Nickel catalyst carbon deposits

Inui (180) and Rostrup-Nielsen et al. (175) reported that the amount of carbon deposited on metal catalysts decreases in the order Ni Rh > Ir = Ru > Pt = Pd at 773 K and Ni > Pd = Rh > Ir > Pt Ru at 923 K. Thus, the noble metals exhibit higher selectivities for a carbon-free operation than nickel. Nevertheless, carbon deposition does also occur on noble metals. 

Naphtha desulfurization is conducted in the vapor phase as described for natural gas. Raw naphtha is preheated and vaporized in a separate furnace. If the sulfur content of the naphtha is very high, after Co—Mo hydrotreating, the naphtha is condensed, H2S is stripped out, and the residual H2S is adsorbed on ZnO. The primary reformer operates at conditions similar to those used with natural gas feed. The nickel catalyst, however, requires a promoter such as potassium in order to avoid carbon deposition at the practical levels of steam-to-carbon ratios of 3.5—5.0. Deposition of carbon from hydrocarbons cracking on the particles of the catalyst reduces the activity of the catalyst for the reforming and results in local uneven heating of the reformer tubes because the firing heat is not removed by the reforming reaction. 

These experiments were performed over a nickel catalyst, and it is speculated that the anomolous free energy of the deposited carbon may be attributable to the formation of a carbide or a solid solution. 

It was shown in laboratory studies that methanation activity increases with increasing nickel content of the catalyst but decreases with increasing catalyst particle size. Increasing the steam-to-gas ratio of the feed gas results in increased carbon monoxide shift conversion but does not affect the rate of methanation. Trace impurities in the process gas such as H2S and HCl poison the catalyst. The poisoning mechanism differs because the sulfur remains on the catalyst while the chloride does not. Hydrocarbons at low concentrations do not affect methanation activity significantly, and they reform into methane at higher levels, hydrocarbons inhibit methanation and can result in carbon deposition. A pore diffusion kinetic system was adopted which correlates the laboratory data and defines the rate of reaction. 

Nickel catalysts were used in most of the methanation catalytic studies they have a rather wide range of operating temperatures, approximately 260°-538°C. Operation of the catalytic reactors at 482°-538°C will ultimately result in carbon deposition and rapid deactivation of the catalysts (10). Reactions below 260°C will usually result in formation of nickel carbonyl and also in rapid deactivation of the catalysts. The best operating range for most fixed-bed nickel catalysts is 288°-482 °C. Several schemes have been proposed to limit the maximum temperature in adiabatic catalytic reactors to 482°C, and IGT has developed a cold-gas recycle process that utilizes a series of fixed-bed adiabatic catalytic reactors to maintain this temperature control. 

The most important undesired metallic impurities are nickel and vanadium, present in porphyrinic structures that originate from plants and are predominantly found in the heavy residues. In addition, iron may be present due to corrosion in storage tanks. These metals deposit on catalysts and give rise to enhanced carbon deposition (nickel in particular). Vanadium has a deleterious effect on the lattice structure of zeolites used in fluid catalytic cracking. A host of other elements may also be present. Hydrodemetallization is strictly speaking not a catalytic process, because the metallic elements remain in the form of sulfides on the catalyst. Decomposition of the porphyrinic structures is a relatively rapid reaction and as a result it occurs mainly in the front end of the catalyst bed, and at the outside of the catalyst particles. 

Nickel catalysts used in steam reforming are more resistant to deactivation by carbon deposition if the surface contains sulfur, or gold. Explain why these elements act as promoters. Would you prefer sulfur or gold as a promoter Explain your answer. 

Temperature plays an important role in determining the amount and type of the carbon deposit. Generally during FTS at higher temperatures the amount of carbon deposited will tend to increase,30-31 but the case is often not so straightforward. An example of temperature dependence on the rate of carbon deposition and deactivation is the case of nickel CO hydrogenation catalysts, as studied by Bartholomew.56 At temperatures below 325°C the rate of surface carbidic carbon removal by hydrogenation exceeds that of its formation, so no carbon is deposited. However, above 325°C, surface carbidic carbon accumulates on the surface... 

In CO2 reforming, most of the reported research has been focused on non-noble metal catalysts, particularly nickel, because nickel has activity and selectivity comparable to those of noble metals, at much less cost. However, thermodynamic investigations indicated that the nickel-containing catalysts are prone to carbon deposition in CO2 reforming, resulting in catalyst deactivation (5). Therefore, an important challenge is to increase the resistance of nickel-containing catalysts to deactivation by carbon deposition. 

Alumina is one of the most commonly used supports for nickel catalysts 111, 178,194-204). Ni/Al203 exhibits carbon deposition (180) that depends on the catalyst structure, composition, and preparation conditions. 

A dependence of the amount of carbon deposition on the nickel loading was observed forNi/Al203 catalysts (197). For example, a l-wt% Ni/Al203 exhibited much less carbon deposition than a 13.6 wt% Ni/Al203 catalyst (197). 

Many promoters have been used to improve the performance of Ni/Al203 catalysts. The effect of the basic oxides of Na, K, Mg, and Ca on Ni/Al203 was examined by a number of authors (178,203,211 -213). They found that these added oxides markedly decrease the carbon deposition. The kinetics results showed that the added metal oxides changed the reaction order in CH4 from negative to positive and that in C02 from positive to negative. This observation implies that the surface of a nickel catalyst incorporating basic metal oxides is abundant in adsorbed C02, whereas the surfaces devoid of these oxides are abundant in adsorbed CH4 (178). The coverage of nickel with C02 is most likely unfavorable to CH4 decomposition... 

Fig. 10. Carbon deposition on nickel-containing catalysts at 973 K as determined by TGA. Before reaction, the catalysts were reduced at 1073 K for 3 h. Reaction conditions temperature, 973 K feed gas molar ratio, C02/CH4 = 1/1 GHSV, 144,000 mL (g catalyst)-1 h-1 (214).

MgO is a basic metal oxide and has the same crystal structure as NiO. As a result, the combination of MgO and NiO results in a solid-solution catalyst with a basic surface (171,172), and both characteristics are helpful in inhibiting carbon deposition (171,172,239). The basic surface increases C02 adsorption, which reduces or inhibits carbon-deposition (Section ALB). The NiO-MgO solid solution can control the nickel particle sizes in the catalyst. This control occurs because in the solid solution NiO has strong interactions with MgO and, as indicated by TPR data (26), the former oxide can no longer be easily reduced. Consequently, only a small amount of NiO is expected to be reduced, and thus small nickel particles are formed on the surface of the solid solution, smaller than the size necessary for coke formation. Indeed, the nickel particles on a reduced 16.7 wt% NiO/MgO solid-solution catalyst were too small to be observed by TEM (171). Furthermore, two additional important qualities stimulated the selection of MgO as a support its high thermal stability and low cost (250,251). 

Alloying the nickel of the anode to improve tolerance for fuel contaminants has been explored. Gold and copper alloying decreases the catalytic activity for carbon deposition, while dispersing the anode with a heavy transition metal catalyst like tungsten improves sulfur resistance. Furthermore, ceria cermets seem to have a higher sulfur tolerance than Ni-YSZ cermets [75],... 

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