ELEMENTARY PRINCIPLES OF CHEMICAL PROCESSES 13.

1 The objective can be described most simply as converting methane and water into methanol and hydrogen, and then purifying the Methanol so that it meets specifications . The overall process stoichiometry is given by the following relationship: CH4 + H2O CH3OH + H2

From this statement, estimate the feed rates of the natural gas (Kmol/h, SCMH ) and steam (Kmol/h, Kg/h) fed as reactants (as opposed to fuel)to the reformer .(Note: the requested estimate neglects formation of by-products and the carbon monoxide and carbon dioxide lost in the purge stream.) 13.2 Five percent excess air is used in burning the reformer fuel; it is drawn into the system at 30 C and 70% relative humidity. Estimate the average molecular weight of the air. Why does it differ from the value of 29 determined in Example 3.3-4 even though the ratio of nitrogen to oxygen is the same? Determine the flow rate of this stream (Kmol,m3) per Kmol of natural gas burned.

13.3 What are the compositions (mole and mass fractions) and volumetric flow rates (m3/Kmol CH4 fed to burners) of (a) the effluent gas from the reformer burners and (b) the gas entering the stack? Use a Methane feed rate to the reformer of 1600 Kmol/h as a basis for subsequent calculations. When all calculations have been completed, scale the results based on the required production rate of specification-grade methanol.

13.4 the primary purpose of the reformer is to convert methane and water to carbon monoxide and hydrogen (Equation 13.1). The extent of this reaction is limited by chemical equilibrium.

Where: Subscript 13.1 refers to the steam-reforming reaction (equation 13.1), Y1 is the mole fraction of species (i), P is the system pressure (atm.) and T is the temperature (K). (a) If equation 13.1 were the only reaction occurring in the reformer, estimate the composition of the product gas that would be leaving

the reformer and the conversion of CH4, assuming the product stream has achieved chemical equilibrium at 855 C and 1.6 MPa. What would be the total flow rate of this stream (Kmol/h, Kg/h)? (b) It is specified that the molar ratio of steam to methane fed to the reformer is 3.0, whereas the stoichiometric ratio for the reforming reaction (Equation 13.1) is 1 mole of water per mole of methane. Estimate the conversion of methane for steam-to-methane feed ratios of 1:1 and 2:1, and compare these to the conversion in part a. Based on your results, explain in your own words why you think the ratio of 3 moles of steam per mole of methane was chosen for the process.

13.5 As pointed out in the Process Description, the water-gas shift reaction (Equation 13.2) occurs in the reformer along with the reforming reaction (Equation 13.1). It to is controlled by chemical equilibrium.

Where the nomenclature is analogous to that in the preceding problem. (a) Taking into account the occurrence of reactions given by both equations 13.1 and 13.2, estimate the composition of the product gas leaving the reformer and the conversion of CH4, assuming the product stream leaving the reformer has achieved chemical equilibrium at 855 C and 1.6 MPa. What is the total flow rate of this stream in both Kmol/h and Kg/h? What effect does the water-gas shift reaction have on the production of CO at the reformer conditions? (b) The ratio of CO to H2 can be an important variable in efficient use of raw materials. In this case study a 3:1 steam-to-methane molar ratio of feed stream was specified. Determine how this feed ratio affects the ratio of CO to H2 in the product from the reformer assuming the reaction products are in chemical equilibrium at 855 C and 1.6 MPa. 13.6 Quantitatively demonstrate that high temperatures and low pressures favor the formation of CO and H2 in the reformer. Do this by calculating and then plotting the production rates (Kmol/Kmol of CH4 fed) of CO and H2 in the reformer product stream over the temperature range 750 C to 950 C at 1.2, 1.6, and 2.0 MPa. Furthermore, construct plots showing the effect of temperature and pressure on selectivity (defined as Kmol CO formed per Kmol CO2 formed) over the same range of conditions. Assuming that your results support the hypothesis that high temperatures and low pressures favor the formation of CO and H2, speculate as to why the temperature and pressure are at the values specified in the process description (855 C and 1.6 MPa) rather than at a higher temperature and lower pressure.

13.7 The reformer product gas leaves the reformer at 855 C. (a) Using the flow rate of the product gas determined in problem 13.5, Calculate the rate (KJ/h) at which heat must be transferred from the combustion gases to the gases flowing through the inside of the reformer tubes. (b) What is the required flow rate of natural gas (Kmol/h and SCMM) to the reformer burners? Assume that the natural gas is burned to completion in the reformer firebox and that the combustion gases leave the firebox at 960 C. (c)The thermal efficiency of the firebox may be defined as the percentage of the lower heating value of the fuel transferred to the reformer gases. Estimate the lower heating value of methane and, assuming the combustion gases leave the firebox at 960 C, the corresponding thermal efficiency of the firebox.

13.8 The heated tube length in the reformer is 10 m and the external diameter of the tubes is 10.5 cm. If the rate of heat transfer () from the combustion gases in the firebox to the reformer gases were accomplished entirely by convection, the following equation would apply: Where Uo is an overall heat transfer coefficient based on the external surface area of the reformer tubes in the firebox, Ao is the total external surface area of the tubes, and Tlm is an average difference between temperatures of the heat source (combustion gases) and the heat sink (reformer reaction gases):

Where T1 and T2 are differences in temperature between the reformer gas and combustion gas at the inlet and at the outlet of the firebox. If the combustion gases are assumed to have a constant temperature in the firebox of 960 C (i.e., they are perfectly mixed), and Uo = 50 Btu/(oF * ft2 * h), what is the required number of tubes in the firebox? In fact, a large fraction of the heat transferred to the tubes is accomplished by a mechanism other than convection. What is that mechanism? (Hint: think of your experience in being close to a flame associated with combustion of natural gas). What will consideration of this additional mechanism mean in terms of the number of tubes required in the firebox?

13.9