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Molecular modeling and rational design of flotation reagents
Pradip*, Beena Rai
Tata Research Development and Design Centre, 54B, Hadapsar Industrial Estate, Pune 411013, India
Received 15 January 2003; received in revised form 10 March 2003; accepted 30 June 2003
A scientific design methodology based on molecular modeling tools available today is presented for arriving at the most suitable reagent combinations for a given flotation separation problem. The power and the utility of this approach are illustratedwith examples taken mainly from our work on mineral flotation with alkyl hydroxamates.
2003 Elsevier B.V. All rights reserved.
flotation reagents; atomistic simulation; hydroxamates; phosphonic acids; molecular modeling; force field
1. Introduction
The design and the selection of highly selectiveflotation reagents for specific applications remain achallenging task. Most commercially successful flo-tation reagents were discovered largely through a trialand error methodology based on educated guesswork and empirical rules of thumb. For the beneficiation of multicomponent, highly disseminated and difficult-to-treat ore deposits, the conventional approaches of reagent design and selection are likely to provewoefully inadequate. Considering the demands madeof reagents, namely, cost and efficiency/selectivity,coupled with environmental constraints, the scientificchallenge facing the mineral engineers today lies indeveloping highly selective reagents customized for aspecific task (Pradip, 1994).Moreover, there is now a  perceptible shift in the mining chemicals industry todesign and market tailor-made performance chemi-cals customized for specific applications rather thanoffer conventional, generic, multi purpose commoditychemicals as flotation reagents(Cappuccitti, 1994;Malhotra, 1994; Nagaraj et al., 1999).A critical review of the recent literature on thistopic(Somasundaran and Nagaraj, 1984; Nagaraj,1988; Pradip, 1988, 1991, 1997, 1998; Marabini et al., 1989; Fuerstenau and Herrera-Urbina, 1989;Aplan, 1994, Fuerstenau, 1999a,b; Klimpel, 1999;Ackermann et al., 2000; Pradip et al., 2002c)clearlyreveals that there is an urgent need to develop atheoretically robust framework that can provide arational basis for design and selection of novel reagent combinations for specific applications. Some of theimportant issues that need to be addressed in thiscontext are discussed in the following paragraphs.It is not only intuitively obvious but also borne out  by several examples in flotation practices that theselectivity of flotation reagents is determined to alarge extent by the molecular recognition phenomenaunderlying their adsorption at mineral/water interfaces(Pradip, 1994).Recognition at a molecular level is a
0301-7516/$ - see front matter 
2003 Elsevier B.V. All rights reserved.doi:10.1016/S0301-7516(03)00090-5* Corresponding author. Tel.: +91-20-4042309; fax: +91-20-4042399.
 E-mail address:
pradip@pune.tcs.co.in (Pradip).www.elsevier.com/locate/ijminproInt. J. Miner. Process. 72 (2003) 95–110
fundamental characteristic of several natural systemsinvolving a wide variety of organic–inorganic inter-faces(Mann, 1988; Weissbuch et al., 1991; Schneider,1991; Lehn, 1993; Abbott, 2001). These molecular recognition mechanisms are essentially based on thestructural/stereochemical compatibility between themolecular architecture of the adsorbing reagent andthe specific surface structure (the nature and thespatial arrangement of adsorption sites on the surface)of the substrate it is interacting with. The strongtemplating effects of the surface have been notedand documented in several cases(Black et al., 1991;Davey et al., 1991; Grases et al., 1991; Heywood andMann, 1992; Arad et al., 1993; Bromely et al., 1994;Pradip, 1994; Ravishankar et al., 1995; Manne andGaub, 1995; Coveney et al., 2000; Davey andRebello, 2001; Rai and Pradip, 2002; Osman andSuter, 2002). It is our contention that one can enhanceselectivity of flotation reagents by orders of magni-tude if we are able to identify the specific molecular recognition mechanism and design the moleculaarchitecture accordingly for a separation task whichinvolves several competing surfaces for the sameflotation reagent. It is therefore imperative to identifyand catalogue different kinds of molecular recognitionmechanisms controlling selectivity in flotation sepa-ration systems that are already known to be amenableto a high degree of separation efficiencies. Thisapproach should help us in providing a scientificrationale as well as a methodology for designing moreselective reagents. It is similar to designing a targeteddrug delivery system guaranteeing the required quan-tity of specific drug molecule to reach the desiredactive site among so many other competing sites in biological systems.Aforementioned strategy is, however, incompletesince there exists a whole host of molecular recogni-tion mechanisms that can be utilized to design severalfamilies of molecular architectures as possible candi-dates for the separation problem under investigation.Since it is not possible to synthesize all possiblemolecules and test each one of them to confirm their efficacy, there is a need for a sound, robust and, most importantly, a quantitative methodology to screen andshortlist the most promising ones from the list of  possible candidates. It is in this context that we have proposed and validated a methodology based onmolecular modeling computations. While there areseveral limitations in this approach and efforts areunderway to overcome them, our results suggest that the essence of the underlying molecular recognition phenomena can certainly be captured in the interac-tion energy computations with the available tools. Inthe absence of any other quantitative methodology for selection, molecular modeling is, in our opinion, the best and most reliable option available at present.We have made considerable progress in developinga robust and reliable methodology based on molecular modeling tools to arrive at the most promising mo-lecular structures for the separation problems whichare considered not amenable to or too complex for asatisfactory solution(Pradip and Rai, 2002; Pradip et al., 2002a,b,c). In this communication, we describethe most important components of this novel para-digm of reagent design with the help of our recent work on alkyl hydroxamates, a relatively new familyof flotation reagents, commercialized recently in themining industry. We demonstrate how molecular modeling tools available today can be gainfullyemployed for reagent design in this area.Firstly, one can design and screen and thus pro-gressively narrow the focus on preferred molecular architecture for a given mineral surface which is basedon the interaction energies computed through a com- pletely theoretical methodology of molecular model-ing. Since this search is based on completelytheoretical computations, one can evaluate a muchlarger number of molecules than what is possible withconventional trial and error experimental approaches.Secondly, based on similar computations, it is possible to select the most efficient (which may not  be the most selective) reagent from several possiblecandidates for a given separation task involving morethan one mineral surface. This selection is based onnot the affinity of a reagent for a particular mineralalone, but a comparative assessment of its ability todiscriminate among several competing surfaces. Thereagent to which a particular mineral responds the best need not be the most preferred choice in case of multicomponent systems.Several other research groups are currently en-gaged in studying surfactant–surface interactionsusing molecular modeling tools(Coveney andHumphries, 1996; Frank et al., 1996; Goddard et al., 1997; de Leeuw et al., 1998; Hass et al., 1998; Numata et al., 1998; Shevchenko and Bailey, 1998;
 Pradip, B. Rai / Int. J. Miner. Process. 72 (2003) 95–110
de Leeuw and Parker, 1999; Hirva and Tikka, 2002;Tunega et al., 2002). We present in this paper theresults of our molecular modeling computations onthe interactions of alkyl hydroxamates with severalminerals of interest. Alkyl hydroxamates have beenfound to be highly selective flotation collectors for awide variety of minerals such as those containingiron, rare earths, tin and tungsten minerals, kaolinand, more recently, for separation among calciumminerals includingflotation separation in apatite– dolomite system(Fuerstenau et al., 1967, 1970,1983; Fuerstenau and Petersen, 1969; Gorlovskii et al., 1969; Bogdanov et al., 1973; Evrard and DeCuyper, 1975; Fuerstenau and Pradip, 1984; Pradip,1987, 1996; Ravishankar et al., 1988; Pradip andFuerstenau, 1989, 1991; Pradip et al., 1991, 1993,1995, 1997; Yoon et al., 1992; Pradip and Chaudhari,1997; Lee et al., 1998; Miller et al., 2001a,b). As presented in the following sections, trends predictedon the basis of theoretically computed interactionenergies correlate quite well with our own experi-mental microflotation results as well as with thoseavailable in the published literature.
2. Molecular modeling methodology
While we have utilized both the quantum chemicaland force field (also known as atomistic simulation)computations in our work, for the sake of uniformity,all the results presented in this paper are confined tothose obtained with one technique only, that is, theuniversal force field (UFF)(Casewit et al., 1992a,b,Rappe´et al., 1992, 1993). The Cerius
 program(Accelrys, USA) has been used to model the sur-face–reagent interactions by UFF. We have success-fully demonstrated through our earlier work that UFFcan be used to model the mineral–reagent systemswith reasonable accuracy. A detailed methodology of modeling the mineral–reagent interactions has been presented recently(Pradip and Rai, 2002; Pradip et al., 2002a,b,c). A brief summary is presented in thefollowing paragraphs.
2.1. Reagent molecule
The UFF-optimized atomic structure of octylhydroxamic acid molecule along with partial chargeson the constituent atoms is shown inFig. 1.The UFF- optimized structural parameters com pare well withthose reported in literature(Table 1).
2.2. Mineral surface
A surface cell was created from the unit cell of themineral at a given Miller plane (usually the cleavage plane) and then was optimized. The surface energywas then calculated for this optimized mineral surface.For a given mineral, the plane selected was eithe based on the literature data (experimentally observedcleavage plane) or the surface energy values (the onewith lowest surface energy was considered as thecleavage plane).To establish the validity of the UFF for modelingmineral surfaces, we optimized their crystal struc-tures and compare them with experimental measure-ments(Dana and Ford, 1949).As summarized in Table 2,the UFF-predicted values of lattice param-eters are in reasonable agreement with those exper-imentally reported. The computed surface energy for corresponding cleavage plane is also included in thetable.
Fig. 1. UFF-optimized structure of HXMA-8 with partial charges onthe constituent atoms.
 Pradip, B. Rai / Int. J. Miner. Process. 72 (2003) 95–110

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