Search Documents

By E. C. Patton

Jan 1, 1947

By Helmut Thielsch

In recent years an ever increasing amount of interest has been directed toward research studying the principles and various applications of sonic and supersonic waves. Though still in their early stages of practical development, sonic vibrations are already used in the emulsifi-cation and degasification of liquids. Metals exposed to sonic or ultrasonic vibrations while solidifying show a considerable amount of grain refinement. Often sound waves are applied instead of radiography to test engineering materials for internal cracks and flaws.' In the field of pure research these waves are used in dispersion and also in coagulation of particles or liquids in gaseous or, under certain conditions, in other liquid systems. In the settling and thickening of slurries considerable time is necessary to compress the solid particles and to squeeze out the liquid to obtain as low a dilution (liquid to solid ratio) as possible. Various methods have been developed to increase the amount of coagulation of the very fine solids (colloidal or semicolloidal) and to shorten the over-all time. The addition of small amounts of electrolytes and the warming of the suspension represent merely the more important techniques. Some of the effects of supersonic vibrations have been reported previously. From preliminary studies, therefore, it was hoped that by application of sonic vibrations it would be possible to reduce the time required to thicken such materials to a specific dilution, as well as to thicken to lower ultimate dilutions than could be obtained by quiescent settling alone. By increasing the volume thickened per unit time—i.e., improving the plant efficiency— great savings in equipment and time would be obtained for industrial processes. Also, faster settling rates should result if coagulation of particles could be increased. Experiments have been conducted for a period of several months in the Allis-Chalmers laboratory to study the effect of sonic vibrations on settling of particles of different sizes and concentrations. Apparatus The sedimentation apparatus used in these experiments is illustrated in Figs. I and 2. The essential features are the stationary field coil and the movable voice coil. Both windings are placed around a solid iron core. A leather diaphragm connected to the steel frame holds the voice coil in place. A brass rod is fastened to the voice coil with a metal disk connected to the other end. This disk is sealed to the lucite cylinder with a flexible rubber diaphragm. The lucite tube is 17 in. long; its inner diameter is 2½ in. and the wall thickness is ¼ in. The tube is calibrated on the outside in 10 c.c. divisions for a total of 1000 cubic centimeters.

Jan 1, 1947

By Grover J. Holt

In order to provide a clear picture of the development of the sink-and-float process of concentration as applied to the iron ores of Minnesota, a few pertinent facts should be brought out concerning the ores and the products of concentration. Iron ore is primarily a cheap commodity handled in immense quantities. The price of iron ore at present, based on a natural iron content of 51.5 per cent, varies from $2.55 to $2.70 per gross ton f.0.b. cars at the mine or washing plant in Minnesota. Last year 92,000,000 gross tons were shipped from the Lake Superior district (Minnesota, Michigan, and Wisconsin) to the furnaces. Concentrated iron ores have no greater value per unit of iron content than ores that can be mined and shipped direct from the shafts or open pits. For years only the higher grades of concentrating ores could be treated and sold in competition with the immense reserves of direct shipping ore available. These higher-grade "straight wash" ores required only the simplest treatment; namely, the washing out of fine sand from coarse ore particles. As the exhaustion of the " straight wash " ore is reached, rock is found replacing part of this sand, and the ore no longer responds to the former sizing treatment. Substantial tonnages of this marginal (jig ore) remained to be treated. Because of the limitations placed on concentrates by the furnaces—namely, low price of product and minimum amount of fines—iron-ore concentration oil has been and must continue to be a one-pass process. Only an increase in price or a change in structure of concentrates allowed by the ore consumer will encourage departure from this practice. Faced with the necessity of handling large tonnages, with the limitations mentioned, iron-ore research men have found their search for new and more efficient methods of treatment seriously handicapped and removed from the field of fine crushing. Sink-and-float treatment appeared to offer the best field in coarse concentration and has been proved by several plants to be well adapted to our problem. The use of ferrosilicon as a medium solid was decided upon. In our present practice, the ferrosilicon metal, carrying about 83 per cent iron, 15 per cent silicon and 2 per cent carbon and nonmagnetics, is crushed to pass 65 mesh and used without further sizing. When mixed with water the specific gravity of the medium may be controlled to within 0.02 per cent above or below the required gravity. Table I shows examples of a change in solid content of the medium for varying gravities. the I is based on clean ferrosilicon, whereas some contamination is always present in the mill circuit, tending to

Jan 1, 1947

By R. R. Knuckey

Having been associated with the operation of the de Vooys process for coal, which has treated 13,000,000 tons per annum, and recognizing the process as of value in ore sorting, Huntington, Heberlein and Co. Ltd. (Great Britain) in 1936 made an examination of all other existing methods. In none of the pioneer applications had recognition been given to the necessity for maintaining certain conditions that are essential for sorting certain ores if a truly efficient separation by gravity alone is to be assured. Consequently, in 1936-1937 Huntington, Heberlein and Co. Ltd., with Pearson, employing certain ideas connected with the de Vooys application, commenced the development of a separator that would allow conformance with optimum conditions in the zone where separation is effected. Later, Holt and Wade added to the value of the original application by Wuensch, Rakowsky and others, whose conceptions are being successfully operated today. Meantime, Trostler had enhanced the value of the original H-H. process by improvements that are now embodied in operating plants, and today the process incorporates an improved apparatus and a stable medium that produce the optimum conditions for separation. These conditions are: 1. Elimination of disturbing currents in the separating zone; 2. Reduction to a minimum of medium-density differences throughout the separating zone; 3. Stable medium of minimum viscosity to permit the unretarded fall of mineralized particles; 4. Removal of products of separation with minimum disturbance to the separating zone. Design of Separator The H-H. sink-and-float separator consists of a pyramidal tank in which the separation actually takes place, connected at the bottom with an inclined bucket elevator. The tank and the elevator are filled with medium to within a few inches of the top of the tank. Medium is fed into the separator at a variety of points, according to the type of ore being treated, and it is withdrawn from the separator at two points: (1) together with the float product, by means of a variable-speed addle, at the surface of the medium, and (2) by flowing over an adjustable weir cut in the side of the elevator casing. The prepared ore is fed onto the surface of the medium. The intermediate paddles, which revolve at a slow speed of 2 to 5 r.p.m., move the floating ore across the bath from feed end to float-discharge end. The ore, which is heavier than the medium, sinks below the sweep of the addles and reaches the boot of the bucket elevator, which discharges it without disturbance of the separating zone. These arrangements for withdrawing medium from the separator allow the use of minimum flows, which connote minimum

Jan 1, 1947

By C. Y Garber

Interest in the sink-float plant operated by the Bunker Hill and Sullivan Mining and Concentrating Co. at Kellogg, Idaho, has recently been largely confined to the preparation and reconditioning of the galena medium. The ease and simplicity of these operations in a concentrating mill producing a flotation lead concentrate has occasioned enough comment to possibly justify a brief description. The subject is treated from an operator's viewpoint only; no effort is made to discuss it in a theoretical or technical manner. Plant at Bunker Hill The sink-float plant was first operated in December 1941. It was built for the purpose of quickly increasing mill capacity with a minimum of equipment. It is the Huntington-Heberlein sink and float process using galena medium and is operated under license from the Sink and Float Corporation, New York city. Lead-zinc ore from the Bunker Hill mine is crushed to pass a 1¼ in, screen and is then washed and separated on vibrating screens having 4½-mm. round-hole punched plates. The screen under-size, amounting to 33 per cent of the mill feed, is dewatered and sent to the ball-mill feed bins. The screen oversize goes to the sink-float plant, where 50 per cent of the oversize, or 33 per cent of the mill feed, is float, which is washed free of medium and disposed of as a tailing. The remaining 33 per cent is sink, which, after washing, is crushed to pass 36 in. and joins the under-size in the ball-mill feed bins. The normal plant capacity is 1700 tons per 24 hr. About 1.7 per cent of the total lead and 3.3 per cent of the total zinc in the feed is lost with the sink-float tailings (Table I). More complete descriptions of the H. H. process and Bunker Hill sink-float plant are given in several recent articles, listed at the end of the paper. Preparation OF Medium at Bunker Hill New medium is made intermittently as needed, usually 12 hr. in each 6 days. A small portion of the current mill flotation concentrate is diverted from the lead cleaner cells to a I-in. vertical sand pump and pumped to a two-cell 36-in. Agitair flotation machine, where NaCn and ZnSO4 are added and the grade of concentrate is improved as shown in Table 2. Tailing from this operation is returned by gravity

Jan 1, 1947

By Harry L. McNeill

The Selective Media Process was developed by the author in a laboratory provided by The Steams-Roger Manufacturing Co. It is the outcome of an investigation into the possibilities of coarse beneficiation by sink and float without using the conventional heavy media. Commercial work to date has been limited to the treatment of minus 3/8-in. iron ore at the Hill Trumbull washing plant of the Cleveland Clifis Iron Co., at Calumet, Minnesota. Two cut away prints of the machine are shown (Figs. I and 2). A rotary conical impeller is mounted within a stationary cone (Fig. 2). This impeller is adjustable vertically by a 12-ton screw jack. The speed of the impeller can be varied from 14 to 32 r.p.m. by the Reeves variable-speed motor pulley mounted on the 7½-hp. motor drive. Attached to the bottom of the stationary cone is the automatic control valve for sink product, actuated by a ¼-hp. gear motor. The sink product is dewatered in a conventional drag driven by a 7½-hp. motor and discharged onto an inclined conveyor containing from 6 to 10 per cent moisture. Two plants are operated at the Hill Trumbull property. All the ore is first treated in a typical washing plant (Fig. 3). when treating "wash ore" a finished concentrate can be produced by the log washers and Akins classifiers, as the separation involves only fine silica (minus 48-mesh) and free iron. However, when "jig ore" is led to the washing plant the coarse

Jan 1, 1947

By A. W. Faheneald, Lewis S. Prater

By taking advantage of the fundamental difference between screening and classification—namely, that specific gravity has no effect on screening but is one of the important factors in classification—a combination of the two may be used as a process of mineral concentration. Although this fact is not new, so far as is known it has had little or no commercial application. The scheme is not presented now as a process for producing finished products but rather as a preliminary operation rejecting part of the barren material from an ore before it is subjected to more costly treatment. That is largely the function of the new heavy-media concentration processes that have been widely accepted. Original installation costs for the present sink-float processes are relatively high, however, which confines their use to operations where large tonnages are handled. Sink-float has been successful on only the relatively coarse (approximately plus 10-mesh) portion of an ore, and it is in this same range that classification screening can function most satisfactorily. Theoretically, there is no upper limit to the size of particles that can be handled in a sink-float operation, but the degree of liberation in the very large pieces usually limits this. With classification screening, particles from % to % in. would be the largest that could be handled, but the lower range could be extended somewhat below 10 mesh. In order to take full advantage of the difference in specific gravities of the minerals being separated, sorting in the classifier should be under as extreme hindered-settling conditions as possible. Laboratory tests have been made on a galena ore and on an artificial mixture of quartz and magnesite to determine the separations that may be expected. Although more than one scheme may be followed, in these tests the separations were made by cutting the underflow from the classifier as a concentrate and then screening the overflow. The screen oversize was rejected as a tailing. Classification was done in a hindered-settling teeter column and screening was done by hand, using the standard 4 2 series. The accompanying flowsheet gives the testing procedure followed.

Jan 1, 1947

By W. M. Bertholf

In 1945 tests were made in the coal washery of the Colorado Fuel and Iron Corporation, at Pueblo, Colo., to determine the value of the Humphreys spiral. So far we have demonstrated that it is of definite value to us in rewashing a portion of our table middlings; and we are fairly certain that this is not necessarily the only place in which it can be used to advantage. Because of manpower and material shortages, experimental work has been discontinued for the present. Three of the spirals are being installed for use in rewashing the middlings, and testing and experimental work will proceed when this installation is completed. All evidence secured so far points to the fact that the spiral call make an effective separation of heavy material below 8-mesh; but that it is ineffective in removing larger, heavy material. This, of course, will limit its use to fine coal or a classified feed containing no heavy material larger than 8-mesh. In considering the results of our tests, it should be noted that the feed was our table middling, and that any real separation of this material is a "moral victory)" as there is little material that could be properly called coal and practically no heavy rock, the consequence being that previous attempts to clean the middlings have not been at all successful. Several articles dealing with the spiral and its use in treating heavy minerals have already been published,' but for the benefit of those who have not seen these we include a brief description of the spiral and of the way it operates, taken from Bulletin 4 of The Humphreys Investment Co.: The Humphreys Spiral Concentrator consists of a spiral conduit of modified semicircular cross section. Ore pulp is fed to the top and, as it flows downward, the heavier particles concentrate in a band along the inner side of the pulp stream (Fig. I). Outlets for removal of products are located at the lowest points in the cross section of the conduit. Wash water, added at the inner edge of the stream, flows outwardly across the concentrate band. The width of concentrate band removed at the outlets is controlled by adjustable splitters. Concentrate is usually removed from the upper portion of the spiral and middling from the lower portion. Tailing is discharged from the lower end. Tests are usually made in closed circuit, since this provides a maximum of information with a minimum amount of sample. Fig. 2 shows the spiral set up for closed-circuit testing, and gives a good idea of the general arrangement of such an installation. The small cyclone separator is used to provide clean wash water without introducing additional water into the circuit.

Jan 1, 1947

By E. H. Rose

The question is often pondered whether the flotation process is still an art or has become a science. The fact is that flotation is a science in so many variables that only art can blend them. It is demonstrable that no less than one hundred variables are involved in any flotation operation, most of them immeasurable on a routine basis. The behavior of every one of them is always governed by orderly and unchanging law, as no man can doubt. There is nothing truly indefinite about that behavior; the only indefiniteness is in our knowledge of it, either in general or from hour to hour in the circuit. In dealing with a simultaneous equation in, say, one hundred variables, all not only affecting the outcome to some degree but many influencing each other as well, it is small wonder that the mineral-dressing profession presents a case history of debate and controversial opinion. The statement of the subject of this symposium—a symposium on flotation machines—seems to delimit and define the matters to be considered and at least the general nature of the conclusions sought. Nevertheless, in such a meeting it is not possible to meditate upon all the variables that do in one way or another affect performance of flotation machines. To attempt it would be much like trying to operate a hundred-ring circus. Perverse variables being what they are, one could expect the elephant in ring 36 to squirt a trunkful of water at the tightrope performer in ring 37 to ruin that artist's act, just as our learning to depress pyrite in the early 1920's ruined the act of the formerly faithful old Callows. Honest Disagreements Selective flotation dates from 1922 or 1923, when several plants established their regular flotation operations on a selective basis. Since then, two decades of efforr have gone into the development of better and better flotation machines. Many have come and gone. The competition has simmered down to perhaps a dozen machines, each one of which is staunchly defended by some operators as being the best for their particular jobs, and as scornfully dismissed by at least a few others elsewhere as being positively the poorest for theirs. These disagreements are honest disagreements, honestly arrived at after plenty of sweat. In many a flotation plant, one machine has been tried out against another under conditions as fair as they could possibly be made. Sometimes the results are on a par but more often one machine shows a consistent and unmistakable margin of superiority over the other. In equally honest and enlightened tests, machine A may win over machine B in one place, and machine B over machine A by as great a margin in another. This paper purposes to identify some of the more prominent reasons why this is so,

Jan 1, 1947

By Gustav S. Preller, A. M. Gaudin

For the past 20 years it has been generally accepted that the flotation process is made possible as a result of the action of certain chemical substances on the surface of the mineral particles. In fact, it has been suspected, but never demonstrated, that this action produces on the mineral particles a layer of chemosorbed ions that is of the order of magnitude of a monolayer; that is, of a layer one ion deep. It is the purpose of this paper to present certain initial results on the relationship of mineral surface area and collecting-agent requirements. Up to about eight years ago, all considerations involving the surface area of finely divided solids were limited by the fact that there was not in existence any general method for determining the extent of such surfaces, especially on mixed materials. However, the method invented by Brunauer, Emmett and Teller1 has changed the situation by providing a general procedure (BET method). This procedure has already been applied to mineral dressing problems2-4 and has now received confirmation as to accuracy by an entirely independent method.' This confirmatory or "absolute" method uses a very tedious calorimetric procedure and is not suitable for routine determinations; but still another method6 now is available to relate the results obtained by the BET method to those obtained calorimetrically. This Harkins-Jura method has the advantage that it does not require an assumption concerning the parking area per molecule of adsorbate (nitrogen). In the original work by Brunauer, Emmett and Teller the parking area per nitrogen molecule was calculated to be either 13.8?2 or 16.2?2. according as the nitrogen was assumed to be closely packed as in crystalline nitrogen or loosely packed as in liquid nitrogen. The initial experimental work from this laboratory2 supported the 13.8?2. figure; that work was done on glass spheres of measurable geometric area and it was based on the assumption that the glass spheres were truly smooth; any deviation from this assumption would, of course, have made the calculated parking area higher. Harkins and Jura's results suggest that the parking area is not the same for all substrata; furthermore, the average of the 87 measurements cited indicates a "preferred" parking area for the nitrogen molecule of about 15.2?2., with extreme values at 13.7 and 16.9?2. The average of 21 determinations made in connection with this study7 gave a parking area of 14.3 ± 0.27?². In view of this result and of the Harkins and Jura

Jan 1, 1947

By M. D. Hassialis, A. F. Taggart

ark' observed some years ago that collector-coating reactions with xanthates and with fatty acids clearly follow paths parallel to those prescribed by the familiar mass-action law for reactions in dilute solutions. He proposed, therefore, the logical hypothesis that they are governed by the solubility-product principle. However, he went astray in the application of his proposal to collector coating by overlooking the fact that coating involves a heterogeneous reaction. A mistaken concept of the meaning of the word adsorption also entered. Wark thought that the concentration of metallic ion that must be used in setting up the solubility-product equation for the coating reaction was that which could be obtained by solution of the mineral. Since this is very low for sulphide ores, and since the amount of the collector ion necessary for coating produces an extremely low concentration, the resulting ion-concentration product, under conditions when coating occurs, is much lower than that which would indicate a saturated solution of the collector-coating compound. Hence he was forced to the position that the solubility product governing the coating is much smaller than the standard solubility product. To justify this position it was necessary to postulate a coating mechanism that did not obey the ordinary laws of chemical reaction. This Wark did by adopting the concept that adsorption is a property of matter, rather than merely a more or less ephemeral local concentration thereof. Thus he says (p. 142 of ref. I): "Adsorption is not a purely physical property of the solid surface, for the specific nature of the adsorbed molecule or ion is important." The result was that he destroyed the great potential utility of his postulate by tying it to this erroneous concept in the words (pp. 142, 143): "It will be obvious that the adsorption solubility product is less than the normal solubility product." The writers have found quantitatively in the case of galena and potassium ethyl xanthate, and semiquantitatively in the case of covellite and the same collector, that the coating reaction does follow the mass-action law to the extent that coating occurs when the ordinary solubility product of the coating compound is exceeded, and that coating does not take place under the reverse conditions. In the course of the investigation leading to the establishment of this fact it was necessary to work with xanthate concentrations so low (down to 0.0004 mg. per liter), that very long conditioning times, and bubble-contact times of as much as 16 hr. were necessary sometimes to follow the reactions. The results have led to some illuminating conclusions as to necessary collector concentrations in normal flotation operations, and the action of the frothing agent in connection therewith' The experimental work comprised accurate determination of the standard solubility product of lead ethyl xanthate, development of a much less laborious

Jan 1, 1947

By A. F. Taggart, Nathaniel Arbiter

The chemical reaction occurring in collection of nonmetallic minerals with amine-type collectors was early postulated by students of flotation phenomena to be metathesis between the mineral and the collector, involving exchange between the amine-bearing (aminium) ion and the cation of the mineral, and formation at the mineral surface of an oriented film of the amine salt of the mineral anion. Qualitative evidence of exchange has been obtained on several occasions at Columbia. Thus 1000 C.C. of a solution containing 495 mg of laurylamine hydrochloride was shaken 17 min. with 100 grams of barite and ground in a porcelain mill to pass a 200-mesh screen; the mixture was then set aside for 48 hr. Filtrate therefrom analyzed 476 mg. per liter of laurylamine hydrochloride. There was no substantial loss of chloride ion (78.4 mg. per liter in the original; 74 in the filtrate). No successful analyses were concluded for barium ion. Earlier, confessedly rough work with scheelite indicated a solution gain in Ca++ equivalent to about one-half the aminium ion lost. Real quantitative roof of the exchange, in the form of an established stoichiometric balance, is unknown to the authors. The data of the present paper, however, obtained from experiments designed on the basis of the exchange hypothesis, constitute strong evidence of its truth, and at the same time point the way to economic utilization of the expensive nitrogen-bearing collectors in concentration of the low-priced nonmetallic minerals. The basic postulate underlying the experiments performed was that, if the collecting reaction is of the type R+ + Y- + MX = RX + M+ + Y- where R = aminium ion, Y = the anion of the amine salt, and M and X are, respectively, the cation and anion of the mineral, the reaction should obey qualitatively the implications of the mass-action and solubility-product laws. This is to say that coating and collection should be aided by the addition to the solution of either ion (R+ or X-) of the collector-coating compound, and hindered by the addition of either of the ions M+ or y-. Experimental work comprised determination of (,) the relative solubilities of the laurylammonium salts of a variety of nonmetallic-mineral anions; and (21 the contact angles' of various minerals in solutions containing different concentrations of the postulated controlling ions. Semiquantitative flotation tests were run With barite as checks on the diagnostic character of the contact angles. The amine

Jan 1, 1947

By G. Gutzeit

An inner complex is a cyclic chemical structure containing an inorganic cation that is bound simultaneously to several atoms in a single organic molecule; on the one hand by means of ordinary valence bonds (electron exchange), on the other hand through the action of the electric field thus created, which satisfies the so-called secondary valences. The relative positions of the salt-forming and complex-forming groups are such that most frequently a four, five, or six-membered ring results through this double attachment of the cation.1-6 The formation of inner-complex ring systems depends not only upon the nature and suitable position of the salt-forming and complex-forming groups for ring closure, but, to a great extent, also on the nature of the metallic cation entering the reaction. This selective character of chelate-forming organic compounds is one of their most interesting and most valuable properties. As a matter of fact, the largest number of their practical applications is based upon their specificity.4,7-l3 Once a chelate compound is formed, its character is definitely "organic" in nature. In other words, its properties are conditioned to a much larger degree by the carbon chains or rings than by the metallic atom. Many inner complexes are soluble in nonpolar solvents such as benzene, paraffin oil or carbon tetrachloride, while the chelate-forming reagent before closure of the metal-organic ring is water soluble. (Example: copper complex of salicyl-aldoxime') It is obvious that such particular properties as those indicated above can be utilized whenever specificity and practically complete binding of inorganic ions into an undissociable complex are required. One of the well-known applications of chelate-forming compounds has been the development of specific reagents in analytical chemistry, creation of the spot-test method,4,14-16 and the application of the same principles to the contact print method for determining minerals." Chelate-forming Compounds as Collectors In the field of flotation, where selectivity is often a quality of paramount importance for the collector, various workers have lately attempted to apply their knowledge of specific organic analytical reagents to this purpose. A. C. Vivian18 has concentrated cassiterite by using ammonium nitrosophenylhydroxyl-amine (Cupferron) C6H5NO(=NONH4). Holmanl9 has tested dimethylglyoxime for the flotation of nickel oxide minerals, while deWitt has shown in a series of systematic experiments that alpha-diox-imes were generally selective collectors for nickel ores. Taurin NH2(CH2)2S03H has been proposed for the concentration Of Oxidized lead ores.19 Diphenylthio-carbazone

Jan 1, 1947

By J. Rogers. K. L. Sutherland, E. E. Wark, I. W. Wark

Soaps have hem used as collectors for many years, but only in the last eight years have other long-chain paraffin salts been used. It may be anticipated that these newer collectors will be used mainly with nonsulphide minerals, for which the xan-thates and similar compounds are of little value. On the other hand, the xanthates are both cheap and effective for sulphide ores and seem likely to retain their present cminence in this field. During 1938 and 1939 two of us (E. E. W. and I. W. W.) commenced a comprehensive investigation of the principles underlying the use of paraffin chain salts as flotation reagents. This research was sponsored jointly by the University of Melbourne and a group of Australian mining companies. † A broad, semiquantitative survey was then made of the field covered in the present paper. This was followed in 1940 by further work by one of us (K. L. S.). In 1941 the investigation was taken over by the Division of Industrial Chemistry of the Commonwealth Council for Scientific and Industrial Research, Australia. Discovery of some principles upon which are based the flotation of minerals by paraffin chain salts was followed by their application in the development of processes for the recovery of certain strategic minerals from their ores. Promising results in the flotation of cassiterite from various ores will be described in a subsequent paper. The Paraffin Chain Salts 'he basic requirements for a "collector " in flotation are that it should form a film over the surface of the mineral to be floated, and that this film should be orientated so that hydrocarbon (nonpolar) groups form the effective surface. When modified in this way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince23 that such a film can be produced only if the collector compound contains an active (polar) group to attract it to the mineral surface as well as the nonpolar group. One section of this large class of polar-nonpolar compounds is the paraffin chain salts: CH3(CH2)nX where .X signifies a polar group that ionizes in aqueous solution. Though the compound can ionize, it may be a weak or a strong electrolyte, and the hydrocarbon chain may be in the cation or the anion (Table I). Many compounds of similar constitution are available, but the usual polar groups are: -Co2Na, -So3Na, -So4Na, — PO4Na2, or an aminonitrogen group, the

Jan 1, 1947

By K. L. Sutherland, J. Rogers

The relationships between collector and mineral, activator and mineral, and activator, collector and mineral will be considered herein. We propose to criticize current theories of flotation but we will not repeat the many pertinent arguments presented by Wark and Cox28 in 1937 in which the "chemical" or more strictly the "solubility" theory proposed by Taggart and co-workers22 is shown to be untenable. Recently Taggart, Arbiter and Kellogg24 have studied the long-chain aliphatic amines as collectors and have attempted to resuscitate the solubility theory for these particular collectors. Dean and Ambrose3 have felt that "we stumble over words" when we distinguish different mechanisms of adsorption. Our view is that nothing is more stultifying to the development of a science than attempts to force widely different phenomena into one classification. This oversimplification leads immediately to difficulties in the interpretation of results. Experimental Procedure The response of minerals to activator and collector was determined by "captive-bubble" tests. The methods of preparation of specimens26 and of testingin have been previously described. Results from captive-bubble tests were confirmed by flotation tests in glass-stoppered cylinders.26 The full lines shown in the figures relating solution composition to contact (flotation) distinguish solutions in which contact (flotation) is possible from those in which it is not. The curve is derived by successive approximation and the accuracy is ±o.2 pH units and ±5 mg. per liter of collector or depressant. Solution compositions for which it was shown experimentally that contact or flotation is possible are marked by a circle, those for which it is not possible by a cross and those for which it is doubtful by a cross within a circle. It is assumed that at all other solution compositions within (without) the curve, contact or flotation is possible (not possible). After testing in the collector solution, the mineral was removed, washed, and tested by the captive-bubble method in water, or floated in a cylinder with frother only. In this way the composition of solutions in which a mineral was conditioned but in which properties of the collector solution prevented contact or flotation can be defined. The composition of solutions in which conditioning was possible lie between the full and broken curve, the experimental results being indicated on the figures by a square. The curves show the limits of composition of solution in which flotation in a cell would be possible. Many factors other than those considered in these tests determine recovery or grade of a given mineral in practice.

Jan 1, 1947

By Kenneth C. Vincent, A. M. Gaudin

In a study1 of the action of amyl xan-thate on chalcocite in water suspension, it was found that if the xanthate is added in relatively large quantity the xanthate group can be accounted for in three forms: (1) as xanthate ion remaining in water, (2) as benzene-soluble cuprous xanthate on the chalcocite, (3) as a benzene-insoluble coating on the chalcocite. Reduction in the amount of xanthate added leads to disappearance of form I then of form 2. With minute quantities of added xanthate, substantially all the reagent is of the "unleachable" kind. Yet this unleach-able xanthate can be dissolved by pyridine to form a soluble cuprous xanthate complex, and it is sufficient in effectiveness to make chalcocite flotable even if insufficient in quantity to form a complete mono-molecular film on the mineral. In that study it was also found that chalcocite abstracts cuprous xanthate from benzene so1ution, in what may (or may not) be a case of molecular adsorption. It seemed desirable, therefore, to study further the "unleachable" xanthate on the chalcocite, and particularly to ascertain whether it is formed as a result of the benzene leach or is actually formed during the conditioning of chalcocite in aqueous xanthate solution. A 'splendid tool to make such studies has recently been perfected; that is, the use of radioactive spies or tracer atoms. With this tool, it was thought possible to answer the problem stated above, but, unfortunately, this did not prove to be true. Answer to the flotation question was clouded by the existence of rapid and selective diffusion of copper atoms in the solid mineral—a phenomenon that was totally unexpected yet remains interesting and perhaps important. Method of Radioactive Spies The method of radioactive spies is discussed in many places. Two convenient references are the article by Evans2 and the book by pollard and Davidson.3 The method was first developed by van Hevesy and paneth in 1013, when only natural radioactive isotopes were available. These isotopes are few in number, and so the method remained limited in scope. Recently the synthesis of over 350 active isotopes of all the known stable chemical elements4 has opened widely expanded possibilities for the method, A fundamental tenet of the method is that a radioactive atom and a nonradio-active atom are exactly alike until disintegration of the radioactive atom. Then, by its sudden death, the spy reveals its location. The relative abundance of spies at various locations makes it possible to ascertain the relative abundance of the corresponding nonradioactive atoms at the same times and locations. A second fundamental tenet of the method of radioactive tracers is that the radioactivity lies in the nucleus of the atom: transfer of radioactivity from one

Jan 1, 1947

By S. C. Sun, A. M. Gaudin

This paper presents the results of a. study of the relationship of the electrokinetic or zeta potential to flotation phenomena. The relationship is established on the experimental evidence that mineral behavior in flotation and in cataphoresis is generally governed by the chemical properties and amount of the reagents adsorbed at mineral surfaces. Cataphoresisl-5 or electrophoresis is the name given to the movement of a charged particle in a liquid medium under the influence of an applied electric field. Mineral behavior in cataphoresis, as indicated by the magnitude and sign of its ionic charge, can be represented by the term zeta potential. In this paper, the zeta potential represents the difference in potential between the immovable liquid layer attached to the surface of a solid particle and the movable liquid layer in the body of the liquid, and is the result of the tendency of ions on the surface of the particle and within the liquid boundary layer to establish a condition of equilibrium. A high positive zeta potential means that the mineral surface is dominated by cations, a high negative zeta potential indicates domination by anions, and a low zeta potential indicates that the surface is influenced almost equally by cations and anions. In terms of observed quantities the zeta potential is given by the relation _ 4µ(300)² Z= kx in which z is the zeta potential expressed in in volts, µ the viscosity of the solution in poises, u the velocity of particles in centimeters per second, x the impressed potential gradient in volts per centimeter, and k the dielectric constant of the solution in c.g.s. units. A convenient source for the derivation of the equation is the book by Thomas. The term zeta coefficient is an expression coined to denote the difference between the magnitude of the zeta potential of a mineral suspended in solution A, and that of the same mineral suspended in solution B, which consists of solution A and an additional chemical agent, but is at the same pH. For example, the difference between the zeta potential of galena particles in distilled water and that in any chemical solution at the same pH is a zeta coefficient. Or, when the zeta potential of a mineral particle is measured first in distilled water, then in a mixture of water and copper sulphate, and finally in a mixture of water, copper sulphate and xan-thate, we can calculate the zeta coefficient

Jan 1, 1947

By Herbert H. Kellogg

In 1930, Taggart, Taylor and Knoll1 found that addition of various electrolytes to suspensions of ground minerals resulted in the stopping or starting of Brownian movement of the suspended particles. On the basis of the many new facts found, they rejected the " classical"† theory of Brownian movement and proposed an "ioniza-tion " theory. This new theory was further supported in later publications by Taggart.3,4 The acceptance of the ionization theory by men in the field of flotation may be judged by the mention given this theory in Gaudin's "Principles of Mineral Dressing,'16 Wark's "Principles of Flotation,"8 as well as in a recent paper by Fitt, Thomas and Taggart.7 The proponents of the ionization theory have gone further than the mere statement of the new theory. A parallelism between the Brownian movement of mineral particles and their behavior in flotation was reported.1,3,4 Likewise, the correlation between flocculation-dispersion of mineral particles and the Brownian movement of these particles has been investigated.' Bankoffl5 has suggested that "slime-coating" can also be directly correlated with the Brownian movement of the slime particles. In each of the instances mentioned it is the ionization theory of Brownian movement that has been used to "explain" the correlations that were found. The essential conflict between the kinetic theory and the ionization theory can be understood best by a brief description of each. The kinetic theory* proposes that Brownian movement is caused by the impacts of liquid molecules against the solid particles. At any instant of time, the molecular impacts on all sides of the solid particle will not balance, and the particle will receive a push in some direction. According to this theory, dl particles suspended in a liquid are in Brownian movement. However, if the particle is very large, the impacts on all sides will very nearly balance and the motion will not be noticeable. Another factor, besides the size of the particle, that affects the magnitude of the Brownian movement is the viscosity of the liquid—the greater the viscosity, the less the displacement of particles by Brownian movement. This theory has been verified experimentally by measurement of the velocity of Brownian movement, and by measurement of the compacting of suspensoid particles under the influence of gravity.2 The originators of the ionization theory found that he addition of various electrolytes to slime pulps caused cessation or commencement of Brownian movement, depending upon the chemical nature of the particle and the electrolyte. The Brownian movement of quartz particles was observed to stop upon the addition of Certain electrolytes, where the conditions of the experiment prevented flocculation

Jan 1, 1947

By W. T. Bishop

For many years pine oil has been used extensively as a frother for the flotation of minerals, particularly sulphides, yet the published information available to the average user on its composition, chemical and physical properties, has been rather meager. It is the purpose of this paper to discuss these points and their relationship to the frothing properties of pine oil used in flotation processes. Pine oil, as the name implies, is a liquid obtained from the processing of wood of the longleaf and other southern pines. It is a complex mixture of naturally occurring terpene derivatives, primarily alcohols, and a smaller amount of terpenes, which has found many uses in various industries. Its use as a frother in flotation processes was the first large-scale application in industry and today the mining industry still consumes large quantities of pine oil but the textile and disinfectant industries consume comparable volumes. Much is used in soap manufacture and laundry operations. The surface-active properties of pine oil are in a large degree responsible for this versatility. History The name "Naval Stores" goes back to the days when pine tar and pitch were used to caulk leaky ships and 'Oat their ropes and rigging. Today this term is still used to include not only the oleoresinous products of the pine tree—rosin and turpentine— but other products such as pine oil, pine tar, and the many terpene and resinous compounds obtained by extracting the pine wood or tapping the tree. That part of the industry known as "wood naval stores" dates from about the beginning of this century and today produces a large part of the country's rosin and turpentine by processing pine wood. In addition, all of our natural pine oil is supplied by the wood naval stores industry, as tapping of the live tree gives only rosin and turpentine. This latter phase is known as the "gum naval stores " industry. The first successful commercial operation of the steam and solvent process of the wood naval stores in industry was carried out by Yaryan at Cadillac, Mich., in 1909.1 This operation did not prove profitable, so Yaryan went south to utilize the longleaf pine, and built a plant at Gulfport, Miss.2 Soon after, another plant was built at Brunswick, Ga., which is still in operation, and in 1914 was reported to have processed about 500 tons of wood per day.' In 1921 Hercules Powder Co. acquired the Yaryan interests, at which time the production of pine oil was only 3 to 5 million pounds per year and flotation was the largest customer. As time went on, technological advances were made, other companies entered the field, and the production of pine oil increased many fold. The growth of the industry was especially marked during the past 10 years, and in

Jan 1, 1947

By W. A. Bates, R. J. Miller

Although cresylic acids have been standard frothers in flotation for many years, there has been little discussion of their nature in the metallurgical literature. Aside from references in the patent literature, the paper by Landolt, Hill, and Lowyl in 1930, which resented a study of the frothing and collecting properties of some of the constituents of crude cresylic acids, represents the only contribution of this type. The close froth control required in the delicate selective separations of present-day flotation operations have required the flotation metallurgist to choose his frothers with care, and have caused him to require of the manufacturer a closely controlled, uniform product. A background of knowledge of the chemical composition and physical and chemical properties of the frothers, by which their action may be correlated, should aid in selecting frothers for particular flotation requirements. Further, the recent almost complete replacement in flotation of coal-tar cresylic acids by those derived from petroleum makes it especially desirable to review the flotation behavior of the acids from the old and the new sources. In view of these facts the Milling Methods Committee of the A.I.M.E. suggested to the Oronite Chemical Co. of San Francisco the preparation of a paper on the subject, and this paper has accordingly been prepared as a contribution by the California Research Corporation, the research affiliate of the Oronite Chemical Co. The discussion is from the following aspects: (I) constitution and properties; (2) sources; (3) comparison of coal-tar and petroleum cresylic acids; (4) characteristics as frothers, with particular reference to the effect of the substitution of petroleum acids for coal-tar acids. Constitution and Properties Cresylic acids are commonly regarded as mixtures of orthocresol, metacresol and paracresol. This was, indeed, the former meaning of the term, but in recent years it has been loosely applied to any mixture of alkyl phenols boiling above 190°C.; that is, excluding only phenol itself. This means that cresylic acids, as they are known today, may consist of mixtures, not only of the three isomeric cresols, but of six xylenols and of a variety of higher boiling homologues. Generically the constituents of cresylic acids are alkyl phenols, and they are often so designated in the literature to avoid the more indefinite term, "cresylic acids." They form an homologous series starting with phenol, which has the familiar benzene ring, with an hydroxyl group in place of one of the hydrogen atoms. The series of alkyl phenols is formed by the substitution of alkyl side chains, such as methyl, ethyl, propyl, butyl, etc., for hydrogen atoms of the benzene ring of phenol. Some

Jan 1, 1947