The chemical industry offers naturally a wide field for the occurrence of industrial poisoning. Daily contact with the actual poisonous substances to be prepared, used, stored, and despatched in large quantity gives opportunity for either acute or chronic poisoning—in the former case from sudden accidental entrance into the system of fairly large doses, as the result of defective or careless manipulation, and, in the latter, constant gradual absorption (often unsuspected) of the poison in small amount.
The industry, however, can take credit for the way in which incidence of industrial poisoning has been kept down in view of the magnitude and variety of the risks which often threaten. This is attributable to the comprehensive hygienic measures enforced in large chemical works keeping abreast of modern advance in technical knowledge. A section of this book deals with the principles underlying these measures. Nevertheless, despite all regulations, risk of poisoning cannot be wholly banished. Again and again accidents and illness occur for which industrial poisoning is responsible. Wholly to prevent this is as impossible as entirely to prevent accidents by mechanical guarding of machinery.
Owing to the unknown sources of danger, successful measures to ward it off are often difficult. The rapid advance of this branch of industry, the constant development of new processes and reactions, the frequent discovery of new materials (with properties at first unknown, and for a long time insufficiently understood, but nevertheless indispensable), constantly give rise to new dangers and possibilities of danger, of which an accident or some disease with hitherto unknown symptoms is the first indication. Further, even when the dangerous effects are recognised, there may often be difficulty in devising appropriate precautions, as circumstances may prevent immediate recognition of the action of the poison. We cannot always tell, for instance, with the substances used or produced in the processes, which is responsible for the poisoning, because, not infrequently, the substances in question are not chemically pure, but may be either raw products, bye-products, &c., producing mixtures of different bodies or liberating different chemical compounds as impurities.
Hence difficulty often arises in the strict scientific explanation of particular cases of poisoning, and, in a text-book such as this, difficulty also of description. A rather full treatment of the technical processes may make the task easier and help to give a connected picture of the risks of poisoning in the chemical industry. Such a procedure may be especially useful to readers insufficiently acquainted with chemical technology.
We are indebted to Leymann1 and Grandhomme2 especially for knowledge of incidence of industrial poisoning in this industry. The statistical data furnished by them are the most important proof that poisoning, at any rate in large factories, is not of very frequent occurrence.
Leymann’s statistics relate to a large modern works in which the number employed during the twenty-three years of observation increased from 640 in the year 1891 to 1562 in 1904, giving an average of about 1000 yearly, one-half of whom might properly be defined as ‘chemical workers.’ The factory is concerned in the manufacture of sulphuric, nitric, and hydrochloric acids, alkali, bichromates, aniline, trinitro-phenol, bleaching powder, organic chlorine compounds, and potassium permanganate.
These statistics are usefully complemented by those of Grandhomme drawn from the colour works at Höchst a-M. This large aniline works employs from 2600 to 2700 workers; the raw materials are principally benzene and its homologues, naphthalene and anthracene. The manufacture includes the production of coal-tar colours, nitro- and dinitro-benzene, aniline, rosaniline, fuchsine, and other aniline colours, and finally such pharmaceutical preparations as antipyrin, dermatol, sanoform, &c. Of the 2700 employed, 1400 are chemical workers and the remainder labourers.
These two series of statistics based on exact observations and covering allied chemical manufacture are taken together. They seek to give the answer to the question—How many and what industrial poisonings are found?
The figures of Leymann (on an average of 1000 workers employed per annum) show 285 cases of poisoning reported between the years 1881 and 1904. Of these 275 were caused by aniline, toluidine, nitro- and dinitro-benzene, nitrophenol, nitrochloro and dinitrochloro benzene. Three were fatal and several involved lengthy invalidity (from 30 to 134 days, owing to secondary pneumonia). Included further are one severe case of chrome (bichromate) poisoning (with nephritis as a sequela), five cases of lead poisoning, three of chlorine, and one of sulphuretted hydrogen gas. In the Höchst a-M. factory (employing about 2500 workers) there were, in the ten years 1883-92, only 129 cases of poisoning, of which 109 were due to aniline. Later figures for the years 1893-5 showed 122 cases, of which 43 were due to aniline and 76 to lead (contracted mostly in the nitrating house). Grandhomme mentions further hyperidrosis among persons employed on solutions of calcium chloride, injury to health from inhalation of methyl iodide vapour in the antipyrin department, a fatal case of benzene poisoning (entering an empty vessel in which materials had previously been extracted with benzene), and finally ulceration and perforation of the septum of the nose in several chrome workers.
The number of severe cases is not large, but it must be remembered that the factories to which the figures relate are in every respect models of their kind, amply provided with safety appliances and arrangements for the welfare of the workers. The relatively small amount of poisoning is to be attributed without doubt to the precautionary measures taken. Further, in the statistics referred to only those cases are included in which the symptoms were definite, or so severe as to necessitate medical treatment. Absorption of the poison in small amount without producing characteristic symptoms, as is often the case with irritating or corrosive fumes, and such as involve only temporary indisposition, are not included. Leymann himself refers to this when dealing with illness observed in the mineral acid department (especially sulphuric acid), and calls attention to the frequency of affections of the respiratory organs among the persons employed, attributing them rightly to the irritating and corrosive effect of the acid vapour. Elsewhere he refers to the frequency of digestive disturbance among persons coming into contact with sodium sulphide, and thinks that this may be due to the action of sulphuretted hydrogen gas.
Nevertheless, the effect of industrial poisons on the health of workers in chemical factories ought on no account to be made light of. The admirable results cited are due to a proper recognition of the danger, with consequent care to guard against it. Not only have Grandhomme and Leymann[A] rendered great services by their work, but the firms in question also, by allowing such full and careful inquiries to be undertaken and published.
Manufacture.—Sulphur dioxide, generally obtained by roasting pyrites in furnaces of various constructions, or, more rarely, by burning brimstone or sulphur from the spent oxide of gas-works, serves as the raw material for the manufacture of sulphuric acid. Before roasting the pyrites is crushed, the ‘lump ore’ then separated from the ‘smalls,’ the former roasted in ‘lump-burners’ or kilns (generally several roasting furnace hearths united into one system), and the latter preferably in Malétra and Malétra-Schaffner shelf-burners (fig. 1) composed of several superimposed firebrick shelves. The pyrites is charged on to the uppermost shelf and gradually worked downwards. Pyrites residues are not suitable for direct recovery of iron, but copper can be recovered from residues sufficiently rich in metal by the wet process; the residues thus freed of copper and sulphur are then smelted for recovery of iron.
Fig. 1.—Pyrites Burner for Smalls (after Lueger)
Utilisation for sulphuric acid manufacture of the sulphur dioxide given off in the calcining of zinc blende (see Spelter works), impracticable in reverberatory furnaces, has been made possible at the Rhenania factory by introduction of muffle furnaces (several superimposed), because by this means the gases led off are sufficiently concentrated, as they are not diluted with the gases and smoke from the heating fires. This method, like any other which utilises the gases from roasting furnaces, has great hygienic, in addition to economical, advantages, because escape of sulphur dioxide gas is avoided. Furnace gases, too poor in sulphur dioxide to serve for direct production of sulphuric acid, can with advantage be made to produce liquid anhydrous sulphur dioxide. Thus, the sulphur dioxide gas from the furnaces is first absorbed by water, driven off again by boiling, cooled, dried, and liquefied by pressure.
The gaseous sulphur dioxide obtained by any of the methods described is converted into sulphuric acid either by (a) the chamber process or (b) the contact process.
In the lead chamber process the furnace gases pass through flues in which the flue dust and a portion of the arsenious acid are deposited into the Glover tower at a temperature of about 300° C., and from there into the lead chambers where oxidation of the sulphur dioxide into sulphuric acid takes place, in the presence of sufficient water, by transference of the oxygen of the air through the intervention of the oxides of nitrogen. The gases containing oxides of nitrogen, &c., which are drawn out of the lead chambers, have the nitrous fumes absorbed in the Gay-Lussac tower (of which there are one or two in series), by passage through sulphuric acid which is made to trickle down the tower. The sulphuric acid so obtained, rich in oxides of nitrogen, and the chamber acid are led to the Glover tower for the purpose of denitration and concentration, so that all the sulphuric acid leaves the Glover as Glover acid of about 136-144° Tw. Losses in nitrous fumes are best made up by addition of nitric acid at the Glover or introduction into the first chamber. The deficiency is also frequently made good from nitre-pots.
The lead chambers (fig. 2) are usually constructed entirely—sides, roof, and floor—of lead sheets, which are joined together by means of a hydrogen blowpipe. The sheets forming the roof and walls are supported, independent of the bottom, on a framework of wood. The capacity varies from 35,000 to 80,000 cubic feet. The floor forms a flat collecting surface for the chamber acid which lutes the chamber from the outer air. The necessary water is introduced into the chamber as steam or fine water spray.
The Glover and Gay-Lussac towers are lead towers. The Glover is lined with acid-proof bricks and filled with acid-proof packing to increase the amount of contact. The Gay-Lussac is filled with coke over which the concentrated sulphuric acid referred to above flows, forming, after absorption of the nitrous fumes, nitro-sulphuric acid.
Fig. 2a.—Lead Chamber System—Section through X X (after Ost)
Fig. 2b.—Lead Chamber System—Plan
As already stated, two Gay-Lussac towers are usually connected together, or where there are several lead-chamber systems there is, apart from the Gay-Lussac attached to each, a central Gay-Lussac in addition, common to the whole series. The introduction of several Gay-Lussac towers has the advantage of preventing loss of the nitrous fumes as much as possible—mainly on economical grounds, as nitric acid is expensive. But this arrangement is at the same time advantageous on hygienic grounds, as escape of poisonous gases containing nitrous fumes, &c., is effectually avoided. The acids are driven to the top of the towers by compressed air. The whole system—chambers and towers—is connected by means of wide lead conduits. Frequently, for the purpose of quickening the chamber process (by increasing the number of condensing surfaces) Lunge-Rohrmann plate towers are inserted in the system—tall towers lined with lead in which square perforated plates are hung horizontally, and down which diluted sulphuric acid trickles.
To increase the draught in the whole system a chimney is usual at the end, and, in addition, a fan of hard lead or earthenware may be introduced in front of the first chamber or between the two Gay-Lussac towers. Maintenance of a constant uniform draught is not only necessary for technical reasons, but has hygienic interest, since escape of injurious gases is avoided (see also Part III).
The chamber acid (of 110°-120° Tw. = 63-70 %) and the stronger Glover acid (of 136°-144° Tw. = 75-82 %) contain impurities. In order to obtain for certain purposes pure strong acid the chamber acid is purified and concentrated. The impurities are notably arsenious and nitrous acids (Glover acid is N free), lead, copper, and iron. Concentration (apart from that to Glover acid in the Glover tower) is effected by evaporation in lead pans to 140° Tw. and finally in glass balloons or platinum stills to 168° Tw. (= 97 %). The lead pans are generally heated by utilising the waste heat from the furnaces or by steam coils in the acid itself, or even by direct firing.
Production of sulphuric acid by the contact method depends on the fact that a mixture of sulphur dioxide and excess of oxygen (air) combines to form sulphur trioxide at a moderate heat in presence of a contact substance such as platinised asbestos or oxide of iron. The sulphur dioxide must be carefully cleaned and dried, and with the excess of air is passed through the contact substance. If asbestos carrying a small percentage of finely divided platinum is the contact substance, it is generally used in the form of pipes; oxide of iron (the residue of pyrites), if used, is charged into a furnace. Cooling by a coil of pipes and condensation in washing towers supplied with concentrated sulphuric acid always forms a part of the process. A fan draws the gases from the roasting furnaces and drives them through the system. The end product is a fuming sulphuric acid containing 20-30 per cent. SO₃. From this by distillation a concentrated acid and a pure anhydride are obtained. From a health point of view it is of importance to know that all sulphuric acid derived from this anhydride is pure and free from arsenic.
The most important uses of sulphuric acid are the following: as chamber acid (110°-120° Tw.) in the superphosphate, ammonium sulphate, and alum industries; as Glover acid (140°-150° Tw.) in the Leblanc process, i.e. saltcake and manufacture of hydrochloric acid, and to etch metals; as sulphuric acid of 168° Tw. in colour and explosives manufacture (nitric acid, nitro-benzene, nitro-glycerine, gun-cotton, &c.); as concentrated sulphuric acid and anhydride for the production of organic sulphonic acids (for the alizarin and naphthol industry) and in the refining of petroleum and other oils. Completely de-arsenicated sulphuric acid is used in making starch, sugar, pharmaceutical preparations, and in electrical accumulator manufacture.
Effects on Health.—The health of sulphuric acid workers cannot in general be described as unfavourable.
In comparison with chemical workers they have, it is said, relatively the lowest morbidity. Although in this industrial occupation no special factors are at work which injure in general the health of the workers, there is a characteristic effect, without doubt due to the occupation—namely, disease of the respiratory organs. Leymann’s figures are sufficiently large to show that the number of cases of diseases of the respiratory organs is decidedly greater in the sulphuric acid industry than among other chemical workers. He attributes this to the irritating and corrosive effect of sulphur dioxide and sulphuric acid vapour on the mucous membrane of the respiratory tract, as inhalation of these gases can never be quite avoided, because the draught in the furnace and chamber system varies, and the working is not always uniform. Strongly irritating vapours escape again in making a high percentage acid in platinum vessels, which in consequence are difficult to keep air-tight. Of greater importance than these injurious effects from frequent inhalation of small quantities of acid vapours, or employment in workrooms in which the air is slightly charged with acid, is the accidental sudden inhalation of large quantities of acid gases, which may arise in the manufacture, especially by careless attendance. Formerly this was common in charging the roasting furnaces when the draught in the furnace, on addition of the pyrites, was not strengthened at the same time. This can be easily avoided by artificial regulation of the draught.
Accidents through inhalation of acid gases occur further when entering the lead chambers or acid tanks, and in emptying the towers. Heinzerling relates several cases taken from factory inspectors’ reports. Thus, in a sulphuric acid factory the deposit (lead oxysulphate) which had collected on the floor of a chamber was being removed: to effect this the lead chambers were opened at the side. Two of the workers, who had probably been exposed too long to the acid vapours evolved in stirring up the deposit, died a short time after they had finished the work. A similar fatality occurred in cleaning out a nitro-sulphuric acid tank, the required neutralisation of the acid by lime before entering having been omitted. Of the two workers who entered, one died the next day; the other remained unaffected. The deceased had, as the post mortem showed, already suffered previously from pleurisy. A fatality from breathing nitrous fumes is described fully in the report of the Union of Chemical Industry for the year 1905. The worker was engaged with two others in fixing a fan to a lead chamber; the workers omitted to wait for the arrival of the foreman who was to have supervised the operation. Although the men used moist sponges as respirators, one of them inhaled nitrous fumes escaping from the chamber in such quantity that he died the following day.
Similar accidents have occurred in cleaning out the Gay-Lussac towers. Such poisonings have repeatedly occurred in Germany. Fatal poisoning is recorded in the report of the Union of Chemical Industry, in the emptying and cleaning of a Gay-Lussac tower despite careful precautions. The tower, filled with coke, had been previously well washed with water, and during the operation of emptying, air had been constantly blown through by means of a Körting’s injector. The affected worker had been in the tower about an hour; two hours later symptoms of poisoning set in which proved fatal in an hour despite immediate medical attention. As such accidents kept on recurring, the Union of Chemical Industry drew up special precautions to be adopted in the emptying of these towers, which are printed in Part III.
Naturally, in all these cases it is difficult to say exactly which of the acid gases arising in the production of sulphuric acid was responsible for the poisoning. In the fatal cases cited, probably nitrous fumes played the more important part.
Poisoning has occurred in the transport of sulphuric acid. In some of the cases, at all events, gaseous impurities, especially arseniuretted hydrogen, were present.
Thus, in the reports of the German Union of Chemical Industry for the year 1901, a worker succumbed through inhalation of poisonous gases in cleaning out a tank waggon for the transport of sulphuric acid. The tank was cleaned of the adhering mud, as had been the custom for years, by a man who climbed into it. No injurious effects had been noted previously at the work, and no further precautions were taken than that one worker relieved another at short intervals, and the work was carried on under supervision. On the occasion in question, however, there was an unusually large quantity of deposit, although the quality of the sulphuric acid was the same, and work had to be continued longer. The worker who remained longest in the tank became ill on his way home and died in hospital the following day; the other workers were only slightly affected. The sulphuric acid used by the firm in question immediately before the accident came from a newly built factory in which anhydrous sulphuric acid had been prepared by a special process. The acid was Glover acid, and it is possible that selenium and arsenic compounds were present in the residues. Arseniuretted hydrogen might have been generated in digging up the mud. Two similar fatalities are described in the report of the same Union for the year 1905. They happened similarly in cleaning out a sulphuric acid tank waggon, and in them the arsenic in the acid was the cause. Preliminary swilling out with water diluted the remainder of the sulphuric acid, but, nevertheless, it acted on the iron of the container. Generation of hydrogen gas is the condition for the reduction of the arsenious acid present in sulphuric acid with formation of arseniuretted hydrogen. In portions of the viscera arsenic was found. Lately in the annual reports of the Union of Chemical Industry for 1908 several cases of poisoning are described which were caused by sulphuric acid. A worker took a sample out of a vessel of sulphuric acid containing sulphuretted hydrogen gas. Instead of using the prescribed cock, he opened the man-hole and put his head inside, inhaling concentrated sulphuretted hydrogen gas. He became immediately unconscious and died. Through ignorance no use was made of the oxygen apparatus.
Another fatality occurred through a foreman directing some workers, contrary to the regulations against accidents from nitrous gases, to clean a vessel containing nitric and sulphuric acids. They wore no air helmets: one died shortly after from inhalation of nitrous fumes. Under certain circumstances even the breaking of carboys filled with sulphuric acid may give rise to severe poisoning through inhalation of acid gases. Thus a fatality1 occurred to the occupier of a workroom next some premises in which sulphuric acid carboys had been accidentally broken. Severe symptoms developed the same night, and he succumbed the next morning in spite of treatment with oxygen. A worker in the factory became seriously ill but recovered.
A similar case is described2 in a factory where concentrated sulphuric acid had been spilt. The workers covered the spot with shavings, which resulted in strong development of sulphur dioxide, leading to unconsciousness in one worker.
The frequent observation of the injurious effect of acid gases on the teeth of workers requires mention; inflammation of the eyes of workers also is attributed to the effects of sulphuric acid.
Leymann’s statistics show corrosions and burns among sulphuric acid workers to be more than five times that among other classes. Such burns happen most frequently from carelessness. Thus, in the reports of the Union of Chemical Industry for 1901, three severe accidents are mentioned which occurred from use of compressed air. In two cases the acid had been introduced before the compressed air had been turned off; in the third the worker let the compressed air into the vessel and forgot to turn off the inlet valve. Although the valves were provided with lead guards, some of the acid squirted into the worker’s face. In one case complete blindness followed, in a second blindness in one eye, and in the third blindness in one eye and impaired vision of the other.
Besides these dangers from the raw material, bye-products, and products of the manufacture, lead poisoning has been reported in the erection and repair of lead chambers. The lead burners generally use a hydrogen flame; the necessary hydrogen is usually made from zinc and sulphuric acid and is led to the iron by a tube. If the zinc and sulphuric acid contain arsenic, the very dangerous arseniuretted hydrogen is formed, which escapes through leakages in the piping, or is burnt in the flame to arsenious acid.
Further, the lead burners and plumbers are exposed to the danger of chronic lead poisoning from insufficient observance of the personal precautionary measures necessary to guard against it (see Part III). Those who are constantly engaged in burning the lead sheets and pipes of the chambers suffer not infrequently from severe symptoms. Unfortunately, the work requires skill and experience, and hence alternation of employment is hardly possible.
Finally, mention should be made of poisoning by arseniuretted hydrogen gas from vessels filled with sulphuric acid containing arsenic as an impurity, and by sulphuretted hydrogen gas in purifying the acid itself. In the manufacture of liquid sulphur dioxide, injury to health can arise from inhalation of the acid escaping from the apparatus. The most frequent cause for such escape of sulphur dioxide is erosion of the walls of the compressor pumps and of the transport vessels, in consequence of the gas being insufficiently dried, as, when moist, it attacks iron.
Sulphur dioxide will come up for further consideration when describing the industrial processes giving rise to it, or in which it is used.
Manufacture.—The production of hydrochloric acid (HCl), sodium sulphate (Na₂SO₄), and sodium sulphide (Na₂S) forms part of the manufacture of soda (Na₂CO₃) by the Leblanc process. The products first named increase in importance, while the Leblanc soda process is being replaced more and more by the manufacture of soda by the Solvay ammonia process, so much so that on the Continent the latter method predominates and only in England does the Leblanc process hold its ground.
Health interests have exercised an important bearing on the development of the industries in question. At first, in the Leblanc process the hydrochloric acid gas was allowed to escape into the atmosphere, being regarded as a useless bye-product. Its destructive action on plant life and the inconvenience caused to the neighbourhood, in spite of erection of high chimneys, demanded intervention. In England the evils led to the enactment of the Alkali Acts—the oldest classical legislative measures bearing on factory hygiene—by which the Leblanc factories were required to condense the vapour by means of its absorption in water, and this solution of the acid is now a highly valued product. And, again, production of nuisance—inconvenience to the neighbourhood through the soda waste—was the main cause of ousting one of the oldest and most generally used methods of chemical industrial production. Although every effort was made to overcome the difficulties, the old classical Leblanc process is gradually but surely yielding place to the modern Solvay process, which has no drawback on grounds of health.
We outline next the main features of the Leblanc soda process, which includes, as has been mentioned, also the manufacture of hydrochloric acid, sodium sulphate and sulphide.
The first part of the process consists in the production of the sulphate from salt and sulphuric acid, during which hydrochloric acid is formed; this is carried out in two stages represented in the following formulæ:
The first stage in which bisulphate is produced is carried out at a moderate heat, the second requires a red heat. The reactions, therefore, are made in a furnace combining a pan and muffle furnace.
This saltcake muffle furnace is so arranged that the pan can be shut off from the muffle by a sliding-door (D). The pan (A) and muffle (E) have separate flues for carrying off the hydrochloric acid developed (B, F). First, common salt is treated with sulphuric (Glover) acid in the cast-iron pan. When generation of hydrochloric acid vapour has ceased, the sliding-door is raised and the partly decomposed mixture is pushed through into the muffle, constructed of fire-resisting bricks and tiles, and surrounded by the fire gases. While the muffle is being raised to red heat, the sulphate must be repeatedly stirred with a rake in order, finally, while still hot and giving off acid vapour, to be drawn out at the working doors into iron boxes provided with doors, where the material cools. The acid vapour given off when cooling is drawn through the top of the box into the furnace.
Fig. 3.—Saltcake Muffle Furnace—Section (after Ost)
A Pan; B, F Pipes for hydrochloric acid vapour; D Shutter; E Muffle, O Coke fire.
Mechanical stirrers, despite their advantage from a health point of view, have not answered because of their short life.
The valuable bye-product of the sulphate process, hydrochloric acid, is led away separately from the pan and the muffle, as is seen, into one absorption system. The reason of the separation is that the gas from the pan is always the more concentrated. The arrangement of the absorbing apparatus is illustrated in fig. 4.
Fig. 4a.—Preparation of Hydrochloric Acid—Plan (after Lueger)
Fig. 4b.—Elevation
The gases are led each through earthenware pipes or channels of stone pickled with tar (A´), first into small towers of Yorkshire flags (B), where they are cooled and freed from flue dust and impurities (sulphuric acid) by washing. They are next led through a series (over fifty) of Woulff bottles (bombonnes) one metre high, made of acid-resisting stoneware. The series is laid with a slight inclination towards the furnace, and water trickles through so that the gases coming from the wash towers are brought into contact with water in the one case already almost saturated, whilst the gas which is poorest in hydrochloric acid meets with fresh water. From the bombonne situated next to the wash tower the prepared acid is passed as a rule through another series. The last traces of hydrochloric acid are then removed by leading the gases from the Woulff bottles up two water towers of stoneware (D and E), which are filled partly with earthenware trays and partly with coke; above are tanks from which the water trickles down over the coke. The residual gases from both sets of absorbing apparatus now unite in a large Woulff bottle before finally being led away through a duct to the chimney stack.
Less frequently absorption of hydrochloric acid is effected without use of Woulff bottles, principally in wash towers such as the Lunge-Rohrmann plate tower.
In the purification of hydrochloric acid, de-arsenicating by sulphuretted hydrogen or by barium sulphide, &c., and separation of sulphuric acid by addition of barium chloride, have to be considered.
Another method for production of sulphate and hydrochloric acid, namely, the Hargreaves process, is referred to later.
We return now to the further working up of the sodium sulphate into sulphide and soda. The conversion of the sulphate into soda by the Leblanc method is effected by heating with coal and calcium carbonate, whereby, through the action of the coal, sodium sulphide forms first, which next with the calcium carbonate becomes converted into sodium carbonate and calcium sulphide.
The reactions are:
The reactions are carried out in small works in open reverberatory furnaces having two platforms on the hearth, and with continuous raking from one to the other which, as the equations show, cause escape of carbonic acid gas and carbonic oxide.
Such handworked furnaces, apart from their drawbacks on health grounds, have only a small capacity, and in large works their place is taken by revolving furnaces—closed, movable cylindrical furnaces—in which handwork is replaced by the mechanical revolution of the furnace and from which a considerably larger output and a product throughout good in quality are obtained.
The raw soda thus obtained in the black ash furnace is subjected to lixiviation by water in iron tanks in which the impurities or tank waste (see below) are deposited. The crude soda liquor so obtained is then further treated and converted into calcined soda, crystal soda, or caustic soda. In the production of calcined soda the crude soda liquor is first purified (‘oxidised’ and ‘carbonised’) by blowing through air and carbonic acid gas, pressed through a filter press, and crystallised by evaporation in pans and calcined, i.e. deprived of water by heat.
Fig. 5.—Revolving Black Ash Furnace—Elevation (after Lueger)
A Firing hearth; B Furnace; C Dust box.
Crystal soda is obtained from well-purified tank liquor by crystallising in cast-iron vessels.
Caustic soda is obtained by introducing lime suspended in iron cages into the soda liquor in iron caustic pots, heating with steam, and agitating by blowing in air.
The resulting clear solution is drawn off and evaporated in cast-iron pans.
As already mentioned, the tank waste in the Leblanc process, which remains behind—in amount about equal to the soda produced after lixiviation of the raw soda with water—constitutes a great nuisance. It forms mountains round the factories, and as it consists principally of calcium sulphide and calcium carbonate, it easily weathers under the influence of air and rain, forming soluble sulphur compounds and developing sulphuretted hydrogen gas—an intolerable source of annoyance to the district.
At the same time all the sulphur introduced into the industry as sulphuric acid is lost in the tank waste. This loss of valuable material and the nuisance created led to attempts—partially successful—to recover the sulphur.
The best results are obtained by the Chance-Claus method, in which the firebrick ‘Claus-kiln’ containing ferric oxide (previously heated to dull redness) is used. In this process calcium sulphide is acted on by carbonic acid with evolution of gas so rich in sulphuretted hydrogen that it can be burnt to sulphur dioxide and used in the lead chambers for making sulphuric acid. Sulphur also as such is obtained by the method.
These sulphur-recovery processes which have hardly been tried on the Continent—only the United Alkali Company in England employs the Chance-Claus on a large scale—were, as has been said, not in a position to prevent the downfall of the Leblanc soda industry. Before describing briefly the Solvay method a word is needed as to other processes for manufacture of sulphate and hydrochloric acid.
Hargreaves’ process produces sodium sulphate (without previous conversion of sulphur dioxide into sulphuric acid) directly by the passage of gases from the pyrites burners, air and steam, through salt blocks placed in vertical cast-iron retorts, a number of which are connected in series. A fan draws the gases through the system and leads the hydrochloric acid fumes to the condenser.
Sodium sulphate is used in the manufacture of glass, ultramarine, &c. Further, the sulphate is converted into Glauber’s salts by dissolving the anhydrous sulphate obtained in the muffle furnace, purifying with lime, and allowing the clear salt solution to crystallise out in pans.
A further use of the sulphate is the preparation of sodium sulphide, which is effected (as in the first part of the Leblanc soda process) by melting together sulphate and coal in a reverberatory furnace. If the acid sulphate (bisulphate) or sulphate containing bisulphate is used much sulphur dioxide gas comes off.
The mass is then lixiviated in the usual soda liquor vats and the lye either treated so as to obtain crystals or evaporated to strong sodium sulphide which is poured like caustic soda into metal drums where it solidifies.
In Solvay’s ammonia soda process ammonia recovered from the waste produced in the industry is led into a solution of salt until saturation is complete. This is effected generally in column apparatus such as is used in distillation of spirit. The solution is then driven automatically by compressed air to the carbonising apparatus in which the solution is saturated with carbonic acid; this apparatus is a cylindrical tower somewhat similar to the series of vessels used for saturating purposes in sugar factories through which carbonic acid gas passes. In this process crystalline bi-carbonate of soda is first formed, which is separated from the ammoniacal mother liquor by filtration, centrifugalisation, and washing. The carbonate is then obtained by heating (calcining in pans), during which carbonic acid gas escapes, and this, together with the carbonic acid produced in the lime kilns, is utilised for further carbonisation again. The lime formed during the production of carbonic acid in the lime kilns serves to drive the ammonia out of the ammoniacal mother liquor, so that the ammonia necessary for the process is recovered and used over and over again. The waste which results from the action of the lime on the ammonium chloride liquor is harmless—calcium chloride liquor.
The electrolytic manufacture of soda from salt requires mention, in which chlorine (at the anode) and caustic soda (at the cathode) are formed; the latter is treated with carbonic acid to make soda.
Effects on Health.—Leymann’s observations show that in the department concerned with the Leblanc soda process and production of sodium sulphide, relatively more sickness is noted than, for example, in the manufacture of sulphuric and nitric acids.
In the preparation of the sulphate, possibility of injury to health or poisoning arises from the fumes containing hydrochloric or sulphuric acid in operations at the muffle furnace; in Hargreaves’ process there may be exposure to the effect of sulphur dioxide. Hydrochloric and sulphuric acid vapours can escape from the muffle furnace when charging, from leakages in it, and especially when withdrawing the still hot sulphate. Large quantities of acid vapours escape from the glowing mass, especially if coal is not added freely and if it is not strongly calcined. Persons employed at the saltcake furnaces suffer, according to Jurisch, apart from injury to the lungs, from defective teeth. The teeth of English workers especially, it is said, from the practice of holding flannel in their mouths with the idea of protecting themselves from the effect of the vapours, are almost entirely eroded by the action of the hydrochloric acid absorbed by the saliva. Hydrochloric acid vapour, further, can escape from the absorbing apparatus if this is not kept entirely sealed, and the hydrochloric acid altogether absorbed—a difficult matter. Nevertheless, definite acute industrial poisoning from gaseous hydrochloric acid is rare, no doubt because the workers do not inhale it in concentrated form.
Injury to the skin from the acid absorbed in water may occur in filling, unloading, and transport, especially when in carboys, but the burns, if immediately washed, are very slight in comparison with those from sulphuric or nitric acids. Injury to health or inconvenience from sulphuretted hydrogen is at all events possible in the de-arsenicating process by means of sulphuretted hydrogen gas. At the saltcake furnace when worked by hand the fumes containing carbonic oxide gas may be troublesome. In the production of caustic soda severe corrosive action on the skin is frequent. Leymann found that 13·8 per cent. of the persons employed in the caustic soda department were reported as suffering from burns, and calls attention to the fact that on introducing the lime into the hot soda lye the contents of the vessel may easily froth over. Heinzerling refers to the not infrequent occurrence of eye injuries in the preparation of caustic soda, due to the spurting of lye or of solid particles of caustic soda.
The tank waste gives rise, as already stated, to inconvenience from the presence of sulphuretted hydrogen. In the recovery of the sulphur and treatment of the tank waste, sulphuretted hydrogen and sulphur dioxide gases are evolved. According to Leymann, workers employed in removing the waste and at the lye vats frequently suffer from inflammation of the eyes. Further, disturbance of digestion has been noted in persons treating the tank waste, which Leymann attributes to the unavoidable development of sulphuretted hydrogen gas.
In the manufacture of sodium sulphide similar conditions prevail. Leymann found in this branch relatively more cases of sickness than in any other; diseases of the digestive tract especially appeared to be more numerous. Leymann makes the suggestion that occurrence of disease of the digestive organs is either favoured by sodium sulphide when swallowed as dust, or that here again sulphuretted hydrogen gas plays a part. Further corrosive effect on the skin and burns may easily arise at work with the hot corrosive liquor.
In the Solvay ammonia process ammonia and carbonic acid gas are present, but, so far as I know, neither injury to health nor poisoning have been described among persons employed in the process. Indeed, the view is unanimous that this method of manufacture with its technical advantages has the merit also of being quite harmless. As may be seen from the preceding description of the process there is no chance of the escape of the gases named into the workrooms.
Ultramarine is made from a mixture of clay, sulphate (Glauber’s salts), and carbon—sulphate ultramarine; or clay, sulphur, and soda—soda ultramarine. These materials are crushed, ground, and burnt in muffle furnaces. On heating the mass in the furnace much sulphur dioxide escapes, which is a source of detriment to the workmen and the neighbourhood.
Sulphonal (CH₃)₂C(SO₂C₂H₅)₂, diethylsulphone dimethylmethane, used medically as a hypnotic, is obtained from mercaptan formed by distillation of ethyl sulphuric acid with sodium or potassium sulphide. The mercaptan is converted into mercaptol, and this by oxidation with potassium permanganate into sulphonal. The volatile mercaptan has a most disgusting odour, and clings for a long time even to the clothes of those merely passing through the room.
Diethyl sulphate ((C₂H₅)₂SO₄).—Diethyl sulphate obtained by the action of sulphuric acid on alcohol has led to poisoning characterised by corrosive action on the respiratory tract.1 As the substance in the presence of water splits up into sulphuric acid and alcohol, this corrosive action is probably due to the acid. It is possible, however, that the molecule of diethyl sulphate as such has corrosive action.
Contact with diethyl sulphate is described as having led to fatal poisoning.2
A chemist when conducting a laboratory experiment dropped a glass flask containing about 40 c.c. of diethyl sulphate, thereby spilling some over his clothes. He went on working, and noticed burns after some time, quickly followed by hoarseness and pain in the throat. He died of severe inflammation of the lungs. A worker in another factory was dropping diethyl sulphate and stirring it into an at first solid, and later semi-liquid, mass for the purpose of ethylating a dye stuff. In doing so he was exposed to fumes, and at the end of the work complained of hoarseness and smarting of the eyes. He died of double pneumonia two days later. Post mortem very severe corrosive action on the respiratory tract was found, showing that the diethyl sulphuric acid had decomposed inside the body and that nascent sulphuric acid had given rise to the severe burns. The principal chemist who had superintended the process suffered severely from hoarseness at night, but no serious consequences followed.
It is stated also that workmen in chemical factories coming into contact with the fumes of diethyl sulphate ester suffer from eye affections.3
Manufacture.—The older processes depend on the preparation of chlorine and hydrochloric acid by an oxidation process in which the oxidising agent is either a compound rich in oxygen—usually common manganese dioxide (pyrolusite)—or the oxygen of the air in the presence of heated copper chloride (as catalytic agent). The former (Weldon process) is less used now than either the latter (Deacon process) or the electrolytic manufacture of chlorine.
In the Weldon process from the still liquors containing manganous chloride the manganese peroxide is regenerated, and this so regenerated Weldon mud, when mixed with fresh manganese dioxide, is used to initiate the process. This is carried out according to the equations: