WO2008084391A1 - Process of purification of minerals based on calcium carbonate by flotation in the presence of quartenary imidazolium methosulfate - Google Patents
Process of purification of minerals based on calcium carbonate by flotation in the presence of quartenary imidazolium methosulfate Download PDFInfo
- Publication number
- WO2008084391A1 WO2008084391A1 PCT/IB2008/000062 IB2008000062W WO2008084391A1 WO 2008084391 A1 WO2008084391 A1 WO 2008084391A1 IB 2008000062 W IB2008000062 W IB 2008000062W WO 2008084391 A1 WO2008084391 A1 WO 2008084391A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- amine
- anyone
- flotation
- calcium carbonate
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 83
- 238000005188 flotation Methods 0.000 title claims abstract description 72
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 27
- 239000011707 mineral Substances 0.000 title claims abstract description 27
- 238000000746 purification Methods 0.000 title claims abstract description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims description 86
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims description 44
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 title claims description 21
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 title description 2
- -1 imidazoline methosulfate compound Chemical class 0.000 claims abstract description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011575 calcium Substances 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims description 44
- WGQKYBSKWIADBV-UHFFFAOYSA-N aminomethyl benzene Natural products NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 150000004693 imidazolium salts Chemical group 0.000 claims description 19
- 239000012535 impurity Substances 0.000 claims description 19
- 125000003277 amino group Chemical group 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 239000007900 aqueous suspension Substances 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 229910021532 Calcite Inorganic materials 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 239000010433 feldspar Substances 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003784 tall oil Substances 0.000 claims description 3
- 229910052889 tremolite Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical group CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 159000000021 acetate salts Chemical class 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 235000012216 bentonite Nutrition 0.000 claims description 2
- 239000004568 cement Substances 0.000 claims description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical class OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000010440 gypsum Substances 0.000 claims description 2
- 229910052602 gypsum Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 239000004579 marble Substances 0.000 claims description 2
- 239000010665 pine oil Substances 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 229960003563 calcium carbonate Drugs 0.000 description 36
- 235000010216 calcium carbonate Nutrition 0.000 description 34
- 235000010755 mineral Nutrition 0.000 description 19
- 239000003153 chemical reaction reagent Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 150000002462 imidazolines Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229960005069 calcium Drugs 0.000 description 7
- 150000004760 silicates Chemical class 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 4
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000008396 flotation agent Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SAAFJTLYBMIPBU-UHFFFAOYSA-N 4,5-dihydro-1H-imidazol-1-ium methyl sulfate Chemical group S(=O)(=O)(OC)[O-].[NH2+]1C=NCC1.[NH2+]1C=NCC1.COS(=O)(=O)[O-] SAAFJTLYBMIPBU-UHFFFAOYSA-N 0.000 description 1
- CAZBGNGNIZEMPG-UHFFFAOYSA-N 4,5-dihydro-1h-imidazol-1-ium;acetate Chemical compound CC([O-])=O.C1CN=C[NH2+]1 CAZBGNGNIZEMPG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
-
- 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
-
- 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
- B03D2203/10—Potassium ores
Definitions
- the object of the present invention is a process for purification of calcium carbonate comprising minerals comprising at least one flotation step, characterised in that this step implements at least one quaternary imidazoline methosulfate compound as collector agent.
- Calcium carbonate-based pigments and/or fillers are used in numerous applications, including paint, paper and plastic applications.
- the impurities that may be present in the pigments and/or fillers are notably silicate-, sulphide- or graphite-based. Beyond the fact that they may deleteriously affect the final properties of these calcium carbonate-based pigments and/or fillers (such as their whiteness), these impurities are also detrimental due to their abrasive nature which causes wear of and damage to the equipment used for further treatment of these pigments and fillers (such as, notably, grinding mills, wire of paper machines and coating blades).
- flotation processes consist of separating the minerals to be treated from their impurities in a selective manner in direct and/or indirect flotation process.
- Flotation calls upon physical and chemical phenomena.
- the principle of this process is to render the particles to be separated hydrophobic (non-wetable by water) using specific reagents referred to as collectors, in a tank within which an agitation of the suspension of the material to be treated takes place.
- collectors specific reagents referred to as collectors
- the foam can subsequently be collected by either skimming it off the surface or simply via the overflow. It is important to review, in chronological order, the different solutions that have been proposed to the skilled man in terms of the chemical nature of the collector agents that can be implemented in a process of flotation to remove impurities from calcium carbonate-containing minerals.
- GB 1 535 143 which describes thione-type compounds, such as, notably, N,N'-bis-(decahydroquinolyl-N-methyl)-imidazolidine-2- thione, which can be employed as a herbicide, but also as flotation agents for non- ferrous metals, although this latter application is not illustrated in the document.
- SU 1 220 695 which describes the selective flotation of potassium-based impurities in clay suspensions, while minimising the degree of insole residues.
- the solution described in this document consists of using a mixture of dialkyl polyethylene glycol esters of phosphoric acid and N,N-bis-(2-hydroxyethyl)-2- alkylimidazolinium chloride.
- EP 0 216002 describes a process of flotation of calcite-based minerals used in the paper industry. This process is based on a flotation step, followed by an upconcentration and several grinding steps, and finally by a classification. Prior to the flotation step, the aqueous calcite suspension is conditioned by introducing a mixture of non-polar hydrocarbon oils and an imidazoline acetate salt. In this way, the quantity of insole impurities based on tremolite, feldspar and quartz is initially reduced.
- US 3 990 966 proposes another solution to the skilled man in order to overcome this disadvantage of the prior art.
- This solution consists in a process to purify calcite-based minerals which involves a step of flotation of pyrite-based impurities using a cationic surfactant selected from l-hydroxyethyl-2-heptadecenyl glyoxalidine and l-hydroxyethyl-2-alkylimidazoline and its salts, when the alkyl group of the imidazoline is a fatty acid.
- CA 1 187 212 therefore proposes another solution, which consists of a process of purification of calcium carbonate-based mineral by flotation of the silicates, when the distinguishing characteristic is the use of a cationic collector selected from the following quaternary amines: a) dimethyl dialkyl with 8 to 16 carbon atoms in the alkyl radicals, said alkyl radicals being saturated or unsaturated, branched or normal aliphatics, b) dimethyl alkyl benzyl with 10 to 22 carbon atoms in the alkyl radical, which is a normal aliphatic, c) bis-imidazoline with 12 to 18 carbon atoms in the alkyl radicals, which are normal saturated or unsaturated aliphatics, d) salts of quaternary amines a), b) and c).
- the imidazoline-based collector is bis-imidazolinium methyl sulfate.
- CA 1 187 212 was identified with a major disadvantage for the skilled man : a poor yield of the collectors implemented, said yield being defined as the weight percentage of calcium carbonate present in the treated product relative to the initial calcium carbonate weight (this disadvantage was also present in US 3 990 966).
- EP 0591 633 which proposes more efficient collectors in terms of yield relative to those of US 3 990966 on page 2 lines 24 to 35 ; and US 4 892 649, which indicates more efficient collectors in terms of yield than the imidazolines of the prior art described in US 3 990966 and CA 1 187 212 in column 1 ;
- EP 0 591 633 proposes collectors based on alkoxylated alkyl guanidines with 8 to 24 carbon atoms and 1 to 10 alkoxylated groups, or based on alkoxylated fatty alkyl amines featuring 8 to 24 carbon atoms and 1 to 6 alkoxy groups.
- US 4 892 649 proposes collectors based on dimethyl(2-ethylhexyl) cocoammonium chloride.
- WO 97 / 26 995 discloses a flotation process using as collector compounds which are quaternized esterified products of mono-, di-, or trialkanolamines with carboxylic acid. They are used, possibly in combination with other anionic, cationic, amphoteric and/or non-ionic substances.
- the flotation aids have good biodegradability and high selectivity (especially for flotation of silicates).
- the Applicant has surprisingly found a new process to purify calcium-carbonate comprising minerals comprising a flotation step, characterised in that this step implements at least one quaternary imidazoline methosulfate compound as collector agent.
- this step implements at least one quaternary imidazoline methosulfate compound as collector agent.
- the calcium carbonate yield is measurably improved since it is superior to 90 %, preferably superior to 95 % and more preferably superior to 98 % by weight relative to the initial calcium carbonate weight.
- the Applicant demonstrates entirely surprising results obtained with 1- methyl-2-noroleyl-3 -oleic acid-amidoethylimidazolium-methylsulfate, with a goal to resolve the abovementioned technical problem with a yield superior to 90 %, preferably superior to 95 % and more preferably superior to 98 % by weight relative to the initial calcium carbonate weight.
- this compound with at least one other imidazoline derivative and/or at least one primary, secondary, tertiary, quaternary amine or its salts leads not only to the solution of the previously mentioned technical problem, but also leads to a yield superior to 90 %, preferably superior to 95 % and more preferably superior to 98 % by weight relative to the initial calcium carbonate weight, and further to obtain a purified product featuring a lower degree of impurities (less than 1 %, preferably less than 0,5 %, more preferably less than 0,2 % by dry weight impurities relative to the total weight of the purified suspension). Furthermore, via such an association, the percentage of insole eliminated from the suspension containing a calcium carbonate-based mineral can be notably decreased, which represents another advantage brought by the technical solution of the present invention.
- the Applicant has developed a purification process comprising at least one flotation step of a calcium carbonate-comprising mineral, characterised in that this step implements at least one collector agent that is a quaternary imidazolium methosulfate.
- a first object of the invention is a process of purification of a calcium carbonate-comprising mineral comprising at least one flotation step, characterised in that this step implements as collector agent at least one compound that is a quaternary imidazolium methosulfate.
- This process is also characterised in that the said quaternary imidazolium methosulfate has a side chain which is saturated or not, the said side chain containing from 8 to 22, preferably from 12 to 20, very preferably from 16 to 18 carbon atoms.
- This process is also characterised in that said quaternary imidazolium methosulfate is l-methyl-2-noroleyl-3-oleic acid-amidoethylimidazolium-methylsulfate.
- the process according to the invention is characterised in that said quaternary imidazolium methosulfate is implemented with at least one primary, secondary, tertiary, quaternary amine and / or at least one of their salts.
- the process according to the invention is also characterised in that the said primary, secondary, tertiary, quaternary amine and / or their salts are selected : a) such that at least one of said amines and / or one of their salts features :
- the process according to the invention is also characterised in that the said quaternary amine and / or its salts are selected among from : a dimethyl dialkyl amine and / or methyl trialkyl amine and / or their salts, featuring preferably featuring from 8 to 22 carbon atoms in the alkyl radicals, said alkyl radicals being saturated or unsaturated, linear or branched aliphatic group, - a dimethyl alkyl benzyl amine and / or methyl dialkyl benzyl amine and / or their salts, preferably featuring 8 to 22 carbon atoms in the radical alkyl which is a linear or branched aliphatic group.
- the process according to the invention is also characterised in that the said quaternary amine is neutralised with a sulphate and / or chloride.
- the process according to the invention is also characterised in that the said salts of primary, secondary and tertiary amine are partially or fully neutralised with an acetate.
- the process according to the invention is characterised in that the weight ratio (quaternary imidazolium methosulfate) : (bis- imidazoline and / or its salt) is between 10 : 90 and 99 : 1, preferably between 25 : 75 and 75 : 25, and more preferably between 35 : 65 and 40 : 60.
- the process according to the invention is also characterised in that an alkyldiamine salt is additionally implemented.
- the process according to the invention is also characterized in that said alkyldiamine salt is an alkyldiamine acetate salt, when the two amine groups are preferably entirely neutralised with acetic acid, and when the alkyl group is preferably a group featuring from 8 to 22 carbon atoms that are entirely or partially hydrated, said alkyl group is even more preferably constituted of at least 70 mole % of a group featuring from 12 to 18 carbon atoms, the most preferred alkyldiamine salt being N-Tallow-alkyltrimethylenediamineacetate.
- the process according to the invention is also characterised in that the weight ratio of (bis-imidazoline) : (alkyldiamine salts) is between 85 :15 and 95 : 5, and preferably is 90 : 10.
- the process according to the invention is also characterized in that the weight ratio (quaternary imidazolium methosulfate) : (dimethyl dialkyl amine and / or methyl trialkyl amine and / or dimethyl alkyl benzyl amine and / or methyl dialkyl benzyl amine and / or their salts) is between 15 : 85 and 20 : 80, preferably between 25 : 75 and 30 : 70, more preferably between 35 : 65 and 40 : 60.
- the process according to the invention is charactarised in that a salt of dimethyl dialkyl amine and / or of a methyl trialkyl amine and / or of a dimethyl alkyl benzyl amine and / or of a methyl dialkyl benzyl amine is implemented, which is preferably a sulfate and / or a chloride, and more preferably a chloride.
- the process according to the invention is also characterised in that said chloride is preferably dicocoalkyl-dimethyl ammonium chloride and / or trimethyltallow alkyl quaternary ammonium chloride and / or cocoalkyl-trimethyl ammonium chloride.
- the process according to the invention is also characterised in that 2-propanol and water are additionally implemented.
- the process according to the invention is also characterised in that the weight ratio of the (dimethyl dialkyl amine and / or methyl trialkyl amine and / or dimethyl alkyl benzyl amine and / or methyl dialkyl benzyl amine and / or their salts) : 2-propanol : water is approximately equal to 75 : 15 : 10.
- the process according to the invention is also characterised in that said quaternary imidazolium methosulfate is implemented with at least one graphite collector, which is preferably a carbinol, said carbinol being preferably a secondary pentyl alcohol, and / or pine oil and / or an ethoxylated amine, which preferably contains from 20 to 40 groups of ethylene oxide.
- at least one graphite collector which is preferably a carbinol, said carbinol being preferably a secondary pentyl alcohol, and / or pine oil and / or an ethoxylated amine, which preferably contains from 20 to 40 groups of ethylene oxide.
- the process according to the invention is also characterised in that the flotation step is a direct or an inverse flotation, and preferably an inverse flotation.
- the process according to the invention is also characterised in that the flotation step implements an agitation cell and / or a flotation column and / or a pneumatic flotation device and / or a flotation device featuring a gas injection and notably an air injection.
- the process according to the invention is also characterised in that the flotation step implements from 100 to 1 000 ppm collector, preferably from 200 to 800 ppm of collector, more preferably from 400 to 600 ppm collector, relative to dry solids in feed.
- the process according to the invention is also characterised in that the flotation step is performed at a temperature between 4°C and 80 0 C, and preferably between 20 0 C and 50 0 C.
- the process according to the invention is also characterised in that the flotation step is performed on an aqueous suspension of calcium carbonate-comprising mineral and features a solid content between 5 % and 80 %, and preferably between 25 % and 70 % of the total suspension weight.
- the process according to the invention is also characterised in that the flotation step is performed on an aqueous suspension of calcium carbonate-comprising mineral which is a natural and / or synthetic calcium carbonate, preferably natural, said natural calcium carbonate being preferably selected from marble, chalk, limestone, calcite and mixtures thereof.
- the process according to the invention is also characterised in that the flotation step is performed on an aqueous suspension of comprising a calcium carbonate-comprising mineral and at least one other mineral material selected from dolomites, bentonites, kaolin, talc, cement, gypsum, lime, magnesia, titanium dioxide, satin white, aluminium trioxide or even aluminium trihydroxide, silicas, micas and mixtures of these fillers among themselves or with calcium carbonate, such as talc-calcium carbonate mixtures, calcium carbonate-kaolin mixtures, or even calcium carbonate mixtures with aluminium trihydroxide or aluminium trioxide, or even mixtures with synthetic or natural fibres or even co-structures of minerals such as co-structures of talc-calcium carbonate or of talc-titanium dioxide, or mixtures thereof.
- a calcium carbonate-comprising mineral selected from dolomites, bentonites, kaolin, talc, cement, gypsum, lime,
- the process according to the invention is also characterised in that the flotation step allows the flotation of one or more impurities such as impurities of the silicate-type, preferably quartz, feldspar, micas, amphiboles, tremolites, chlorites and talc, and / or of the sulphide-type, preferably pyrites, pyrrhotites and markasites, and / or of the oxide-type, preferably magnetites, hematites and goethites.
- impurities of the silicate-type preferably quartz, feldspar, micas, amphiboles, tremolites, chlorites and talc
- the sulphide-type preferably pyrites, pyrrhotites and markasites
- oxide-type preferably magnetites, hematites and goethites.
- the process according to the invention is also characterised in that the flotation step leads to an aqueous suspension comprising calcium carbonate, when at least 90 %, preferably 95 %, more preferably 98 % by weight relative to the initial calcium carbonate weight is recovered.
- the process according to the invention is also characterised in that the flotation step is followed and / or preceded by at least one step of dispersing and / or grinding, possibly in the presence of at least one dispersing agent and / or grinding aid agent.
- the process according to the invention is also characterised in that the flotation step is followed by at least one classification step and / or at least one treatment step and / or at least one drying step.
- the process according to the invention is also characterised in that the flotation step is performed during a time period of at least 10 minutes, preferably of at least 15 minutes, and more preferably of at least 20 minutes.
- the skilled man in the art knows how to adjust the pH to an optimum of mineral selection using at least one acid and / or one base : it depends on the nature of the mineral and of the flotation agent used.
- the process according to the invention is also characterised in that the flotation step is performed at a pH of from 6.5 to 10.5, and preferably of from 7 to 8.5.
- the process according to the invention is at least characterised in that the flotation step is performed batchwise and / or in a continuous process.
- the flotation process was performed in mechanical laboratory flotation machine Type. Outokumpu laboratory featuring a capacity of 4 litres, under an agitation of 1500 rpm and at a pulp temperature of 20 0 C.
- the solids content of the calcium carbonate slurry in the pulp added to the mechanical laboratory flotation machine was of 30% by weight, said calcium carbonate being pre-ground and featuring a median diameter of 32 ⁇ m as measured on a laser granularmeter commercialised under the name Cilas 920 by the company Quantrachrome. It contained 7.2 % by weight of impurities as characterised by Hydrochloric acid insoluble residue (HCl-insoluble residues).
- a flotation gas consisting of air, was introduced via orifices situated along the axis of the agitator during a given time period indicated hereunder.
- the foam created was separated from the calcium carbonate slurry and both were the slurry and foam were dried in order to form two concentrates, and then weighed.
- a quantity of hydrochloric acid was then added to a weighed quantity of each of the concentrates in order to destroy the calcium carbonate. The weight of the remaining insoles was measured in order to determine the quantity of calcium carbonate and the quantity of insoles.
- Reagent A This liquid reagent consisted of :
- This liquid reagent consisted of :
- This liquid reagent consisted of : 75 % by weight dicocoalkyl-dimethyl ammonium chloride 15 % by weight 2-propanol 10 % by weight water
- the quantity of impurities in the flotation product was low, notably when using the combinations including reagents B and C. Excellent resukts are obtained with tests n° 11 and 12, leading to a % of HCl insoles in the flotation product lower than 0.40 %.
- the tested products are liquids which are very easy to handle.
- This liquid reagent consisted of :
- This liquid reagent consisted of :
- This liquid reagent sold under the trade name OMC 5044 G by the company Cognis essentially consisted of a mixture of approximately the following:
- the tested products are liquids which are very easy to handle. All the tested products are slightly corrosive.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009545250A JP5432722B2 (en) | 2007-01-12 | 2008-01-11 | Purification of calcium carbonate minerals by flotation in the presence of quaternary imidazolium methosulfate |
CA2674994A CA2674994C (en) | 2007-01-12 | 2008-01-11 | Process of purification of minerals based on calcium carbonate by flotation in the presence of quartenary imidazolium methosulfate |
US12/448,700 US8381915B2 (en) | 2007-01-12 | 2008-01-11 | Process of purification of minerals based on calcium carbonate by flotation in the presence of quaternary imidazolium methosulfate |
KR1020097016292A KR101384462B1 (en) | 2007-01-12 | 2008-01-11 | Process of purification of minerals based on calcium carbonate by flotation in the presence of quartenary imidazolium methosulfate |
MX2009007335A MX2009007335A (en) | 2007-01-12 | 2008-01-11 | Process of purification of minerals based on calcium carbonate by flotation in the presence of quartenary imidazolium methosulfate. |
CN2008800021087A CN101583431B (en) | 2007-01-12 | 2008-01-11 | Process of purification of minerals based on calcium carbonate by flotation in the presence of quartenary imidazolium methosulfate |
EP08702225A EP2104569A1 (en) | 2007-01-12 | 2008-01-11 | Process of purification of minerals based on calcium carbonate by flotation in the presence of quartenary imidazolium methosulfate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07000640A EP1944088A1 (en) | 2007-01-12 | 2007-01-12 | Process of purification of minerals based on calcium carbonate by flotation in the presence of quaternary imidazollum methosulfate |
EP07000640.8 | 2007-01-12 |
Publications (1)
Publication Number | Publication Date |
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WO2008084391A1 true WO2008084391A1 (en) | 2008-07-17 |
Family
ID=38229971
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/IB2008/000062 WO2008084391A1 (en) | 2007-01-12 | 2008-01-11 | Process of purification of minerals based on calcium carbonate by flotation in the presence of quartenary imidazolium methosulfate |
Country Status (10)
Country | Link |
---|---|
US (1) | US8381915B2 (en) |
EP (2) | EP1944088A1 (en) |
JP (1) | JP5432722B2 (en) |
KR (1) | KR101384462B1 (en) |
CN (1) | CN101583431B (en) |
AR (1) | AR064844A1 (en) |
CA (1) | CA2674994C (en) |
CL (1) | CL2008000076A1 (en) |
MX (1) | MX2009007335A (en) |
WO (1) | WO2008084391A1 (en) |
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EP2700680A1 (en) | 2012-08-20 | 2014-02-26 | Omya International AG | Process for manufacturing white pigment containing products |
EP3025786A1 (en) | 2014-11-28 | 2016-06-01 | Omya International AG | Apparatus for simultaneous grinding and froth flotation |
EP3208315A1 (en) | 2016-02-16 | 2017-08-23 | Omya International AG | Process for manufacturing white pigment containing products |
EP3208314A1 (en) | 2016-02-16 | 2017-08-23 | Omya International AG | Process for manufacturing white pigment containing products |
EP3444036A1 (en) | 2017-08-16 | 2019-02-20 | Omya International AG | Indirect flotation process for manufacturing white pigment containing products |
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RU2012155713A (en) * | 2010-05-28 | 2014-07-10 | Акцо Нобель Кемикалз Интернэшнл Б.В. | QUATERNARY AMMONIUM COMPOUNDS AND THEIR USE AS COLLECTORS IN FOAM FLOTATION PROCESSES |
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- 2008-01-11 WO PCT/IB2008/000062 patent/WO2008084391A1/en active Application Filing
- 2008-01-11 CN CN2008800021087A patent/CN101583431B/en not_active Expired - Fee Related
- 2008-01-11 MX MX2009007335A patent/MX2009007335A/en active IP Right Grant
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Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2366456A1 (en) | 2010-03-19 | 2011-09-21 | Omya Development AG | Froth flotation process for the separation of silicates and alkaline earth metal carbonates using a collector comprising at least one hydrophobically modified polyalkyleneimine |
WO2011113866A1 (en) | 2010-03-19 | 2011-09-22 | Omya Development Ag | Froth flotation process for the separation of silicates and alkaline earth metal carbonates using a collector comprising at least one hydrophobically modified polyalkyleneimine |
US8662311B2 (en) | 2010-03-19 | 2014-03-04 | Omya International Ag | Froth flotation process for the separation of silicates and alkaline earth metal carbonates using a collector comprising at least one hydrophobically modified polyalkyleneimine |
EP2700680A1 (en) | 2012-08-20 | 2014-02-26 | Omya International AG | Process for manufacturing white pigment containing products |
WO2014029634A1 (en) | 2012-08-20 | 2014-02-27 | Omya International Ag | Process for manufacturing white pigment containing products |
US9725576B2 (en) | 2012-08-20 | 2017-08-08 | Omya International Ag | Process for manufacturing white pigment containing products |
EP3025786A1 (en) | 2014-11-28 | 2016-06-01 | Omya International AG | Apparatus for simultaneous grinding and froth flotation |
US11413622B2 (en) | 2014-11-28 | 2022-08-16 | Omya International Ag | Apparatus for simultaneous grinding and froth flotation |
EP3208314A1 (en) | 2016-02-16 | 2017-08-23 | Omya International AG | Process for manufacturing white pigment containing products |
WO2017140633A1 (en) | 2016-02-16 | 2017-08-24 | Omya International Ag | Process for manufacturing white pigment containing products |
WO2017140630A1 (en) | 2016-02-16 | 2017-08-24 | Omya International Ag | Process for manufacturing white pigment containing products |
US11168218B2 (en) | 2016-02-16 | 2021-11-09 | Omya International Ag | Process for manufacturing white pigment containing products |
EP3208315A1 (en) | 2016-02-16 | 2017-08-23 | Omya International AG | Process for manufacturing white pigment containing products |
EP3444036A1 (en) | 2017-08-16 | 2019-02-20 | Omya International AG | Indirect flotation process for manufacturing white pigment containing products |
WO2019034491A1 (en) | 2017-08-16 | 2019-02-21 | Omya International Ag | Indirect flotation process for manufacturing white pigment containing products |
US11014096B2 (en) | 2017-08-16 | 2021-05-25 | Omya International Ag | Indirect flotation process for manufacturing white pigment containing products |
Also Published As
Publication number | Publication date |
---|---|
KR101384462B1 (en) | 2014-04-10 |
JP2010515649A (en) | 2010-05-13 |
JP5432722B2 (en) | 2014-03-05 |
CA2674994C (en) | 2014-07-08 |
CN101583431A (en) | 2009-11-18 |
MX2009007335A (en) | 2009-07-15 |
CA2674994A1 (en) | 2008-07-17 |
US20100040528A1 (en) | 2010-02-18 |
US8381915B2 (en) | 2013-02-26 |
EP1944088A1 (en) | 2008-07-16 |
AR064844A1 (en) | 2009-04-29 |
EP2104569A1 (en) | 2009-09-30 |
KR20090110846A (en) | 2009-10-22 |
CN101583431B (en) | 2013-09-18 |
CL2008000076A1 (en) | 2008-07-18 |
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