A Dictionary of Arts, Manufactures and Mines / containing a clear exposition of their principles and practice

by Andrew Ure

Sulphur may be most easily analyzed, even by the manufacturer himself; for I find it to be soluble in one tenth of its weight of boiling oil of turpentine, at 316° Fahrenheit, forming a solution which remains clear at 180°. As it cools to the atmospheric temperature, beautiful crystalline needles form, which may be washed sufficiently with cold alcohol, or even tepid water. The usual impurities of the sulphur, which are carbonate and sulphate of zinc, oxide and sulphuret of iron, sulphuret of arsenic and silica, will remain unaffected by the volatile oil, and may be separately eliminated by the curious, though such separation is of little practical importance.

Two modes of refining sulphur for the gunpowder works have been employed; the first is by fusion, the second by distillation. Since the combustible solid becomes as limpid as water, at the temperature of about 230° Fahrenheit, a ready mode offers of removing at once its denser and lighter impurities, by subsidence and skimming. But I may take the liberty of observing, that the French melting pot, as described in the elaborate work of MM. Bottée and Riffault, is singularly ill-contrived, for the fire is kindled right under it, and plays on its bottom. Now a pot for subsidence ought to be cold set; that is, should have its bottom part imbedded in clay or mortar for four or six inches up the side, and be exposed to the circulating flame of the fire only round its middle zone. This arrangement is adopted in many of our great chemical works, and is found to be very advantageous. With such a boiler, judiciously heated, I believe that crude sulphur might be made remarkably pure; whereas by directing the heat against the bottom of the vessel, the crudities are tossed up, and incorporated with the mass. See [Evaporation].

The sulphur of commerce occurs in three prevailing colours; lemon yellow verging on green, dark yellow, and brown yellow. As these different shades result from the different degrees of heat to which it has been exposed in its original extraction on the great scale, we may thereby judge to what point it may still be heated anew in the refinery melting. Whatever be the actual shade of the crude article, the art of the refiner consists in regulating the heat, so that after the operation it may possess a brilliant yellow hue, inclining somewhat to green.

In seeking to accomplish this purpose, the sulphur should first be sorted according to its shades; and if a greenish variety is to be purified, since this kind has been but little heated in its extraction, the fusion may be urged pretty smartly, or the fire may be kept up till every thing is melted but the uppermost layer.

Sulphur of a strong yellow tinge cannot bear so great a heat, and therefore the fire must be withdrawn whenever three fourths of the whole mass have been melted.

Brown-coloured brimstone, having been already somewhat scorched, should be heated as little as possible, and the fire may be removed as soon as one half of the mass is fused.

Instead of melting, separately, sulphurs of different shades, we shall obtain a better result by first filling up the pot to half its capacity, with the greenish-coloured article, putting over this layer one quarter volume of the deep yellow, and filling it to the brim with the brown-coloured. The fire must be extinguished as soon as the yellow is fused. The pot must then be closely covered for some time; after which the lighter impurities will be found on the surface in a black froth, which is skimmed off, and the heavier ones sink to the bottom. The sulphur itself must be left in the pot for ten or twelve hours, after which it is laded out into the crystallizing boxes or casks.

Distillation affords a more complete and very economical means of purifying sulphur, which was first introduced into the French gunpowder establishments, when their importation of the best Italian and Sicilian sulphur was obstructed by the British navy. Here the sulphur need not come over slowly in a rare vapour, and be deposited in a pulverulent form called flowers; for the only object of the refiner is to bring over the whole of the pure sulphur into his condensing chamber, and to leave all its crudities in the body of the still. Hence a strong fire is applied to elevate a denser mass of vapours, of a yellowish colour, which passing over into the condenser, are deposited in a liquid state on its bottom, whilst only a few lighter particles attach themselves to the upper and lateral surfaces. The refiner must therefore give to the heat in this operation very considerable intensity; and, at some height above the edge of the boiler, he should provide an inclined plane, which may let the first ebullition of the sulphur overflow into a safety recipient. The condensing chamber should be hot enough to maintain the distilled sulphur in a fluid state,—an object most readily procured by leading the pipes of several distilling pots into it; while the continuity of the operations is secured, by charging each of the stills alternately, or in succession. The heat of the receiver must be never so high as to bring the sulphur to a syrupy consistence, whereby its colour is darkened.

In the sublimation of sulphur, a pot containing about four cwt. can be worked off only once in twenty-four hours, from the requisite moderation of its temperature, and the precaution of an inclined plane, which restores to it the accidental ebullitions. But, by distillation, a pot containing fully ten cwt. may complete one process in nine hours at most, with a very considerable saving of fuel. In the former plan of procedure, an interval must elapse between the successive charges; but in the latter, the operation must be continuous to prevent the apparatus from getting cooled: in sublimation, moreover, where communication of atmospheric air to the condensing chamber is indispensable, explosive combustions of the sulphurous vapours frequently occur, with a copious production of sulphurous acid, and correspondent waste of the sulphur; disadvantages from which the distillatory process is in a great measure exempt.

I shall here describe briefly the form and dimensions of the distilling apparatus employed at Marseilles in purifying sulphur for the national gunpowder works, which was found adequate to supply the wants of Napoleon’s great empire. This apparatus consists of only two still-pots of cast iron, formed like the large end of an egg, each about three feet in diameter, two feet deep, and nearly half an inch thick at the bottom, but much thinner above, with a horizontal ledge four inches broad. A pot of good cast iron is capable of distilling 1000 tons of sulphur before it is rendered unserviceable, by the action of the brimstone on its substance, aided by a strong red heat. The pot is covered in with a sloping roof of masonry, the upper end of which abuts on the brickwork of the vaulted dome of condensation. A large door is formed in the masonry in front of the mouth of the pot, through which it is charged and cleared out; and between the roof-space over the pot, and the cavity of the vault, a large passage is opened. At the back of the pot a stone-step is raised to prevent the sulphur boiling over into the condenser. The vault is about ten feet wide within, and fourteen feet from the bottom up to the middle of the dome, which is perforated, and carries a chimney about twelve feet high, and twelve feet diameter inside.