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By G. Gutzeit

METAL-ORGANIC INNER COMPLEXES 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. 4,1-13 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.17 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 nitrosophenylhydroxylamine (Cupferron) C6H5NO(=NONH4). Holman19 has tested dimethylglyoxime for the flotation of nickel oxide minerals, while deWitt has shown in a series of systematic experiments that alpha-dioximes were generally selective collectors for nickel ores. Taurin NH2(CH2)2SO3H has been proposed for the concentration of oxidized lead ores.19 Diphenylthiocarbazone

Jan 1, 1946

By L Usoni

Collectors commonly used in flotation to date fall into two main classes: ionic and nonionic. The use of neutral or oily collectors is generally limited to the flotation of nonpolar minerals onto which they are adsorbed by forces of a physical or 'Van der Waals' type, while ionizable chemical collectors are utilized for all other types of minerals, adsorption in this case involving bonds essentially of a chemical nature. Though chemical adsorption is more selective than physical adsorption, even heteropolar collectors are active towards certain classes of minerals (sulphides for example) rather than towards one individual mineral. Thus, in order to float a given mineral from a mixture of minerals belonging to the same class, modifiers have to be used to render the action of the collector more specific. However, there are often considerable difficulties involved in this procedure and the desired results are not always attained, especially in the case of minerals of complex composition whose surface properties are not sufficiently well known. Hence the importance of seeking out collectors capable of linking selectively with given minerals. Selective linkage is possible if the collector structure incorporates active groups having specific affinity for certain cations characteristic of the mineral surface. The decision to investigate the possibility of utilizing chelate--forming reagents for flotation was based on the premise that phenomena which occur in solution and involve chemical reactions in the strict sense of the meaning and those which occur on the surface are closely correlated (1)

Jan 1, 1971

By D. R. Nagaraj

Based on our finding that commercial copper chelating solvent extractants such as LIX65N® and LIX63® are excellent collectors for copper minerals, a detailed study was made using several water-soluble chelating agents belonging to the class of aromatic hydroxyoximes and having a gradual structural variation. A basic study of the system salicylaldoxime-tenorite was also carried out. Microflotation tests as a function of concentration of oxime, pH, addition of copper etc., using oxidic copper minerals such as chrysocolla and tenorite, and batch laboratory flotation tests using synthetic mixtures of quartz and oxidic copper minerals were carried out. The studies were aimed at an understanding of the collector function of the hydroxyoximes and of the general flotation behavior in these systems, in addition to studying the structural aspects of oximes vis-a-vis flotation. The results have demonstrated that all of the hydroxyoximes studied here have comparable collector property, and in all cases the oxime was found to be partitioned between the mineral surface and the copper in the bulk aqueous phase in the form of a bulk copper chelate. The occurrence of the latter could be accounted for by the formation in the bulk phase of a chelate between oxime and copper released from the mineral and/or by the detachment of the surface chelate. The role of surface and bulk chelates in flotation is discussed based on the results of partitioning of chelating agent into bulk and surface chelates in the system salicylaldoximetenorite. The effect of substitution of CH2 groups or benzene ring in the chelating agent molecule on its collector property is also discussed, in addition to the finding that only the anti-isomer has the ability to collect.

Jan 1, 1979

By P. Somasundaran, D. R. Nagaraj

Based on our finding that commercial copper chelating solvent extractants such as LIX65NR and LIX63R are excellent collectors for copper minerals, a detailed study was made using several water-soluble chelating agents belonging to the class of aromatic hydroxyoximes and having a gradual structural variation. A basic study of the system salicylaldoximetenorite was also carried out. Microflotation tests as a function of concentration of oxime, pH, addition of copper, etc., using oxidic copper minerals such as chrysocolla and tenorite, and batch laboratory flotation tests using synthetic mixtures of quartz and oxidic copper minerals were carried out. The results have demonstrated that the hydroxyoximes studied have comparable collector property, and in all cases the oxime was found to be partitioned between the mineral surface and the copper in the bulk aqueous phase in the form of a bulk copper chelate. The occurrence of the latter could be accounted for by formation in the bulk phase of a chelate between oxime and copper released from the mineral and/or by the detachment of the surface chelate. The role of surface and bulk chelates in flotation is discussed based on the results of partitioning of chelating agent into bulk and surface chelates in the salicylaldoxime-tenorite system. The effect of structural aspects such as isomerism and substitution in the molecule on the collector property of the oximes is also discussed. Substitution on oximic carbon by alkyl groups is found to promote collector activity. Only the anti-isomer has the ability to collect.

Jan 1, 1982

By Maurice C. Fuerstenau

INTRODUCTION The term, chelate, from the Greek for 'claw,' has its origin in the pincer-like representation of more than one atom of a single ligand bonded to the same metal atom, forming a ring-like structure. Depending on how many attachments exist on the sphere of coordination around the metal ion, ligands are referred to as bidentate, tridentate, tetradentate, pentadentate and hexadentate According to Calvin and Martell (1952) and Somasundaran and Nagaraj (1984), chelating agents must contain suitable functional groups, and their location within the ligand molecule must enable ring formation that is sterically possible. Typical structures that meet these requirements have been given by Fuerstenau and Herrera-Urbina (1988) and are listed in Figure 1. As noted, the functional groups of these reagents contain electron donor atoms such as oxygen, nitrogen and sulfur. Basic groups, such as amino (-NH,), are those that contain an atom with a lone pair of electrons. Acid groups are those, such as carboxylic (-COOH) which lose a hydrogen ion and coordinate with the metal atom. Examples of each of these types chelating reagents are given in Tables 1-4. The specificity of chelating agents for various metal ions has long been known and was utilized early in the search for new flotation collectors. In 1927, Vivian used ammonium nitrosophenylhydroxylamine as a collector for cassiterite. Holman (1929) tested dimethylglyoxime as a collector for nickel oxide. He also suggested taurin as a collector for oxidized lead ores. DeWitt and von Batchelder (1939) suggested the use of oximes as flotation collectors. Gutzeit (1946) conducted an extensive investigation on the use of chelating agents as collectors and as depressants for gangue minerals. The depressants are those reagents that form soluble chelates with metal ions that could function as

Jan 1, 2005

By Kuzugundenli OE, Nagaraj DR

Organic complexing agents have received special attention over the past few decades in the search for reagents for improved flotation separation of minerals, especially non-sulphides. The majority of such reagents that have been proposed over the past few decades have remained largely a laboratory curiosity, except perhaps alkyl hydroxamates, because their selection is seldom based on commercial viability. In this regard, the choice of complexing agents such as oximes may be more realistic because of their widespread use in solvent extraction of copper. Our earlier studies have confirmed that they are also effective as collectors for copper oxide minerals, including chrysocolla which is the most difficult copper mineral to beneficiate. The flotation behaviour of chrysocolla for several structurally-related hydroxyoximes were studied as a function of pH and oxime concentration and the role of structural features examined. The structural changes studied included substitutions in both chelating and non-chelating parts of the molecule. The results indicated that, contrary to expectations, many of the structural changes in the basic molecule, salicylaldoxime, do not have a positive effect on collector efficiency. The reduction in collector efficiency is rationalised on the basis of possible steric factors affecting complexation and packing of the collector species on the mineral surface as well as effects due to changes in electron density brought about by substituents. Introduction of alkyl substituents on the oximic carbon of salicylaldoxime yielded the highest collector efficiency.

Jan 1, 1993

By R. S. Rickard, H. D. Peterson, M. C. Fuerstenau, J. D. Miller

The flotation characteristics of the oxide copper minerals, malachite, azurite, and cuprite, have not presented the difficulty for concentration as have those of the copper silicate, chrysocolla. The copper carbonates and oxides respond reasonably well to flotation with conventional collectors, whereas chrysocolla will not respond to flotation with fatty acids or xanthates under normal flotation conditions. In this view then, other reagents will have to be devised to function as collectors for chrysocolla. The most obvious general class of reagents for this purpose would seem to be the organic copper chelating compounds. The utility of chelating agents as collectors in flotation systems has already been demonstrated.1-6

Jan 4, 1966

By S. C. Termes, R. L. Wilfong

As part of an effort to provide basic data on the fundamental scientific and engineering principles of minerals beneficiation, the Bureau of Mines is conducting research on the flocculation of mineral fines. This paper presents results of studies using cross-linked starches containing carboxyl, diethanolamine, iminodiacetic acid, and xanthate groups to flocculate hematite, goethite, chromite, manganite, pyrolusite, cuprite, and cassiterite fines. The carboxyl and xanthate derivatives flocculated all minerals except cassiterite; the latter was flocculated by only the diethanolamine derivative. The imlnodiacetic acid derivative flocculated hematite, goethite, chromite, cuprite, and pyrolusite fines. Zeta potential measurements were made to help define the reaction mechanism responsible for flocculation. These measurements indicate that electrostatic attraction probably is not involved, except possibly in the case of the diethanolamine derivative. The separation of hematite from quartz by selective flocculation with chelating crosslinked starches under two pH conditions and with two dispersing agents is described. Best recoveries and grades were found when either the carboxyl or xanthate derivatives was added at the natural pH of the pulp in the absence of a dispersing agent.

Jan 1, 1984

By S. C. Termes

As part of an effort to provide basic data on the fundamental scientific and engineering principles of minerals beneficiation, the Bureau of Mines is conducting research on the flocculation of mineral fines. This paper presents results of studies using crosslinked starches containing carboxyl, diethanolamine, iminodiacetic acid, and xanthate groups to flocculate hematite, goethite, chromite, manganrte, pyrolusite, cuprite, and cassiterite fines. The carboxyl and xanthate derivatives flocculated all minerals except cassiterite; the latter was flocculated by only the diethanolamine derivative. The iminodiacetic acid derivative flocculated hematite, goethite, chromite, cuprite, and pryolusite fines. Zeta potential measurements were made to help define the reaction mechanism responsible for flocculation. These measurements indicate that electrostatic attraction probably is not involved, except possibly in the case of the diethano lamine derivative. The separation of hematite from quartz by selective flocculation with chelating cross- linked starches under two pH conditions and with two dispersing agents is described. Best recoveries and grades were found when either the carboxyl or xanthate derivatives was added at the natural pH of the pulp in the absence of a dupersing agent.

Jan 1, 1983

By H. Dho

Two aromatic-type chelating agents, 1,10 phenanthroline (phen) and 8-quinolinol (quin), were tested as specific depressants for magnetite in the cationic silica flotation of magnetic taconite concentrates. Micro and batch flotation tests, along with zeta potential and adsorption measurements were used. In the presence of a cationic collector, dodecylammonium chloride (DAC), the Fe/phen surface chelate electro-statically repelled DAC, and magnetite was depressed. The negatively charged Fe(quin)2(OH)2-on the magnetite surface attracted the cationic collector and made magnetite floatable.

Jan 1, 1995

By I. Iwasaki, H. Dho

Two aromatic-type chelating agents, 1,10 phenanthroline (phen) and 8-quinolinol (quip), were tested as specific depressants for magnetite in the cationic silica flotation of magnetic taconite concentrates. Micro and batch flotation tests, along with zeta potential and adsorption measurements, were used. In the presence of a cationic collector, dodecylammonium chloride (DAC), the Fe/phen surface chelate electrostatically repelled DAC, and the magnetite was depressed. The negatively charged Fe(quin)2(OH)2- on the magnetite surface attracted the cationic collector and made magnetite floatable.

Jan 1, 1997

By A. Marabini, J. Cases, M. Barbaro

Outlined is a review of the application of new selective chelating reagents as flotation collectors; calculation methods for the selection of chelating structures, limitation of the function of commercial chelating agents as collectors, and the synthesis of two new classes of chelating collectors with mixed aliphatic-aromatic structure for oxidized lead-zinc ores. Given are: examples of substituted mercaptobenzothiazole and aminothiophenol structures, flotation and adsorption study of an alcoxyl-mercaptobenzothiazole on cerussite, comparison of adsorption of conventional and chelating collectors, study of the influence of the aliphatic structure1 component on the collecting power of chelating type reagent and the design of chelating collectors with optimal structure.

Jan 1, 1989

Chelopech Mining EAD and Best Available Techniques for Management of Waste Rock in Mining Activities

Sep 13, 2010

By J. A. Relf

The construction of refineries and gas conservation plants in the general Edmonton area in the early 1950's made available large quantities of by-product liquified petroleum gases (LPG). These gases, together with discovery of increasing reserves of natural gas in the Edmonton area, provided Canadian Chemical Company with two of the necessities for petrochemical production, namely, available and reasonably priced raw materials and fuel. This paper outlines the development of the $83 million Edmonton plant from its origin, together with a brief description of the processes and some of the interesting features involved. Several economic aspects of the petrochemical industry are high-lighted including its importance to the local community and the province. The paper reviews the relationship between the oil and gas industry and petrochemical manufacturing and indicates some of the factors that may affect the future growth of the petro-chemical industry in Wes tern Canada.

Jan 1, 1962

By Don Opacic

The disposal of sludges and other similar industrial wastes is a major problem. Liquid wastes from industrial operations, when treated, produce significant volumes of sludge which are difficult to dispose of, because of the chemical and physical properties of the sludge. In the mining industry sludge is produced from various water treatment operations, in particular mine drainage neutralization. Waste water from coal preparation plants also produces a sludge however the sludge is in fact a slurry containing clays, coal fines and coal impurities. In many areas the disposal of these sludges is producing a serious problem. Mine drainage sludge consists of a variety of hydrous iron oxides, usually ferric oxides, contaminated with other neutralization products such as calcium sulfate. The volume of sludge from mine water or mine

Jan 1, 1973

By Alan R. Grant

Interpretation of presently available geological information indicates that most of the periods of significant metal deposition in the Washington Cascades Range are, at least in part, genetically related to late Cretaceous -Tertiary intrusive episodes. Chemically, the most favorable environment for base metal deposition is high in potassium. Characterizing the advanced stages of these chemical alteration conditions are the silicate mineral assemblages orthoclase and/or secondary biotite. Wall rock alteration includes both deuteric and hydrothermal processes, the intensity of which primarily depends upon the degree of fracturing in the country rock prior to the introduction of secondary material. Broadly speaking, the primary physical controls for the distribution and concentration of sulfides appear to be a series of structural couples involving both northwest (paralleling regional trends) and northeast--striking systems. Meaningful base metal exploration in the Washington Cascades demands a basic understanding of the various geologic factors related to the distribution of the sulfide deposits. Any geologist contemplating Cascade work should be well grounded in the fundamental concepts of petrology and structure.as these constitute two of his most beneficial aids. The acquisition of the detailed data necessary for this understanding may seem a bit academic, yet it has been demonstrated in numerous instances that a fair economic appraisal of a particular property or mining district depends primarily upon the ability of the geologist to recognize the subtle environmental differences which could lead to the discovery of a major ore deposit.

Jan 1, 1971

By V. L. Zajakowski, J. D. Gargulak

The current political climate has forced multinational cement manufacturers to consider technology that minimizes GO, emissions. Along with this environmental issue, individual manufacturing facilities are under constant pressure to increase productivity and lower costs. The use of processing or functional additions can help address these difficult demands by maximizing the extender content in blended cements. Recently, cement standards have been modified such that additions can be employed to improve quality. By using these "cement performance enhancers," the cement manufacturer can maximize extender content of cement thus optimizing plant economics, while meeting local quality standards and minimizing greenhouse gas emissions.

Jan 1, 2003

By R. Samuels, R. Klimpel

"IntroductionLaboratory and industrial grinding tests have shown that the process of size reduction of metal containing ores can be significantly influenced by chemicals added to the slurry being ground.,The terms grinding aid or grinding additive refer to a substance which, when mixed into the mill contents, causes an increase in the rate of size reduction. The increased rate can be used to grind a higher feed rate to the desired product size or it can be used to produce a finer product size at a fixed rate. Whether the use of a grinding aid is justified in any given situation depends on the cost of the substance versus the improvement of output or product quality obtained with its use.A wide variety of grinding additive mechanisms have been suggested in the general mining literature (1,2,3,4,5,6,7). The prevention of particle agglomeration, slurry cushioning of grinding media impact, grinding media coating, changing the strength of macro porous rocks, and chemical adsorption on flaw surfaces to change bonding forces and surface energy have all been suggested. More recently, some grinding additive work has been carried out (8,9,10,11) which suggests that the use of efficient chemicals to control the fluidity of dense slurries is a viable economic approach to achieve improved grinding rates. These increased grinding rates are achieved with no increase in power to the grinding mills and apparently with no increase in media consumption costs. Unlike much of the previous work with grinding additives, this recent work is accompanied by a rather complete engineering characterization and prediction of performance capability. The chemicals involved were chosen so as to efficiently control the viscosities of slurries under conditions of high shear yet not adversely affecting flotation, flocculation, and other downstream surface chemistry operations."

Jan 1, 1979

By K. R. Gardner, P. B. Altringer, R. H. Lien, B. E. Dinsdale

The Bureau of Mines, U.S. Department of the Interior, is investigating chemical and biological decontamination of complex wastewaters such as tailings pond water containing 280 ppm CN and 5 ppm Se as well as significant concentrations of arsenic, copper, iron, silver, and zinc. The most effective chemical procedure involves cyanide oxidation using hydrogen peroxide or sodium hypochlorite followed by selenium reduction using ferrous hydroxide. The effluent contains ?1 ppm CN and 20 ppb Se; concentrations of other - major contaminants meet National Drinking Water Standards. Preliminary research indicates that biological cyanide oxidation is possible even in highly alkaline solutions (pH 10.5) containing high cyanide concentrations; indigenous bacteria destroyed 85% of the cyanide. Exploratory research shows that other bacteria removed up to 79% of the selenium from chemically oxidized, low- cyanide water. These promising results may lead to a final processing scheme that involves a combination of chemical and biological techniques.

Jan 1, 1990

By R. H. Lien

The Bureau of Mines, U. S. Department of the Interior, is investigating chemical and biological decontamination of complex wastewaters such as tailings pond water containing 280 ppm CN and 5 ppm Se as well as significant concentrations of arsenic, copper, iron, silver, and zinc. The most effective chemical procedure involves cyanide oxidation using hydrogen peroxide or sodium hypochlorite followed by selenium reduction using ferrous hydroxide. The effluent contains <l ppm CN and 20 ppb Se; concentrations of other major contaminants meet EPA drinking water standards. Preliminary research indicates that biological cyanide oxidation is possible even in highly alkaline solutions (pH 10.5) containing high cyanide concentrations; indigenous bacteria destroyed 85 pet of the cyanide. Exploratory research shows that other bacteria removed up to 79 pet of the selenium from chemically oxidized, low-cyanide water. These promising results may lead to a final processing scheme that involves a combination of chemical and biological techniques.

Jan 1, 1990