CN114787397A - Method and apparatus for purifying bayer process streams - Google Patents
Method and apparatus for purifying bayer process streams Download PDFInfo
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- CN114787397A CN114787397A CN202080082187.8A CN202080082187A CN114787397A CN 114787397 A CN114787397 A CN 114787397A CN 202080082187 A CN202080082187 A CN 202080082187A CN 114787397 A CN114787397 A CN 114787397A
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- 238000004131 Bayer process Methods 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000002608 ionic liquid Substances 0.000 claims abstract description 294
- 238000001914 filtration Methods 0.000 claims abstract description 72
- 230000008929 regeneration Effects 0.000 claims abstract description 70
- 238000011069 regeneration method Methods 0.000 claims abstract description 70
- 238000000605 extraction Methods 0.000 claims abstract description 66
- 239000013618 particulate matter Substances 0.000 claims abstract description 53
- 239000012535 impurity Substances 0.000 claims description 81
- 239000003518 caustics Substances 0.000 claims description 54
- 150000004820 halides Chemical class 0.000 claims description 45
- 239000008346 aqueous phase Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 37
- 150000003839 salts Chemical class 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 30
- 239000012074 organic phase Substances 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 24
- -1 tricalcium aluminate hexahydrate Chemical class 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 13
- 150000002892 organic cations Chemical group 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 10
- 238000004891 communication Methods 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- 230000004907 flux Effects 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- 239000008394 flocculating agent Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000012267 brine Substances 0.000 description 15
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 150000001450 anions Chemical class 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- JDAJRHLAMCYXAN-UHFFFAOYSA-M tributyl(octyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCC[P+](CCCC)(CCCC)CCCC JDAJRHLAMCYXAN-UHFFFAOYSA-M 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000010451 perlite Substances 0.000 description 4
- 235000019362 perlite Nutrition 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910001570 bauxite Inorganic materials 0.000 description 3
- 235000012970 cakes Nutrition 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910001679 gibbsite Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 150000004684 trihydrates Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000009533 lab test Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229940039748 oxalate Drugs 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- KEHGIVWHHBDQAD-UHFFFAOYSA-N tributyl(octyl)phosphanium Chemical compound CCCCCCCC[P+](CCCC)(CCCC)CCCC KEHGIVWHHBDQAD-UHFFFAOYSA-N 0.000 description 2
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 description 2
- PXELHGDYRQLRQO-UHFFFAOYSA-N 1-butyl-1-methylpyrrolidin-1-ium Chemical compound CCCC[N+]1(C)CCCC1 PXELHGDYRQLRQO-UHFFFAOYSA-N 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- WYRIQSJBDPBLDQ-UHFFFAOYSA-O 2-hydroxyethyl-dimethyl-[3-(octadecanoylamino)propyl]azanium Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCC[N+](C)(C)CCO WYRIQSJBDPBLDQ-UHFFFAOYSA-O 0.000 description 1
- HNWNELAGDBSCDG-UHFFFAOYSA-O 2-hydroxyethyl-dimethyl-[3-(octadecanoylamino)propyl]azanium;nitrate Chemical compound [O-][N+]([O-])=O.CCCCCCCCCCCCCCCCCC(=O)NCCC[N+](C)(C)CCO HNWNELAGDBSCDG-UHFFFAOYSA-O 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910017048 AsF6 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-O Pyrazolium Chemical compound C1=CN[NH+]=C1 WTKZEGDFNFYCGP-UHFFFAOYSA-O 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 1
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical compound CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 244000299461 Theobroma cacao Species 0.000 description 1
- 235000009470 Theobroma cacao Nutrition 0.000 description 1
- 241001625808 Trona Species 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- OHDZVKBRHQNCIO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide 1,2-dimethyl-3-octylimidazol-1-ium Chemical compound CCCCCCCCn1cc[n+](C)c1C.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F OHDZVKBRHQNCIO-UHFFFAOYSA-N 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003196 chaotropic effect Effects 0.000 description 1
- 239000003251 chemically resistant material Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- TVWHTOUAJSGEKT-UHFFFAOYSA-N chlorine trioxide Chemical compound [O]Cl(=O)=O TVWHTOUAJSGEKT-UHFFFAOYSA-N 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical class OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 229940110456 cocoa butter Drugs 0.000 description 1
- 235000019868 cocoa butter Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003866 digestant Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 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
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 235000021463 dry cake Nutrition 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical compound [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-O hydron;1,3-oxazole Chemical compound C1=COC=[NH+]1 ZCQWOFVYLHDMMC-UHFFFAOYSA-O 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-O hydron;pyrimidine Chemical compound C1=CN=C[NH+]=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-O 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-O hydron;quinoline Chemical compound [NH+]1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-O 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-O isoquinolin-2-ium Chemical compound C1=[NH+]C=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-O 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-M n-octyl sulfate Chemical compound CCCCCCCCOS([O-])(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-M 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229940067739 octyl sulfate Drugs 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 235000021003 saturated fats Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- DTIFFPXSSXFQCJ-UHFFFAOYSA-N tetrahexylazanium Chemical compound CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC DTIFFPXSSXFQCJ-UHFFFAOYSA-N 0.000 description 1
- SYZCZDCAEVUSPM-UHFFFAOYSA-M tetrahexylazanium;bromide Chemical compound [Br-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC SYZCZDCAEVUSPM-UHFFFAOYSA-M 0.000 description 1
- AGWJLDNNUJKAHP-UHFFFAOYSA-N tetrahexylphosphanium Chemical compound CCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC AGWJLDNNUJKAHP-UHFFFAOYSA-N 0.000 description 1
- CHYBTAZWINMGHA-UHFFFAOYSA-N tetraoctylazanium Chemical compound CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC CHYBTAZWINMGHA-UHFFFAOYSA-N 0.000 description 1
- WFIYFFUAOQKJJS-UHFFFAOYSA-N tetraoctylphosphanium Chemical compound CCCCCCCC[P+](CCCCCCCC)(CCCCCCCC)CCCCCCCC WFIYFFUAOQKJJS-UHFFFAOYSA-N 0.000 description 1
- GJSGYPDDPQRWPK-UHFFFAOYSA-N tetrapentylammonium Chemical compound CCCCC[N+](CCCCC)(CCCCC)CCCCC GJSGYPDDPQRWPK-UHFFFAOYSA-N 0.000 description 1
- LRPOXSSMNVVCMT-UHFFFAOYSA-N tetrapentylphosphanium Chemical compound CCCCC[P+](CCCCC)(CCCCC)CCCCC LRPOXSSMNVVCMT-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- NQLUTERLOYQICV-UHFFFAOYSA-N tributyl(8-hydroxyoctyl)phosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCCCCCCO NQLUTERLOYQICV-UHFFFAOYSA-N 0.000 description 1
- CRJKUPPOFPASRM-UHFFFAOYSA-M tributyl(8-hydroxyoctyl)phosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCCCCCCO CRJKUPPOFPASRM-UHFFFAOYSA-M 0.000 description 1
- HJHUXWBTVVFLQI-UHFFFAOYSA-N tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC HJHUXWBTVVFLQI-UHFFFAOYSA-N 0.000 description 1
- GYOFRJOMHLYJNZ-UHFFFAOYSA-N tributyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC GYOFRJOMHLYJNZ-UHFFFAOYSA-N 0.000 description 1
- AKUNSPZHHSNFFX-UHFFFAOYSA-M tributyl(tetradecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC AKUNSPZHHSNFFX-UHFFFAOYSA-M 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- VLHULKFZDRGQAJ-UHFFFAOYSA-N trihexyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC VLHULKFZDRGQAJ-UHFFFAOYSA-N 0.000 description 1
- PYVOHVLEZJMINC-UHFFFAOYSA-N trihexyl(tetradecyl)phosphanium Chemical compound CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC PYVOHVLEZJMINC-UHFFFAOYSA-N 0.000 description 1
- JCQGIZYNVAZYOH-UHFFFAOYSA-M trihexyl(tetradecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC JCQGIZYNVAZYOH-UHFFFAOYSA-M 0.000 description 1
- 125000002077 trioxo-lambda(7)-bromanyloxy group Chemical group *O[Br](=O)(=O)=O 0.000 description 1
- 238000013024 troubleshooting Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D37/00—Processes of filtration
- B01D37/02—Precoating the filter medium; Addition of filter aids to the liquid being filtered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0446—Juxtaposition of mixers-settlers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0488—Flow sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0492—Applications, solvents used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D37/00—Processes of filtration
- B01D37/03—Processes of filtration using flocculating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D37/00—Processes of filtration
- B01D37/04—Controlling the filtration
- B01D37/048—Controlling the filtration by temperature measuring
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/46—Purification of aluminium oxide, aluminium hydroxide or aluminates
- C01F7/47—Purification of aluminium oxide, aluminium hydroxide or aluminates of aluminates, e.g. removal of compounds of Si, Fe, Ga or of organic compounds from Bayer process liquors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/46—Purification of aluminium oxide, aluminium hydroxide or aluminates
- C01F7/47—Purification of aluminium oxide, aluminium hydroxide or aluminates of aluminates, e.g. removal of compounds of Si, Fe, Ga or of organic compounds from Bayer process liquors
- C01F7/473—Removal of organic compounds, e.g. sodium oxalate
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
Abstract
An apparatus and method for purifying a bayer process stream includes a filtration stage including at least one filter configured to filter particulate matter from at least one ionic liquid stream from an extraction stage, a stripping stage, and a regeneration stage. Filtering particulate matter from at least one of the ionic liquid streams reduces the amount of circulating particulate matter and reduces the likelihood of scale formation.
Description
Technical Field
The present invention relates generally to a method and apparatus for purifying bayer process streams.
In particular, although not exclusively, the invention relates to a method and apparatus for cleaning bayer process streams by the use of ionic liquids to remove impurities.
Background
The bayer process is used to produce alumina from bauxite ore.
Bauxite ores typically contain organic and inorganic impurities in amounts that are specific to the source of the bauxite.
Part of the process involves purifying the aluminate liquor to remove dissolved impurities and undissolved impurities to form a purified filtrate. Alumina is then precipitated from the filtrate as alumina trihydrate crystals.
The purification step is important because alumina trihydrate containing high levels of organic impurities tends to produce a final product having an undesirably high level of color.
The remaining liquid phase or spent liquid may be concentrated to form a "concentrated" liquid. The spent stream is typically returned to the original digestion step and used as a digestant for additional ore after being reconstituted with additional caustic.
Because the bayer process is a closed loop, impurities entering the process stream tend to accumulate with each cycle of the process. These impurities can have a negative impact on the process.
Ionic liquids may be used to remove impurities from the bayer process. However, such liquids are often expensive and toxic.
Accordingly, it would be desirable to provide a method and apparatus for purifying bayer process streams that would allow for the recycling of these ionic liquids.
The above description is not to be taken as an admission of the common general knowledge in australia or elsewhere.
Summary of The Invention
The present invention is a method and apparatus for purifying bayer process streams that uses ionic liquids as an extractant of impurities in liquid/liquid extraction methods and apparatus to remove impurities from bayer process streams.
In one embodiment, the bayer process stream is a liquor stream produced during a bayer process, and may be one or more of a concentrator overflow, a pregnant liquor, a spent liquor, and a pregnant liquor stream.
The term "impurities" is understood to mean compounds that may contaminate the bayer process stream. Impurities include, but are not limited to, organic and/or inorganic species. A particularly relevant class of impurities is the non-oxalate organic compounds (NOOC), which are commonly and empirically expressed as Na2C5And O. However, it will be appreciated that customized selection of ionic liquids will allow for the removal of other classes of impurities from bayer process streams.
More specifically, the present invention is a method and apparatus for purifying bayer process streams that uses an ionic liquid that can reversibly associate with impurities from the bayer process stream. The method/apparatus controls the operating parameters such that the impurities can be associated with the ionic liquid to remove the impurities from the bayer process stream, and such that the impurities can be dissociated from the ionic liquid to remove the impurities from the ionic liquid and regenerate the ionic liquid for recycle in the method/apparatus.
The invention was carried out after working with a small scale pilot plant (herein referred to as bench top pilot or BTP) using ionic liquids for the process/apparatus by the applicant. BTP work was performed after successful small-scale laboratory experiments on the process/apparatus.
During BTP work, applicants have encountered a number of problems not present in small-scale laboratory experiments.
One such problem is the effect of particulate matter circulating in the ionic liquid recirculation loop.
More specifically, the applicant found that when a threshold concentration of particulate matter in the circuit is reached, an emulsion stabilized by the particulate matter is formed between the ionic liquid and the aqueous solution, which makes the recirculation circuit inoperable.
This is a surprising discovery, as it was previously unknown that particulate matter, particularly but not limited to particulate matter derived from bayer liquor, would behave in such a detrimental manner when the method/apparatus is scaled up to operate in essentially an industrial process flow.
In order to find a solution to this problem, the applicant carried out a series of experiments to determine the nature of the particulate matter.
In one experiment, particulate matter was isolated and analyzed using XRD, and the determination of particulate matter included:
·Al(OH)3(gibbsite) -major component
·CaCO3-Components
·Al(OH)3(bayerite) -Trace
·Na3H(CO3)2.2H2O (trona) -trace
·Na2C2O4(sodium oxalate) -Trace
·Ca3Al2(SiO4) (OH) -Trace
A plurality of other minor components.
Compositional analysis showed that the particulate matter was derived from bayer liquor. However, it will be appreciated that the particulate matter is not limited to this source and may also originate from other sources, such as NaCl brine impurities, or may be externally derived particulate matter.
It was also determined that the particulate matter was not soluble in any of the aqueous streams in the process/apparatus and remained locked in the ionic liquid.
Without being bound by theory, it is believed that the particulate matter stabilizes the emulsion formed between the ionic liquid used in the recycle process and any aqueous phase stream used. These stable emulsions are described herein as "fouling" (crud). It is also believed that the various ions present in the purified process water stream combine to form a precipitate, which together with any trapped foreign particles (such as fugitive dust) is described herein as particulate matter, and is carried around the loop in the ionic liquid.
Additional analysis revealed that fouling formed at the ionic liquid (organic) phase/aqueous phase interface, and subsequently coalesced at that interface, separating the aqueous phase from the ionic liquid phase. The resulting fouled coalescing layer between the ionic liquid phase and the aqueous phase may hinder further separation of the freshly entering mixed phase from the mixer, resulting in a loss of efficiency and loss of ionic liquid to the water stream exiting the settler. This makes separation of the organic ionic liquid phase and the aqueous phase difficult. Fouling in the organic phase also builds up and concentrates in the process. This affects the efficiency of the liquid/liquid extraction that occurs at each stage. It should be noted that the settler may be completely filled with fouling, so that no further process stream can be pumped into the settler, rendering the entire recirculation loop inoperable.
During the troubleshooting process, it was observed that the settler for BTP was plugged by fouling after a plant run time equivalent to about 35-40 hours.
It has also been found that scale can form independently in each of the aqueous and organic phases, and that scale formation can occur at all stages of the process.
It was observed that scale formation was more pronounced in the extraction stage (EXTRACT stage) when the ionic liquid feed stream to this stage interacted with the bayer process stream.
In some BTP work it was also observed that once the NaCl impurity-derived precipitate reaches a threshold concentration, the focus of scale formation shifts to the regeneration stage (REGEN stage), where scale formation increases to such an extent that the entire settler is rendered inoperable.
Applicants tested methods that applicants believe would successfully remove fouling from the circuit, but with no or limited success.
1. Mixing or settling out the ionic liquid, heating the ionic liquid, dissolving in water, and salting out a solution of the ionic liquid. This method was unsuccessful. The salting-out process studied by the applicant involves adding a salt solution, such as sodium hydroxide, to the ionic liquid solution and allowing the ionic liquid to separate from the salt solution, which allows recovery of the ionic liquid.
2. Temporary removal of the scale is not a viable solution due to the rapid build-up of scale.
3. The ionic liquid stream from one or more of the extraction stage, stripping stage (STRIP stage) and regeneration stage is filtered to determine whether controlling the concentration of particulate matter in the regenerated ionic liquid will affect scale formation. The initial filtering option tested by the applicant was unsuccessful.
Finally, further testing work on the filtration led to the development of the present invention.
As a result of further testing work, the present invention provides an apparatus for purifying a bayer process stream, comprising:
an extraction stage comprising at least one contact/separation device configured to receive and combine a bayer process stream containing impurities and an ionic liquid stream comprising quaternary organic cations (quaternary organic sites) to form a purified bayer process stream and an ionic liquid stream loaded with impurities;
a stripping stage comprising at least one contacting/separating device configured to receive and mix an impurity-laden ionic liquid stream and a halide-laden salt stream to form a halide-laden ionic liquid stream and an impurity-laden salt stream;
a regeneration stage comprising at least one contacting/separating device configured to receive and mix a halide-containing ionic liquid stream and a caustic stream to form a regenerated ionic liquid stream and a halide-containing caustic effluent stream, wherein the extraction stage is configured to be in fluid communication with the regeneration stage via a recirculation loop to receive at least a portion of the regenerated ionic liquid stream to form an ionic liquid feed stream, and
a filtration stage (FILTER stage) comprising at least one FILTER configured to FILTER particulate matter from at least one ionic liquid stream from the extraction stage, the stripping stage and the regeneration stage.
Filtering particulate matter from the at least one ionic liquid stream reduces the amount of circulating particulate matter and reduces the likelihood of scale formation.
The present invention also provides an apparatus for recycling ionic liquid used to purify bayer process streams, comprising:
a stripping stage comprising at least one contacting/separating device configured to receive and mix a stream of impurity-loaded ionic liquid and a stream of stripping solution to form a reduced impurity ionic liquid stream and an impurity-loaded stripping solution stream;
a regeneration stage comprising at least one contacting/separating device configured to receive and mix an impurity-reduced ionic liquid stream and a caustic solution stream to form a regenerated ionic liquid stream and a caustic effluent stream; wherein at least one contacting/separating device from the regeneration stage is configured to recycle at least a portion of the regenerated ionic liquid stream and form an ionic liquid feed stream to purify the bayer process stream, an
A filtration stage comprising at least one filter configured to filter particulate matter from at least one ionic liquid stream from the extraction stage, the stripping stage, and the regeneration stage.
The term "particulate matter" is understood herein to mean any particulate matter in one of the streams of ionic liquid. The "particulate matter" may be particulate matter in a bayer process stream. The "particulate matter" may be any solid that interacts with ionic species in the circuit and forms a material, such as "fouling" that interferes with the purification or recirculation circuit.
The term "filter" is understood herein as any suitable device for separating particulate material from an ionic liquid feed stream.
The contacting/separating means for the extraction, stripping and regeneration stages may be selected from mixer-settlers, columns, centrifuges, static mixers, reactors or other devices suitable for mixing and separating two at least partially immiscible liquid streams. The preferred contacting/separating device is a mixer-settler, such as is commonly used in solvent extraction loops.
The ionic liquid may be any suitable ionic liquid.
By way of example, an ionic liquid may comprise an alkyl phosphonium salt in three forms, depending on the molecule to which the phosphonium ion is bonded. These forms are: exfoliated (Cl)-) Regenerated (OH)-) And loaded (NOOC)-). The transition between these forms enables the ionic liquid to reversibly associate with the impurity.
At least one of the ionic liquid-containing operating units for the extraction stage, stripping stage and regeneration stage may comprise a filter of a filtration stage to remove particulate matter, in particular colloidal solids, from the ionic liquid stream to control the concentration of particulate matter in the regenerated ionic liquid.
In other words, the filtration stage may be part of the extraction stage, stripping stage and regeneration stage. By way of example, the filtration stage may be part of a storage tank, a fluid conduit or contacting/separating device of the extraction, stripping and regeneration stages.
The filtration stage may also be an operating unit separate from the operating units forming the extraction stage, stripping stage and regeneration stage.
The filtration stage may be located after the stripping stage. In one embodiment, the filtration in the filtration stage is performed on the ionic liquid stream after the stripping stage.
It should be emphasized that the invention is not limited to this embodiment.
As is evident from the above, the ionic liquid stream that is transferred to the filtration stage is typically an ionic liquid that contains particulate matter that may form scale.
The concentration of solids, i.e. the concentration of particulate matter, in the ionic liquid stream transferred to the filtration stage may be as high as 0.3g/L solids.
Applicants have tested solids concentrations as high as 5.5g/L and the results of the test work have provided evidence for conclusions that the solids concentration may be higher.
The solids concentration can be as high as 6 g/L.
The solids concentration can be as high as 10 g/L.
Typically, the concentration of solids in the ionic liquid stream transferred to the filtration stage is less than 3g/L in the ionic liquid stream.
The ionic liquid stream may comprise a stable emulsion comprising an aqueous phase and an ionic liquid phase.
The aqueous phase may be up to 50 vol.% of the stable emulsion. More suitably, the aqueous phase of the stable emulsion is <10 vol.%.
Typically, filtration in the filtration stage breaks the stable emulsion into an aqueous phase and an ionic liquid phase.
The filtration stage may be performed using any suitable filter capable of separating solid material, i.e. particulate matter, from the ionic liquid stream transferred to the filtration stage.
The filter may be configured to use the pressure differential as a driving force for filtration.
The filter may be a positive pressure filter.
The filter may be a candle filter.
The filtration stage may include a candle filter with a perlite filter aid.
Any suitable filter media may be used in the filter.
Suitably, the filter medium is compatible with the ionic liquid.
Based on short-term testing work, the applicant has found that polypropylene (PP) and Polytetrafluoroethylene (PTFE) are suitable.
The filter media may have a multi-filament construction or a monofilament construction.
The filter media may have a density of at least 3L/dm2/min-200L/dm2Air permeability between/min.
The filtration stage may include the use of filter aids such as ceramic materials, tricalcium aluminate hexahydrate (TCA), and flocculants.
The filter aid may be selected for higher flux and life of the filter media.
The filter aid material may be any suitable chemically resistant material that does not react with the ionic liquid.
The filter aid material may be expanded perlite.
The filter aid material may have a median particle size of between 10 μm and 100 μm. Suitably, the median particle size of the filter aid is between 50 μm and 85 μm. More suitably, a filter aid having a median particle size of 68 μm is used for filtration.
The filter aid may be introduced into the ionic liquid stream transferred to the filtration stage by direct addition to the ionic liquid stream.
More suitably, the filter aid is pre-batch treated with an aqueous solution at a temperature between 20 ℃ and 80 ℃ prior to being added to the ionic liquid stream. Most suitably, the filter aid is batch treated with an aqueous solution at a temperature of 55 ℃.
The solution of the pre-batch filter aid may be prepared to a solids concentration of between 10g/L and 200 g/L. More suitably, the solids concentration is between 40g/L and 100 g/L. More suitably, the solids concentration is 60 g/L.
The filter aid may be added to the ionic liquid stream transferred to the filtration stage at a solids ratio (solids in the feed-stabilized emulsion: filter aid solids) of between 1:0.1 and 1: 5. More suitably, the ratio of addition is between 1:1 and 1: 2.
The filtration stage may be configured to operate at a temperature in the range of 20 ℃ to 70 ℃. Most suitably, the filtration stage operates at a temperature in the range 55 ℃ to 60 ℃.
When operating with a pressure filter, the filtration stage may operate in a pressure difference range between 2 bar and 8 bar. More suitably, the pressure is between 4 bar and 6 bar. Most suitably, the operating pressure is 6 bar.
The filtration stage may be configured to operate at 10L/m2/h-700L/m2Filtration flux rate between/h. More suitably, the filtration process is at 50L/m2/h-200L/m2Flux rate between/h. Most suitably, the filtration process is at 100L/m2/h-150L/m2Flux rate between/h operation.
The filtration stage may include a cleaning process for removing the filter aid and the wrapped ionic liquid within the solid filter cake.
The cleaning process may include a cake washing step, typically wherein the recovered ionic liquid is returned to the process.
The subsequently washed and cleaned cake can be discharged as a slurry or as a dry cake for disposal.
The filter may be a filter having a pore size in the range from 5 μm to 100 μm. Suitably, a filter having a pore size in the range of from 10 μm to 100 μm is used for the filtration step. More suitably, a filter having a pore size of 10 μm to 30 μm is used for the filtration. The filter may be any device capable of solid-liquid separation, such as a buchner funnel or centrifuge.
Positive pressure filtration systems, vacuum filtration systems, or centrifuges may be used to facilitate filtration.
The apparatus may include a controller to control parameters of the caustic stream, such as flow rate and concentration, to account for dilution of the halide-containing ionic liquid.
The apparatus may comprise at least three mixer settlers. Suitably, the apparatus comprises ten mixer-settlers.
In the extraction stage, the at least one mixer-settler may be configured to receive and mix the impurity-containing bayer process stream and the ionic liquid feed stream to form a purified bayer process stream and an impurity-loaded ionic liquid stream, respectively. Suitably, the extraction stage comprises three mixer-settlers arranged in series.
In the stripping stage, at least one mixer-settler may be configured to receive and mix the impurity-laden ionic liquid stream with the halide-laden salt stream to form a halide-laden ionic liquid stream and an impurity-laden salt stream, respectively. Suitably, the stripping stage comprises three mixer-settlers arranged in series.
In the regeneration stage, at least one mixer-settler may be configured to receive and mix the halide-containing ionic liquid stream with the caustic stream to form a regenerated ionic liquid stream and a halide-containing caustic effluent stream, respectively. Suitably, the regeneration stage comprises four mixer-settlers arranged in series.
The first mixer settler in the extraction stage may be configured to be in fluid communication with the end mixer settler in the regeneration stage via a recirculation loop to receive at least a portion of the regenerated ionic liquid stream to form the ionic liquid feed stream.
In one embodiment, in use, in the mixer-settler of the extraction stage, hydroxide ions in the ionic liquid feed stream are replaced by NOOC ions in the impurity-containing bayer process stream to form a purified bayer process stream and an impurity-loaded ionic liquid stream (NOOC-form). The impurity-loaded ionic liquid stream exiting the mixer-settler of the third extraction stage then flows into the first mixer-settler of the stripping stage.
In one embodiment, in use, the NOOC ions are transferred from the impurity-laden ionic liquid stream to the halide-containing salt stream within the mixer-settler of the stripping stage. The NOOC ions in the impurity-laden ionic liquid stream are replaced with chloride ions from the halide-containing salt stream to form a halide-containing ionic liquid stream (Cl-form) and an impurity-laden salt stream. The mass transfer is driven by the high concentration of chloride ions in the aqueous phase.
The stripped ionic liquid leaving the mixer-settler of the third stripping stage then flows into the first mixer-settler of the regeneration stage.
In one embodiment, in use, the stripped ionic liquid is converted to regenerated ionic liquid (OH "form) upon contact with a caustic stream in a mixer-settler of the regeneration stage to form a regenerated ionic liquid stream and a halide-containing caustic effluent stream. The regenerated ionic liquid stream leaving the mixer-settler of the fourth regeneration stage is then recycled to the first mixer-settler of the extraction stage. The halide-containing caustic effluent stream is pumped to a salt separation unit.
The apparatus may be installed after the alumina trihydrate precipitation stage to treat spent bayer liquor.
The filtration stage may be configured such that the concentration of particulate matter in the regenerated ionic liquid stream is below a predetermined threshold concentration before the regenerated ionic liquid is returned to the extraction stage as at least a portion of the ionic liquid feed stream.
The predetermined threshold concentration may be any suitable concentration that takes into account any one or more of the following factors: bayer process liquors, specific ionic liquids and processing conditions being processed.
Suitably, the filtrate solids are less than 3g/L of particulate matter. More suitably, the filtrate solids are less than 0.5g/L of particulate matter. Most suitably, the filtrate solids are less than 0.1g/L of particulate matter.
The filtration stage may provide multiple stages of filtration.
The invention also provides a method for purifying a bayer process stream, comprising:
providing an ionic liquid feed stream comprising a quaternary organic cation, wherein the ionic liquid feed stream is at least partially immiscible with the bayer process stream;
combining the bayer process stream with an ionic liquid feed stream and forming an aqueous phase comprising a purified bayer process liquor and an organic phase comprising an impurity-loaded ionic liquid, wherein the combining reduces the concentration of impurities in the bayer process liquor;
at least partially separating the aqueous phase from the organic phase and forming a purified bayer process stream and an impurity-loaded ionic liquid stream;
mixing the impurity-loaded ionic liquid stream and the halide-containing salt stream to form an aqueous phase comprising the impurity-loaded salt and an organic phase comprising the halide-containing ionic liquid, wherein the mixing reduces the concentration of the impurity in the impurity-loaded ionic liquid stream;
at least partially separating the aqueous phase from the organic phase and forming a halide-containing ionic liquid stream and an impurity-laden salt stream;
mixing the halide-containing ionic liquid stream with a caustic solution and forming an aqueous phase comprising the halide-containing caustic solution and an organic phase comprising regenerated ionic liquid, wherein said mixing replaces at least some of the halide groups in the halide-containing ionic liquid with hydroxyl groups from the caustic solution;
at least partially separating the aqueous phase from the organic phase and forming a halide-containing salt stream and a regenerated ionic liquid stream;
filtering at least one of the ionic liquid streams from the extraction stage, stripping stage and regeneration stage and removing particulate matter; and
at least a portion of the regenerated ionic liquid stream is recycled and forms at least a portion of the ionic liquid feed stream.
The present invention also provides a method for recycling an ionic liquid for use in purifying a bayer process stream, comprising:
mixing the impurity-loaded ionic liquid stream with a stripping solution stream and forming an aqueous phase comprising the impurity-loaded stripping solution and an organic phase comprising the impurity-reduced ionic liquid;
at least partially separating the aqueous phase from the organic phase and forming a reduced impurity ionic liquid stream and an impurity-laden stripping solution stream;
mixing the reduced impurity ionic liquid stream with a caustic solution stream and forming an aqueous phase comprising a used caustic solution and an organic phase comprising regenerated ionic liquid;
filtering at least one of the ionic liquid streams from the extraction stage, stripping stage and regeneration stage and removing particulate matter; and
recycling at least a portion of the regenerated ionic liquid stream to form the ionic liquid feed stream.
The filtering step may comprise removing particulate matter such that the concentration of particulate matter in the regenerated ionic liquid stream is below a predetermined threshold concentration.
In one embodiment, the ionic liquid comprises an alkyl phosphonium salt in three forms, depending on the molecule to which the phosphonium ion is bonded. These forms are: stripped (Cl-), regenerated (OH-), and loaded (NOOC-). The transition between these forms enables the ionic liquid to reversibly associate with the impurity.
The method may include providing an ionic liquid feed stream that is at least partially immiscible with the bayer process stream. The ionic liquid feed stream may comprise an ionic liquid comprising a quaternary organic cation.
Australian patent 2010337293 in the name of Cytec Technology corp. discloses ionic liquids comprising quaternary organic cations and methods and compositions for removing impurities from ionic liquids loaded with impurities.
Reference herein to a Cytec australian patent is not an admission that the disclosure in the patent is part of the common general knowledge in australia or elsewhere.
The following description of quaternary organic cations is closely based on that described in Cytec australian patents.
As reported in Cytec australian patents, the quaternary organic cation may be selected from the group consisting of: phosphonium, ammonium, sulfonium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, pyrazolium, imidazolium, thiazolium, oxazolium, pyrrolidinium, quinolinium, isoquinolinium, guanidinium, piperidinium, and methylmorpholinium.
Suitably, the quaternary organic cation is selected from the group consisting of:
wherein R isa、Rb、Rc、Rd、Re、RfMay each be independently selected from hydrogen or substituted C1-C50An alkyl group, wherein the substituents include one or more selected from the group consisting of: alkyl, cycloalkyl, alkenyl, cycloalkynyl, alkynyl, alkoxy, alkoxyalkyl, aldehyde, ester, ether, ketone, carboxylic acid, alcohol, carboxylic acid ester, hydroxyl, nitro, silyl, aryl, and halide functional groups.
RaTo RfAnd may individually contain from about 1 to about 50 carbon atoms. It is understood that RaTo RfTwo or more of which may form a ring structure.
R1To R7May each be independently selected from hydrogen, halogen or substituted C1-C50An alkyl group, wherein the substituents include one or more selected from the group consisting of: alkyl, cycloalkyl, alkenyl, cycloalkynyl, alkynyl, alkoxy, alkoxyalkyl, aldehyde, ester, ether, ketone, carboxylic acid, alcohol, carboxylic acid ester, hydroxyl, nitro, silyl, aryl, and halogen functional groups. R1To R7And may individually contain from about 1 to about 50 carbon atoms. It will be understood that R1To R7Two or more of which may form a ring structure.
Examples of quaternary organic cations include, but are not limited to, tributyloctylphosphonium, tetrabutylphosphonium, tributyl-8-hydroxyoctylphosphonium, tetrabutylphosphonium, tetrapentylphosphonium, tetrahexylphosphonium, tetraoctylphosphonium, octyl (tributyl) phosphonium, tetradecyl (trihexyl) phosphonium, tributyl (methyl) ammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraoctylammonium, tetradecyl (tributyl) ammonium, tetradecyl (trihexyl) ammonium, dimethyl dicoconium, stearamidopropyldimethyl-2-hydroxyethylammonium, ethyl (tetradecylbisindecyl) ammonium, tallowyltrimethylammonium, N, N, N-trimethyl-1-dodecylammonium, benzyldimethylcocoalkylammonium, N, N-dimethyl-N-dodecylglycine, Butylmethylpyrrolidinium, 1-octyl-2, 3-dimethylimidazolium, 1-butyl-3-methylimidazolium, sulfonium and guanidinium. The term "cocoa-based" (coco) refers to an alkyl group derived from a mixture of fatty acids found in cocoa butter, which is typically a saturated fat having about 12 carbon atoms.
The preferred quaternary organic cation is tributyloctylphosphonium.
The quaternary organic cation is typically associated with an anionic counterion or anion. The anion may be a chaotropic anion or a solvent-stable (kosmotropic) anion.
Examples of suitable anions include, but are not limited to, halides (e.g., fluoride, chloride, bromide, iodide), hydroxide, alkylsulfates (e.g., methylsulfate, ethylsulfate, octylsulfate), dialkylphosphates, sulfates, nitrates, phosphates, sulfites, phosphites, nitrites, hypochlorites, chlorites, perchlorates, carbonates, bicarbonates, carboxylates (e.g., formate, acetate, propionate, butyrate, hexanoate, fumarate, maleate, lactate, oxalate, pyruvate), bis (trifluoromethyl) sulfonimide ([ NTF)2]) Tetrafluoroborate, hexafluorophosphate, CN-、SCN-And an OCN.
Halides and halogen-containing compounds may include, but are not limited to: f-、Cl-、Br-、I-、BF4 -、ClO3 -、ClO4 -、BrO3-、BrO4 -、IO3 -、IO4-、PF6 -、AlCl4 -、Al2Cl-、Al3Cl10 -、AlBr4 -、FeCl4 -、BCl4 -、SbF6 -、AsF6 -、ZnCl3 -、SnCl3 -、CuCl2 -、CF3SO3 -、(CF3SO3)2N-、CF3CO2 -And CCl3CO2 -。
A preferred class of anions is halides. The preferred anion is chloride.
The ionic liquid may comprise any pair of any quaternary organic cation and anion.
The ionic liquid may be selected from the group consisting of: tributyloctylphosphonium chloride, trihexyltetradecylphosphonium chloride, tetrabutylphosphonium chloride, tetradecyl (tributyl) phosphonium chloride, tributyl (8-hydroxyoctyl) phosphonium chloride and octyl (tributyl) phosphonium chloride.
The ionic liquid may be selected from the group consisting of: tetrabutylammonium hydroxide, tetrabutylammonium chloride, stearamidopropyl dimethyl-2-hydroxyethyl ammonium nitrate, ethyltetradecylbutanylammonium chloride, tetrahexylammonium bromide, dodecyltrimethylammonium chloride, benzyldimethyl cocoammonium chloride, N-dimethyl-N-dodecylglycine betaine, Adogen
HTA-1 and tallow alkyl trimethyl ammonium chloride.
Ionic liquids can be phosphonium salts in three forms, depending on the molecule to which the phosphonium ion is bonded. These forms are: stripped (Cl-), regenerated (OH-) and supported (NOOC-).
The ionic liquid may be tributyloctylphosphonium salt, which exists in three forms: stripped (Cl-), regenerated (OH-), and loaded (NOOC-).
The ionic liquid feed stream may include a diluent. The diluent may be an alcohol (e.g., isopropyl alcohol), a polyol, and/or polyethylene oxide. Such diluents may promote phase separation.
The ionic liquid feed stream may comprise at least 1 wt.% ionic liquid. Suitably, the ionic liquid feed stream comprises at least about 10% by weight of ionic liquid. More suitably, the ionic liquid feed stream comprises at least about 50% by weight of ionic liquid. Even more suitably, the ionic liquid feed stream comprises about 70% ionic liquid by weight.
The method includes blending an ionic liquid feed stream with a bayer process stream.
Although the ionic liquid stream and the bayer process stream may be mutually soluble to some extent, typically the two phases are at least partially immiscible with each other to form a liquor/liquor mixture in the extraction stage.
The ionic liquid entering the extraction stage may be in its regenerated form. Suitably, the ionic liquid entering the extraction stage is tributyloctylphosphonium hydroxide.
In the extraction stage, the external O/a ratio may be in the range of 0.5 to 2. Suitably, the external O/a ratio is in the range from 0.67 to 1. Most suitably, the external O/a ratio is in the range from 0.75 to 0.85.
The external O/A ratio defines the O/A ratio of each stage. This is in contrast to the internal O/a ratio, which defines the O/a ratio of each mixer-settler within each stage.
During mixing, impurities, such as NOOC, are extracted from the used liquid and transferred to the ionic liquid. This reduces the concentration of impurities in the bayer process stream and forms an aqueous phase comprising the purified bayer process liquor and an organic phase comprising the impurity-laden ionic liquid.
The aqueous phase and the organic phase are then at least partially separated to form a purified bayer process stream and an impurity-loaded ionic liquid stream.
The purified bayer process stream from the extraction stage is sent out for additional processing, for example to a refinery, while the impurity-loaded ionic liquid stream is directed to a stripping stage.
The ionic liquid entering the stripping stage may be in its supported form. Suitably, the ionic liquid entering the extraction stage is NOOC associated tributyl octyl phosphonium salt.
In the stripping stage, the external O/a ratio may be in the range of 0.5 to 3. Suitably, the external O/a ratio is in the range from 0.67 to 2.5. Most suitably, the external O/A ratio is 1.89.
The internal O/a ratio may range from 0.5 to 2. Suitably, the internal O/a ratio is in the range from 0.8 to 1.2.
In the stripping stage, a stream of impurity-loaded ionic liquid is mixed with a stripping solution. Suitably, the stripping solution is a halide-containing salt stream. More suitably, the halide-containing salt stream is a brine solution (sodium chloride).
During mixing, an ion exchange occurs between the ionic liquid and the halide-containing salt, wherein anionic impurities from the ionic liquid are exchanged with halide groups from the salt to reduce the concentration of impurities in the impurity-loaded ionic liquid stream. This forms a mixture comprising an aqueous phase comprising the impurity-laden salt and an organic phase comprising the halide-containing ionic liquid.
The aqueous phase and the organic phase are then at least partially separated to form an impurity-laden salt stream and a halide-containing ionic liquid stream.
The impurity laden salt stream is processed to remove residual ionic liquid prior to discharge to the environment. Due to the nature of the mixing/settling process, some level of ionic liquid entrainment is expected in the impurity-laden salt stream, typically in the range from 300ppm to 400 ppm. Thus, the impurity-loaded salt stream passes through a coalescer designed to accumulate and collect residual ionic liquid for recycle back into the circuit.
The impurity-loaded salt stream may also be passed through at least one activated carbon column to further reduce the final ionic liquid concentration before being discharged into the environment. At least a portion of the salt from the stream may be recycled back to the stripping stage.
The final ionic liquid concentration in the salt stream may be <1 ppm.
The halide-containing ionic liquid stream is directed to a regeneration stage.
The ionic liquid entering the regeneration stage may be in its exfoliated form. Suitably, the ionic liquid entering the regeneration stage is tributyloctylphosphonium chloride.
In this stage, the external O/a ratio may be in the range of 0.5 to 2. Suitably, the external O/a ratio is in the range from 0.67 to 1.5. Most suitably, the external O/A ratio is 1.13.
The internal O/a ratio may range from 0.5 to 2. Suitably, the internal O/a ratio is in the range from 0.8 to 1.2.
In the regeneration stage, a halide-containing ionic liquid stream is mixed with a caustic stream.
The caustic concentration may be less than 50 wt%. Suitably, the caustic concentration is less than 30 wt%. More suitably, the caustic concentration is less than 20 wt%. Most suitably, the caustic concentration is 10 wt%.
The caustic stream can comprise sodium hydroxide.
During mixing, halide groups from the halide-containing ionic liquid are replaced with hydroxyl groups from the caustic stream. This forms a liquid/liquid mixture comprising an aqueous phase containing regenerated ionic liquid and halide-containing caustic solution.
The aqueous phase and the organic phase are then at least partially separated to form a regenerated ionic liquid stream and a halide-containing caustic stream.
The halide-containing caustic stream is processed for discharge to the environment.
At least a portion of the regenerated ionic liquid stream will be recycled to the extraction stage to form the ionic liquid feed stream.
The ionic liquid inventory is gradually degraded or lost in the circuit, particularly in the extraction and regeneration stages with high caustic concentrations. To maintain the concentration of ionic liquid in the loop, fresh ionic liquid may be added to the process, suitably at the regeneration stage. Suitably, the fresh ionic liquid is in its exfoliated form. More suitably, the fresh ionic liquid is tributyloctylphosphonium chloride.
Suitably, either or both of the entering and exiting regenerated organic ionic liquid is filtered.
Since the viscosity of the ionic liquid at ambient temperature is too high to effectively filter clean ionic liquid, the ionic liquid can be diluted prior to being filtered to facilitate the filtration process. Suitably, the ionic liquid is diluted with water in a ratio in the range of from 0.5(1:2) to 2(2: 1). Suitably, the ratio of ionic liquid to water is 1(1: 1).
Parameters of the caustic solution stream, such as flow rate and concentration, may be adjusted to account for dilution of the ionic liquid.
Dilution of the ionic liquid may occur on the stream entering the regeneration stage. Suitably, water is added to the stream entering the regeneration stage to dilute the ionic liquid stream.
Once the colloidal solids are filtered out, at least a portion of the resulting filtered stream can be recycled to the ionic liquid feed stream.
The filtered stream may be mixed with a metal halide salt and/or a caustic solution to recover the ionic liquid. Suitably, the recovered ionic liquid is recycled back into the loop. The recovered ionic liquid may be decanted before being recycled back into the loop.
The regenerated ionic liquid stream may be diluted with water prior to the filtration step.
In each of the extraction stage, stripping stage and regeneration stage, the water stream may flow counter-currently to the stream comprising the organic ionic liquid. Operation in a counter-current mode enhances the transfer of impurities from the impurity-containing stream to the extractant stream by maintaining an almost constant concentration gradient between the two streams over the entire contact length of the two streams.
In each of the extraction, stripping and regeneration stages, the flow per stream may be from 2m3/h-44m3In the range of/h.
The organic ionic liquid stream in the extraction stage may have a particle size of from 10m3/h-26m3Flow rate in the range of/h.
The water flow in the extraction stage may be of any suitable flow rate.
The water flow in the stripping stage may be of from 4m3/h-14m3Flow rate in the range of/h.
The water flow in the regeneration stage may have a flow rate of from 6m3/h-23m3Flow rate in the range of/h.
In each of the extraction stage, stripping stage, and regeneration stage, the mixing step may be performed in a variety of ways, including by a batch process, a semi-continuous process, or a continuous process. Suitably, the mixing step is a continuous process.
Each mixing step may comprise feeding the organic and aqueous streams to any suitable apparatus that may be used for mixing and phase separation or settling. Examples of mixing and phase separation or settling devices that may be suitable include, but are not limited to, continuous mixer/settler units, static mixers, in-line mixers, columns, centrifuges, and hydrocyclones. The preferred apparatus is a mixer-settler.
In each of the extraction, stripping and regeneration stages, the operating temperature may be as high as 100 ℃. The operating temperature may be varied to control the rate of phase separation.
The operating temperature of each of the extraction, stripping and regeneration stages may be in the range from 50 ℃ to 80 ℃, suitably 65 ℃ to 75 ℃, more suitably 60 ℃ to 65 ℃.
The method may include controlling an internal O/a ratio and/or an external O/a ratio of each of the extraction stage, the stripping stage, and the regeneration stage. The O/A ratio may be in the range of 0.001(1:1000) to 100(100: 1). In one embodiment, the O/A ratio is in the range of from 0.01 to 100. In another embodiment, the ratio is in the range of from 0.1 to 10. In further embodiments, the ratio is in a range from 0.25 to 6.67. In yet another embodiment, the ratio is in the range of from 0.25 to 2.
Brief Description of Drawings
Embodiments of the invention are described hereinafter, by way of example only, with reference to the accompanying drawings, in which:
FIG. 1 is a flow diagram of an embodiment of a method of recycling an ionic liquid according to the present invention; and
fig. 2 is a diagram of an embodiment of an apparatus configured to recycle ionic liquid according to the present invention.
Detailed Description
Embodiments described herein are embodiments of methods and apparatus for purifying bayer process streams using ionic liquids to remove impurities from bayer process streams, according to the present disclosure.
The examples described therein focus on the application of the invention to the removal of impurities from spent bayer process streams. As mentioned above, one particularly relevant class of impurities in spent bayer liquor streams is NOOC.
An embodiment of a method of purifying a bayer process stream according to the present disclosure is labeled 10 in fig. 1.
An embodiment of an apparatus for purifying a bayer process stream according to the invention is labeled 110 in fig. 2.
Referring to the figure, the basic unit operations for the apparatus are an extraction stage 16, a stripping stage 18 and a regeneration stage 20.
Stripping stage 18 includes three mixer-settlers, including mixers 52A-52C and settlers 50A-50C (FIG. 2). The peel mixer-settler is arranged in series with a first peel mixer-settler S1 comprising mixer 52A and settler 50A and a terminal peel mixer-settler S3 comprising mixer 52C and settler 50C.
The methods and apparatus of the present invention are characterized by a filtration stage comprising at least one filter configured to filter particulate matter from at least one ionic liquid stream from extraction stage 16, stripping stage 18, and regeneration stage 20.
An ionic liquid feed stream 12 comprising 70% by weight of tributyloctylphosphonium hydroxide and 30% by weight of water and a spent bayer liquor stream 14 comprising NOOC as carbon in a concentration of 22.5g/L are fed counter-currently into the extraction stage 16 (fig. 1) at an external O/a ratio in the range from 0.67 to 1.0 and an internal O/a ratio in the range from 0.8 to 1.2 to mix. The spent bayer liquor stream 14 enters via end extraction mixer-settler E3, while the ionic liquid feed stream 12 enters via first extraction mixer-settler E1.
The temperature of the spent bayer stream 14 is in the range from 60 ℃ to 80 ℃, while the temperature of the ionic liquid feed stream is in the range from 20 ℃ to 30 ℃, preferably from 20 ℃ to 25 ℃.
The operating temperature in the extraction stage is maintained in the range from 50 ℃ to 80 ℃, preferably 60 ℃ to 65 ℃.
As noted above, the mixer-settlers of extraction stage 16 include mixers 48A-48C and settlers 46A-46C (fig. 2).
First mixer settler E1 is in fluid communication with an end mixer settler R4, which includes mixer 56C and settler 54C, in regeneration stage 20, via a recirculation loop. E1 receives regenerated ionic liquid from the regeneration stage to form ionic liquid feed stream 12, and end extraction mixer-settler E3 is in fluid communication with first mixer-settler S1 of stripping stage 18, including mixer 52A and settler 50A.
During the mixing in the mixers 48A-C, NOOC is extracted from the spent bayer stream 14 and transferred to the ionic liquid feed stream 12. This reduces the concentration of NOOC in the spent bayer liquor stream 14 and forms an aqueous cleaned spent bayer liquor and an organic NOOC-laden ionic liquid.
The aqueous and organic phases are then separated to form a purified spent bayer process stream 24 having a lower concentration of NOOC than the spent bayer liquor stream 14 (e.g., 6.9g/L or less lower) and an NOOC-loaded ionic liquid stream 26 exiting the extraction stage.
The purified spent bayer liquor stream 24 (exiting via first extractive mixer-settler E1) is transferred for further processing in a refinery, while the NOOC-loaded ionic liquid stream 26 is transferred to stripping stage 18.
As mentioned above, stripping stage 18 includes three mixer-settlers, including mixers 52A-52C and settlers 50A-50C (fig. 2) arranged in series.
First stripping mixer-settler S1 is in fluid communication with end mixer-settler E3 of extraction stage 16, which includes mixer 48C and settler 46C, and end stripping mixer-settler S3 is in fluid communication with first mixer-settler R1 of regeneration stage 20, which includes mixer 56A and settler 54A.
In stripping stage 18, the NOOC-loaded ionic liquid stream 26 is counter-currently flowed to a brine (sodium chloride) stream 28 at an external O/a ratio in the range of from 0.67 to 2.5 and an internal O/a ratio in the range of from 0.8 to 1.2 for mixing. Brine (sodium chloride) stream 28 is fed to end stripping mixer-settler S3, while the NOOC-loaded ionic liquid stream 26 enters via first stripping mixer-settler S1.
The operating temperature in the stripping stage is maintained in the range from 60 ℃ to 80 ℃, preferably 70 ℃ to 75 ℃.
During mixing in 52A-52C, ion exchange takes place between the ionic liquid and the brine, wherein the anions NOOC are exchanged for chloride groups in the brine. This forms a mixture comprising an aqueous phase comprising the NOOC-laden brine and an organic phase comprising the chloride-containing ionic liquid.
The aqueous and organic phases are then separated to form a salt water stream loaded with NOOC 30 having a NOOC concentration typically of at least 20g/L and a chloride containing ionic liquid stream 32 leaving the stripping stage.
The NOOC-loaded brine stream 30 (exiting via the first stripping mixer-settler S1) is diverted for additional processing before being discharged into the environment.
Additional processing includes passing the NOOC-loaded brine stream 30 through a coalescer to collect and collect any entrained ionic liquid, typically in the range from 300ppm to 500ppm, for recovery back into the loop.
Additional processing also includes passing the NOOC-loaded brine stream 30 through a series of activated carbon columns to reduce the final ionic liquid concentration to <1ppm before the clean brine stream is discharged into the environment.
A portion of the clean brine stream is recycled to the regeneration stage.
Chloride-containing ionic liquid stream 32 is directed to regeneration stage 20, which includes four mixer-settlers.
As mentioned above, fig. 2 shows four regenerative mixer-settlers as mixers 56A-56C and settlers 54A-54C arranged in series.
First mixer-settler R1 of regeneration stage 20 is in fluid communication with end mixer-settler S3 of stripping stage 18 and end mixer-settler R4 of regeneration stage 20 is in fluid communication with first mixer-settler E1 of extraction stage 16 to transfer regenerated ionic liquid to extraction stage 16.
In the regeneration stage 20, the chloride-containing ionic liquid stream 32 is counter-currently flowed to a caustic (sodium hydroxide) stream 35, typically having a concentration of at least 10 wt%, at an external O/a ratio in the range of from 0.67 to 1.5 and an internal O/a ratio in the range of from 0.8 to 1.2 for mixing. Caustic (sodium hydroxide) stream 35 is fed to end regenerative mixer-settler R4, while chloride-containing ionic liquid stream 32 is fed to first regenerative mixer-settler R1.
The temperature of the caustic stream 35 is in the range of from 10 ℃ to 30 ℃, preferably 25 ℃.
The operating temperature in the regeneration stage is maintained in the range from 50 ℃ to 80 ℃, preferably 60 ℃ to 65 ℃.
During mixing in mixers 56A-56C, chloride groups from the ionic liquid are replaced with hydroxyl groups from the caustic solution. This forms an aqueous phase comprising regenerated ionic liquid and chloride-containing caustic solution.
The aqueous and organic phases are then separated to form regenerated ionic liquid stream 12 and chloride containing caustic stream 36, which chloride containing caustic stream 36 exits regeneration stage 20 via first regeneration mixer-settler R1.
The chloride containing caustic stream 36 is further processed in a salt separation unit 40. The processed caustic stream produces a sodium chloride stream 42 that is at least partially fed to the brine stream 28 or a sodium hydroxide stream 44 that is at least partially fed to the caustic stream 35.
The ionic liquid inventory is gradually degraded or lost in the circuit.
To maintain the ionic liquid concentration, fresh ionic liquid 37 in the form of tributyloctylphosphonium chloride is added to the regeneration stage 20.
As previously discussed, one problem encountered during BTP working processes is that once a threshold concentration of particulate matter in the ionic liquid recirculation loop is reached, an emulsion stabilized by particulate matter (referred to above as "fouling") is formed between the ionic liquid and aqueous solution used and renders the purification or recirculation loop inoperable.
To reduce the formation of fouling, the exiting stripped organic ionic liquid stream is passed through a filtration device sized to maintain a solids concentration (i.e., particulate matter) below a threshold concentration in the filtered stream before being transferred to a regeneration stage as chloride-containing ionic liquid stream 32.
In another embodiment, to reduce the formation of fouling, the exiting regenerated organic ionic liquid stream is passed through a filtration device of suitable size to maintain the solids concentration (i.e., particulate matter) below a threshold concentration in the filtered stream before being recycled as the ionic liquid feed stream 12.
Once the colloidal solids are filtered out, the resulting stream can be salted out using sodium chloride and/or caustic to recover the ionic liquid before it is decanted and recycled back to the loop.
As mentioned above, the present invention extends to filtering the organic ionic liquid stream before or after any one or more of the extraction, stripping and regeneration stages 16, 18, 20.
To evaluate the present invention, the above-mentioned Bench-Top Pilot (BTP) was operated using the operating parameters outlined in table 1 using methods and equipment similar to those described above.
Table 1: parameters of BTP
The measured operating parameters are listed in the "actual" column, while the set parameters are listed in the "standard" column.
Table 2 provides a summary of the results of the analysis of BTP.
Table 2: summary of analysis results of BTP
Three samples were taken from each of the three feed water storage tanks (extract-DSL, strip-SA, regenerate-RA) and each settler water overflow weir for a total of 39 samples. Each sample was analyzed individually for phosphorus, chlorine, and total organic carbon content. Once the sample results were received, the median of each set of three results was taken and presented in table 2 above.
Phosphorus was chosen as a representative species of ionic liquids because pback was expected and has been shown to be low enough not to interfere with the analysis, and because ionic liquids contain phosphorus.
All values less than 20ppm were reported as "< 20 ppm". In the above table, where "< 20 ppm" is reported for SA and RA, the value is entered as 0 in the above table, as this is the pure solution prior to contact with any ionic liquid. In all other cases where a "< 20 ppm" value is reported, a 10ppm value is instead entered as a working estimate of the P content of the sample.
Based on the results in table 2, the following observations were made:
the clarification of the spent bayer liquor stream 14 containing NOOC takes place in the extraction stage. This is demonstrated by reducing the TOC content in the spent bayer liquor stream 14 fed into E3 from 22,900mg/L to 6,910mg/L in the cleaned spent bayer process stream 24 leaving E1.
NOOC removal mainly in the stripping stage. This was demonstrated by increasing the TOC content of the brine (S3; SA) stream 28 supplied to S3 from 6,880mg/L to 21,700mg/L in the NOOC-loaded brine stream (S1; SSA)30 exiting S1.
The regeneration of the ionic liquid in the regeneration stage was demonstrated by increasing the Cl concentration of the caustic (R4; RA) stream 35 supplied to R4 from 14.4ppm to 23,900ppm in the chloride-containing caustic (R1; SRA) stream 36 exiting R1.
A small amount of ionic liquid is removed by the chloride containing caustic stream (R1; SRA)36 leaving the regeneration stage 20. This is demonstrated by increasing the P concentration of the caustic (R4; RA) stream 35 supplied to R4 from 0mg/L to 10mg/L in the chloride containing caustic (SRA) stream 36 exiting R1.
The effectiveness of filtering the organic ionic liquid stream is demonstrated by the following filtration experiments summarized in examples 1-3 below.
Example 1
-a filtering device: a DrM TSD filter in 316L stainless steel with a 32mm diameter candle filter.
Without filter aid or diluent
-temperature: 51 deg.C
G11M 080/30 cloth (Polypropylene)
Feed solids 1.7g/L
-maximum filtration pressure: 4 bar
Solid filtrate after cake development, 0.43 g/kg.
After 240 minutes, a total flux of 48L/m2/h
Example 2
-a filtering device: a DrM TSD filter in 316L stainless steel with a 32mm diameter candle filter.
Crude perlite AP 70, without diluting the feed with water
-temperature: 57 deg.C
Filter aid bulk feed ratio 1:1
G11M 080/30 cloth (Polypropylene)
4.3g/L of feed solids
-maximum filtration pressure: 3 bar
After 117 minutes, total flux 89L/m2/h
No visible filtrate solids observed (correlation of vision with measurements of previous tests, indicating <0.1g/L)
Example 3
-a filtering device: a DrM TSD filter in 316L stainless steel with a 32mm diameter candle filter.
Crude perlite AP 70, undiluted
-temperature: 58 deg.C
Filter aid bulk feed ratio 2:1
G11M 080/30 cloth (Polypropylene)
Feed solids 0.7g/L
-maximum filtration pressure: 3 bar
After 23 minutes, total flux 378L/m2/h
No visible filtrate solids observed (correlation of vision with measurements of previous tests, indicating <0.1g/L)
The above observations show that filters installed in the apparatus effectively remove circulating particulate matter to prevent scale formation and allow the apparatus to function.
Many modifications may be made to the embodiments of the present invention described above without departing from the spirit and scope of the present invention.
By way of example, the mixers and settlers in extraction stage 16, stripping stage 18, and regeneration stage 20 may be any suitable mixers and settlers.
In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features in various embodiments of the invention, but not to preclude the presence or addition of further features.
Glossary
Claims (21)
1. An apparatus for purifying a bayer process stream, comprising:
an extraction stage comprising at least one contacting/separating device configured to receive and blend a bayer process stream containing impurities and an ionic liquid stream comprising quaternary organic cations to form a purified bayer process stream and an ionic liquid stream loaded with impurities;
a stripping stage comprising at least one contacting/separating device configured to receive and mix the impurity-laden ionic liquid stream and the halide-laden salt stream to form a halide-laden ionic liquid stream and an impurity-laden salt stream;
a regeneration stage comprising at least one contacting/separating device configured to receive and mix the halide-containing ionic liquid stream and a caustic stream to form a regenerated ionic liquid stream and a halide-containing caustic effluent stream, wherein the extraction stage is configured to be in fluid communication with the regeneration stage via a recycle loop to receive at least a portion of the regenerated ionic liquid stream to form an ionic liquid feed stream, and
a filtration stage comprising at least one filter configured to filter particulate matter from at least one of the ionic liquid streams from the extraction stage, the stripping stage, and the regeneration stage.
2. The apparatus of claim 1, wherein the filtration stage is configured such that the concentration of particulate matter in the regenerated ionic liquid stream is below a predetermined threshold concentration before the regenerated ionic liquid is returned to the extraction stage as at least a portion of the ionic liquid feed stream.
3. An apparatus according to claim 1 or claim 2, wherein at least one ionic liquid-containing operational unit for the extraction stage, stripping stage and regeneration stage comprises a filter of the filtration stage to remove particulate matter from the ionic liquid stream to control the concentration of particulate matter in the regenerated ionic liquid.
4. The apparatus of claim 1 or claim 2, wherein the filtration stage is an operating unit separate from the operating units forming the extraction stage, the stripping stage and the regeneration stage.
5. The apparatus according to any one of the preceding claims, wherein the contacting/separating devices for the extraction stage, the stripping stage and the regeneration stage are selected from mixer-settlers, columns, centrifuges, static mixers, reactors, which are suitable for mixing and separating two at least partially immiscible liquid streams.
6. The apparatus of claim 5, wherein the contacting/separating device for each of the extraction stage, stripping stage, and regeneration stage comprises at least three mixer-settlers.
7. The apparatus of any preceding claim, wherein the filtration stage follows the stripping stage.
8. The apparatus of any one of the preceding claims, wherein the filter is configured to use a pressure differential as a driving force for filtration.
9. The apparatus of any of the preceding claims, wherein the filter comprises a filter having a filter area of 3L/dm2/min-200L/dm2Air permeability between/min.
10. The apparatus of claim 9, wherein the filter media has a multi-filament or a monofilament construction.
11. The apparatus according to any one of claims 1 to 8, wherein the filtration stage comprises a filter aid, such as a ceramic material, tricalcium aluminate hexahydrate (TCA) and a flocculating agent.
12. The apparatus of any preceding claim, wherein the filter is a candle filter.
13. The apparatus according to any one of the preceding claims, wherein the filtration stage is configured to operate at a temperature in the range of 20-70 ℃.
14. The apparatus of any preceding claim, wherein the filtration stage is configured to operate at 10L/m2/h-700L/m2Filtration flux rate between/h.
15. An apparatus for recycling ionic liquid used to purify a bayer process stream, comprising:
a stripping stage comprising at least one contacting/separating device configured to receive and mix a stream of impurity-loaded ionic liquid and a stream of stripping solution to form a reduced impurity ionic liquid stream and an impurity-loaded stripping solution stream;
a regeneration stage comprising at least one contacting/separating device configured to receive and mix the impurity-reduced ionic liquid stream and a caustic solution stream to form a regenerated ionic liquid stream and a caustic effluent stream; wherein at least one contacting/separating device from the regeneration stage is configured to recycle at least a portion of the regenerated ionic liquid stream and form an ionic liquid feed stream to purify a bayer process stream, an
A filtration stage comprising at least one filter configured to filter particulate matter from at least one of the ionic liquid streams from the extraction stage, the stripping stage, and the regeneration stage.
16. A method of purifying a bayer process stream, comprising:
providing an ionic liquid feed stream comprising a quaternary organic cation, wherein the ionic liquid feed stream is at least partially immiscible with the bayer process stream;
combining the bayer process stream with the ionic liquid feed stream and forming an aqueous phase comprising a purified bayer process liquor and an organic phase comprising an impurity-laden ionic liquid, wherein the combining reduces the concentration of impurities in the bayer process liquor;
at least partially separating the aqueous phase from the organic phase and forming a purified bayer process stream and an impurity-loaded ionic liquid stream;
mixing the impurity-loaded ionic liquid stream and halide-containing salt stream to form an aqueous phase comprising impurity-loaded salt and an organic phase comprising halide-containing ionic liquid, wherein the mixing reduces the concentration of impurities in the impurity-loaded ionic liquid stream;
at least partially separating the aqueous phase from the organic phase and forming a halide-containing ionic liquid stream and an impurity-laden salt stream;
mixing the halide-containing ionic liquid stream with a caustic solution and forming an aqueous phase comprising halide-containing caustic solution and an organic phase comprising regenerated ionic liquid, wherein the mixing replaces at least some of the halide groups in the halide-containing ionic liquid with hydroxyl groups from the caustic solution;
at least partially separating the aqueous phase from the organic phase and forming a halide-containing salt stream and a regenerated ionic liquid stream;
filtering at least one of the ionic liquid streams from the extraction stage, the stripping stage, and the regeneration stage and removing particulate matter; and
recycling at least a portion of the regenerated ionic liquid stream and forming at least a portion of the ionic liquid feed stream.
17. A method for recycling an ionic liquid for purifying a bayer process stream, comprising:
mixing the impurity-loaded ionic liquid stream with a stripping solution stream and forming an aqueous phase comprising the impurity-loaded stripping solution and an organic phase comprising the impurity-reduced ionic liquid;
separating the aqueous phase from the organic phase at least in part and forming a reduced impurity ionic liquid stream and an impurity-laden stripping solution stream;
mixing the reduced-impurity ionic liquid stream and a caustic solution stream and forming an aqueous phase comprising a used caustic solution and an organic phase comprising regenerated ionic liquid;
filtering at least one of the ionic liquid streams from the extraction stage, the stripping stage, and the regeneration stage and removing particulate matter; and
recycling at least a portion of the regenerated ionic liquid stream to form the ionic liquid feed stream.
18. The process of claim 16 or 17, wherein the filtering step comprises adding a filter aid directly to the ionic liquid stream.
19. The process according to claim 17, comprising pre-batch treating the filter aid with an aqueous solution at a temperature between 20 ℃ and 80 ℃ prior to being added to the ionic liquid stream.
20. The process according to claim 19, comprising preparing a solution of the pre-batch filter aid to a solids concentration of between 10g/L and 200 g/L.
21. The process according to claim 19 or 20, comprising adding a filter aid to the ionic liquid stream at a solids ratio (solids in feed-stabilized emulsion: filter aid solids) of between 1:0.1 and 1: 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2019904448 | 2019-11-25 | ||
| AU2019904448A AU2019904448A0 (en) | 2019-11-25 | A method and apparatus of purifying a bayer process stream | |
| PCT/IB2020/061113 WO2021105889A1 (en) | 2019-11-25 | 2020-11-25 | A method and an apparatus of purifying a bayer process stream |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114787397A true CN114787397A (en) | 2022-07-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080082187.8A Pending CN114787397A (en) | 2019-11-25 | 2020-11-25 | Method and apparatus for purifying bayer process streams |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP4065738A4 (en) |
| CN (1) | CN114787397A (en) |
| AU (1) | AU2020393071A1 (en) |
| BR (1) | BR112022010081A2 (en) |
| WO (1) | WO2021105889A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85109376A (en) * | 1984-12-27 | 1986-08-27 | 诺尔科化学公司 | The purifying of BAYER process liquors |
| CN101932526A (en) * | 2007-12-28 | 2010-12-29 | 塞特克技术公司 | Methods and compositions for the removal of impurities and water from the bayer process |
| US20110140037A1 (en) * | 2009-12-15 | 2011-06-16 | Cytec Technology Corp. | Methods and compositions for the removal of impurities from an impurity-loaded organic salt |
| CN102994757A (en) * | 2012-11-27 | 2013-03-27 | 淄博旭德环境工程技术有限公司 | Method for preparing ferro-silico-aluminum alloy by using Bayer process red mud |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4119698A (en) * | 1976-11-26 | 1978-10-10 | Kernforschungsanlage Julich, Gesellschaft Mit Beschrankter Haftung | Reclamation treatment of red mud |
| RU2609112C2 (en) * | 2011-09-05 | 2017-01-30 | Сайтек Текнолоджи Корп. | Processes for recovering organic solvent extractant from solid-stabilised emulsions formed in hydrometallurgical solvent extraction circuits |
| EP3060690B1 (en) * | 2013-10-21 | 2020-10-14 | Peloton Resources Pty Ltd. | Deriving high value products from waste red mud |
| US10030286B1 (en) * | 2013-11-13 | 2018-07-24 | Ii-Vi Incorporated | Method of direct solvent extraction of rare earth metals from an aqueous acid-leached ore slurry |
-
2020
- 2020-11-25 EP EP20894864.6A patent/EP4065738A4/en active Pending
- 2020-11-25 BR BR112022010081A patent/BR112022010081A2/en unknown
- 2020-11-25 WO PCT/IB2020/061113 patent/WO2021105889A1/en active Search and Examination
- 2020-11-25 CN CN202080082187.8A patent/CN114787397A/en active Pending
- 2020-11-25 AU AU2020393071A patent/AU2020393071A1/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85109376A (en) * | 1984-12-27 | 1986-08-27 | 诺尔科化学公司 | The purifying of BAYER process liquors |
| CN101932526A (en) * | 2007-12-28 | 2010-12-29 | 塞特克技术公司 | Methods and compositions for the removal of impurities and water from the bayer process |
| US20110140037A1 (en) * | 2009-12-15 | 2011-06-16 | Cytec Technology Corp. | Methods and compositions for the removal of impurities from an impurity-loaded organic salt |
| CN102994757A (en) * | 2012-11-27 | 2013-03-27 | 淄博旭德环境工程技术有限公司 | Method for preparing ferro-silico-aluminum alloy by using Bayer process red mud |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021105889A1 (en) | 2021-06-03 |
| BR112022010081A2 (en) | 2022-08-30 |
| EP4065738A4 (en) | 2024-01-03 |
| EP4065738A1 (en) | 2022-10-05 |
| AU2020393071A1 (en) | 2022-06-23 |
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