Steam hydrocarbon reforming composition

The steam-carbon dioxide-hydrocarbon conversion is conducted over a catalyst such as nickel (oxide) on alumina. This type of catalyst can be purchased in quite similar composition from a number of catalyst vendors. In the case in which the feed stock is processed over a catalyst as in steam-hydrocarbon reforming, it is essential that the gas be purified, at least to some extent, prior to its passage over the reforming catalyst, particularly if the catalyst is of the typical composition of supported and promoted nickel (oxide). In steam hydrocarbon reforming, the methane (natural gas) is usually detoxified using an adsorbent such as carbon on which is impregnated suitable chemical adsorbents such as elemental iron or copper. There are at least two of these metallized carbon desulfurizers in parallel with one on... 

Figure 9. Effect of steam-hydrocarbon ratio on gas composition for reforming hexane (same as predicted from equilibrium calculations)...

In another process, tested by Uhde, reforming of hydrocarbons in catalyst-filled tubes was combined with the partial oxidation of the reformed gas at 1300°C within a single vessel (Figure 9.10). The primary reforming reaction was similar to that of the CRG process and operated endothermically at a low steam/ratio. The composition of the product gas and control of the reaction was... 

Steam reforming is the reaction of steam with hydrocarbons to make town gas or hydrogen. The first stage is at 700 to 830°C (1,292 to 1,532°F) and 15-40 atm (221 to 588 psih A representative catalyst composition contains 13 percent Ni supported on Ot-alumina with 0.3 percent potassium oxide to minimize carbon formation. The catalyst is poisoned by sulfur. A subsequent shift reaction converts CO to CO9 and more H2, at 190 to 260°C (374 to 500°F) with copper metal on a support of zinc oxide which protects the catalyst from poisoning by traces of sulfur. 

The first step in the production of synthesis gas is to treat natural gas to remove hydrogen sulfide. The purified gas is then mixed with steam and introduced to the first reactor (primary reformer). The reactor is constructed from vertical stainless steel tubes lined in a refractory furnace. The steam to natural gas ratio varies from 4-5 depending on natural gas composition (natural gas may contain ethane and heavier hydrocarbons) and the pressure used. 

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... 

Composition of Some Industrial Steam Reforming Catalysts (NG = natural gas, HC = hydrocarbon, PR = prereforming, LPG = liquefied petroleum gas, SEC = secondary reforming)... 

Steam reforming is the reaction of steam with hydrocarbons to make town gas or hydrogen. For town gas a representative catalyst composition contains 13wt% Ni, 12.1% U, and... 

Well-established anode materials are Ni cermets such as Ni/YSZ composites. The presence of the second phase increases the contact area and prevents the catalytically active Ni particles from aggregating. The use of the composite becomes problematic if hydrocarbons are to be directly converted Ni catalyzes cracking, and the resulting carbon deposition deactivates the fuel cells. Therefore either pure H2 has to be used or the fuel has to be externally reformed. A third way is internal conversion of CHV with H20 to synthesis gas. The necessary steam addition, however, reduces the overall efficiency. Another problem of Ni cermets, if they are to be used at lower temperatures, is a potential oxidation of the Ni. Alternatives are Cu/Ce02 cermets in which Cu essentially provides the electronic conductivity and Ce02 the catalytic activity. Note that an efficient current collecting property of the electrode presupposes a metal concentration above the percolation threshold. 

Although the above-discussed studies have defined sulfur-poisoning tolerances for conventional nickel catalysts used in steam reforming of natural gas and naptha, they have not considered in sufficient detail the kinetics of poisoning at above-threshold concentrations nor the effects of catalyst and/or gas compositions on rate of deactivation and tolerance level. Nor is there any previous report on the effects of sulfur on product distribution (i.e., relative rates of production of H 2, CO, CH4) in steam reforming of hydrocarbons. 

The raw synthesis gases from partial oxidation of heavy hydrocarbons and coal differ mainly in two aspects from that produced from light hydrocarbons by steam reforming. First, depending on the feedstock composition, the gas may contain a rather high amount of sulfur compounds (mainly H2S with smaller quantities of COS) second, the CO content is much higher, in some cases in excess of 50%. The sulfur compounds (Section 4.3.1.4) can be removed ahead of the shift conversion to give a sulfur-free gas suitable for the classical iron HTS catalyst. In another process variant the sulfur compounds are removed after shift conversion at lower concentration because of dilution by C02. The standard iron catalyst can tolerate only a limited amount of sulfur compounds. With a sulfur concentration in the feed >100 ppm sulfur will be stored as iron sulfide (Eq. 87) ... 

Steam reforming is the reaction of steam with hydrocarbons to make a manufactured gas containing mostly methane with trace amounts of ethylene, ethane, and hydrogen. For the manufacture of this gas, a representative catalyst composition contains 13 wt % Ni, 12.1 wt % U, and 0.3 wt % K it is particularly resistant to poisoning by sulfur. To make hydrogen, the catalyst contains oxides of Ni, Ca, Si, Al, Mg, and K. Specific formulations are given by Satterfield (1980). 

The results obtained can be explained by considering the reactions involved in the processes. We can assume that the main reactions in catalytic pyrolysis are catalytic cracking of tars and light hydrocarbons, which will explain the increase in gas yields when the catalyst is present in the reaction bed (18). Steam reforming of tars (reac. 1), methane (reac. 2) and Cj (reac. 3), and the water-gas shift reaction (reac. 4) can explain the final gas composition generated in catalytic steam gasification. 

Carbon deposition is one of the luost serious problems of the steam reforming catalyst process (ref 1). The deposition of carbon on naphtha steam reforming catalysts depends ori the chemical composition of the hydrocarbon oil, the steam/carbon ratio in the feedstock, as well as the pi ocesa temperature and pressure, it is also affected by tlie presence of sulfur poisons Our past research of SNG catalysts ejiamined the nature of the carbon deposits as a function of the sulfur level on the catalyst (refs, 2 4). A small amount of sulfur was found to promote the formation of carbon that is non-reactive with steam and hydrogen under steam reforming reaction conditions. The continuous accumulation of this less reactive carbon [continuous carbon deposition (CCD)l on the catalyst surface leads to coke fouling Studies of the occurrence of CCD in our laboratory tests allow ua to predict, that coke fouling is likely to occur on the same catalyst used in real Indusl.rlal applications. 

Typical compositions of gasoline, diesel, and jet fuel are summarized in Table 2.13123,124 while their energy densities and the H/C ratios are included in Table 2.1. Steam reforming of these liquid hydrocarbons can be expressed by a general equation as shown in Equation 2.47 ... 

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