CN104801426A - Schiff base caproate mineral flotation collecting agent as well as preparation method and application thereof - Google Patents
Schiff base caproate mineral flotation collecting agent as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN104801426A CN104801426A CN201510226788.2A CN201510226788A CN104801426A CN 104801426 A CN104801426 A CN 104801426A CN 201510226788 A CN201510226788 A CN 201510226788A CN 104801426 A CN104801426 A CN 104801426A
- Authority
- CN
- China
- Prior art keywords
- caproate
- flotation
- schiff base
- ore
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005188 flotation Methods 0.000 title claims abstract description 95
- -1 Schiff base caproate Chemical class 0.000 title claims abstract description 77
- 239000002262 Schiff base Substances 0.000 title claims abstract description 58
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 45
- 239000011707 mineral Substances 0.000 title claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 235000010755 mineral Nutrition 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000006482 condensation reaction Methods 0.000 claims abstract description 11
- 239000010436 fluorite Substances 0.000 claims abstract description 11
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 10
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 9
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 9
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 9
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 9
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 229940113721 aminocaproate Drugs 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000002250 absorbent Substances 0.000 claims description 7
- 230000002745 absorbent Effects 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000007142 ring opening reaction Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 125000006024 2-pentenyl group Chemical group 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 239000008396 flotation agent Substances 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 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 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 238000009291 froth flotation Methods 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 33
- 229910052708 sodium Inorganic materials 0.000 description 33
- 239000007787 solid Substances 0.000 description 27
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 24
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 15
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 15
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 14
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 14
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 14
- 239000005642 Oleic acid Substances 0.000 description 14
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 14
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 14
- LRQKBLKVPFOOQJ-UHFFFAOYSA-N 2-aminohexanoic acid Chemical class CCCCC(N)C(O)=O LRQKBLKVPFOOQJ-UHFFFAOYSA-N 0.000 description 13
- WSTCXUGSWREQFF-UHFFFAOYSA-N 2-iminohexanoic acid Chemical compound CCCCC(=N)C(O)=O WSTCXUGSWREQFF-UHFFFAOYSA-N 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000000344 soap Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000012188 paraffin wax Substances 0.000 description 8
- 235000019353 potassium silicate Nutrition 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 150000004753 Schiff bases Chemical class 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- PYLMCYQHBRSDND-VURMDHGXSA-N (Z)-2-ethyl-2-hexenal Chemical compound CCC\C=C(\CC)C=O PYLMCYQHBRSDND-VURMDHGXSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000010428 baryte Substances 0.000 description 2
- 229910052601 baryte Inorganic materials 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002192 fatty aldehydes Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000000879 imine group Chemical group 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- FYZUCVSCZVWCBR-UHFFFAOYSA-N sodium;n-oxidobenzamide Chemical compound [Na+].[O-]NC(=O)C1=CC=CC=C1 FYZUCVSCZVWCBR-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000001094 effect on targets Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CLUHWBURHNNGPK-UHFFFAOYSA-M sodium;6-aminohexanoate Chemical compound [Na+].NCCCCCC([O-])=O CLUHWBURHNNGPK-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a Schiff base caproate mineral flotation collecting agent, a preparation method thereof and application thereof. A Schiff base caproate has an aliphatic group and a carbon-nitrogen double bond and carboxyl structure and is prepared by performing ammonia aldehyde condensation reaction on hydrolyzed caprolactam and aliphatic aldehyde. The Schiff base caproate has the characteristics of good water solubility, high dispersibility and high selective adsorption capacity to a target mineral, serves as the flotation collecting agent of bauxite, ilmenite, scheelite, wolframite, rare earth mine, tin ore, fluorite ore or manganese carbonate ore, and can effectively float and separate available minerals; furthermore, the preparation method of the Schiff base caproate is simple in process, easy in control on operation, low in cost, and high in product yield, and industrial production is easy to realize.
Description
Technical Field
The invention relates to a Schiff base caproate mineral flotation collecting agent and a preparation method and application thereof, and belongs to the field of mineral flotation.
Background
The fatty acid and the soaps thereof contain active carboxyl functional groups, so that the useful minerals can be effectively separated from gangue, and the collector is an excellent non-sulfide ore flotation collector. Because higher fatty acid is solid at normal temperature, is difficult to dissolve in water and is inconvenient to use, oleic acid, linoleic acid, linolenic acid, tall oil fatty acid and liquid saturated fatty acid are commonly used, and oleic acid and modified products thereof and oxidized paraffin soap are most commonly used in the industrial flotation process at present. Chinese patent (publication No. CN102921537A) discloses a method for flotation of limonite with oleic acid; chinese patent (publication No. CN102600985A) discloses a method for flotation of ilmenite and iron oxide ore by using a collecting agent prepared by mixing oleic acid, oxidized paraffin soap and fatty acid in proportion and then saponifying; chinese patent (publication No. CN101585016) discloses a method for flotation separation of low-grade fluorite barite by using oleic acid as a collecting agent and using starch, sodium sulfate, hydrochloric acid and sodium hexametaphosphate as inhibitors of the barite minerals; chinese patent (publication No. CN101712014A) discloses a method for sectional flotation of multi-type impurity single fluorite ore by using alkaline oleic acid, neutral oleic acid and acidic oleic acid respectively; chinese patent (publication No. CN103657860A) discloses a method for enriching zinc silicate minerals by flotation under acidic conditions with a collector prepared by blending oxidized paraffin soap and sodium dodecyl sulfate; chinese patents (publication nos. CN101648157 and CN101757983A) disclose a method for floating scheelite and scheelite by using mixed fatty acids containing oleic acid; chinese patent (publication No. CN102302982A) discloses a beneficiation method for recovering scheelite from gneiss type ore; chinese patent (publication No. CN102716811A) discloses a method for floating water-soluble weathered apatite ore by mixed acid flotation of gossypoleic acid and erucic acid; chinese patent publication No. CN102962144A discloses a method for flotation of bauxite with oleic acid having a saponification degree of about 50%.
Oleic acid is used as a collecting agent and is popular with mineral flotation manufacturers due to strong collecting capability and wide application range, but has obvious defects in flotation, namely low selectivity, poor freezing resistance, poor dispersibility and the like; the oxidized paraffin soap as a substitute of oleic acid has the advantages of low price, small influence of the temperature of ore pulp on the flotation result and the like, but also has the defects of poor flotation performance, poor selectivity, low concentrate grade and the like when being used alone. Aiming at different mineral feeding properties, climatic characteristics and the defects of oleic acid and oxidized paraffin soap collectors, the development of a novel and efficient collector becomes one of the hotspots for the development of mineral separation technology.
At present, amino acid Schiff bases are reported to be mainly prepared into metal complexes, and the Schiff base metal complexes have good biological activity and catalytic activity and can be used in the field of biomedicine or the field of chemical catalysis. Amino acid schiff bases are usually formed by reacting aldehydes or ketones with amino acids, are particularly easy to hydrolyze, and generally need to be synthesized under anhydrous conditions. Amino acid schiff bases from fatty aldehydes or ketones have been reported in very few documents due to their poor stability. European patent publication No. WO 2008/127760A1 discloses a process for the preparation of amino acid Schiff bases obtained by reacting n-octanal with lysine, but it has been found that the amino acid is unstable and rapidly agglomerates into an oil. Samy B.Said reports that the yield of Schiff base prepared by reacting an aromatic ring-containing aldehyde with tert-butylamine is above 80%, but when the corresponding Schiff base is prepared by reacting an aliphatic aldehyde (e.g., 2-ethyl-2-hexenal) with tert-butylamine, pure Schiff base is not obtained because the Schiff base is unstable and easily oxidized (Samy B.Said, Jacek Mlochowski, Jacek Scaraweski. Synthesisof 2-Alkyl-3-vinyloxazidins Potenial antibodies Agents. Liebigs Annalen der Chemie,1990(5), 461-.
The research on amino acid Schiff bases is limited to amino acid Schiff bases containing aromatic rings (formula 3), and the Schiff bases mainly show good application prospects in the fields of medicine, catalysis, analytical chemistry, electrochemistry, magnetism and the like, and the preparation method of Schiff base fatty acid salts and the application of the Schiff base fatty acid salts as collecting agents in flotation are not reported at present.
Disclosure of Invention
Aiming at the defects of low selectivity, poor freezing resistance, poor dispersibility and the like of flotation collectors such as oleic acid and oxidized paraffin soap in the prior art, the invention aims to provide Schiff base caproate simultaneously having fatty alkyl, carbon-nitrogen double bond and carboxyl structure, which has good selective adsorbability to non-sulfide ores, good water solubility and good dispersibility and can be used as a mineral flotation collector.
The invention also aims to provide a method for preparing the Schiff base caproate mineral flotation collector with simple process, easy operation control, low cost and high yield.
The invention also aims to provide the application of the Schiff base caproate mineral flotation collector, and the Schiff base caproate has the characteristics of good water solubility and dispersibility, strong collection capacity on non-sulfide ores and good selectivity, and is suitable for flotation and collection of various minerals.
In order to overcome the defects in the prior art, the invention provides a Schiff base caproate mineral flotation collector which has a structure shown in a formula 1:
wherein,
r is C3～C11An alkyl or alkenyl group of (a);
m is Na+Or K+。
In the preferable Schiff base caproate mineral flotation collector, R is C7An alkyl group or an alkenyl group.
In the more preferable Schiff base caproate mineral flotation collector, R is C7Linear or branched alkanyl radical of (A) or (C)7The monoolefin base of (1).
In the most preferable Schiff base caproate mineral flotation collector, R is an n-heptyl group, a 1-ethyl-n-pentyl group or a 1-ethyl-1, 2-pentenyl group.
The Schiff base caproate disclosed by the invention has imine groups and carboxylic acid simultaneously, and the imine groups and the carboxyl groups have a synergistic chelation adsorption effect on target elements on the surface of minerals, so that the collecting capacity of the target minerals is greatly improved. The preferable Schiff base caproate mineral flotation collector has carboxyl and aliphatic groups with proper length, and is more favorable for improving the hydrophilicity and the dispersion performance in the flotation and collection process.
The invention also provides a method for preparing the Schiff base caproate mineral flotation collector, which comprises the steps of carrying out hydrolysis ring-opening reaction on caprolactam in sodium hydroxide and/or potassium hydroxide solution at the temperature of 80-105 ℃ to obtain amino caproate; carrying out an amino-aldehyde condensation reaction on the amino caproate and an aldehyde compound with a structure shown in a formula 2 at a temperature of 90-120 ℃ under the catalysis of acid to obtain the amino caproate;
wherein,
r is C3～C11An alkyl group or an alkenyl group.
In a preferred embodiment, R is C7An alkyl or alkenyl group of (a); more preferably C7Linear or branched alkanyl radical of (A) or (C)7A monoolefin group of (a); most preferred is n-heptyl, 1-ethyl-n-pentyl or 1-ethyl-1, 2-pentenyl.
In a preferable scheme, the molar ratio of sodium hydroxide and/or potassium hydroxide to water in the potassium hydroxide and/or sodium hydroxide solution is 1: 1-1: 2.
In a preferred embodiment, the molar ratio of potassium hydroxide and/or sodium hydroxide to caprolactam is 1: 1.
In a preferred embodiment, a water-carrying agent or water-absorbing agent is added to the ammonia-aldehyde condensation reaction to remove water produced by the ammonia-aldehyde condensation reaction.
In a more preferred embodiment, the water-carrying agent is at least one of benzene, toluene and chloroform. The invention adds the water-carrying agent in the ammonia-aldehyde condensation reaction process, and after the reaction is finished, the azeotrope of water and the water-carrying agent is removed by reduced pressure distillation.
In a more preferable scheme, the water absorbent is at least one of anhydrous potassium carbonate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride and a 4A molecular sieve. The water absorbent is added in the ammonia-aldehyde condensation reaction process, and after the reaction is finished, the water absorbent after water absorption is removed by filtering while the reaction is hot.
In a preferred scheme, the acid catalyst is at least one of concentrated sulfuric acid, concentrated hydrochloric acid, glacial acetic acid and p-toluenesulfonic acid.
In the preferable scheme, the time for the hydrolytic ring-opening reaction is 0.5-3 h.
In the preferred scheme, the time for the ammonia-aldehyde condensation reaction is 2-5 h.
In a preferred embodiment, the molar ratio of the aldehyde compound to the aminocaproate salt is 1:1 to 1.3: 1.
In a preferred embodiment, the aminocaproate salt is added slowly or in portions to the aldehyde compound to effect the reaction.
The caprolactam adopted by the invention is a conventional raw material sold in the market, and is preheated and melted firstly in the using process, and then potassium hydroxide and/or sodium hydroxide solution is added for hydrolysis reaction.
The preparation method of the Schiff base caproate mineral flotation collector comprises the following specific steps:
(1) hydrolytic ring-opening reaction of caprolactam: adding caprolactam into a reaction container, heating the temperature of the reactor to be more than 80 ℃ to melt the caprolactam into liquid, adding sodium hydroxide and/or potassium hydroxide solution into the liquid caprolactam, reacting for 0.5-3 h at the temperature of 80-105 ℃, and cooling to room temperature to obtain light yellow solid 6-sodium aminocaproate and/or 6-potassium aminocaproate; wherein the molar ratio of the sodium hydroxide and/or the potassium hydroxide to the caprolactam is 1: 1; the molar ratio of the sodium hydroxide and/or the potassium hydroxide to the water is 1: 1-1: 2;
(2) ammal condensation of 6-aminocaproate and aldehyde compounds: sequentially adding an aldehyde compound, an acid catalyst and a water-carrying agent or a water absorbent into a reaction vessel, adding solid 6-sodium aminocaproate in batches or slowly under stirring, and reacting for 2-5 hours at 90-120 ℃ after the addition is finished, wherein the molar ratio of the aldehyde compound to the aminocaproate is 1: 1-1.3: 1;
(3) and (3) post-treatment: if the water absorbent is used, filtering the water absorbent when the ammonia-aldehyde condensation reaction is finished, cooling to room temperature, separating out solid substances, washing the solid substances for 2-3 times by using acetone and anhydrous ether respectively, and performing vacuum drying to obtain the Schiff base caproate mineral flotation collector; and if the water-carrying agent is used, after the ammonia-aldehyde condensation reaction is finished, carrying out reduced pressure distillation to remove the water-carrying agent, separating out solid substances, washing the solid substances for 2-3 times by using acetone and anhydrous ether respectively, and drying to obtain the Schiff base caproate mineral flotation collector.
The invention also provides application of the Schiff base caproate mineral flotation collecting agent in flotation separation of useful minerals in bauxite, ilmenite, scheelite, wolframite, rare earth ore, tin ore, fluorite ore or manganese carbonate ore.
In the preferred application method, a flotation agent including Schiff base caproate mineral flotation collecting agent is added in the process of ore grinding or flotation after ore grinding for size mixing, and useful minerals are separated by flotation through a foam flotation method; wherein the Schiff base caproate mineral collecting agent is added according to the proportion of 50-1600 g/t ore.
In a more preferable application method, the pH value of the ore slurry is maintained in the range of 6-12 during the froth flotation.
In a more preferable application method, the ore with the granularity of-200 meshes in the ore slurry accounts for 50-90% of the whole ore mass.
The Schiff base caproate can be used as a collecting agent independently or can be compounded with other flotation reagents for use.
Compared with the prior art, the invention has the beneficial effects that: the invention firstly obtains the Schiff base caproate which simultaneously has imino and carboxyl and has an aliphatic chain structure. The imino and carboxyl have a synergistic chelation adsorption effect on metal ions on the surface of the mineral, so that the collecting capacity of the mineral is greatly improved; and the carboxyl and the aliphatic hydrocarbon with adaptive length are more beneficial to improving the hydrophilicity and the dispersion performance in the flotation and collection process. The Schiff base caproate serving as a flotation collector is applied to mineral flotation, and has the characteristics of good selectivity, strong collecting capacity, good dispersibility and water solubility and the like. Compared with the defects of poor freezing resistance, poor dispersibility and the like of the conventional fatty acid medicament in the prior art, the Schiff base caproate has excellent water solubility, is beneficial to dissolving the medicament in ore pulp, is convenient to use, can be widely applied to flotation and collection of non-sulfide ores, and is particularly suitable for flotation and collection of minerals such as bauxite, ilmenite, scheelite, wolframite, rare earth ore, tin ore, fluorite ore, manganese carbonate ore and the like. More importantly, the Schiff base caproate of the invention is easy to be hydrolyzed into fatty aldehyde and 6-amino caproate in an acid medium, which makes minerals easy to be subjected to drug removal treatment after flotation. In addition, the preparation method of the Schiff base caproate has the advantages of simple flow, easy control of operation and low cost.
Drawings
FIG. 1 is an infrared spectrum of sodium 6- (2-ethyl-2-alkenylhexyl) iminohexanoate.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrogram of sodium 6- (2-ethyl-2-alkenylhexyl) iminohexanoate.
FIG. 3 is a flow chart of a primary fluorite roughing process for sodium 6- (2-ethyl-2-alkenylhexyl) iminohexanoate.
FIG. 4 is a flow chart of a primary rough concentration process of ilmenite with sodium 6- (2-ethyl-2-alkenylhexyl) iminohexanoate.
FIG. 5 is a flow chart of a process for flotation of scheelite with sodium 6- (2-ethyl-2-alkenylhexyl) iminohexanoate.
FIG. 6 is a flow chart of the process for flotation of bauxite with sodium 6- (2-ethyl-2-alkenylhexyl) iminohexanoate.
FIG. 7 is a process flow chart of the flotation of manganese carbonate ore from sodium 6- (2-ethyl-2-alkenylhexyl) imine caproate.
Detailed Description
The following examples are intended to further illustrate the present invention and are not intended to further limit the scope of the invention.
All parts and percentages in examples 1 to 12 are by mass unless otherwise specified.
Example 1
Preparation of sodium 6- (2-ethyl-2-alkenylhexyl) iminohexanoate:
adding 5.66 parts of caprolactam into a reactor with a stirring device, melting the caprolactam at the temperature of 80 ℃, dissolving 2 parts of solid sodium hydroxide into 3 parts of distilled water to prepare an alkali solution, adding the alkali solution into the melted caprolactam liquid, heating to 100 ℃, stirring for reacting for 2 hours, and cooling to room temperature to precipitate a white solid, namely 6-sodium aminocaproate.
7.56 parts of 2-ethyl-2-hexenal, 0.48 part of p-toluenesulfonic acid, 60 parts of toluene and 6-sodium aminocaproate prepared by hydrolysis are sequentially added into a reactor, a water separator is arranged, the mixture reacts for 3 hours at the reaction temperature of 115 ℃, after the toluene is removed by reduced pressure distillation, the solid is sequentially washed for 2 times by anhydrous ether and acetone, the obtained orange-red solid is dried for 24 hours in a vacuum drier at the temperature of 50 ℃, and 11.82 parts of solid is obtained, wherein the yield is 90.57%. FIG. 1 is an infrared spectrum of the product, and FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the product.
Example 2
Preparation of sodium 6- (2-ethyl-2-alkenylhexyl) iminohexanoate:
adding 11.32 parts of caprolactam into a reactor with a stirring device, melting the caprolactam at the temperature of 80 ℃, dissolving 4 parts of solid sodium hydroxide into 6 parts of distilled water to prepare an alkali solution, adding the alkali solution into the melted caprolactam liquid, heating to 100 ℃, stirring for reaction for 2 hours, and cooling to room temperature to precipitate a white solid, namely 6-sodium aminocaproate.
15.12 parts of 2-ethyl-2-hexenal, 0.95 part of p-toluenesulfonic acid, 80 parts of toluene and 6-sodium aminocaproate prepared by hydrolysis are sequentially added into a reactor, a water separator is arranged, the mixture reacts for 4 hours at the reaction temperature of 115 ℃, after the toluene is removed by reduced pressure distillation, the solid is sequentially washed for 2 times by anhydrous ether and acetone respectively, and the obtained orange-red solid is dried for 24 hours in a vacuum drier at the temperature of 50 ℃ to obtain 23.82 parts of solid with the yield of 91.26%.
Example 3
Preparation of sodium n-octylimidocaproate:
adding 11.32 parts of caprolactam into a reactor with a stirring device, melting the caprolactam at the temperature of 80 ℃, dissolving 4 parts of solid sodium hydroxide into 6 parts of distilled water to prepare an alkali solution, adding the alkali solution into the melted caprolactam liquid, heating to 100 ℃, stirring for reaction for 2 hours, and cooling to room temperature to precipitate a white solid, namely 6-sodium aminocaproate.
Adding 15.12 parts of n-octanal, 0.95 part of p-toluenesulfonic acid and 80 parts of toluene into a reactor in sequence, dripping the molten sodium 6-aminocaproate liquid prepared by hydrolysis at 100 ℃, installing a water separator after finishing dripping, reacting for 4 hours at the reaction temperature of 115 ℃, removing the toluene by reduced pressure distillation, washing the solid for 2 times by using anhydrous ether and acetone in sequence, and drying the obtained yellow solid in a vacuum drier at 50 ℃ for 24 hours to obtain 25.65 parts of solid with the yield of 97.53%.
Example 4
Preparation of sodium 6- (2-ethylhexyl) iminohexanoate:
adding 5.66 parts of caprolactam into a reactor with a stirring device, melting the caprolactam at the temperature of 80 ℃, dissolving 2 parts of solid sodium hydroxide into 3 parts of distilled water to prepare an alkali solution, adding the alkali solution into the melted caprolactam liquid, heating to 100 ℃, stirring for reacting for 2 hours, and cooling to room temperature to precipitate a white solid, namely 6-sodium aminocaproate.
7.68 parts of 2-ethylhexanal, 0.48 part of p-toluenesulfonic acid, 45 parts of toluene and the 6-sodium aminocaproate prepared by hydrolysis are sequentially added into a reactor, a water separator is arranged, the mixture reacts for 4 hours at the reaction temperature of 115 ℃, after the toluene is removed by reduced pressure distillation, the solid is sequentially washed for 2 times by anhydrous ether and acetone respectively, and the obtained light yellow solid is dried for 24 hours in a vacuum drier at the temperature of 50 ℃ to obtain 10.82 parts of solid with the yield of 82.28%.
The Schiff base caproate prepared in examples 1-4 was compared with the prior art conventional sodium oleate flotation agent for the front line orbital energy:
according to the molecular design theory of the collecting agent, Schiff base caproate has stronger selective collecting capability than oleate. The front-line orbital energies of the Schiff base sodium caproate and the sodium oleate were calculated by using Gaussian 03 software using the B3LYP method of the density functional theory and the group 6-31G (d) and the results are shown in Table 1. As can be seen from Table 1, the highest occupied orbital (HOMO) energy of sodium oleate is about 4kJ/mol higher than that of sodium Schiff base caproate, which indicates that the sodium oleate has slightly stronger ability to provide electrons for transition metal elements; however, the lowest unoccupied orbital (LUMO) energy of the Schiff base sodium caproate is lower than that of sodium oleate LUMO by more than 100kJ/mol, which shows that the Schiff base sodium caproate is easier to accept d-orbital electrons of transition metal atoms to form feedback pi bonds than sodium oleate, and is favorable for enhancing the coordination selectivity of the Schiff base sodium caproate to the transition metal elements.
TABLE 1 comparison of front-line orbital energies of collector molecules
Example 5
The application of 6- (2-ethyl-2-alkenyl hexyl) imine sodium caproate in fluorite flotation:
CaF of raw fluorite ore2The grade is 38.92 percent, the ore is ground to 60 percent of minus 200 meshes, the ground ore is placed in a flotation tank, the rough concentration operation is carried out once under the conditions of 1400g/t of sodium carbonate dosage, 400g/t of water glass dosage, 500g/t of collecting agent dosage and 30 ℃ of flotation temperature, and the flow chart of the flotation process is shown in attached figure 3. The results of the flotation comparison experiment of the sodium 6- (2-ethyl-2-alkenylhexyl) iminohexanoate collector and the commonly used sodium oleate collector in the invention are shown in table 2. As can be seen from the table, the flotation recovery rate of the sodium 6- (2-ethyl-2-allyl hexyl) imine caproate to fluorite is 1.89 percent higher than that of the traditional sodium oleate when the flotation temperature is 30 ℃, and CaF2The grade is improved by 0.53 percentage point.
TABLE 2 comparative experimental results of collector flotation fluorite at a flotation temperature of 30 deg.C
| Collecting agent dosage (g/t raw ore) | Coarse concentrate CaF2Grade (%) | CaF2Recovery (%) |
| Sodium oleate 500 | 80.88 | 96.05 |
| 6- (2-Ethyl-2-en-exyl) iminohexanoic acid sodium salt 500 | 81.41 | 97.94 |
Example 6
Application of sodium 6- (2-ethyl-2-ethylhexyl) iminohexanoate in ilmenite flotation:
TiO of some ilmenite raw ore2The grade is 22.85 percent, the ore is ground to 60 percent of minus 200 meshes, the ground ore is placed in a flotation tank, the rough concentration operation is carried out once under the conditions of 1800g/t of sulfuric acid dosage, 1500g/t of collecting agent dosage and 30 ℃ of flotation temperature, and the flow chart of the flotation process is shown in attached figure 4. The results of the flotation comparison experiment of the sodium 6- (2-ethyl-2-alkenylhexyl) iminohexanoate collector and the commonly used sodium oleate collector in the invention are shown in table 3. As can be seen from the table, the flotation recovery rate of the 6- (2-ethyl-2-allyl hexyl) imine sodium caproate to the ilmenite is 2.01 percent higher than that of the traditional sodium oleate when the flotation temperature is 30 ℃, and the TiO is2The grade is improved by 0.63 percentage points.
TABLE 3 comparative experimental results of collector flotation ilmenite at a flotation temperature of 30 ℃
Example 7
The application of 6- (2-ethyl-2-alkenyl hexyl) sodium monohexoate in scheelite flotation:
tungsten grade WO of certain scheelite raw ore30.47 percent of ore is ground to 80 percent of minus 200 meshes, firstly, desulfurization flotation is carried out, 40g of butyl xanthate, 10g of butyl amine black powder and 36g of foaming agent No. 2 oil are added into each ton of ore, then 3000g of sodium carbonate, 2500g of water glass and 500g of collecting agent are added into each ton of ore to carry out white tungsten roughing operation, 100g of collecting agent is added into each ton of ore to carry out scavenging, 500g of water glass is added into each ton of ore to carry out primary concentration, 300g of water glass is added into each ton of ore to carry out secondary concentration, and the flow chart of the flotation process is shown in attached figure 5. The results of the flotation comparative experiment of the sodium 6- (2-ethyl-2-alkenylhexyl) iminohexanoate collector of the present invention with the conventional oxidized paraffin soap 731 are shown in table 4. As can be seen from the table, the flotation recovery rate of the sodium 6- (2-ethyl-2-ethylhexyl) iminohexanoate to the scheelite is 3.35 percentage points higher than that of the traditional oxidized paraffin soap 731, WO3The grade is improved by 0.39 percentage points.
TABLE 4 comparative experimental results of collector flotation scheelite
Example 8
The application of 6- (2-ethyl-2-alkenyl hexyl) imine sodium caproate in bauxite flotation:
some bauxite containing Al2O365.15％，SiO210.27 percent of the ore is ground to 80 percent of minus 200 meshes, and the ore is placed in a flotation tank, and the amount of sodium carbonate is used4000g/t of coarse aluminum concentrate is obtained by performing one-time roughing operation on the bauxite under the conditions that the using amount of sodium hexametaphosphate is 60g/t and the using amount of 6- (2-ethyl-2-alkenyl hexyl) sodium monohexoate or the using amount of the sodium oleate and the sodium benzohydroxamate combined collecting agent is 1000g/t, wherein the flow chart of the flotation process is shown in the attached figure 6, and the flotation result is shown in the table 5. As can be seen, the combination of sodium 6- (2-ethyl-2-ethylhexyl) iminohexanoate and sodium benzohydroxamate resulted in Al after primary roughing of bauxite2O3The recovery rate is improved by 3.10 percent, and the ratio of aluminum to silicon is improved by 0.57.
TABLE 56 comparison of flotation bauxite results with sodium (2-ethyl-2-alkenylhexyl) iminohexanoate
Example 9
The application of the 6- (2-ethyl-2-alkenyl hexyl) imine sodium caproate in the flotation of manganese carbonate ore comprises the following steps:
the manganese grade of the magnetic tailings of a certain manganese carbonate ore is 7.58 percent, the ore is ground to 80 percent of minus 200 meshes, 3000g of sodium carbonate, 2500g of water glass and 1000g of collecting agent are added into each ton of ore feeding for roughing, 500g of water glass and 200g of collecting agent are added into each ton of ore feeding for scavenging, 500g of water glass is added into each ton of ore feeding for primary concentration, 300g of water glass is added into each ton of ore feeding for secondary concentration, and the flow chart of the flotation process is shown in the attached figure 7. The results of the flotation comparison experiment of the sodium 6- (2-ethyl-2-alkenylhexyl) iminohexanoate collector and the commonly used sodium oleate collector in the invention are shown in table 6. As can be seen from the table, the flotation recovery rate of the manganese carbonate ore by the 6- (2-ethyl-2-allyl hexyl) sodium monohexoate is improved by 1.78 percent compared with that of the sodium oleate, and the concentrate manganese grade is improved by 1.69 percent.
TABLE 6 flotation comparative experiment results of manganese carbonate ore magnetic separation tailings
| Species of collector | Manganese grade of concentrate (%) | Manganese recovery (%) |
| Sodium oleate | 16.56 | 80.62 |
| 6- (2-Ethyl-2-en-exyl) iminohexanoic acid sodium salt | 18.25 | 82.40 |
Claims (10)
1. A Schiff base caproate mineral flotation collector is characterized by having a structure shown in formula 1:
wherein,
r is C3～C11An alkyl or alkenyl group of (a);
m is Na+Or K+。
2. The Schiff base caproate mineral flotation collector of claim 1, wherein R is C7An alkyl group or an alkenyl group.
3. The schiff base caproate mineral flotation collector of claim 2, wherein R is n-heptyl, 1-ethyl-n-pentyl, or 1-ethyl-1, 2-pentenyl.
4. The preparation method of the Schiff base caproate mineral flotation collector of claim 1, characterized in that caprolactam is subjected to hydrolysis ring-opening reaction in sodium hydroxide and/or potassium hydroxide solution at the temperature of 80-105 ℃ to obtain amino caproate; carrying out an amino-aldehyde condensation reaction on the amino caproate and an aldehyde compound with a structure shown in a formula 2 at a temperature of 90-120 ℃ under the catalysis of acid to obtain the amino caproate;
wherein,
r is C3～C11An alkyl group or an alkenyl group.
5. The method according to claim 4, wherein the molar ratio of sodium hydroxide and/or potassium hydroxide to water in the potassium hydroxide and/or sodium hydroxide solution is 1: 1-1: 2; the molar ratio of potassium hydroxide and/or sodium hydroxide to caprolactam is 1: 1.
6. The method of claim 4, wherein a water-carrying agent or water-absorbing agent is added to the reaction for removing water produced by the reaction.
7. The method according to claim 6, wherein the water-carrying agent is at least one of benzene, toluene and chloroform; the water absorbent is at least one of anhydrous potassium carbonate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride and a 4A molecular sieve.
8. The method of claim 4, wherein the acid catalyst is at least one of concentrated sulfuric acid, concentrated hydrochloric acid, glacial acetic acid, and p-toluenesulfonic acid; the time for the hydrolytic ring-opening reaction is 0.5-3 h; the time for the ammonia-aldehyde condensation reaction is 2-5 h.
9. The application of the Schiff base caproate mineral flotation collector disclosed by any one of claims 1 to 3, which is characterized by being applied to flotation separation of useful minerals in bauxite, ilmenite, scheelite, wolframite, rare earth ore, tin ore, fluorite ore or manganese carbonate ore.
10. The application of the method as claimed in claim 9, wherein a flotation agent including a Schiff base caproate mineral flotation collector is added to the ore during grinding or during flotation after grinding for size mixing, and the useful minerals are separated by flotation through a froth flotation method; wherein the Schiff base caproate flotation collecting agent is added according to the proportion of 50-1600 g/t ore.
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|---|---|---|---|---|
| CN105880034A (en) * | 2016-04-22 | 2016-08-24 | 北京矿冶研究总院 | Ilmenite chelating collector |
| CN107520058A (en) * | 2017-08-23 | 2017-12-29 | 中南大学 | A kind of rutile ore dressing composite reagent and its beneficiation method |
| CN115090422A (en) * | 2022-06-17 | 2022-09-23 | 山东理工大学 | Amino acid type collecting agent and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105880034A (en) * | 2016-04-22 | 2016-08-24 | 北京矿冶研究总院 | Ilmenite chelating collector |
| CN105880034B (en) * | 2016-04-22 | 2019-02-05 | 北京矿冶研究总院 | Ilmenite chelating collector |
| CN107520058A (en) * | 2017-08-23 | 2017-12-29 | 中南大学 | A kind of rutile ore dressing composite reagent and its beneficiation method |
| CN107520058B (en) * | 2017-08-23 | 2019-05-17 | 中南大学 | A kind of rutile ore dressing composite reagent and its beneficiation method |
| CN115090422A (en) * | 2022-06-17 | 2022-09-23 | 山东理工大学 | Amino acid type collecting agent and preparation method and application thereof |
| CN115090422B (en) * | 2022-06-17 | 2024-04-26 | 山东理工大学 | Amino acid type collector, and preparation method and application thereof |
Also Published As
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|---|---|
| CN104801426B (en) | 2017-04-05 |
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