EP1949964A1 - Verfahren für die Flotation nichtsulfidischer Mineralien und Erze - Google Patents

Verfahren für die Flotation nichtsulfidischer Mineralien und Erze Download PDF

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Publication number
EP1949964A1
EP1949964A1 EP07001678A EP07001678A EP1949964A1 EP 1949964 A1 EP1949964 A1 EP 1949964A1 EP 07001678 A EP07001678 A EP 07001678A EP 07001678 A EP07001678 A EP 07001678A EP 1949964 A1 EP1949964 A1 EP 1949964A1
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EP
European Patent Office
Prior art keywords
flotation
collectors
ores
minerals
monoesters
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07001678A
Other languages
English (en)
French (fr)
Inventor
Klaus Dr. Hinrichs
Joaquin Dr. Bigorra Liosas
Simone Hoffmann-Doerr
Dietger KÖPPL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cognis IP Management GmbH
Original Assignee
Cognis IP Management GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cognis IP Management GmbH filed Critical Cognis IP Management GmbH
Priority to EP07001678A priority Critical patent/EP1949964A1/de
Priority to PCT/EP2008/000310 priority patent/WO2008089907A1/en
Publication of EP1949964A1 publication Critical patent/EP1949964A1/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/01—Organic compounds containing nitrogen
    • 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
    • B03D1/01—Organic compounds containing nitrogen
    • B03D1/011—Quaternary ammonium compounds
    • 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
    • B03D2203/04—Non-sulfide ores

Definitions

  • This invention relates to the flotation of non-sulfidic minerals and ores, and more particularly the use of certain cationic surfactants as collectors in a froth flotation process.
  • Flotation is a separation technique commonly used in the dressing of minerals and crude ores for separating valuable materials from the gangue.
  • Non-sulfidic minerals and ores in the context of the present invention include, for example calcite, apatite, fluorite, scheelite, baryta, iron oxides and other metal oxides, for example the oxides of titanium and zirconium, and also certain silicates and aluminosilicates.
  • the mineral or ore is normally first subjected to preliminary size-reduction, dry-ground, but preferably wet-ground and suspended in water.
  • Collectors are then normally added, often in conjunction with frothers and, optionally, other auxiliary reagents such as regulators, depressors (deactivators) and/or activators, in order to facilitate separation of the valuable materials from the unwanted gangue constituents of the ore in the subsequent flotation process.
  • auxiliary reagents such as regulators, depressors (deactivators) and/or activators, in order to facilitate separation of the valuable materials from the unwanted gangue constituents of the ore in the subsequent flotation process.
  • These reagents are normally allowed to act on the finely ground ore for a certain time (conditioning) before air is blown into the suspension (flotation) to produce a froth at its surface.
  • the collector hydrophobicizes the surface of the minerals so that they adhere to the gas bubbles formed during the activation step.
  • the valuable constituents are selectively hydrophobicized so that the unwanted constituents of the mineral or ore do not adhere to the gas bubbles.
  • Surfactants and, in particular, anionic, cationic and ampholytic surfactants are used as collectors in the flotation-based dressing of minerals and ores, in particular of calcite which is of considerable value especially for the paper industry.
  • Calcite represents an important filler with the ability for adjusting the whiteness and transparency of the paper.
  • Calcite minerals are often accompanied by silicates so that, to purify the calcite, the silicate - which is undesirable for many applications - has to be removed.
  • Another problem which has a serious impact on the selectivity of the froth flotation process is related to the magnesium content of the minerals or ores. Magnesium salts seriously improve the stability of the froth, which collapses slowly and therefore increases the flotation time, while the selectivity drops.
  • an object of the present invention is to provide improved collectors which make flotation processes more economical, i.e. with which it is possible to obtain either greater yields of valuable material for the same quantities of collector and for the same selectivity or at least the same yields of valuable materials for reduced quantities of collector.
  • a second object is to supply collectors which simultaneously meet the needs for high biodegradability.
  • the present invention refers to a process for the flotation of non-sulfidic minerals or ores, in which crushed crude minerals or ores are mixed with water and a collector to form a suspension, air is introduced into the suspension in the presence of a reagent system and a floated foam containing said non-sulfidic minerals or ores formed therein along with a flotation residue comprising the gangue, wherein the improvement comprises using quaternised alkanolamine-monoesters as the collector.
  • quaternised triethanolamine-monooleates are extremely effective as collectors for the flotation of non-sulfidic minerals and ores.
  • the collectors according to the present invention have been found even more effective compared to conventional mono/diesterquat mixtures while exhibiting a similarly high degree of biodegradability.
  • the products have been found rather useful for the separation of silicate minerals from calcite by froth flotation.
  • Quaternised esters of alkanolamines and fatty acids are well known from the state of the art which may be obtained by the relevant methods of preparative organic chemistry. Reference is made in this connection to International patent application WO 91/01295 (Henkel), which is a very early reference disclosing this subject matter, according to which triethanolamine is partly esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and the resulting reaction mixture is quatemised with dimethyl sulfate or ethylene oxide.
  • suitable quatemised alkanolamine-monoesters derived from alkanolamines are derived from amines following general formula (I). in which R 1 represents a hydroxyethyl radical, and R 2 and R 3 independently from each other stand for hydrogen, methyl or a hydroxyethyl radical.
  • R 1 represents a hydroxyethyl radical
  • R 2 and R 3 independently from each other stand for hydrogen, methyl or a hydroxyethyl radical.
  • Typical examples are methyldiethanolamin (MDA), monoethanolamine (MES), diethanolamine (DEA) and triethanolamine (TEA).
  • MDA methyldiethanolamin
  • MES monoethanolamine
  • DEA diethanolamine
  • TAA triethanolamine
  • quatemised triethanolaminemonoesters are used.
  • the products are derived from fatty acids following general formula (II), R 4 CO-OH (II) in which R 4 CO stands for a linear or branched acyl radical having 8 to 22 carbon atoms, preferably 16 to 18 carbon atoms, and 0 or 1 to 3 double bonds.
  • R 4 CO stands for a linear or branched acyl radical having 8 to 22 carbon atoms, preferably 16 to 18 carbon atoms, and 0 or 1 to 3 double bonds.
  • Typical examples are caprylic acid, caprinic acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidinic acid, linoic acid, conjugated linoic acid (CLA), linoleic acid, ricinoleic acid, arachidonic acid, gadoleic acid, behenic acid, erucic acid and also technical grade fatty acids obtained from renewable resources.
  • the collectors are obtained from unsaturated fatty acids.
  • the preferred compounds are quaternised alkanolamine-monooleates.
  • the most preferred collectors are quaternised alkanolamine-monoesters following general formula (III) in which R 5 CO represents the acyl residue of oleic acid.
  • quaternised alkanolamine-monoesters may be modified, adjust or even support the properties of the quaternised alkanolamine-monoesters by adding defined co-collectors, such as, for example, cationic surfactants others than the quaternised alkanolamine-monoesters or amphotheric surfactants.
  • defined co-collectors such as, for example, cationic surfactants others than the quaternised alkanolamine-monoesters or amphotheric surfactants.
  • cationic surfactants are to be used as co-collectors in accordance with the invention, they may be selected in particular from
  • the amine compounds mentioned above may be used as such or in the form of their water-soluble salts.
  • the salts are obtained in given cases by neutralization which may be carried out both with equimolar quantities and also with more than or less than equimolar quantities of acid.
  • Suitable acids are, for example, sulfuric acid, phosphoric acid, acetic acid and formic acid.
  • ampholytic surfactants used as co-collectors in accordance with the invention are compounds which contain at least one anionic and one cationic group in the molecule, the anionic groups preferably consisting of sulfonic acid or carboxyl groups, and the cationic groups consisting of amino groups, preferably secondary or tertiary amino groups.
  • Suitable ampholytic surfactants include, in particular,
  • Said collectors and said co-collectors can be used in a weight ratio of about 10:90 to about 90:10, preferably about 25:75 to about 75:25, and most preferably about 40:60 to about 60:40.
  • the collectors or, respectively, the mixtures of collectors and co-collectors must be used in a certain minimum quantity.
  • a maximum quantity of collectors/co-collectors should not be exceeded, because otherwise frothing is too vigorous and selectivity with respect to the valuable minerals decreases.
  • the quantities in which the collectors to be used in accordance with the invention are used are governed by the type of minerals or ores to be floated and by their valuable mineral content.
  • the particular quantities required may vary within wide limits.
  • the collectors and collector/co-collector mixtures according to the invention are used in quantities of from 50 to 2000 g/metric ton, and preferably in quantities of from 100 to 1500 g/metric ton of crude ore.
  • Typical steps in the process sequence are, generally, firstly the dry or preferably wet grinding of the minerals or ores, suspension of the resulting ground mineral or ore in water in the presence of the flotation aids and, preferably after a contact time of the collectors and optionally co-collectors present in the flotation aids to be determined in each individual case, injection of air into the plant.
  • the nature of the starting materials as well as the flotation aids is illustrated in more detail.
  • Another object of the present invention is the use of quaternised alkanolamine-monoesters as collectors for the froth flotation of non-sulfidic minerals or ores.
  • the collectors to be used in accordance with the invention may be used with advantage in the dressing of such minerals or ores as s quartz, kaolin, mica, phlogopite, feldspar, silicates and iron ores.
  • the collectors according to the present invention lead to a faster collapse of the foam compared to the state of the art which is desirable in the flotation of minerals and ores.

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  • Manufacture And Refinement Of Metals (AREA)
  • Physical Water Treatments (AREA)
  • Separation Of Solids By Using Liquids Or Pneumatic Power (AREA)
EP07001678A 2007-01-26 2007-01-26 Verfahren für die Flotation nichtsulfidischer Mineralien und Erze Withdrawn EP1949964A1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP07001678A EP1949964A1 (de) 2007-01-26 2007-01-26 Verfahren für die Flotation nichtsulfidischer Mineralien und Erze
PCT/EP2008/000310 WO2008089907A1 (en) 2007-01-26 2008-01-17 Process for the flotation of non-sulfidic minerals and ores

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP07001678A EP1949964A1 (de) 2007-01-26 2007-01-26 Verfahren für die Flotation nichtsulfidischer Mineralien und Erze

Publications (1)

Publication Number Publication Date
EP1949964A1 true EP1949964A1 (de) 2008-07-30

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EP07001678A Withdrawn EP1949964A1 (de) 2007-01-26 2007-01-26 Verfahren für die Flotation nichtsulfidischer Mineralien und Erze

Country Status (2)

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EP (1) EP1949964A1 (de)
WO (1) WO2008089907A1 (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010051895A1 (de) * 2008-11-07 2010-05-14 Clariant International Ltd Mischung aus einem aminalkoxylatester und einer quarternären ammoniumverbingung als sammler für silikathaltige mineralien
CN102600985A (zh) * 2012-03-28 2012-07-25 四川晶大矿业科技有限公司 一种选矿捕收剂及其使用方法
WO2016099532A1 (en) * 2014-12-19 2016-06-23 Halliburton Energy Services, Inc. Purification of organically modified surface active minerals by air classification
CN106733222A (zh) * 2016-12-07 2017-05-31 广西大学 一种从白钨精矿中去除钼铁矿的浮选方法
WO2019141343A1 (de) * 2018-01-16 2019-07-25 Clariant International Ltd Esterquats zur flotation von nicht-sulfidischen mineralien und erzen und verfahren
WO2021128771A1 (zh) * 2019-12-23 2021-07-01 中南大学 2-氰基-n-(取代氨甲酰)乙酰胺类化合物在含钙矿物浮选中的应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HUE037082T2 (hu) 2008-11-10 2018-08-28 Arbutus Biopharma Corp Új lipidek és készítmények terápiás hatóanyagok szállítására
CN103977907B (zh) * 2014-05-15 2016-03-23 中南大学 一种黄原酸酰基酯捕收剂及其制备和应用方法
CN106733206A (zh) * 2017-01-03 2017-05-31 昆明理工大学 一种超声波在白钨矿加温搅拌脱药过程中的应用
CN108722660B (zh) * 2018-05-18 2020-05-22 中国地质科学院郑州矿产综合利用研究所 低品位白钨矿的选矿方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2173909A (en) * 1937-06-28 1939-09-26 Ninol Inc Ore dressing
US3459299A (en) * 1967-09-01 1969-08-05 Engelhard Min & Chem Talc beneficiation
WO1991001295A1 (de) * 1989-07-17 1991-02-07 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung von quartären ammoniumverbindungen
US4995965A (en) * 1988-06-13 1991-02-26 Akzo America Inc. Calcium carbonate beneficiation
WO1997026995A1 (de) * 1996-01-26 1997-07-31 Henkel Kommanditgesellschaft Auf Aktien Biologisch abbaubare esterquats als flotationshilfsmittel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2173909A (en) * 1937-06-28 1939-09-26 Ninol Inc Ore dressing
US3459299A (en) * 1967-09-01 1969-08-05 Engelhard Min & Chem Talc beneficiation
US4995965A (en) * 1988-06-13 1991-02-26 Akzo America Inc. Calcium carbonate beneficiation
WO1991001295A1 (de) * 1989-07-17 1991-02-07 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung von quartären ammoniumverbindungen
WO1997026995A1 (de) * 1996-01-26 1997-07-31 Henkel Kommanditgesellschaft Auf Aktien Biologisch abbaubare esterquats als flotationshilfsmittel

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010051895A1 (de) * 2008-11-07 2010-05-14 Clariant International Ltd Mischung aus einem aminalkoxylatester und einer quarternären ammoniumverbingung als sammler für silikathaltige mineralien
CN102112235A (zh) * 2008-11-07 2011-06-29 科莱恩金融(Bvi)有限公司 作为用于含硅酸盐矿物的捕收剂的由胺烷氧基化酯和季铵化合物组成的混合物
RU2508950C2 (ru) * 2008-11-07 2014-03-10 Клариант Финанс (Бви) Лимитед Композиция сложного эфира аминоалкоксилата и четвертичного аммониевого соединения в качестве собирателя (коллектора) для силикатсодержащих минералов
US9027757B2 (en) 2008-11-07 2015-05-12 Clariant Finance (Bvi) Limited Mixture of an amine alkoxylate ester and a quaternary ammonium compound as a collector for minerals containing silicate
AU2009313103B2 (en) * 2008-11-07 2015-08-27 Clariant Finance (Bvi) Limited Mixture of an amine alkoxylate ester and a quaternary ammonium compound as a collector for minerals containing silicate
CN102600985A (zh) * 2012-03-28 2012-07-25 四川晶大矿业科技有限公司 一种选矿捕收剂及其使用方法
GB2547156A (en) * 2014-12-19 2017-08-09 Halliburton Energy Services Inc Purification of organically modified surface active minerals by air classification
WO2016099532A1 (en) * 2014-12-19 2016-06-23 Halliburton Energy Services, Inc. Purification of organically modified surface active minerals by air classification
US10232381B2 (en) 2014-12-19 2019-03-19 Halliburton Energy Services, Inc. Purification of organically modified surface active minerals by air classification
GB2547156B (en) * 2014-12-19 2021-07-21 Halliburton Energy Services Inc Purification of organically modified surface active minerals by air classification
CN106733222A (zh) * 2016-12-07 2017-05-31 广西大学 一种从白钨精矿中去除钼铁矿的浮选方法
WO2019141343A1 (de) * 2018-01-16 2019-07-25 Clariant International Ltd Esterquats zur flotation von nicht-sulfidischen mineralien und erzen und verfahren
EA038655B1 (ru) * 2018-01-16 2021-09-29 Клариант Интернэшнл Лтд Эстеркваты для флотации несульфидных минералов и руд и способ
US11596952B2 (en) 2018-01-16 2023-03-07 Clariant International Ltd Esterquats for the flotation of non-sulfidic minerals and ores, and method
WO2021128771A1 (zh) * 2019-12-23 2021-07-01 中南大学 2-氰基-n-(取代氨甲酰)乙酰胺类化合物在含钙矿物浮选中的应用
US12303915B2 (en) 2019-12-23 2025-05-20 Central South University Carbamoyl)acetamide compound in flotation of calcium-bearing minerals

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Publication number Publication date
WO2008089907A8 (en) 2008-12-11
WO2008089907A1 (en) 2008-07-31

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