US3238127A - Ion flotation method - Google Patents
Ion flotation method Download PDFInfo
- Publication number
- US3238127A US3238127A US142483A US14248361A US3238127A US 3238127 A US3238127 A US 3238127A US 142483 A US142483 A US 142483A US 14248361 A US14248361 A US 14248361A US 3238127 A US3238127 A US 3238127A
- Authority
- US
- United States
- Prior art keywords
- solution
- ion
- layer
- collector
- collectors
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title description 28
- 238000005188 flotation Methods 0.000 title description 18
- 150000002500 ions Chemical class 0.000 description 37
- 239000000243 solution Substances 0.000 description 33
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 24
- 239000007795 chemical reaction product Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 239000007788 liquid Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000003570 air Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- -1 n-decylarnine Chemical compound 0.000 description 7
- 125000000129 anionic group Chemical group 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000000638 solvent extraction Methods 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 description 3
- 229940012189 methyl orange Drugs 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- JDPSPYBMORZJOD-UHFFFAOYSA-L copper;dodecanoate Chemical compound [Cu+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O JDPSPYBMORZJOD-UHFFFAOYSA-L 0.000 description 2
- 235000005687 corn oil Nutrition 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- 235000012343 cottonseed oil Nutrition 0.000 description 2
- 239000002385 cottonseed oil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- GZNACENTEXAZDR-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;iodide Chemical compound [I-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GZNACENTEXAZDR-UHFFFAOYSA-M 0.000 description 1
- KKRURATZPAVIHA-UHFFFAOYSA-M 1-hexadecylquinolin-1-ium;bromide Chemical compound [Br-].C1=CC=C2[N+](CCCCCCCCCCCCCCCC)=CC=CC2=C1 KKRURATZPAVIHA-UHFFFAOYSA-M 0.000 description 1
- TTXLFUJSPVEFDO-UHFFFAOYSA-M 1-octadecylpyridin-1-ium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 TTXLFUJSPVEFDO-UHFFFAOYSA-M 0.000 description 1
- ZRSZLLTWCAFTIX-UHFFFAOYSA-M 2-decyl-1-(2-phenylethenyl)pyridin-1-ium chloride Chemical compound [Cl-].C(CCCCCCCCC)C1=[N+](C=CC=C1)C=CC1=CC=CC=C1 ZRSZLLTWCAFTIX-UHFFFAOYSA-M 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical class CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BPDDKZUKUVNLCQ-UHFFFAOYSA-M C1(=CC=CC=C1)S(=O)(=O)[O-].C[N+](C1=CC=CC=C1)(CCCCCCCCCCCC)C Chemical compound C1(=CC=CC=C1)S(=O)(=O)[O-].C[N+](C1=CC=CC=C1)(CCCCCCCCCCCC)C BPDDKZUKUVNLCQ-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000003975 aryl alkyl amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- NJVHCUNZAMFQNA-UHFFFAOYSA-N azane;n-hydroxy-n-phenylnitrous amide Chemical compound N.O=NN(O)C1=CC=CC=C1 NJVHCUNZAMFQNA-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- TWFQJFPTTMIETC-UHFFFAOYSA-N dodecan-1-amine;hydron;chloride Chemical compound [Cl-].CCCCCCCCCCCC[NH3+] TWFQJFPTTMIETC-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005351 foam fractionation Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002461 imidazolidines Chemical class 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SUBFIBLJQMMKBK-UHFFFAOYSA-K iron(3+);trithiocyanate Chemical compound [Fe+3].[S-]C#N.[S-]C#N.[S-]C#N SUBFIBLJQMMKBK-UHFFFAOYSA-K 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- ITFGZZGYXVHOOU-UHFFFAOYSA-N n,n-dimethylmethanamine;methyl hydrogen sulfate Chemical compound C[NH+](C)C.COS([O-])(=O)=O ITFGZZGYXVHOOU-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- MJCJUDJQDGGKOX-UHFFFAOYSA-N n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC MJCJUDJQDGGKOX-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical class Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- YHIXOVNFGQWPFW-UHFFFAOYSA-N octadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[NH3+] YHIXOVNFGQWPFW-UHFFFAOYSA-N 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- KAQHZJVQFBJKCK-UHFFFAOYSA-L potassium pyrosulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OS([O-])(=O)=O KAQHZJVQFBJKCK-UHFFFAOYSA-L 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- UTYXJYFJPBYDKY-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide;trihydrate Chemical compound O.O.O.[K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UTYXJYFJPBYDKY-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- QFGWYYQGDCVPFQ-UHFFFAOYSA-M triethyl(hexadecyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCC[N+](CC)(CC)CC QFGWYYQGDCVPFQ-UHFFFAOYSA-M 0.000 description 1
- AQZSPJRLCJSOED-UHFFFAOYSA-M trimethyl(octyl)azanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(C)C AQZSPJRLCJSOED-UHFFFAOYSA-M 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/01—Organic compounds containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N3/02—Details
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/09—Reaction techniques
- Y10S423/14—Ion exchange; chelation or liquid/liquid ion extraction
Definitions
- This invention relates to ion flotation method, and more particularly to a process for the recovery of organic ions and inorganic ions from solution by contacting the ions with an ionic organic reagent to form an insoluble reaction product, which adheres to a gas- Water interface and is thereby buoyed to the surface by bubbling, and thereafter separating the insoluble reaction product from the solution.
- An object of the present invention is to provide a process in which frothing and the creation of turbid colloids are substantially avoided.
- a still further object is to provide an effective process in which the desired product, as it rises with the air bubbles, is collected within a liquid layer which may be withdrawn for the recovery of the product.
- a still further object is to provide in an ion flotation process of the character described a liquid layer supported on the solution body, the liquid layer being immiscible with the body and serving to catch and retain the product as it is buoyed upwardly by the bubbles.
- Yet another object is to provide a process in which an aqueous solution of the desired product is surmounted by a non-aqueous layer by which the product is wettable, which layer takes up the prodnot as it is raised in the flotation operation, the process being continuous in that the non-aqueous layer may be continuously withdrawn and the solution continuously fed during the separating operation.
- ions are recovered from solution in the substantial absence of undissolved mineral particles recoverable by usual flotation procedures by contacting the same in aqueous solution with a collector ion of opposite charge to form an insoluble reaction product, and the insoluble reaction product is buoyed by air bubbles to the surface and the insoluble reaction product is then recovered from the resulting scum.
- I provide a liquid layer, immiscible with Water, above the solution, and thus catch the product as it rises up with the bubbles. If the bubbling rate is kept relatively slow, no froth at all is produced and the desired product is captured by the layer before colloids are formed.
- a layer of octyl alcohol was placed over the solution body for the recovery of ferrocyanide ion, using lauryl pyridinium chloride as a collector. No froth at all was produced, and the insoluble reaction product was recovered entirely in the layer of octyl alcohol.
- the process was carried on con- Patented Mar. 1, 19%6 tinuously in a tank holding the aqueous solution and the supernatant non-aqueous layer, bubbles being introduced at a slow rate into the lower portion of the tank and the supernatant non-aqueous layer being drawn otf continuously.
- the octyl alcohol is a solvent having polar characteristics adapting it very well for collection of products such as are produced by the contacting of ions with amphipathic substances of opposite charge.
- the collectors utilized in the process of my invention are, generally speaking, the ionic surface-active collectors which are utilized in ore flotation procedures. These collectors must have at least one hydrophilic center of activity and at least one aerophilic center of activity. They must have an electrical charge which is opposite to the ion which it is desired to collect it the process is to be operative.
- a surface-active anionic collector i.e., a collector yielding, in aqueous solution, a surface-active ion bearing a negative charge, for example, a lauric acid soap, is used to remove a soluble cation from solution.
- a surface-active cationic collector i.e., a collector yielding, in aqueous solution, a surface-active ion bearing a positive charge, for example, lauryl pyridinium chloride, is used when it is desired to remove a desired anion from solution.
- Cationic collectors used in my novel process are compounds having one or more amine nitrogens. These compounds include primary, secondary and tertiary fatty alkyl, aryl and arylalkylamines, and their salts and the corresponding fatty quaternary ammonium salts.
- the arylamines include the picolines, pyridines, quinoliines, and 'their homologs and lower alkyl substituted analogs.
- Examples of cationic collectors which will react with organic anions in polar solutions include the quaternary ammonium compounds, such as trimethyl-n-octylammonium chloride, trimethyl-n-decylamrnonium chloride, trimethyl n dodecylammonium chloride, trirnethyl n octadecylammonium bromide, triethyl-n-hexadecylammonium iodide; mixtures of quaternary salts derived from ta-llow fatty acids, from cottonseed oil fatty acids, from soybean oil fatty acids and coconut oil fatty acids, from mixtures of fatty acids derived from tallow, corn oil, soybean oil, coconut oil; alkyl amines such as diamylamine, didodecylamine, n-decylarnine, n-tetradecylamine, tri-noctadecylamine, n-oc
- Anionic collectors are of two types: the oxhydry l compounds, where a metal or hydrogen is connected to the hydrocarbon element of the collector through an oxygen atom, and the sulfhydryl type Where the connection is made through a sulfur atom.
- the oxhydryl collectors include carboxylates, acid alkylsulfates, snlfonates and phosphates and phosphonates.
- the sulfhydryl compounds include mercaptazrs, thiocarborrates (xanthates), thioureas and dithiophosphates.
- anionic collectors llTD- clude the acids and sodium, potassium or ammonium salts of rosin, the tall oils and animal and vegetable oils; naphthenic acids; sodium-n-octylsulfate; potassium-n-dodecylsul-fate; the ammonium salt of n-dodecyldiethyleneglycolsurlfate; the sodium salt of crude or refined petroleum sulfonic acid; fi-phenylpropionic acid; pelargonic acid; mixtures of acids derived from linseed oil, soybean oil, palm oil, corn oil and cottonseed oil; monosodium ot-sulfopalmitate; disodium ot-sulfosterate, 1,'3-diphenyl-2-thi0- urea and thiocarbanilide.
- the above-described examples of cationic anionic collectors are but a few of the many collectors which are known to be commercially practicable and which are used in flotation procedures
- the number of carbon atoms in the aerophilic portion or portions of the collector molecule required to impart desired aerophilic properties to the collector varies with the type of collector. Generally from 5 to about 24 and preferably from 8 to 22 carbon atoms are required in at least one aerophilic portion of the collector molecule.
- My preferred cationic and anionic collectors are derived from plant and animal triglycerides, preferably vegetable or marine animal triglycerides. These glycerides canbe hydrolyzed to free their fatty acids which can then be utilized as anionic collectors per se, or which can be converted to ammonium or alkali metal salts for similar purposes.
- the fatty acids are converted to amines, nitriles or quaternary salts by known means. It is also preferred that the hydrocarbon chains of these collectors contain carbon to carbon unsaturaltion. Where quaternary ammonium collectors, di-arnine collectors or triamine collectors are utilized, it is especially preferred that the collectors contain at least 1 hydrocarbon radical containing from 8 to 22 carbon atoms.
- insoluble reaction products and similar terms are used throughout my specification.
- the term insoluble does not mean that the solubility is an equilibrium between the ions in solution and a solid ionic crystal, rather it is intended that the term encompass instances wherein the reaction product is composed of oppositely charged ions which are not independent as they have lost some entropy.
- the term applies to products (other than soluble reaction products) adsorbed at the solventbubble interface, i.e., the unitary product molecules are no longer randomly dispersed throughout the solution but are, in a major proportion, localized at the solventabubble interface.
- the products at the interface may be thought of as crystals containing only one molecule of product. As these crystals are forced closer together in the drain ing froth, they form a scum which is highly insoluble rather than larger crystals.
- the range of amounts of collector required to collect a given amount of ion is great. I prefer to utilize an amount of collector ranging from about 0.001 to equivalents of collector/ equivalent of ion. A still more preferable ran-ge of equivalents is 0.1-10 equivalents of collector/ equivalent of ion. Still more preferable is the utilization of stoichiometrically equivalent amounts of collector/ equivalent of ion to be collected.
- reaction products formed when the above-identified collectors are contacted are removed from solution by flotation, i.e., are removed from solution by means of substantially nonreactive gaseous bubbles.
- Useful bubble materials include gaseous hydrocarbons such as methane, ethane and butane; gaseous halogenated hydrocarbons such as the Freons; and gases such as air, carbon dioxide, nitrogen and argon. I prefer to utilize air to remove insoluble reaction products from the solvents used in the ion recovery process of my invention.
- the liquid collection layer should be immiscible with the liquid from which the ions are being recovered and should have some polar characteristics adapting it for 001- le'ction of the desired ions.
- octyl alcohol is useful, because it has suflicient polar characteristic to dissolve the flotation product but is not so polar that it itself is soluble in water.
- the supernatant layer be a solvent; it is sufiicient that the reaction product be wettable by the layer or phase. In other words, the reaction product is taken up or held by the liquid collection layer either by way of solution or by wetting.
- suitable solvents or wetting agents are: benzene, mixtures of benzene and octyl alcohol, mixtures of petrolether and higher alcohols.
- liquid collection layer mus-t be insoluble or only very slightly soluble in water, it must be lighter than water or solutions of salts in water, it should not react chemically with the water or with the flotation product.
- reaction product is taken up into the layer, while any entrained liquid carried to the surface drops back into the solution as small droplets. Frothing or the formation of turbid colloids are minimized and may be entirely eliminated.
- Example I 3 mg. of methyl orange was dissolved in 300 ml. of water, buffered to pH 6.5 with sodium bicarbonate and placed in a No. 4 sintered glass Biichner funnel, diameter 3". 25 ml. of isooctyl alcohol was placed on the surface of the solution. 3 mg. of dodecyl trimethyl ammonium chloride was dissolved in 3 ml. of absolute alcohol, heated to boiling for a few seconds and added to the solution by means of a capillary tube that passed through the 'o'ctyl alcohol layer and reached almost to the sintered glass plate. Nitrogen gas was sparged through the sintered glass, thus generating very small bubbles.
- the bubble rate was carefully adjusted so as to disturb the octyl alcohol layer as little as possible. This resulted in the small bubbles accumulating under the octyl alcohol and gradually coalescing to form larger bubbles which rose through the octyl alcohol. As they did so, the product formed between the methyl orange anion, and the quaternary ammonium cation was stripped from the bubble and dissolved in the octyl alcohol. From time to time, any entrained water carried to the surface dropped back as small droplets. After 15 minutes, the aqueous layer was completely decolorized and the octyl alcohol layer was bright yellow, showing that the methyl orange anion had been removed from the water and dissolved in the non-aqueous solvent.
- Example II ized, and the color had gone into the octyl alcohol, showing that the cation dye had combined with the sulpholaurate anion and been collected by the octyl alcohol.
- Example III 0.01 g. each of cobalt and nickel chlorides were dissolved in 300 ml. water and just enough ammonia was added to redissolve the hydroxides formed. The solution was placed in a similar vessel to that in Example I and 25 ml. of isooctyl alcohol was placed on the surface. 6 mg. of lauric acid was dissolved in 10 ml. of alcohol and 3 mg. KOH added to convert to potassium laurate and taken to boiling. This solution was added, under the octyl alcohol, 2 ml. at a time with bubbling as before. After each addition, bubbling was contained for 5 minutes and the contents of the funnel was removed to a separatory funnel, and the octyl alcohol layer was sepa rated.
- the solution was then put back in the Buchner funnel and fresh octyl alcohol added, and the next 2 ml. of collector added. After the first addition, the octyl alcohol was greenish, there being some undissolved product in it. The octyl alcohol contained cobalt but only a trace of nickel. The fifth and final sample of octyl alcohol, which was blue green, contained only nickel. This illustrates that the selectivity shown by ion flotation applies also if flotation is into a non-miscible solvent. It also illustrates that the product, brought up by the bubble, does not necessarily need to be soluble in the non-aqueous phase, but that it is sufficient if it is wettable by the non-aqueous phase.
- Example IV 300 ml. of a saturated solution of cupric chloride was placed in a Biichner funnel as before and 25 ml. of isooctyl alcohol placed on the surface. 50 mg. of laurylamine was dissolved in 5 ml. of absolute alcohol, just acidified with HCl and heated to boiling and added to the solution of cupric chloride. Air was bubbled for minutes, by which time the octyl alcohol had become bright yellow.
- Example V 4 mg. of potassium ferrocyanide trihydrate was dissolved in 200 ml. of Water and the solution adjusted with potassium hydroxide to pH 10.5. It was placed in a No. 4 sintered glass Biiohner funnel, 2" diameter, and 10 ml. of isooctyl alcohol was placed on the surface. 10.8 mg. of lauryl pyridinium chloride, an amount exactly equivalent to the ferrocyanide ion was dissolved in petrol ether (60-80 C.) and carefully taken to dryness. It was then dissolved in 5 ml. of absolute alcohol, taken to boiling and added to the ferrocyanide solution under the octyl alcohol.
- Example V1 0.3 g. of copper sulphate was dissolved in 250 m1. of water. Ammonia was added until the hydroxide just redissolved. The solution was added to a Biichner funnel as in Example I. 30 ml. of benzene and 10 ml. of butyl alcohol was mixed and placed above the surface of the solution. 0.2 g. of lauric acid was dissolved in 10 ml. of alcohol and converted to the laurate by adding potassium hydroxide. This was added in two stages at 10 minute intervals, through a capillary below the surface of the non-aqueous layer. Air was bubbled through slowly for 20 minutes.
- the upper layer was a deep blue showing that most of the copper had concentrated in it, but there was still a pale blue color in the aqueous solution. This is attributed to the fact that butyl alcohol is slightly soluble in water and takes some of the copper laurate with it. The copper laurate, dissolved in the benzene-butyl alcohol mixture, was easily extracted by shaking with dilute HCl.
- the new process provides a number of advantages in the flotation separation of ions.
- the process is versatile in that it separates the collector and the solvent stages.
- the quantity of solvent is related to the quantity of aqueous solution
- the quantity is related to the amount of ion extracted, the upper limit being imposed by the solubility of the ion-soap compound in the solvent.
- the rate of extraction is determined by the rate of diffusion into the solvent droplets, whereas here the adsorption is on the surface of the bubbles, and desorption into the solvent is off the surface of the bubbles, so that the rate is controlled by the bubble rate.
- the present process lends itself to continuous processing. Reclaiming the ion and the solvent may be accomplished through any of the well-known methods, as, for example, by distilling the solvent to produce a residue of the same soap compound that would have been collected in the scum in ion flotation.
- a process for the recovery of ions from an aqueous solution thereof comprising adding to the solution collector ions having an electrical charge opposite to that of the ions to be recovered to form an insoluble reaction product of said ions in said solution, disposing upon the surface of the solution a floating layer of a non-aqueous liquid immiscible with said solution and having polar characteristics adapting it for collecting said reaction product, introducing gas into the solution having the floating liquid layer disposed thereover in the form of small bubbles at a rate which leaves the floating liquid layer substantially undisturbed to buoy the reaction product to the surface of the solution and into the floating liquid layer where it is collected.
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Description
United States Patent 3,238,127 ION FLOTATION METHOD Felix Sebba, Johannesburg, Transvaal, Republic of South Africa, assiguor to Armour and Company, Chicago, 11]., a corporation of Delaware No Drawing. Filed Get. 3, 1961, Ser. No. 142,483 1 Claim. (Cl. 210-44) This application is a continuation-in-part of my copending applications Serial No. 818,501 filed June 3, 1959, and Serial No. 862,482 filed December 29, 1959, both of said applications being incorporated herewith by reference.
This invention relates to ion flotation method, and more particularly to a process for the recovery of organic ions and inorganic ions from solution by contacting the ions with an ionic organic reagent to form an insoluble reaction product, which adheres to a gas- Water interface and is thereby buoyed to the surface by bubbling, and thereafter separating the insoluble reaction product from the solution.
In ion flotation procedures in which insolubilized ions are contacted with air bubbles to buoy or lift the insolubilized ions to the surface, care must be exercised in order to avoid the formation of superfluous froth on the surface and also the creation of turbid colloids near the surface. Both of these phenomena are liable to result in inefliciency in the recovery of the desired ions.
An object of the present invention is to provide a process in which frothing and the creation of turbid colloids are substantially avoided. A still further object is to provide an effective process in which the desired product, as it rises with the air bubbles, is collected within a liquid layer which may be withdrawn for the recovery of the product. A still further object is to provide in an ion flotation process of the character described a liquid layer supported on the solution body, the liquid layer being immiscible with the body and serving to catch and retain the product as it is buoyed upwardly by the bubbles. Yet another object is to provide a process in which an aqueous solution of the desired product is surmounted by a non-aqueous layer by which the product is wettable, which layer takes up the prodnot as it is raised in the flotation operation, the process being continuous in that the non-aqueous layer may be continuously withdrawn and the solution continuously fed during the separating operation. Other specific objects and advantages will appear as the specification proceeds.
In the separating operations described in my copending applications Serial No. 818,501 and Serial No. 862,- 482, ions are recovered from solution in the substantial absence of undissolved mineral particles recoverable by usual flotation procedures by contacting the same in aqueous solution with a collector ion of opposite charge to form an insoluble reaction product, and the insoluble reaction product is buoyed by air bubbles to the surface and the insoluble reaction product is then recovered from the resulting scum. To avoid the disadvantages that may arise from frothing and the formation of turbid colloids, I provide a liquid layer, immiscible with Water, above the solution, and thus catch the product as it rises up with the bubbles. If the bubbling rate is kept relatively slow, no froth at all is produced and the desired product is captured by the layer before colloids are formed.
By Way of example, a layer of octyl alcohol was placed over the solution body for the recovery of ferrocyanide ion, using lauryl pyridinium chloride as a collector. No froth at all was produced, and the insoluble reaction product was recovered entirely in the layer of octyl alcohol. The process was carried on con- Patented Mar. 1, 19%6 tinuously in a tank holding the aqueous solution and the supernatant non-aqueous layer, bubbles being introduced at a slow rate into the lower portion of the tank and the supernatant non-aqueous layer being drawn otf continuously. The octyl alcohol is a solvent having polar characteristics adapting it very well for collection of products such as are produced by the contacting of ions with amphipathic substances of opposite charge.
The collectors utilized in the process of my invention are, generally speaking, the ionic surface-active collectors which are utilized in ore flotation procedures. These collectors must have at least one hydrophilic center of activity and at least one aerophilic center of activity. They must have an electrical charge which is opposite to the ion which it is desired to collect it the process is to be operative.
A surface-active anionic collector; i.e., a collector yielding, in aqueous solution, a surface-active ion bearing a negative charge, for example, a lauric acid soap, is used to remove a soluble cation from solution. Conversely, a surface-active cationic collector, i.e., a collector yielding, in aqueous solution, a surface-active ion bearing a positive charge, for example, lauryl pyridinium chloride, is used when it is desired to remove a desired anion from solution.
Cationic collectors used in my novel process, for the most part, are compounds having one or more amine nitrogens. These compounds include primary, secondary and tertiary fatty alkyl, aryl and arylalkylamines, and their salts and the corresponding fatty quaternary ammonium salts. The arylamines include the picolines, pyridines, quinoliines, and 'their homologs and lower alkyl substituted analogs.
Examples of cationic collectors which will react with organic anions in polar solutions include the quaternary ammonium compounds, such as trimethyl-n-octylammonium chloride, trimethyl-n-decylamrnonium chloride, trimethyl n dodecylammonium chloride, trirnethyl n octadecylammonium bromide, triethyl-n-hexadecylammonium iodide; mixtures of quaternary salts derived from ta-llow fatty acids, from cottonseed oil fatty acids, from soybean oil fatty acids and coconut oil fatty acids, from mixtures of fatty acids derived from tallow, corn oil, soybean oil, coconut oil; alkyl amines such as diamylamine, didodecylamine, n-decylarnine, n-tetradecylamine, tri-noctadecylamine, n-octadecylamine and mixtures of amines; and miscellaneous collectors such as ammonium phenyl nitrosohydroxylamine, 1 n-dodecylpyridinium iodide, octadecyl B-hydroxyethyl morpholinium bromide, ,B-steararnidophenyl trimethylammonium methylsulfate, octadecyl pyridinium iodide, octadecyl u-picolinium bromide, hexadecyl quinolinium bromide, decylstyrylpyridinium chloride, dodecylpyridiniu-m phenylsulfonate, dimethyldodecylphenylammonium phenylsulfonate, 2 mercaptobenzothioazole derivatives, various imid-azoline and imidazolidine derivatives, and dimethyl-n-hexadecylbenzylammoniun chloride.
Anionic collectors are of two types: the oxhydry l compounds, where a metal or hydrogen is connected to the hydrocarbon element of the collector through an oxygen atom, and the sulfhydryl type Where the connection is made through a sulfur atom. The oxhydryl collectors include carboxylates, acid alkylsulfates, snlfonates and phosphates and phosphonates. The sulfhydryl compounds include mercaptazrs, thiocarborrates (xanthates), thioureas and dithiophosphates. Examples of anionic collectors llTD- clude the acids and sodium, potassium or ammonium salts of rosin, the tall oils and animal and vegetable oils; naphthenic acids; sodium-n-octylsulfate; potassium-n-dodecylsul-fate; the ammonium salt of n-dodecyldiethyleneglycolsurlfate; the sodium salt of crude or refined petroleum sulfonic acid; fi-phenylpropionic acid; pelargonic acid; mixtures of acids derived from linseed oil, soybean oil, palm oil, corn oil and cottonseed oil; monosodium ot-sulfopalmitate; disodium ot-sulfosterate, 1,'3-diphenyl-2-thi0- urea and thiocarbanilide. The above-described examples of cationic anionic collectors are but a few of the many collectors which are known to be commercially practicable and which are used in flotation procedures.
The number of carbon atoms in the aerophilic portion or portions of the collector molecule required to impart desired aerophilic properties to the collector varies with the type of collector. Generally from 5 to about 24 and preferably from 8 to 22 carbon atoms are required in at least one aerophilic portion of the collector molecule. My preferred cationic and anionic collectors are derived from plant and animal triglycerides, preferably vegetable or marine animal triglycerides. These glycerides canbe hydrolyzed to free their fatty acids which can then be utilized as anionic collectors per se, or which can be converted to ammonium or alkali metal salts for similar purposes. When a cationic collector is desired, the fatty acids are converted to amines, nitriles or quaternary salts by known means. It is also preferred that the hydrocarbon chains of these collectors contain carbon to carbon unsaturaltion. Where quaternary ammonium collectors, di-arnine collectors or triamine collectors are utilized, it is especially preferred that the collectors contain at least 1 hydrocarbon radical containing from 8 to 22 carbon atoms.
The term insoluble reaction products and similar terms are used throughout my specification. The term insoluble does not mean that the solubility is an equilibrium between the ions in solution and a solid ionic crystal, rather it is intended that the term encompass instances wherein the reaction product is composed of oppositely charged ions which are not independent as they have lost some entropy. Thus, the term applies to products (other than soluble reaction products) adsorbed at the solventbubble interface, i.e., the unitary product molecules are no longer randomly dispersed throughout the solution but are, in a major proportion, localized at the solventabubble interface. The products at the interface may be thought of as crystals containing only one molecule of product. As these crystals are forced closer together in the drain ing froth, they form a scum which is highly insoluble rather than larger crystals.
The range of amounts of collector required to collect a given amount of ion is great. I prefer to utilize an amount of collector ranging from about 0.001 to equivalents of collector/ equivalent of ion. A still more preferable ran-ge of equivalents is 0.1-10 equivalents of collector/ equivalent of ion. Still more preferable is the utilization of stoichiometrically equivalent amounts of collector/ equivalent of ion to be collected.
The reaction products formed when the above-identified collectors are contacted are removed from solution by flotation, i.e., are removed from solution by means of substantially nonreactive gaseous bubbles. Useful bubble materials include gaseous hydrocarbons such as methane, ethane and butane; gaseous halogenated hydrocarbons such as the Freons; and gases such as air, carbon dioxide, nitrogen and argon. I prefer to utilize air to remove insoluble reaction products from the solvents used in the ion recovery process of my invention.
The liquid collection layer should be immiscible with the liquid from which the ions are being recovered and should have some polar characteristics adapting it for 001- le'ction of the desired ions. For example, octyl alcohol is useful, because it has suflicient polar characteristic to dissolve the flotation product but is not so polar that it itself is soluble in water. It is not necessary that the supernatant layer be a solvent; it is sufiicient that the reaction product be wettable by the layer or phase. In other words, the reaction product is taken up or held by the liquid collection layer either by way of solution or by wetting. Other examples of suitable solvents or wetting agents are: benzene, mixtures of benzene and octyl alcohol, mixtures of petrolether and higher alcohols.
Other characteristics of the liquid collection layer are that it mus-t be insoluble or only very slightly soluble in water, it must be lighter than water or solutions of salts in water, it should not react chemically with the water or with the flotation product.
By utilizing the collection layer of liquid, immiscible with the liquid from which the ions are recovered, it is found that the reaction product is taken up into the layer, while any entrained liquid carried to the surface drops back into the solution as small droplets. Frothing or the formation of turbid colloids are minimized and may be entirely eliminated.
Specific examples of the process which may be set out as illustrative of the process are as follows:
Example I 3 mg. of methyl orange was dissolved in 300 ml. of water, buffered to pH 6.5 with sodium bicarbonate and placed in a No. 4 sintered glass Biichner funnel, diameter 3". 25 ml. of isooctyl alcohol was placed on the surface of the solution. 3 mg. of dodecyl trimethyl ammonium chloride was dissolved in 3 ml. of absolute alcohol, heated to boiling for a few seconds and added to the solution by means of a capillary tube that passed through the 'o'ctyl alcohol layer and reached almost to the sintered glass plate. Nitrogen gas was sparged through the sintered glass, thus generating very small bubbles. The bubble rate was carefully adjusted so as to disturb the octyl alcohol layer as little as possible. This resulted in the small bubbles accumulating under the octyl alcohol and gradually coalescing to form larger bubbles which rose through the octyl alcohol. As they did so, the product formed between the methyl orange anion, and the quaternary ammonium cation was stripped from the bubble and dissolved in the octyl alcohol. From time to time, any entrained water carried to the surface dropped back as small droplets. After 15 minutes, the aqueous layer was completely decolorized and the octyl alcohol layer was bright yellow, showing that the methyl orange anion had been removed from the water and dissolved in the non-aqueous solvent.
Example II ized, and the color had gone into the octyl alcohol, showing that the cation dye had combined with the sulpholaurate anion and been collected by the octyl alcohol.
Example III 0.01 g. each of cobalt and nickel chlorides were dissolved in 300 ml. water and just enough ammonia was added to redissolve the hydroxides formed. The solution was placed in a similar vessel to that in Example I and 25 ml. of isooctyl alcohol was placed on the surface. 6 mg. of lauric acid was dissolved in 10 ml. of alcohol and 3 mg. KOH added to convert to potassium laurate and taken to boiling. This solution was added, under the octyl alcohol, 2 ml. at a time with bubbling as before. After each addition, bubbling was contained for 5 minutes and the contents of the funnel was removed to a separatory funnel, and the octyl alcohol layer was sepa rated. The solution was then put back in the Buchner funnel and fresh octyl alcohol added, and the next 2 ml. of collector added. After the first addition, the octyl alcohol was greenish, there being some undissolved product in it. The octyl alcohol contained cobalt but only a trace of nickel. The fifth and final sample of octyl alcohol, which was blue green, contained only nickel. This illustrates that the selectivity shown by ion flotation applies also if flotation is into a non-miscible solvent. It also illustrates that the product, brought up by the bubble, does not necessarily need to be soluble in the non-aqueous phase, but that it is sufficient if it is wettable by the non-aqueous phase.
Example IV 300 ml. of a saturated solution of cupric chloride was placed in a Biichner funnel as before and 25 ml. of isooctyl alcohol placed on the surface. 50 mg. of laurylamine was dissolved in 5 ml. of absolute alcohol, just acidified with HCl and heated to boiling and added to the solution of cupric chloride. Air was bubbled for minutes, by which time the octyl alcohol had become bright yellow. On separating this layer, the yellow color was proved to be due to the CuCL; ion, so that the experiment shows the presence of this ion in a saturated solution of cupric chloride, and that it is collected by laurylamine, the laurylaminium cupric tetrachloride being coluble in octyl alcohol.
Example V 4 mg. of potassium ferrocyanide trihydrate was dissolved in 200 ml. of Water and the solution adjusted with potassium hydroxide to pH 10.5. It was placed in a No. 4 sintered glass Biiohner funnel, 2" diameter, and 10 ml. of isooctyl alcohol was placed on the surface. 10.8 mg. of lauryl pyridinium chloride, an amount exactly equivalent to the ferrocyanide ion was dissolved in petrol ether (60-80 C.) and carefully taken to dryness. It was then dissolved in 5 ml. of absolute alcohol, taken to boiling and added to the ferrocyanide solution under the octyl alcohol. Air was bubbled through slowly for 30 minutes, the octyl alcohol layer was carefully separated, the octyl alcohol carefully evaporated off, and the residue destroyed with concentrated sulphuric acid and then ignited with potassium pyrosulphate. The iron was determined colorimetrically as ferric thiocyanate and showed that 97.5% of the ferrocyanide ion had been collected in the octyl alcohol layer.
Example V1 0.3 g. of copper sulphate was dissolved in 250 m1. of water. Ammonia was added until the hydroxide just redissolved. The solution was added to a Biichner funnel as in Example I. 30 ml. of benzene and 10 ml. of butyl alcohol was mixed and placed above the surface of the solution. 0.2 g. of lauric acid was dissolved in 10 ml. of alcohol and converted to the laurate by adding potassium hydroxide. This was added in two stages at 10 minute intervals, through a capillary below the surface of the non-aqueous layer. Air was bubbled through slowly for 20 minutes. At the end of that time, the upper layer was a deep blue showing that most of the copper had concentrated in it, but there was still a pale blue color in the aqueous solution. This is attributed to the fact that butyl alcohol is slightly soluble in water and takes some of the copper laurate with it. The copper laurate, dissolved in the benzene-butyl alcohol mixture, was easily extracted by shaking with dilute HCl.
The new process provides a number of advantages in the flotation separation of ions. In comparison with solvent extraction, the process is versatile in that it separates the collector and the solvent stages. Whereas in solvent extraction, the quantity of solvent is related to the quantity of aqueous solution, in the present process the quantity is related to the amount of ion extracted, the upper limit being imposed by the solubility of the ion-soap compound in the solvent. By regulating the height of the solvent bed or layer, it is possible to prevent entrained water drops rising to the top of it. Furthermore, loss of solvent, which is always a bugbear in solvent extraction, is minimized.
There is the further advantage in that the danger of ernulsification is minimized. In solvent extraction, the rate of extraction is determined by the rate of diffusion into the solvent droplets, whereas here the adsorption is on the surface of the bubbles, and desorption into the solvent is off the surface of the bubbles, so that the rate is controlled by the bubble rate.
Further, in comparison with solvent extraction, it is pointed out that the selectivity, which is one of the main values of ion flotation, is well retained by the present process, the operation combining, in effect, the advantages of ion-exchange with solvent extraction or wettability.
Finally, the present process lends itself to continuous processing. Reclaiming the ion and the solvent may be accomplished through any of the well-known methods, as, for example, by distilling the solvent to produce a residue of the same soap compound that would have been collected in the scum in ion flotation.
While, in the foregoing specification, I have set forth illustrative examples and procedures in considerable detail for the purpose of setting out embodiments of the invention, it will be understood that such details of procedure may be varied widely by those skilled in the art without departing from the spirit of my invention.
I claim:
A process for the recovery of ions from an aqueous solution thereof comprising adding to the solution collector ions having an electrical charge opposite to that of the ions to be recovered to form an insoluble reaction product of said ions in said solution, disposing upon the surface of the solution a floating layer of a non-aqueous liquid immiscible with said solution and having polar characteristics adapting it for collecting said reaction product, introducing gas into the solution having the floating liquid layer disposed thereover in the form of small bubbles at a rate which leaves the floating liquid layer substantially undisturbed to buoy the reaction product to the surface of the solution and into the floating liquid layer where it is collected.
References Cited by the Examiner Textile Research, vol. 8, Aug. 1938, pp. 357-363.
New Separation Method, Foamet, Eng. & Mining 1., vol. 161, Aug. 1960, pp. 104 and 106.
Rabone, Flotation Plant Practice, 1957, 4th ed., Min- Ling Publ. Ltd., London, pp. 8388 relied on.
Schnepf et al., Foam Fractionation: Metals, Chem. Eng. Prog., vol. 55, May 1959, pp. 42-46.
Walling et al., The Adsorption of Cations by Anionic Foams, J. Phys. Chem, vol. 61, April 1957, pp. 486-489.
MORRIS O. WOLK, Primary Examiner.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1352145D FR1352145A (en) | 1961-10-03 | Ion flotation process | |
US142483A US3238127A (en) | 1961-10-03 | 1961-10-03 | Ion flotation method |
GB37383/62A GB966069A (en) | 1961-10-03 | 1962-10-02 | Ion flotation method |
DES85051A DE1175622B (en) | 1961-10-03 | 1963-05-04 | Process for the extraction of metals from solutions by flotation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US142483A US3238127A (en) | 1961-10-03 | 1961-10-03 | Ion flotation method |
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US3238127A true US3238127A (en) | 1966-03-01 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US142483A Expired - Lifetime US3238127A (en) | 1961-10-03 | 1961-10-03 | Ion flotation method |
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US (1) | US3238127A (en) |
DE (1) | DE1175622B (en) |
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Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3898159A (en) * | 1970-10-30 | 1975-08-05 | Lion Fat Oil Co Ltd | Method for removing anionic surface active component from drainage |
US3932274A (en) * | 1971-08-27 | 1976-01-13 | Director-General Of The Agency Of Industrial Science And Technology | Method for eliminating metals from a solution containing a very slight amount of the metals |
US3959131A (en) * | 1974-10-17 | 1976-05-25 | Swift & Company | Apparatus and method for removing pollutants from wastewater |
US3975265A (en) * | 1974-08-26 | 1976-08-17 | Vojislav Petrovich | Froth flotation method for the recovery of minerals by means of ternary sulfonium nitrites and ternary stibine dinitrites |
US3976566A (en) * | 1975-04-23 | 1976-08-24 | Vojislav Petrovich | Froth flotation method for the recovery of minerals by means of quaternary phosphonium nitrites and ternary phosphine dinitrites |
US3976565A (en) * | 1975-06-02 | 1976-08-24 | Vojislav Petrovich | Froth flotation method for the recovery of minerals by means of quaternary ammonium nitrites and ternary phosphine dinitrites |
US4054516A (en) * | 1974-03-04 | 1977-10-18 | Director-General Of The Agency Of Industrial Science And Technology | Method for selectively capturing metal ions |
US4105545A (en) * | 1976-09-14 | 1978-08-08 | Treadwell Corp. | Process for removing cyanide-containing components from aqueous media |
US4198297A (en) * | 1976-01-19 | 1980-04-15 | The United States Of America As Represented By The Secretary Of The Interior | Removal of trace copper ions from water |
US4203837A (en) * | 1976-01-16 | 1980-05-20 | Hoge John H | Process for removal of discrete particulates and solutes from liquids by foam flotation |
US4219416A (en) * | 1978-06-29 | 1980-08-26 | Dravo Corporation | Process for recovering molybdenum and tungsten from mining wastewater |
US4737273A (en) * | 1986-01-03 | 1988-04-12 | International Minerals & Chemical Corp. | Flotation process for recovery of phosphate values from ore |
US4758353A (en) * | 1987-06-19 | 1988-07-19 | Nalco Chemical Company | Removal of heavy metals from waste streams |
US5055201A (en) * | 1989-08-04 | 1991-10-08 | Tiegel Manufacturing Company | Process for removing dissolved contaminants from aqueous solutions using reversibly dispersible getters |
US5078900A (en) * | 1989-08-04 | 1992-01-07 | Tiegel Manufacturing Co. | Process for removing dissolved contaminants from aqueous solutions using getters and reversibly dispersible carriers |
US5616251A (en) * | 1995-11-20 | 1997-04-01 | Kareem Batarseh | Methods to prevent and treat acid mine drainage and to remove metals and non-metals from aqueous sources |
US20130092604A1 (en) * | 2011-10-18 | 2013-04-18 | Cytec Technology Corp. | Froth Flotation Processes |
US20130092603A1 (en) * | 2011-10-18 | 2013-04-18 | Cytec Technology Corp. | Collector Compositions and Methods of Using the Same |
US20130092605A1 (en) * | 2011-10-18 | 2013-04-18 | Cytec Technology Corp. | Froth Flotation Processes |
US11097205B2 (en) * | 2017-03-27 | 2021-08-24 | Cidra Corporate Services Llc | Removal of hydrophobic particles using carbon dioxide |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0004953B1 (en) * | 1978-04-19 | 1982-03-03 | Klaus Prof. Dr. Heckmann | Process and apparatus for the selective separation of uranium from its accompanying metals and for its recovery |
NL8002743A (en) * | 1980-05-13 | 1981-12-16 | Estel Hoogovens Bv | METHOD FOR PROCESSING ZINC AND LEAD-CONTAINING GAS SUBSTANCES FROM SIDERURGIC PROCESSES |
DE3224803A1 (en) * | 1982-07-02 | 1984-01-05 | Heckmann, Klaus, Prof. Dr., 8400 Regensburg | METHOD FOR SELECTIVE SEPARATION OF PLUTONIUM FROM URANIUM AND OTHER METALS |
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US1619036A (en) * | 1920-09-28 | 1927-03-01 | Ravnestad Andreas Johan | Clarifying and purifying liquids and waste waters |
US2757081A (en) * | 1954-03-17 | 1956-07-31 | Commissariat Energie Atomique | Method for separating and purifying zirconium and hafnium |
US2869979A (en) * | 1955-08-09 | 1959-01-20 | Robert R Grinstead | Slurry solvent extraction process for the recovery of metals from solid materials |
US2953569A (en) * | 1958-02-27 | 1960-09-20 | Kennecott Copper Corp | Process for reclaiming oxine flotation reagent from products of flotation |
US3054747A (en) * | 1960-07-22 | 1962-09-18 | Radiation Applic Inc | Method of separating non-surface active ionic materials from solution |
-
0
- FR FR1352145D patent/FR1352145A/en not_active Expired
-
1961
- 1961-10-03 US US142483A patent/US3238127A/en not_active Expired - Lifetime
-
1962
- 1962-10-02 GB GB37383/62A patent/GB966069A/en not_active Expired
-
1963
- 1963-05-04 DE DES85051A patent/DE1175622B/en active Pending
Patent Citations (5)
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US1619036A (en) * | 1920-09-28 | 1927-03-01 | Ravnestad Andreas Johan | Clarifying and purifying liquids and waste waters |
US2757081A (en) * | 1954-03-17 | 1956-07-31 | Commissariat Energie Atomique | Method for separating and purifying zirconium and hafnium |
US2869979A (en) * | 1955-08-09 | 1959-01-20 | Robert R Grinstead | Slurry solvent extraction process for the recovery of metals from solid materials |
US2953569A (en) * | 1958-02-27 | 1960-09-20 | Kennecott Copper Corp | Process for reclaiming oxine flotation reagent from products of flotation |
US3054747A (en) * | 1960-07-22 | 1962-09-18 | Radiation Applic Inc | Method of separating non-surface active ionic materials from solution |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3898159A (en) * | 1970-10-30 | 1975-08-05 | Lion Fat Oil Co Ltd | Method for removing anionic surface active component from drainage |
US3932274A (en) * | 1971-08-27 | 1976-01-13 | Director-General Of The Agency Of Industrial Science And Technology | Method for eliminating metals from a solution containing a very slight amount of the metals |
US4054516A (en) * | 1974-03-04 | 1977-10-18 | Director-General Of The Agency Of Industrial Science And Technology | Method for selectively capturing metal ions |
US3975265A (en) * | 1974-08-26 | 1976-08-17 | Vojislav Petrovich | Froth flotation method for the recovery of minerals by means of ternary sulfonium nitrites and ternary stibine dinitrites |
US3959131A (en) * | 1974-10-17 | 1976-05-25 | Swift & Company | Apparatus and method for removing pollutants from wastewater |
US3976566A (en) * | 1975-04-23 | 1976-08-24 | Vojislav Petrovich | Froth flotation method for the recovery of minerals by means of quaternary phosphonium nitrites and ternary phosphine dinitrites |
US3976565A (en) * | 1975-06-02 | 1976-08-24 | Vojislav Petrovich | Froth flotation method for the recovery of minerals by means of quaternary ammonium nitrites and ternary phosphine dinitrites |
US4203837A (en) * | 1976-01-16 | 1980-05-20 | Hoge John H | Process for removal of discrete particulates and solutes from liquids by foam flotation |
US4198297A (en) * | 1976-01-19 | 1980-04-15 | The United States Of America As Represented By The Secretary Of The Interior | Removal of trace copper ions from water |
US4105545A (en) * | 1976-09-14 | 1978-08-08 | Treadwell Corp. | Process for removing cyanide-containing components from aqueous media |
US4219416A (en) * | 1978-06-29 | 1980-08-26 | Dravo Corporation | Process for recovering molybdenum and tungsten from mining wastewater |
US4737273A (en) * | 1986-01-03 | 1988-04-12 | International Minerals & Chemical Corp. | Flotation process for recovery of phosphate values from ore |
US4758353A (en) * | 1987-06-19 | 1988-07-19 | Nalco Chemical Company | Removal of heavy metals from waste streams |
US5055201A (en) * | 1989-08-04 | 1991-10-08 | Tiegel Manufacturing Company | Process for removing dissolved contaminants from aqueous solutions using reversibly dispersible getters |
US5078900A (en) * | 1989-08-04 | 1992-01-07 | Tiegel Manufacturing Co. | Process for removing dissolved contaminants from aqueous solutions using getters and reversibly dispersible carriers |
US5616251A (en) * | 1995-11-20 | 1997-04-01 | Kareem Batarseh | Methods to prevent and treat acid mine drainage and to remove metals and non-metals from aqueous sources |
US20130092604A1 (en) * | 2011-10-18 | 2013-04-18 | Cytec Technology Corp. | Froth Flotation Processes |
US20130092603A1 (en) * | 2011-10-18 | 2013-04-18 | Cytec Technology Corp. | Collector Compositions and Methods of Using the Same |
US20130092605A1 (en) * | 2011-10-18 | 2013-04-18 | Cytec Technology Corp. | Froth Flotation Processes |
US9302274B2 (en) * | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Collector compositions and methods of using the same |
US9302273B2 (en) * | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Froth flotation processes |
US9302272B2 (en) * | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Froth flotation processes |
AU2012326311B2 (en) * | 2011-10-18 | 2016-09-01 | Cytec Technology Corp. | Collector compositions and methods of using the same |
US11097205B2 (en) * | 2017-03-27 | 2021-08-24 | Cidra Corporate Services Llc | Removal of hydrophobic particles using carbon dioxide |
Also Published As
Publication number | Publication date |
---|---|
GB966069A (en) | 1964-08-06 |
FR1352145A (en) | 1964-05-13 |
DE1175622B (en) | 1964-08-13 |
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