Methanation, Fischer-Tropsch

The purification step in the route 1 approach removes all of the H2S and COS in the raw product gas from the gasifier in addition to the carbon dioxide. Sulfur acts as a catalyst poison to Fischer-Tropsch, methanation and methanol catalyst systems, so pure sulfur-free gases must be used in these synthesis reactions. 

The Fischer-Tropsch reaction is essentially that of Eq. XVIII-54 and is of great importance partly by itself and also as part of a coupled set of processes whereby steam or oxygen plus coal or coke is transformed into methane, olefins, alcohols, and gasolines. The first step is to produce a mixture of CO and H2 (called water-gas or synthesis gas ) by the high-temperature treatment of coal or coke with steam. The water-gas shift reaction CO + H2O = CO2 + H2 is then used to adjust the CO/H2 ratio for the feed to the Fischer-Tropsch or synthesis reactor. This last process was disclosed in 1913 and was extensively developed around 1925 by Fischer and Tropsch [268]. 

The mechanism of the Fischer-Tropsch reactions has been the object of much study (note Eqs. XVI11-55-XV111-57) and the subject of much controversy. Fischer and Tropsch proposed one whose essential feature was that of a metal carbide—patents have been issued on this basis. It is currently believed that a particular form of active adsorbed carbon atoms is involved, which is then methanated through a series of steps such as... 

A topic of current interest is that of methane activation to give ethane or selected oxidation products such as methanol or formaldehyde. Oxide catalysts are used, and there may be mechanistic connections with the Fischer-Tropsch system (see Ref. 285). 

Fischer-Tropsch Process. The Hterature on the hydrogenation of carbon monoxide dates back to 1902 when the synthesis of methane from synthesis gas over a nickel catalyst was reported (17). In 1923, F. Fischer and H. Tropsch reported the formation of a mixture of organic compounds they called synthol by reaction of synthesis gas over alkalized iron turnings at 10—15 MPa (99—150 atm) and 400—450°C (18). This mixture contained mostly oxygenated compounds, but also contained a small amount of alkanes and alkenes. Further study of the reaction at 0.7 MPa (6.9 atm) revealed that low pressure favored olefinic and paraffinic hydrocarbons and minimized oxygenates, but at this pressure the reaction rate was very low. Because of their pioneering work on catalytic hydrocarbon synthesis, this class of reactions became known as the Fischer-Tropsch (FT) synthesis. 

Secunda discharges no process water effluents. AU. water streams produced are cleaned and reused in the plant. The methane and light hydrocarbons in the product are reformed with steam to generate synthesis gas for recycle (14). Even at this large scale, the cost of producing fuels and chemicals by the Fischer-Tropsch process is dominated by the cost of synthesis gas production. Sasol has estimated that gas production accounts for 58% of total production costs (39). 

Goal Upgrading via Fischer-Tropsch. The synthesis of methane by the catalytic reduction of carbon monoxide and hydrogen over nickel and cobalt catalysts at atmospheric pressure was reported in 1902 (11). 

Fischer-Tropsch Synthesis The best-known technology for producing hydrocarbons from synthesis gas is the Fischer-Tropsch synthesis. This technology was first demonstrated in Germany in 1902 by Sabatier and Senderens when they hydrogenated carbon monoxide (CO) to methane, using a nickel catalyst. In 1926 Fischer and Tropsch were awarded a patent for the discovery of a catalytic technique to convert synthesis gas to liquid hydrocarbons similar to petroleum. 

The Fischer-Tropsch reaction is highly exothermic. Therefore, adequate heat removal is critical. High temperatures residt in high yields of methane, as well as coking and sintering of the catalyst. Three types of reac tors (tubular fixed bed, fluidized bed, and slurry) provide good temperature control, and all three types are being used for synthesis gas conversion. The first plants used tubular or plate-type fixed-bed reactors. Later, SASOL, in South Africa, used fluidized-bed reactors, and most recently, slurry reactors have come into use. 

Synthesis gas consists of a nonhydrocarhon mixture (H2,CO) ohtain-ahle from more than one source. It is included in this chapter and is further noted in Chapter 5 in relation to methane as a major feedstock for this mixture. This chapter discusses the use of synthesis gas obtained from coal gasification and from different petroleum sources for producing gaseous as well as liquid hydrocarbons (Fischer Tropsch synthesis). 

Fischer Tropsch synthesis is catalyzed by a variety of transition metals such as iron, nickel, and cobalt. Iron is the preferred catalyst due to its higher activity and lower cost. Nickel produces large amounts of methane, while cobalt has a lower reaction rate and lower selectivity than iron. By comparing cobalt and iron catalysts, it was found that cobalt promotes more middle-distillate products. In FTS, cobalt produces... 

Catalysts. The methanation of CO and C02 is catalyzed by metals of Group VIII, by molybdenum (Group VI), and by silver (Group I). These catalysts were identified by Fischer, Tropsch, and Dilthey (18) who studied the methanation properties of various metals at temperatures up to 800°C. They found that methanation activity varied with the metal as follows ruthenium > iridium > rhodium > nickel > cobalt > osmium > platinum > iron > molybdenum > palladium > silver. 

Interesting features of this process include the potential for one-stage methanation to completion without the need for gas recycle. This feature was cited by Chem Systems, but, according to Rheinpruessen-Koppers work on the Fischer-Tropsch (52, 53), gas recycle was necessary with high H2 CO ratios. Drawbacks include such factors as catalyst attrition (48, 50), and low volume productivities of the methanator (less than one-tenth that reported for fixed bed adiabatic reactors) (48, 50, 52, 53, 61). 

Dr. Moeller We have done this, and we compared an iron catalyst used for the Fischer-Tropsch plant and a nickel catalyst used in the methanation plant. By the same x-ray techniques, we found no nickel carbide on the used methanation catalyst, but we did find iron carbide on the used Fischer-Tropsch catalyst. 

L. Seglin Why has Lurgi selected the hot gas recycle process for methanation rather than the isothermal reactor (ARGE) design which they used for the Fischer-Tropsch plant in SASOL s plant in South Africa ... 

Dr. Moeller A methanation plant does not have a problem of selectivity. Whether you operate at low or high temperature, when using a nickel catalyst you will form only methane and no higher hydrocarbon. But with the Fischer-Tropsch synthesis, you have a wide range of possible products which can be formed. If you want to have a certain product, you must keep your temperature at a certain constant value. 

This you cannot do in an adiabatic reactor unless you go to extremely high mixing ratios of fresh feed and recycle gas. In summary, it is a question of selectivity, which is the reason for using the isothermal reactor for Fischer-Tropsch. An adiabatic reactor with a waste heat boiler is cheaper than an isothermal feactor, and hence it is used for methanation. 

The catalytic partial oxidation of methane for the production of synthesis gas is an interesting alternative to steam reforming which is currently practiced in industry [1]. Significant research efforts have been exerted worldwide in recent years to develop a viable process based on the partial oxidation route [2-9]. This process would offer many advantages over steam reforming, namely (a) the formation of a suitable H2/CO ratio for use in the Fischer-Tropsch synthesis network, (b) the requirement of less energy input due to its exothermic nature, (c) high activity and selectivity for synthesis gas formation. 

Ruthenium is a known active catalyst for the hydrogenation of carbon monoxide to hydrocarbons (the Fischer-Tropsch synthesis). It was shown that on rathenized electrodes, methane can form in the electroreduction of carbon dioxide as weU. At temperatures of 45 to 80°C in acidihed solutions of Na2S04 (pH 3 to 4), faradaic yields for methane formation up to 40% were reported. On a molybdenium electrode in a similar solution, a yield of 50% for methanol formation was observed, but the yield dropped sharply during electrolysis, due to progressive poisoning of the electrode. 

The Fischer-Tropsch reaction has now been known for almost 70 years and is of great importance partly for itself and also as part of a coupled set of processes whereby steam or oxygen plus coal or coke is transformed into methane, alkenes, alcohols, and gasolines. According to Eqs.I-IV in the most... 

One of the most important, and perhaps the best studied, applications of three-phase fluidization is for the hydrogenation of carbon monoxide by the Fischer-Tropsch (F-T) process in the liquid phase. In this process, synthesis gas of relatively low hydrogen to carbon monoxide ratio (0.6 0.7) is bubbled through a slurry of precipitated catalyst suspended in a heavy oil medium. The F-T synthesis forms saturated and unsaturated hydrocarbon compounds ranging from methane to high-melting paraffin waxes (MW > 20,000) via the following two-step reaction ... 

During the past several decades, coal made hydrogen is mainly used in areas for the production of chemicals such as ammonia, methanol, methane, and Fischer-Tropsch products (Figure 3.2). 

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