Carbides formation

United States included Waspaloy and M-252, which utilized molybdenum for s ohd-solution strengthening and carbide formation in addition to the y ... 

Various appHcations such as lubricant additives, dyes, pigments, and catalysts are under investigation. Tungsten can be deposited from tungsten hexacarbonyl, but carbide formation and gas-phase nucleation present serious problems (1,2). As a result, tungsten halides are the preferred starting material. 

Group 5 (3), diamondlike carbides and (3), volatile nonmetallic carbides. A line through the box, eg, 0, indicates no carbide formation however, there may be some solubiUty of carbon in the melt. A question mark, eg, Ac , indicates the possibiUty of a carbide. 

Thermal Expansion. The averaged value of the coefficient of linear thermal expansion of diamond over the range 20 to 100°C is 1.34 X 10 cm/cm/ C and 3.14 x 10 from 20 to 800°C. At room temperature the values for sihca glass and diamond ate 0.5 X 10 and 0.8 X 10 , respectively. The relatively low expansion combined with the low reactivity of diamonds, except for carbide formation, leads to some challenges in making strong bonds between diamond and other materials. 

The methanation reaction is carried out over a catalyst at operating conditions of 503—723 K, 0.1—10 MPa (1—100 atm), and space velocities of 500—25,000 h . Although many catalysts are suitable for effecting the conversion of synthesis gas to methane, nickel-based catalysts are are used almost exclusively for industrial appHcations. Methanation is extremely exothermic (AT/ qq = —214.6 kJ or —51.3 kcal), and heat must be removed efficiently to minimise loss of catalyst activity from metal sintering or reactor plugging by nickel carbide formation. 

The main differences in the SteUite aUoy grades of the 1990s versus those of the 1930s are carbon and tungsten contents, and hence the amount and type of carbide formation in the microstmcture during solidification. Carbon content influences hardness, ductUity, and resistance to abrasive wear. Tungsten also plays an important role in these properties. 

Specify stabilized grades of stainless steel. An alternative method to prevent chromium carbide formation is to charge the alloy with substances whose affinity for carbon is greater than that of chromium. These substances will react preferentially with the carbon, preventing chromium carbide formation and thereby leaving the chromium uniformly distributed in the metal. The carbon content of the alloy does not have to be reduced if sufficient quantities of these stabilizing elements are present. Titanium is used to produce one stabilized alloy (321) and niobium is used to provide another (347). Note the cautions below. 

Carbides may also be prepared, either by dhect carburizing, as in the case of steel, in which a surface carbide film dissolves into the subsuate steel, or by refractoty metal carbide formation as in die cases when one of the refractory metal halides is mixed with methane in the plasma gas. 

The ferritic steels may also undergo intercrystalline corrosion as a result of grain boundary carbide formation. In the normal softened state (treated i 800 C) the carbon is largely precipitated and the ferrite composition homogenised so that further heating at lower temperatures has no adverse effect. During solution treatment above 950 C, however, carbon is redissolved. Sensitisation can then occur at lower temperatures but the rate is so rapid that it can only be suppressed by very rapid cooling which is not practically feasible. Thus weld decay is very possible in service unless a remedial... 

Metal dusting usually occurs in high carbon activity environments combined with a low oxygen partial pressure where carburisation and graphi-tisation occur. Usually pits develop which contain a mixture of carbon, carbides, oxide and metal (Fig. 7.52). Hochmann" proposed that dusting occurs as the result of metastable carbide formation in the high carbon activity gas mixture which subsequently breaks down into metal plus free carbon. The dependence of the corrosion resistance of these nickel alloys on the protective oxide him has been described accelerated or internal oxidation occurs only under conditions that either prevent the formation, or lead to the disruption, of this him. In many petrochemical applications the pO is too low to permit chromia formation (ethylene furnaces for example) so that additions of silicon" or aluminium are commonly made to alloys to improve carburisation resistance (Fig. 7.53). 

In some circumstances it is found advantageous to coat graphite rods (or tubes) with a layer of pyrolytic graphite this leads to improved sensitivity with elements such as vanadium and titanium which are prone to carbide formation. 

Four pilot plant experiments were conducted at 300 psig and up to 475°C maximum temperature in a 3.07-in. i.d. adiabatic hot gas recycle methanation reactor. Two catalysts were used parallel plates coated with Raney nickel and precipitated nickel pellets. Pressure drop across the parallel plates was about 1/15 that across the bed of pellets. Fresh feed gas containing 75% H2 and 24% CO was fed at up to 3000/hr space velocity. CO concentrations in the product gas ranged from less than 0.1% to 4%. Best performance was achieved with the Raney-nickel-coated plates which yielded 32 mscf CHh/lb Raney nickel during 2307 hrs of operation. Carbon and iron deposition and nickel carbide formation were suspected causes of catalyst deactivation. 

The metal surface area at the inlet end of the catalyst bed in experiment HGR-12 was smaller than that at the outlet end this indicates that a decrease in nickel metal sites is part of the deactivation process. Sintering of the nickel is one possible mechanism, but carbon and carbide formation are suspected major causes. Loss of active Raney nickel sites could also conceivably result from diffusion of residual free aluminum from unleached catalyst and subsequent alloying with the free nickel to form an inactive material. 

Wm. Haynes The nickel carbide formation has been reversed. That is,nickel carbide has been eliminated by hydrogen treatment in some of the laboratory tests at the Bureau of Mines, and catalyst activity has been restored that way. In the pilot plant, however, we have not been able to achieve any such regeneration of the catalyst. 

Carbon has been removed to very low levels in sodium at 600°C by the use of Type 316 stainless steel". Neither Zr nor Nb is efficient at C removal, since oxide films inhibit carbide formation. ... 

After reduction and surface characterization, the iron sample was moved to the reactor and brought to the reaction conditions (7 atm, 3 1 H2 C0, 540 K). Once the reactor temperature, gas flow and pressure were stabilized ( 10 min.) the catalytic activity and selectivity were monitored by on-line gas chromatography. As previously reported, the iron powder exhibited an induction period in which the catalytic activity increased with time. The catalyst reached steady state activity after approximately 4 hours on line. This induction period is believed to be the result of a competition for surface carbon between bulk carbide formation and hydrocarbon synthesis.(6,9) Steady state synthesis is reached only after the surface region of the catalyst is fully carbided. 

As was demonstrated in the preceding sections, structure-sensitivity phenomena are mostly confined to particle size regimes smaller than 3-4 nm. A process of industrial relevance was investigated by de Jong et al. [127] in their study on cobalt particle size effects in the Fischer-Tropsch reaction. Earlier works noted distinct drop in activity for Co particles smaller than lOnm and ascribed this phenomenon to either a partial oxide or carbide formation which should be enhanced for particles in this size regime [128-139]. In order to avoid similar effects, de Jong used... 

H2/CO = 1 was used, the usage ratio of hydrogen to carbon monoxide was always greater than the feed ratio, and thus the catalyst was uniformly exposed to a low H2/CO ratio, which increases the chance for carbide formation. 

To summarize, from literature there does not seem to be much consensus on whether bulk cobalt carbide forms during realistic FTS conditions. Bulk carbide is generally considered a metastable species. However, it is clear that it may form under upset conditions. Furthermore, there is strong evidence to show that if bulk cobalt carbide is present, it is deleterious in terms of both catalyst activity and selectivity. With this in mind, it would be prudent to operate the catalyst in a regime (sufficiently high H2/CO ratio) where bulk carbide formation is avoided. 

Also, manganese added to cobalt on activated carbon catalysts resulted in a decrease in bulk carbide formation during reduction and a decrease in the subsequent deactivation rate.84 Magnesium and yttrium added to the support in alumina-supported cobalt catalysts showed a lower extent of carburization. This was explained by a decrease in Lewis acidity of the alumina surface in the presence of these ions.87... 

Temperature-Programmed EXAFS/ XANES Characterization of the Impact of Cu and Alkali Promoters to Iron-Based Catalysts on the Carbide Formation Rate... 

An example of activity developing with a Co catalyst is shown in Figure 9.9 (right). CO-conversion (respectively the yield of products) increases with time by a factor of about 10, from ca. 4% to ca. 55%.7,17 Figure 9.9 (left) shows the time dependence of FT with an iron catalyst. There are a strong initial carbon deposition (referring to iron carbide formation) and fast water gas shift reaction, and FT... 

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