CN117732599B - Fatty acid modifier, low temperature resistant spodumene ore medicament, preparation method thereof and method for floating spodumene by using same - Google Patents
Fatty acid modifier, low temperature resistant spodumene ore medicament, preparation method thereof and method for floating spodumene by using same Download PDFInfo
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- CN117732599B CN117732599B CN202410171769.3A CN202410171769A CN117732599B CN 117732599 B CN117732599 B CN 117732599B CN 202410171769 A CN202410171769 A CN 202410171769A CN 117732599 B CN117732599 B CN 117732599B
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- spodumene
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- fatty acid
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- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910052642 spodumene Inorganic materials 0.000 title claims abstract description 109
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 54
- 239000000194 fatty acid Substances 0.000 title claims abstract description 54
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 54
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 47
- 239000003814 drug Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003607 modifier Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 fatty acid ester compound Chemical class 0.000 claims abstract description 33
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 18
- 239000011707 mineral Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 34
- 230000002000 scavenging effect Effects 0.000 claims description 30
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 239000012141 concentrate Substances 0.000 claims description 24
- 238000005188 flotation Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000009472 formulation Methods 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000013067 intermediate product Substances 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000002910 solid waste Substances 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012874 anionic emulsifier Substances 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- YKHVVNDSWHSBPA-BLHCBFLLSA-N (2E,4E)-deca-2,4-dienoic acid Chemical compound CCCCC\C=C\C=C\C(O)=O YKHVVNDSWHSBPA-BLHCBFLLSA-N 0.000 claims description 2
- OOJGMLFHAQOYIL-SQIWNDBBSA-N (2e,4e)-hexadeca-2,4-dienoic acid Chemical compound CCCCCCCCCCC\C=C\C=C\C(O)=O OOJGMLFHAQOYIL-SQIWNDBBSA-N 0.000 claims description 2
- ADHNUPOJJCKWRT-JLXBFWJWSA-N (2e,4e)-octadeca-2,4-dienoic acid Chemical compound CCCCCCCCCCCCC\C=C\C=C\C(O)=O ADHNUPOJJCKWRT-JLXBFWJWSA-N 0.000 claims description 2
- ZUUFLXSNVWQOJW-MBIXAETLSA-N (2e,4e,6e)-octadeca-2,4,6-trienoic acid Chemical compound CCCCCCCCCCC\C=C\C=C\C=C\C(O)=O ZUUFLXSNVWQOJW-MBIXAETLSA-N 0.000 claims description 2
- ADLXTJMPCFOTOO-BQYQJAHWSA-N (E)-non-2-enoic acid Chemical compound CCCCCC\C=C\C(O)=O ADLXTJMPCFOTOO-BQYQJAHWSA-N 0.000 claims description 2
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims description 2
- WXBXVVIUZANZAU-UHFFFAOYSA-N 2E-decenoic acid Natural products CCCCCCCC=CC(O)=O WXBXVVIUZANZAU-UHFFFAOYSA-N 0.000 claims description 2
- YWWVWXASSLXJHU-UHFFFAOYSA-N 9E-tetradecenoic acid Natural products CCCCC=CCCCCCCCC(O)=O YWWVWXASSLXJHU-UHFFFAOYSA-N 0.000 claims description 2
- GTWXTRCCDGNHAS-UHFFFAOYSA-N CCCCCCCCCCCCCCCC=C(C(O)=O)Cl Chemical compound CCCCCCCCCCCCCCCC=C(C(O)=O)Cl GTWXTRCCDGNHAS-UHFFFAOYSA-N 0.000 claims description 2
- GZZPOFFXKUVNSW-UHFFFAOYSA-N Dodecenoic acid Natural products OC(=O)CCCCCCCCCC=C GZZPOFFXKUVNSW-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims description 2
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 claims description 2
- XDQQQSFYCSYSCP-UHFFFAOYSA-N kaempferol 3-O-beta-D-glucopyranosyl(1-3)-alpha-L-rhamnopyranosyl(1-6)-beta-D-glucopyranoside Natural products CC=CCCC=CCCC(O)=O XDQQQSFYCSYSCP-UHFFFAOYSA-N 0.000 claims description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 2
- NNNVXFKZMRGJPM-KHPPLWFESA-N sapienic acid Chemical compound CCCCCCCCC\C=C/CCCCC(O)=O NNNVXFKZMRGJPM-KHPPLWFESA-N 0.000 claims description 2
- IBYFOBGPNPINBU-UHFFFAOYSA-N tetradecenoic acid Natural products CCCCCCCCCCCC=CC(O)=O IBYFOBGPNPINBU-UHFFFAOYSA-N 0.000 claims description 2
- WXBXVVIUZANZAU-CMDGGOBGSA-N trans-2-decenoic acid Chemical compound CCCCCCC\C=C\C(O)=O WXBXVVIUZANZAU-CMDGGOBGSA-N 0.000 claims description 2
- IBYFOBGPNPINBU-OUKQBFOZSA-N trans-2-tetradecenoic acid Chemical compound CCCCCCCCCCC\C=C\C(O)=O IBYFOBGPNPINBU-OUKQBFOZSA-N 0.000 claims description 2
- LKOVPWSSZFDYPG-WUKNDPDISA-N trans-octadec-2-enoic acid Chemical compound CCCCCCCCCCCCCCC\C=C\C(O)=O LKOVPWSSZFDYPG-WUKNDPDISA-N 0.000 claims description 2
- 229960002703 undecylenic acid Drugs 0.000 claims description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 239000004530 micro-emulsion Substances 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 6
- 239000005642 Oleic acid Substances 0.000 description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010433 feldspar Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KVGOXGQSTGQXDD-UHFFFAOYSA-N 1-decane-sulfonic-acid Chemical compound CCCCCCCCCCS(O)(=O)=O KVGOXGQSTGQXDD-UHFFFAOYSA-N 0.000 description 2
- LGNQGTFARHLQFB-UHFFFAOYSA-N 1-dodecyl-2-phenoxybenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1OC1=CC=CC=C1 LGNQGTFARHLQFB-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical compound CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- WLGDAKIJYPIYLR-UHFFFAOYSA-N octane-1-sulfonic acid Chemical compound CCCCCCCCS(O)(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- BITHHVVYSMSWAG-KTKRTIGZSA-N (11Z)-icos-11-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCC(O)=O BITHHVVYSMSWAG-KTKRTIGZSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- PCWGTDULNUVNBN-UHFFFAOYSA-N 4-methylpentan-1-ol Chemical compound CC(C)CCCO PCWGTDULNUVNBN-UHFFFAOYSA-N 0.000 description 1
- ZVHAANQOQZVVFD-UHFFFAOYSA-N 5-methylhexan-1-ol Chemical compound CC(C)CCCCO ZVHAANQOQZVVFD-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052612 amphibole Inorganic materials 0.000 description 1
- 229910052849 andalusite Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 229940108623 eicosenoic acid Drugs 0.000 description 1
- BITHHVVYSMSWAG-UHFFFAOYSA-N eicosenoic acid Natural products CCCCCCCCC=CCCCCCCCCCC(O)=O BITHHVVYSMSWAG-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940006295 sulfonated oleic acid Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application provides a fatty acid modifier, a low-temperature-resistant spodumene ore medicament, a preparation method thereof and a method for floating spodumene by using the fatty acid modifier, and relates to the field of mineral floatation. The chemical formula of the fatty acid modifier is as follows: r 1-(SO3·N(C2H4OH)n)m-R2 -COOH; wherein R 1、R2 is substituted or unsubstituted alkyl; n is 1,2 or 3, m is 1,2 or 3; the low temperature resistant spodumene ore medicament comprises the following raw materials in percentage by mass as 100 percent: 40-55% of fatty acid modifier, 5-15% of fatty acid ester compound, 5-15% of hydrocarbon oil, 5-15% of emulsifier and 5-15% of alcohol compound. The low-temperature-resistant spodumene ore medicament provided by the application has good water solubility, and can improve the dispersibility, low-temperature resistance and mud resistance in ore pulp after forming an oil-in-water type microemulsion with an emulsifier.
Description
Technical Field
The application relates to the field of mineral flotation, in particular to a fatty acid modifier, a low-temperature-resistant spodumene ore medicament, a preparation method thereof and a method for floating spodumene by using the same.
Background
Lithium is known as one of the high-tech metal elements which promotes the world to advance in the 21 st century, has excellent physical and chemical properties, and is widely applied to the fields of aerospace, military industry, nuclear reaction, chemical synthesis, crystal optics and the like. In recent years, the high-tech industry powered by lithium batteries has rapidly developed, driving the demand for lithium resources. The lithium ore resources have low grade and great difficulty in development and utilization. The lithium ore resources are mainly divided into hard rock type lithium ores and salt lake type lithium ores. The minimum industrial grade of Li 2 O in the granite pegmatite ore deposit in the hard rock type lithium ore is 0.8-1.1%. The minimum industrial grade of Li 2 O in the salt lake type is 1000mg/L, and the lithium extraction in the salt lake is not realized in industrial production. Spodumene is an important component of hard rock type lithium ores and is an important source for extracting lithium, and the difficulty in sorting spodumene is that spodumene is associated with silicate minerals with different structures such as quartz, feldspar, andalusite, amphibole, mica and garnet.
The spodumene separation method mainly comprises a flotation method, a magnetic separation method, a heavy medium method, a manual separation method and the like, and the flotation is an effective means for separating and enriching spodumene. Spodumene flotation has two processes, namely forward flotation and reverse flotation. In the positive flotation, naOH is usually adopted for size mixing, in high-alkali ore pulp (pH is usually 10.5-11), spodumene and gangue minerals such as quartz feldspar have different corrosion characteristics, so that the exposed Al active sites on the surface of the spodumene are more than quartz and feldspar, and the Al on the surface of the minerals is an important site combined with fatty acid collectors such as oleic acid, thus enlarging the floatability difference between the spodumene and the gangue minerals and achieving the purpose of floating the spodumene. Lime is generally adopted for reverse flotation, dextrin and starch are added to inhibit spodumene, a cationic collector is used for floating silicate gangue minerals, and the product in the tank is spodumene concentrate.
Spodumene collectors can be classified according to useful group charging characteristics into cationic collectors such as dodecyl amine and anionic collectors such as oleic acid. The two types of collectors are greatly affected by temperature in production. The freezing point of oleic acid is 13.2 ℃ and the freezing point of dodecylamine is 28.3 ℃. The temperature in summer is high, the fluidity of the agent is high, and the floatation index is normal. The air temperature in winter is low and is lower than the solidifying point of the collecting agent, and the medicine adding is difficult, so that the production index is fluctuated. It is therefore necessary to develop a low temperature resistant spodumene collector.
Disclosure of Invention
The application aims to provide a fatty acid modifier, a low-temperature-resistant spodumene ore medicament, a preparation method thereof and a method for floating spodumene by using the same, so as to solve the problems.
To achieve the above object, a first aspect of the present application provides a fatty acid modified product, wherein the fatty acid modified product has a chemical formula: r 1-(SO3·N(C2H4OH)n)m-R2 -COOH;
wherein R 1、R2 is substituted or unsubstituted alkyl;
n is 1, 2 or 3, and m is 1, 2 or 3.
The second aspect of the present application provides a method for producing the fatty acid modified product, comprising:
mixing fatty acid with sulfuric acid, and performing a first reaction to obtain an intermediate product A;
and carrying out a second reaction on the intermediate product A and fatty alcohol amine to obtain the fatty acid modified product.
Optionally, the preparation method of the fatty acid modifier meets one or more of the following conditions:
a. The mole ratio of the fatty acid to the sulfuric acid is 1 (1-3);
b. the time of the first reaction is 2-8h, and the reaction temperature is normal temperature;
c. The mol ratio of the intermediate product A to the fatty alcohol amine is 1 (1-3);
d. The second reaction time is 2-8h, and the reaction temperature is 40-80 ℃.
In a third aspect, the application provides a low temperature resistant spodumene mineral medicament comprising the following raw materials in percentage by mass of 100%: 40-55% of fatty acid modifier, 5-15% of fatty acid ester compound, 5-15% of hydrocarbon oil, 5-15% of emulsifier and 5-15% of alcohol compound.
Optionally, the low temperature resistant spodumene mineral formulation satisfies one or more of the following conditions:
A. The chemical formula of the fatty acid ester compound is R 3-COOR4, R 3 is saturated alkane or arene, and R 4 is saturated alkane containing 1-8 carbon atoms;
B. the hydrocarbon oil is saturated or unsaturated hydrocarbon oil containing 10-22 carbon atoms;
C. the emulsifier is a sulfonate type anionic emulsifier, the chemical formula is R 5-SO3 Na, and R 5 is a carbon chain containing 8-22 carbon atoms;
D. the carbon content of the alcohol compound is 1-8.
The fourth aspect of the application provides a preparation method of the low-temperature-resistant spodumene medicament, and the low-temperature-resistant spodumene medicament is obtained by mixing the raw materials.
In a fifth aspect, the present application provides a method for flotation of spodumene using the low temperature resistant spodumene mineral formulation comprising the steps of:
Crushing spodumene raw ore, and grinding to obtain ore pulp;
Adding a pH regulator and the low-temperature-resistant spodumene ore reagent into the ore pulp, and carrying out roughing to obtain rough concentrate and roughing tailings;
adding a concentration reagent into the rough concentrate, and concentrating to obtain spodumene concentrate;
and scavenging the roughing tailings to obtain scavenging middlings and scavenging tailings, wherein the scavenging tailings are used as solid waste for treatment.
Optionally, the temperature of the flotation is 10-25 ℃;
the flotation is carried out under weakly alkaline conditions.
Optionally, the method for floating spodumene using the low temperature resistant spodumene mineral formulation satisfies one or more of the following conditions:
(1) The fineness of the grinding is-200 meshes and accounts for 60-75%;
(2) The weight percentage concentration of the ore pulp is 30-40%;
(3) The pH regulator comprises sodium carbonate and/or sodium hydroxide, wherein the addition amount of the sodium carbonate is 0-1000g/t of raw ore, and the addition amount of the sodium hydroxide is 0-500g/t of raw ore;
(4) The pH value of the floatation is 8-10;
(5) The dosage of the low-temperature-resistant spodumene ore medicament in the roughing is 500-2000g/t of raw ore;
(6) The weight percentage concentration of the carefully selected ore pulp is 10-30%;
(7) The carefully chosen medicament is sodium carbonate, and the dosage of the carefully chosen medicament is less than or equal to 500g/t of raw ore.
Compared with the prior art, the application has the beneficial effects that:
1. the fatty acid modifier provided by the application is structurally optimized, so that the collecting capacity, selectivity and mud resistance of the prepared spodumene medicament can be obviously improved.
2. Compared with the prior art, the low-temperature-resistant spodumene ore medicament provided by the application has good water solubility, and after the low-temperature-resistant spodumene ore medicament and the emulsifier form an oil-in-water type microemulsion, the dispersibility, the low-temperature resistance and the mud resistance in ore pulp can be improved, the winter flotation index of the spodumene ore medicament can be effectively improved, the spodumene ore medicament can keep good fluidity at 0 ℃, and the spodumene ore medicament still has good dispersibility at 10 ℃.
3. The method for floating spodumene by using the low-temperature-resistant spodumene ore medicament provided by the application can keep better floatation index and is less affected by temperature.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a representation of fatty acid modification I;
FIG. 2 is a representation of fatty acid modification II;
FIG. 3 is a graph showing the characterization of fatty acid modification III.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"Parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g, 2.689g, or the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. or the mass of the A component is aK, the mass of the B component is bK (K is any number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"And/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
The application provides a fatty acid modifier, which has a chemical formula as follows: r 1-(SO3·N(C2H4OH)n)m-R2 -COOH;
wherein R 1、R2 is substituted or unsubstituted alkyl;
For example, R 1 may be a substituted or unsubstituted alkane of 4 to 11 carbons; r 2 can be substituted or unsubstituted alkane with 4-11 carbons;
Alternatively, R 1 can be any alkane, substituted or unsubstituted, having a carbon number of 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14; r 2 can be any alkane, substituted or unsubstituted, with a carbon number of 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14;
n is 1, 2 or 3, and m is 1, 2 or 3.
The second aspect of the present application provides a method for producing the fatty acid modified product, comprising:
mixing fatty acid with sulfuric acid, and performing a first reaction to obtain an intermediate product A;
Alternatively, the fatty acid may be octenoic acid, nonenoic acid, decenoic acid, undecylenic acid, dodecenoic acid, tetradecenoic acid, hexadecenoic acid, octadecenoic acid, eicosenoic acid, decadienoic acid, tetradecanediole acid, hexadecadienoic acid, octadecadienoic acid, octadecatrienoic acid, chlorohexadecenoic acid, or chlorooctadecenoic acid;
and carrying out a second reaction on the intermediate product A and fatty alcohol amine to obtain the fatty acid modified product.
Alternatively, the fatty alcohol amine may be one or more of monoethanolamine, diethanolamine or triethanolamine.
In some alternative embodiments, the method of preparing the fatty acid modification satisfies one or more of the following conditions:
a. The mole ratio of the fatty acid to the sulfuric acid is 1 (1-3);
Optionally, the molar ratio of the fatty acid to the sulfuric acid is 1:1, 1:1.5, 1:2, 1:2.5, 1:3 or 1 (1-3);
b. the time of the first reaction is 2-8h, and the reaction temperature is normal temperature;
alternatively, the time of the first reaction may be any value between 2h, 3h, 4h, 5h, 6h, 7h, 8h, or 2-8 h;
c. The mol ratio of the intermediate product A to the fatty alcohol amine is 1 (1-3);
optionally, the molar ratio of intermediate a to fatty alcohol amine is 1:1, 1:1.5, 1:2, 1:2.5, 1:3 or 1 (1-3);
d. The second reaction time is 2-8h, and the reaction temperature is 40-80 ℃.
Alternatively, the second reaction time may be any value between 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or 2-8 hours, and the second reaction temperature may be any value between 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, or 40-80 ℃.
In a third aspect, the application provides a low temperature resistant spodumene mineral medicament comprising the following raw materials in percentage by mass of 100%: 40-55% of fatty acid modifier, 5-15% of fatty acid ester compound, 5-15% of hydrocarbon oil, 5-15% of emulsifier and 5-15% of alcohol compound.
In some alternative embodiments, the low temperature resistant spodumene formulation satisfies one or more of the following conditions:
A. The chemical formula of the fatty acid ester compound is R 3-COOR4, R 3 is saturated alkane or arene, and R 4 is saturated alkane containing 1-8 carbon atoms;
optionally, the carbon number of R 4 may be 1,2,3, 4, 5, 6, 7, or 8;
For example, R 3 can be n-butyl, t-butyl, isobutyl, n-pentyl, t-pentyl, isopentyl, n-hexyl, t-hexyl, isohexyl, or a benzene ring, and R 4 can be methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, t-pentyl, isopentyl, n-hexyl, t-hexyl, isohexyl, n-heptyl, t-heptyl, isoheptyl, n-octyl, t-octyl, or isooctyl;
B. the hydrocarbon oil is saturated or unsaturated hydrocarbon oil containing 10-22 carbon atoms;
optionally, the hydrocarbon oil may have a carbon number of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;
For example, one or more of kerosene, diesel oil, aromatic oil and transformer oil;
C. the emulsifier is a sulfonate type anionic emulsifier, the chemical formula is R 5-SO3 Na, and R 5 is a carbon chain containing 8-22 carbon atoms;
optionally, the carbon number of R 5 may be 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;
For example, R 5 may be linear octane sulfonic acid, branched octane sulfonic acid, linear decanesulfonic acid, branched decanesulfonic acid, linear C12 alkylbenzene sulfonic acid, branched C12 alkylbenzene sulfonic acid, isopropylbenzene sulfonic acid, dodecyldiphenyl ether disulfonic acid, or naphthalene sulfonic acid;
D. the carbon content of the alcohol compound is 1-8.
Optionally, the carbon-containing number of the alcohol compound may be 1, 2, 3, 4, 5, 6, 7 or 8.
For example, the alcohol compound may be methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, zhong Gengchun n-octanol, isooctanol, or sec-octanol.
The fourth aspect of the application provides a preparation method of the low-temperature-resistant spodumene medicament, and the low-temperature-resistant spodumene medicament is obtained by mixing the raw materials.
In a fifth aspect, the present application provides a method for flotation of spodumene using the low temperature resistant spodumene mineral formulation comprising the steps of:
Crushing spodumene raw ore, and grinding to obtain ore pulp;
Adding a pH regulator and the low-temperature-resistant spodumene ore reagent into the ore pulp, and carrying out roughing to obtain rough concentrate and roughing tailings;
adding a concentration reagent into the rough concentrate, and concentrating to obtain spodumene concentrate;
and scavenging the roughing tailings to obtain scavenging middlings and scavenging tailings, wherein the scavenging tailings are used as solid waste for treatment.
In some alternative embodiments, the temperature of the flotation is 10-25 ℃;
Alternatively, the temperature of the flotation may be any value between 10 ℃, 11.5 ℃,12 ℃, 13.1 ℃,14 ℃, 15.5 ℃,16 ℃,17 ℃, 17.9 ℃,18 ℃,19 ℃, 20 ℃, 21.3 ℃,22 ℃, 23 ℃, 24 ℃, 25 ℃, or 10-25 ℃;
the flotation is carried out under weakly alkaline conditions.
In some alternative embodiments, the method of floating spodumene using the low temperature resistant spodumene mineral formulation described satisfies one or more of the following conditions:
(1) The fineness of the grinding is-200 meshes and accounts for 60-75%;
optionally, the fineness of the grinding is any value between 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75% or 60-75% for-200 mesh;
(2) The weight percentage concentration of the ore pulp is 30-40%;
alternatively, the weight percent concentration of the pulp may be any value between 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40% or 30-40%;
(3) The pH regulator comprises sodium carbonate and/or sodium hydroxide, wherein the addition amount of the sodium carbonate is 0-1000g/t of raw ore, and the addition amount of the sodium hydroxide is 0-500g/t of raw ore;
Alternatively, the sodium carbonate may be added in an amount of 0g/t、1g/t、10g/t、20.1g/t、50g/t、100g/t、150g/t、200g/t、300g/t、400g/t、500g/t、600g/t、700g/t、800g/t、900g/t、1000g/t or any value between 0 and 1000g/t, and the sodium hydroxide may be added in an amount of 0g/t, 1g/t, 10g/t, 20.1g/t, 50g/t, 100g/t, 150g/t, 200g/t, 300g/t, 400g/t, 500g/t, or any value between 0 and 500 g/t;
(4) The pH value of the floatation is 8-10;
alternatively, the pH of the flotation may be any value between 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10 or 8-10;
(5) The dosage of the low-temperature-resistant spodumene ore medicament in the roughing is 500-2000g/t of raw ore;
Optionally, the amount of the low temperature resistant spodumene ore formulation in the roughing may be 500g/t、600g/t、700g/t、800g/t、900g/t、1000g/t、1100g/t、1200g/t、1300g/t、1400g/t、1500g/t、1600g/t、1700g/t、1800g/t、1900g/t、2000g/t or any value between 500-2000 g/t;
(6) The weight percentage concentration of the carefully selected ore pulp is 10-30%;
Alternatively, the concentration of the beneficiated pulp may be any value between 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% or 10-30% by weight;
(7) The carefully chosen medicament is sodium carbonate, and the dosage of the carefully chosen medicament is less than or equal to 500g/t of raw ore.
Alternatively, the beneficiation reagent can be used in an amount of any of 1g/t, 10g/t, 20.1g/t, 50g/t, 100g/t, 150g/t, 200g/t, 300g/t, 400g/t, 500g/t, or less than or equal to 500 g/t.
In some alternative embodiments, the low temperature resistant spodumene ore formulation is added during the scavenging in an amount of 10% -25% of the amount of the low temperature resistant spodumene ore formulation added during the roughing.
Alternatively, the low temperature resistant spodumene mineral formulation added in the scavenger may be any value between 10%, 11.5%, 12%, 13.1%, 14%, 15.5%, 16%, 17%, 17.9%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25% or 10% -25% of the roughing amount.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The spodumene raw ore is 1.72% spodumene in southwest regions of China.
Example 1
The embodiment provides a fatty acid modifier I, which is prepared by the following steps:
Adding 100g of fatty acid into a three-neck flask, slowly adding 35g of sulfuric acid under stirring, controlling the dropping speed, reacting for 6 hours to obtain sulfonated oleic acid, continuously adding 37g of diethanolamine, heating to 80 ℃, and reacting for 5 hours to obtain a fatty acid modifier I.
The embodiment also provides a low-temperature-resistant spodumene medicament LHS-01, and the preparation method thereof is as follows:
Then the fatty acid modifier I is mixed with fatty acid methyl ester, diesel oil, isopropylbenzene sulfonic acid and ethanol according to 45 percent by weight based on 100 percent of total mass: 20:5:10:20 to obtain the low temperature resistant spodumene ore medicament named LHS-01.
The embodiment also provides a method for floating spodumene by using the low-temperature-resistant spodumene ore reagent LHS-01, which comprises the following specific operations:
Crushing spodumene raw ore, grinding to obtain ore pulp with the grinding fineness of-0.074 mm accounting for 65%, and processing to obtain ore pulp with the concentration of 40%; adding 100g/t sodium hydroxide and 1500g/t low-temperature-resistant spodumene ore reagent LHS-01, and roughing to obtain rough concentrate and roughing tailings; selecting, adding 500g/t sodium carbonate, and selecting to obtain spodumene concentrate; scavenging is carried out by adding low-temperature-resistant spodumene ore reagent LHS-01200g/t into the roughing tailings to obtain scavenging middlings and scavenging tailings, the scavenging tailings are used as solid waste for treatment, and the obtained floatation results are shown in table 1.
The characterization of fatty acid modification I is shown in figure 1.
Example 2
The embodiment provides a fatty acid modifier II, which is prepared by the following steps:
100g of linoleic acid is added into a three-neck flask, 60g of sulfuric acid is slowly added under stirring, the dripping speed is controlled, the sulfonated linoleic acid is obtained after reaction for 6 hours, 37g of monoethanolamine is continuously added, the mixture is heated to 70 ℃, and the fatty acid modifier II is obtained after reaction for 5 hours.
The embodiment also provides a low-temperature-resistant spodumene ore medicament LHS-02, and the preparation method thereof is as follows:
Then, the mixture is mixed with fatty acid methyl ester, diesel oil, dodecylbenzene sulfonic acid and ethanol according to the total mass of 50 percent as 100 percent: 20:5:8:17 to obtain the low temperature resistant spodumene ore medicament LHS-02.
The embodiment also provides a method for floating spodumene by using the low-temperature-resistant spodumene mineral medicament LHS-02, which comprises the following specific operations:
Crushing spodumene raw ore, grinding to obtain ore pulp with the grinding fineness of-0.074 mm accounting for 65%, and processing to obtain ore pulp with the concentration of 40%; adding 100g/t sodium hydroxide and 1500g/t low-temperature-resistant spodumene ore reagent LHS-02, and roughing to obtain rough concentrate and roughing tailings; adding 300g/t sodium carbonate into the rough concentrate, and concentrating to obtain spodumene concentrate; scavenging is carried out by adding low-temperature-resistant spodumene ore reagent LHS-02180g/t into the roughing tailings to obtain scavenging middlings and scavenging tailings, the scavenging tailings are used as solid waste for treatment, and the obtained floatation results are shown in table 1.
The characterization of fatty acid modification II is shown in FIG. 2.
Example 3
The embodiment provides a fatty acid modifier II I, which is prepared by the following steps: adding 100g of eicosanoic acid into a three-neck flask, slowly adding 20g of sulfuric acid under stirring, controlling the dropping speed, reacting for 6 hours, continuously adding 34g of monoethanolamine, heating to 85 ℃, and reacting for 6 hours to obtain a fatty acid modifier II I.
The embodiment also provides a low temperature resistant spodumene mineral medicament LHS-03, and the preparation method thereof is as follows:
then, the mixture is mixed with fatty acid methyl ester, diesel oil, dodecyl diphenyl ether disulfonic acid and butanol according to 55 percent by weight, wherein the total mass is 100 percent: 15:8:5:17 to obtain the low temperature resistant spodumene medicament LHS-03.
The embodiment also provides a method for floating spodumene by using the low-temperature-resistant spodumene ore reagent LHS-03, which comprises the following specific operations:
Crushing spodumene raw ore, grinding to obtain ore pulp with the grinding fineness of-0.074 mm accounting for 65%, and processing to obtain ore pulp with the concentration of 40%; adding 200g/t sodium hydroxide and 1200g/t low-temperature-resistant spodumene ore reagent LHS-03, and roughing to obtain rough concentrate and roughing tailings; adding 500g/t sodium carbonate into the rough concentrate, and concentrating to obtain spodumene concentrate; scavenging is carried out by adding low-temperature-resistant spodumene ore medicament LHS-03 150g/t into the roughing tailings to obtain scavenging middlings and scavenging tailings, the scavenging tailings are used as solid waste for treatment, and the obtained floatation results are shown in table 1.
The characterization of fatty acid modification III is shown in FIG. 3.
Comparative example 1
The comparative example provides a spodumene ore collector and a flotation test thereof, and the preparation method is as follows:
oleic acid, fatty acid methyl ester, diesel oil, dodecylbenzene sulfonic acid and ethanol are calculated by taking the total mass as 100 percent, and the weight ratio is 50:20:5:8:17 to obtain the oleic acid type spodumene medicament.
Crushing spodumene raw ore, grinding to obtain ore pulp with the grinding fineness of-0.074 mm accounting for 65%, and processing to obtain ore pulp with the concentration of 40%; adding 100g/t sodium hydroxide and 1500g/t oleic acid spodumene ore medicament, and roughing to obtain rough concentrate and roughing tailings; adding 300g/t sodium carbonate into the rough concentrate, and concentrating to obtain spodumene concentrate; scavenging the roughing tailings by adding 180g/t of spodumene ore with oil acid type to obtain scavenging middlings and scavenging tailings, wherein the scavenging tailings are used as solid waste treatment, and a one-coarse and three-fine flotation process is adopted, so that the obtained flotation results are shown in table 1.
TABLE 1 spodumene ore flotation index
Compared with comparative example 1, the lithium concentrate recovery rate of the embodiment 1-3 is improved, and particularly the concentrate grade is remarkably improved, so that a qualified lithium concentrate product is obtained.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (7)
1. A low temperature resistant spodumene ore formulation characterized by comprising the following raw materials in total 100% by mass: 40-55% of fatty acid modifier, 5-15% of fatty acid ester compound, 5-15% of hydrocarbon oil, 5-15% of emulsifier and 5-15% of alcohol compound;
The preparation method of the fatty acid modifier comprises the following steps:
mixing fatty acid with sulfuric acid, and performing a first reaction to obtain an intermediate product A;
the intermediate product A and fatty alcohol amine undergo a second reaction to obtain the fatty acid modified substance;
The fatty acid is one or more of octenoic acid, nonenoic acid, decenoic acid, undecylenic acid, dodecenoic acid, tetradecenoic acid, hexadecenoic acid, octadecenoic acid, eicosanoic acid, decadienoic acid, tetradecanedioic acid, hexadecadienoic acid, octadecadienoic acid, octadecatrienoic acid, chlorohexadecenoic acid and chlorooctadecenoic acid;
The fatty alcohol amine is one or more of monoethanolamine, diethanolamine and triethanolamine;
the mole ratio of the fatty acid to the sulfuric acid is 1 (1-3);
the time of the first reaction is 2-8h, and the reaction temperature is normal temperature;
the mol ratio of the intermediate product A to the fatty alcohol amine is 1 (1-3);
the second reaction time is 2-8h, and the reaction temperature is 40-80 ℃.
2. The low temperature resistant spodumene ore formulation of claim 1, wherein one or more of the following conditions are met:
A. The chemical formula of the fatty acid ester compound is R 3-COOR4, R 3 is saturated alkane or arene, and R 4 is saturated alkane containing 1-8 carbon atoms;
B. the hydrocarbon oil is saturated or unsaturated hydrocarbon oil containing 10-22 carbon atoms;
C. the emulsifier is a sulfonate type anionic emulsifier, the chemical formula is R 5-SO3 Na, and R 5 is a carbon chain containing 8-22 carbon atoms;
D. the carbon content of the alcohol compound is 1-8.
3. A method for preparing the low temperature resistant spodumene medicament according to claim 1 or 2, wherein the low temperature resistant spodumene medicament is obtained by mixing the raw materials.
4. A method of floating spodumene using the low temperature resistant spodumene mineral formulation of claim 1 or 2, comprising the steps of:
Crushing spodumene raw ore, and grinding to obtain ore pulp;
Adding a pH regulator and the low-temperature-resistant spodumene ore reagent into the ore pulp, and carrying out roughing to obtain rough concentrate and roughing tailings;
adding a concentration reagent into the rough concentrate, and concentrating to obtain spodumene concentrate;
and scavenging the roughing tailings to obtain scavenging middlings and scavenging tailings, wherein the scavenging tailings are used as solid waste for treatment.
5. The method of floating spodumene using a low temperature resistant spodumene mineral formulation according to claim 4, wherein the temperature of the floating is between 10 and 25 ℃;
the flotation is carried out under weakly alkaline conditions.
6. The method of claim 4, wherein one or more of the following conditions are met:
(1) The fineness of the grinding is-200 meshes and accounts for 60-75%;
(2) The weight percentage concentration of the ore pulp is 30-40%;
(3) The pH regulator comprises sodium carbonate and/or sodium hydroxide, wherein the addition amount of the sodium carbonate is 0-1000g/t of raw ore, and the addition amount of the sodium hydroxide is 0-500g/t of raw ore;
(4) The pH value of the floatation is 8-10;
(5) The dosage of the low-temperature-resistant spodumene ore medicament in the roughing is 500-2000g/t of raw ore;
(6) The weight percentage concentration of the carefully selected ore pulp is 10-30%;
(7) The carefully chosen medicament is sodium carbonate, and the dosage of the carefully chosen medicament is less than or equal to 500g/t of raw ore.
7. The method of claim 4, wherein the low temperature resistant spodumene ore formulation is added during the scavenging in an amount of 10% -25% of the amount of the low temperature resistant spodumene ore formulation added during the roughing.
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| US4098687A (en) * | 1977-01-13 | 1978-07-04 | Board Of Control Of Michigan Technological University | Beneficiation of lithium ores by froth flotation |
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