Pyrolytic reformer

The pyrolytic reforming reactor was a packed bed in a quartz tube reactor. Quartz was selected to reduce the effect of the reactor construction material on the hydrocarbon decomposition rate. ° The reactor was packed with 5.0 0.1 g of AC (Darco KB-B) or CB (BP2000) carbon-based catalyst. The reactor was heated electrically and operated at 850—950 °C, and the reactants had a residence time of 20—50 s, depending on the fuel. The reactor was tested with propane, natural gas, and gasoline as the fuels. Experiments showed that a flow of 80% hydrogen, with the remainder being methane, was produced for over 180 min of continuous operation.The carbon produced was fine particles that could be blown out... 

The surface analyses of the Co/MgO catalyst for the steam reforming of naphthalene as a model compound of biomass tar were performed by TEM-EDS and XPS measurements. From TEM-EDS analysis, it was found that Co was supported on MgO not as particles but covering its surface in the case of 12 wt.% Co/MgO calcined at 873 K followed by reduction. XPS analysis results showed the existence of cobalt oxide on reduced catalyst, indicating that the reduction of Co/MgO by H2 was incomplete. In the steam reforming of naphthalene, film-like carbon and pyrolytic carbon were found to be deposited on the surface of catalyst by means of TPO and TEM-EDS analyses. 

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. 

Carbonaceous compounds can also form in the absence of a catalyst by free-radical, gas-phase condensation reactions. The formation of this pyrolytic carbon is known in steam-reforming reactors where it can be controlled to some extent by minimizing the free volume within the reactor chamber. This type of carbon does not form readily with methane but can be severe with larger hydrocarbons. The compounds formed by free-radical reactions tend to be quite different from the graphitic carbon formed by metal catalysts. For example, Lee et al. showed that the compounds formed by passing pure, undi-... 

Figure 15.6 Process flow for commercial pyrolysis plant (Thermofuel ) for converting waste plastics into diesel fuel. The plastic is heated to 375-425°C and the pyrolysis vapours are catalytically cracked and then selectively condensed. Note that the pyrolysis vessel is purged with nitrogen gas and that the hot pyrolytic vapours pass from the pyrolysis vessel to the catalytic reaction tower where they are cracked and reformed to give a high-purity diesel stream. (Reproduced by permission of Ozmotech Pty Ltd)...

The Likun Process (China) uses a two-stage cracking process under normal pressures where the waste plastics are first pyrolyzed at 350-400°C in the pyrolysis reactor and then the hot pyrolytic gases flow to a catalyst tower where they undergo catalytic reforming over zeolite at 300-380°C. By having the catalyst in the second stage this overcomes the problems of rapid catalyst deactivation from coke deposits on the surface of the catalyst. 

Ozmotech have developed a Thermofuel process whereby waste plastic is converted into diesel by thermal degradation in the absence of oxygen. In this process the plastic waste is first melted and then cracked in a stainless steel chamber at a temperature of 350-425°C under inert gas (nitrogen). The catalytic reaction tower is designed in such a way that hot pyrolytic gases take a spiral or zigzag path to maximize contact area and time with the metal catalyst. The metal catalyst cracks hydrocarbon chains longer than C25 and reforms chains shorter than Ce. This leads to the formation of saturated alkanes. 

One of the main problems associated with hydrocarbon steam reforming over Ni is the deactivation of the Ni catalyst as a result of the formation of carbon deposits on Ni. The C-induced deactivation of Ni has been studied extensively [10,18,28-35], For example, Rostrup-Nielsen reported that steam reforming of various hquid fuels on Ni leads to the formation of encapsulating, whisker-like, or pyrolytic carbon on the catalyst [18, 30], To illustrate the problem of carbon poisoning, in Fig. 13.1 we show a transmission electron micrograph (TEM) of a Ni particle taken after steam reforming of propane at steam to carbon ratio of 1.5. The micrograph shows that carbon deposits are formed on Ni [16],... 

It is imperative that carbon formation is avoided in tubular reformers. Carbon formation may lead to the breakdown of catalysts resulting in an uneven flow distribution between different tubes in the reformer, causing local overheating and shorter tube life. Formation of pyrolytic carbon may result in carbon deposits near the tube wall. This may lead to a reduced heat transfer coefficient and development of hot bands as evidenced by the reddish zone on the tube wall during operation. 

Carbon formation on steam reforming catalysts takes place in three different forms whisker-like carbon, encapsulated carbon, and pyrolytic carbon as described in Table 2.2 [1]. Whisker-like carbon grows as a fiber from the catalyst surface with a pear-shaped nickel crystal on the end. Strong fibers can even break down catalyst particles increasing the pressure drop across the reformer tubes [4], The carbon for whisker formation is formed by the reaction of hydrocarbons as well as CO over transition metal catalysts [1], The whisker growth is a result of diffusion through the catalyst and nucleation to form a long carbonaceous fiber. 

Pyrolytic carbon is formed mainly by three different reactions, namely, the reversible decomposition of methane (Reaction 2.5), the irreversible cracking of higher hydrocarbons (Reaction 2.6), and/or coke formation (Reaction 2.7). The formation of these carbon deposits leads to the breakdown of the catalyst and hot spots in the reactor. Pyrolytic carbon is usually found as dense shales on the reformer wall or encapsulating the catalyst particles. The process leads to the deactivation of the catalyst and increase of pressure drop across the reformer tubes. The thermal cracking of hydrocarbon occurs at high temperatures and at low steam to hydrocarbon ratios. 

A schematic flow diagram of the biomass pyrolyzer-reformer designed and constructed for Phase 2 is shown in Figure 3. The pyrolyzer is designed to process up to 188 lbs (85 kg) per hour of pelletized biomass into char and pyrolytic off-gas. 

Hydrocarbon cracking [see Eq. (3.22), Section 3.2] may lead to coke formation. This reaction is well known from nickel catalysts, which form whisker-like coke deposits at high temperature [270]. This type of pyrolytic carbon formation takes place above a critical temperature [81], which is about 600 °C for methane [271]. Precious metal catalysts such as rhodium generally have a lower tendency towards coke formation [272] and are more active, which makes them attractive for hydrocarbon reforming in smaller-scale systems (see Section 4.2). 

Carbon Formation. Steam reforming involves the risk of carbon formation by the decomposition of methane and other hydrocarbons or by the Boudouard reaction (reactions (7) -(10)). Reactions (7) - (8) are catalyzed by nickel (Rostrup-Nielsen, 1984a). The carbon grows as a fibre (whisker) with a nickel crystal at the tip. The methane or carbon monoxide is adsorbed dissociatively on the nickel surface (Alstrup, 1988). Carbon atoms not reacting to gaseous molecules are dissolved in the nickel crystal, and solid carbon nucleates at the non-exposed side of the nickel crystal, preferably from Ae dense (111) surface planes. Reaction (10) results in pyrolytic carbon encapsulating the catalyst. 

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