Having expounded the chemical constitution of prussian blue and prussiate of potash, I shall now treat of their manufacture upon the commercial scale.
1. Of blood-lye, the phlogisticated alkali of Scheele. Among the animal substances used for the preparation of this lixivium, blood deserves the preference, where it can be had cheap enough. It must be evaporated to perfect dryness, reduced to powder, and sifted. Hoofs, parings of horns, hides, old woollen rags, and other animal offals, are, however, generally had recourse to, as condensing most azotized matter in the smallest bulk. Dried funguses have been also prescribed. These animal matters may either be first carbonized in cast-iron cylinders, as for the manufacture of [sal ammoniac] (which see), and the residual charcoal may be then taken for making the ferroprussiate; or the dry animal matters may be directly employed. The latter process is apt to be exceedingly offensive to the workmen and neighbourhood, from the nauseous vapours that are exhaled in it. Eight pounds of horn (hoofs), or ten pounds of dry blood, afford upon an average one pound of charcoal. This must be mixed well with good pearlash, (freed previously from most of the sulphate of potassa, with which it is always contaminated,) either in the dry way, or by soaking the bruised charcoal with a strong solution of the alkali; the proportion being one part of carbonate of potassa to from 11⁄2 to 2 parts of charcoal, or to about eight parts of hard animal matter. Gautier has proposed to calcine three parts of dry blood with one of nitre; with what advantage to the manufacturer, I cannot discover.
The pot for calcining the mixture of animal and alkaline matter is egg-shaped as represented at a, [fig. 928], and is considerably narrowed at the neck e, to facilitate the closing of the mouth with a lid i. It is made of cast iron, about two inches thick in the belly and bottom; this strength being requisite because the chemical action of the materials wears the metal fast away. It should be built into the furnace in a direction sloping downwards, (more than is shown in the figure,) and have a strong knob b, projecting from its bottom to support it upon the back wall, while its shoulder is embraced at the arms c, c, by the brickwork in front. The interior of the furnace is so formed as to leave but a space of a few inches round the pot, in order to make the flame play closely over its whole surface. The fire-door f, and the draught-hole z, of the ash-pit, are placed in the posterior part of the furnace, in order that the workmen may not be incommoded by the heat. The smoke vent o, issues through the arched top h of the furnace, towards the front, and is thence led backwards by a flue to the main chimney of the factory. d is an iron or stone shelf, inserted before the mouth of the pot, to prevent loss in shovelling out the semi-liquid paste. The pot may be half filled with the materials.
The calcining process is different, according as the animal substances are fresh or carbonized. In the first case, the pot must remain open, to allow of diligent stirring of its contents, with a slightly bent flat iron bar or scoop, and of introducing more of the mixture as the intumescence subsides, during a period of five or six hours, till the nauseous vapours cease to rise, till the flame becomes smaller and brighter, and till a smell of ammonia be perceived. At this time, the heat should be increased, the mouth of the pot should be shut, and opened only once every half hour, for the purpose of working the mass with the iron paddle. When on opening the mouth of the pot, and stirring the pasty mixture, no more flame rises, the process is finished.
If the animal ingredients are employed in a carbonized state, the pot must be shut as soon as its contents are brought to ignition by a briskly urged fire, and opened for a few seconds only every quarter of an hour, during the action of stirring. At first, a body of flame bursts forth every time that the lid is removed; but by degrees this ceases, and the mixture soon agglomerates, and then softens into a paste. Though the fire be steadily kept up, the flame becomes less and less each time that the pot is opened; and when it ceases, the process is at an end. The operation, with a mass of 50 pounds of charcoal and 50 pounds of purified pearlash, lasts about 12 hours, the first time that the furnace is kindled; but when the pot has been previously brought to a state of ignition, it takes only 7 or 8 hours. In a well-appointed factory, the fire should be invariably maintained at the proper pitch, and the pots should be worked with relays of operatives.
The molten mass is now to be scooped out with an appropriate iron shovel, having a long shank, and caused to cool in small portions, as quickly as possible; but not by throwing it into water, as has sometimes been prescribed; for in this way a good deal of the cyanogen is converted into ammonia. If it be heaped up and kept hot in contact with air, some of the ferrocyanide is also decomposed, with diminution of the product. The crude mass is to be then put into a pan with cold water, dissolved by the application of a moderate heat, and filtered through cloths. The charcoal which remains upon the filter possesses the properties of decolouring syrups, vinegars, &c., and of destroying smells in a pre-eminent degree. It may also serve, when mixed with fresh animal coal, for another calcining operation.
As the iron requisite for the formation of the ferrocyanide is in general derived from the sides of the pot, this is apt to wear out into holes, especially at its under side, where the heat is greatest. In this event, it may be taken out of the furnace, patched up with iron-rust cement, and re-inserted with the sound side undermost. The erosion of the pot may be obviated in some measure by mixing iron borings or cinder (hammerschlag) with the other materials, to the amount of one or two hundredths of the potash.