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Ludwig Mond, chemist, discovered an important, previously-unknown class of compounds called metal carbonyls. He was also well into the chemical industries, here's what he has to say about his investigations concerning the production of ammonia from coal, from Scientific American (supplement) 1889 -
As exemplifying to a certain extent the application of methodical research to an industrial problem, I propose to bring before you to-day an account of the work I have been engaged in for many years in relation to the procuring of new and abundant supplies of ammonia, and to investigations connected therewith.
Through the classic researches of Lawes and Gilbert, who proved, in opposition to no less an authority than Liebig, that ammonia is a most valuable manure which enables us not only to maintain, but to multiply, the yield of our fields, and thus to feed on the same area a much larger number of inhabitants, the immense importance of an abundant supply of ammonia, more particularly for the Old World, with its teeming population and worn-out soil, has been apparent to every one.
For many years Europe has paid to South America millions upon millions of pounds for ammonia in the shape of guano, and more recently, since the supply of guano practically ceased, for nitrate of soda, which effectually serves the same purpose as ammonia. During the past year South America exported 750,000 tons of nitrate, of which 650,000 went to Europe, representing a value of not less than 6,500,000l.
The problem of saving this immense expenditure to Europe, of making ourselves independent of a country so far away for the supply of a material upon which the prosperity of our agriculture - our most important industry - depends, by supplying this ammonia from sources at our own command, is certainly one of the most important which our science has to solve.
It is more than 100 years since Berthollet ascertained that ammonia consists of nitrogen and hydrogen, two elements which we have in great abundance at our command, and innumerable attempts have been made during this century to produce this valuable product by the direct combination of the elements, as well as by indirect means. It has been equally well known that we are in possession of three abundant sources of nitrogen:
(1.) In the shape of matter of animal origin.
(2.) In the shape of matter of vegetable origin.
(3.) In the atmosphere, which contains no less than 79 per cent. of uncombined nitrogen.
In olden times ammonia was principally obtained from animal matter, originally in Egypt by the distillation of camel dung, later on from urine, and from the distillation of bones and horn. The quantity so obtained was very small and the products very expensive. The introduction of coal gas for illumination gave us a considerable and constantly increasing supply of ammonia as a by-product of the gas manufacture, and until recently all practical efforts to increase our supply of ammonia were directed toward collecting and utilizing in the best possible manner the ammonia so obtained. The immense extension of the coal gas industry all over the world has in this way put us into possession of a very considerable amount of sulphate of ammonia, amounting in Europe now to 140,000 tons per annum. In recent years this has been augmented by the ammonia obtained by the distillation of shale, by the introduction of closed ovens for the manufacture of coke, combined with apparatus for condensing the ammonia formed in this manufacture, and also by the condensation of the ammonia contained in the gases from blast furnaces working with coal.
But all these new sources have so far added only about 40,000 tons of sulphate of ammonia to our supply, making a total of 180,000 tons per annum, of which about 120,000 are produced in the United Kingdom, while we still import 650,000 tons of nitrate of soda, equivalent to 500,000 tons of sulphate of ammonia, to make up our requirements.
Many processes have from time to time been proposed to obtain ammonia from other sources. The distillation of turf, which contains upward of 3 per cent. of nitrogen, has received much attention, and a large number of inventors have endeavored to produce ammonia from the nitrogen of the air; but none of these processes has to my knowledge been successful on a manufacturing scale.
My attention was called to this subject at an early part of my career. Already, as far back as 1861, I undertook experiments to utilize, for the production of ammonia, waste leather, a waste material of animal origin at once abundant and very rich in nitrogen, containing from 12 per cent. to 15 per cent. of this element. Distillation in iron retorts yielded about half the nitrogen of this material in the form of ammonia, the carbon remaining in the retorts containing still from 6 per cent. to 8 per cent. Distillation with a moderate quantity of hydrate of lime increased the yield of ammonia only by 1 per cent. to 1½ per cent. A rather better result was obtained by distilling the ground residual carbon with hydrate of lime, but this operation proceeded very slowly, and the total yield of ammonia still remained very far below the quantity theoretically obtainable, so that I came to the conclusion that it was more rational to utilize the leather, reduced to powder by mechanical means, by mixing it directly with other manures.
A few years later I became connected with a large animal charcoal works, in which sulphate of ammonia was obtained as a by-product. Here again I was met with the fact that the yield of ammonia by no means corresponded with the nitrogen in the raw material and that the charcoal remaining in the retorts contained still about half as much nitrogen as had been present in the bones used.
From this time forward my attention was for many years given exclusively to the soda manufacture, and it was only in 1879 that I again took up the question of ammonia. I then determined to submit the various processes which had been proposed for obtaining ammonia from the nitrogen of the air to a searching investigation, and engaged Mr. Joseph Hawliczek to carry out the experimental work.
These processes may be broadly divided into three classes:
(1.) Processes which propose to combine nascent hydrogen with nitrogen at high temperatures or by electricity, with or without the presence of acid gases.
(2.) Processes in which nitrides are first formed, from which ammonia is obtained by the action of hydrogen or steam.
(3.) Processes in which cyanides are first formed and the ammonia obtained from these by the action of steam.
We began with an investigation of those processes in which a mixture of steam and nitrogen or of steam and air is made to act upon coke at a high temperature, sometimes in the presence of lime, baryta, or an alkali, sometimes in the presence of hydrochloric acid.
Very numerous patents have been taken out in this direction and there is no doubt that ammonia has been obtained by these processes by many inventors, but as I was aware that coke contains a considerable quantity of nitrogen, frequently as much as 1.5 per cent., which might be the source of the ammonia obtained, I determined to carry on the investigation in such a way as to make quite certain whether we obtained the ammonia from the coke or from the nitrogen of the atmosphere, or from both. For this purpose we made for every experiment carried on by a mixture of nitrogen or air with steam another experiment with steam alone, carefully excluding nitrogen from the apparatus. A very large number of experiments carried on at carefully determined temperatures, ranging from 500° to 1,200°C., and in which the directions given by the various inventors were most carefully observed, all led to the same result, viz., that the quantities of ammonia obtained were the same whether nitrogen was introduced into the apparatus with the steam or whether steam alone was used, thus proving conclusively that the ammonia obtained was derived from the nitrogen contained in the coke.
Further, on carefully determining the nitrogen in the coke used, it was found that the quantity of ammonia we had obtained in burning coke in a current of nitrogen and steam very nearly corresponded with the total nitrogen in the coke, so that we subsequently made our nitrogen determinations in the coke by simply burning it in a current of steam.
A process belonging to this class, proposed by Hugo Fleck, in which a mixture of carbonic oxide, steam, and nitrogen is made to pass over lime at a moderate red heat in order to obtain ammonia, was also carefully tried. It was claimed for this process that it produced nascent hydrogen at temperatures at which the ammonia is not dissociated, and for this reason succeeded where others had failed. We found that a considerable amount of hydrogen was obtained in this way at a temperature not exceeding 350°C., and that the reaction was nearly complete at 500°C.; but although we tried many experiments over a great range of temperatures, we never obtained a trace of ammonia by this process.
Among experiments with processes of the second class, based upon the formation of nitrides and their subsequent decomposition, the nitrides of boron and titanium had received most attention from inventors. The nitride of boron, which is obtained by treating boracic acid with carbon in the presence of nitrogen, when acted upon by steam, forms boracic acid again and yields the whole of its nitrogen in the form of ammonia, but the high temperature at which the first reaction takes place, and the volatility of boracic acid in a current of steam, make it impossible to utilize this reaction industrially.
There seemed to be a better chance for a process patented by M. Tessier du Mothay, who proposed to bring a mixture of nitrogen and hydrogen into contact with titanium nitride and thus to form ammonia continuously. Titanium is the only element of which we know at present several combinations with nitrogen, and the higher of these does, on being acted upon by a current of hydrogen at an elevated temperature, produce ammonia and a lower nitride of titanium; but this lower nitride does not absorb nitrogen under any of the conditions under which we tried it, which explains the fact that if we passed a current of hydrogen and nitrogen over the higher nitride, we at first obtained a quantity of ammonia corresponding to the quantity which the nitride would give with hydrogen alone, but that the formation of ammonia then ceased completely.
Thus far we had quite failed to get the nitrogen of the air into action.
With the third class of processes, however, based upon the formation in the first instance of cyanides, we found by our very first experiments that the nitrogen of the atmosphere can be easily led into combination. A few experiments showed that the cyanide of barium was much more readily formed than any other cyanide; so we gave our full attention from this time to the process for obtaining ammonia by means of cyanide of barium invented by MM. Margueritte and Sourdeval. This process consists in heating a mixture of carbonate of barium with carbon in the presence of nitrogen, and subsequently treating the cyanide of barium produced with steam, thus producing ammonia and regenerating the carbonate of barium. A great difficulty in this process is that the carbonate of barium fuses at high temperatures, and when fused attacks fireclay goods very powerfully.
We found that this can be overcome by mixing the carbonate of barium with a sufficient quantity of carbon and a small quantity of pitch, and that in this way balls can be made which will not fuse, so that they can be treated in a continuous apparatus in which the broken briquettes can be charged from the top, and after treatment can be withdrawn from the bottom.
We found that the formation of cyanides required a temperature of at least 1,200° C., and proceeded most readily at 1,400° C., temperatures which, although difficult to attain, are still quite within the range of practical working, and we found no difficulty in obtaining a product containing 30 per cent. of barium cyanide, corresponding to a conversion into cyanide of 40 per cent. of the barium present.
We found, however, that the cyanide when exposed to the atmosphere at a temperature above 300° C. is readily destroyed under reformation of carbonate of barium, so that it is absolutely necessary to cool it down to this temperature before exposing it to the atmosphere, a fact of great importance that had hitherto been overlooked.
The operation for producing ammonia and regenerating the carbonate of barium by acting upon the cyanide with steam offers no difficulty whatever, and if the temperature is not allowed to exceed 500° C., the results are quantitative. The regenerated carbonate of barium acts actually better than the ground witherite used in the first instance, and if care is taken that no impurities are introduced by the pitch which is used to remake the briquettes and to replace the small amount of carbon consumed at each operation, I see no reason why it should not continue to act for a very long time.
The cyanide is not acted on by carbonic oxide, but carbonic acid destroys it at high temperatures, so that it is not possible to produce it by heating the briquettes directly in a flame free from oxygen, but containing carbonic acid. The process has, therefore, to be carried out in closed vessels, and I designed for this purpose the following apparatus:
Clay retorts of moderate dimensions and thin walls are placed vertically in a furnace, passing through the hearth as well as through the arch of the furnace. These are joined at the bottom to cast iron retorts of the same shape as the earthenware retort. Through a cast iron mouthpiece on the top of the retort the material was introduced, while in the cast iron retort below the material was cooled to the necessary temperature by radiation and by the cold nitrogen gas introduced into the bottom of it. The lower end of the cast iron retort was furnished with an arrangement for taking out from time to time small quantities of the material, while fresh material was in the same proportion fed in at the top. As a source of nitrogen I used the gases escaping from the carbonating towers of the ammonia-soda process. The formation of cyanide of barium from barium carbonate, carbon, and nitrogen absorbs a very large amount of heat - no less than 97,000 calories per equivalent of the cyanide formed - which heat has to be transmitted through the walls of the retort.
I therefore considered it necessary to use retorts with very thin walls, but I did not succeed in obtaining retorts of this description which would resist the very high temperatures which the process requires, and for this reason I abandoned these experiments. I was at that time not acquainted with the excellent quality of clay retorts used in zinc works, with which I have since experimented for a different purpose. I have no doubt that with such retorts the production of cyanides by this process can be carried out without great difficulty.
I believe that the process will prove remunerative for the manufacture of cyanogen products, which, if produced more cheaply, may in the future play an important role in organic synthesis, in the extraction of noble metals, and possibly other chemical and metallurgical operations.
The process certainly also offers a solution of the problem of obtaining ammonia from the nitrogen of the atmosphere, but whether this can be done with satisfactory commercial results is a question I cannot at present answer, as I have not been able to secure the data for making the necessary calculations.
I am the more doubtful about this point, as in the course of our investigations I have found means to produce ammonia at small cost and in great abundance from the immense store of combined nitrogen which we possess in our coal fields.
Among the processes for obtaining ammonia from the nitrogen of the air which we investigated, was one apparently of great simplicity, patented by Messrs. Rickman and Thompson. These gentlemen state that by passing air and steam through a deep coal fire, the nitrogen so passed through is to a certain extent converted into ammonia. In investigating this statement we found that the process described certainly yields a considerable quantity of ammonia, but when we burned the same coal at a moderate temperature by means of steam alone in a tube heated from the outside, we obtained twice as much ammonia as we had done by burning it with a mixture of air and steam, proving in this case, as in all others, the source of the ammonia to have been the nitrogen contained in the coal. The quantity of ammonia obtained was, however, so large that I determined to follow up this experience, and at once commenced experiments on a semi-manufacturing scale to ascertain whether they would lead to practical and economic results.
I came to the conclusion that burning coal by steam alone at a temperature at which the ammonia formed should not be dissociated, although it yielded more ammonia, would not lead to an economic process, because it would require apparatus heated from the outside, of great complication, bulk, and costliness, on account of the immense quantity of raw material to be treated for a small amount of ammonia obtainable.
On the other hand, if the coal could be burned in gas producers by a mixture of air and steam, the plant and working of it would be simple and inexpensive, the gas obtained could be utilized in the same way as ordinary producer gas, and would pay to a large extent for the coal used in the operation, so that although only one-half of the ammonia would be obtained, it seemed probable that the result would be economical.
I consequently constructed gas producers and absorbing plant of various designs and carried on experiments for a number of years. These experiments were superintended by Mr. G. H. Beckett, Dr. Carl Markel, and, during the last four years, by Dr. Adolf Staub, to whose zeal and energy I am much indebted for the success that has been achieved. The object of these experiments was to determine the most favorable conditions for the economic working of the process with respect to both the cost of manufacture as well as the first cost and simplicity of plant. The cost of manufacture depends mainly upon the yield of ammonia, as the expenses remain almost the same whether a large or a small amount of ammonia is obtained; the only other item of importance is the quantity of steam used in the process. We found the yield of ammonia to vary with the temperature at which the producer was working, and to be highest when the producer was worked as cool as was compatible with a good combustion of the fuel. The temperature again depended upon the amount of steam introduced into the producer, and of course decreased the more steam increased. We obtained the best practical results by introducing about two tons of steam for every ton of fuel consumed.
We experimented upon numerous kinds of fuel, common slack and burgy of the Lancashire, Staffordshire, and Nottinghamshire districts. We found not much difference in the amount of nitrogen contained in these fuels, which varied between 1.2 and 1.6 per cent., nor did we find much difference in the ammonia obtained from these fuels if worked under similar conditions. Employing the quantity of steam just named we recovered about half the nitrogen in the form of ammonia, yielding on an average 0.8 per cent. of ammonia, equal to 32 kilos, of sulphate per ton of fuel. In order to obtain regular results we found it necessary to work with a great depth of fuel in the producers, so that slight irregularities in the working would not affect results. Open burning kinds of slack do of course work with the greater ease, but there is no difficulty in using a caking fuel, as the low temperature at which the producers work prevents clinkering and diminishes the tendency of such fuels to cake together.
The quantity of steam thus required to obtain a good yield of ammonia is rather considerable, and threatened to become a serious item of expense. Only one-third of this steam is decomposed, in its passage through the producer, and two-thirds remain mixed with the gases which leave the producer. My endeavors were consequently directed toward finding means to recover this steam, and to return it to the producers, and also to utilize the heat of the gases which leave the producers with a temperature of 450° to 500° C., for raising steam for the same purpose. The difficulties in the way of attaining this end and at the same time of recovering, in a simple manner, the small amount of ammonia contained in the immense volume of gas we have to deal with, were very great. We obtain from one ton of coal 160,000 cubic feet of dry gas at 0° C. and atmospheric pressure. The steam mixed with this gas as it leaves the producer adds another 80,000 cubic feet to this, and the large amount of latent heat in this quantity of steam makes the problem still more difficult.
The application of cooling arrangements, such as have been successfully applied to blast furnace gases, in which there is no steam present, and which depend upon the cooling through the metallic sides of the apparatus, is here practically out of the question. After trying a number of different kinds of apparatus, I have succeeded in solving the problem in the following way:
The gases issuing from the producers are led through a rectangular chamber partly filled with water, which is thrown up in a fine spray by revolving beaters so as to fill the whole area of the chamber. This water, of course, becomes hot; a certain quantity of it evaporates, the spray produced washes all dust and soot out of the gases, and also condenses the fixed ammonia. The water thus becomes, to a certain degree, saturated with ammonia salts, and a certain portion of it is regularly removed from the chamber and distilled with lime to recover the ammonia.
Longitudinal Section of Plant for obtaining Ammonia from Gas Producers.
Cross Section through Gas Producers.
This chamber is provided with water lutes, through which the tar condensed in it is from time to time removed. From this chamber the gases, which are now cooled down to about 100° C., and are loaded with a large amount of water vapor, are passed through a scrubber filled with perforated bricks, in which the ammonia contained in the gases is absorbed by sulphuric acid. In this scrubber a fairly concentrated solution of sulphate of ammonia containing 36 to 38 per cent. is used, to which a small quantity of sulphuric acid is added, so that the liquid leaving the scrubber contains only 2.5 per cent. of free acid. This is necessary, as a liquid containing more acid would act upon the tarry matter and produce a very dark-colored solution. The liquid running from the scrubber is passed through a separator in which the solution of sulphate of ammonia separates from the tar. The greater portion of the clear liquid is, after adding a fresh quantity of acid to it, pumped back through the scrubber. A certain portion of it is, after treatment with a small quantity of heavy tar oils, which take the tarry matter dissolved in it out, evaporated in conical lead-lined pans furnished with lead steam coils, and which are kept constantly filled by the addition of fresh liquor until the whole mass is thick.
This is then run out on a strainer and yields, after draining and washing with a little water, a sulphate of ammonia of very fair quality, which finds a ready sale. The mother liquor, which contains all the free acid, is pumped back to the scrubber.
The gas on entering this scrubber contains only 0.13 volume per cent. of ammonia, and on leaving the scrubber it contains not more than one-tenth of this quantity. Its temperature has been reduced to 80° C., and is fully saturated with moisture, so that practically no condensation of water takes place in the scrubber. The gas is next passed through a second scrubber filled with perforated wood blocks. In this it meets with a current of cold water which condenses the steam, the water being thereby heated to about 78° C. In this scrubber the gas is cooled down to about 40°-50° C., and passes from it to the gas main leading to the various places where it is to be consumed. The hot water obtained in this second scrubber is passed through a vessel suitably constructed for separating the tar which is mixed with it, and is then pumped through a third scrubber, through which, in an opposite direction to the hot water, cold air is passed. This is forced by means of a Roots blower through the scrubber into the producer.
The air gets heated to about 76° C. and saturated with moisture at that temperature by its contact with the hot water, and the water leaves this third scrubber cold enough to be pumped back through the second scrubber. The same quantity of water is thus constantly used for condensing the water vapor in one scrubber and giving it up to the air in the other. In this way we recover and return to the producer fully two-thirds of the steam which has been originally introduced, so that we have to add to the air, which has thus been loaded with moisture, an additional quantity of steam equal to only one-third of the total quantity required before it enters the producer. This additional quantity of steam, which amounts to 0.6 ton of steam for every ton of fuel burnt, we obtain as exhaust steam from the engines driving the blowers and pumps required for working the plant.
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A STEAMPUNK NOVEL, FULL OF
ANARCHIC EXPERIMENTAL SCIENCE
"Hodges emitted a scream the like of which
I hadn't heard since his scrotum was burned off
Unrelated to this post, below is an example of
eclectic science esoterica
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