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WO1993007110A1 - Procede d'enrichissement et/ou de purification de charbon et de mineraux par flottation, a l'aide d'hydroxylimonene-ethers - Google Patents

Procede d'enrichissement et/ou de purification de charbon et de mineraux par flottation, a l'aide d'hydroxylimonene-ethers

Info

Publication number
WO1993007110A1
WO1993007110A1 PCT/EP1992/002260 EP9202260W WO9307110A1 WO 1993007110 A1 WO1993007110 A1 WO 1993007110A1 EP 9202260 W EP9202260 W EP 9202260W WO 9307110 A1 WO9307110 A1 WO 9307110A1
Authority
WO
WIPO (PCT)
Prior art keywords
flotation
ethers
carbon atoms
coal
hydroxylimone
Prior art date
Application number
PCT/EP1992/002260
Other languages
German (de)
English (en)
Inventor
Manfred Biermann
Holger Tesmann
Rita Köster
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1993007110A1 publication Critical patent/WO1993007110A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/18—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C43/196—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring containing hydroxy or O-metal groups
    • 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
    • B03D1/008—Organic compounds containing oxygen
    • 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
    • B03D2201/04—Frothers
    • 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
    • B03D2203/08—Coal ores, fly ash or soot
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the invention relates to a process for the enrichment and / or purification of coal and minerals by flotation, in which hydroxylimone ether is used as a foamer, hydroxylimone ether and a process for their preparation.
  • Raw coal from mining in coal mining is processed to a large extent using the density differences.
  • the raw coal is mechanically separated into coal fractions and a so-called recovery fraction.
  • For the fine grain fraction particle size smaller than 0.5 mm
  • flotation is preferred as a sorting process, with the fine grain coal being separated from the ash fraction due to the different surface properties of coal particles and rock particles. This takes advantage of the natural, water-repellent character of the surface of the carbon particles and reinforces it by adsorbing hydrophobic reagents.
  • suitable media The separation of fine grain coal and ash is possible using a flotation process and has also proven itself as an industrially used process.
  • the fine carbon particles are bound to foam bubbles of a sufficiently stable foam produced by adding a foamer and thus removed from the slurry.
  • the aim is to bring out the highest possible coal, but the ash content in the floated coal should be as low as possible, since this reduces the calorific value of the coal.
  • foamer is not limited to the simple generation of the foam.
  • the type and amount of foaming agents can be used to control important foam characteristics, such as bubble size, bubble strength and cohesion of the bubbles.
  • an influence of the foamer on the other components of the flotation slurry is usually observed.
  • An influence of the foamer is undesirable if it acts unselectively on the collectors used in ore flotation, which change the hydrophilicity of the particle surface and should ensure better adhesion of the particles to the foam bubbles.
  • the minerals can be enriched through the successive application of individual flotation steps.
  • the ore is crushed, preferably ground wet, and floated after adding the reagents necessary for the flotation.
  • Appropriate adjustment of the slurry with regard to pH value, type and concentration of the collector, pusher and foamer enables a selective separation of valuable mineral and gait with high yield.
  • foams where there is no parallel orientation of the individual molecules. For this reason, substances with branched chains and asymmetrically arranged hydrocarbon groups are preferred.
  • the optimal use of the foamer mentioned depends not only on the separation problem to be solved, but also - as stated above - on the other components present in the slurry, such as collectors, activators etc.
  • German Offenlegaungsschrift DE-OS 19 30 671 for example, a method based on flotation is used Separation of minerals from ore is described in aqueous slurry, in which air is fed to the slurry containing a foamer and with the help of the resulting air bubbles, the removal of the valuable minerals is made possible.
  • An adduct of ethylene oxide or propylene oxide with alcohols or glycols or their lower alkyl monoethers is used as the foamer.
  • German Offenlegungsschrift DE-OS 19 30 864 is a process in which the foamer represents the reaction product of ethylene oxide, propylene oxide or their mixtures with a polyhydric alcohol having at least 3 hydroxyl groups in the molecule.
  • the foaming agents mentioned in the two aforementioned disclosure documents can be used both for the flotation of coal and for the flotation of a large number of ores and lead to a satisfactory discharge of the fractions, the enrichment of which is desired by the flotation process.
  • no adverse effect of the foamer on the properties of the collector in the flotation slurry was observed.
  • the selectivity of some separation processes was not completely satisfactory, so that there was still a need for selective foaming agents which also lead to a high discharge of the desired fraction.
  • Flotation processes for coal using foaming agents are also known from European patent application EP 0 113 310 AI.
  • Reaction products of a mono- or dibasic carboxylic acid with 1 to 10 carbon atoms and a polyhydroxy compound are used as foaming agents, the resulting ester alcohols having at least one free one Have hydroxy group.
  • Substances which have branched alkyl groups and have a total number of 6 to 19 carbon atoms are preferably used.
  • the object of the invention was therefore an improved flotation process for enrichment and / or
  • the invention relates to a process for the enrichment and / or purification of minerals and coal by flotation, in which ground ore or coal is mixed with water to form a suspension, air is introduced into the suspension in the presence of a reagent system and the resulting foam together with the foam therein contained contained floated solids, which is characterized in that hydroxylimone ethers of the formulas (Ia) and / or (Ib),
  • R 1 is a linear or branched alkyl radical having 1 to 12 carbon atoms, a hydroxyethyl or a hydroxypropyl radical, optionally in admixture with other commercially available foamers and / or collectors.
  • reaction products of limonene epoxide with monohydric alcohols or diols so-called “hydroxylimone ethers” have excellent properties as foaming agents not only in coal flotation, but can also be used as universally usable foaming agents in ore flotation. It was also shown that the The reaction products mentioned are not only compatible with other constituents of the flotation slurry, as is required for conventional foaming agents, but also have a positive effect on the influence of the collector in the flotation slurry, ie increase the collector effect and thereby reduce the amount used for those added as collectors Connections can contribute.
  • the hydroxylimone ethers can be used alone or in a mixture with other commercially available foams and / or collectors.
  • Examples include aliphatic alcohols with 5 to 8 carbon atoms, carbinols, phenols, terpene alcohols, polyalkylene glycols and / or alkyl polyalkylene glycol ethers.
  • hydroxylimone ethers with 2-ethylhexanol, ortho-cresol, pine oil, alpha-terpineol, methylisobutylcarbinol, polyethylene or polypropylene glycol ethers with average molecular weights of 300 to 3000, addition products of ethylene and / or propylene oxide onto aliphatic alcohols with 1 to 4 carbon atoms, gasoline fractions or mineral oils.
  • the mixtures can contain the hydroxylimone ethers in amounts of 5 to 99, preferably 50 to 70% by weight, based on the mixture.
  • the foamer To achieve economically useful results in flotation, the foamer must be in a certain minimum amount be used. However, a maximum amount of hydroxylimone ethers must not be exceeded, since otherwise the foam formation becomes too strong and the selectivity towards the valuable minerals decreases.
  • the amounts in which the hydroxylimone ethers to be used according to the invention or their mixtures with other commercially available foaming agents are used depend on the type of material to be floated and on its content of valuable components. As a result, the amounts required can vary within wide limits.
  • the hydroxylimone ethers to be used according to the invention or their mixtures with other commercially available foaming agents are used in amounts of 5 to 1000, preferably 100 to 500 g, per ton of crude ore or coal.
  • the process according to the invention includes the use of reagents customary for flotation, such as collectors, regulators, activators, deactivators, etc.
  • the flotation is carried out under the conditions of the methods of the prior art.
  • a preferred application of the method is the flotation of coal and sulfidic ores. While reaction products of limonene epoxide with ethanol are known, for example, from J. Org. Chem. 31, 1937 (1966), the higher hydroxylimone ethers are new substances. Another object of the invention therefore relates to hydroxylimone ethers of the formulas (Ia) and / or (Ib)
  • R 1 represents a linear or branched alkyl radical having 3 to 12 carbon atoms, a hydroxyethyl or a hydroxypropyl radical.
  • Another object of the invention finally relates to a process for the preparation of hydroxylimone ethers of the formulas (Ia) and / or (Ib)
  • R 1 represents a linear or branched alkyl radical having 3 to 12 carbon atoms, a hydroxyethyl or a hydroxypropyl radical, which is characterized in that limonene epoxide in the presence of linear or branched aliphatic alcohols having 3 to 12 carbon atoms, ethylene glycol or propylene glycol in subject to a ring opening reaction known per se.
  • the preparation of the hydroxylimone ethers to be used according to the invention is based on limonene epoxide, which is reacted at elevated temperature with the nucleophile - that is to say the alcohol or glycol.
  • nucleophiles which are suitable for ring opening are n-propanol, isopropyl alcohol, n-butanol, i-butanol, sec-butanol, tert-butanol, pentanol, hexanol, heptanol, n-octanol, 2- Ethyl hexyl alcohol, decanol, dodecanol, ethylene glycol or propylene glycol.
  • the two positionally isomeric vicinal hydroxyethers (la) and (Ib) are formed, the ratio of which is approximately 1: 1.
  • the ring opening can be carried out at temperatures from 80 to 130, preferably 100 to 110 ° C and preferably in the presence of acidic catalysts, such as sulfuric acid or phosphoric acid; neutralization of the acid with a base, preferably sodium methylate, is then recommended.
  • the reaction can take place in the presence of an inert organic solvent.
  • EP 0 361 080 AI With regard to the known ring opening of epoxides For example, reference is made to EP 0 361 080 AI.
  • MIBC isobutyl carbinol
  • AMX amylxanthate (collector)
  • IMX isopropyl xanthate (collector)
  • NAC sodium cyanide (modifier)
  • the coal flotation was carried out in accordance with the working specification DIN 22 017. Of the six flotation levels prescribed in the regulation, three levels were carried out, since in particular the first flotation levels provide information about the effectiveness of the foamer to be examined; all foaming agents were added gradually and undiluted. The ash content was determined in accordance with DIN 51 719.
  • Fine grain coal (32% by weight ash, approx. 1.5% by weight total sulfur) with the following particle size distribution was used for the flotation tests:
  • Ash content of the flotation feed approx. 31% by weight
  • the flotation was carried out in a KHD laboratory flotation cell MN 935/4 (volume: 2 l) with a solids concentration of 150 g / l water (16 ° d). From the 1st flotation stage, the material to be flotated was conditioned over a period of 1 min at a speed of 2000 rpm; from the second and third stages there was no conditioning carried out. The flotation was carried out in all three stages over a period of 1 min each at a speed of 2000 rpm. In addition to testing the pure foamer, combinations of the foamer with a naphthenic mineral oil (M ⁇ ) were also tested, which are also used in coal preparation. The weight ratio of foamer / mineral oil is 1: 1 in all flotation examples. The results of the flotation are summarized in Table 1:
  • the flotation task consisted of a cassiterite ore, which had the following composition:
  • the flotation was carried out in a Denver laboratory flotation cell, type Dl (volume: 1 1) with turbidity densities of approx. 400 g / 1 tap water (16 ° d); styrene phosphonic acid was used as a collector.
  • the slurry was added at pH 7 to 8 as a pusher glass in a dosage of 2200 g / t.
  • the preconditioning was carried out over a period of 15 minutes at a speed of 1500 rpm.
  • the slurry was then adjusted to pH 5 with sulfuric acid, the collector and, if appropriate, the undiluted foamer were metered in and finally conditioned at 1500 rpm for a further 10 min.
  • the flotation was carried out in two stages (6 min each, 1200 rpm) without a subsequent cleaning stage. The results are summarized in Table 2. IV. Flotation of sulfidic ores
  • the flotation task consisted of a finely overgrown sulfide ore, which, in addition to sphalerite, pyrite, galena and chalcogenite, contained barite, carbonates and shale as the secondary rock.
  • the composition was determined by X-ray fluorescence (average analysis):

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Des minéraux et du charbon sont enrichis et/ou purifiés selon un procédé par flottation, en utilisant comme agents moussants des hydroxylimonène-éthers de formule (Ia) et/ou (Ib) dans lesquelles R1 désigne un reste alkyle linéaire ou ramifié de 1 à 12 atomes de carbone, un reste hydroxyéthyle ou un reste hydroxypropyle, le cas échéant mélangés à d'autres agents moussants et/ou collecteurs de type commercial.
PCT/EP1992/002260 1991-10-09 1992-09-30 Procede d'enrichissement et/ou de purification de charbon et de mineraux par flottation, a l'aide d'hydroxylimonene-ethers WO1993007110A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4133388.8 1991-10-09
DE4133388A DE4133388A1 (de) 1991-10-09 1991-10-09 Verfahren zur anreicherung und/oder reinigung von kohle und mineralien durch flotation

Publications (1)

Publication Number Publication Date
WO1993007110A1 true WO1993007110A1 (fr) 1993-04-15

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Application Number Title Priority Date Filing Date
PCT/EP1992/002260 WO1993007110A1 (fr) 1991-10-09 1992-09-30 Procede d'enrichissement et/ou de purification de charbon et de mineraux par flottation, a l'aide d'hydroxylimonene-ethers

Country Status (2)

Country Link
DE (1) DE4133388A1 (fr)
WO (1) WO1993007110A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116213130A (zh) * 2023-02-23 2023-06-06 长江师范学院 一种高硫铁矿提铁降硫工艺

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110773325A (zh) * 2019-11-08 2020-02-11 南昌航空大学 一种胺类捕收剂的应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE851485C (de) * 1945-01-11 1952-10-06 Lech Chemie Gersthofen Verfahren zur Schaumschwimmaufbereitung
DE1930671A1 (de) * 1968-06-18 1970-01-02 American Cyanamid Co Erzflotationsverfahren
EP0281029A2 (fr) * 1987-03-05 1988-09-07 Henkel Kommanditgesellschaft auf Aktien Utilisation de dérivés du tricyclo-[5.3.1.0 2,6]-décène-3 comme agents moussants dans la flottation du charbon et de minerais
US4915825A (en) * 1989-05-19 1990-04-10 Nalco Chemical Company Process for coal flotation using 4-methyl cyclohexane methanol frothers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE851485C (de) * 1945-01-11 1952-10-06 Lech Chemie Gersthofen Verfahren zur Schaumschwimmaufbereitung
DE1930671A1 (de) * 1968-06-18 1970-01-02 American Cyanamid Co Erzflotationsverfahren
EP0281029A2 (fr) * 1987-03-05 1988-09-07 Henkel Kommanditgesellschaft auf Aktien Utilisation de dérivés du tricyclo-[5.3.1.0 2,6]-décène-3 comme agents moussants dans la flottation du charbon et de minerais
US4915825A (en) * 1989-05-19 1990-04-10 Nalco Chemical Company Process for coal flotation using 4-methyl cyclohexane methanol frothers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 88, no. 3, 1978, Columbus, Ohio, US; abstract no. 23161, Seite 660 ; *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116213130A (zh) * 2023-02-23 2023-06-06 长江师范学院 一种高硫铁矿提铁降硫工艺

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Publication number Publication date
DE4133388A1 (de) 1993-04-15

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