CA2037883A1 - Process for the selective flotation of phosphorus minerals - Google Patents
Process for the selective flotation of phosphorus mineralsInfo
- Publication number
- CA2037883A1 CA2037883A1 CA002037883A CA2037883A CA2037883A1 CA 2037883 A1 CA2037883 A1 CA 2037883A1 CA 002037883 A CA002037883 A CA 002037883A CA 2037883 A CA2037883 A CA 2037883A CA 2037883 A1 CA2037883 A1 CA 2037883A1
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- Prior art keywords
- flotation
- mixture
- alkyl
- collecting agent
- minerals
- 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.)
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Classifications
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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
- B03D1/008—Organic compounds containing oxygen
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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
- B03D1/01—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
- B03D1/012—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
- B03D1/014—Organic compounds containing phosphorus
-
- 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
- B03D1/021—Froth-flotation processes for treatment of phosphate ores
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/01—Treating phosphate ores or other raw phosphate materials to obtain phosphorus or phosphorus compounds
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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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
- Detergent Compositions (AREA)
Abstract
Abstract of the disclosure Process for the selective flotation of phosphorus minerals The process for the selective flotation of phosphorus minerals, wherein a mixture of a compound of the formula 1a and/or 1b (1a) and/or (1b) in which R1 is branched or unbranched C8-C24-alkenyl, R2 is branched or unbranched C1-C4-alkyl and M is hydrogen, ammonium, triethanolammonium, an alkali metal atom or an alkaline earth metal atom, and of one or more of the following compounds (2) (3) (4) (5) (6) (7) (8)
Description
203r~33 `HOECHST AKTIENGESELLSCHAFT HOE 90/F 084 Dr.GT/~e Description Process for the selective flotation of phasphorus minerals ~his invention relates to the separation of phosphorus minerals such as apatite, phosphorite, francolite and the like by means of flotation from raw ores or preconcen-trates with the aid of mixtures of anionic oxhydril collecting agents, of which one component comes from the group of the monoalkyl alkenylsuccinates.
According to Winnacker and KUchler: Chemische Technologie [Chemical Technology], Volume 4 (Metalle [Metals]), 4th edition, Carl Hanser Verlag Munich Vienna, 1986, page 66, collecting agents are organochemical compounds which, in addition to one or more apolar hydrocarbon radicals, carry one or more chemically active polar groups which are capable of being adsorbed on active centers of the mineral and thus rendering the latter hydrophobic.
As is known, flotation (froth flotation dressing) is a widely used sorting method for mineral raw materials, in which one or more minerals of value are separated from the worthless ones. The mineral raw material is prepared for flotation by dry, but preferably wet grinding of the precomminuted ore to a suitable grain size which depends, on the one hand, on the degree of intergrowth, i.e. on the size of the individual qrains in a mineral assembly, and, on the other hand, also on the maximum grain size which is still to be floated and which can differ very widely depending on the mineral. The type of flotation machine used also has an influence on the maximum grain size which is still to be floated. Although not the rule, it is frequently the case that the well crystallized magmatic phosphate ores allow coarser grinding (for example <0.25 mm) than those of marine-sedimentary origin - 2 - ~7~83 (for example ~0.15 mm).
Further steps in the preparation of the ores for flota-tion can comprise a preseparation of worthless material on the one hand, for example, by gravimetric sorting or gravity dressinq (separation of relatively coarse con-stituents) and, on the other hand, by de-sludging (separation of extreme fines). The removal of magnetic minerals which, for example, are almost always present in phosphate ores of magmatic origin, by means of magnetic separation is a further possible pre-enrichment method.
However, the invention is not restricted to flotation processes which have been preceded by any preconcentra-tion.
A distinction is made between two procedures with respect to the minerals to be obtained in the froth. In direct flotation, the mineral or minerals of value are collected in the froth, which is produced on the surface of the flotation pulp, which re~uires that their surfaces have been rendered hydrophobic beforehand by means of one or more collecting agents. The worthless minerals are then found in the flotation tailings. In the converse flota-tion, the worthless minerals are rendered hydrophobic by collecting agents, whereas the flotating tailings form the actual concentrate of value. The present invention relates to the direct flotation of phosphorus minerals, but this can also follow a preceding converse flotation stage which, for example, comprises a flotation of silicate minerals by means of cationic collecting agents.
A large number of anionic and amphoteric chemical com-pounds are known as collecting agents for phosphorus minerals, and these include, for example, saturated and unsaturated fatty acids, (stearic acid, oleic acid, linoleic acid, linolenic acid) and sodium, potassium or ammonium soaps thereof, monoalkyl and dialkyl phosphates, alkanesulfocarboxylic acids, alkylarylsulfonates, acyl-aminocarboxylic acids and alkylaminocarboxylic acids.
According to Winnacker and KUchler: Chemische Technologie [Chemical Technology], Volume 4 (Metalle [Metals]), 4th edition, Carl Hanser Verlag Munich Vienna, 1986, page 66, collecting agents are organochemical compounds which, in addition to one or more apolar hydrocarbon radicals, carry one or more chemically active polar groups which are capable of being adsorbed on active centers of the mineral and thus rendering the latter hydrophobic.
As is known, flotation (froth flotation dressing) is a widely used sorting method for mineral raw materials, in which one or more minerals of value are separated from the worthless ones. The mineral raw material is prepared for flotation by dry, but preferably wet grinding of the precomminuted ore to a suitable grain size which depends, on the one hand, on the degree of intergrowth, i.e. on the size of the individual qrains in a mineral assembly, and, on the other hand, also on the maximum grain size which is still to be floated and which can differ very widely depending on the mineral. The type of flotation machine used also has an influence on the maximum grain size which is still to be floated. Although not the rule, it is frequently the case that the well crystallized magmatic phosphate ores allow coarser grinding (for example <0.25 mm) than those of marine-sedimentary origin - 2 - ~7~83 (for example ~0.15 mm).
Further steps in the preparation of the ores for flota-tion can comprise a preseparation of worthless material on the one hand, for example, by gravimetric sorting or gravity dressinq (separation of relatively coarse con-stituents) and, on the other hand, by de-sludging (separation of extreme fines). The removal of magnetic minerals which, for example, are almost always present in phosphate ores of magmatic origin, by means of magnetic separation is a further possible pre-enrichment method.
However, the invention is not restricted to flotation processes which have been preceded by any preconcentra-tion.
A distinction is made between two procedures with respect to the minerals to be obtained in the froth. In direct flotation, the mineral or minerals of value are collected in the froth, which is produced on the surface of the flotation pulp, which re~uires that their surfaces have been rendered hydrophobic beforehand by means of one or more collecting agents. The worthless minerals are then found in the flotation tailings. In the converse flota-tion, the worthless minerals are rendered hydrophobic by collecting agents, whereas the flotating tailings form the actual concentrate of value. The present invention relates to the direct flotation of phosphorus minerals, but this can also follow a preceding converse flotation stage which, for example, comprises a flotation of silicate minerals by means of cationic collecting agents.
A large number of anionic and amphoteric chemical com-pounds are known as collecting agents for phosphorus minerals, and these include, for example, saturated and unsaturated fatty acids, (stearic acid, oleic acid, linoleic acid, linolenic acid) and sodium, potassium or ammonium soaps thereof, monoalkyl and dialkyl phosphates, alkanesulfocarboxylic acids, alkylarylsulfonates, acyl-aminocarboxylic acids and alkylaminocarboxylic acids.
- 3 _ ~37g~3 Moreover, collecting agents are known which are adducts of sulfosuccinic acid (cf., for example, US Patents 4,207,178, 4,192,739, 4,158,623 and 4,139,481 and SV
Patent 1,113,317). Many of these chemical compound classes have, however, an inadequate selectivity which does not allow the production of saleable concentrates or necessitates the use of larger quantities of regulating reagents, specifically of deadening agents for the gangue minerals.
In USSR Inventor~s Certificate 1,084,076, collecting agents for phosphorus minerals, specifically apatite, of the type of monoalkyl alkyl- and alkenylsuccinates of the general formula where R1 = R2 = C,-Cl6-alkyl or -alkenyl, are described.
~hese collecting agents are classified as particularly selective. In the flotation tests given as examples in this inventor's certificate with carbonate-silicate apatite ores, monoalkyl alkenylsuccinates with R1=Ca-C1o~
alkenyl and R2=C7-C12-alkyl or R2=C10-C1~-alkyl were used.
In a further publication by W. A. Iwanowa and I. B. Bredermann: ~Alkyl(Alkenyl)bernsteinsaure-alkyl-monoester - effektiver Sammler fUr die Apatitflotation [Monoalkyl alkyl(alkenyl)succinates - effective collec-ting agents for apatite flotation3" (from the book:
A. M. Golman and I. L. Dimitrijewa (Editors): Flotations-reagenzien [Flotation agents], published by "Nauka", Moscow, 1986; cf also Chem. Abstr. 106 (14): 104652n), R1 in the abovement~oned formula is likewise restricted to C~-C12-alkenyl and/or C10-C13-alkyl radicals and the primary alcohols used for the esterification are restricted to those with R2=C7-C12 radicals.
.
. ~- .
2~3i~3 In German Patent Application 3,900,827, the use of those monoalkyl alkenylsuccinates for the flotation of phos-phorus minerals is described which are esterified with short-chain alcohols (R2 = Cl-C4-alkyl).
It has now been found that a further improvement can be achieved if the monoalkyl alkenylsuccinates described in German Patent Application 3,900,827 are combined with one or more, known co-collecting agents. A mutually boosting synergistic effect of the flotation collecting agents occurs in this case.
The invention thus relates to a process for the selective flotation of phosphorus minerals, wherein a mixture or combination of a compound of the formula la and/or lb Rl - CH - COOM (la) and/or Rl - CH - COOR2 (lb) in which R1 is branched or unbranched C8-Ca4-alkenyl and preferably C12-C18-alkenyl, R2 is branched or unbranched C1-C4-alkyl and M is hydrogen, ammonium, triethanol-ammonium, an alkali metal atom or an alkaline earth metalatom, with one or more of the following compounds (co-collecting agents) R - CO-N - (CH2) n ~ COOM (2) X
RO - CH2CHCH2 - N - CH2 - COOM (3) OH X
R - NH - CO - CH2 - CH - COOM (4) RO - CO - CH2 - CH - COOM (5) ~ 5 - 2~3~
R - N - CH - COOM t6) CO - CH~ - CH - COOM
R -- N -- ( CH2 ) n ~ COOM ( 7 ) X
R -- N -- ( CH2 ) n ~ COOM ( 8 ) ( CH2 ) n ~ COOM
R - C - [Po(oH)2]2 (9) OH
R - N - [CH2 ~ P(H)2]2 ( 10) R - CO - NH - OM ( 11) R - COOH (12) 2 0 R - SO2NH - CH2COOM ( 13 ) and petroleumsulfonates R'SO3M (14) in which R is C12-C24-alkyl and preferably C12-C18-alkyl and/or C12-C24-alkenyl and preferably C12-C1a-alkenyl, R' is an aliphatic/alicyclic and/or aromatic radical from petroleum fractions, X i8 hydrogen or C1-C4-alkyl, M is hydrogen, ammonium, triethanolammonium, an alkali metal atom or the equivalent of an alkaline earth metal atom, and n is a number from 1 to 6, is used as the collecting agent for the flotation.
- 6 - 2~37~
The mixture or combination which is to be used according to the invention i8 preferably composed to the extent of 5 to 95~ by weight of the compound of the formula la and/or lb and correspondingly to the extent of 95 to 5%
by weight of one or more of the co-collecting agent6 described above.
The preparation of the monoalkyl alkenylsuccinates of the formulae la and/or lb is carried out in a known manner by reacting alkenylsuccinic anhydrides with Cl-C4-alcohols in a l:l molar ratio. For complete conversion, the mixture is either heated for 5 hours to about 80-l20nC, or catalytic quantities of the corresponding alcoholate are added. In this case, the reaction is complete after one hour. The co-collecting agents ~2) to (14) are known and commercially available products.
The addition of the collecting agent combination of monoalkyl alkenylsuccinate and co-collectinq agents to the flotation is possible together or separately, un-diluted or in the form of aqueous solutions.
The collecting agent mixtures or combinations aacording to the invention are suitable for the flotation of all phosphorus minerals such as apatite, phosphorite or francolite from raw ores or preconcentrates with carbon-ate gangue, silicate gangue and/or quartz gangue, both from ores of magmatic genesis and sedimentary or meta-morphic genesis.
The synergistic collecting agent mixtures or combinations are added to the flotation pulp in quantities of pre-ferably 20 to 2000 and especially 50 to 200 g/tonne of raw ore or preconcentrate to be floated. The collecting agent mixture or combination can be added stepwise in several portions or in a single step.
As compared with the individual components, the mixtures or combinations according to the invention show a - 7 _ 2~3 ~ ~3 synergistic effect. A synergistic effect i8 here under-stood as meaning that the recovery R of the collecting agent combination of the collecting agents A, B, C ... N, i-e- R~A ~ C ... N~ in % is, at the same applied quantity of collecting agent (in g of collecting agent per tonne of raw ore) greater than the total of the proportionate individual recoveries, determined by calculation, i.e.
a RA + b R~ + c FC + n RN r R~ ~ C N being the recovery by the individual collecting agents A, B, C ... N and a, b, c ... n being the proportion of the individual col-lecting agents A, B, C ... N in the overall mixture (A, B, C ... N), and 100~ of the overall mixture being set at 1.
R(A B C ... N~ > a RA + b RE~ + c Rc + ... + n RN
It is known to modify the flotation properties of anionic oxhydril collecting agents in a positive direction by means of co-adsorbents. In most cases, this relates not 80 much to the selectivity of the primary collecting agent, but rather to the activity thereof, i.e. to the applied quantity thereof, and to the regulation of the froth evolution. Modification with nonionic substances, preferably those which are water-insoluble and have a polar character, i8 also possible for the collecting agent mixtures or combinations to be used according to the invention. Examples of suitable compounds are alco-hols having n- or iso-alkyl chains, alkylene oxide adducts of alcohols, alkylphenols and fatty acids, fatty acid alkanolamides, sorbitan fatty acid esters, poly-alkylene glycols, alkyl or alkenyl glycosides, saturated and unsaturated hydrocarbons, and the like.
The activity and froth evolution of monoalkyl alkenyl-succinates and mixtures or combinations thereof with co-collecting agents can also be positively influenced by a content of ~-olefins.
If ~uch co-adsorbents are used for the flotation, the - ' .~ , - 8 - 2 ~ 3 ~
collecting agent mixture or combination/co-adsorbent ratio can vary within wide limits, for example from 10 to 90% by weight for the collecting agent combinstion and from 90 to 10~ by weight for the co-adsorbents. Usually, the active compound quantity of the collecting agent combination is greater than that of the co-ad~orbent6, but this does not exclude converse ratios.
In most cases, the collecting agent mixtures or combina-tions render the phosphorus minerals hydrophobic in such a selective manner that the other minerals present in the ore remain hydrophilic, i.e. are not collected in the froth on the surface of the flotation pulp. Depending on the mineral composition of the particular ore, however, it cannot be excluded that, to improve the success of the separation, one or more deadening agents for the gangue minerals might have to be employed. Examples of suitable inorganic- or organic-chemical deadening agents are soda waterglass, hydrofluoric acid (HF), sodium fluoride (NaF), sodium silicofluoride (Na2SiF6), hexametaphosphates or tripolyphosphates, ligninsulfonates and hydrophilic, relatively low-molecular weight polysaccharides such as starch (corn starch, rice starch or potato starch, after alkaline digestion), carboxymethylstarch, carboxymethyl-cellulose, sulfomethylcellulose, gum arabic, guar gum, substituted guar derivatives (for example carboxymethyl guars, hydroxypropyl guar6 and carboxymethyl-hydroxy-propyl guars), tannins, alginates, phenolic polymers (e.g. resole, novolak), phenol/formaldehyde copalymers, polyacrylates, polyacrylamides and the like.
As froth flotation agents in the process according to the invention, all products known for this purpose can be used/ if required, such as e.g. aliphatic alcohols and alcohol mixtures, terpene alcohols (pine oils), alkyl polyalkylene glycol ethers or polyalkylene glycols.
The pH of the flotation pulp also plays a part in the froth flotation of phosphate ores. Usually, it is between 2~37~
g 7 and 11, the flotation in the case of apatite ores being preferably carried out at pH values from 9 to 11, and preferably at pH values from 7 to 9 in the case of phosphorite ores. The optimum pH of the flotation pulp, which can be decisive for the success of the flotation, differs from ore to ore and must be determined by labora-tory tests and plant tests. Soda (Na2CO3), caustic soda (NaOH) or caustic potash (ROH) can be used for regulating the pH.
The results of the flotation tests are given in the Examples which follow.
The following reagents were used as components for the collecting agent mixtures (A+B) according to the inven-tion:
A: Collecting agents of the formulae la and/or lb:
Collecting aqent Al: sodium mono-C2H5 nCl6 18-alkenyl-succinate Collecting agent A2: sodium mono-iC3H7 nCl6 l~-alkenyl-succinate Collecting agent A3: sodium mono-C2H5 nC14 16-alkenyl-succinate Collecting agent A4: sodium mono-iC3H7 nC14 16-alkenyl-succinate Collecting agent A5: sodium mono-CH3 nC18-alkenyl-succinate Collecting agent B3: mixture of 55% by mass of sodium N-talloyl-N-methyl-aminoacetate and 45% by mass of the sodium salt of tall oil fatty acid (content of unsaponifiable matter 5.4%, content of rosin acids 14.7%) Collecting agent B4: mixture of 75% by mass of sodium N-talloyl-N-methyl-aminoacetate and - 10 - 2~7~,?3 25~ by mass of collecting agent B8 Collecting agent B5: mixture of 66.7% by mass of sodium N-talloyl-N-methyl-aminoacetate and 33.3% by mass of collecting agent Collecting agent B6: mixture of 66.7% by mass of sodium N-talloyl-N-methyl-aminoacetate and 33.3~ by mass of collecting agent Collecting agent B7: sodium N-talloyl-aminohexanoate Collecting agent B8: sodium salt of tall oil fatty acid (content of unsaponifiable matter 2%, content of rosin acids 1.8%) Collecting agent B9: ~odium oleate (technical grade, iodine number = 80-100) Collecting agent BlO: sodium Cl2l5-alkylsulfonamidoacetate Collecting agent B11: sodium N-tallow fatty alkyl-N-sulfosuccinyl-aspartate Collecting agent Bl2: sodium petroleum sulfonate (alkyl-aryl-sulfonate) with about 80% of active substance In all the phosphate flotation examples which follow, about 400 g of natural phosphate ore in each case were floated using a type D-12 laboratory flotation machine from Denver Equipment, USA, in a flotation cell of 1.0 l volume (rougher and cleaner).
The natural ore used for the tests can be characterized as follows:
P2O5 content about 15.3%, corresponding to about 36% by mass of apatite; gangue minerals: titanite, titano-magnetite, feldspar, feldspathoids (essentially nephe-lite), pyroxenes (essentially aegirite) and mica;
grinding to 80% by mass smaller than 110 ~m.
11- 2~3~
Examples of pho~phate flotation The ore type A was ground wet to 80% by weight smaller than 110 ~m. A water having a total salinity of 690 mg/l, whose content of dissolved salts was of such a qualita-tive and quantitative composition as results in the waterof an industrial flotation plant, was added to the grinding and to the flotation. Each flotation test comprised the following stages:
Conditioning of the flotation pulp with 150 g/tonne of soda waterglass as a dispersant for a period of 3 minutes; conditioning of the flotation pulp with the collecting agent, the added quantity of which was varied (cf. results), for a period of 3 minutes;
rougher flotation for a period of 2 minutes;
three-fold further purification (cleaner flotation) of the frothed product obtained in the rougher flotation (rougher concentrate), flotation period 2 minutes each time.
The symbols in the tables mean C = concentrate; F = feed;
M1, M2 and M3 = middlings and T = tailings.
Example 1 The collecting agents A2 and B4 were tested alone and in a 1:1 mixture with one another at various added quan-tities. The recovery of the collecting agent mixture A2+B4 is higher than would be expected from the calcu-lated average of the recoveries from A2 and B4 if used alone.
Fxample 2 The 1:1 mixture of the collecting agents A1 and ~4 also gives a higher recovery than would be expected from the calculated average between the recovery values of A1 and B4 if used alone.
- 12 ~ 7~3 ~xample 3 In this Example, the combination of the collecting agents A2 and B3 was examined. This is a three-component com-bination, since the collecting agent B3 contains two components. The recovery of the 1:1 mixture A2+B3 is not only higher than the average calculated from the indivi-dual recovery values of collecting agents A and ~, but also higher than the recovery values of the better collecting agent B3.
~xample 4 The recovery of the 1:1 mixture Al+B5 is higher than the average calculated from the individual recovery values and at the same time also higher than the recovery of the better collecting agent B5. The mixture A2+B5 is likewise a three-component combination, since B5 comprises two components.
Example 5 The recovery of the 1:1 mixture Al+B6 likewise exceeds the average from the individual recovery values Al and B6 and the recovery of the better collecting agent B6. As in Examples 3 and 4 this is again a three-component combina-tion.
Example 6 The recovery of the 1:1 mixture Al+B8 likewise exceeds the average of the individual recovery values of Al and B8 and also the recovery of the better collecting agent A1. The collecting agent B8 is also a constituent of the collecting agent B5, cf. Example 4.
Example 7 Recovery of the 1:1 mixture Al+B9 exceeds the average 2~3 ~f~g~
calculated from the individual recovery values of Al and B9. ~he collecting agent B9 is also a constituent in the collecting agent B6, cf. Example 5.
Example 8 The recovery of the l:l mixture Al+B7 is substantially above the average calculated from the recovery values of the individual collecting agents and also substantially above the recovery of the better collecting agent Al.
Example 9 As in Example 8, the recovery of the 1:1 mixture A2+B7 in Example 9 is also substantially above the average of the recovery values of the individual collecting a~ents and also above the recovery of the better collecting agent A2.
lS Example 10 The recovery of the 1:1 mixture Al+B10 is considerably above the average of the individual recovery values of the collecting agents Al and BlO.
Example 11 The recovery of the l:l mixture Al+B12 is considerably above the average calculated from the individual recovery values of the collecting agents Al and B12.
Example 12 The recovery of the 1:1 mixture Al+Bll is above both the average calculated from the individual recovery values and above the recovery of the better collecting agent Al.
- 14 - 2 ~3 l~g 3 ~xample 13 Tests supplementing Example 8 were carried out with the Al~B7 combination in mixing ratios of 1:3, l:1 and 3:1 at a collectin~ agent dosage of 70 g/tonne of raw ore. In the tests, the best recovery results were obtained at an Al:B7 ratio of 1:1.
Example 14 Tests supplementing Example 6 were carried out with the Al~B8 combination in mixing ratios of 1:3, 1:1 and 3:1 at a collecting agent dosage of gO g/tonne of raw ore. In the tests, the best recovery results were obtained at an Al:B8 ratio of 3:1.
~xample 15 Tests supplementing Example 12 were carried out with the Al+B11 combination in mixing ratios of 1:3, 1:1 and 3:1 at a collecting agent dosage of 90 g/tonne of raw ore.
In the tests, the best recovery results were obtained at an Al:B11 ratio of 1:3.
The results obtained with the mixtures according to the invention are listed in the Tables which follow. For comparison with these, the Tables also contain the values achieved with the individual components not according to the invention.
- 15- 2~37~
-- N N a~ ~ 0 _ ~D 0 ~ 0 ~ N 1~ _ 1~ lD 0 ~D 0 1~ 0 ~t 0 ~ O
0 U~ J O ~ N In .r 117 ID ~r 0 U~ ~ N ~) ~ ~ U ) ~i O U:~ Ul _ 1~ U~
0 ~ U~ (D N ~ '-t ~ O O 1/~ 0 _ 1~ ~ ~ ~ O O N 1~ 0 N 1~ O) ~ 1 _ ~D er 0 _, _ _ _ _ _ _ 0 N 0 ~D 0 li~
0 ~ _ U1 0 U~ _ ~D ~ ~ ~ _ 0 0 ~ ~ _ ~ ~ ~ U~
L _ _I _ _ _ _ _ O CD ~ I~ ID O~ O O 1 N
~: t~ 0 1~ ~t _ D 0 _ O O O ~q N _ ~n 0 _ O OD C~. O ~ _ D ~D _ N
a~ o 0 IO N 0 0 N ~D N _ _ O N ~ O 0 ~ 0 N 0 0 tD N
O D N 0~ 0 0 ~ 0~ _ --I 0 0 U') 0 0) 0~ 0 _ 0 N ~D 0 0 ~ ~ )~ ~D
_ 1~ 0 0 ~ N ~0D ~ 0 ~D 0 ID 1~ U') ~ 0 ¢1 0 -- ~ D 0 ~ ~ 0 N
~-- NU~_ 1~0~ N~ ~0N et0 er N~ 1~ I O~
N__ N__ ~__ ~__ N__ ~__ ~_ N__ ~N~
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Patent 1,113,317). Many of these chemical compound classes have, however, an inadequate selectivity which does not allow the production of saleable concentrates or necessitates the use of larger quantities of regulating reagents, specifically of deadening agents for the gangue minerals.
In USSR Inventor~s Certificate 1,084,076, collecting agents for phosphorus minerals, specifically apatite, of the type of monoalkyl alkyl- and alkenylsuccinates of the general formula where R1 = R2 = C,-Cl6-alkyl or -alkenyl, are described.
~hese collecting agents are classified as particularly selective. In the flotation tests given as examples in this inventor's certificate with carbonate-silicate apatite ores, monoalkyl alkenylsuccinates with R1=Ca-C1o~
alkenyl and R2=C7-C12-alkyl or R2=C10-C1~-alkyl were used.
In a further publication by W. A. Iwanowa and I. B. Bredermann: ~Alkyl(Alkenyl)bernsteinsaure-alkyl-monoester - effektiver Sammler fUr die Apatitflotation [Monoalkyl alkyl(alkenyl)succinates - effective collec-ting agents for apatite flotation3" (from the book:
A. M. Golman and I. L. Dimitrijewa (Editors): Flotations-reagenzien [Flotation agents], published by "Nauka", Moscow, 1986; cf also Chem. Abstr. 106 (14): 104652n), R1 in the abovement~oned formula is likewise restricted to C~-C12-alkenyl and/or C10-C13-alkyl radicals and the primary alcohols used for the esterification are restricted to those with R2=C7-C12 radicals.
.
. ~- .
2~3i~3 In German Patent Application 3,900,827, the use of those monoalkyl alkenylsuccinates for the flotation of phos-phorus minerals is described which are esterified with short-chain alcohols (R2 = Cl-C4-alkyl).
It has now been found that a further improvement can be achieved if the monoalkyl alkenylsuccinates described in German Patent Application 3,900,827 are combined with one or more, known co-collecting agents. A mutually boosting synergistic effect of the flotation collecting agents occurs in this case.
The invention thus relates to a process for the selective flotation of phosphorus minerals, wherein a mixture or combination of a compound of the formula la and/or lb Rl - CH - COOM (la) and/or Rl - CH - COOR2 (lb) in which R1 is branched or unbranched C8-Ca4-alkenyl and preferably C12-C18-alkenyl, R2 is branched or unbranched C1-C4-alkyl and M is hydrogen, ammonium, triethanol-ammonium, an alkali metal atom or an alkaline earth metalatom, with one or more of the following compounds (co-collecting agents) R - CO-N - (CH2) n ~ COOM (2) X
RO - CH2CHCH2 - N - CH2 - COOM (3) OH X
R - NH - CO - CH2 - CH - COOM (4) RO - CO - CH2 - CH - COOM (5) ~ 5 - 2~3~
R - N - CH - COOM t6) CO - CH~ - CH - COOM
R -- N -- ( CH2 ) n ~ COOM ( 7 ) X
R -- N -- ( CH2 ) n ~ COOM ( 8 ) ( CH2 ) n ~ COOM
R - C - [Po(oH)2]2 (9) OH
R - N - [CH2 ~ P(H)2]2 ( 10) R - CO - NH - OM ( 11) R - COOH (12) 2 0 R - SO2NH - CH2COOM ( 13 ) and petroleumsulfonates R'SO3M (14) in which R is C12-C24-alkyl and preferably C12-C18-alkyl and/or C12-C24-alkenyl and preferably C12-C1a-alkenyl, R' is an aliphatic/alicyclic and/or aromatic radical from petroleum fractions, X i8 hydrogen or C1-C4-alkyl, M is hydrogen, ammonium, triethanolammonium, an alkali metal atom or the equivalent of an alkaline earth metal atom, and n is a number from 1 to 6, is used as the collecting agent for the flotation.
- 6 - 2~37~
The mixture or combination which is to be used according to the invention i8 preferably composed to the extent of 5 to 95~ by weight of the compound of the formula la and/or lb and correspondingly to the extent of 95 to 5%
by weight of one or more of the co-collecting agent6 described above.
The preparation of the monoalkyl alkenylsuccinates of the formulae la and/or lb is carried out in a known manner by reacting alkenylsuccinic anhydrides with Cl-C4-alcohols in a l:l molar ratio. For complete conversion, the mixture is either heated for 5 hours to about 80-l20nC, or catalytic quantities of the corresponding alcoholate are added. In this case, the reaction is complete after one hour. The co-collecting agents ~2) to (14) are known and commercially available products.
The addition of the collecting agent combination of monoalkyl alkenylsuccinate and co-collectinq agents to the flotation is possible together or separately, un-diluted or in the form of aqueous solutions.
The collecting agent mixtures or combinations aacording to the invention are suitable for the flotation of all phosphorus minerals such as apatite, phosphorite or francolite from raw ores or preconcentrates with carbon-ate gangue, silicate gangue and/or quartz gangue, both from ores of magmatic genesis and sedimentary or meta-morphic genesis.
The synergistic collecting agent mixtures or combinations are added to the flotation pulp in quantities of pre-ferably 20 to 2000 and especially 50 to 200 g/tonne of raw ore or preconcentrate to be floated. The collecting agent mixture or combination can be added stepwise in several portions or in a single step.
As compared with the individual components, the mixtures or combinations according to the invention show a - 7 _ 2~3 ~ ~3 synergistic effect. A synergistic effect i8 here under-stood as meaning that the recovery R of the collecting agent combination of the collecting agents A, B, C ... N, i-e- R~A ~ C ... N~ in % is, at the same applied quantity of collecting agent (in g of collecting agent per tonne of raw ore) greater than the total of the proportionate individual recoveries, determined by calculation, i.e.
a RA + b R~ + c FC + n RN r R~ ~ C N being the recovery by the individual collecting agents A, B, C ... N and a, b, c ... n being the proportion of the individual col-lecting agents A, B, C ... N in the overall mixture (A, B, C ... N), and 100~ of the overall mixture being set at 1.
R(A B C ... N~ > a RA + b RE~ + c Rc + ... + n RN
It is known to modify the flotation properties of anionic oxhydril collecting agents in a positive direction by means of co-adsorbents. In most cases, this relates not 80 much to the selectivity of the primary collecting agent, but rather to the activity thereof, i.e. to the applied quantity thereof, and to the regulation of the froth evolution. Modification with nonionic substances, preferably those which are water-insoluble and have a polar character, i8 also possible for the collecting agent mixtures or combinations to be used according to the invention. Examples of suitable compounds are alco-hols having n- or iso-alkyl chains, alkylene oxide adducts of alcohols, alkylphenols and fatty acids, fatty acid alkanolamides, sorbitan fatty acid esters, poly-alkylene glycols, alkyl or alkenyl glycosides, saturated and unsaturated hydrocarbons, and the like.
The activity and froth evolution of monoalkyl alkenyl-succinates and mixtures or combinations thereof with co-collecting agents can also be positively influenced by a content of ~-olefins.
If ~uch co-adsorbents are used for the flotation, the - ' .~ , - 8 - 2 ~ 3 ~
collecting agent mixture or combination/co-adsorbent ratio can vary within wide limits, for example from 10 to 90% by weight for the collecting agent combinstion and from 90 to 10~ by weight for the co-adsorbents. Usually, the active compound quantity of the collecting agent combination is greater than that of the co-ad~orbent6, but this does not exclude converse ratios.
In most cases, the collecting agent mixtures or combina-tions render the phosphorus minerals hydrophobic in such a selective manner that the other minerals present in the ore remain hydrophilic, i.e. are not collected in the froth on the surface of the flotation pulp. Depending on the mineral composition of the particular ore, however, it cannot be excluded that, to improve the success of the separation, one or more deadening agents for the gangue minerals might have to be employed. Examples of suitable inorganic- or organic-chemical deadening agents are soda waterglass, hydrofluoric acid (HF), sodium fluoride (NaF), sodium silicofluoride (Na2SiF6), hexametaphosphates or tripolyphosphates, ligninsulfonates and hydrophilic, relatively low-molecular weight polysaccharides such as starch (corn starch, rice starch or potato starch, after alkaline digestion), carboxymethylstarch, carboxymethyl-cellulose, sulfomethylcellulose, gum arabic, guar gum, substituted guar derivatives (for example carboxymethyl guars, hydroxypropyl guar6 and carboxymethyl-hydroxy-propyl guars), tannins, alginates, phenolic polymers (e.g. resole, novolak), phenol/formaldehyde copalymers, polyacrylates, polyacrylamides and the like.
As froth flotation agents in the process according to the invention, all products known for this purpose can be used/ if required, such as e.g. aliphatic alcohols and alcohol mixtures, terpene alcohols (pine oils), alkyl polyalkylene glycol ethers or polyalkylene glycols.
The pH of the flotation pulp also plays a part in the froth flotation of phosphate ores. Usually, it is between 2~37~
g 7 and 11, the flotation in the case of apatite ores being preferably carried out at pH values from 9 to 11, and preferably at pH values from 7 to 9 in the case of phosphorite ores. The optimum pH of the flotation pulp, which can be decisive for the success of the flotation, differs from ore to ore and must be determined by labora-tory tests and plant tests. Soda (Na2CO3), caustic soda (NaOH) or caustic potash (ROH) can be used for regulating the pH.
The results of the flotation tests are given in the Examples which follow.
The following reagents were used as components for the collecting agent mixtures (A+B) according to the inven-tion:
A: Collecting agents of the formulae la and/or lb:
Collecting aqent Al: sodium mono-C2H5 nCl6 18-alkenyl-succinate Collecting agent A2: sodium mono-iC3H7 nCl6 l~-alkenyl-succinate Collecting agent A3: sodium mono-C2H5 nC14 16-alkenyl-succinate Collecting agent A4: sodium mono-iC3H7 nC14 16-alkenyl-succinate Collecting agent A5: sodium mono-CH3 nC18-alkenyl-succinate Collecting agent B3: mixture of 55% by mass of sodium N-talloyl-N-methyl-aminoacetate and 45% by mass of the sodium salt of tall oil fatty acid (content of unsaponifiable matter 5.4%, content of rosin acids 14.7%) Collecting agent B4: mixture of 75% by mass of sodium N-talloyl-N-methyl-aminoacetate and - 10 - 2~7~,?3 25~ by mass of collecting agent B8 Collecting agent B5: mixture of 66.7% by mass of sodium N-talloyl-N-methyl-aminoacetate and 33.3% by mass of collecting agent Collecting agent B6: mixture of 66.7% by mass of sodium N-talloyl-N-methyl-aminoacetate and 33.3~ by mass of collecting agent Collecting agent B7: sodium N-talloyl-aminohexanoate Collecting agent B8: sodium salt of tall oil fatty acid (content of unsaponifiable matter 2%, content of rosin acids 1.8%) Collecting agent B9: ~odium oleate (technical grade, iodine number = 80-100) Collecting agent BlO: sodium Cl2l5-alkylsulfonamidoacetate Collecting agent B11: sodium N-tallow fatty alkyl-N-sulfosuccinyl-aspartate Collecting agent Bl2: sodium petroleum sulfonate (alkyl-aryl-sulfonate) with about 80% of active substance In all the phosphate flotation examples which follow, about 400 g of natural phosphate ore in each case were floated using a type D-12 laboratory flotation machine from Denver Equipment, USA, in a flotation cell of 1.0 l volume (rougher and cleaner).
The natural ore used for the tests can be characterized as follows:
P2O5 content about 15.3%, corresponding to about 36% by mass of apatite; gangue minerals: titanite, titano-magnetite, feldspar, feldspathoids (essentially nephe-lite), pyroxenes (essentially aegirite) and mica;
grinding to 80% by mass smaller than 110 ~m.
11- 2~3~
Examples of pho~phate flotation The ore type A was ground wet to 80% by weight smaller than 110 ~m. A water having a total salinity of 690 mg/l, whose content of dissolved salts was of such a qualita-tive and quantitative composition as results in the waterof an industrial flotation plant, was added to the grinding and to the flotation. Each flotation test comprised the following stages:
Conditioning of the flotation pulp with 150 g/tonne of soda waterglass as a dispersant for a period of 3 minutes; conditioning of the flotation pulp with the collecting agent, the added quantity of which was varied (cf. results), for a period of 3 minutes;
rougher flotation for a period of 2 minutes;
three-fold further purification (cleaner flotation) of the frothed product obtained in the rougher flotation (rougher concentrate), flotation period 2 minutes each time.
The symbols in the tables mean C = concentrate; F = feed;
M1, M2 and M3 = middlings and T = tailings.
Example 1 The collecting agents A2 and B4 were tested alone and in a 1:1 mixture with one another at various added quan-tities. The recovery of the collecting agent mixture A2+B4 is higher than would be expected from the calcu-lated average of the recoveries from A2 and B4 if used alone.
Fxample 2 The 1:1 mixture of the collecting agents A1 and ~4 also gives a higher recovery than would be expected from the calculated average between the recovery values of A1 and B4 if used alone.
- 12 ~ 7~3 ~xample 3 In this Example, the combination of the collecting agents A2 and B3 was examined. This is a three-component com-bination, since the collecting agent B3 contains two components. The recovery of the 1:1 mixture A2+B3 is not only higher than the average calculated from the indivi-dual recovery values of collecting agents A and ~, but also higher than the recovery values of the better collecting agent B3.
~xample 4 The recovery of the 1:1 mixture Al+B5 is higher than the average calculated from the individual recovery values and at the same time also higher than the recovery of the better collecting agent B5. The mixture A2+B5 is likewise a three-component combination, since B5 comprises two components.
Example 5 The recovery of the 1:1 mixture Al+B6 likewise exceeds the average from the individual recovery values Al and B6 and the recovery of the better collecting agent B6. As in Examples 3 and 4 this is again a three-component combina-tion.
Example 6 The recovery of the 1:1 mixture Al+B8 likewise exceeds the average of the individual recovery values of Al and B8 and also the recovery of the better collecting agent A1. The collecting agent B8 is also a constituent of the collecting agent B5, cf. Example 4.
Example 7 Recovery of the 1:1 mixture Al+B9 exceeds the average 2~3 ~f~g~
calculated from the individual recovery values of Al and B9. ~he collecting agent B9 is also a constituent in the collecting agent B6, cf. Example 5.
Example 8 The recovery of the l:l mixture Al+B7 is substantially above the average calculated from the recovery values of the individual collecting agents and also substantially above the recovery of the better collecting agent Al.
Example 9 As in Example 8, the recovery of the 1:1 mixture A2+B7 in Example 9 is also substantially above the average of the recovery values of the individual collecting a~ents and also above the recovery of the better collecting agent A2.
lS Example 10 The recovery of the 1:1 mixture Al+B10 is considerably above the average of the individual recovery values of the collecting agents Al and BlO.
Example 11 The recovery of the l:l mixture Al+B12 is considerably above the average calculated from the individual recovery values of the collecting agents Al and B12.
Example 12 The recovery of the 1:1 mixture Al+Bll is above both the average calculated from the individual recovery values and above the recovery of the better collecting agent Al.
- 14 - 2 ~3 l~g 3 ~xample 13 Tests supplementing Example 8 were carried out with the Al~B7 combination in mixing ratios of 1:3, l:1 and 3:1 at a collectin~ agent dosage of 70 g/tonne of raw ore. In the tests, the best recovery results were obtained at an Al:B7 ratio of 1:1.
Example 14 Tests supplementing Example 6 were carried out with the Al~B8 combination in mixing ratios of 1:3, 1:1 and 3:1 at a collecting agent dosage of gO g/tonne of raw ore. In the tests, the best recovery results were obtained at an Al:B8 ratio of 3:1.
~xample 15 Tests supplementing Example 12 were carried out with the Al+B11 combination in mixing ratios of 1:3, 1:1 and 3:1 at a collecting agent dosage of 90 g/tonne of raw ore.
In the tests, the best recovery results were obtained at an Al:B11 ratio of 1:3.
The results obtained with the mixtures according to the invention are listed in the Tables which follow. For comparison with these, the Tables also contain the values achieved with the individual components not according to the invention.
- 15- 2~37~
-- N N a~ ~ 0 _ ~D 0 ~ 0 ~ N 1~ _ 1~ lD 0 ~D 0 1~ 0 ~t 0 ~ O
0 U~ J O ~ N In .r 117 ID ~r 0 U~ ~ N ~) ~ ~ U ) ~i O U:~ Ul _ 1~ U~
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c~ o~ ~ n ~ N t~
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Claims (10)
1. A process for the selective flotation of phosphorus minerals, wherein a mixture or combination of a compound of the formula 1a and/or 1b (1a) and/or (1b) in which R1 is branched or unbranched C8-C24-alkenyl, R2 is branched or unbranched C1-C4-alkyl and M is hydrogen, ammonium triethanolammonium, an alkali metal atom or an alkaline earth metal atom, and of one or more of the following compounds (2) (3) (4) (5) (6) (7) (8) (9) R - N - [CH2 - PO(OH)2]2 (10) R - CO - NH - OM (11) R - COOH (12) R - SO2NH - CH2COOM (13) and petroleumsulfonates R'SO3M (14) in which R is C12-C24-alkyl or C12-C24-alkenyl, R' is an aliphatic/alicyclic and/or aromatic radical from petroleum fractions, X is hydrogen or C1-C4-alkyl, M
is hydrogen, ammonium, triethanolammonium or an alkali metal atom or the equivalent of an alkaline earth metal atom and n is a number from 1 to 6, is added as a collecting agent to the flotation pulp.
is hydrogen, ammonium, triethanolammonium or an alkali metal atom or the equivalent of an alkaline earth metal atom and n is a number from 1 to 6, is added as a collecting agent to the flotation pulp.
2. The process as claimed in claim 1, wherein a com-pound of the formulae 1a and/or 1b is used, in which R1 is branched or unbranched C12-C18-alkenyl and R2 is branched or unbranched C1-C4-alkyl.
3. The process as claimed in claim 1 or 2, wherein a compound of the formulae (2) to (14) is used, in which R is C12-C18-alkyl or C12-C18-alkenyl.
4. The process as claimed in any of claims 1 to 3, wherein a mixture or combination is used which is composed to the extent of 5 to 95% by weight of a compound of the formula 1a and/or 1b and to the extent of 95 to 5% by weight of one or more com-pounds (2) to (14).
5. The process as claimed in any of claims 1 to 4, wherein the phosphorus minerals from those ores or preconcentrates are floated which contain carbonate minerals and/or silicate minerals and/or quartz as gangue components.
6. The process as claimed in any of claims 1 to 5, wherein the flotation pulp has a pH from 7 to 11.
7. The process as claimed in any of claims 1 to 6, wherein the mixture or combination is used together with nonionic co-adsorbents.
8. The process as claimed in any of claims 1 to 7, wherein the mixture or combination is used together with conventional froth flotation agents and/or together with conventional deadening agents for the gangue minerals.
9. The process as claimed in any of claims 1 to 8, wherein the collecting agent mixture or combination is added in a quantity of 20 to 2000 g per tonne of ore to the flotation pulp.
10. The process as claimed in any of claims 1 to 9, wherein the collecting agent mixture or combination is added in a quantity of 50 to 200 g per tonne of ore to the flotation pulp.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4007499 | 1990-03-09 | ||
| DEP4007499.4 | 1990-03-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2037883A1 true CA2037883A1 (en) | 1991-09-10 |
Family
ID=6401801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002037883A Abandoned CA2037883A1 (en) | 1990-03-09 | 1991-03-08 | Process for the selective flotation of phosphorus minerals |
Country Status (5)
| Country | Link |
|---|---|
| BR (1) | BR9100940A (en) |
| CA (1) | CA2037883A1 (en) |
| FI (1) | FI911145A (en) |
| SE (1) | SE9100592L (en) |
| ZA (1) | ZA911722B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5295584A (en) * | 1991-08-16 | 1994-03-22 | Hoechst Ag | Process for selective flotation of phosphorus minerals |
| WO2014040686A1 (en) * | 2012-09-13 | 2014-03-20 | Clariant International Ltd | Composition for dressing phosphate ore |
| CN109761837A (en) * | 2019-02-21 | 2019-05-17 | 中南大学 | The preparation method and application of amido-carboxylic acid class compound |
-
1991
- 1991-03-01 SE SE9100592A patent/SE9100592L/en not_active Application Discontinuation
- 1991-03-07 FI FI911145A patent/FI911145A/en unknown
- 1991-03-08 ZA ZA911722A patent/ZA911722B/en unknown
- 1991-03-08 CA CA002037883A patent/CA2037883A1/en not_active Abandoned
- 1991-03-08 BR BR919100940A patent/BR9100940A/en unknown
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5295584A (en) * | 1991-08-16 | 1994-03-22 | Hoechst Ag | Process for selective flotation of phosphorus minerals |
| WO2014040686A1 (en) * | 2012-09-13 | 2014-03-20 | Clariant International Ltd | Composition for dressing phosphate ore |
| US20150238976A1 (en) * | 2012-09-13 | 2015-08-27 | Clariant Finance (Bvi) Limited | Composition For Dressing Phosphate Ore |
| EP2895272B1 (en) * | 2012-09-13 | 2018-01-10 | Clariant International Ltd | Process for dressing phosphate ore and use of a collector composition |
| CN109761837A (en) * | 2019-02-21 | 2019-05-17 | 中南大学 | The preparation method and application of amido-carboxylic acid class compound |
Also Published As
| Publication number | Publication date |
|---|---|
| SE9100592L (en) | 1991-09-10 |
| FI911145A0 (en) | 1991-03-07 |
| ZA911722B (en) | 1991-11-27 |
| BR9100940A (en) | 1991-11-05 |
| FI911145A (en) | 1991-09-10 |
| SE9100592D0 (en) | 1991-03-01 |
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