Steam Reformers Coking

The TEM images of deposits observed on Catalyst I used for the steam reforming of naphthalene are shown in Fig. 5. Two types of deposits were observed and they were proved to be composed of mainly carbon by EDS elemental analysis. One of them is film-like deposit over catalysts as shown in Fig. 5(a). This type of coke seems to consist of a polymer of C H, radicals. The other is pyrolytic carbon, which gives image of graphite-like layer as shown in Fig. 5(b). Pyrolytic carbon seems to be produced in dehydrogenation of naphthalene. TPO profile is shown in Fig. 6. The peaks around 600 K and 1000 K are attributable to the oxidation of film-like carbon and pyrolytic carbon, respectively [11-13]. These results coincide with TEM observations. 

TEM-EDS and XPS analyses were conducted on Co/MgO catalysts. The results of surface analyses showed that Co metal is not supported on the MgO as particles, but covers MgO surface in the case of 12 wt.% Co/MgO calcined at 873 K followed by reduction. After the reduction of catalyst at 1173 K, both cobalt oxide and CoO-MgO solid solution are observed on the surface of catalyst. In the steam reforming of naphthalene, two types of coke deposited on the surface of catalyst are observed. These are assigned to film-like and graphite type carbon by TPO analysis. 

Rostrup-Nielsen, J. R. 1974. Coking on nickel catalysts for steam reforming of hydrocarbons./. Catal. 33 184-201. 

Hydrogen availability is an important issue and refiners must be persuaded that gasification will prove to be as reliable a technology in the future as natural gas steam reforming is today. Many refineries produce sufficient pet coke to more than satisfy refinery hydrogen requirements. This would allow co-production of hydrogen and power or F-T liquids. 

CH4 can be oxidized directly using a solid oxide fuel cell however, high concentrations of CH4 lead to severe coking problems. Only cells containing dilute concentrations of CH4 can be oxidized directly in current SOFCs. In addition, the oxidation of CH4, like that of CO, may not actually occur at active electrochemical sites within an SOFC. Rather, CH4 is probably reformed within the cell through steam reforming. 

There is a need for low-cost methane steam reforming catalysts that are active at low temperature and resistant to coke formation under membrane reactor conditions. Low-cost (Ni-based) catalysts are also needed that can withstand regeneration conditions in a sorption-enhanced reformer. 

There are three major gas reformate requirements imposed by the various fuel cells that need addressing. These are sulfur tolerance, carbon monoxide tolerance, and carbon deposition. The activity of catalysts for steam reforming and autothermal reforming can also be affected by sulfur poisoning and coke formation. These requirements are applicable to most fuels used in fuel cell power units of present interest. There are other fuel constituents that can prove detrimental to various fuel cells. However, these appear in specific fuels and are considered beyond the scope of this general review. Examples of these are halides, hydrogen chloride, and ammonia. Finally, fuel cell power unit size is a characteristic that impacts fuel processor selection. 

Employing process conditions similar to those used for steam reforming of natural gas (e.g. fixed-bed reactors, temperatures in the 800-900 °C range) has been demonstrated to be inadequate for processing thermally unstable biomass liquids [29]. The most important problem is represented by coke formation, especially in the upper layer of the catalyst bed and in the reactor freeboard, that limits the operation time (e.g. 3—4 h on commercial Ni-based catalysts) and requires a long regeneration process for the catalyst (e.g. 6-8 h on commercial Ni-based catalysts). 

Notably, since high-temperature steam reforming enhances the r-WGSR, which would produce CO, the undesirable poison of fuel cells, low-temperature reforming is preferable. Low temperatures can be achieved over strong acid catalysts, although the strong acid at the same time tends to cause deactivation by coke formation. 

The complete steam reforming of acetic acid can be achieved over commercial Ni-based catalysts [79]. The operating temperature of these systems is aWays higher than 650 °C. The robustness of the catalysts based on Ni guarantees operation over thousands of hours, but this metal leads to extensive coke formation. In order to improve the stability, La203 vas introduced in the catalyst formulation [258]. 

Carbon monoxide may be prepared by several methods. Large scale production is carried out by controlled oxidation of natural gas or by the catalytic steam reforming of methane or light petroleum fractions. The products obtained are mixtures of CO, H2, and CO2. It also is made by gasification of coal and coke with oxygen at about 1,500°C. 

Ce02-supported noble-metal catalysts such as Pt, Pd and Rh are of interest because of their importance in the so-called three-way converter catalysts (TWC), designed to reduce emissions of CO, NOx and uncombusted hydrocarbons in the environment and to purify vehicle-exhaust emissions. Such catalysts are also of current interest in steam reforming of methane and other hydrocarbons. Conventional practical catalysts for steam reforming consist of nickel supported on a ceramic carrier with a low surface area and are used at high temperatures of 900 C. This catalyst suffers from coke formation which suppresses the intrinsic catalyst activity. Promoters such as Mo are added to suppress coke formation. Recently, Inui etal(l991) have developed a novel Ni-based composite... 

Several operating conditions have been found which satisfy the requirements for no coke formation. The optimum S/C ratio at 3.5 appears to fulfill the requirements for temperatures around 800°C for steam reforming process. The optimum O/C and S/C ratios are found 0.45 and 1.5 respectively for ATR reactor simulations at the inlet temperature of 700°C. 

The reactor temperature required to prevent coke formation varies considerably for the different processes. Table 2.1 summarizes the values calculated assuming thermodynamic equilibrium for 2,2,4-trimethylpentane reforming. Generally, the coking tendency increases in the following order at constant O/C ratio SR > ATR > POx. These calculations demonstrate that at steam to carbon ratios (S/C) > 2 and reaction temperatures > 600 °C, which is very common for hydrocarbon fuel processors, coke seems to be an unstable species especially under the conditions of steam reforming. 

Higher Hydrocarbons. - A number of papers describing the steam reforming of higher hydrocarbons are particularly concerned with the subject of carbon deposition on the catalysts. The subject of carbon deposition on nickel catalysts is considered to be somewhat outside the subject of this review, especially as the subject is covered by two excellent recent discussions of papers on carbon deposition and coking during steam reforming, methanation, and other reactions.202 203... 

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