in the retort, with the length of time the distillation has been going on, and with an infinity of other factors of a more or less complex Destructive distillation of coal. nature. If bituminous coal is distilled at a low temperature, the tar is found to contain considerable quantities of light paraffin oils; and there is no doubt that paraffin hydrocarbons are present in the original coal. These paraffins, under the influence of heat, split up into simpler members of the same series and into olefines; and if we imagine the action in its simplest form, we should have the gases, as they were evolved, consisting of (say) ethane and ethylene. These have now to pass down the heated retort on their way to the ascension pipe, and the contact with the heated sides of the retort, and the baking from the radiant heat in the retort, set up an infinity of changes. Ethane, when heated to this degree, splits up into ethylene and hydrogen, whilst ethylene decomposes to methane and acetylene, and the acetylene at once polymerizes to benzene, styrolene, retene, &c. A portion also condenses, and at the same time loses some hydrogen, becoming naphthalene; and the compounds so formed by interactions amongst themselves build up the remainder of the hydrocarbons present in the coal tar, whilst the organic substances containing oxygen in the coal break down, and cause the formation of the phenols in the tar.
There is very little doubt that the general course of the decompositions follows these lines; but any such simple explanation of the actions taking place is rendered impossible by the fact that, instead of the breaking-down of the hydrocarbons being completed in the coal, and only secondary reactions taking place in the retort, in practice the hydrocarbons to a great extent leave the coal as the vapours of condensible hydrocarbons, and the breaking down of these to such simple gaseous compounds as ethylene is proceeding in the retort at the same time as the breaking up of the ethylene already formed into acetylene and methane, and the polymerization of the former into higher compounds. Starting with a solid hydrocarbon of definite composition, it would be theoretically possible to decompose it entirely into carbon, hydrogen, ethylene and methane, and, by rapidly removing these from the heating zone before any secondary actions took place, to prevent formation of tar. But any such ideal is hopeless in practice, as the coal is not a definite compound, and it is impossible to subject it to a fixed temperature.
If the retorts are at a temperature of 1000° C. when the charge of coal is put in, the temperature of the distillation will vary from about 800° C. close to the walls, to about 400° C. in the centre of the coal; and in the same way, in the space above the coal, the products which come in contact with the sides of the Effect of temperature in the retort. retort are heated to 1000° C., whilst the gas near the coal is probably heated to only 600° C. Moreover, the gases and vapours in the retort are subjected to a period of heating which varies widely with the distance from the mouth of the retort of the coal that is undergoing carbonization. The gas developed by the coal near the mouth of the retort is quickly washed out into the ascension pipe by the push of the gas behind, and the period for which it has been exposed to the radiant heat from the walls of the retort is practically nil; whilst the gas evolved in the portion of the retort farthest from the mouthpiece has only its own rate of evolution to drive it forward, and has to traverse the longest run possible in the retort, exposed during the whole of that period to radiant heat and to contact with the highly heated surface of the retort itself. Hence we find that the tar is formed of two distinct sets of products, the first due to incomplete decomposition and the second to secondary reactions due to the products of the decomposition being kept too long in the zone of heat.
Of the first class, the light paraffin oils and pitch may be taken as examples; whilst benzene, naphthalene and retort carbon represent the second. The formation of the second class of bodies is a great loss to the gas manufacturer, as, with the exception of the trace of benzene carried with the gas as vapour, these products are not only useless in the gas, but one of them, naphthalene, is a serious trouble, because any trace carried forward by the gas condenses with sudden changes of temperature, and causes obstructions in the service pipes, whilst their presence in the tar means the loss of a very large proportion of the illuminating constituents of the gas. Moreover, these secondary products cannot be successfully reduced, by further heating, to simpler hydrocarbons of any high illuminating value, and such bodies as naphthalene and anthracene have so great a stability that, when once formed, they resist any efforts again to decompose them by heat, short of the temperature which breaks them up into methane, carbon and hydrogen.
The ammonia is derived from the nitrogen present in the coal combining with hydrogen during destructive distillation, the nitrogen becoming distributed amongst all three classes of products. The following table will give an approximate idea of the proportions which go to each:—
| Per cent. | |
| Nitrogen as ammonia | 14.50 |
| Nitrogen as cyanogen | 1.56 |
| Nitrogen free in gas and combined in tar | 35.26 |
| Nitrogen remaining in coke | 48.68 |
| ——— | |
| 100.00 |
The effect produced by alteration in the temperature of the retort upon the composition of both gas and tar is very marked. As the temperature is raised, the yield of gas from a given weight of coal increases; but with the increase of volume there is a marked decrease in the illuminating value of the gas evolved. Lewis T. Wright found, in a series of experiments, that, when four portions of the same coal were distilled at temperatures ranging from a dull red heat to the highest temperature attainable in an iron retort, he obtained the following results as to yield and illuminating power:—
| Temperature. | Cubic ft. of Gas per ton. | Illuminating Power, Candles. | Total Candles per ton. |
| 1. Dull red | 8,250 | 20.5 | 33.950 |
| 2. Hotter | 9,693 | 17.8 | 34.510 |
| 3. 〃 | 10,821 | 16.7 | 36.140 |
| 4. Bright orange | 12,006 | 15.6 | 37.460 |
Composition of the Gas.
| 1. Per cent. | 2. Per cent. | 4. Per cent. | |
| Hydrogen | 38.09 | 43.77 | 48.02 |
| Marsh gas | 42.72 | 34.50 | 30.70 |
| Olefines | 7.55 | 5.83 | 4.51 |
| Carbon monoxide | 8.72 | 12.50 | 13.96 |
| Nitrogen | 2.92 | 3.40 | 2.81 |
| 100.00 | 100.00 | 100.00 |
The gas analysis of No. 3 was lost, but the illuminating power shows that it was intermediate in composition between Nos. 2 and 4. From this it will be seen that, with the increase of temperature, the hydrocarbons—the olefines and marsh gas series—gradually break up, depositing carbon in the crown of the retort, and liberating hydrogen, the percentage of which steadily increases with the rise of temperature.
The tar formed is affected to an even greater extent than the gas by alterations in the temperature at which the destructive distillation takes place. The lower the temperature, the smaller will be the volume of gas produced, and the lighter the specific gravity of the tar, whilst with increase of temperature, the volume of gas rapidly rises, and so does the specific gravity of the tar. Working with a caking coal Wright obtained the following results:—
| Yield of Gas per ton, Cub. ft. | Specific Gravity of Tar. |
| 6,600 | 1.086 |
| 7,200 | 1.120 |
| 8,900 | 1.140 |
| 10,162 | 1.154 |
| 11,700 | 1.206 |
Analysis of the tar showed that the increase of the specific gravity was due to the increase in the quantity of pitch, which rose from 28.89 to 64.08% in the residuals; whilst the ammonia, naphtha and light oils steadily fell in quantity, the creosote and anthracene oils doing the same, but to a smaller extent. Naphthalene also begins to show in quantity in the tar as soon as the yield of gas reaches 10,000 cub. ft. per ton of coal carbonized.
In spite of these variations, however, the products in their main characteristics will remain the same. They may be divided into—(a) Solids, such as the coke and retort carbon; (b) liquids, consisting of the tar and ammoniacal liquor; and (c) gases, consisting of the unpurified coal gas. The proportions in which the products are approximately obtained from a ton of gas coal have been given as follows:—
| 10,000 cub. ft. of gas | = | 380 | ℔ = | 17.0 | per cent. |
| 10 gallons of tar | = | 115 | 〃 = | 5.1 | 〃 |
| Gas liquor[1] | = | 177 | 〃 = | 7.9 | 〃 |
| Coke | = | 1568 | 〃 = | 70.0 | 〃 |
| —— | —— | ||||
| 2240 | 100.0 |
The chief solid residue, coke, is not absolutely pure carbon, as it contains the mineral non-volatile constituents which remain behind as ash when the original coal is burnt, and which, to a great extent, existed in the sap that filled the cells of the plant from which the coal was formed. The retort carbonSolid products. formed as a dense deposit on the crown of the retort by the action of the high temperature on the hydrocarbons is, however, carbon in a very pure form, and, on account of its density, is largely used for electrical purposes.
- ↑ Liquor condensed from gas alone, without wash water.
