Catalytic carbon deposition

McConnell, C. F. Catalytic Carbon Deposition and Gasification during... 

In this study we have shown that the catalytic method—carbon deposition during hydrocarbons conversion—can be widely used for nanotubule production methods. By variation of the catalysts and reaction conditions it is possible to optimize the process towards the preferred formation of hollow... 

Hall et a/. pointed out that carburisation is controlled by three independent processes, i.e. carbon deposition, carbon ingress (through the protective scale) and carbon diffusion through the matrix. Carbon deposition usually occurs by decomposition of CH4 adsorbed on the surface or the catalytic decomposition of CO (Boudouard reaction). Hydrogen... 

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. 

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. 

To reduce the formation of carbon deposited on the anode side [2], MgO and Ce02 were selected as a modification agent of Ni-YSZ anodic catalyst for the co-generation of syngas and electricity in the SOFC system. It was considered that Ni provides the catalytic activity for the catalytic reforming and electronic conductivity for electrode, and YSZ provides ionic conductivity and a thermal expansion matched with the YSZ electrolyte. 

How relevant are these phenomena First, many oscillating reactions exist and play an important role in living matter. Biochemical oscillations and also the inorganic oscillatory Belousov-Zhabotinsky system are very complex reaction networks. Oscillating surface reactions though are much simpler and so offer convenient model systems to investigate the realm of non-equilibrium reactions on a fundamental level. Secondly, as mentioned above, the conditions under which nonlinear effects such as those caused by autocatalytic steps lead to uncontrollable situations, which should be avoided in practice. Hence, some knowledge about the subject is desired. Finally, the application of forced oscillations in some reactions may lead to better performance in favorable situations for example, when a catalytic system alternates between conditions where the catalyst deactivates due to carbon deposition and conditions where this deposit is reacted away. 

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. 

Cracking is an endothermic reaction, implying that the temperature must be rather high (500 °C), with the consequence that catalysts deactivate rapidly by carbon deposition. The fluidized catalytic cracking (FCC) process, developed by Standard Oil Company of New Jersey (1940) (better known as ESSO and nowadays EXXON), offers a solution for the short lifetime of the catalyst. Although cracking is... 

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. 

Figure 3 Catalytic activity of Pt/y-AlfO as function of the carbon deposited on the catalyst (875K)...

Herreyrc, S. and Gadelle, P., Effect of hydrogen on the morphology of carbon deposited from the catalytic disproportionation of CO, Carbon, 1995, 33(2), 234 237. 

In summary, the basicity and the strong NiO-MgO interactions in binary NiO/MgO solid solution catalysts, which inhibit carbon deposition and catalyst sintering, result in an excellent catalytic performance for C02 reforming. The characteristics of MgO play an important role in the performance of a highly efficient NiO/MgO solid-solution catalyst. Moreover, the NiO/MgO catalyst performance is sensitive to the NiO content a too-small amount of NiO in the solid solution leads to a low activity, and a too-high amount of NiO to a low stability. CoO/MgO solid solutions have catalytic performances similar to those of NiO/MgO solid solutions, but require higher reaction temperatures. So far, no experimental information is available regarding the use of a FeO/MgO solid solution for CH4 conversion to synthesis gas. 

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