Coal, and What We Get from It

by Raphael Meldola

Of the hydrocarbons thus separated, benzene and toluene are by far the most important; there is but a limited use for the xylenes at present, and these and the hydrocarbons of higher boiling-point belonging to the same series which distil over between 140° and 150° constitute what is known as “solvent naphtha,” because it is used for dissolving india-rubber for waterproofing purposes. The hydrocarbons of still higher boiling-point which remain in the still are used as burning naphtha for lamps. If benzene of a higher degree of purity is required—as it is for the manufacture of certain colouring-matters—the fraction containing this hydrocarbon can be again distilled through the rectifying column, and a large proportion of the toluene thus separated from it. Finally, pure benzene can be obtained by submitting the rectified hydrocarbon to a process of refrigeration in a mixture of ice and salt, when the benzene solidifies to a white crystalline solid, while the toluene does not solidify, and can be drained away from the benzene crystals which liquefy at about 5° C.

The account rendered by the technologist with respect to the light oils of the tar is thus a pretty good one. Already we see that benzene, toluene, solvent naphtha, and burning naphtha are separated from them. Even the alkaline and acid washings may be made to surrender their contained products, for the first of these contains a certain quantity of carbolic acid, and the acid contains a strongly smelling base called pyridine, for which there is at present no great demand, but which may one day become of importance. The actual quantity of benzene in tar is a little over one per cent. by weight, and of toluene there is somewhat less. The naphthas are present to the extent of about 35 per cent.

Now let us consider some of the transformations which benzene and toluene undergo in the hands of the manufacturing chemist. The production of aniline from benzene by acting upon this hydrocarbon with nitric acid, and then reducing the nitrobenzene, has already been referred to. For this purpose we now heat the nitrobenzene with iron dust and a little hydrochloric (muriatic) acid, and then distil over the aniline by means of a current of steam blown through the still. By a similar process toluene is converted into nitrotoluene, and the latter into toluidine.

The large quantity of aniline and toluidine now made has opened up a channel for the use of the waste borings from cast-iron. These are ground to a fine powder under heavy mill-stones, and constitute a most valuable reducing agent, known technically as “iron swarf.” The metallic iron introduced in this form into the aniline still is converted into an oxide of iron by the action of the nitrobenzene, and this oxide of iron is used by the gas-maker for purifying the gas from sulphur as already described. When the oxide of iron is exhausted, i.e. when it has taken up as much sulphur as it can, it goes to the vitriol-maker to be burnt as a source of this acid. Here we have a waste product of the aniline manufacture utilized for the purification of coal-gas, and finally being made to give up the sulphur, which it obtained primarily from the coal, for the production of sulphuric acid, which is consumed in nearly every branch of chemical industry.

Nitrotoluene and toluidine each exist in three distinct modifications, so that it is more correct to speak of the nitrotoluenes and the toluidines; but the explanation of these differences belongs to pure chemical theory, and cannot now be attempted in detail. It must suffice to say that many compounds having the same chemical composition differ in their properties, and are said to be “isomeric,” the isomerism being regarded as the result of the different order of arrangement of the atoms within the molecule.

Consider a homely illustration. A child’s box of bricks contains a certain number of wooden blocks, by means of which different structures can be built up. Supposing all the bricks to be employed for every structure erected, the latter must in every case contain all the blocks, and yet the result is different, because in each structure the blocks are arranged in a different way. The bricks represent atoms, and the whole structure represents a molecule; the structures all have the same ultimate composition, and are therefore isomeric. This will serve as a rough analogy, only it must not be understood that the different atoms of the elements composing a molecule are of different sizes and shapes; on this point we are as yet profoundly ignorant.

Now as long ago as 1856, at the time when Perkin began making mauve by oxidizing aniline with bichromate of potash, it was observed by Natanson, that when aniline was heated with a certain oxidizing agent a red colouring-matter was produced. The same fact was observed in 1858 by Hofmann, who used the tetrachloride of carbon as an oxidizing agent. These chemists obtained the red colouring-matter as a by-product; it was formed only in small quantity, and was regarded as an impurity. In the same year, 1858, two French manufacturers patented the production of a red dye formed by the action of chromic acid and other oxidizing agents on aniline, the colouring matter thus made being used for dying artificial flowers. Then, a year later, the French chemist Verguin found that the best oxidizing agent was the tetrachloride of tin, and this with many other oxidizing substances was patented by Renard Frères and Franc, and under their patent the manufacture of the aniline red was commenced on a small scale in France. Finally, in 1860, an oxidizing agent was made use of almost simultaneously by two English chemists, Medlock and Nicholson, which gave a far better yield of the red than any of the other materials previously in use, and put the manufacture of the colouring-matter on quite a new basis. The oxidizing material patented by Medlock and Nicholson is arsenic acid, and their process is carried on at the present time on an enormous scale in all the chief colour factories in Europe, the colouring-matter produced by this means being generally known as fuchsine or magenta.

In four years the accidental observation of Natanson and Hofmann, made, be it remembered, in the course of abstract scientific investigation, had thus developed into an important branch of manufacture. A demand for aniline on an increased scale sprung up, and the light oils of coal-tar became of still greater importance. The operations of the tar-distiller had to undergo a corresponding increase in magnitude and refinement; the production of nitrobenzene and necessarily of nitric acid had to be increased, and a new branch of manufacture, that of arsenic acid from arsenious acid and nitric acid, was called into existence. Perkin’s mauve prepared the way for the manufacture of aniline, and the discovery of a good process for the production of magenta increased this branch of manufacture to a remarkable extent. Still later in the history of the magenta manufacture, attempts were made, with more or less success, to use nitrobenzene itself as an oxidizing agent, and a process was perfected in 1869 by Coupier, which is now in use in many factories.

The introduction of magenta into commerce marks an epoch in the history of the coal-tar colour industry—pure chemistry and chemical technology both profited by the discovery. The brilliant red of this colouring-matter is objected to by modern æstheticism, but the dye is still made in large quantities, its value having been greatly increased by a discovery made about the same time by John Holliday and the Baden Aniline and Soda Company, and patented by the latter in 1877. Magenta is the salt of a base now known as rosaniline, and it belongs therefore to the class of basic colouring-matters. The dyes of this kind are as a group less fast, and have a more limited application than those colouring-matters which possess an acid character, so that the discovery above referred to—that magenta could be converted into an acid without destroying its colouring power by acting upon it with very strong sulphuric acid—opened up a new field for the employment of the dye, and greatly extended its usefulness. In this form the colouring-matter is met with under the name of “acid magenta.”

It must be understood that the production of magenta from aniline by the oxidizing action of arsenic acid or nitrobenzene is the result of chemical change; the colouring-matter is no more present in the aniline than the latter is contained in the benzene. And just in the same way that the colourless aniline oil by chemical transformation gives rise to the intensely colorific magenta, so the latter by further chemical change can be made to give rise to whole series of different colouring-matters, each consisting of definite chemical compounds as distinct in individuality as magenta itself. Thus in 1860, about the time when the arsenic acid process was inaugurated, two French chemists, Messrs. Girard and De Laire, observed that by heating rosaniline for some time with aniline and an aniline salt, blue and violet colouring-matters were produced. This observation formed the starting-point of a new manufacture proceeding from magenta as a raw material. The production of the new colouring-matters was perfected by various investigators, and a magnificent blue was the final result. But here also the dye was of a basic character, and being insoluble in water had only a limited application, as a spirit bath had to be used for dissolving the substance. In 1862, however, an English technologist, the late E. C. Nicholson, found that by the action of strong sulphuric acid the aniline blue could be rendered soluble in water or alkali, and the value of the colouring-matter was enormously increased by this discovery. The basic and slightly soluble spirit blue was by this means converted into acid blues, which are now made in large quantities, and sold under the names of Nicholson’s blue, alkali blue, soluble blue, and other trade designations. There is at the present time hardly any other blue which for fastness, facility of dyeing, and beauty can compete with this colouring-matter introduced by Nicholson as the outcome of the work of Girard and De Laire.