The conditions existing in the destructive distillation of coal All solids and liquids which do not decompose below

their boiling point can be converted by the action of heat into vapors. This is dependent upon the fact that all substances are built up of extremely minute particles, which are termed molecules and on heating repel each other. If we take a bar of zinc at the ordinary air temperature and carefully determine its size, and then heat it, we find that the action of heat is to increase in bulk, this increase proceeding at a definite rate until we has raised the temperature to 4230C, when it becomes liquid. If, now the liquid be further heated, it will be found to still continue to expand until a temperature of 1040oC is reached , when it boils like water, and is converted into gaseous state. During the alternation of volume and final conversion into vapors the work which the heat is doing in spacing asunder the particles is, in the first place, to reduce the force of cohesion, which in the solid state holds them rigidly together, and so to endow them with the mobility of the liquid state; whilst the still together spacing apart that takes place when the liquid is heated to its boiling point entirely does away with cohesion and each particle is free to move independently, and gives us the vaporous or gaseous condition. If now the heat which has performed this inter-molecular work is again absorbed from the gas or vapor, the latter condenses to the liquid state, and with a further removal of heat from the liquid the solid is once more produced. An action of this character, in which merely by the aid of heat a solid or liquid is converted into a vapor which can be condensed by cooling again to the original substance, is called one of distillation. And if the body which is distilled decomposes at the temperature necessary to convert it into gaseous matter, so that the products cannot be again condensed into the solids which remain behind in the retort, the liquids which condense in the hydraulic main , and the gaseous products. In considering the actions taking place the destructive distillation of coal we are met at the outset by the difficulty that little or nothing is known as to the heat of formation of coal. When two substances combine together under ordinary conditions heat is evolved, and the compound is called exothermic and when this compound is again broken up, as much heat has to be poured into it as heat or in some other form of energy as was given out during its formation. A few bodies are known, acetylene being one of them, which instead of giving out, absorb heat during formation ; these bodies are called endothermic and when once decomposition has started the heat of formation is again given out, and in many cases adds to the rapidity of decomposition.

Now it is well known that some hydrocarbons are like acetylene of an endothermic character, and coal itself has been suspected of processing this property. Amongst the bodies formed by the destructive distillation of coal, some liberate heat in their formation , whilst others absorb it. These bodies may be tabulated as follows :Bodies formed with Liberation of heat (Exothermic)

substance Carbon dioxide Carbon monoxide Methane Water Sulphuretted hydrogen Ammonia gas

B.T.U per lb. +14646 +3223 +2417 +62100 +243 +1290

Bodies formed with Absorption of Heat (Endothermic)

substance Benzene ethylene Carbon disulphide cyanogen Tar vapor

B.T.U per lb -107 -797 -739 -2374 -540

The determination of the heat of formation of a body like coal is one thought with greatest difficult, for it is evident that, as the composition of coal in a mine will vary not only in different seams but even in the same seam, there is no definite composition , and that

nothing can be known as to the heat of formation except by direct determination, which necessities experimental estimations of error is extremely likely to vitiate the results. When a coal is carbonized it decomposes into gases and vapors, leaving behind in the retort the solid coke, and heat is used up in the decomposition in the change from the solid to the gaseous form, and in raising the gases and vapors to the temperature of the retort. The amount of heat needed to raise a unit weight of any form of matter through one degree is called its specific heat, but the specific heat of gases often is found to vary considerably as the temperature rises, so that it is impossible to say from the specific heat of a gas taken under ordinary conditions what its specific heat will be at high temperatures. Mallard and Le Chateliar made a no. of experiments upon this point, from which the following table was deduced by Euchene :-BTU needed to raise one cubic foot of gas to given temperature : Gas name 1050oC 1922oF Nitrogen Oxygen Hydrogen Carbon monoxide steam Carbon dioxide methane Sulphur dioxide benzene Cyanogens Ammonia tar 44.0 113.6 68.6 102.8 108.4 62.4 97.6 96.4 48 85.0 86.8 37.2 45.2 71.0 145.6 38.8 36.0 29.2 23.6 975oC 1787oF 800oC 1472oF 650oC 1202oF

Of thes etemperatures 650oC is the important one, as this may be taken as the temperature of the gas in the retort. For each lb. of coal decomposed in the retort the heat used up in the decomposition and distillation amounts to 462 BTU over and above the heat due to andothermic reactions. Yhe heat withdrawn from the retort by hot gas vapours amounts to 324 BTU and the heat in the red hot coke when it is drawn accounts for another 442 BTU , so that the heat that has to be accurately supplied for the carbonization is 462 + 324 + 442 = 1228 BTU. The losses in the setting, however, exceed this , and in an ordinary horizontal bench would be 1463 BTU escaping with the flue gases, 398 BTU lost due to air by radiation and convection and 25 BTU in the ash, making in all 1884 BTU. In the horizontal retort setting quoted above the total heat used would be 1228 + 1884 = 3112. Now 1 lb. of gas coke gives an average of 142000 BTU in its combustion, so it would give enough heat t o carbonize 4.5 lb.s of coal or in other words , the coal would require 21.9 percent of its weight of coke to carbonize it, whilist if the whole of the heat of combustion could be used in the retort 8.6 percent would be sufficient. A fair idea of the economics that are possible can be obtained by stating the heat in the setting and retort in percentages BTU per lb. Used in retort 1. Decomposition and distillation 2. Escaping in gas and vapours 3. in hot coke Lost in setting 1. Flue gas 2. radiation and convection 3. Ash 462 324 442 1463 398 23 percent of heat used 15.7 10.4 13.2 47.2 12.8 0.7

We make elaborate tables of the composition of gases and tars produced at various distillation temperatures , but the only information that they give us what is left undecomposed under unknown and varying conditions, the only certain factors being that the heat was nowhere above that which we are pleased to call the temperature of distillation.

If the coal is carbonized in a 6 inch diameter tube filled so that the heat shall be penetrating from every side, there is an almost immediate rise in temperature through the mass, owing to the hot gases and vapors passing through the intersects between of coal , and the coke attains its maximum temperature at the rate of about one inch per hour, so that in three hours, with a wall temperature of 1000oC , the centre of the mass would be at about 950oC, and the carbonization would be finished. Moreover, the rate at which the heat travels in the carbonizing mass depends to a great extent on the initial temperature employed , the figures given being attained only when the flues and outer walls of the retort or chamber are heated to about 1100oC. If the flue temp. is lowered the transmission of hest become slower, and a longer period therefore is required for the complete carbonization, so that if in a 6 inch tube with a temp. Of 1000oC, it takes three times hours to complete carbonization, it would take six hours to do the same work with a temp. of 500oC. Consequently , in making lo temperature coke, such as coalite, in tubular retorts 5.5 to 6.5 inches diameter, it takes four hours to drive off two thirds of the volatile matter that is in the coal. The temp. of the coke through which the gas and tar vapors have to pass, and the length of travel they have un reaching the exit from the retort or chamber in which carbonization os proceeding, are two of the most important factors in determining their decomposition, as it is these which give rise to the secondary reactions that largely determine the final composition of gas and tar. Many attempts have been made to trace the passage of heat through the charge of coal in a retort , on the centre of the charge and one in the space above it at 14 inches and 4 feet from the mouth of the retort, and from their indications prepared the following two diagrams. If an ordinary horizontal retort , 18 to 20 inches wide and 15 inches high, has a 6 inch charge fed into it, the space from the apex to the crown of the top of the charge will be 9 inches deep. If now thermo couples properly protected are placed (1) at the top of the charge (2) in the centre (3) at the top of the charge , we can gain a good idea of the way in which the heat at the bottom of the retort rapidly heats up, and in fifteen minutes has reached 700oC, after which its rise in temperature slows down, and it takes two hours to reach 8000CAfter this its heats more rapidly and attains 10000C at the end of four hours, and then there is practically no rise in the last two hours of carbonization. The temperature at the top of the charge rises more slowly, and by the end of the second hour is only 7400C or 600Ccooler than the bottom, and remains at a lower temperature throughout the whole carbonization. This is not to be wondered at , as although the top flue of the setting is 1150oC, and the bottom flue barely 11000C, the coal at the top of the charge is being heated

largely by radiant heat acting across a considerable space, whilst the bottom of the charge is in direct contact with the heated bottom of the retort, and is taking in heat by conduction.