PART V LIME-ROASTING OF GALENA (continued 3)
Reading edition
It may now be attempted to summarize the cost of the converting process. Assuming the case of an ore assaying lead, 50 per cent.; iron, 15; sulphur, 22; silica, 8, and alumina, etc., 5, let it be supposed that it is to be fluxed with pure limestone and pure quartz, with the aim to make a slag containing silica, 30; ferrous oxide, 40; and lime, 20 per cent. A ton of ore will make, in round numbers, 1000 lb. of slag, and will require 344 lb. of limestone and 130 lb. of quartz, or we may say roughly one ton of flux must be added to four tons of ore, wherefore the ore will constitute 80 per cent. of the charge. In reducing the charge to 3 per cent. sulphur it will lose ultimately through expulsion of sulphur and carbon dioxide (of the limestone) about 20 per cent. in weight, wherefore the quantity of material to be smelted in the blast furnace will be practically equivalent to the raw sulphide ore in the charge for the roasting furnaces; but in the roasting furnace the charge is likely to gain weight, because of the formation of sulphates. Taking the charge, which I have assumed above, and reckoning that as it comes from the roasting furnace it will contain 10 per cent. sulphur, all in the form of sulphate, either of lead or of lime, and that the iron be entirely converted to ferric oxide, in spite of the expulsion of the carbon dioxide of the limestone and the combustion of a portion of the sulphur of the ore as sulphur dioxide, the charge will gain in weight in the ratio of 1:1.19. This, however, is too high, inasmuch as a portion of the sulphur will remain as sulphide while a portion of the iron may be as ferrous oxide. The actual gain in weight will consequently be probably not more than one-tenth. The following theoretical calculation will illustrate the changes:
Raw Charge Semi-Roasted Charge Finished Charge
Ore 1000 lb. Pb 1154 lb. PbO 1154 lb. PbO
300 lb. Fe 428 lb. Fe2O3 428 lb. Fe2O3(?)
160 lb. SiO2 160 lb. SiO2 160 lb. SiO2
100 lb. Al2O3, etc. 100 lb. Al2O3, etc. 100 lb. Al2O3, etc.
440 lb. S 300 lb. S 68 lb. S
Flux 130 lb. SiO2 130 lb. SiO2 130 lb. SiO2
344 lb. CaCO3 193 lb. CaO 193 lb. CaO
450 lb. O
—— ——— ———
2474 lb. 2915 lb. 2233 lb.
10% S. 3% S.
Ratios:
2474:2915 :: 1:1.18.
2915:2233 :: 1:0.76⅔.
2474:2233 :: 1:0.90.
It may be assumed that for every ton of charge (containing about 80 per cent. of ore) there will be 1.1 ton of material to go to the converter, and that the product of the latter will be 0.9 of the weight of the original charge of raw material.
Each converter requires 400 cu. ft. of air per minute. The blast pressure is variable, as different pots are always at different stages of the process, but assuming the maximum of 16 oz. pressure, with a blast main of sufficient diameter (at least 15 in.) and the blower reasonably near the battery of pots, the total requirement is 21 h.p. The cost of converting will be approximately as follows:
Labor, 3 foremen at $3.20 $ 9.60
Labor, 9 men at $2.50 22.50
Power, 21 h.p. at 30c 6.30
Supplies, repairs and renewals 5.00
Total $43.40 = 60c. per ton of charge.
The cost of converting is, of course, reduced directly as the time is reduced. The above estimate is based on unfavorable conditions as to time required for working a charge.
The total cost of treatment, from the initial stage to the delivery of the desulphurized ore to the blast furnaces, will be, per 2000 lb. of charge, approximately as follows:
Crushing 1.0 ton at 10c $0.10
Mixing 1.0 ton at 10c .10
Roasting 1.0 ton at 63c .63
Delivering 1.1 ton to converters at 12c .13
Converting 1.1 ton at 60c .66
Breaking 0.9 ton at 60c .54
Total $2.16
The cost per ton of ore will be 2.16 ÷ 0.80 = $2.70. Making allowance for the crushing of the ore, which is not ordinarily included in the cost of roasting, and possibly some overestimates, it appears that the cost of desulphurization by this method, under the conditions assumed in this paper, is rather higher than in good practice with ordinary hand-worked furnaces, but it is evident that the cost can be reduced to approximately the same figure by introduction of improvements, as for example in breaking the desulphurized ore, and by shortening the time of converting, which is possible in the case of favorable ores. The chief advantage must be, however, in the further stage of the smelting. As to this, there is the evidence that the Broken Hill Proprietary Company was able to smelt the same quantity of ore in seven furnaces, after the introduction of the Huntington-Heberlein process, that formerly required thirteen. A similar experience is reported at Friedrichshütte, Silesia.
This increase in the capacity of the blast furnace is due to three things: (1) In delivering to the furnace a charge containing a reduced percentage of fine ore, the speed of the furnace is increased, i.e., more tons of ore can be smelted per square foot of hearth area. (2) There is less roasted matte to go into the charge. (3) Under some conditions the percentage of lead in the charge can be increased, reducing the quantity of gangue that must be fluxed.
It is difficult to generalize the economy that is effected in the blast-furnace process, since this must necessarily vary within wide limits because of the difference in conditions. An increase of 60 to 100 per cent. in blast-furnace capacity does not imply a corresponding reduction in the cost of smelting. The fuel consumption per ton of ore remains the same. There is a saving in the power requirements, because the smelting can be done with a lower blast pressure; also, a saving in the cost of reworking matte. There will, moreover, be a saving in other labor, in so far as portions thereof are not already performed at the minimum cost per ton. The net result under American conditions of silver-lead smelting can only be determined closely by extensive operations. That there will be an important saving, however, there is no doubt.
The cost of smelting a ton of charge at Denver and Pueblo, exclusive of roasting and general expense, is about $2.50, of which about $0.84 is for coke and $1.66 for labor, power and supplies. General expense amounts to about $0.16 additional. If it should prove possible to smelt in a given plant 50 per cent. more ore than at present without increase in the total expense, except for coke, the saving per ton of charge would be 70c. That is not to be expected, but the half of it would be a satisfactory improvement. With respect to sulphur in the charge, the cost is commonly reckoned at 25c. per unit. As compared with a charge containing 2 per cent. of sulphur there would be a saving rising toward 50c. per ton as the maximum. It is reasonable to reckon, therefore, a possible saving of 75c. per ton of charge in silver-lead smelting, no saving in the cost of roasting, and an increase of about 3 per cent. in the extraction of lead, and perhaps 1 per cent. in the extraction of silver, as the net results of the application of the Huntington-Heberlein process in American silver-lead smelting.
On a charge averaging 12 per cent. lead and 33 oz. silver per ton, an increase of 3 per cent. in the extraction of lead and 1 per cent. in the extraction of silver would correspond to 25c. and 35c. respectively, reckoning lead at 3.5c. per lb., and silver at 60c. per oz. In this, however, it is assumed that all lead-bearing ores will be desulphurized by this process, which practically will hardly be the case. A good deal of pyrites, containing only a little lead, will doubtless continue to be roasted in Brückner cylinders, and other mechanical furnaces, which are better adapted to the purpose than are the lime-roasting pots. Moreover, a certain proportion of high-grade lead ore, which is now smelted raw, will be desulphurized outside of the furnace, at additional expense. It is comparatively simple to estimate the probable benefit of the Huntington-Heberlein process in the case of smelting works which treat principally a single class of ore, but in such works as those in Colorado and Utah, which treat a wide variety of ores, we must anticipate a combination process, and await results of experience to determine just how it will work out. It should be remarked, moreover, that my estimates do not take into account the royalty on the process, which is an actual debit, whether it be paid on a tonnage basis or be computed in the form of a lump sum for the license to its use.
However, in view of the immense tonnage of ore smelted annually for the extraction of silver and lead, it is evident that the invention of lime-roasting by Huntington and Heberlein was an improvement of the first order in the metallurgy of lead.
In the case of non-argentiferous galena, containing 65 per cent. of lead (as in southeastern Missouri), comparison may be made with the slag-roasting and blast-furnace smelting of the ore. Here, no saving in cost of roasting may be reckoned and no gain in the speed of the blast furnaces is to be anticipated. The only savings will be in the increase in the extraction of lead from 92 to 98 per cent., and the elimination of matte-roasting, which latter may be reckoned as amounting to 50c. per ton of ore. The extent of the advantage over the older method is so clearly apparent that it need not be computed any further. In comparison with the Scotch-hearth bag-house method of smelting, however, the advantage, if any, is not so certain. That method already saves 98 per cent. of the lead, and on the whole is probably as cheap in operation as the Huntington-Heberlein could be under the same conditions. The Huntington-Heberlein method has replaced the old roast-reaction method at Tarnowitz, Silesia, but the American Scotch-hearth method as practised near St. Louis is likely to survive.
A more serious competitor will be, however, the Savelsberg process, which appears to do all that the Huntington-Heberlein process does, without the preliminary roasting. Indeed, if the latter be omitted (together with its estimated expense of 63c. per ton of charge, or 79c. per ton of ore), all that has been said in this paper as to the Huntington-Heberlein process may be construed as applying to the Savelsberg. The charge is prepared in the same way, the method of operating the converters is the same, and the results of the reactions in the converters are the same. The litigation which is pending between the two interests, Messrs. Huntington and Heberlein claiming that Savelsberg infringes their patents, will be, however, a deterrent to the extension of the Savelsberg process until that matter be settled.
The Carmichael-Bradford process may be dismissed with a few words. It is similar to the Savelsberg, except that gypsum is used instead of limestone. It is somewhat more expensive because the gypsum has to be ground and calcined. The process works efficiently at Broken Hill, but it can hardly be of general application, because gypsum is likely to be too expensive, except in a few favored localities. The ability to utilize the converter gases for the manufacture of sulphuric acid will cut no great figure, save in exceptional cases, as at Broken Hill, and anyway the gases of the other processes can be utilized for the same purpose, which is in fact being done in connection with the Huntington-Heberlein process in Silesia.
The cost of desulphurizing a ton of galena concentrate by the Carmichael-Bradford process is estimated by the company controlling the patents as follows, labor being reckoned at $1.80 per eight hours, gypsum at $2.40 per 2240 lb., and coal at $8.40 per 2240 lb.:
0.25 ton of gypsum $0.60
Dehydrating and granulating gypsum .48
Drying mixture of ore and gypsum .12
Converting 0.24
Spalling sintered material .12
0.01 ton coal .08
Total $1.64
The value of the lime in the sintered product is credited at 12c., making the net cost $1.52 per 2240 lb. of ore.
The cost allowed for converting may be explained by the more rapid action that appears to be attained with the ores of Broken Hill than with some ores that are treated in North America, but the low figure estimated for spalling the sintered material appears to be highly doubtful.
The theory of the lime-roasting processes is not yet well established. It is recognized that the explanation offered by Huntington and Heberlein in their original patent specification is erroneous. There is no good evidence in their process, or any other, of the formation of the higher oxide of lime, which they suggest.
At the present time there are two views. In one, formulated most explicitly by Professor Borchers, there is formed in this process a plumbate of calcium, which is an active oxidizing agent. A formation of this substance was also described by Carmichael in his original patent, but he considered it to be the final product, not the active oxidizing agent.
In the other view, the lime, or limestone, serves merely as a diluent of the charge, enabling the air to obtain access to the particles of galena, without liquefaction of the latter. The oxidation of the lead sulphide is therefore effected chiefly by the air, and the process is analogous to what takes place in the bessemer converter or in the Germot process of smelting, or perhaps more closely to what might happen in an ordinary roasting furnace, provided with a porous hearth, through which the air supply would be introduced. Roasting furnaces of that design have been proposed, and in fact such a construction is now being tested for blende roasting in Kansas.
Up to the present time, the evidence is surely too incomplete to enable a definite conclusion to be reached. Some facts may, however, be stated.
There is clearly reaction to a certain extent between lead sulphide and lead sulphate, as in the reverberatory smelting furnace, because prills of metallic lead are to be observed in the lime-roasted charge.
There is a formation of sulphuric acid in the lime-roasting, upon the oxidizing effect of which Savelsberg lays considerable stress, since its action is to be observed on the iron work in which it condenses.
Calcium sulphate, which is present in all of the processes, being specifically added in the Carmichael-Bradford, evidently plays an important chemical part, because not only is the sulphur trioxide expelled from the artificial gypsum, but also it is to a certain extent expelled from the natural gypsum, which is added in the Carmichael-Bradford process; in other words, more sulphur is given off by the charge than is contained by the metallic sulphides alone.
Further evidence that lime does indeed play a chemical part in the reaction is presented by the phenomena of lime-roasting in clay dishes in the assay muffle, wherein the air is certainly not blown through the charge, which is simply exposed to superficial oxidation as in ordinary roasting.
The desulphurized charge dropped from the pot is certainly at much below the temperature of fusion, even in the interior, but we have no evidence of the precise temperature condition during the process itself.
Pyrite and even zinc blende in the ore are completely oxidized. This, at least, indicates intense atmospheric action.
The papers by Borchers,[39] Doeltz,[40] Guillemain,[41] and Hutchings[42] may profitably be studied in connection with the reactions involved in lime-roasting. The conclusion will be, however, that their precise nature has not yet been determined. In view of the great interest that has been awakened by this new departure in the metallurgy of lead, it is to be expected that much experimental work will be devoted to it, which will throw light upon its principles, and possibly develop it from a mere process of desulphurization into one which will yield a final product in a single operation.