US3590997A - Flotation of sulfide ores - Google Patents

Flotation of sulfide ores Download PDF

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Publication number
US3590997A
US3590997A US799071A US3590997DA US3590997A US 3590997 A US3590997 A US 3590997A US 799071 A US799071 A US 799071A US 3590997D A US3590997D A US 3590997DA US 3590997 A US3590997 A US 3590997A
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formula
flotation
carbon atoms
compounds
compound
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US799071A
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English (en)
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Guy H Harris
Terry D Filer
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Dow Chemical Co
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Dow Chemical Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/012—Organic compounds containing sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02—Ores
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S209/00—Classifying, separating, and assorting solids
    • Y10S209/901—Froth flotation; copper

Definitions

  • Kanuch ABSTRACT An improvement in the concentration of ores by flotation which comprises subjecting a sulfide ore in the form of a pulp to a flotation process in the presence of an effective quantity ofa flotation collector corresponding to the formula wherein A is a radical corresponding to the formula X and Y consist of S- or -O; R, R and R are hydrocarbyl groups, R, is an alkylene group and R is H or a lower alkyl group. Certain of the indicated compounds provide for enhanced selectivity and/or recovery of sulfide minerals of Cu, Zn, Mo, Co, Ni and Pb over iron sulfide.
  • FLOTATION OF SULFIDE ORES BACKGROUND Flotation is a process of treating a mixture of finely divided mineral solids, e.g. a pulverulent ore, suspended in a liquid whereby a portion of such solids are separated from other finely divided mineral solids e.g. clays and the like materials present in the ore, by introducing a gas into the liquid (or providing a gas in situ) to produce a froth mass containing certain of the solids on the top of the liquid, and leaving suspended (unfrothed) other solid components of the ore.
  • a gas into the liquid (or providing a gas in situ) to produce a froth mass containing certain of the solids on the top of the liquid, and leaving suspended (unfrothed) other solid components of the ore.
  • Flotation is based on the principle that introducing a gas into a liquid containing solid particles of different materials suspended therein causes adherence of some gas to certain suspended solids and not to others and makes the particles having the gas thus adhered thereto lighter than the liquid. Accordingly, they rise to the top of the liquid to form a froth.
  • Various flotation agents have been admixed with the suspension to improve the frothing process.
  • Such added agents are classed according to the function to be performed:
  • Collectors e.g. high carbon chain compounds such as collectors for sulfide minerals including xanthates, thionocarbamates, and the like; frothers which impart the property of forming a stable froth, e.g. natural oils such as pine oil and eucalyptus oil; modifiers such as activators to induce flotation in the presence of a collector, e.g. copper sulfate; depressants, e.g.
  • sodium cyanide which tend to prevent a collector from functioning as such on a certain mineral which it is desired to retain in the liquid, and thereby discourage a substance from being carried up and forming a part of the froth; pH regulators to produce optimum metallurgical results, e.g. lime, soda ash, and the like.
  • the flotation principle is applied in a number of mineral separation processes among which is the selective separation of such minerals as sulfide copper minerals, sulfide zinc minerals, sulfide molybdenum minerals and others from sulfide iron minerals.
  • the present invention concerns a novel class of compounds. These unique compounds can be used as collection agents in a flotation process. With some of the compounds better recoveries are realized and with others improved selectivity is achieved. Certain of the novel compounds produce an improvement in both aspects.
  • novel compounds of the present invention correspond to the general formula wherein a.
  • R is an alkylene group containing up to about carbon atoms, preferably up to about 5 carbon atoms;
  • R is a hydrocarbyl group, other than an aryl group wherein an atom in the ring structure is bonded directly to Y,
  • Y is -S- or -O-;
  • A is a radical corresponding to the formula wherein i. R is H or a lower alkyl group containing up to about 7 carbon atoms and preferably up to about 3 carbon atoms;
  • R is an alkyl group, X and X are both -S- or -O-;
  • R and R are independently an alkyl, alkenyl, cycloalkyl or cycloalkenyl group containing up to about 7 carbon atoms and preferably up to 3 carbon atoms;
  • R and R are the same alkyl, alkenyl, cycloalkyl or cycloalkenyl group containing up to about 7 carbon atoms and preferably up to about 3 carbon atoms;
  • R is H
  • X and X are independently -S- or -O- and R and R' are independently an alkyl, alkenyl, cycloalkyl or cycloalkenyl group containing up to about 7 carbon atoms and preferably up to 3 carbon atoms;
  • A is a radical corresponding to the formula wherein X and-X are independently -O- or -S-; R and R are independently H, or an alkyl group containing up to about 5 carbon atoms and preferably up to about 3 carbon atoms, and R is H or an alkyl group containing up to 7 carbon atoms, preferably up to 3 carbon atoms.
  • R is a member selected from the group consisting of an alkyl or alkenyl group containing up to 18 carbon atoms, preferably up to about 10 carbons; a cycloalkyl, or cycloalkenyl group containing up to about 8 carbon atoms, or an aralkenyl or aralkyl group wherein the alkyl or alkenyl portion contains up to about 5 carbon atoms and is bonded to Y.
  • novel compounds can be prepared, for example, by reacting an aminoacetal, aminoketal, aminothioacetal or aminothioketal compound corresponding to the formula,
  • R, R, X, X, R, and R are the same as defined hereinbefore, with a xanthate ester corresponding to the formula s BJ'T T T T J wherein R is the same as defined hereinbefore and R., is usually a lower alkyl group such as methyl or ethyl.
  • a mercaptan R,SH is evolved during the reaction.
  • the compounds as defined herein are particularly suitable for use in standard flotation processes as flotation collectors to concentrate copper sulfide and other like minerals from sulfide ores.
  • a pulp is first prepared by wet grinding theore to a suitable size with or without a pH modifier.
  • a suitable frothing agent is then added, e.g., pine oil. cresylic acid, polyalkoxyparaffin and the like.
  • An effective quantity of a compound as defined herein is then added, preferably ranging from about 0.0l lb. to about 0.25 lb. per ton of pulp and the pulp is then agitated and aerated.
  • the copper minerals and other like sulfide minerals collect as a froth which is readily overflowed or skimmed off from the residual gangue and nondesired materials and the metal values therein recovered.
  • Example 1 One species of a compound within the scope of the present invention and corresponding to the formula S CH;
  • Example 2 Another compound within the scope of the present invention corresponding to the formula was prepared in the following manner:
  • Example 3 Another compound within the scope of the present invention, corresponding to the formula was prepared in the following manner. To 138 grams of dimethyl trithiocarbonate was added 16.1 grams of the diethyl acetal of 4-aminobutanal.
  • the temperature of the reaction mixture rose to about 50 C. with the evolution ofCl-l sl-l.
  • the reaction was completed by heating the mixture at a temperature of from about to C. under a reduced pressure of about 30 mm. until CH SH was no longer evolved.
  • the product was an oil, obtained in about 92 percent yield.
  • the above assigned structure for the compound was confirmed by infrared and NMR analysis.
  • Cyclic aminoacetals useful in preparing compounds within the scope of the present invention can be prepared by a number of procedures known in the organic synthesis art. For example potassium phthalimide can be reacted with an achloro (or a-bromo) carboxylic acid to form a compound corresponding to the formula This compound can then be contacted with thionyl chloride and a base to provide a compound corresponding to the formula C ll 0 After this compound is purified it is reduced by the Rosenmund method with hydrogen over a regulated Pd catalyst at the lowest temperatures at which HCl evolves to form the corresponding aldehyde. The aldehyde is condensed in the presence of SnCl with an alkylene oxide,
  • Cyclic aminoketals i.e. compounds corresponding to the general formula manner.
  • a chloro or bromo ketone is reacted with a phthalimide salt.
  • the product is condensed in the presence of SnCl ing product treated with hydrazine to produce the cyclic aminoketal.
  • the sequence of the reaction steps can be suinmarized as follows
  • Other cyclic species can be prepared by the condensation of cyano or nitro substituted ketones or aldehydes with epoxides, followed by the reduction of the cyano or nitro group to the NH group.
  • Noncyclic aminoacetals can be made by known methods for converting carbonyl compounds to the corresponding acetal or ketal, employing carbonyl compounds substituted with cyano or nitro groups and then effecting reduction of the groups to the -Nl-l group, and also be employing certain aminocarbonyl compounds directly.
  • aminoacetal and aminoketal compounds, both cyclic and noncyclic can be made by amination of halo acetals, etc., the latter compounds being prepared by halogenation of carbonyl compounds prior to their conversion to the acetals or ketals by known methods.
  • Wagner and Zook Synthetic Organic Chemistry, PP 26l- 275, 1953, can be referred to for detailed description of various procedures for preparing various acetals and ketal starting materials employed in the present invention.
  • the xanthate starting materials can be prepared, for example, by reacting an alkali metal alkoxide with CS and then with methyl chloride.
  • the reaction is represented by *To prepare the alkoxide of a tertiary alcohol a separate preliminary reaction with potassium metal is employed.
  • Suitable alcohols include cyclohexanol, cyclohexenol, allyl alcohol, cinnamyl alcohol, crotyl alcohol, 2,3,5-trimethyl-3-hexanol; 2,3,4-trimethyl-2-hexanol and other like alcohols.
  • Both cyclic and noncyclic aminothioacetals and aminothioketals can be prepared in a manner similar to those previously described for the preparation of the cyclic and noncyclic aminoacetal and aminoketal compounds.
  • a process for preparing dithiolane acids and esters is taught in US. Pat. No. 2,839,445.
  • the so prepared compounds can be converted by methods known in the art to the corresponding nitriles or amides and the latter reduced to the amine intermediates which can then be reacted with suitable xanthate compounds to provide compounds within the scope of the present invention.
  • One specific compound within the scope of the present invention is prepared in the following manner: To 13.6 grams of methyl ethyl xanthate is added 12.9 grams of 3,3-
  • Qr sS is produced in substantially quantitative amounts.
  • aminoacetals which can be employed to prepared compounds within the scope of the present invention wherein A- corresponds to the radical I RS g 7 v are prepared in the following manner.
  • RSNa dry hydrogen halide
  • novel compounds which can be prepared by a method as defined hereinbefore and which are useful as flotation collectors in the concentration of sulfide compound containing ores include for example:
  • R is an alkylene group containing up to about 10 carbon atoms; wherein R is a member selected from the group consisting of an alkyl or alkenyl group containing up to 18 carbon atoms, a cycloalkyl or cycloalkenyl group containing up to about 8 carbon atoms, or an aralkyl or aralkenyl group wherein the alkyl or alkenyl portion contains up to about 5 carbon atoms and is bonded to Y.
  • Y is a member selected from the group consisting of -S- or -O-; and d.
  • A is a radical selected from the group consisting of a radical corresponding to the formula i.
  • R is a member selected from the group consisting of H or an alkyl group containing up to about 7 carbon atoms; and
  • R and R are both the same member selected from the group consisting of alkyl, alkenyl, cycloalkyl. cycloalkenyl group containing up to about 7 carbon atoms;
  • X and X are independently a member selected from the group consisting of -S- and -O and R and R are independently an alkyl, alkenyl, cycloalkyl or cycloalkenyl group containing up to about 7 carbon 5.
  • said flotation 10 collector corresponds to the formula atoms; 3 (CzHsOhCHCHzOH CHM-O-SCH;
  • A is a radical corresponding to the formula 6.
  • said flotation collector corresponds to the formula 1 1 1 s wherein W (CH5O) CHOH CH CH Nl :oCH CH;
  • X and X are independently a member selected from the group consisting of -0- or -S-; R and R' are independently a 7.
  • said flotation member selected from the group consisting of H or an alkyl collector corresponds to the formula group containing up to about 5 carbon atoms, and R is a member selected from the group consisting of H or an alkyl group containing up to 7 carbon atoms.

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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US799071A 1969-02-13 1969-02-13 Flotation of sulfide ores Expired - Lifetime US3590997A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852167A (en) * 1972-02-08 1974-12-03 Dow Chemical Co Flotation of nickel sulfide ores
US3853751A (en) * 1972-02-08 1974-12-10 Dow Chemical Co Flotation of sulfide ores using dithiocarbamates
US3975264A (en) * 1973-07-13 1976-08-17 Minerec Corporation Flotation of copper sulfide ores with improved thionocarbamates
US4387034A (en) * 1981-10-23 1983-06-07 Thiotech, Inc. Mixed alkylthionocarbamates flotation collectors and ore dressing methods in which the collectors are employed
US4511464A (en) * 1983-07-22 1985-04-16 The Dow Chemical Company 1,3-Oxathiolane-2-thiones as sulfide mineral collectors in froth flotation
US4618461A (en) * 1983-07-25 1986-10-21 The Dow Chemical Company O,O'-, O,S'- or S,S'-dithiodialkylene-bis(mono- or dihydrocarbyl carbamothioates) and S,S'-dithiodialkylene-bis(mono- or dihydrocarbyl carbamodithioates) and method of preparation thereof
US4702822A (en) * 1985-07-12 1987-10-27 The Dow Chemical Company Novel collector composition for froth flotation
US5015368A (en) * 1990-06-15 1991-05-14 The Lubrizol Corporation Ore flotation process using carbamate compounds
CN104475266A (zh) * 2014-12-25 2015-04-01 昆明冶金研究院 一种硫化铜浮选捕收剂及其制备方法与应用

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2342332A (en) * 1941-12-30 1944-02-22 American Cyanamid Co Dithiocarbamic acid derivative
US2691635A (en) * 1953-05-20 1954-10-12 Dow Chemical Co Process for the manufacture of dialkyl thionocarbamates
US2701253A (en) * 1955-02-01 Substituted dithiolanes
DE1032733B (de) * 1956-03-13 1958-06-26 Dehydag Gmbh Verfahren zur Herstellung von im Alkoholrest Sulfonsaeuregruppen enthaltenden Derivaten N-disubstituierter Dithiocarbaminsaeureester bzw. deren Salzen
US2895980A (en) * 1955-11-10 1959-07-21 Monsanto Chemicals Allyl esters of mono-substituted dithiocarbamic acids
US3025214A (en) * 1957-09-09 1962-03-13 Diamond Alkali Co Chemical composition and process
US3082237A (en) * 1959-10-12 1963-03-19 Monsanto Chemicals 2-cyclohexenyl esters of hydrogen substituted dithiocarbamic acids
US3290351A (en) * 1959-01-16 1966-12-06 Monsanto Canada Ltd Aryl esters of 3, 4-dichloro-phenyl thionocarbamates
US3464551A (en) * 1967-11-01 1969-09-02 American Cyanamid Co Dialkyl dithiocarbamates as collectors in froth flotation

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2701253A (en) * 1955-02-01 Substituted dithiolanes
US2342332A (en) * 1941-12-30 1944-02-22 American Cyanamid Co Dithiocarbamic acid derivative
US2691635A (en) * 1953-05-20 1954-10-12 Dow Chemical Co Process for the manufacture of dialkyl thionocarbamates
US2895980A (en) * 1955-11-10 1959-07-21 Monsanto Chemicals Allyl esters of mono-substituted dithiocarbamic acids
DE1032733B (de) * 1956-03-13 1958-06-26 Dehydag Gmbh Verfahren zur Herstellung von im Alkoholrest Sulfonsaeuregruppen enthaltenden Derivaten N-disubstituierter Dithiocarbaminsaeureester bzw. deren Salzen
US3025214A (en) * 1957-09-09 1962-03-13 Diamond Alkali Co Chemical composition and process
US3290351A (en) * 1959-01-16 1966-12-06 Monsanto Canada Ltd Aryl esters of 3, 4-dichloro-phenyl thionocarbamates
US3082237A (en) * 1959-10-12 1963-03-19 Monsanto Chemicals 2-cyclohexenyl esters of hydrogen substituted dithiocarbamic acids
US3464551A (en) * 1967-11-01 1969-09-02 American Cyanamid Co Dialkyl dithiocarbamates as collectors in froth flotation

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852167A (en) * 1972-02-08 1974-12-03 Dow Chemical Co Flotation of nickel sulfide ores
US3853751A (en) * 1972-02-08 1974-12-10 Dow Chemical Co Flotation of sulfide ores using dithiocarbamates
US3975264A (en) * 1973-07-13 1976-08-17 Minerec Corporation Flotation of copper sulfide ores with improved thionocarbamates
US4387034A (en) * 1981-10-23 1983-06-07 Thiotech, Inc. Mixed alkylthionocarbamates flotation collectors and ore dressing methods in which the collectors are employed
US4511464A (en) * 1983-07-22 1985-04-16 The Dow Chemical Company 1,3-Oxathiolane-2-thiones as sulfide mineral collectors in froth flotation
US4618461A (en) * 1983-07-25 1986-10-21 The Dow Chemical Company O,O'-, O,S'- or S,S'-dithiodialkylene-bis(mono- or dihydrocarbyl carbamothioates) and S,S'-dithiodialkylene-bis(mono- or dihydrocarbyl carbamodithioates) and method of preparation thereof
US4702822A (en) * 1985-07-12 1987-10-27 The Dow Chemical Company Novel collector composition for froth flotation
US5015368A (en) * 1990-06-15 1991-05-14 The Lubrizol Corporation Ore flotation process using carbamate compounds
CN104475266A (zh) * 2014-12-25 2015-04-01 昆明冶金研究院 一种硫化铜浮选捕收剂及其制备方法与应用

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BE745889A (fr) 1970-08-12
ES376280A1 (es) 1972-03-16
GB1298151A (en) 1972-11-29
FR2035370A5 (fr) 1970-12-18

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