Theory of Cold-Blast Iron Production with Stack-Gas of Low Notrogen Content

Published in the Journal, September 1970, and presented at a colloquium on 'Future of the Steel Industry', 17th March, 1971. Errata (a) The final sentence in the penultimate paragraph, left hand column p. 34 of the text should read: 'In the hot regions of the bosh and stack the C+CO2=2CO reaction proceeds to CO from coke carbon and carbon dioxide generated by reduction of iron oxides by CO (the so-called solution loss of carbon)'. The italicised words have been omitted in the text. (b) Temperature in Fig. 3 is K not C. (c) In Fig. 9, connection from top plate of column 10 to heat exchanger 9 has been omitted. DISCUSSION J. B. BEEDON AND C. J. JONKER* Dr Bleloch's paper has outlined the advantages of recycling stack-gas of low nitrogen content in the blast furnace. In the first instance it would appear to be extremely beneficial in controlling the hearth temperature and allowing a 100 per cent oxygen-blast to be used. On a second point however we have to disagree. It is claimed that heat is liberated in the combustion zones by the oxidation of CO to CO2 near the tuyeres and in the subsequent reduction of the CO2 by CO. The author has hypothesized as follows, and we quote: 'The C+CO2=2 CO reaction in the outer combustion zone at about 1 700°C is no longer endothermic due to loss of stability of CO2 and its consequent dissociation into CO and free oxygen.' This statement requires closer examination. If we consider the individual events occurring with the CO in the recycled topgas, with the oxygen in the blast and with the coke in the burden, as done by Dr Bleloch, the following heat considerations emerge. All heats of reaction are calculated from the enthalpy values of each reactant and product, as well as the temperature dependence of their molar heat capacities. (a) At the tuyeres: CO+1/2 O2-+CO2 . . . . . (1) CO, CO2 at 500°C; O2 at 25°C. ?H reaction = -65 000 cals/mole CO The reaction (1) is exothermic. (b) In the outer combustion zone: CO2+C?2 CO . . . . . . . . (2) C, CO at 1 700°C; CO2 at 500 0C. ?H reaction = -56 000 cals/mole CO Reaction (2) is endothermic. The overall heat gain of reactions (1) and (2) is ?H=+56 000 - 65 000= -9000 cals/mole CO i.e. the overall reaction is slightly exothermic, the amount of heat liberated is however smaller than suggested by Dr Bleloch. (c) The dissociation CO2+CO+1/2 O2 . . . . . (3) is a highly endothermic reaction at 1 700 0C, requiring 82 000 cals/mole CO2 to proceed to completion. Furthermore, this reaction (3) is energetically not favoured to proceed, as can be observed from the free energy-temperature relationship of figure (3), which favours the formation of CO2 at 1 700 0C. Hence direct dissociation of CO2 at 1 700 0C appears to be unlikely.* The concept of recycling topgas is however still intriguing from many other points of view. Apart from providing a very efficient method of hearth temperature control, it will create a much higher CO partial pressure in the stack. Whether the rate of indirect reduction in the stack will be proportional to this partial pressure or not is un-