Carbon steam reforming

Synthesis Gas Chemicals. Hydrocarbons are used to generate synthesis gas, a mixture of carbon monoxide and hydrogen, for conversion to other chemicals. The primary chemical made from synthesis gas is methanol, though acetic acid and acetic anhydride are also made by this route. Carbon monoxide (qv) is produced by partial oxidation of hydrocarbons or by the catalytic steam reforming of natural gas. About 96% of synthesis gas is made by steam reforming, followed by the water gas shift reaction to give the desired H2 /CO ratio. 

Methane. The largest use of methane is for synthesis gas, a mixture of hydrogen and carbon monoxide. Synthesis gas, in turn, is the primary feed for the production of ammonia (qv) and methanol (qv). Synthesis gas is produced by steam reforming of methane over a nickel catalyst. 

Fig. 1. Hydrogen production flow sheet, showing steam reforming, shift, hot potassium carbonate CO2 removal, and methanation.

After the steam reforming step, the product gas stream contains a considerable quantity of carbon monoxide which may undergo reaction with additional steam, thereby increasing the hydrogen yield ... 

Synthesis gas, a mixture of CO and o known as syngas, is produced for the oxo process by partial oxidation (eq. 2) or steam reforming (eq. 3) of a carbonaceous feedstock, typically methane or naphtha. The ratio of CO to may be adjusted by cofeeding carbon dioxide (qv), CO2, as illustrated in equation 4, the water gas shift reaction. 

Steam-Reforming Natural Gas. Natural gas is the single most common raw material for the manufacture of ammonia. A typical flow sheet for a high capacity single-train ammonia plant is iadicated ia Figure 12. The important process steps are feedstock purification, primary and secondary reforming, shift conversion, carbon dioxide removal, synthesis gas purification, ammonia synthesis, and recovery. 

Steam Reforming Processes. In the steam reforming process, light hydrocarbon feedstocks (qv), such as natural gas, Hquefied petroleum gas, and naphtha, or in some cases heavier distillate oils are purified of sulfur compounds (see Sulfurremoval and recovery). These then react with steam in the presence of a nickel-containing catalyst to produce a mixture of hydrogen, methane, and carbon oxides. Essentially total decomposition of compounds containing more than one carbon atom per molecule is obtained (see Ammonia Hydrogen Petroleum). 

The carbon monoxide concentration of gas streams is a function of many parameters. In general, increased carbon monoxide concentration is found with an increase in the carbon-to-hydrogen ratio in the feed hydrocarbon a decrease in the steam-to-feed-carbon ratio increase in the synthesis gas exit temperature and avoidance of reequiUbration of the gas stream at a temperature lower than the synthesis temperature. Specific improvement in carbon monoxide production by steam reformers is made by recycling by-product carbon dioxide to the process feed inlet of the reformer (83,84). This increases the relative carbon-to-hydrogen ratio of the feed and raises the equiUbrium carbon monoxide concentration of the effluent. 

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. 

There aie a number of major indusuial problems in the operation of the steam reforming of metlrane. These include the formation of carbon on the surface of the catalyst, the sulphidation of the catalyst by the H2S impurity in commercial natural gas, and die decline of catalytic activity due to Ostwald ripening of the supported catalyst particles by migration of catalyst atoms from the smaller to tire larger particles, as the temperamre is increased. A consideration of tire thermodynamics of the principal reaction alone would suggest that the reaction shifts more favourably to the completion of the reaction as the temperature is increased. 

In the steam reforming reaction, /rC02/p C0 = 2.08 (hr = 5.64) at this temperamre, and at lOOOK the results are hr A = 0.55 for carbon formation, and the PCO2/p CO ratio is 0.155 (hr A = 1.16), and tlrus the tendency for carbon formation passes from zero to unity in tlris temperature range. The presence of CO2 is not indicated in this reaction as given above, but its partial pressure can be obtained from data for the concunent reaction... 

Carbon monoxide is a colourless, odourless gas and - without chemical analysis - its presence is undetectable. It is produced by steam reforming or incomplete combustion of carbonaceous fuels typical carbon monoxide concentrations in common gases are given in Table 5.30. 

The operation of a large synthetic ammonia plant based on natural gas involves a delicately balanced sequence of reactions. The gas is first desulfurized to remove compounds which will poison the metal catalysts, then compressed to 30 atm and reacted with steam over a nickel catalyst at 750°C in the primary steam reformer to produce H2 and oxides of carbon ... 

Recently, a new process has been developed to manufacture hydrogen by steam reforming methanol. In this process, an active catalyst is used to decompose methanol and shift convert carbon monoxide to carbon dioxide. The produced gas is cooled, and carbon dioxide is removed ... 

Catalytic methanation is the reverse of the steam reforming reaction. Hydrogen reacts with carbon monoxide and carbon dioxide, converting them to methane. Methanation reactions are exothermic, and methane yield is favored at lower temperatures ... 

The various processes involving carbon monoxide steam reforming, water-gas shift, methanation, and methanol synthesis illustrate the operation of thermodynamic constraints and some of their attendant economic consequences. 

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