WO1992004981A1 - Verfahren zur gewinnung von mineralien aus nichtsulfidischen erzen durch flotation - Google Patents
Verfahren zur gewinnung von mineralien aus nichtsulfidischen erzen durch flotation Download PDFInfo
- Publication number
- WO1992004981A1 WO1992004981A1 PCT/EP1991/001758 EP9101758W WO9204981A1 WO 1992004981 A1 WO1992004981 A1 WO 1992004981A1 EP 9101758 W EP9101758 W EP 9101758W WO 9204981 A1 WO9204981 A1 WO 9204981A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- salts
- flotation
- maleic acid
- partial esters
- Prior art date
Links
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
- B03D1/008—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
- B03D2201/02—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 extracting minerals from non-sulfidic ores by flotation, in which salts of esterification products of maleic acid with oligoglycerol partial esters, optionally in a mixture with other anionic or nonionic surfactants, are used as collectors.
- Flotation is a generally used sorting process for separating valuable minerals from the gangue, which is used to prepare mineral ores.
- the ore is first ground and dry, but preferably wet, and suspended in water.
- a collector is added, often in conjunction with other reagents, which include foaming agents, regulators, pushers (deactivators) and / or Beieber (activators), to separate the valuable minerals from the gangue minerals in the ore during the subsequent flotation supports.
- these reagents are usually allowed to act on the finely ground ore for a certain time (conditioning).
- the collector causes the surface of the minerals to become hydrophobic, so that these minerals adhere to the gas bubbles formed during the aeration.
- the hydrophobization of the mineral Ingredients are selected in such a way that the undesirable components of the ore do not adhere to the gas bubbles and remain behind, while the mineral-containing foam is stripped off and further processed.
- the aim of the flotation is to extract the valuable mineral of the ores in the highest possible yield and at the same time to obtain the best possible enrichment of the valuable mineral.
- collectors In the flotative processing of non-sulfidic ores, mainly anionic or cationic surfactants are used as collectors. These have the task of adsorbing as selectively as possible on the surface of the valuable minerals in order to ensure a high concentration in the flotation concentrate. In addition, the collectors should develop a stable, but not too stable, flotation foam.
- collectors frequently used in the flotation of non-sulfidic ores, such as. B. fatty acids or alkyl sulfosuccinates [ Aufberei ⁇ tionstechnik, 26, 632 (1985)], but in many cases do not lead to a satisfactory yield of valuable minerals with economically justifiable collector quantities.
- the object of the invention was therefore to provide collectors with improved properties in the sense of a more economical design of the flotation process.
- the invention relates to a process for the extraction of minerals from non-sulfidic ores by flotation, in which ground ore 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 contained therein separates floated solids, and also as a collector
- X is an alkali metal or ammonium and n is 0 or numbers from 1 to 18
- salts of the formula (I) in which n is from 2 to 5 and R 1 is a saturated acyl radical having 12 to 18 carbon atoms is particularly advantageous for the flotation.
- salt-type minerals e.g. B. fluorite, Scheelite, barite, apatite, iron oxides and other metal oxides, e.g. B. to understand the oxides of titanium and zirconium, as well as certain silicates and aluminosilicates.
- the salts of the esterification products of maleic acid with oligoglycerol partial esters are known substances and can be prepared by the relevant methods of preparative organic chemistry.
- oligoglycerols ie self-condensation products of glycerol with average degrees of condensation from 2 to 20, with fatty acids to oligoglycerol partial esters that still have free hydroxyl groups, esterify one or two of these OH functions with maleic acid, and the Then neutralize the non-esterified acid functions of the dicarboxylic acid component with an aqueous alkali solution.
- Corresponding methods are in Seifen- ⁇ le-Fette-Wwachs 104, 3 (1978) and 70%.Kosm. 60, 37 (1979).
- Typical fatty acids which may be present as components in the salts of the formula (I) are caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pal itic acid and stearic acid.
- the fatty acids can also be present as technical mixtures, such as those found in B. after pressure splitting of natural fats and oils (eg coconut oil, palm oil, palm kernel oil, rapeseed oil, sunflower oil or beef tallow) and subsequent hardening.
- the reaction of the fatty acid with the oligoglycerin leads to a statistical mixture of esters of different substitution patterns.
- oligoglycerin and fatty acid are used in a molar ratio of 1: 1 to 1: 2.
- the resulting esterification products according to formula (I) have at least one primary fatty acid ester group.
- esterification with maleic acid or maleic anhydride likewise statistical laws. If primary hydroxyl groups are still present, it can be assumed that these are the first to be esterified.
- the process according to the invention permits the use of the salts of esterification products of maleic acid with oligoglycerol partial esters as collectors for the extraction of minerals from non-sulphide ores by flotation alone or in the presence of further anionic or nonionic surfactants.
- anionic surfactants are to be understood as meaning fatty acids, alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzene sulfonates, alkyl sulfonates, petroleum sulfonates, acyl lactylates, sarcosides, alkyl phosphates and alkyl ether phosphates. All of these anionic surfactants are known compounds, the preparation of which - unless otherwise stated - e.g. in J. Falbe, U.
- Hasserodt ed.
- Catalysts ed.
- surfactants ed.
- mineral oil additives ed.
- J. Falbe ed.
- the fatty acids are, in particular, the vegetable or animal fats and oils, for example by fat splitting and optionally fractionation and / or separation after the Crosslinking process, straight-chain fatty acids of the formula (II) into consideration,
- V ⁇ - represents an aliphatic hydrocarbon radical having 12 to 18 carbon atoms and 0, 1, 2 or 3 double bonds and Y represents an alkali metal, alkaline earth metal or an ammonium radical.
- Y represents an alkali metal, alkaline earth metal or an ammonium radical.
- Suitable alkyl sulfates are the water-soluble salts of sulfuric acid half-esters of fatty alcohols of the formula (III)
- Suitable alkyl ether sulfates are the water-soluble salts of sulfuric acid semiesters of fatty alcohol polyglycol ethers of the formula (IV)
- Suitable alkylsulfosuccinates are sulfosuccinic acid monoesters of fatty alcohols of the formula (V)
- R ⁇ represents a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms and Z has the meaning given above.
- Suitable alkylsulfosuccinamates are sulfosuccinic acid monoamides of fatty amines of the formula (VI),
- Suitable alkylbenzenesulfonates are substances of the formula (VII)
- R 11 represents a straight-chain or branched alkyl radical having 4 to 16, preferably 8 to 12 carbon atoms and Z has the meaning given above.
- Suitable alkyl sulfonates are substances of the formula (VIII)
- Suitable petroleum sulfonates are substances which are obtained by reacting lubricating oil fractions with sulfur trioxide or oleu and then neutralizing with sodium hydroxide solution. Products in which the hydrocarbon residues predominantly have chain lengths of 8 to 22 carbon atoms are particularly suitable here.
- Suitable acyl lactylates are substances of the formula (IX)
- R 13 represents an aliphatic, cycloaliphatic or alicyclic, optionally substituted with hydroxyl groups, hydrocarbon radical having 7 to 23 carbon atoms and 0, 1, 2 or 3 double bonds and Z has the meaning given above.
- Suitable sarcosides are substances of the formula (X)
- alkyl phosphates and alkyl ether phosphates are substances of the formulas (XI) and (XII)
- R-- and R 1 ⁇ independently of one another represent an alkyl or alkenyl radical with 8 to 22 carbon atoms and p and q in the case of the alkyl phosphates for zero, in the case of the alkyl ether phosphates for numbers from 1 to 15 and Z has the meaning given above be ⁇ sits.
- the phosphates can be present as mono- or diphosphates. In this case, preference is given to using mixtures of mono- and dialkylphosphates as are obtained in the industrial production of such compounds.
- nonionic surfactants are to be understood as meaning fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, mixed ethers, hydroxy mixed ethers and alkyl glycosides. All of these nonionic surfactants are Known compounds whose preparation - unless otherwise stated - for example in J.Falbe, U.
- Hasserodt ed.
- Catalysts ed.
- surfactants ed.
- mineral oil additives e.g
- Suitable fatty acid alcohols are addition products of an average of n moles of ethylene and / or propylene oxide with fatty alcohols, which follow the formula (XIII),
- R * 7 represents a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms, hydrogen or a methyl group and n represents numbers from 1 to 30, preferably 2 to 15.
- Suitable alkylphenol polyglycol ethers are addition products of an average of n moles of ethylene and / or propylene glycol with alkylphenols which follow the formula (XIV)
- R * 8 represents an alkyl radical having 4 to 15, preferably 8 to 10 carbon atoms and R 8 and n have the meanings given above.
- Suitable fatty acid polyglycol esters are adducts of an average of n moles of ethylene and / or propylene oxide with fatty acids which follow the formula (XV)
- R 1 ⁇ represents an aliphatic carbon radical having 5 to 21 carbon atoms and 0, 1, 2 or 3 double bonds and R and n have the meanings given above.
- Suitable fatty acid amide polyol ethers are addition products of an average of n moles of ethylene oxide and / or propylene oxide onto fatty acid amides which follow the formula (XVI)
- R ⁇ O represents an aliphatic hydrocarbon radical having 5 to 21 carbon atoms and 0, 1, 2 or 3 double bonds and R ⁇ and n have the meanings given above.
- Suitable fatty amine polymer ethers are addition products of an average of n moles of ethylene oxide and / or propylene oxide onto fatty acids which follow the formula (XVII)
- Suitable mixed ethers are reaction products of fatty alcohol polyglycol ethers with alkyl chlorides of the formula (XVIII)
- R 22 represents an aliphatic carbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds
- R 23 represents an alkyl radical having 1 to 4 carbon atoms and R and n have the meanings given above.
- Suitable Hroxroxy mixed ethers are substances of the formula (XIX)
- R 24 represents an alkyl radical having 6 to 16 carbon atoms
- R 5 represents an alkyl radical having 1 to 4 carbon atoms
- R 8 and n have the meanings given above.
- the preparation of the hydroxy mixed ethers is described in German patent application DE-A-37 23 323.
- G represents a symbol for a glycose unit derived from a sugar with 5 or 6 carbon atoms, x for a number between 1 and 10 and R ⁇ for an aliphatic hydrocarbon radical with 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.
- G is preferably a Glucose unit and x for numbers from 1.1 to 1.6.
- salts of esterification products of maleic acid with oligoglycerol partial esters are not used alone, but in a mixture with other anionic or nonionic surfactants, these mixtures advantageously have a content of 5 to 95% by weight, preferably 10 to 60% by weight, of the salts of esterification ⁇ products of maleic acid with oligoglycerol partial esters.
- the surfactant mixture must be used in a certain minimum amount. However, a maximum amount of surfactant mixture must not be exceeded, since otherwise the foam formation becomes too strong and the selectivity towards the valuable minerals decreases.
- the salts of esterification products of maleic acid to be used according to the invention with oligoglycerol partial esters or their mixtures with other anionic or nonionic surfactants depend on the type of ores to be floated and on their content of valuable minerals. Accordingly, the amounts required in each case can vary within wide limits.
- the salts of esterification products of maleic acid to be used according to the invention with oligoglycerol partial esters or their mixtures with anionic or nonionic surfactants in amounts of 50 to 2000, preferably 100 to 1500 g, per ton of crude ore.
- the method according to the invention includes the use of reagents customary for flotation, such as foaming agents, regulators, activators, deactivators, etc.
- the flotation is carried out under the conditions of the prior art methods.
- a preferred field of application of the method is the flotation of salt-type minerals, in particular apatite ores.
- A2 C12 / 14-CO H CO-CH CH-COONa CO-CH-CH-COONa 0
- the ore was already ground up in the slurry. After wet sieving, a particle size fraction of 50-100 ⁇ m was used as the task. A modified Hallimond tube with a volume of 165 ml and a stirring speed of 400 rpm was used as the flotation cell. 2 g of ore (dry content) were conditioned and floated at pH 10 (adjusted with sodium hydroxide) in water at 20 ° d (calcium ions only). The conditioning time for the hardening water was 5 minutes, for the collector 10 minutes; the flotation was carried out over a period of 2 minutes.
- the collectors according to the invention were used alone or in a mixture with the co-collectors (alkyl sulfosuccinate sodium salt, B1 and oleic acid sodium salt, B2); B1 and B2 were also used individually as reference substances.
- the results are summarized in Table 2. Examples 1-10 show that salts of esterification products of maleic acid with oligoglycerol partial esters can advantageously be used both as collectors, but in particular as co-collectors in a mixture with other anionic or nonionic surfactants in the flotation of non-sulfidic ores.
- Tab. 2 Flotation of Swedish apatite ore in the modified halli tube; Percentages as% by weight
- collector EM MA GI G2 G3 PA g / t%%%%%
- the flotation task had the following grain size distribution:
- the collectors according to the invention were used alone and in combination with an alkyl sulfosuccinate Na / NH4 salt (B1) or a technical oleic acid (B3) as co-collectors, the mixture ratio collector: co-collectors 33: 67 to 67: 33 Parts by weight.
- Technical oleic acid which was brought into solution with sodium hydroxide solution (B3), served as the reference substance.
- a Denver laboratory flotation machine type D1 was floated in the 2-1 cell, the cleaning stages (2 to 4 Post-cleanings) were carried out in a corresponding 1-1 cell.
- Water of 3 ° d was used as the flotation water; the cloud density during pre-flotation was approx. 500 g / 1.
- a phenol-formaldehyde condensate (Cl) was used in a dosage of 200 g / t.
- the pH of the slurry was adjusted to 10 with sodium hydroxide.
- the conditioning of the reagents was carried out with stirring at a stirrer speed of 1000 rpm, the conditioning time for pushers and collectors was 5 minutes in each case.
- the flotation was carried out at a speed of 1100 rpm (2-1 cell) or 1000 rpm (1-1 cell), the flotation time was approximately 4 minutes, during which the flotation foam was removed manually.
- the flotation concentrate of the pre-flotation (rougher concentrate) was added to the 1-1 cell without the addition of reagents and flotated at 1000 rpm for about 4 minutes.
- Examples 11, 14, 16 and 18 and comparative example V5 were each carried out with four, examples 12 and 15 with three and examples 13 and 17 with two cleaning stages. The results obtained are summarized in Table 3.
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- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NO930245A NO930245D0 (no) | 1990-09-24 | 1993-01-25 | Fremgangsmaate for flotasjonsekstrahering av mineraler inneholdt i ikke-sulfidiske malmer |
FI931267A FI931267A0 (fi) | 1990-09-24 | 1993-03-23 | Foerfarande foer anrikning av mineraler av icke-sulfimalmar genom flotation |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4030160A DE4030160A1 (de) | 1990-09-24 | 1990-09-24 | Verfahren zur gewinnung von mineralien aus nichtsulfidischen erzen durch flotation |
DEP4030160.5 | 1990-09-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992004981A1 true WO1992004981A1 (de) | 1992-04-02 |
Family
ID=6414849
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1991/001758 WO1992004981A1 (de) | 1990-09-24 | 1991-09-16 | Verfahren zur gewinnung von mineralien aus nichtsulfidischen erzen durch flotation |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0550483A1 (de) |
AU (1) | AU8510191A (de) |
CA (1) | CA2092440A1 (de) |
DE (1) | DE4030160A1 (de) |
FI (1) | FI931267A0 (de) |
MX (1) | MX9101215A (de) |
TR (1) | TR25169A (de) |
WO (1) | WO1992004981A1 (de) |
ZA (1) | ZA917574B (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10024667C2 (de) | 2000-05-18 | 2002-02-28 | Clariant Gmbh | Mittel zur Aufbereitung von Phosphaterz |
US11179312B2 (en) | 2017-06-05 | 2021-11-23 | Momentive Performance Materials Inc. | Aqueous compositions for the treatment of hair |
US11090255B2 (en) | 2018-12-04 | 2021-08-17 | Momentive Performance Materials Inc. | Use of polycarboxylic acid compounds for the treatment of fibrious amino acid based substrates, especially hair |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2312466A (en) * | 1940-02-08 | 1943-03-02 | American Cyanamid Co | Oxygen-bearing ore flotation |
US2362432A (en) * | 1941-07-03 | 1944-11-07 | Emulsol Corp | Flotation of ores |
EP0067137A1 (de) * | 1981-05-18 | 1982-12-15 | Berol Kemi Ab | Veresterte Dicarboxylsäuren und ihre Verwendung |
US4511463A (en) * | 1977-06-24 | 1985-04-16 | West-Point Pepperell, Inc. | Process for recovery of phosphate ore |
-
1990
- 1990-09-24 DE DE4030160A patent/DE4030160A1/de not_active Withdrawn
-
1991
- 1991-09-13 TR TR91/0908A patent/TR25169A/xx unknown
- 1991-09-16 CA CA002092440A patent/CA2092440A1/en not_active Abandoned
- 1991-09-16 AU AU85101/91A patent/AU8510191A/en not_active Abandoned
- 1991-09-16 EP EP91916056A patent/EP0550483A1/de not_active Withdrawn
- 1991-09-16 WO PCT/EP1991/001758 patent/WO1992004981A1/de not_active Application Discontinuation
- 1991-09-23 ZA ZA917574A patent/ZA917574B/xx unknown
- 1991-09-23 MX MX9101215A patent/MX9101215A/es unknown
-
1993
- 1993-03-23 FI FI931267A patent/FI931267A0/fi not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2312466A (en) * | 1940-02-08 | 1943-03-02 | American Cyanamid Co | Oxygen-bearing ore flotation |
US2362432A (en) * | 1941-07-03 | 1944-11-07 | Emulsol Corp | Flotation of ores |
US4511463A (en) * | 1977-06-24 | 1985-04-16 | West-Point Pepperell, Inc. | Process for recovery of phosphate ore |
EP0067137A1 (de) * | 1981-05-18 | 1982-12-15 | Berol Kemi Ab | Veresterte Dicarboxylsäuren und ihre Verwendung |
Also Published As
Publication number | Publication date |
---|---|
AU8510191A (en) | 1992-04-15 |
FI931267A (fi) | 1993-03-23 |
MX9101215A (es) | 1992-05-04 |
FI931267A0 (fi) | 1993-03-23 |
DE4030160A1 (de) | 1992-03-26 |
EP0550483A1 (de) | 1993-07-14 |
TR25169A (tr) | 1992-11-01 |
ZA917574B (en) | 1992-06-24 |
CA2092440A1 (en) | 1992-03-25 |
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