

Renewable carbon resources is a misnomer the earth s carbon is in a perpetual state of flux. Carbon is not consumed such that it is no longer available in any form. Reversible and irreversible chemical reactions occur in such a manner that the carbon cycle makes all forms of carbon, including fossil resources, renewable. It is simply a matter of time that makes one carbon from more renewable than another. If it is presumed that replacement does in fact occur, natural processes eventually will replenish depleted petroleum or natural gas deposits in several million years. Eixed carbon-containing materials that renew themselves often enough to make them continuously available in large quantities are needed to maintain and supplement energy suppHes biomass is a principal source of such carbon. 

Of the many forms of carbon and graphite produced commercially, only pyrolytic graphite (8,9) is produced from the gas phase via the pyrolysis of hydrocarbons. The process for making pyrolytic graphite is referred to as the chemical vapor deposition (CVD) process. Deposition occurs on some suitable substrate, usually graphite, that is heated at high temperatures, usually in excess of 1000°C, in the presence of a hydrocarbon, eg, methane, propane, acetjiene, or benzene. 

Of the possible substituting ions, COi ion is by far the most important followed by Na, S04 and Mg. The most common form of natural apatite in sedimentary rocks is francolite, a substituted form of carbonate fluorapatite deposited in marine systems. The substitution of col ior>s into the mineral lattice has a substantial effect on apatite solubility (Jahnke, 1984). More studies are required, however, before the effects of all substituting ions are imderstood and an accurate assessment of the solubility of complex, natural apatites can be made. 

The results indicate that the working catalytic surface is a "carbided form of iron which is synthesized under CO/H2. It is also found, that the type of carbon deposit that forms on the surface is sensitive to the presence of surface alkali. 

Two forms of carbon (carbidic and graphitic) have been observed by x-ray photoelectron spectroscopy (XPS) on polycrystalline cobalt foil during the disproportionation of CO by Nakamura et al.57 The dissociation of adsorbed CO occurred at temperatures higher than 60°C, and carbidic carbon and adsorbed oxygen were formed on the cobalt surface. After the surface is covered with adsorbed carbon and oxygen, no further dissociation of adsorbed CO occurs. Contrary to the dissociation of adsorbed CO, the deposition of carbon by the concerted Boudouard reaction continues on the carbidic carbon-deposited surface. The deposition of carbon increases... 

The field of carbon nanostructure research is vast and novel, and it experienced a major breakthrough after the discovery of fullerenes in 1985 [1], and their subsequent bulk synthesis in 1990 [2]. This event opened the minds of various scientists towards discovering novel carbon allotropes. Promptly, yet another allotrop of carbon was observed by Iijima [3], although it had previously been produced by M. Endo et al. in the 1970s by chemical vapor deposition (CVD) [4]. The most recent important advance in the quest for novel forms of carbon constitutes the isolation of graphene layers [5], which exhibit unique and exceptional electrical properties [6]. In addition, graphene nanoribbons have recently been synthesized and produced using diverse methods [7]. 

Nanocarbon emitters behave like variants of carbon nanotube emitters. The nanocarbons can be made by a range of techniques. Often this is a form of plasma deposition which is forming nanocrystalline diamond with very small grain sizes. Or it can be deposition on pyrolytic carbon or DLC run on the borderline of forming diamond grains. A third way is to run a vacuum arc system with ballast gas so that it deposits a porous sp2 rich material. In each case, the material has a moderate to high fraction of sp2 carbon, but is structurally very inhomogeneous [29]. The material is moderately conductive. The result is that the field emission is determined by the field enhancement distribution, and not by the sp2/sp3 ratio. The enhancement distribution is broad due to the disorder, so that it follows the Nilsson model [26] of emission site distributions. The disorder on nanocarbons makes the distribution broader. Effectively, this means that emission site density tends to be lower than for a CNT array, and is less controllable. Thus, while it is lower cost to produce nanocarbon films, they tend to have lower performance. 

The addition of H2O and CO2 to the fuel gas modifies the equilibrium gas composition so that the formation of CH4 is not favored. Carbon deposition can be reduced by increasing the partial pressure of H2O in the gas stream. The measurements (20) on 10 cm x 10 cm cells at 650°C using simulated gasified coal GF-1 (38% H2/56% CO/6% CO2) at 10 atm showed that only a small amount of CH4 is formed. At open circuit, 1.4 vol% CH4 (dry gas basis) was detected, and at fuel utilizations of 50 to 85%, 1.2 to 0.5% CH4 was measured. The experiments with a high CO fuel gas (GF-1) at 10 atmospheres and humidified at 163°C showed no indication of carbon deposition in a subscale MCFC. These studies indicated that CH4 formation and carbon deposition at the anodes in an MCFC operating on coal-derived fuels can be controlled, and under these conditions, the side reactions would have little influence on power plant efficiency. 

Surface treatments of carbon fibers can in general be classified into oxidative and non-oxidative treatments. Oxidative treatments are further divided into dry oxidation in the presence of gases, plasma etching and wet oxidation the last of which is carried out chemically or electrolytically. Deposition of more active forms of carbon, such as the highly effective whiskerization, plasma polymerization and grafting of polymers are among the non-oxidative treatments of carbon fiber surfaces. 

There are few reported analyses of the thermodynamics of carbon deposition in the ATR of liquid fuels. Though typically not stated in these analyses, the calculations were presumably carried out using the thermodynamic properties of elemental carbon e.g., as formed in reactions (6)-(8) above), rather than any coke species (which consist of a wide range of polynuclear aromatic compounds with quite different thermodynamic properties). This is an important difference, since the results apply only to elemental carbon, not coke deposition in general. 

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