Journal of Mining Science, Vol. 45, No.

4, 2009

MINERAL DRESSING
ROLE OF DIXANTOGEN IN FROTH FLOTATION V. E. Vigdergauz and S. A. Kondratev* UDC 622.765.4

Mechanism of dixantogen action in froth flotation is discussed. It is shown that this reagent eliminates kinetic constraints during formation of a flotation complex, rather than improves hydrophobicity of a mineral surface. Flotation agent, physical and chemical sorption forms, xanthate, dixantogen, surface pressure, electrochemical polarization, induction time

Conditions, providing efficient floatability of minerals, generally comprise hydrophobization of mineral surface, elimination of kinetic constraints in formation of a flotation complex and preventive measures to escape its failure in turbulent fluxes, i.e. to gain the irreversible formation of three-phase wetting perimeter. Previous investigations imperatively indicate the necessity of a physically sorbed agent to be present at the surface of an extracted mineral [1, 2]. The lack of physical sorption forms inevitably results in suppression of flotation even at higher density of the agent chemically fixed at mineral surface. There is widely known positive experimental and practical experience in application of physically sorbed additives and their combinations with surfactants in mineral flotation. The physically adsorbed reagent is supposed to eliminate kinetic constraints in a thermodynamic opportunity to form a flotation contact. What are the kinetic constraints and what are the ways of their elimination by applying respective agents are problems to be cleared up today. Moreover, there is no commonly accepted concept in solving the problem of crucial significance in flotation, namely, identification of optimal properties of collecting agents and their combinations. The goal of the present paper is to study the effect of dixantogen, an apolar, physically adsorbed flotation reagent on fixation of a bubble at a solid surface and compare it with the proposed mechanism. Earlier was shown that a physically adsorbed reagent contributes to higher rate thinning of a water interlayer between a mineral particle and a gas bubble at the final stage of their approach [3]. The agent transits from a mineral particle to surface of meniscus formed at failure of the water interlayer and spreads over a gas bubble. Transition of a physically adsorbed reagent (oil) from a mineral particle to a new-formed meniscus surface and its further spreading over a bubble are possible when a water interlayer fails between the mentioned interacting objects. Oil spreading is initiated at free water surface bubble surface contact. Therefore, it is of prime importance to form a local perimeter of
Institute of Complex Exploitation of Mineral Resources, Russian Academy of Sciences, E-mail: vigderg@mail.ru, Moscow, Russia. *Institute of Mining, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia. Translated from Fiziko-Tekhnicheskie Problemy Razrabotki Poleznykh Iskopaemykh, No. 4, pp. 104-110, July-August, 2009. Original article submitted May 27, 2009. 1062-7391/09/4504-0398 2009 Springer Science + Business Media, Inc.
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contact for three aggregate states preferably at hydrophobic surfaces when a liquid interlayer fails. Surface flux of the spreading oil also forms a bulk water flow from an interlayer. The higher is the velocity of oil spreading at gas liquid interface, the stronger is the effect of water entrainment by an oil flux. Velocity of the film front motion (Voil, oil) is the function of surface pressure within it, difference of the active component concentration in an agent and its surface activity [4]: 0 3 / 4 d , voil = C , Voil = K t dC where is solution viscosity; t is time of film motion; d / dC is surface activity of the reagent; o is surface pressure of the reagent film; C is difference between concentrations of the active component in the reagent and in the pulp; K is numerical factor. Pressure of dixantogen spreading at gas liquid interface grows with increase in the hydrocarbon radical length (Table 1) [5]. Increase in velocity of a bulk water flow and its high-speed removal from an interlayer promotes expansion of dry spot perimeter on a particle as far as its contour. The influence of the physical agent sorption on thinning of an interlayer is observed within the period from a local rupture of the interlayer (Fig. 1a) till its thickness reaches the value at which an advancing contact angle formed at the moment of meniscus rupture reaches the value of a receding contact angle (Fig. 1b) and the wetting line reaches the size of the particle contour. Irreversibility of the flotation complex formation can be considered completed at the moment when the perimeter of the contact of three aggregate states is fixed on particle edges (Fig. 1c), namely, when the contact angle reaches the value of the receding contact angle and the wetting perimeter reaches an expanded state [3]. The fixation of the perimeter of the three-aggregatestates contact at particle edges guarantees formation of the stable flotation complex for particles of a certain size fraction. Thus, interface rupture for poorly wetted surfaces explains the selective recovery of natural hydrophobic and hydrophobizated minerals. Oil content in them eliminates kinetic constraints in formation of flotation complexes and promotes higher recovery of a valuable component. Surfactant additions to oil enhance its adhesion to water, prevent hydrophobic sliding, and intensify water drawing from an interlayer. At the final stage the approach of objects is mainly initiated under influence of a physically sorbed collector, rather than hydrodynamic forces or inertia. Thus, it is proved that kinetic constraints of a potential opportunity to form a flotation contact relates to as quick as possible water drawing from an interlayer [3]. As established experimentally, it takes less time for a bubble to fix at a solid surface containing dixantogen. Dixantogen effect on kinetics of the air bubble adhesion to a solid surface was studied on a platinum electrode [6]. Figure 2 illustrates influence of the platinum electrode potential on kinetics of electrochemical oxidation of xanthate in a neutral medium.
TABLE 1. Surface Tension and Spreading Pressure for a Number of Dixantogens
Dixantogen Chemical formula Surface tension of dixantogen, mN/m Spreading pressure , mN/m

Metyl Ethyl Propyl Butyl

CH 3 OCS2 S2 CO CH 3 C 2 H 5 OCS2 S2 CO C 2 H 5 C3 H 7 OCS2 S2 CO C3 H 7 C 4 H 9 OCS2 S2 CO C 4 H 9

45 42 39 37

27 30 33 35
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Fig. 1. Stages of the formation of contact perimeter: a rupture of interlayer and formation of local perimeter with advancing contact angle; b transformation of advancing contact angle into receding contact angle; c expansion of contact perimeter as far as particle contour

Fig. 2. Time versus kinetics of xanthate oxidation in a neutral medium at different potentials of platinum electrode. Light and dark marks show concentrations of xanthate and dixantogen, respectively

The electrochemical oxidation rate generally lowers with growth, but quantity of formed dixantogen is proportional to quantity of electricity under the Faraday law. Kinetics of a gas bubble fixation at the electrode was studied under electrochemical polarization in presence of xanthate. Induction time was measured at 20 mg/l potassium butyl xanthate concentration. Table 2 summarizes experimental data on time of the gas bubble fixation on platinum in solution containing 20 mg/l of butyl xanthate versus potential, time of anodic polarization and of solution. It is explicit that reduction in solution , rise of electrode potential and increase in time of xanthate oxidation increase dixantogen content and reduce time of bubble adhesion to platinum.
TABLE 2. Induction Time on Platinum versus Potential and Time of Anodic Polarization in Xanthate Solution in Neutral and Alkaline Media
7.52 EPt, mV 1.5 4.5 7.5 10 pH 9.18 Oxidation time, min 1.5 4.5 7.5 10 Induction time, ms pH 12.4 1.5 4.5 7.5 10

150 200 300 400 600 700

3500 3500 3500 1000 1000 1000

3000 2500 400 300 200 200

2500 450 250 250 150 150

1000 400 200 200 100 100

4000 4000 3500 3000 2000 1500

4000 3500 3000 2500 1000 450

3500 3000 2500 2000 450 400

3500 3000 2000 1000 450 350

N.a.* N.a. N.a. N.a. 2000 2000

N.a. N.a. N.a. 2500 2000 1000

N.a. N.a. 3000 1500 1500 1000

N.a. N.a. 1500 1000 1000 1000

N.a. is no adhesion

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Fig. 3. Time of air bubble fixation at platinum electrode versus dixantogen quantity formed at surface of platinum electrode in anode polarization at 700 mV potential and values: 1 7.5; 2 9.2; 3 12.5

Velocity of air bubble adhesion on a platinum electrode depends on dixantogen quantity at its surface (Fig. 3). Figure 3 illustrates some critical values of sorption density, which promotes easy adhesion. This value of sorption density is approximately 0.9 M/m2 in neutral and weakly alkaline solutions. An increase in pH value hampers the adhesion and decreases the critical thickness of the rupturing film due to the influence of sorption of hydroxyl groups. Figure 4 shows the variation in the picture of bubble detachment from the platinum electrode surface. The anodic polarization increases the detachment force (Fig. 4b). The three-phase wetting perimeter increases due to an enhancement in the bubble adhesion to the platinum surface. The better adhesion is caused by the formation of dixantogen on the electrode surface as a result of xanthate oxidation under the anodic polarization. Subsequent additional introduction of xanthate ions reduces the adhesion of bubble to the surface up to its cessation. The xanthate ions are not surface active at the liquid - gas interface; in the presence of surface active dixantogen, they are sorbed on the surfaces of bubble and platinum electrode, with their polar groups oriented to the solution, thus ceasing the adhesion (Fig. 4c). Chemical decomposition of xanthate ions by the hydrochloric acid additive restores the adhesion (Fig. 4d).

Fig. 4. Air bubble adhesion to platinum electrode: a at currentless potential; b after the anodic polarization at 500 mV potential during 3 min; c after the addition of 30 mg/l xanthate; d after the decomposition of xanthate by 0.1 M HCl solution
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The observed effect can be explained in the following way. Anodic oxidation of xanthate results in formation of dixantogen on an electrode. Xanthate residue in the solution and new-introduced extra xanthate adsorb on a dixantogen layer, preserved on the electrode. Under formation is an oriented xanthate ion layer. Apolar hydrocarbon branch is directed inward to dixantogen layer and a polar branch is directed towards the water phase. This orientation provides that oil water system has the minimum energy and hydrophobic groups tend to locate outside the water phase, while the polar branch is directed to the water phase. This location induces the formation of a denser hydrated layer around the electrode as compared to the layer composed of exclusively apolar dixantogen molecules. Formation of an oriented layer of xanthate molecules on dixantogen film improves its hydrophilic properties and worsens bubble adhesion to platinum surface. To check this statement, the test on recovery of bubble adhesion to an electrode was performed when sorbed xanthate was removed. The latter is known to decompose in the acid medium with formation of alcohol, carbon disulfide and alkali. Solution of HCl 0.1 M was introduced into the cell to decompose xanthate. Level of pH was lowered down to 3.7 by adding hydrochloric acid. The pryout force was measured on the bubble, adhesion of which to the electrode surface was earlier cancelled (Fig. 4c). The bubble recovered adhesion capability and adhered to the electrode after pH was lowered and xanthate was decomposed (Fig. 4d). Xanthate was decomposed both in the solution and in the film of sorbed dixantogen, whereby hydrophobic properties of oiled electrode improved and structuring of the hydrated layer around the electrode were broken. High efficiency of xanthates in presence of both sorption forms is explained by high velocity of dixantogen spreading and its capability to entrain water and to continue concurrent motion with the film. Interaction of water with apolar dixantogen is due to xanthate anion content in it, because xanthate anions adsorb on dixantogen film and arrange by the described mechanism. Conclusions on the oriented fixation of reagent anions and improved wettability of the surface with water are verified experimentally. As it was established, the area of a dixantogen drop spreading over hydrophobizated solid surface, immersed into water, was reduced as compared to spreading over the same surface, being in the air [7]. As soon as dixantogen drop on hydrophobizated surface system is generated in a polar liquid, the sorbed reagent anions cover the surface of an oil drop and interact with water molecules, thus hampering the bond of oil molecules with hydrophobic surface. Penetration of water molecules between oil and a solid surface prevent the drop spreading. Exposure this system to the air excludes the described orientation of reagent anions and the oil drop spreads over the hydrophobizated underlayer. It is experimentally proved that application of xanthate in combination with dixantogen improves recovery of sulfide minerals into a concentrate [8]. The maximum recovery can be provided at the optimal concentration of dixantogen, produced by electrochemical oxidation of xanthate. Further increase in dixantogen concentration lowers recovery [9], and reasons of this phenomenon are to be cleared up. It is reasonable to suppose from the above that the mechanism for suppression of flotation by excess of disulfide is similar to the mechanism for suppression of flotation by oxyhydride and cation collectors. It is a well known fact that the dominating flotation activity is provided by high concentrations of long-chain flotation collectors. Oxyhydride and cation collecting agents are surfactants and apt to adsorb at gas liquid interface. At higher concentrations the surface tension lowers for a few seconds, namely for the time, comparable with the time of air bubble life in a flotation cell. When density of reagent sorption on a bubble reaches a sufficient value, the surface tension lowers down to a value, close to the surface tension of condensed phase of carboxylic acid or amine. The
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pressure of the oil film spreading lowers and the driving force of reagent spreading reduces respectively due to difference between surface tensions of water and oil. Lack of the physical reagent sorption, namely, impossibility for the reagent to spread over bubble surface, hampers expansion of the perimeter of three aggregate states in order to reach a particle size. The length of the wetting line and, therefore, capillary adhesion force is not high enough to hold a particle attached on a bubble. The initially formed meniscus fails at the moment of particle bounce with no chance to form a flotation complex, for example, flotation of coal without an apolar agent. The expansion of perimeter for three aggregate states to the required size appears to be feasible for rather large, dense and highly hydrophobic particles, collision of which with a bubble contribute to appreciable thinning of a liquid interlayer. High hydrophobicity makes it possible to form a receding contact angle at much higher thickness as compared to fairly wettable particles. The excessive number of carboxylic acid molecules and molecular forms of amine on a mineral particle can cause saturation of gas liquid interface by oil molecules and lower surface tension. Even a few particles with surplus oil content on a bubble are enough to saturate its surface layer and to exclude fixation of other particles. Lower mineral load per a unit of air volume reduces the rate of flotation and suppresses it. The mechanism for water withdrawal from an interlayer between interacting objects fails to operate and flotation is suppressed. Similar effects are observed for higher xanthates as flotation agents. In a number of cases they fail to provide high mineral recovery into a concentrate. As the length of hydrocarbon radical grows, the flotation activity of xanthates and dithiophosphates first increases and then lowers. To conclude, the described experiments prove that the sense of dixantogen application in flotation is, in the greater degree, to eliminate kinetic constraints of the flotation complex formation, rather than to improve hydrophobic properties of mineral surface. The study was conducted with financial support from the Russian Foundation for Basic Research, Project No. 08-05-00147.
REFERENCES

1. V. I. Klassen and I. N. Plaksin, On mechanism of apolar reagent action in coal flotation, Dokl. Akad. Nauk SSSR, 95, No. 4 (1954). 2. A. A. Abramov, S. B. Leonov, and M. M. Sorokin, Chemistry of Flotation Systems [in Russian], Nedra, Moscow (1982). 3. S. A. Kondratev, Physically sorbed collectors in froth flotation and their activity, Parts I and II, Journal of Mining Science, respectively, No. 6 (2008) and No. 2 (2009). 4. D. G. Suciu, . Smigelschi, and . Ruckenstein, The spreading of liquids on liquids, Journal of Colloid and Interface Science, 33, No. 4 (1970). 5. I. A. Kakovsky and V. M. Arashkevich, Studies of properties of organic disulfides, in: Proceedings of the 8th International Congress on Mineral Processing [in Russian], Leningrad (1969). 6. V. E. Vigdergauz and A. I. Dorofeev, Electrochemical study of xanthate redox-transitions on a platinum electrode and their effect on flotation, Vest. RUDN, Engineering Researches Series, 12, No. 1 (2006). 7. B. E. Goryachev, Surface tension of dixantogen air dixantogen water interface, Tsvet. Metally, No. 11 (2006). 8. V. A. Chanturia, Perspectives of Monitoring the Degree of Oxidation of Xanthate to Dixantogen in Flotation Process. Control of Ion Composition of Ore Pulp in Flotation [in Russian], Nauka, Moscow (1974).
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