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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.
The gas producers which I prefer to use are of rectangular shape, so that a number of them can be put into a row. They are six feet wide and 12 feet long inside. The air is introduced and the ashes removed at the two small sides of the producer which taper toward the middle and are closed at the bottom by a water lute of sufficient depth for the pressure under which the air is forced in, equal to about 4 inches of water. The ashes are taken out from underneath the water, the producers having no grate or fire bars at all. The air enters just above the level of the water through a pipe connected with the blower. These small sides of the producer rest upon cast iron plates lined to a certain height with brickwork, and this brickwork is carried by horizontal cast iron plates above the air entrance. In this way a chamber is formed of triangular shape, one side of which is closed by the ashes, and thus the air is distributed over the whole width of the producer.
The gas is taken out in the middle of the top of the producer by an iron pipe, and fuel charged in by hoppers on both sides of this pipe. Between the pipe and the hoppers two hanging arches are put into the producers a certain distance down, and the fuel is kept above the bottom level of these hanging arches. This compels the products of distillation, produced when fresh fuel is charged in, to pass through the incandescent fuel between the two hanging arches, whereby the tarry products are to a considerable extent converted into permanent gas, and the coal dust arising from the charging is kept back in the producer.
The details of construction of this plant will be easily understood by reference to the diagrams before you.
The fuel we use is a common kind of slack, and contains, on an average, 33.5 per cent. of volatile matter, including water, and 11.5 per cent. of ashes, leaving 55 per cent. of non-volatile carbon.
The cinders which we take out of the producer contain, on an average, 33 per cent. of carbon. Of this we recover about one-half by riddling or picking, which we return to the producer. The amount of unburnt carbon lost in the cinders is thus not more than 3 per cent. to 4 per cent. on the weight of fuel used.
The gas we obtain contains, in a dry state, on an average, 15 per cent. of carbonic acid, 10 per cent. of carbonic oxide, 23 per cent. of hydrogen, 3 per cent. of hydrocarbons, and 49 per cent. of nitrogen.
The caloric value of this gas is very nearly equal to 73 per cent. of the caloric value of the fuel used, but in using this gas for heating purposes, such as raising steam or making salt, we utilize the heat it can give very much better than in burning fuel, as we can completely burn it with almost the theoretical quantity of air, so that the products of combustion resulting do not contain more than 1 to 2 per cent. of free oxygen. Consequently the heat escaping into the chimney is very much less than when fuel is burnt direct, and we arrive at evaporating, by means of the gas, 85 per cent. of the water that we would evaporate by burning the fuel direct, in ordinary fireplaces.
We have, however, to use a certain quantity of steam in the producers and in evaporating the sulphate of ammonia liquors, which has to be deducted from the steam that can be raised by the gas in order to get at the quantity of available steam therefrom obtainable. The former amounts, as already stated, to 0.6 ton, the latter to 0.1 ton of steam per ton of fuel burnt, making a total of 0.7 ton. The gas obtained from one ton of fuel evaporates 5.8 tons of water in good steam boilers, working at a rate of evaporation of 50 to 55 tons per 24 hours under 90 lb. pressure. Deducting from this the 0.7 ton necessary for working the plant leaves an available amount of steam raised by the gas from one ton of fuel of 5.1 tons, equal to 75 per cent. of the steam that we can obtain from the same fuel by hand firing.
In addition to the gas, we obtain about 3 per cent. of tar from the fuel. This tar is very thick, and of little commercial value. It contains only 4 per cent. of oils volatile below 200° C., and 38 per cent. of oils of a higher boiling point, consisting mostly of creosote oils very similar to those obtained from blast furnaces; and only small quantities of anthracene and paraffin wax.
I have made no attempts to utilize this tar except as fuel. It evaporates nearly twice as much water as its weight of coal, and we have thus to add its evaporative efficiency to that of the gas given above, leading to a total of about 80 per cent. of the evaporative efficiency of the fuel used in the producers. The loss involved in gasifying the fuel to recover the ammonia therefrom amounts thus to 20 per cent. of the fuel used. This means that, where we have now to burn 100 tons of fuel, we shall have to burn 125 tons in the producers in order to obtain ammonia equal to about half the nitrogen contained therein. Our actual yield of ammonia on a large scale amounting on an average to 32 kilos., equal to 70.6 lb. per ton of fuel, 125 tons of fuel will turn out 4 tons of sulphate of ammonia. We thus consume 6.25 tons of fuel for every ton of sulphate obtained, or nearly the same quantity as is used in producing a ton of caustic soda by the Le Blanc process - a product not more than half the value of ammonium sulphate.
At present prices in Northwich this fuel represents a value of 35s. If we add to this the extra cost of labor over and above the cost of burning fuel in ordinary fireplaces, the cost of sulphuric acid, bags, etc., we come to a total of 4l. 10s. to 5l. per ton of sulphate of ammonia, which at the present selling price of this article, say 12l. per ton, leaves, after a liberal allowance for wear and tear of plant, an ample margin of profit. With a rise in the price of fuel, this margin, however, rapidly decreases, and the working of the process will, of course, be much more expensive on a small scale, as will also be the cost of the plant, which under all circumstances is very considerable. The great advantages incidental to this process over and above the profit arising from the manufacture of sulphate of ammonia, viz., the absolute impossibility of producing smoke and the great regularity of the heating resulting from the use of gas, are, therefore, as far as I can see for the present, only available for large consumers of cheap fuel.
We have tried many experiments to produce hydrochloric acid in the producers, with the hope of thereby increasing the yield of ammonia, as it is well known that ammonium chloride vapor, although it consists of a mixture of ammonia gas and hydrochloric acid gas, is not at all dissociated at temperatures at which the dissociation of ammonia alone has already taken place to a considerable extent.
I had also hoped that I might in this way produce the acid necessary to combine with the ammonia at very small cost. For this purpose we moistened the fuel used with concentrated brine, and also with the waste liquors from the ammonia soda manufacture, consisting mainly of chloride of calcium; and we also introduced with the fuel balls made by mixing very concentrated chloride of calcium solution with clay, which allowed us to produce a larger quantity of hydrochloric acid in the producer than by the other methods.
We did in this way succeed in producing hydrochloric acid sometimes less and sometimes more than was necessary to combine with the ammonia, but we did not succeed in producing with regularity the exact amount of acid necessary to neutralize the ammonia. When the ammonia was in excess, we had therefore to use sulphuric acid as before to absorb this excess, and we were never certain that sometimes the hydrochloric acid might not be in excess, which would have necessitated to construct the whole plant so that it could have resisted the action of weak hydrochloric acid - a difficulty which I have not ventured to attack. The yield of ammonia was not in any case increased by the presence of the hydrochloric acid. This explains itself if we consider that there is only a very small amount of ammonia and hydrochloric acid diffused through a very large volume of other gases, so that the very peculiar protective action which the hydrochloric acid does exercise in retarding the dissociation of ammonia in ammonium chloride vapor, where an atom of ammonia is always in contact with an atom of hydrochloric acid, will be diminished almost to zero in such a dilute gas where the atoms of hydrochloric acid and ammonia will only rarely come into immediate contact with each other.
When we burnt coke by a mixture of air and steam in presence of a large excess of hydrochloric acid, the yield of ammonia certainly was thereby considerably increased, but such a large excess cannot be used on an industrial scale. I have therefore for the present to rest satisfied with obtaining only half the nitrogen contained in the fuel in the form of ammonia.
The enormous consumption of fuel in this country - amounting to no less than 150 million tons per annum - would at this rate yield as much as five million tons of sulphate of ammonia a year, so that if only one-tenth of this fuel would be treated by the process, England alone could supply the whole of the nitrogenous compounds, sulphate of ammonia, and nitrate of soda at present consumed by the Old World. As the process is especially profitable for large consumers of fuel situated in districts where fuel is cheap, it seems to me particularly suitable to be adopted in this country. It promises to give England the privilege of supplying the Old World with this all-important fertilizer, and while yielding a fair profit to the invested capital and finding employment for a considerable number of men, to make us, last not least, independent of the New World for our supply of so indispensable a commodity.
Before leaving my subject, I will, if you will allow me, give you in a few words a description of two other inventions which have been the outcome of this research. While looking one day at the beautiful, almost colorless, flame of the producer gas burning under one of our boilers, it occurred to me that a gas so rich in hydrogen might be turned to better use, and that it might be possible to convert it direct into electricity by means of a gas battery.
You all know that Lord Justice Grove showed, now fifty years ago, that two strips of platinum partly immersed in dilute sulphuric acid, one of which is in contact with hydrogen and the other with oxygen, produce electricity. I will not detain you with the many and varied forms of gas batteries which Dr. Carl Langer (to whom I intrusted this investigation) has made and tried during the last four years, in order to arrive at the construction of a gas battery which would give a practical result, but I will call your attention to the battery before me on the table, which is the last result of our extended labors in this direction, and which we hope will mark a great step in advance in the economic production of electricity.
The distinguishing feature of this battery is that the electrolyte is not employed as a mobile liquid, but in a quasi-solid form, and it is, therefore, named dry gas battery. It consists of a number of elements, which are formed of a porous diaphragm of a non-conducting material (in this instance plaster of Paris), which is impregnated with dilute sulphuric acid. Both sides of this diaphragm are covered with very fine platinum leaf perforated with very numerous small holes, and over this a thin film of platinum black. Both these coatings are in contact with frameworks of lead and antimony, insulated one from the other, which conduct the electricity to the poles of the battery.
A number of these elements are placed side by side, with non-conducting frames intervening, so as to form chambers through which the hydrogen gas is passed along one side of the element and air along the other.
This peculiar construction allows us to get a very large amount of duty from a very small amount of platinum. One of the batteries before you, consisting of seven elements, with a total effective surface of half a square meter, contains 2½ grammes of platinum leaf and 7 grammes of platinum black, a total of 9½ grammes of platinum, and produces a current of 2 amperes and 5 volts, or 10 watts, when the outer resistance is properly adjusted. This current is equal to nearly 50 per cent. of the total energy obtainable from the hydrogen absorbed in the battery.
In order to maintain a constant current, we have from time to time (say once an hour) to interchange the gases, so as to counteract the disturbing influence produced by the transport of the sulphuric acid gas from one side of the diaphragm to the other. This operation can easily be performed automatically by a commutator worked by a clock.
The water produced in the battery by the oxidation of the hydrogen is carried off by the inert gas mixed with the hydrogen, and by the air, of which we use a certain excess for this purpose. This is important, as if the platinum black becomes wet, it loses its absorbing power for the gases almost completely and stops the work of the battery. To avoid this was in fact the great difficulty in designing a powerful gas battery, and all previous constructions which employed the electrolyte as a mobile liquid failed in consequence.
The results obtained by our battery are practically the same whether pure oxygen and hydrogen or air and gases containing 25 per cent. of hydrogen are used; but we found that the latter gases must be practically free from carbonic oxide and hydrocarbons, which both interfere very much with the absorbing power of the platinum black.
We had thus to find a cheap method of eliminating these two gases from the producer gas, and converting them at the same time into their equivalent of hydrogen. The processes hitherto known for this purpose, viz., passing a mixture of such gases with steam over lime (which I mentioned some time ago) or over oxide of iron or manganese, require high temperatures, which render them expensive, and the latter do not effect the reaction to a sufficient extent for our purpose.
We have succeeded in attaining our object at a temperature below that at which the gases leave my producers, viz., at 350° C. to 450° C., by passing the producer gases, still containing a considerable excess of steam, over metallic nickel or cobalt. These metals have the extraordinary property of decomposing almost completely, even at the low temperature named, carbonic oxide into carbon and carbonic acid and hydrocarbons into carbon and hydrogen.
In order to carry the process out with small quantities of nickel and cobalt, we impregnate pumice stone or similar material with a salt of nickel or cobalt, and reduce this by means of hydrogen or producer gas. These pieces of pumice stone are filled into a retort or chamber and the hot gases passed through them. As the reaction produces heat, it is not necessary to heat the chambers or retorts from the outside when the necessary temperature has once been attained. This process has not yet been carried out on a large scale, but the laboratory experiments have been so satisfactory that we have no doubt as to its complete success. It will enable us to obtain gases containing 36 per cent. to 40 per cent. of hydrogen and practically free from carbonic oxide and hydrocarbons from producer gas at a very small cost, and thus to make the latter suitable for the production of electricity by our gas battery. We obtain, as stated before, 50 per cent. of the energy in the hydrogen absorbed in the battery in the form of electricity, while, if the same gas was consumed under steam boilers to make steam, which, as I have shown before, could in this way be raised cheaper than by burning fuel direct, and if this steam was turned into motive power by first-rate steam engines, and the motive power converted into electricity by a dynamo, the yield of electricity would in the most favorable case not exceed 8 per cent. of the energy in the gas.
I hope that this kind of battery will one day enable us to perform chemical operations by electricity on the largest scale, and to press this potent power into the service of the chemical industries.
The statement is frequently made that "Necessity is the mother of invention." If this has been the case in the past, I think it is no longer so in our days, since science has made us acquainted with the correlation of forces, teaching us what amount of energy we utilize and how much we waste in our various methods for attaining certain objects, and indicating to us where and in what direction and how far improvement is possible; and since the increase in our knowledge of the properties of matter enables us to form an opinion beforehand as to the substances we have available for obtaining a desired result.
We can now foresee, in most cases, in what direction progress in technology will move, and in consequence the inventor is now frequently in advance of the wants of his time. He may even create new wants, to my mind a distinct step in the development of human culture. It can then no longer be stated that "Necessity is the mother of invention;" but I think it may truly be said that the steady, methodical investigation of natural phenomena is the father of industrial progress.
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Sir Lowthian Bell, Bart., F.R.S., in moving a vote of thanks, said that the meeting had had the privilege of listening to a description of results obtained by a man of exceptional intelligence and learning, supplemented by that devotion of mind which qualified him to pursue his work with great energy and perseverance. The importance of the president's address could not possibly be overrated. At various periods different substances had been put forward as indications of the civilization of the people. He remembered hearing from Dr. Ure that he considered the consumption of sulphuric acid to be the most accurate measure of the civilization of the people.
In course of time sulphuric acid gave way to soap, the consumption of which was probably still regarded as the great exponent of civilization by such of his fellow citizens as had thereby made their name. From what he had heard that morning, however, he should be inclined to make soap yield to ammonia, as sulphuric acid had in its time succumbed to soap. For not only was ammonia of great importance to us as a manufacturing nation, but it almost appeared to be a condition of our existence. England had a large population concentrated on an area so small as to make it almost a matter of apprehension whether the surface could maintain the people upon it.
We were now importing almost as much food as we consumed, and were thus more and more dependent on the foreigner. Under certain conditions this would become a very serious matter, and thus any one who showed how to produce plenty of ammonia at a cheap rate was a benefactor to his country. Mr. Mond's process seemed to come nearer to success than any which had preceded it, and it needed no words from him to induce the meeting to accord a hearty vote of thanks to the president for his admirable paper.
Mr. J. C. Stevenson, M.P., in seconding the motion, said that no paper could be more interesting and valuable to the society than that delivered by the president. It opened out a future for the advancement of chemical industry which almost overcame one by the greatness of its possibilities. Mr. Mond had performed an invaluable service by investigating the various methods proposed for the manufacture of ammonia, and clearing the decks of those processes supposed by their inventors to be valuable, but proved by him to be delusive. It gave him hearty pleasure therefore to second the vote of thanks proposed by Sir Lowthian Bell.
A paper read at the annual general meeting of the Society of Chemical Industry, London, July 10, 1889.
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