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Gas

GAS, a general term for one of the three states of aggregation of matter; also more specifically applied to coal-gas, the gaseous product formed in the destructive distillation of coal or other carbonaceous matter (see below, section Gas Manufacture; for gas engines see the separate heading Gas Engine).

The Gaseous State. - Matter is studied under three physical phases - solids, liquids and gases, the latter two being sometimes grouped as "fluids." The study of the physical properties of fluids in general constitutes the science of hydromechanics, and their applications in the arts is termed hydraulics; the special science dealing with the physical properties of gases is named pneumatics.

The gaseous fluid with which we have chiefly to do is our atmosphere. Though practically invisible, it appeals in its properties to other of our senses, so that the evidences of its presence are manifold. Thus we feel it in its motion as wind, and observe the dynamical effects of this motion in the quiver of the leaf or the motion of a sailing ship. It offers resistance to the passage of bodies through it, destroying their motion and transforming their energy - as is betrayed to our hearing in the whiz of the rifle bullet, to our sight in the flash of the meteor.

The practically obvious distinction between solids and fluids may be stated in dynamical language thus: - solids can sustain a longitudinal pressure without being supported by a lateral pressure; fluids cannot. Hence any region of space enclosed by a rigid boundary can be easily filled with a fluid, which then takes the form of the bounding surface at every point of it. But here we distinguish between fluids according as they are gases or liquids. The gas will always completely fill the region, however small the quantity put in. Remove any portion and the remainder will expand so as to fill the whole space again. On the other hand, it requires a definite quantity of liquid to fill the region. Remove any portion and a part of the space will be left unoccupied by liquid. Part of the liquid surface is then otherwise conditioned than by the form of the wall or bounding surface of the region; and if the portion of the wall not in contact with the liquid is removed the form and quantity of the liquid are in no way affected. Hence a liquid can be kept in an open vessel; a gas cannot so be. To quote the differentia of Sir Oliver Lodge: "A solid has volume and shape; a liquid has volume, but no shape; a gas has neither volume nor shape."

It is necessary to distinguish between a gas and a "vapour." The latter possesses the physical property stated above which distinguishes a gas from a fluid, but it differs from a gas by being readily condensible to a liquid, either by lowering the temperature or moderately increasing the pressure. The study of the effects of pressure and temperature on many gases led to the introduction of the term "permanent gases" to denote gases which were apparently not liquefiable. The list included hydrogen, nitrogen and oxygen; but with improved methods these gases have been liquefied and even solidified, thus rendering the term meaningless (see Liquid Gases). The term "perfect gas" is applied to an imaginary substance in which there is no frictional retardation of molecular motion; or, in other words, the time during which any molecule is influenced by other molecules is infinitesimally small compared with the time during which it traverses its mean free path. It serves as a means of research, more particularly in mathematical investigations, the simple laws thus deduced being subsequently modified by introducing assumptions in order to co-ordinate actual experiences.

The gaseous state was well known to the ancients; for instance, in Greek cosmology, "air" was one of the fundamental elements. The alchemists used such terms as spiritus, flatus, halitus, aura, emanatio nubila, etc., words implying a "wind" or "breath." The word "gas" was invented by J.B. van Helmont in his Ortus medicinae, posthumously published in 1648, in the course of his description of the gas now known as carbon dioxide. He found that charcoal on burning yielded a "spirit," which he named spiritus sylvestris on account of its supposed untamable nature ("Gas sylvestre sive incoërcibile, quod in corpus cogi non potest visibile"); and he invented the word "gas" in the expression: "... this spirit, hitherto unknown, ... I call by a new name gas" ("hunc spiritum, incognitum hactenus, novo nomine gas voco"). The word was suggested by the Gr., chaos, for he also writes: "I have called this spirit gas, it being scarcely distinguishable from the Chaos of the ancients" ("halitum illum Gas vocavi, non longe a Chao veterum secretum"). The view that the word was suggested by the Dutch geest, spirit, is consequently erroneous. Until the end of the 18th century the word "air," qualified by certain adjectives, was in common use for most of the gases known - a custom due in considerable measure to the important part which common air played in chemical and physical investigations.

The study of gases may be divided into two main branches: the physical and the chemical. The former investigates essentially general properties, such as the weight and density, the relation between pressure, volume and temperature (piezometric and thermometric properties), calorimetric properties, diffusion, viscosity, electrical and thermal conductivity, etc., and generally properties independent of composition. These subjects are discussed in the articles Density; Thermometry; Calorimetry; Diffusion; Conduction of Heat; and Condensation of Gases. The latter has for its province the preparation, collection and identification of gases, and the volume relations in which they combine; in general it deals with specific properties. The historical development of the chemistry of gases - pneumatic chemistry - is treated in the article Chemistry; the technical analysis of gaseous mixtures is treated below under Gas Analysis. Connecting the experimental study of the physical and chemical properties is the immense theoretical edifice termed the kinetic theory of gases. This subject, which is discussed in the article Molecule, has for its purpose (1) the derivation of a physical structure of a gas which will agree with the experimental observations of the diverse physical properties, and (2) a correlation of the physical properties and chemical composition.

Gas Analysis. - The term "gas analysis" is given to that branch of analytical chemistry which has for its object the quantitative determination of the components of a gaseous mixture. The chief applications are found in the analysis of flue gases (in which much information is gained as to the completeness and efficiency of combustion), and of coal gas (where it is necessary to have a product of a definite composition within certain limits). There are, in addition, many other branches of chemical technology in which the methods are employed. In general, volumetric methods are used, i.e. a component is absorbed by a suitable reagent and the diminution in volume noted, or it is absorbed in water and the amount determined by titration with a standard solution. Exact analysis is difficult and tedious, and consequently the laboratory methods are not employed in technology, where time is an important factor and moderate accuracy is all that is necessary. In this article an outline of the technical practice will be given.

The apparatus consists of (1) a measuring vessel, and (2) a series of absorption pipettes. A convenient form of measuring vessel is that devised by W. Hempel. It consists of two vertical tubes provided with feet and connected at the bottom by flexible rubber tubing. One tube, called the "measuring tube," is provided with a capillary stopcock at the top and graduated downwards; the other tube, called the "level tube," is plain and open. To use the apparatus, the measuring tube is completely filled with water by pouring water into both tubes, raising the level tube until water overflows at the stopcock, which is then turned. The test gas is brought to the stopcock, by means of a fine tube which has been previously filled with water or in which the air has been displaced by running the gas through. By opening the stopcock and lowering the level tube any desired quantity of the gas can be aspirated over. In cases where a large quantity of gas, i.e. sufficient for several tests, is to be collected, the measuring tube is replaced by a large bottle.

(By permission of Messrs Baird & Tatlock.)
Fig. 1. Fig. 2.

The volume of the gas in the measuring tube is determined by bringing the water in both tubes to the same level, and reading the graduation on the tube, avoiding parallax and the other errors associated with recording the coincidence of a graduation with a meniscus. The temperature and atmospheric pressure are simultaneously noted. If the tests be carried out rapidly, the temperature and pressure may be assumed to be constant, and any diminution in volume due to the absorption of a constituent may be readily expressed as a percentage. If, however, the temperature and pressure vary, the volumes are reduced to 0° and 760 mm. by means of the formula V0 = V(P − p)/(1 + .00366t)760, in which V is the observed volume, P the barometric pressure, p the vapour tension of water at the temperature t of the experiment. This reduction is facilitated by the use of tables.

Some common forms of absorption pipettes are shown in figs. 1 and 2. The simpler form consists of two bulbs connected at the bottom by a wide tube. The lower bulb is provided with a smaller bulb bearing a capillary through which the gas is led to the apparatus, the higher bulb has a wider outlet tube. The arrangement is mounted vertically on a stand. Sometimes the small bulb on the left is omitted. The form of the pipette varies with the nature of the absorbing material. For solutions which remain permanent in air the two-bulbed form suffices; in other cases a composite pipette (fig. 2) is employed, in which the absorbent is protected by a second pipette containing water. In the case of solid reagents, e.g. phosphorus, the absorbing bulb has a tubulure at the bottom. To use a pipette, the absorbing liquid is brought to the outlet of the capillary by tilting or by squeezing a rubber ball fixed to the wide end, and the liquid is maintained there by closing with a clip. The capillary is connected with the measuring tube by a fine tube previously filled with water. The clip is removed, the stopcock opened, and the level tube of the measuring apparatus raised, so that the gas passes into the first bulb. There it is allowed to remain, the pipette being shaken from time to time. It is then run back into the measuring tube by lowering the level tube, the stopcock is closed, and the volume noted. The operation is repeated until there is no further absorption.

The choice of absorbents and the order in which the gases are to be estimated is strictly limited. Confining ourselves to cases where titration methods are not employed, the general order is as follows: carbon dioxide, olefines, oxygen, carbon monoxide, hydrogen, methane and nitrogen (by difference). This scheme is particularly applicable to coal-gas. Carbon dioxide is absorbed by a potash solution containing one part of potash to between two and three of water; the stronger solution absorbs about 40 volumes of the gas. The olefines - ethylene, etc. - are generally absorbed by a very strong sulphuric acid prepared by adding sulphur trioxide to sulphuric acid to form a mixture which solidifies when slightly cooled. Bromine water is also employed. Oxygen is absorbed by stick phosphorus contained in a tubulated pipette filled with water. The temperature must be above 18°; and the absorption is prevented by ammonia, olefines, alcohol, and some other substances. An alkaline solution of pyrogallol is also used; this solution rapidly absorbs oxygen, becoming black in colour, and it is necessary to prepare the solution immediately before use. Carbon monoxide is absorbed by a solution of cuprous chloride in hydrochloric acid or, better, in ammonia. When small in amount, it is better to estimate as carbon dioxide by burning with oxygen and absorbing in potash; when large in amount, the bulk is absorbed in ammoniacal cuprous chloride and the residue burned. Hydrogen may be estimated by absorption by heated palladium contained in a capillary through which the gas is passed, or by exploding (under reduced pressure) with an excess of oxygen, and measuring the diminution in volume, two-thirds of which is the volume of hydrogen. The explosion method is unsatisfactory when the gas is contained over water, and is improved by using mercury. Methane cannot be burnt in this way even when there is much hydrogen present, and several other methods have been proposed, such as mixing with air and aspirating over copper oxide heated to redness, or mixing with oxygen and burning in a platinum tube heated to redness, the carbon dioxide formed being estimated by absorption in potash. Gases soluble in water, such as ammonia, hydrochloric acid, sulphuretted hydrogen, sulphur dioxide, etc., are estimated by passing a known volume of the gas through water and titrating the solution with a standard solution. Many types of absorption vessel are in use, and the standard solutions are generally such that 1 c.c. of the solution corresponds to 1 c.c. of the gas under normal conditions.

(By permission of Messrs Baird & Tatlock.)
Fig. 3.

Many forms of composite gas-apparatus are in use. One of the commonest is the Orsat shown in fig. 3. The gas is measured in the graduated cylinder on the right, which is surrounded by a water jacket and provided with a levelling bottle. At the top it is connected by a capillary tube bent at right angles to a series of absorbing vessels, the connexion being effected by stopcocks. These vessels consist of two vertical cylinders joined at the bottom by a short tube. The cylinder in direct communication with the capillary is filled with glass tubes so as to expose a larger surface of the absorbing solution to the gas. The other cylinder is open to the air and serves to hold the liquid ejected from the absorbing cylinder. Any number of bulbs can be attached to the horizontal capillary; in the form illustrated there are four, the last being a hydrogen pipette in which the palladium is heated in a horizontal tube by a spirit lamp. At the end of the horizontal tube there is a three-way cock connecting with the air or an aspirator. To use the apparatus, the measuring tube is completely filled with water by raising the levelling bottle. The absorbing vessels are then about half filled with the absorbents, and, by opening the cocks and aspirating, the liquid is brought so as completely to fill the bulbs nearer the capillary. The cocks are then closed. By opening the three-way cock to the supply of the test gas and lowering the levelling bottle, any desired amount can be drawn into the measuring tube. The absorption is effected by opening the cock of an absorbing vessel and raising the levelling bottle. The same order of absorption and general directions pertaining to the use of Hempel pipettes have to be adopted.

Although the earliest attempts at gas analysis were made by Scheele, Priestley, Cavendish, Lavoisier, Dalton, Gay-Lussac and others, the methods were first systematized by R. Bunsen, who began his researches in 1838. He embodied his results in his classical Gasometrische Methoden (1857, second edition 1877), a work translated into English by H. Roscoe. Clemens Winkler contributed two works, Anleitung zur chemischen Untersuchung der Industriegase (1876-1877) and Lehrbuch der technischen Gasanalyse (2nd ed., 1892), both of which are very valuable for the commercial applications of the methods. W. Hempel's researches are given in his Neue Methode zur Analyse der Gase (1880) and Gasanalytische Methoden (1890, 3rd ed. 1900).

Gas Manufacture

1. Illuminating Gas. - The first practical application of gas distilled from coal as an illuminating agent is generally ascribed to William Murdoch, who between the years of 1792 and 1802 demonstrated the possibility of making gas from coal and using it as a lighting agent on a large scale. Prior to 1691, however, Dr John Clayton, dean of Kildare, filled bladders with inflammable gas obtained by the distillation of coal, and showed that on pricking the bladders and applying a light to the escaping gas it burnt with a luminous flame, and in 1726 Stephen Hales published the fact that by the distillation of 158 grains of Newcastle coal, 180 cub. in. of inflammable air would be obtained. Jean Pierre Minckelers, professor of natural philosophy in the university of Louvain, and later of chemistry and physics at Maestricht, made experiments on distilling gas from coal with the view of obtaining a permanent gas sufficiently light for filling balloons, and in 1785 experimentally lighted his lecture room with gas so obtained as a demonstration to his students, but no commercial application was made of the fact. Lord Dundonald, in 1787, whilst distilling coal for the production of tar and oil, noticed the formation of inflammable gas, and even used it for lighting the hall of Culross Abbey. It is clear from these facts that, prior to Murdoch's experiments, it was known that illuminating gas could be obtained by the destructive distillation of coal, but the experiments which he began at Redruth in 1792, and which culminated in the lighting of Messrs Boulton, Watt & Co.'s engine works at Soho, near Birmingham, in 1802, undoubtedly demonstrated the practical possibility of making the gas on a large scale, and burning it in such a way as to make coal-gas the most important of the artificial illuminants. An impression exists in Cornwall, where Murdoch's early experiments were made, that it was a millwright named Hornblower who first suggested the process of making gas to Murdoch, but, as has been shown, the fact that illuminating gas could be obtained from coal by distillation was known a century before Murdoch made his experiments, and the most that can be claimed for him is that he made the first successful application of it on a practical scale.

In 1799 a Frenchman named Philippe Lebon took out a patent in Paris for making an illuminating gas from wood, and gave an exhibition of it in 1802, which excited a considerable amount of attention on the European continent. It was seen by a German, F.A. Winsor, who made Lebon an offer for his secret process for Germany. This offer was, however, declined, and Winsor returned to Frankfort determined to find out how the gas could be made. Having quickly succeeded in discovering this, he in 1803 exhibited before the reigning duke of Brunswick a series of experiments with lighting gas made from wood and from coal. Looking upon London as a promising field for enterprise, he came over to England, and at the commencement of 1804 took the Lyceum theatre, where he gave demonstrations of his process. He then proceeded to float a company, and in 1807 the first public street gas lighting took place in Pall Mall, whilst in 1809 he applied to parliament to incorporate the National Heat and Light Company with a capital of half a million sterling. This application was opposed by Murdoch on the ground of his priority in invention, and the bill was thrown out, but coming to parliament for a second time in 1810, Winsor succeeded in getting it passed in a very much curtailed form, and, a charter being granted later in 1812, the company was called the Chartered Gas Light and Coke Company, and was the direct forerunner of the present London Gas Light and Coke Company. During this period Frederick C. Accum (1769-1838), Dr W. Henry and S. Clegg did so much by their writings and by the improvements they introduced in the manufacture, distribution and burning of coal gas, that their names have become inseparably connected with the subject.

The growth of gas lighting

In 1813 Westminster Bridge, and in the following year the streets of Westminster, were lighted with gas, and in 1816 it became common in London. After this so rapid was the progress of this new mode of illumination that in the course of a few years it was adopted by all the principal towns in the United Kingdom for lighting streets as well as shops and public edifices. In private houses it found its way more slowly, partly from an apprehension of danger attending its use, and partly from the discomfort which was experienced in many cases through the gas being distributed without purification, and to the careless and imperfect manner in which the service pipes were first fitted. It was during the last four decades of the 19th century that the greatest advance was made, this period having been marked not only by many improvements in the manufacture of illuminating gas, but by a complete revolution in the methods of utilizing it for the production of light. In 1875 the London Argand, giving a duty of 3.2 candles illuminating power per cubic foot of ordinary 16 candle gas, was looked upon as the most perfect burner of the day, and little hope was entertained that any burner capable of universal adoption would surpass it in its power of developing light from the combustion of coal gas; but the close of the century found the incandescent mantle and the atmospheric burner yielding six times the light that was given by the Argand for the consumption of an equal volume of gas, and to-day, by supplying gas at an increased pressure, a light of ten times the power may be obtained. Since the advent of the incandescent mantle, the efficiency of which is dependent upon the heating power of the gas more than on its illuminating power, the manufacture of coal gas has undergone considerable modifications.

Coals used for gas-making

Coal, the raw material from which the gas is produced by a process of destructive distillation, varies very widely in composition (see Coal), and it is only the class of coals rich in hydrogen, known as bituminous coal, that can with advantage be utilized in gas manufacture. Coals of this character are obtained in England from the Newcastle and Durham field, South Yorkshire, Derbyshire and Barnsley districts, and an idea of their ultimate composition may be derived from the following table: -

Carbon. Hydrogen Sulphur. Nitrogen Oxygen. Ash. Moisture.
Newcastle gas coal 82.16 4.83 1.00 1.23 6.82 3.20 0.76
Durham gas coal 84.34 5.30 0.73 1.73 4.29 2.42 1.14
South Yorkshire silkstone 80.46 5.09 1.66 1.67 6.79 3.30 1.03
Derbyshire silkstone 76.96 5.04 2.39 1.77 6.92 3.28 3.64
Barnsley gas coal 75.64 4.94 2.84 1.65 7.25 4.28 3.40

Our knowledge of the composition of coal is limited to the total amount of carbon, hydrogen, nitrogen, oxygen and foreign materials which it contains; and at present we know practically but little of the way in which these bodies are combined. This being so, the ordinary analysis of a coal affords but little indication of its value for gas-making purposes, which can only be really satisfactorily arrived at by extended use on a practical scale. Bituminous coal, however, may be looked upon as containing carbon and also simple hydrocarbons, such as some of the higher members of the paraffin series, and likewise organic bodies containing carbon, hydrogen, nitrogen, oxygen and sulphur.

Destructive distillation of coal

On submitting a complex substance of this character to destructive distillation, it will be found that the yield and quality of the products will vary very considerably with the temperature existing in the retorts, with the size of the charge of coal used, with its distribution in the retort, with the length of time the distillation has been going on, and with an infinity of other factors of a more or less complex nature. If bituminous coal is distilled at a low temperature, the tar is found to contain considerable quantities of light paraffin oils; and there is no doubt that paraffin hydrocarbons are present in the original coal. These paraffins, under the influence of heat, split up into simpler members of the same series and into olefines; and if we imagine the action in its simplest form, we should have the gases, as they were evolved, consisting of (say) ethane and ethylene. These have now to pass down the heated retort on their way to the ascension pipe, and the contact with the heated sides of the retort, and the baking from the radiant heat in the retort, set up an infinity of changes. Ethane, when heated to this degree, splits up into ethylene and hydrogen, whilst ethylene decomposes to methane and acetylene, and the acetylene at once polymerizes to benzene, styrolene, retene, etc. A portion also condenses, and at the same time loses some hydrogen, becoming naphthalene; and the compounds so formed by interactions amongst themselves build up the remainder of the hydrocarbons present in the coal tar, whilst the organic substances containing oxygen in the coal break down, and cause the formation of the phenols in the tar.

There is very little doubt that the general course of the decompositions follows these lines; but any such simple explanation of the actions taking place is rendered impossible by the fact that, instead of the breaking-down of the hydrocarbons being completed in the coal, and only secondary reactions taking place in the retort, in practice the hydrocarbons to a great extent leave the coal as the vapours of condensible hydrocarbons, and the breaking down of these to such simple gaseous compounds as ethylene is proceeding in the retort at the same time as the breaking up of the ethylene already formed into acetylene and methane, and the polymerization of the former into higher compounds. Starting with a solid hydrocarbon of definite composition, it would be theoretically possible to decompose it entirely into carbon, hydrogen, ethylene and methane, and, by rapidly removing these from the heating zone before any secondary actions took place, to prevent formation of tar. But any such ideal is hopeless in practice, as the coal is not a definite compound, and it is impossible to subject it to a fixed temperature.

Effect of temperature in the retort

If the retorts are at a temperature of 1000° C. when the charge of coal is put in, the temperature of the distillation will vary from about 800° C. close to the walls, to about 400° C. in the centre of the coal; and in the same way, in the space above the coal, the products which come in contact with the sides of the retort are heated to 1000° C., whilst the gas near the coal is probably heated to only 600° C. Moreover, the gases and vapours in the retort are subjected to a period of heating which varies widely with the distance from the mouth of the retort of the coal that is undergoing carbonization. The gas developed by the coal near the mouth of the retort is quickly washed out into the ascension pipe by the push of the gas behind, and the period for which it has been exposed to the radiant heat from the walls of the retort is practically nil; whilst the gas evolved in the portion of the retort farthest from the mouthpiece has only its own rate of evolution to drive it forward, and has to traverse the longest run possible in the retort, exposed during the whole of that period to radiant heat and to contact with the highly heated surface of the retort itself. Hence we find that the tar is formed of two distinct sets of products, the first due to incomplete decomposition and the second to secondary reactions due to the products of the decomposition being kept too long in the zone of heat.

Of the first class, the light paraffin oils and pitch may be taken as examples; whilst benzene, naphthalene and retort carbon represent the second. The formation of the second class of bodies is a great loss to the gas manufacturer, as, with the exception of the trace of benzene carried with the gas as vapour, these products are not only useless in the gas, but one of them, naphthalene, is a serious trouble, because any trace carried forward by the gas condenses with sudden changes of temperature, and causes obstructions in the service pipes, whilst their presence in the tar means the loss of a very large proportion of the illuminating constituents of the gas. Moreover, these secondary products cannot be successfully reduced, by further heating, to simpler hydrocarbons of any high illuminating value, and such bodies as naphthalene and anthracene have so great a stability that, when once formed, they resist any efforts again to decompose them by heat, short of the temperature which breaks them up into methane, carbon and hydrogen.

The ammonia is derived from the nitrogen present in the coal combining with hydrogen during destructive distillation, the nitrogen becoming distributed amongst all three classes of products. The following table will give an approximate idea of the proportions which go to each: -

Per cent.
Nitrogen as ammonia 14.50
Nitrogen as cyanogen 1.56
Nitrogen free in gas and combined in tar 35.26
Nitrogen remaining in coke 48.68
- - -
100.00

The effect produced by alteration in the temperature of the retort upon the composition of both gas and tar is very marked. As the temperature is raised, the yield of gas from a given weight of coal increases; but with the increase of volume there is a marked decrease in the illuminating value of the gas evolved. Lewis T. Wright found, in a series of experiments, that, when four portions of the same coal were distilled at temperatures ranging from a dull red heat to the highest temperature attainable in an iron retort, he obtained the following results as to yield and illuminating power: -

Temperature. Cubic ft. of
Gas per ton. Illuminating
Power,
Candles. Total
Candles
per ton.
1. Dull red 8,250 20.5 33.950
2. Hotter 9,693 17.8 34.510
3. " 10,821 16.7 36.140
4. Bright orange 12,006 15.6 37.460

Composition of the Gas.

1.
Per cent. 2.
Per cent. 4.
Per cent.
Hydrogen 38.09 43.77 48.02
Marsh gas 42.72 34.50 30.70
Olefines 7.55 5.83 4.51
Carbon monoxide 8.72 12.50 13.96
Nitrogen 2.92 3.40 2.81
100.00 100.00 100.00

The gas analysis of No. 3 was lost, but the illuminating power shows that it was intermediate in composition between Nos. 2 and 4. From this it will be seen that, with the increase of temperature, the hydrocarbons - the olefines and marsh gas series - gradually break up, depositing carbon in the crown of the retort, and liberating hydrogen, the percentage of which steadily increases with the rise of temperature.

The tar formed is affected to an even greater extent than the gas by alterations in the temperature at which the destructive distillation takes place. The lower the temperature, the smaller will be the volume of gas produced, and the lighter the specific gravity of the tar, whilst with increase of temperature, the volume of gas rapidly rises, and so does the specific gravity of the tar. Working with a caking coal Wright obtained the following results: -

Yield of Gas
per ton,
Cub. ft. Specific Gravity
of Tar.
6,600 1.086
7,200 1.120
8,900 1.140
10,162 1.154
11,700 1.206

Analysis of the tar showed that the increase of the specific gravity was due to the increase in the quantity of pitch, which rose from 28.89 to 64.08% in the residuals; whilst the ammonia, naphtha and light oils steadily fell in quantity, the creosote and anthracene oils doing the same, but to a smaller extent. Naphthalene also begins to show in quantity in the tar as soon as the yield of gas reaches 10,000 cub. ft. per ton of coal carbonized.

In spite of these variations, however, the products in their main characteristics will remain the same. They may be divided into - (a) Solids, such as the coke and retort carbon; (b) liquids, consisting of the tar and ammoniacal liquor; and (c) gases, consisting of the unpurified coal gas. The proportions in which the products are approximately obtained from a ton of gas coal have been given as follows: -

10,000 cub. ft. of gas = 380 lb = 17.0 per cent.
10 gallons of tar = 115 " = 5.1 "
Gas liquor [1] = 177 " = 7.9 "
Coke = 1568 " = 70.0 "
- - - -
2240 100.0

Solid products

The chief solid residue, coke, is not absolutely pure carbon, as it contains the mineral non-volatile constituents which remain behind as ash when the original coal is burnt, and which, to a great extent, existed in the sap that filled the cells of the plant from which the coal was formed. The retort carbon formed as a dense deposit on the crown of the retort by the action of the high temperature on the hydrocarbons is, however, carbon in a very pure form, and, on account of its density, is largely used for electrical purposes.

Liquid products

The liquid products of the destructive distillation of coal are tar and ammoniacal liquor. Tar derived from ordinary bituminous coal is a black, somewhat viscid liquid, varying in specific gravity from 1.1 to 1.2. The ultimate composition of tar made in the London Gas Works is approximately as follows: -

Carbon 77.53
Hydrogen 6.33
Nitrogen 1.03
Sulphur 0.61
Oxygen 14.50
- - -
100.00

These elements in tar are built up into an enormous number of compounds (see Coal Tar), and its value as a by-product may be gathered from the fact that on fractional distillation it yields - (1) benzene and its homologues, from which aniline, the source of most of the coal-tar colours, can be derived; (2) carbolic acid, from which picric acid, used as a dye, a powerful explosive, and to give the bitter flavour to some kinds of beer, is made, also many most valuable disinfectants; (3) naphthalene, used for disinfecting, and also as the "Albo-carbon" employed in an enriching burner for gas; (4) pitch, extensively used in path-making, from which such bodies as anthracene and saccharin can be extracted.

The second liquid product of the destructive distillation of coal is the ammoniacal or gas liquor, which consists of water containing ammonia salts in solution, partly condensed from the hot gas, and partly added to wash the gas in the scrubbers. It contains, as its principal constituents, ammonia, partly combined with carbonic acid and sulphuretted hydrogen to form compounds which are decomposed on boiling, with evolution of ammonia gas, and partly combined with stronger acids to form compounds which require to be acted upon by a strong alkali before the ammonia contained in them can be liberated. The ammonia in the first class of compounds is technically spoken of as "free"; that present in the latter as "fixed." The following analysis by L.T. Wright will give an idea of the relative quantities in which these compounds exist in the liquor: -

Grammes per litre.
Free Ammonium sulphide 3.03
Ammonium carbonate 39.16
Ammonium chloride 14.23
Fixed Ammonium thiocyanate 1.80
Ammonium sulphate 0.19
Ammonium thiosulphate 2.80
Ammonium ferrocyanide 0.41

From a scientific point of view, the term "free" is absolutely incorrect, and in using it the fact must be clearly borne in mind that in this case it merely stands for ammonia, which can be liberated on simply boiling the liquor.

Gaseous products

The gas which is obtained by the destructive distillation of coal, and which we employ as our chief illuminant, is not a definite compound, but a mechanical mixture of several gases, some of which are reduced to the lowest limit, in order to develop as fully as possible the light-giving properties of the most important constituents of the gas. The following analysis gives a fair idea of the composition of an average sample of gas made from coal, purified but without enrichment: -

Hydrogen 52.22
Unsaturated hydrocarbons 3.47
Saturated hydrocarbons 34.76
Carbon monoxide 4.23
Carbon dioxide 0.60
Nitrogen 4.23
Oxygen 0.49
- - -
100.00

These constituents may be divided into - (a) light-yielding hydrocarbons, (b) combustible diluents and (c) impurities. The hydrocarbons, upon which the luminosity of the flame entirely depends, are divided in the analysis into two groups, saturated and unsaturated, according to their behaviour with a solution of bromine in potassium bromide, which has the power of absorbing those termed "unsaturated," but does not affect in diffused daylight the gaseous members of the "saturated" series of hydrocarbons. They may be separated in a similar way by concentrated sulphuric acid, which has the same absorbent effect on the one class, and not on the other. The chief unsaturated hydrocarbons present in coal gas are: ethylene, C2H4, butylene, C4H8, acetylene, C2H2, benzene, C6H6, and naphthalene, C10H8, and the saturated hydrocarbons consist chiefly of methane, CH4, and ethane, C2H6.

The light-giving power of coal gas is undoubtedly entirely due to the hydrocarbons. The idea held up to about 1890 was that the illuminating value depended upon the amount of ethylene present. This, however, is manifestly incorrect, as, if it were true, 4% of ethylene mixed with 96% of a combustible diluent such as hydrogen should give 16- to 17-candle gas, whereas a mixture of 10% of ethylene and 90% of hydrogen is devoid of luminosity. In 1876 M.P.E. Berthelot came to the conclusion that the illuminating value of the Paris coal gas was almost entirely due to benzene vapour. But here again another mistaken idea arose, owing to a faulty method of estimating the benzene, and there is no doubt that methane is one of the most important of the hydrocarbons present, when the gas is burnt in such a way as to evolve from it the proper illuminating power, whilst the benzene vapour, small as the quantity is, comes next in importance and the ethylene last. It is the combined action of the hydrocarbons which gives the effect, not any one of them acting alone.

The series of operations connected with the manufacture and distribution of coal gas embraces the processes of distillation, condensation, exhaustion, wet purification by washing and scrubbing, dry purification, measuring, storing and distribution to the mains whence the consumer's supply is drawn.

River.
Fig. 4. - Plan of Works.

Site of gas works

The choice of a site for a gas works is necessarily governed by local circumstances; but it is a necessity that there should be a ready means of transport available, and for this reason the works should be built upon the banks of a navigable river or canal, and should have a convenient railway siding. By this means coal may be delivered direct to the store or retort-house, and in the same way residual products may be removed. The fact that considerable area is required and that the works do not improve the neighbourhood are important conditions, and although economy of space should be considered, arrangements should be such as to allow of extension. In the case of a works whose daily make of gas exceeds four to five million cub. ft., it is usual to divide the works into units, there being an efficiency limit to the size of apparatus employed. Under these conditions the gas is dealt with in separate streams, which mix when the holder is reached. From the accompanying ground plan of a works (fig. 4) it will be possible to gain an idea of the order in which the operations in gas manufacture are carried out and the arrangement of the plant.

Fig. 5. - Cross Section of Retorts.

Retorts

The retorts in which the coal is carbonized are almost universally made of fire-clay, and in all but small country works the old single-ended retort, which was about 9 ft. in length, has given way to a more economical construction known as doubles, double-ended, or "through" retorts. These are from 18 to 22 ft. long, and as it is found inconvenient to produce this length in one piece, they are manufactured in three sections, the jointing together of which demands great care. The two outer pieces are swelled at one end to take an iron mouthpiece. The cross sections generally employed for retorts are known as "D-shaped," "oval" and "round" (fig. 5). The "D" form is mostly adopted owing to its power of retaining its shape after long exposure to heat, and the large amount of heating surface it presents at its base. The life of this retort is about thirty working months. A cast iron mouthpiece and lid is bolted to the exterior end of each retort, the mouthpiece carrying a socket end to receive the ascension pipe, through which the gas passes on leaving the retort. The retorts are heated externally and are set in an arch, the construction depending upon the number of retorts, which varies from three to twelve. The arch and its retorts is termed a bed or setting, and a row of beds constitutes a bench. It is usual to have a separate furnace for each setting, the retorts resting upon walls built transversely in the furnace.

The heating of the retorts is carried out either by the "direct firing" or by the "regenerative" system, the latter affording marked advantages over the former method, which is now becoming extinct. In the regenerative system of firing, a mixture of carbon monoxide and nitrogen is produced by passing air through incandescent gas coke in a generator placed below the bench of retorts, and the heating value of the gases so produced is increased in most cases by the admixture of a small proportion of steam with the primary air supply, the steam being decomposed by contact with the red-hot coke in the generator into water gas, a mixture of carbon monoxide and hydrogen (see Fuel: Gaseous). The gases so formed vary in proportion with the temperature of the generator and the amount of steam, but generally contain 32 to 38% of combustible gas, the remainder being the residual nitrogen of the air and carbon dioxide. These gases enter the combustion chamber around the retorts at a high temperature, and are there supplied with sufficient air to complete their combustion, this secondary air supply being heated by the hot products of combustion on their way to the exit flue. This method of firing results in the saving of about one-third the weight of coke used in the old form of furnace per ton of coal carbonized, and enables higher temperatures to be obtained, the heat being also more equally distributed.

Fig. 6. - Regenerative Setting.

There are a great number of methods of applying the regenerative principle which vary only in detail. Fig. 6 gives an idea of the general arrangement. The furnace A is built of fire-brick, coke is charged at the top through the iron door B, and near the bottom are placed fire bars C, upon which the fuel lies. The primary air necessary for the partial combustion of the coke to "producer" gas enters between these bars. The gases are conducted from the furnace to the combustion chamber E through the nostrils D D, and the secondary air is admitted at the inlet F a little above, this air having been already heated by traversing the setting. Complete combustion takes place at this point with the production of intense heat, the gases on rising are baffled in order to circulate them in every direction round the retorts, and upon arriving at the top of the setting they are conducted down a hollow chamber communicating with the main flue and shaft. The amount of draft which is necessary to carry out the circulation of the gases and to draw in the adequate amount of air is regulated by dampers placed in the main flue. By analysis of the "producer" and "spent" gases this amount can be readily gauged.

Retorts are set in either the horizontal, inclined or vertical position, and the advantages of the one over the other is a question upon which almost every gas engineer has his own views.

Charging and drawing

The introduction of labour-saving appliances into gas works has rendered the difficult work of charging and discharging horizontal retorts comparatively simple. Formerly it was the practice to carry out such operations entirely by hand, men charging the retorts either by means of shovel or hand-scoop, and the coke produced being withdrawn with hand rakes. Now, however, only the smaller gas works adhere to this system, and this work is done by machinery driven by either compressed air, hydraulic or electric power. In the first two cases a scoop, filled with coal from an overhead hopper carried by the travelling machine, is made to enter the retort and is turned over; the operation is then repeated, but this time the scoop is turned over in the opposite direction, the coal thus assuming such a position that as much of its under surface as possible is exposed to the heated side of the retort. With "through" retorts charging machines feed the retorts at both ends, the scoop, which has a capacity of about 1 cwt., entering and discharging its contents twice at each end, so that the total charge is about 6 cwt., which is allowed from four to six hours to distil off according to the quality of the gas required. The machines charge simultaneously at each end, so that the lids of the retorts may be shut immediately the coal enters. The charging machines travel on lines in front of the retort bench, and the power is transmitted by connexions made with flexible hose. A device of more recent introduction is an electrically-driven charging machine, in which the centrifugal force created by a fly-wheel revolving at high speed is applied to drive coal into the retort. If the velocity is sufficiently high the coal may be carried the whole length of a 20-ft. retort, the coal following banking up until an even layer is formed throughout the length of the retort.

For the purpose of discharging the coke from the retort either compressed air or hydraulic machinery is employed, a rake being made to enter the retort and withdraw the coke on returning. With this method it is necessary that the rake should enter and discharge several times before the retort is clear, and thus the use of a telescopic ram worked by hydraulic power, which pushes the coke before it and discharges it at the other end, is an advantage. As much as one-third on each ton of coal carbonized is saved by the use of machinery in the retort-house. Taking into account the original cost of such machines, and the unavoidable wear and tear upon the retorts brought about by using labour-saving appliances, and the fact that the coke-dust is very detrimental to the machinery, it is clear that the suggestion of setting the retorts at an incline in order to facilitate the work presented great inducements to the gas manager. The object aimed at in thus setting retorts is to allow gravity to play the part of charging and discharging the coal and coke, the retorts being inclined at an angle to suit the slip of the class of coal used; this angle is between 28° and 34°. The coal, previously elevated to hoppers, is dropped into the feeding chambers, which are so arranged that they can travel from end to end of the retort-house and feed the coal into the retorts. When the retort is to be charged, an iron stop or barrier is placed in the lower mouthpiece, and the door closed. The shoot is placed in the upper mouthpiece, and the stop or door, which retains the coal in the chamber, is released; the coal is then discharged into the retort, and rushing down the incline, is arrested by the barrier, and banks up, forming a continuous backing to the coal following. By experience with the class of coal used and the adjustment of the stops in the shoot, the charge can be run into the retort to form an even layer of any desired depth. For the withdrawal of the residual coke at the end of the carbonization, the lower mouthpiece door is opened, the barrier removed and the coke in the lower part of the retort is "tickled" or gently stirred with an iron rod to overcome a slight adhesion to the retort; the entire mass then readily discharges itself. Guides are placed in front of the retort to direct its course to the coke hoppers or conveyer below, and to prevent scattering of the hot material. This system shows a greater economy in the cost of carbonizing the coal, but the large outlay and the wear and tear of the mechanical appliances involved have so far prevented its very general adoption.

The vertical retort was one of the first forms experimented with by Murdoch, but owing to the difficulty of withdrawing the coke, the low illuminating power of the gas made in it, and the damage to the retort itself, due to the swelling of the charge during distillation, it was quickly abandoned. About the beginning of the 20th century, however, the experiments of Messrs Settle and Padfield at Exeter, Messrs Woodall and Duckham at Bournemouth, and Dr Bueb in Germany showed such encouraging results that the idea of the vertical retort again came to the front, and several systems were proposed and tried. The cause of the failure of Murdoch's original vertical retort was undoubtedly that it was completely filled with coal during charging, with the result that the gas liberated from the lower portions of the retort had to pass through a deep bed of red-hot coke, which, by over-baking the gas, destroyed the illuminating hydrocarbons. There is no doubt that the question of rapidly removing the gas, as soon as it is properly formed, from the influence of the highly-heated walls of the retort and residual coke, is one of the most important in gas manufacture.

In the case of horizontal retorts the space between the top of the coal and the retort is of necessity considerable in order to permit the introduction of the scoop and rake; the gas has therefore a free channel to travel along, but has too much contact with the highly heated surface of the retort before it leaves the mouthpiece. In the case of inclined retorts this disadvantage is somewhat reduced, but with vertical retorts the ideal conditions can be more nearly approached. The heating as well as the illuminating value of the gas per unit volume is lowered by over-baking, and Dr Bueb gives the following figures as to the heating value of gas obtained from the same coal but by different methods of carbonization: -

Vertical Retorts, 604 British thermal units per cub. ft.
Inclined Retorts, 584 British thermal units per cub. ft.
Horizontal Retorts, 570 British thermal units per cub. ft.

Of the existing forms of vertical retort it remains a matter to be decided whether the coal should be charged in bulk to the retort or whether it should be introduced in small quantities at regular and short intervals; by this latter means (the characteristic feature of the Settle-Padfield process) a continuous layer of coal is in process of carbonization on the top, whilst the gas escapes without contact with the mass of red-hot coke, a considerable increase in volume and value in the gas and a much denser coke being the result.

Fig. 7. - Hydraulic Main.

Hydraulic main

From the retort the gas passes by the ascension pipe to the hydraulic main (fig. 7). This is a long reservoir placed in a horizontal position and supported by columns upon the top of the retort stack, and through it is maintained a slow but constant flow of water, the level of which is kept uniform. The ascension pipe dips about 2 in. into the liquid, and so makes a seal that allows of any retort being charged singly without the risk of the gas produced from the other retorts in the bench escaping through the open retort. Coal gas, being a mixture of gases and vapours of liquids having very varying boiling points, must necessarily undergo physical changes when the temperature is lowered. Vapours of liquids of high boiling point will be condensed more quickly than those having lower boiling points, but condensation of each vapour will take place in a definite ratio with the decrease of temperature, the rate being dependent upon the boiling point of the liquid from which it is formed. The result is that from the time the gaseous mixture leaves the retort it begins to deposit condensation products owing to the decrease in temperature. Condensation takes place in the ascension pipe, in the arch piece leading to the hydraulic main, and to a still greater extent in the hydraulic main itself where the gas has to pass through water.

Ascension pipes give trouble unless they are frequently cleared by an instrument called an "auger," whilst the arch pipe is fitted with hand holes through which it may be easily cleared in case of stoppage. The most soluble of the constituents of crude coal gas is ammonia, 780 volumes of which are soluble in one volume of water at normal temperature and pressure, and the water in the hydraulic main absorbs a considerable quantity of this compound from the gas and helps to form the ammoniacal liquor, whilst, although the liquor is well agitated by the gas bubbling through it, a partial separation of tar from liquor is effected by gravitation. The liquor is run off at a constant rate from the hydraulic main to the store tank, and the gas passes from the top of the hydraulic main to the foul main.

Condensation

The gas as it leaves the hydraulic main is still at a temperature of from 130° to 150° F., and should now be reduced as nearly as possible to the temperature of the surrounding atmosphere. The operation of efficient condensing is not by any means as simple as might be supposed. The tar and liquor when condensed have a dissolving action on various valuable light-giving constituents of the gas, which in the ordinary way would not be deposited by the lowering of temperature, and for this reason the heavy tar, and especially that produced in the hydraulic main, should come in contact with the gas as little as possible, and condensation should take place slowly.

The main difficulty which the condenser ought to overcome and upon which its efficiency should depend is the removal of naphthalene: this compound, which is present in the gas, condenses on cooling to a solid which crystallizes out in the form of white flakes, and the trouble caused by pipe stoppages in the works as well as in the district supplied is very considerable. The higher the heat of carbonization the more naphthalene appears to be produced, and gas managers of to-day find the removal of naphthalene from the gas a difficult problem to solve. It was for some time debated as to whether naphthalene added materially to the illuminating value of the gas, and whether an endeavour should be made to carry it to the point of combustion; but it is now acknowledged that it is a troublesome impurity, and that the sooner it is extracted the better. Gas leaves the retorts saturated with naphthalene, and its capacity for holding that impurity seems to be augmented by the presence of water vapour. The condenser, by effecting the condensation of water vapour, also brings about the deposition of solid naphthalene, apart from that which naturally condenses owing to reduction of temperature.

Condensers are either air-cooled or water-cooled, or both. In the former case the gas traverses pipes exposed to the atmosphere and so placed that the resulting products of condensation may be collected at the lowest point. Water is a more efficient cooling medium than air, owing to its high specific heat, and the degree of cooling may be more easily regulated by its use. In water-cooled condensers it is usual to arrange that the water passes through a large number of small pipes contained in a larger one through which the gas flows, and as it constantly happened that condenser pipes became choked by naphthalene, the so-called reversible condenser, in which the stream of gas may be altered from time to time and the walls of the pipes cleaned by pumping tar over them, is a decided advance.

The solubility of naphthalene by various oils has led some engineers to put in naphthalene washers, in which gas is brought into contact with a heavy tar oil or certain fractions distilled from it, the latter being previously mixed with some volatile hydrocarbon to replace in the gas those illuminating vapours which the oil dissolves out; and by fractional distillation of the washing oil the naphthalene and volatile hydrocarbons are afterwards recovered.

Exhauster

The exhauster is practically a rotary gas pump which serves the purpose of drawing the gas from the hydraulic main through the condensers, and then forcing it through the purifying vessels to the holder. Moreover, by putting the retorts under a slight vacuum, the amount of gas produced is increased by about 12%, and is of better quality, owing to its leaving the heated retort more quickly. A horizontal compound steam-engine is usually employed to drive the exhauster.

At this point in the manufacturing process the gas has already undergone some important changes in its composition, but there yet remain impurities which must be removed, these being ammonia, sulphuretted hydrogen, carbon disulphide and carbon dioxide. Ammonia is of considerable marketable value, and even in places where the local Gas Act does not prescribe that it shall be removed, it is extracted. Sulphuretted hydrogen is a noxious impurity, and its complete removal from the gas is usually imposed by parliament. As nearly as possible all the carbon dioxide is extracted, but most gas companies are now exempt from having to purify the gas from sulphur compounds other than sulphuretted hydrogen. Cyanogen compounds also are present in the gas, and in large works, where the total quantity is sufficient, their extraction is effected for the production of either prussiate or cyanide of soda.

Atkinson Butterfield gives the composition of the gas at this point to be about

per cent. by vol.
Hydrogen from 42 to 53
Methane " 32 " 39
Carbon monoxide " 3 " 10
Hydrocarbons -
Gases " 2.5 " 4.5
Light condensable vapours " 0.5 " 1.2
Carbon dioxide " 1.1 " 1.8
Nitrogen " 1.0 " 5.0
Sulphuretted hydrogen " 1.0 " 2.0
Ammonia " 0.5 " 0.95
Cyanogen " 0.05 " 0.12
Carbon disulphide " 0.02 " 0.035
Naphthalene " 0.005 " 0.015

Washers

It happens that ammonia, being a strong base, will effect the extraction of a certain proportion of such compounds as sulphuretted hydrogen, carbon dioxide and hydrocyanic acid, and the gas is now washed with water and ammoniacal liquor. The process is termed washing or scrubbing, and is carried out in various forms of apparatus, the efficiency of which is dependent upon the amount of contact the apparatus allows between the finely divided gas and water in a unit area and the facility with which it may be cleared out. The "Livesey" washer, a well-known type, is a rectangular cast iron vessel. The gas enters in the centre, and to make its escape again it has to pass into long wrought iron inverted troughs through perforations one-twentieth of an inch in diameter. A constant flow of liquor is regulated through the washer, and the gas, in order to pass through the perforations, drives the liquor up into the troughs. The liquor foams up owing to agitation by the finely divided streams of gas, and is brought into close contact with it. Two or three of these washers are connected in series according to the quantity of gas to be dealt with.

Scrubbers

The final washing for ammonia is effected in an apparatus termed a "scrubber," which is a cylindrical tower packed with boards  in. thick by 11 in. broad, placed on end and close together; water is caused to flow down over the surface of these boards, the object being to break up the gas as much as possible and bring it into close contact with the water. In this wet purifying apparatus the gas is almost wholly freed from ammonia and from part of the sulphuretted hydrogen, whilst carbon dioxide and carbon disulphide are also partially extracted.

Fig. 8. - Purifier.

Purifiers

The final purification is carried out in rectangular vessels, known as "dry purifiers" (fig. 8). Internally, each purifier is filled with ranges of wooden trays or sieves A, made in the form of grids (fig. 9), and covered with the purifying material B to a depth of about 6 in., the number of tiers and size of purifier boxes being proportional to the quantity of gas to be purified. The gas enters at the bottom by the pipe C, the inlet being protected from any falling material by the cover D; it forces its way upwards through all the trays until, reaching the lid or cover E, it descends by the exit tube F, which leads to the next purifier. The edges of the lid dip into an external water seal or lute G, whereby the gas is prevented from escaping.

Fig. 9. - Purifier Grid.

When the gas had to be purified from carbon disulphide as well as from sulphuretted hydrogen, slaked lime was employed for the removal of carbon dioxide and the greater quantity of the sulphur compounds, whilst a catch box or purifier of oxide of iron served to remove the last traces of sulphuretted hydrogen. Not fewer than four lime purifiers were employed, and as the one which was first in the series became exhausted, i.e. began to show signs of allowing carbon dioxide to pass through it unabsorbed, it was filled with fresh slaked lime and made the last of the series, the one which was second becoming first, and this procedure went on continuously. This operation was necessitated by the fact that carbon dioxide has the power of breaking up the sulphur compounds formed by the lime, so that until all carbon dioxide is absorbed with the formation of calcium carbonate, the withdrawal of sulphuretted hydrogen cannot proceed, whilst since it is calcium sulphide formed by the absorption of sulphuretted hydrogen by the slaked lime that absorbs the vapour of carbon disulphide, purification from the latter can only be accomplished after the necessary calcium sulphide has been formed. The foul gas leaving the scrubbers contains, as a general average, 30 grains of sulphuretted hydrogen, 40 grains of carbon disulphide and 200 grains of carbon dioxide per 100 cub. ft. On entering the first purifier, which contains calcium thiocarbonate and other combinations of calcium and sulphur in small quantity, the sulphuretted hydrogen and disulphide vapour have practically no action upon the material, but the carbon dioxide immediately attacks the calcium thiocarbonate, forming calcium carbonate with the production of carbon disulphide vapour, which is carried over with the gas into the second box. In the connexion between the first and the second box the gas is found to contain 500 grains of sulphuretted hydrogen and 80 grains of carbon disulphide per 100 cub. ft., but no trace of carbon dioxide. In the second box the formation of calcium thiocarbonate takes place by the action of carbon disulphide upon the calcium sulphide with the liberation of sulphuretted hydrogen, which is carried over to the third purifier. The gas in the connecting pipe between the second and third purifier will be found to contain 400 grains of sulphuretted hydrogen and 20 grains of carbon disulphide. The contents of the third box, being mostly composed of slaked lime, take up sulphuretted hydrogen forming calcium sulphide, and practically remove the remaining impurities, the outlet gas showing 20 grains of sulphuretted hydrogen and 8 grains of carbon disulphide per 100 cub. ft., whilst the catch box of oxide of iron then removes all traces of sulphuretted hydrogen. It will be noticed that in the earlier stages the quantity of sulphur impurities is actually increased between the purifiers - in fact, the greater amount of sulphiding procures the ready removal of the carbon disulphide, - but it is the carbon dioxide in the gas that is the disturbing element, inasmuch as it decomposes the combinations of sulphur and calcium; consequently it is a paramount object in this system to prevent this latter impurity finding its way through the first box of the series. The finding of any traces of carbon dioxide in the gas between the first two boxes is generally the signal for a new clean purifier being put into action, and the first one shut off, emptied and recharged with fresh lime, the impregnated material being sometimes sold for dressing certain soils.

The action of oxide of iron, which has now partly replaced the lime purification, depends on its power of combining with sulphuretted hydrogen to form sulphide of iron. Such is the affinity of the oxide for this impurity that it may contain from 50 to 60% by weight of free sulphur after revivification and still remain active. Upon removing the material from the vessel and exposing it to the atmosphere the sulphide of iron undergoes a revivifying process, the oxygen of the air displacing the sulphur from the sulphide as free sulphur, and with moisture converting the iron into hydrated oxide of iron. This revivification can be carried on a number of times until the material when dry contains about 50% of free sulphur and even occasionally 60% and over; it is then sold to manufacturers of sulphuric acid to be used in the sulphur kilns instead of pyrites (see Sulphuric Acid).

Apart from the by-products coke, coke-breeze, tar and retort carbon, which are sold direct, gas companies are now in many cases preparing from their spent purifying material pure chemical products which are in great demand. The most important of these is sulphate of ammonia, which is used for agricultural purposes as a manure, and is obtained by passing ammonia into sulphuric acid and crystallizing out the ammonium sulphate produced. To do this, saturated ammoniacal liquor is decomposed by lime in the presence of steam, and the freed ammonia is passed into strong sulphuric acid, the saturated solution of ammonium sulphate being carefully crystallized. The market value of the salt varies, but an average figure is £12 per ton, whilst the average yield is about 24 lb of salt per ton of coal carbonized. In large works the sulphuric acid is usually manufactured on the spot from the spent oxide, so that the sulphuretted hydrogen, which in the gas is considered an undesirable impurity, plays a valuable part in the manufacture of an important by-product.

Cyanogen compounds are extracted either direct from the gas, from the spent oxide or from ammoniacal liquor, and some large gas works now produce sodium cyanide, this being one of the latest developments in the gas chemical industry.

Fig. 10. - Gasholder.

Fig. 11. - Cup and Grip.

The purified gas now passes to a gasholder (sometimes known as a gasometer), which may be either single lift, i.e. a simple bell inverted in a tank of water, or may be constructed on the telescopic principle, in which case much ground space is saved, as a holder of much greater capacity can be contained in the same-sized tank. The tank for the gasholder is usually made by excavating a circular reservoir somewhat larger in diameter than the proposed holder. A banking is allowed to remain in the centre, as shown in fig. 10, which is known as the "dumpling," this arrangement not only saving work and water, but acting as a support for the king post of a trussed holder when the holder is empty. The tank must be water-tight, and the precaution necessary to be taken in order to ensure this is dependent upon the nature of the soil; it is usual, however, for the tanks to be lined with concrete. Where the conditions of soil are very bad, steel tanks are built above ground, but the cost of these is much greater. The holder is made of sheet iron riveted together, the thickness depending upon the size of the holder. The telescopic form consists of two or more lifts which slide in one another, and may be described as a single lift holder encircled by other cylinders of slightly larger diameter, but of about the same length. Fig. 10 shows the general construction. Gas on entering at A causes the top lift to rise; the bottom of this lift being turned up all round to form a cup, whilst the top of the next lift is turned down to form a so-called grip, the two interlock (see fig. 11), forming what is known as the hydraulic cup. Under these conditions the cup will necessarily be filled with water, and a seal will be formed, preventing the escape of gas. A guide framing is built round the holder, and guide rollers are fixed at various intervals round the grips of each lift, whilst at the bottom of the cup guide rollers are also fixed (fig. 11). In the year 1892 the largest existing gasholder was built at the East Greenwich works of the South Metropolitan Gas Company; it has six lifts, its diameter is 293 ft., and when filled with gas stands 180 ft. high. The capacity for gas is 12 million cub. ft.

Governor

The governor consists usually of a bell floating in a cast iron tank partially filled with water, and is in fact a small gasholder, from the centre of which is suspended a conical valve controlling the gas inlet and closing it as the bell fills. Any deviation in pressure will cause the floating bell to be lifted or lowered, and the size of the inlet will be decreased or increased, thus regulating the flow.

Enrichment

The fact that coal gas of an illuminating power of from 14 to 16 candles can be made from the ordinary gas coal at a fairly low rate, while every candle power added to the gas increases the cost in an enormous and rapidly growing ratio, has, from the earliest days of the gas industry, caused the attention of inventors to be turned to the enrichment of coal gas. Formerly cannel coal was used for producing a very rich gas which could be mixed with the ordinary gas, thereby enriching it, but as the supply became limited and the price prohibitive, other methods were from time to time advocated to replace its use in the enrichment of illuminating gas. These may be classified as follows: -

1. Enriching the gas by vapours and permanent gases obtained by decomposing the tar formed at the same time as the gas.

2. Mixing with the coal gas oil gas, obtained by decomposing crude oils by heat.

3. The carburetting of low-power gas by impregnating it with the vapours of volatile hydrocarbons.

4. Mixing the coal gas with water gas, which has been highly carburetted by passing it with the vapours of various hydrocarbons through superheaters in order to give permanency to the hydrocarbon gases.

Enrichment by tar

Very many attempts have been made to utilize tar for the production and enrichment of gas, and to do this two methods may be adopted: -

(a) Condensing the tar in the ordinary way, and afterwards using the whole or portions of it for cracking into a permanent gas.

(b) Cracking the tar vapours before condensation by passing the gas and vapours through superheaters.

If the first method be adopted, the trouble which presents itself is that the tar contains a high percentage of pitch, which tends rapidly to choke and clog up all the pipes. A partly successful attempt to make use of certain portions of the liquid products of distillation of coal before condensation by the second method was the Dinsmore process, in which the coal gas and vapours which, if allowed to cool, would form tar, were made to pass through a heated chamber, and a certain proportion of otherwise condensible hydrocarbons was thus converted into permanent gases. Even with a poor class of coal it was claimed that 9800 cub. ft. of 20- to 21-candle gas could be made by this process, whereas by the ordinary process 9000 cub. ft. of 15-candle gas would have been produced. This process, although strongly advocated by the gas engineer who experimented with it, was never a commercial success. The final solution of the question of enrichment of gas by hydrocarbons derived from tar may be arrived at by a process which prevents the formation of part of the tar during the carbonization of the coal, or by the process devised by C.B. Tully and now in use at Truro, in which tar is injected into the incandescent fuel in a water-gas generator and enriches the water gas with methane and other hydrocarbons, the resulting pitch and carbon being filtered off by the column of coke through which the gas passes.

Enrichment by oil gas

The earliest attempts at enrichment by oil gas consisted in spraying oil upon the red hot mass in the retort during carbonization; but experience soon showed that this was not an economical method of working, and that it was far better to decompose the liquid hydrocarbon in the presence of the diluents which are to mingle with it and act as its carrier, since, if this were done, a higher temperature could be employed and more of the heavier portions of the oil converted into gas, without at the same time breaking down the gaseous hydrocarbons too much. In carburetting poor coal gas with hydrocarbons from mineral oil it must be borne in mind that, as coal is undergoing distillation, a rich gas is given off in the earlier stages, but towards the end of the operation the gas is very poor in illuminants, the methane disappearing with the other hydrocarbons, and the increase in hydrogen being very marked. Lewis T. Wright employed a coal requiring six hours for its distillation, and took samples of the gas at different periods of the time. On analysis these yielded the following results: -

Time after beginning Distillation.

10
minutes. 1 hour
30 minutes. 3 hours
25 minutes. 5 hours
35 minutes.
Sulphuretted hydrogen 1.30 1.42 0.49 0.11
Carbon dioxide 2.21 2.09 1.49 1.50
Hydrogen 20.10 38.33 52.68 67.12
Carbon monoxide 6.19 5.66 6.21 6.12
Saturated hydrocarbons 57.38 44.03 33.54 22.58
Unsaturated " 10.62 5.98 3.04 1.79
Nitrogen 2.20 2.47 2.55 0.78

This may be regarded as a fair example of the changes which take place in the quality of the gas during the distillation of the coal. In carburetting such a gas by injecting mineral oil into the retort, many of the products of the decomposition of the oil being vapours, it would be wasteful to do so for the first two hours, as a rich gas is being given off which has not the power of carrying in suspension a much larger quantity of hydrocarbon vapours without being supersaturated with them. Consequently, to make it carry any further quantity in a condition not easily deposited, the oil would have to be completely decomposed into permanent gases, and the temperature necessary to do this would seriously affect the quality of the gas given off by the coal. When, however, the distillation has gone on for three hours, the rich portions of coal have distilled off and the temperature of the retort has reached its highest point, and this is the best time to feed in the oil.

Undoubtedly the best process which has been proposed for the production of oil gas to be used in the enrichment of coal gas is the "Young" or "Peebles" process, which depends on the principle of washing the oil gas retorted at a moderate temperature by means of oil which is afterwards to undergo decomposition, because in this way it is freed from all condensible vapours, and only permanent gases are allowed to escape to the purifiers. In the course of this treatment considerable quantities of the ethylenes and other fixed gases are also absorbed, but no loss takes place, as these are again driven out by the heat in the subsequent retorting. The gas obtained by the Young process, when tested by itself in the burners most suited for its combustion, gives on the photometer an illuminating value averaging from 50 to 60 candle-power, but it is claimed, and quite correctly, that the enriching power of the gas is considerably greater. This is accounted for by the fact that it is impossible to construct a burner which will do justice to a gas of such illuminating power.

The fundamental objections to oil gas for the enrichment of coal gas are, first, that its manufacture is a slow process, requiring as much plant and space for retorting as coal gas; and, secondly, that although on a small scale it can be made to mix perfectly with coal gas and water gas, great difficulties are found in doing this on the large scale, because in spite of the fact that theoretically gases of such widely different specific gravities ought to form a perfect mixture by diffusion, layering of the gas is very apt to take place in the holder, and thus there is an increased liability to wide variations in the illuminating value of the gas sent out.

Enrichment by volatile hydrocarbons

The wonderful carburetting power of benzol vapour is well known, a large proportion of the total illuminating power of coal gas being due to the presence of a minute trace of its vapour carried in suspension. For many years the price of benzol has been falling, owing to the large quantities produced in the coke ovens, and at its present price it is by far the cheapest enriching material that can be obtained. Hence at many gas-works where it is found necessary to do so it is used in various forms of carburettor, in which it is volatilized and its vapour used for enriching coal gas up to the requisite illuminating power.

Enrichment by carburetted water gas

One of the most generally adopted methods of enrichment now is by means of carburetted water gas mixed with poor coal gas. When steam acts upon carbon at a high temperature the resultant action may be looked upon as giving a mixture of equal volumes of hydrogen and carbon monoxide, both of which are inflammable but non-luminous gases. This water gas is then carburetted, i.e. rendered luminous by passing it through chambers in which oils are decomposed by heat, the mixture being made so as to give an illuminating value of 22 to 25 candles. This, mixed with the poor coal gas, brings up its illuminating value to the required limit. Coke or anthracite is heated to incandescence by an air blast in a generator lined with fire-brick, and the heated products of combustion as they leave the generator and enter the superheaters are supplied with more air, which causes the combustion of carbon monoxide present in the producer gas and heats up the fire-brick baffles with which the superheater is filled. When the necessary temperature of the fuel and superheater has been reached, the air blast is cut off, and steam is blown through the generator, forming water gas, which meets the enriching oil at the top of the first superheater, called the carburettor, and carries the vapours with it through the main superheaters, where the fixing of the hydrocarbons takes place. The chief advantage of this apparatus is that a low temperature can be used for fixing owing to the enormous surface for superheating, and thus to a great extent the deposition of carbon is avoided. This form of apparatus has been very generally adopted in Great Britain as well as in America, and practically all carburetted water-gas plants are founded upon the same set of actions. Important factors in the use of carburetted water gas for enrichment are that it can be made with enormous rapidity and with a minimum of labour; and not only is the requisite increase in illuminating power secured, but the volume of the enriched gas is increased by the bulk of carburetted water gas added, which in ordinary English practice amounts to from 25 to 50%. The public at first strongly opposed its introduction on the ground of the poisonous properties of the carbon monoxide, which is present in it to the extent of about 28 to 30%. Still when this comes to be diluted with 60 to 75% of ordinary coal gas, containing as a rule only 4 to 6% of carbon monoxide, the percentage of poisonous monoxide in the mixture falls to below 16%, which experience has shown to be a fairly safe limit.

A rise in the price of oil suitable for carburetting has caused the gas industry to consider other methods by which the volume of gas obtainable from coal can be increased by admixture with blue or non-luminous water gas. In Germany, at several important gas-works, non-luminous water gas is passed into the foul main or through the retorts in the desired proportion, and the mixture of water gas and coal gas is then carburetted to the required extent by benzol vapour, a process which at the present price of oil and benzol is distinctly more economical than the use of carburetted water gas. In 1896 Karl Dellwik introduced a modification in the process of making water gas which entirely altered the whole aspect of the industry. In all the attempts to make water gas, up to that date, the incandescence of the fuel had been obtained by "blowing" so deep a bed of fuel that carbon monoxide and the residual nitrogen of the air formed the chief products, this mixture being known as "producer" gas. In the Dellwik process, however, the main point is the adjustment of the air supplied to the fuel in the generator in such a way that carbon dioxide is formed instead of carbon monoxide. Under these conditions producer gas ceases to exist as a by-product, and the gases of the blow consist merely of the incombustible products of complete combustion, carbon dioxide and nitrogen, the result being that more than three times the heat is developed for the combustion of the same amount of fuel, and nearly double the quantity of water gas can be made per pound of fuel than was before possible. The runs or times of steaming can also be continued for longer periods. The possibility of making from 60,000 to 70,000 cub. ft. of water gas per ton of coke used in the Dellwik generator as against 34,000 to 45,000 cub. ft. per ton made by previous processes reduces the price of water gas to about 3d. per thousand, so that the economic value of using it in admixture with coal gas and then enriching the mixture by any cheap carburetting process is manifest. The universal adoption of the incandescent mantle for lighting purposes has made it evident that the illuminating value of the gas is a secondary consideration, and the whole tendency now is to do away with enrichment and produce a gas of low-candle power but good heating power at a cheap rate for fuel purposes and incandescent lighting. (See also Lighting: Gas.)

(V. B. L.)

2. Gas for Fuel and Power - The first gas-producers, which were built by Faber du Faur at Wasseralfingen in 1836 and by C.G.C. Bischof at Mägdesprung (both in Germany), consisted of simple perpendicular shafts of masonry contracted at the top and the bottom, with or without a grate for the coal. Such producers, frequently strengthened by a wrought iron casing, are even now used to a great extent. Sometimes the purpose of a gas-producer is attained in a very simple manner by lowering the grate of an ordinary fireplace so much that a layer of coal 4 or 5 ft. deep is maintained in the fire. The effect of this arrangement is that the great body of coal reaches a higher temperature than in an ordinary fireplace, and this, together with the reduction of the carbon dioxide formed immediately above the grate by the red-hot coal in the upper part of the furnace, leads to the formation of carbon monoxide which later on, on the spot where the greatest heat is required, is burned into dioxide by admitting fresh air, preferably pre-heated. This simple and inexpensive arrangement has the further advantage that the producer-gas is utilized immediately after its formation, without being allowed to cool down. But it is not very well adapted to large furnaces, and especially not to those cases where all the space round the furnace is required for manipulating heavy, white-hot masses of iron, or for similar purposes. In these cases the producers are arranged outside the iron-works, glass-works, etc., in an open yard where all the manipulations of feeding them with coal, of stoking, and of removing the ashes are performed without interfering with the work inside. But care must always be taken to place the producers at such a low level that the gas has an upward tendency, in order to facilitate its passage to the furnace where it is to be burned. This purpose can be further promoted by various means. The gas-producers constructed by Messrs Siemens Brothers, from 1856 onwards, were provided with a kind of brick chimney; on the top of this there was a horizontal iron tube, continued into an iron down-draught, and only from this the underground flues were started which sent the gas into the single furnaces. This arrangement, by which the gas was cooled down by the action of the air, acted as a gas-siphon for drawing the gas out of the producer, but it has various drawbacks and has been abandoned in all modern constructions. Where the "natural draught" is not sufficient, it is aided either by blowing air under the grate or else by suction at the other end.

We shall now describe a few of the very large number of gas-producers producers constructed, selecting some of the most widely applied in practice.

Fig. 12 [2] - Siemens Producer (Sectional Elevation).

Fig. 13. - Lürmann's Producer.

Figs. 14 and 15. - Liegel's Producer.

The Siemens Producer in its original shape, of which hundreds have been erected and many may be still at work, is shown in fig. 12. A is the charging-hole; B, the inclined front wall, consisting of a cast iron plate with fire-brick lining; C, the equally inclined "step-grate"; D, a damper by which the producer may be isolated in case of repairs; E, a water-pipe, by which the cinders at the bottom may be quenched before taking away; the steam here formed rises into the producer where it forms some "semi-water gas" (see Fuel: Gaseous). Openings like that shown at G serve for introducing a poker in order to clean the brickwork from adhering slags. H is the gas flue; I, the perpendicularly ascending shaft, 10 or 12 ft. high; JJ, the horizontal iron tube; K, the descending branch mentioned above, for producing a certain amount of suction by means of the gas-siphon thus formed. In the horizontal branch JJ much of the tar and flue-dust is also condensed, which is of importance where bituminous coal is employed for firing.

Fig. 16. - Taylor's Producer.

Fig. 17. - Dowson Gas Plant.

Fig. 18. - Mond Gas Plant.

Fig. 19. - Mond Gas Plant.

This as well as most other descriptions of gas-producers, is not adapted to being worked with such coal as softens in the heat and forms cakes, impenetrable to the air and impeding the regular sinking of the charge in the producer. The fuel employed should be non-bituminous coal, anthracite or coke, or at least so much of these materials should be mixed with ordinary coal that no semi-solid cakes of the kind just described are formed. Where it is unavoidable to work with coal softening in the fire, Lürmann's producer may be employed, which is shown in fig. 13. V shows a gas-producer of the ordinary kind, which during regular work is filled with the coke formed in the horizontal retort E. The door b serves for removing the slags and ashes from the bottom of V, as far as they do not fall through the grate. The hot producer-gas formed in V is passed round the retort E in the flues n2 n2, and ultimately goes away through K to the furnace where it is to be used. The retort E is charged with ordinary bituminous coal which is submitted to destructive distillation by the heat communicated through the flues n2 n2 and is thus converted into coke. The gases formed during this process pass into the upper portion of V and get mixed with the producer-gas formed in the lower portion. From time to time, as the level of the coke in V goes down, some of the freshly formed coke in E is pushed into V, whereby the level of the coke in V should assume the shape shown by the dotted line l ... m. If the level became too low, such as is shown by the dotted line x ... y, the working of the producer would be wrong, as in this case the layer of coke at the front side would be too low, and carbon dioxide would be formed in lieu of monoxide.

Fig. 20. - Blass' Gas Plant.

Figs. 14 and 15 show Liegel's producer, the special object of which is to deal with any fuel (coal or coke) giving a tough, pasty slag on combustion. Such slags act very prejudicially by impeding the up-draught of the air and the sinking of the fuel; nor can they be removed by falling through a grate, like ordinary coal-ashes. To obviate these drawbacks the producer A is kept at a greater heat than is otherwise usual, the air required for feeding the producer being pre-heated in the channels e, e. The inside shape of the producer is such that the upper, less hot portion cannot get stopped, as it widens out towards the bottom; the lower, hotter portion, where the ashes are already fluxed, is contracted to a slit a, through which the air ascends. The grate b retains any small pieces of fuel, but allows the liquid cinder to pass through. The lateral flues c, c prevent the brickwork from being melted.

One of the best-known gas-producers for working with compressed air from below is Taylor's, shown in fig. 16. A is the feeding-hopper, on the same principle as is used in blast-furnaces. L is the producer-shaft, with an iron casing B and peep-holes B1 to B4, passing through the brick lining M. F is the contracted part, leading to the closed ash-pit, accessible through the doors D. An injector I, worked by means of the steam-pipe J, forces air through K into F. The circular grate G can be turned round K by means of the crank E from the outside. This is done, without interfering with the blast, in order to keep the fuel at the proper level in L, according to the indications of the burning zone, as shown through the peep-holes B1 to B4. The ashes collecting at the bottom are from time to time removed by the doors D. As the steam, introduced by J, is decomposed in the producer, we here obtain a "semi-water gas," with about 27% CO and 12% H2.

Fig. 17 shows the Dowson gas-producer, together with the arrangements for purifying the gas for the purpose of working a gas engine. a is a vertical steam boiler, heated by a central shaft filled with coke, with superheating tubes b passing through the central shaft. c is the steam-pipe, carrying the dry steam into the air-injector d. This mixture of steam and air enters into the gas-producer e below the fire-grate f. g is the feeding-hopper for the anthracite which is usually employed in this kind of producer. h, h are cooling-pipes for the gas where most of the undecomposed steam (say 10% of the whole employed in d) is condensed. i is a hydraulic box with water seal; j, a coke-scrubber; k, a filter; l, a sawdust-scrubber; m, inlet of gas-holder; n, gas-holder; o, outlet of same; p, a valve with weighted lever to regulate the admission of steam to the gas-producer; q, the weight which actuates the lever automatically by the rise or fall of the bell of the gas-holder. In practical work about  lb of steam is decomposed for each pound of anthracite consumed, and no more than 5% of carbon dioxide is found in the resulting gas. The latter has an average calorific power of 1732 calories per cubic metre, or 161 B.T.U. per cubic foot, at 0° and 760 mm.

The Mond plant is shown in figs. 18 and 19. The gases produced in the generators G are passed through pipes r into washers W, in which water is kept in violent motion by means of paddle-wheels. The spray of water removes the dust and part of the tar and ammonia from the gases, much steam being produced at the same time. This water is withdrawn from time to time and worked for the ammonia it contains. The gases, escaping from W at a temperature of about 100° C., and containing much steam, pass though g and a into a tower, fed with an acid-absorbing liquid, coming from the tank s, which is spread into many drops by the brick filling of the tower. This liquid is a strong solution of ammonium sulphate, containing about 2.5% free sulphuric acid which absorbs nearly all the ammonia from the gases, without dissolving much of the tarry substances. Most of the liquor arriving at the bottom, after mechanically separating the tar, is pumped back into s, but a portion is always withdrawn and worked for ammonium sulphate. When escaping from the acid tower, the gas contains about 0.013% NH3, and has a temperature of about 80° C. and is saturated with aqueous vapour. It is passed through c into a second tower B, filled with blocks of wood, where it meets with a stream of comparatively cold water. At the bottom of this the water runs away, its temperature being 78° C.; at the top the gas passes away through d into the distributing main. The hot water from B, freed from tar, is pumped into a third tower C, through which cold air is forced by means of a Root's blower by the pipe w. This air, after being heated to 76° C., and saturated with steam in the tower C, passes through l into the generator G. The water in C leaves this tower cold enough to be used in the scrubber B. Thus two-thirds of the steam originally employed in the generator is reintroduced into it, leaving only one-third to be supplied by the exhaust steam of the steam-engine. The gas-generators G have a rectangular section, 6  12 ft., several of them being erected in series. The introduction of the air and the removal of the ashes takes place at the narrower ends. The bottom is formed by a water-tank and the ashes are quenched here. The air enters just above the water-level, at a pressure of 4 in. The Mond gas in the dry state contains 15% carbon dioxide, 10% monoxide, 23% hydrogen, 3% hydrocarbons, 49% nitrogen. The yield of ammonium sulphate is 75 lb from a ton of coal (slack with 11.5% ashes and 55% fixed carbon).

Fig. 21. - Dellwik-Fleischer Producer.

One of the best plants for the generation of water-gas is that constructed by E. Blass (fig. 20). Steam enters through the valve V at D into the generator, filled with coke, and passes away at the bottom through A. The pressure of the gas should not be such that it could get into the pipe conveying the air-blast, by which an explosive mixture would be formed. This is prevented by the water-cooled damper S, which always closes the air-blast when the gas-pipe is open and vice versa. Below the entry W of the air-blast there is a throttle valve d which is closed as soon as the damper S opens the gas canal; thus a second security against the production of a mixture of air and gas is afforded. The water-cooled ring channel K protects the bottom outlet of the generator and causes the cinders to solidify, so that they can be easily removed. But sometimes no such cooling is effected, in which case the cinders run away in the liquid form. Below K the fuel is lying in a conical heap, leaving the ring channel A free. During the period of hot-blowing (heating-up) S is turned so that the air-blast communicates with the generator; d and G are open; g (the damper connected with the scrubber) and V are closed. During the period of gas-making G and d are closed, S now closes the air-blast and connects the generator with the scrubber; V is opened, and the gas passes from the scrubber into the gas-holder, the inlet w being under a pressure of 4 in. All these various changes in the opening of the valves and dampers are automatically performed in the proper order by means of a hand-wheel H, the shaft m resting on the standards t and shaft v. This hand-wheel has merely to be turned one way for starting the hot-blowing, and the opposite way for gas-making, to open and shut all the connexions, without any mistake being possible on the part of the attendant. The feeding-hopper E is so arranged that, when the cone e2 opens, e1 is shut, and vice versa, thus no more gas can escape, on feeding fresh coke into the generator, than that which is contained in E. G is the pipe through which the blowing-up gas (Siemens gas) is carried away, either into the open air (where it is at once burned) or into a pre-heater for the blast, or into some place where it can be utilized as fuel. This gas, which is made for 10 or 11 minutes, contains from 23 to 32% carbon monoxide, 7 to 1.5% carbon dioxide, 2 to 3% hydrogen, a little methane, 64 to 66% nitrogen, and has a heating value of 950 calories per cub. metre. The water-gas itself is made for 7 minutes, and has an average composition of 3.3% carbon dioxide, 44% carbon monoxide, 0.4% methane, 48.6% hydrogen, 3.7% nitrogen, and a heating value of 2970 calories per cub. metre. 1 kilogram coke yields 1.13 cub. metre water-gas and 3.13 Siemens gas. 100 parts coke (of 7000 calories) furnish 42% of their heat value as water-gas and 42% as Siemens gas.

Lastly we give a section of the Dellwik-Fleischer gas-producer (fig. 21). The feeding-hoppers A are alternately charged every half-hour, so that the layer of fuel in the generator always remains 4 ft. deep. B is the chimney-damper, C the grate, D the door for removing the slags, E the ash-door, F the inlet of the air-blast, G the upper, G1 the lower outlet for the water-gas which is removed alternately at top and bottom by means of an outside valve, steam being always admitted at the opposite end. The blowing-up generally lasts 1 minutes, the gas-making 8 or 10 minutes. The air-blast works under a pressure of 8 or 9 in. below the grate, or 4 to 4 in. above the coke. The blowing-up gas contains 17 or 18% carbon dioxide and 1.5% oxygen, with mere traces of carbon monoxide. The water-gas shows 4 to 5% carbon dioxide, 40% carbon monoxide, 0.8% methane, 48 to 51% hydrogen, 4 or 5% nitrogen. About 2.5 cub. metres is obtained per kilogram of best coke.

See Mills and Rowan, Fuel and its Application (London, 1889); Samuel S. Wyer, Producer-Gas and Gas-Producers, published by the Engineering and Mining Journal (New York); F. Fischer, Chemische Technologie der Brennstoffe (1897-1901); Gasförmige Heizstoffe, in Stohmann and Kerl's Handbuch der technischen Chemie, 4th edition, iii. 642 et seq.

(G. L.)

[1] Liquor condensed from gas alone, without wash water.

[2] Figs. 12, 13, 14, 15, 16, 18, 19, 20, 21 of this article are from Lunge's Coal-tar and Ammonia, by permission of Friedr. Vieweg u. Sohn.

Note - this article incorporates content from Encyclopaedia Britannica, Eleventh Edition, (1910-1911)

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