EP0193109B1 - Procédé de traitement de la kaolinite par flottation - Google Patents

Procédé de traitement de la kaolinite par flottation Download PDF

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Publication number
EP0193109B1
EP0193109B1 EP86102193A EP86102193A EP0193109B1 EP 0193109 B1 EP0193109 B1 EP 0193109B1 EP 86102193 A EP86102193 A EP 86102193A EP 86102193 A EP86102193 A EP 86102193A EP 0193109 B1 EP0193109 B1 EP 0193109B1
Authority
EP
European Patent Office
Prior art keywords
flotation
kaolinite
feldspar
collectors
water
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.)
Expired - Lifetime
Application number
EP86102193A
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German (de)
English (en)
Other versions
EP0193109A3 (en
EP0193109A2 (fr
Inventor
Wolfgang Dr. Von Rybinski
Holger Dr. Tesmann
Bohuslav Prof. Dr. Dobias
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT86102193T priority Critical patent/ATE70469T1/de
Publication of EP0193109A2 publication Critical patent/EP0193109A2/fr
Publication of EP0193109A3 publication Critical patent/EP0193109A3/de
Application granted granted Critical
Publication of EP0193109B1 publication Critical patent/EP0193109B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • B03D1/02—Froth-flotation processes
    • 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
    • B03D1/002—Inorganic 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
    • 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
    • B03D2201/007—Modifying reagents for adjusting pH or conductivity
    • 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

  • the invention relates to a process for the preparation of kaolinite by flotation, in particular a process by which kaolin and feldspar can be separated in the finest grain area and both minerals can be obtained in high yield in pure form.
  • Kaolinite is a naturally occurring industrial mineral, for whose diverse and different applications as filler in the paper and ceramic industry, in the plastics industry, in the production of paints, varnishes, rubber and cables, there is a growing and increasing demand.
  • Kaolinite arises from exogenous (weather, groundwater) and endogenous (hydrothermal hot solutions, deep vapors) influences with predominantly acidic pH values from feldspar (Ullmanns Encyclopedia of Technical Chemistry, Volume 13, page 509 (1977)).
  • feldspar Ullmanns Encyclopedia of Technical Chemistry, Volume 13, page 509 (1977)
  • High quality demands on the kaolinite product in terms of purity are more difficult to meet, the higher in existing and newly developed ones Kaolinite deposits are the proportions of not yet kaolinized feldspar and quartz. Kaolinite must be selectively separated from these accompanying rocks.
  • raw kaolin which in addition to the main mineral kaolinite mostly also contains feldspar, quartz and various iron and titanium minerals, is usually carried out by wet processes in which the kaolinite-containing raw earth is suspended in water.
  • the following separation process is based on a separation of the different mineral components according to the grain size and the specific weight. Since the minerals quartz and feldspar accompanying the kaolinite are generally coarser ("antiparallel grain distribution"), it is possible to satisfactorily separate the coarser quartz and feldspar from kaolinite down to grain sizes of 20 ⁇ m (cf. M. Clement and HM Tröndle; Erzmetall 22 , H. 3, 131 (1969)).
  • feldspar is a raw material that is sought after in the ceramic industry
  • the separation of kaolinite and feldspar from raw kaolin is aimed at obtaining a feldspar product in addition to the purest possible kaolinite, which has high standards for industrial use in glass and Ceramic industry is enough.
  • mechanical separation processes in aqueous turbidity are used for this.
  • the effectiveness of such separation processes reaches a limit if the grain sizes of kaolinite and feldspar are very close to each other in the fine grain range, since the specific weight of the two minerals (approx. 2.58 g / cm3) is practical is equal to.
  • Flotation processes are used in mineral cleaning practice to remove heavy metal oxides, such as oxides of iron and titanium, from kaolinite and thus improve the whiteness of the product.
  • Hydrochlorides and hydroacetates of long-chain aliphatic amines were used as collectors in acidic turbidity.
  • the area of fine grain size of both mineral particles is of particular interest for the treatment of aqueous turbidity containing kaolinite and feldspar; So far, it has not been possible to separate the two minerals in this grain range on an industrial scale. In practice, however, this area plays an outstanding role in that mineral deposits with a particle size distribution of 90% less than 30 ⁇ m for kaolinite and 10% less than 30 ⁇ m for feldspar are obtained when washing out the deposits containing kaolinite and feldspar.
  • Kaolins suitable for use in ceramics even have a fine grain fraction (less than 2 ⁇ m) of 50% and more. In the range of these grain sizes, selective flotation in aqueous turbidity causes great problems. The direct flotation for the separation of kaolinite and feldspar in this grain area has not yet been described.
  • polyvalent cations are adsorbed on the surfaces of the mineral particles which are suspended in the aqueous slurry and the floatability these can influence mineral particles within wide limits (B. Dobias, 6th International Congress for Surfactants, Zurich 1972, page 563 (1973)).
  • polyvalent cations are able to react with the collector surfactant to form complex compounds or poorly soluble precipitates, and in this way remove the surfactant from the desired adsorption process on the surface of the mineral particles.
  • this reduces the flotation yield unless increased amounts of the collector surfactant are used.
  • one and the same multivalent cation can have both activating and deactivating effects in the flotation of mineral particles for the selected collector (surfactant).
  • surfactant When which of the two properties dominates can only be determined empirically. As a rule, these effects, whose mechanisms of action are not fully known in detail, are more disruptive than beneficial in the flotation process itself. Preventing the undesired effect of polyvalent cations in the flotation process is therefore a special problem in the preparation of the respective minerals.
  • the activating or deactivating ("pressing") effect of polyvalent metal cations on silicate minerals is known in part from the literature.
  • Chemical Abstracts 68 , 116 041x (1968) reports that aluminum, iron and calcium ions have an activating effect in the flotation of quartz, Have feldspar and sillimanite. If the concentration of iron (III) and aluminum (III) salts is increased to values above 300 mg per liter, the activating effect of silicate flotation will decrease significantly in acidic and alkaline pH ranges.
  • the invention therefore relates to a process for the selective separation of kaolinite and feldspar by flotation in aqueous slurry, which is characterized in that the flotation is carried out at a pH of the slurry, which occurs naturally when the mineral mixture is slurried in water water-soluble salts with trivalent metal ions as activators and depressors and in the presence of anionic surfactants as collectors and, if appropriate, with the addition of foams and / or foam regulators.
  • the pH at which the process is carried out according to the invention is generally in the range between 5 and 8. This pH then results if the solid mineral mixtures are slurried in tap water or fully demineralized water or the mineral mixture is washed out of the rock under high pressure with water jet and brought to light.
  • activating acids for example hydrohalic acid or sulfuric acid
  • salts of trivalent metal ions are also added to the aqueous slurries as activators or depressors.
  • Salts or polysalts of aluminum and iron (III) salts are used.
  • the sulfuric salts of trivalent metals are used with advantage.
  • the concentration of the salts is in the range from 50 to 2000 g / t, preferably 100 to 1000 g / t, based on the anhydrous metal salt.
  • Aluminum salts for example aluminum sulfate, are particularly preferably used according to the present invention. It has been found that the Al (III) ion has an activating action on kaolinite and a deactivating action on feldspar in aqueous turbidity at pH values in the range from 5 to 8. By adding aluminum salts to the aqueous slurry, concentrates with a higher kaolinite concentration are obtained during flotation. At the same time, the kaolinite output is increased, so that feldspar with a higher purity is also obtained as a flotation residue.
  • Anionic surfactants can be used as collectors in the process according to the invention.
  • the use of aluminum ions in the separation of kaolinite and feldspar obtained by flotation enables, in particular, a process with the addition of anionic surfactants as collectors.
  • the flotation with anionic collectors has surprisingly been found to be particularly advantageous over the flotation with cationic surfactants in that heavy mineral components present in the ore can be separated from the kaolinite before the flotation, which leads to a higher degree of whiteness of the kaolinite concentrate and also an improved quality of the feldspar residue.
  • the subsequent processing of the kaolinite is facilitated in that anionic surfactants can be more easily desorbed from the surface of the kaolinite particles than cationic surfactants. It should also be borne in mind that anionic surfactants should be preferred over cationic surfactants due to their environmental behavior alone.
  • the concentration of surfactants used as collectors according to the invention is in the range from 50 to 2000 g / t, preferably from 100 to 1000 g / t.
  • auxiliaries known to be used in flotation can be added for the separation of kaolinite and feldspar from the aqueous slurry caused by flotation.
  • auxiliaries are foaming agents on the one hand or anti-foaming agents on the other hand, which, in contrast to methods known from the prior art, are not absolutely necessary.
  • the first component is floated in the mineral mixture of kaolinite and feldspar, while feldspar with surprisingly high purity is obtained as a flotation residue in comparison with processes from the prior art.
  • the respective flotation steps are repeated, depending on the quality requirements for the products, a selective separation of the two components being achieved, particularly in the fine grain area.
  • a further post-cleaning step is sufficient to obtain concentrates with a kaolinite content between 93 and 97%.
  • the kaolinite fraction obtained by flotation is worked up in subsequent process steps.
  • the surfactants adsorbed on the surface are desorbed.
  • the binding of the surfactant molecule to the negatively charged surface of the kaolinite particles takes place via the ion bridges consisting of trivalent metal ions, so that the anionic surfactants can be desorbed more easily from the surface of the kaolinite than cationic surfactant molecules.
  • Another advantage of the process according to the invention is that the flotation of kaolinite caused by anionic surfactants in the presence of trivalent metal ions, preferably aluminum (III) ions, is largely independent of the water hardness and of the turbidity content of indifferent electrolytes.
  • Divalent ions for example calcium or magnesium ions, also improve the selectivity in the flotation of the kaolinite / feldspar mineral mixture, but this effect only occurs at very high ion concentrations, which would make the addition of the ions mentioned to the flotation cloudy uneconomical.
  • the quartz content of the raw products in question for the flotative separation of kaolinite and feldspar is due to a previously passed through Separation process extremely low, so that quartz does not have to be separated.
  • the flotation tests were carried out in a Humboldt-Wedag laboratory flotation cell of 1 l or 2 l content with a kaolinite / feldspar / quartz fraction with a particle size of 90% less than 20 ⁇ m. This fraction was taken from the intermediate stage of a conventional kaolinite processing plant.
  • the selectivity of the flotation ie the content of kaolinite and feldspar in the concentrate or in the flotation residue, was determined using the known method of loss on ignition (DIN 51 081 for testing ceramic raw materials by changing the weight during annealing (July 1979)).
  • the flotation was carried out with an anionic collector (sodium alkylbenzenesulfonate) in the absence (Example 1) or in the presence (Examples 2 to 4) of activating additives.
  • an anionic collector sodium alkylbenzenesulfonate
  • Example 1 sodium alkylbenzenesulfonate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Paper (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Treatment Of Sludge (AREA)

Claims (7)

  1. Procédé de séparation sélective de la kaolinite et du feldspath par flottation en suspension aqueuse, caractérisé en ce qu'on effectue la flottation
    (a) avec une valeur de pH de la suspension de l'ordre de 5 à 8, qui est obtenue naturellement au cours de la mise en suspension du mélange de minéraux dans l'eau,
    (b) en utilisant des sels solubles dans l'eau d'ions de métaux trivalents servant d'activateurs et de dépresseurs et
    (c) en présente d'agents tensioactifs anioniques servant de collecteurs ainsi que
    (d) avec addition éventuelle d'agents moussants et/ou de régulateurs de mousse.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise comme sels solubles dans l'eau des chlorures et/ou des sulfates d'ions métalliques trivalents.
  3. Procédé selon les revendications 1 et 2, caractérisé en ce qu'on utilise comme sels d'ions métalliques trivalents des sels d'aluminium et/ou de fer (III).
  4. Procédé selon les revendications 1 à 3, caractérisé en ce qu'on utilise comme activateur du sulfate d'aluminium.
  5. Procédé selon les revendications 1 à 4, caractérisé en ce qu'on utilise comme collecteurs des agents tensioactifs anioniques ayant de 12 à 18 atomes de carbone dans le radical alkyle, choisis dans le groupe constitué des sulfonates d'alkylbenzène, des sulfonates de pétrole, des sulfates d'alcools gras, des sulfonates d'esters et/ou des sulfosuccinates d'alkyles.
  6. Procédé selon les revendications 1 à 5, caractérisé en ce qu'on utilise les activateurs et les dépresseurs en quantités de 50 à 2000 g/tonne et, de préférence, de 100 à 1000 g/tonne rapportées au sel anhydre.
  7. Procédé selon les revendications 1 à 5, caractérisé en ce qu'on utilise les collecteurs en quantités comprises entre 50 et 2000 g/tonne et de préférence entre 100 et 1000 g/tonne.
EP86102193A 1985-02-27 1986-02-20 Procédé de traitement de la kaolinite par flottation Expired - Lifetime EP0193109B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86102193T ATE70469T1 (de) 1985-02-27 1986-02-20 Verfahren zur aufbereitung von kaolinit durch flotation.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3506808 1985-02-27
DE19853506808 DE3506808A1 (de) 1985-02-27 1985-02-27 Verfahren zur aufbereitung von kaolinit durch flotation

Publications (3)

Publication Number Publication Date
EP0193109A2 EP0193109A2 (fr) 1986-09-03
EP0193109A3 EP0193109A3 (en) 1989-11-08
EP0193109B1 true EP0193109B1 (fr) 1991-12-18

Family

ID=6263637

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86102193A Expired - Lifetime EP0193109B1 (fr) 1985-02-27 1986-02-20 Procédé de traitement de la kaolinite par flottation

Country Status (4)

Country Link
US (2) US4714544A (fr)
EP (1) EP0193109B1 (fr)
AT (1) ATE70469T1 (fr)
DE (2) DE3506808A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019200191A1 (de) 2018-06-08 2019-12-12 Sms Group Gmbh Trockenaufbereitung von Kaolin bei der Herstellung von HPA

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3615385A1 (de) * 1985-05-22 1986-11-27 Skw Trostberg Ag, 8223 Trostberg Verfahren zur trennung von mineralien durch flotation
US5411149A (en) * 1992-08-11 1995-05-02 Arch Development Corporation Aqueous biphasic extraction process with pH and particle control
US7250494B2 (en) * 1998-06-15 2007-07-31 Biosynexus Incorporated Opsonic monoclonal and chimeric antibodies specific for lipoteichoic acid of Gram positive bacteria
FR2855829B1 (fr) * 2003-06-06 2005-09-09 Valois Sas Joint de valve et dispositif de distribution de produit fluide comportant un tel joint
CA2605053A1 (fr) 2007-10-02 2009-04-02 Institut National De La Recherche Scientifique (Inrs) Traitement de milieux contamines par des composes organiques hydrophobes et des metaux
EP2343131B1 (fr) * 2010-01-08 2016-03-30 Université de Lorraine Procédé de flottement pour la récupération de feldspath à partir de minerai de feldspath
CN113231193B (zh) * 2021-05-14 2023-08-15 中国地质科学院郑州矿产综合利用研究所 一种高岭土尾矿制备高纯石英砂的方法
CN115582207B (zh) * 2022-08-26 2024-10-18 中南大学 一种用于弱碱性环境下选择性捕收石英的药剂及应用方法
CN117101872A (zh) * 2023-09-27 2023-11-24 中南大学 一种石英长石碱法浮选分离方法及组合捕收剂

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3203968A (en) * 1959-06-03 1965-08-31 Sebba Felix Ion flotation method
US3337048A (en) * 1964-12-02 1967-08-22 Minerals & Chem Philipp Corp Method for beneficiating clay by flotation
US3462013A (en) * 1967-07-19 1969-08-19 Engelhard Min & Chem Method for beneficiating clay by flotation of colored impurities
US3979282A (en) * 1968-03-11 1976-09-07 English Clays Lovering Pochin & Company Limited Flotation of fine-grained materials
US3599879A (en) * 1970-02-17 1971-08-17 English Clays Lovering Pochin Grinding treatment of clay
JPS5220923B1 (fr) * 1971-03-10 1977-06-07
US3804243A (en) * 1972-06-26 1974-04-16 Engelhard Min & Chem Separation of mica from clay by froth flotation
US3837488A (en) * 1972-08-01 1974-09-24 Engelhard Min & Chem Separation of mica from clay by froth flotation of clay
US4038179A (en) * 1975-06-02 1977-07-26 Akira Katayanagi Hydrochloric acid flotation process for separating feldspar from siliceous sand
US4501658A (en) * 1982-08-25 1985-02-26 Freeport Kaolin Company Method of conditioning clay for flotation using in situ ferrous activator
US4518491A (en) * 1982-09-13 1985-05-21 Anglo-American Clays Corporation Beneficiation of clays by froth flotation

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019200191A1 (de) 2018-06-08 2019-12-12 Sms Group Gmbh Trockenaufbereitung von Kaolin bei der Herstellung von HPA
US11833520B2 (en) 2018-06-08 2023-12-05 Sms Group Gmbh Dry preparation of kaolin in the production of HPA

Also Published As

Publication number Publication date
EP0193109A3 (en) 1989-11-08
ATE70469T1 (de) 1992-01-15
US4714544A (en) 1987-12-22
US4744892A (en) 1988-05-17
DE3506808A1 (de) 1986-08-28
DE3682916D1 (de) 1992-01-30
EP0193109A2 (fr) 1986-09-03

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