WO2023038541A1 - Procédé de production de sels de bromure - Google Patents
Procédé de production de sels de bromure Download PDFInfo
- Publication number
- WO2023038541A1 WO2023038541A1 PCT/RU2022/000265 RU2022000265W WO2023038541A1 WO 2023038541 A1 WO2023038541 A1 WO 2023038541A1 RU 2022000265 W RU2022000265 W RU 2022000265W WO 2023038541 A1 WO2023038541 A1 WO 2023038541A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bromine
- brine
- commercial
- flow
- absorption
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 80
- 150000003842 bromide salts Chemical class 0.000 title claims abstract description 22
- 239000012267 brine Substances 0.000 claims abstract description 170
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 166
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 118
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 116
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 112
- 239000000243 solution Substances 0.000 claims abstract description 112
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 102
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 56
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 claims abstract description 52
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000012141 concentrate Substances 0.000 claims abstract description 39
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 37
- 238000000605 extraction Methods 0.000 claims abstract description 36
- 238000000746 purification Methods 0.000 claims abstract description 33
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 28
- 238000003795 desorption Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 27
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 22
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 22
- 235000012254 magnesium hydroxide Nutrition 0.000 claims abstract description 22
- 239000002594 sorbent Substances 0.000 claims abstract description 21
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 239000011572 manganese Substances 0.000 claims abstract description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 17
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 17
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 16
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 14
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 13
- 230000007935 neutral effect Effects 0.000 claims abstract description 10
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims abstract description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910001509 metal bromide Inorganic materials 0.000 claims abstract description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 6
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 6
- 239000003209 petroleum derivative Substances 0.000 claims abstract description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims description 67
- 239000002250 absorbent Substances 0.000 claims description 48
- 230000002745 absorbent Effects 0.000 claims description 48
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 46
- 239000011575 calcium Substances 0.000 claims description 46
- 239000003921 oil Substances 0.000 claims description 39
- 239000002994 raw material Substances 0.000 claims description 35
- 239000012159 carrier gas Substances 0.000 claims description 32
- 239000012535 impurity Substances 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 30
- 125000001246 bromo group Chemical group Br* 0.000 claims description 28
- 239000000460 chlorine Substances 0.000 claims description 28
- 229910052801 chlorine Inorganic materials 0.000 claims description 27
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 26
- 239000011777 magnesium Substances 0.000 claims description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 229910052749 magnesium Inorganic materials 0.000 claims description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 21
- 238000012545 processing Methods 0.000 claims description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 19
- 238000001556 precipitation Methods 0.000 claims description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 18
- 229910052791 calcium Inorganic materials 0.000 claims description 18
- 238000005188 flotation Methods 0.000 claims description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 17
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000007900 aqueous suspension Substances 0.000 claims description 16
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 16
- 238000005868 electrolysis reaction Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 229910014265 BrCl Inorganic materials 0.000 claims description 15
- 239000000920 calcium hydroxide Substances 0.000 claims description 15
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 15
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 15
- -1 hypochlorite ions Chemical class 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 11
- 230000033001 locomotion Effects 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000007790 solid phase Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- DTYCRHCCLVCUDT-UHFFFAOYSA-J calcium;magnesium;tetrachloride Chemical compound [Mg+2].[Cl-].[Cl-].[Cl-].[Cl-].[Ca+2] DTYCRHCCLVCUDT-UHFFFAOYSA-J 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 7
- 238000012546 transfer Methods 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 239000004568 cement Substances 0.000 claims description 6
- 239000000701 coagulant Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 230000001174 ascending effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 4
- 150000002484 inorganic compounds Chemical class 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- VXJIMUZIBHBWBV-UHFFFAOYSA-M lithium;chloride;hydrate Chemical compound [Li+].O.[Cl-] VXJIMUZIBHBWBV-UHFFFAOYSA-M 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims description 2
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 2
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 abstract description 5
- 235000017550 sodium carbonate Nutrition 0.000 abstract description 4
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 41
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000011780 sodium chloride Substances 0.000 description 13
- 150000001649 bromium compounds Chemical class 0.000 description 12
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 239000000155 melt Substances 0.000 description 10
- 229910001622 calcium bromide Inorganic materials 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910019440 Mg(OH) Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 238000011109 contamination Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 229910001503 inorganic bromide Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 235000010216 calcium carbonate Nutrition 0.000 description 4
- 235000013877 carbamide Nutrition 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019093 NaOCl Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical class C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 101100437861 Caenorhabditis elegans brc-1 gene Proteins 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical class [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000001987 Pyrus communis Species 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YKOWBJJOJNGCAD-SHYZEUOFSA-N [(2r,3s,5r)-3-hydroxy-5-[4-(hydroxyamino)-2-oxopyrimidin-1-yl]oxolan-2-yl]methyl dihydrogen phosphate Chemical compound O=C1N=C(NO)C=CN1[C@@H]1O[C@H](COP(O)(O)=O)[C@@H](O)C1 YKOWBJJOJNGCAD-SHYZEUOFSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910000435 bromine oxide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000002084 dioxo-lambda(5)-bromanyloxy group Chemical group *OBr(=O)=O 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000004674 formic acids Chemical class 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical class BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YJPVTCSBVRMESK-UHFFFAOYSA-L strontium bromide Chemical compound [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 description 1
- 229910001625 strontium bromide Inorganic materials 0.000 description 1
- 229940074155 strontium bromide Drugs 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
-
- 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
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
- C01F5/06—Magnesia by thermal decomposition of magnesium compounds
- C01F5/10—Magnesia by thermal decomposition of magnesium compounds by thermal decomposition of magnesium chloride with water vapour
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
-
- 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
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
Definitions
- the present invention relates to the field of chemical technology and can be used in relation to the complex processing of polycomponent hydro-mineral raw materials and, in particular, natural bromine chloride brines containing bromide ions, lithium, magnesium, calcium, sodium and strontium ions, containing in addition, impurities of petroleum products, iron and manganese.
- elemental (oxidized) bromine Depending on the concentration level of elemental (oxidized) bromine, it is distilled off with a carrier gas flow, which is either superheated water vapor or air.
- a carrier gas flow which is either superheated water vapor or air.
- live steam is considered effective at concentrations of elemental bromine in brine of 1 kg/m 3 and above, provided that the primary product of production is elemental bromine.
- inorganic bromides can be produced from solutions obtained by absorbing bromine directly from bromine-air flows without the need to obtain elemental bromine as a reagent
- modern trends in the production of inorganic bromide salts are based on the implementation of interactions of solutions or slurries of compounds of alkali, alkaline earth metals and magnesium , as well as compounds of other metals in the presence of reducing agents that exclude contamination of bromide solutions, with elemental bromine in the composition of bromine-air mixtures.
- UK Patent No. 285915 discloses the technological process for obtaining a concentrated solution of calcium bromide by reacting pulps based on calcium hydroxide or carbonate with bromine, which is part of the bromine-air mixture in the presence of reducing agents, for example, urea, cyanide, ammonium carbonate, formamide, formic acids, excluding contamination of the bromide solution with any foreign cations or anions.
- reducing agents for example, urea, cyanide, ammonium carbonate, formamide, formic acids, excluding contamination of the bromide solution with any foreign cations or anions.
- the main disadvantage of this method is the formation of by-products of hypobromite and bromate.
- the method of obtaining metal bromides [US Patent No. 1863375, US Patent No. 2007758] using ammonia as a reducing agent reduces the risk of formation of hypobromites and bromates in bromide solutions.
- the disadvantage of this method is the risk of contamination of bromide solutions with chloride ions at the stage of oxidation by bromide ions with chlorine gas in violation of the ratio 2Br/Ch in favor of chlorine.
- the second stage of the process involves the introduction of a certain amount of hydrazine and is described by a chemical reaction:
- the disadvantage of this method is the limited range of products produced only by calcium bromide in the processing of polycomponent bromine brines containing, along with bromine, other valuable elements, such as lithium, calcium, magnesium, as well as the need to use imported commercial calcium hydroxide and a poisonous reagent - hydrazine as a reagent.
- the disadvantages of this method include the impossibility of implementing this method in a non-arid climate, since the method is based on the classical gallurgical scheme of staged evaporation of lake brine in artificial pools.
- Another disadvantage of this method is the lack of a real possibility of cost-effective production of lithium products from this raw material source, despite the rather high content of lithium in the one stripped off (final) brine.
- a part of the lithium concentrate after purification from impurities and concentration, is subjected to membrane electrolysis, producing a solution of LiOH, which is processed into LiOH H2O, and anodic chlorine, which is used as an oxidizer of bromide ions into elemental bromine.
- this method is the closest to the claimed one and was chosen by us as a prototype.
- this method has disadvantages.
- the disadvantages of the method are:
- the method is highly effective only in the processing of bromine-bearing brines supersaturated in salt content, in particular, in calcium content;
- inorganic bromides by this method only through the bromination of bases or carbonates of alkali, alkaline earth metals with elemental bromine, desorbed from the brine with live steam, followed by condensation into the liquid phase upon cooling;
- the technical result is achieved by the fact that the flow of the original commercial brine is alkalized, maintaining the pH in the commercial brine flow at the level of 6.5 - 7.0, then the commercial brine flow is mixed with the flow of atmospheric air at the rate of 0.4 - 0.5 m 3 atmospheric air per 1 m 3 of commercial brine to transfer the soluble form of valence iron (+2) into the insoluble phase of iron with valency (+3), the resulting mixed air-brine flow is degassed by pouring it into a vessel having a blow-off into the atmosphere, with the output of the oil-enriched ascending part of the degassed flow of the commercial brine through the upper drain, followed by supply to the settling tank for separating oil and commercial brine and the output of the main descending part depleted in oil products degassed flow of commercial brine through the lower drain for mixing with an oxidizing agent containing hypochlorite ions to transfer the soluble form of manganese with a valence (+2) into an insoluble form of manganese with
- the technical result is achieved by the fact that the commercial brine stream, which has passed the stages of flotation and control filtration, purified from impurities of oil products, iron and manganese, is sent to the operation of extracting lithium chloride on a granular sorbent DGAL-C1, the basis of which is the inorganic compound LiCl 2A1 (OH) 3 selective to LiCl pNgO, with the production of primary lithium chloride concentrate.
- the technical result is achieved by the fact that the commercial brine that has passed the stage of extracting lithium chloride is sent to the operation of ejecting chlorine gas and oxidizing the bromide ions contained in the commercial brine into elemental bromine, while the desorption of elemental bromine from the commercial brine is carried out with a carrier gas flow returned to the operation desorption of elemental bromine after passage of a carrier gas stream saturated with bromine in succession of operations of absorption purification from active chlorine impurities in the form of an interhalogen compound BrCl, absorption purification from bromine and thus constantly circulating in a closed circuit: desorption of elemental bromine from a stream of commercial brine - purification from excess active chlorine in the form of the interhalogen compound BrCl - absorption of elemental bromine by alkaline and carbonate absorbents containing reducing agents to obtain aqueous solutions of bromide salts as bromine absorption products - desorption of elemental bromine from the field flow brine.
- the technical result is achieved by the fact that part of the stream of commercial brine that has undergone the extraction of lithium is used to extract magnesium in the form of magnesium hydroxide by introducing hydroxyl ions into the brine, extracting calcium in the form of calcium hydroxide, introducing hydroxide ions into the brine, extracting strontium in the form of carbonate strontium concentrate introduction of carbonate ions into the brine.
- the technical result is achieved by the fact that in the case of the formation of carbon dioxide during the operation of absorption of bromine by alkaline carbonate absorbents in the presence of reducing agents, the flow of circulating carrier gas that has passed the operation of absorption of bromine is additionally subjected to purification from carbon dioxide by alkaline absorbents to obtain solutions or suspensions of carbonate salts as products absorption of carbon dioxide.
- the technical result is achieved by the fact that the flow of bromine-containing carrier gas is purified from impurities of active chlorine in the composition of the interhalogen compound BgCl by absorption of BgCl by an aqueous solution of metal bromide, directing the spent absorbent to mixing with bromine-bearing commercial brine before its chlorination, the processes of absorption of bromine vapor from the gas stream - the carrier is carried out in two stages in the circulation-flow motion of the bromine absorbent in relation to the movement of the carrier gas stream being cleaned, while the output of the volume of the completely spent absorbent, which is a productive solution of the bromide salt, is carried out per unit time in a continuous mode from the first stage of absorption when the indicator is reached pH in the circulating absorbent is 5.0 - 5.5, compensating for the loss of absorbent by supplying an equivalent volume of absorbent to the first stage from the second absorption stage, in turn compensating the loss of absorbent in the second stage by supplying an equivalent volume to the second stage of absorption original
- the technical result is achieved by the fact that the purification of the carrier gas from carbon dioxide is carried out in two stages in the circulation-flow mode of movement of the absorbent containing sodium hydroxide in relation to the movement of the carrier gas stream purified from bromine, while the output of the volume of completely spent absorbent, which is with a productive sodium carbonate solution, is carried out in a continuous mode from the first absorption stage when the pH value in the circulating absorbent solution reaches 9.0 - 9.5, compensating for the volume loss by supplying an equivalent volume of absorbent to the first absorption stage from the second absorption stage, in turn, compensating loss of absorbent in the second stage of absorption by supplying to the second stage of absorption of an equivalent volume of the initial sodium hydroxide solution.
- the technical result is achieved by the fact that the chlorine gas ejected by a stream purified from petroleum products, iron and manganese is produced by membrane electrolysis of a solution of sodium chloride obtained as a result of separation from a stream purified from oil products, iron and manganese commercial brine of bromine, lithium chloride, magnesium in the form of magnesium hydroxide, calcium in the form of calcium hydroxide, strontium in the form of carbonate strontium concentrate and purified from the remnants of impurities of calcium, magnesium, strontium and sulfate ions, first reagent alkaline carbonate method, then by ion exchange on the Lewatit TR-208 ion exchanger in the Na-form or on the ion exchanger analog in the Na-form, the NaOH solution produced as a by-product in the production of chlorine gas by membrane electrolysis is used as an alkaline reagent for the production of sodium bromide and soda solution, as well as a precipitating agent for the precipitation of manganese and calcium from the past
- the technical result is achieved by the fact that the Ca(OH)g, NaOH and Ch products produced from the components of the commercial brine are used as raw materials for the production of neutral calcium hypochlorite.
- the technical result is achieved by the fact that to obtain productive solutions: sodium bromide, lithium bromide, magnesium bromide, calcium bromide, strontium bromide as absorbents of elemental bromine from the carrier gas flow, respectively, use: an aqueous solution of sodium hydroxide or an aqueous solution of sodium carbonate, an aqueous solution lithium hydroxide or an aqueous suspension of lithium carbonate, an aqueous suspension of magnesium hydroxide or an aqueous suspension of magnesium carbonate, an aqueous suspension of calcium hydroxide or an aqueous suspension of calcium carbonate, an aqueous suspension of strontium hydroxide or an aqueous suspension of strontium carbonate, and as a reducing agent ammonia, hydrazine, hydrazine hydrate, hydroxylamine , carbamide, formic acid or analogues of these reducing agents, the elemental composition of which excludes the risk of contamination of bromine absorbents by side ingredients.
- the technical result is achieved by the fact that the resulting solutions of bromide salts are evaporated to obtain melts of bromide salts, the melts of bromide salts are cooled and either anhydrous solid-phase bromide salts, for example sodium bromide, or solid-phase crystalline hydrates of bromide salts, for example, calcium bromide dihydrate crystalline hydrate, are obtained.
- anhydrous solid-phase bromide salts for example sodium bromide
- solid-phase crystalline hydrates of bromide salts for example, calcium bromide dihydrate crystalline hydrate
- the technical result is achieved by the fact that the solid phase of particles removed from the composition of the flotators, which is a mixture of FeO3 and MgCh with oil products, is used as a raw material additive at metallurgical enterprises.
- the technical result is achieved by the fact that the primary lithium chloride concentrate obtained using the chloride-selective granular sorbent DGAL-C1 (based on the inorganic compound LiCl 2A1 (OH) 3 T1H2O of a disordered structure) after concentration by LiCl and purification from impurities is used to produce lithium carbonate, lithium chloride monohydrate, lithium hydroxide monohydrate, while anodic chlorine, formed during the production of lithium hydroxide monohydrate at the operation of membrane electrolysis of a solution of lithium chloride into a solution of lithium hydroxide, is used to oxidize bromide ions to elemental bromine in the technology for producing bromide salts from commercial brines of calcium chloride -magnesium type oil and gas producing enterprises.
- the technical result is achieved by the fact that the flow of the original commercial brine is alkalized by mixing with an alkaline reagent, the pH in the commercial brine flow is maintained at the level of 6.5 - 7.0, then the commercial brine flow is mixed with the atmospheric air flow at the rate of 0.4 - 0.5 m3 of atmospheric air per 1 m3 of commercial brine to transfer the soluble form of iron with valence (+2) into the insoluble form of iron with valence (+3), the resulting mixed air-brine flow is degassed by pouring it into a vessel having a blow-off into the atmosphere, with output of the ascending part of the degassed commercial brine stream enriched with oil products through the upper drain with subsequent supply to the source of the initial commercial brine and the withdrawal of the main descending part of the degassed commercial brine stream depleted in oil products through the lower drain for mixing with an oxidizing agent containing hypochlorite ions to convert the soluble form of manganese with a valence (+ 2) in non-rac
- the mixed brine-air flow of the brine is degassed in the process of its downward movement through a container having a blow-off into the atmosphere.
- the oil In the process of degassing, the oil is partially floated by air and coagulated.
- the upper layer of brine enriched with oil in the process of degassing is constantly withdrawn from the process with a small flow through the upper drain and returned to the oil and brine separation stage.
- the main flow of degassed and partially depleted in oil products and containing suspended particles of Fe 2 O 3 is removed through the bottom drain and mixed with an oxidizing agent solution in the form of a compound containing hypochlorite ions (NaOCl or Ca(OC1)g) to oxidize soluble Mn 2+ to insoluble Mn 4+ by reaction:
- the proposed technology for the complex processing of commercial polycomponent bromine brines also allows you to change the sequence of input of bromine and lithium technological stages without changing the main indicators of these industries.
- the implementation option for the advanced introduction into production of lithium processing unit in relation to bromine is shown by a dash-dotted line. If the technological scheme for the production of complex processing of commercial bromine-bearing multicomponent brines is implemented according to the option involving the extraction of bromine from the purified brine before the extraction of lithium chloride (on the basic technological scheme, the implementation option for the advanced introduction of bromine redistribution into production in relation to lithium is shown by a solid line), then the past operations flotation and control filtration, the brine is sent to the operation of chlorine gas ejection.
- the ejection operation provides, firstly, uniform dissolution of chlorine gas in the volume of the commercial brine flow, and secondly, optimal conditions for the oxidation of bromide ions contained in the commercial brine into elemental bromine, which is described by the following chemical reaction equation:
- the commercial brine containing in its composition dissolved Br with an admixture of BrCl, enters the operation of desorption of bromine from the commercial brine into the gas phase.
- a process is used based on countercurrent contact of the carrier gas flow with the commercial brine flow in apparatuses that provide a highly developed contact surface of the interacting phases.
- the process of bromine desorption is carried out in a circulation-countercurrent mode of movement of the commercial brine with respect to the movement of the carrier gas flow saturated with Br and BrCl vapors, which allows changing the depth of bromine desorption during operation with a change in the bromine concentration in the commercial brine.
- the carrier gas is first purified from chlorine bromide by countercurrent absorption from the carrier gas flow by an absorbent containing bromide ions in its composition.
- an absorbent containing bromide ions in its composition.
- BrCl can act as a part of the commercial brine that has passed the stage of purification from iron, manganese and oil products, and a part of the productive solution of metal bromide, which is the final product of the bromine absorption operation.
- the process of BrCl absorption by bromide absorbents is described by the following chemical reaction equation:
- the carrier gas flow is enriched with elemental bromine, and the active chlorine, which is in the composition of BrCl, passes into the absorbent, being reduced to chlorine ions.
- the carrier gas enters the bromine absorption operation.
- the operation of absorbing elemental bromine from a carrier gas stream to obtain a productive bromide solution as the end product of this operation is carried out with alkaline solutions or carbonate solutions (NaOH, arCO3, LiOH, KOH, K2CO3), alkaline (Ca(OH)g, Mg(OH) 2, 8g (OH)g) or carbonate (CaCO3, MgCOs, ZrCO3.
- N2CO3 pulps in the presence of reducing agents such as NH3, N2H2, (NH2)2CO, which exclude contamination of bromide solutions with foreign cations or anions.
- reducing agents such as NH3, N2H2, (NH2)2CO, which exclude contamination of bromide solutions with foreign cations or anions.
- the process of alkali-carbonate absorption is carried out in the mode of countercurrent movement of the carrier gas flow and the absorbent flow in two stages with the flow-circulation movement of the absorbent in stages.
- the first absorption stage mainly performs the function of finishing the absorbent coming from the second stage to a productive bromide solution (NaBr, CaBr, MgBr 2 , LiBr, SrBn) with a concentration close to 300 g/dm 3 with a pH value of 5.0 - 5.5. At this stage, the degree of absorption does not exceed 65%.
- the second stage of absorption performs the functions of deep purification of the carrier gas from bromine vapor by maintaining a sufficient precisely high alkalinity in the circulation tank of the second absorption stage.
- the absorbent of the second stage of bromine absorption, transferred to the first stage, has a pH value of 8.5 - 9.0.
- the proposed scheme for the absorption of bromine from a carrier gas makes it possible to simplify the process control by outputting a given volume of a productive bromide solution per unit of time equivalent to the volume of the initial absorbent supplied for absorption.
- the carrier gas purified from bromine vapors if it contains carbon dioxide resulting from the absorption of bromine by carbonate solutions or pulps, as well as from the absorption of bromine by alkaline solutions using urea as a reducing agent, is subjected to purification from carbon dioxide by its absorption with NaOH solution , described by the following chemical reaction equation:
- the organization scheme of the carbon dioxide absorption process is similar to the organization scheme of bromine absorption with the complete identity of the equipment used.
- a deep removal of CO2 from the carrier gas stream is ensured by maintaining the pH value in the absorbent at a level of 11.0 - 11.5.
- the productive NaOH solution is withdrawn from the first stage, compensating the withdrawn volume by supplying the NaOH solution to the second stage of absorption, the concentration determined by the calculation of the material balance.
- Produced productive bromide solution is used for the production of anhydrous bromides or for the production of their crystalline hydrates by deep evaporation and crystallization upon cooling.
- the production of anhydrous NaBr from a productive solution of sodium bromide is carried out in two steps. At the first stage, the solution is evaporated until the density of the evaporated medium reaches 1400 - 1420 g / dm 3 , that is, until a melt is obtained
- the evaporation of the productive CaBrg solution is carried out until a melt corresponding to the composition CaBr 2HgO is obtained.
- the melt is converted into a solid phase by pouring onto the cooled surface of a rotating drum.
- the layer “freezing” on the surface of the drum is cut off with toothed scrapers, obtaining a flaky calcium bromide crystalline hydrate corresponding to the general formula CaBr 2HrO.
- Bromides of other metals are produced in a similar way, using hydroxides or carbonates of the corresponding metals (Li, Mg, Sr, Zn, Fe, etc.). Technological processes in this case will differ only in the values of the concentrations of the corresponding bromides in the produced productive solutions and the temperature conditions for dehydration of the productive solutions of bromides.
- the commercial brine which has passed the bromine extraction stage, is directed to the extraction of lithium chloride.
- the extraction of lithium chloride is carried out on a granular selective sorbent DGAL-C1, the basis of which is a compound of lithium and aluminum, corresponding to the general formula NCH2A1(OH)3 pH 2 O and having a disordered structure.
- DGAL-C1 granular selective sorbent
- this compound Upon contact with a highly mineralized lithium-bearing chloride brine, this compound is able to selectively sorb (intercalate) LiCl from the brine until it is completely saturated with lithium, while giving an equivalent amount of water to the brine.
- the primary lithium concentrate obtained without reagents after purification from impurities and concentration in the form of a productive solution of LiCl is used for the production of lithium products Li 2 CC> 3 and LiOH H 2 O.
- Lithium carbonate is obtained from the productive solution by precipitation.
- precipitants concentrated solutions of Na 2 CC> 3 or (MH ⁇ gCO3) are used in accordance with the reactions taking place:
- Lithium hydroxide monohydrate is produced by obtaining a productive solution of LiCl by membrane electrolysis to obtain a solution of LiOH, cathodic hydrogen and anodic chlorine. The process is described by the following overall reaction:
- LiOH solution obtained by membrane electrolysis is evaporated, LiOH H2O crystallizes.
- Anode chlorine is used as an oxidizing agent for bromide ions at the technological stage for the production of bromide salts from commercial brine.
- Cathodic hydrogen is used as a heat carrier in the production of heating steam.
- Precipitation of magnesium with a suspension of Ca(OH) 2 is preferred because it eliminates the risk of formation of colloidal solutions that make it difficult to separate the solid phase of Mg(OH) 2 from the mother field solution.
- the resulting precipitate Mg(OH) 2 is used either to obtain magnesia by drying and calcining according to the reaction: t>450°C
- Ca(OH) 2 precipitate produced is used as an absorbent for the production of CaBr 2 2H 2 O, as a magnesium precipitant, and also as a reagent for the production of neutral calcium hypochlorite.
- the commercial brine which is transformed into NaCl brine during the extraction of lithium, bromine, magnesium, calcium and strontium after reagent purification from sulfate ions and the remainder of calcium, magnesium and strontium, is sent for ion-exchange purification using Lewatit 208TP polyampholyte in Na as a sorbent -form or analogues of this ion exchange resin.
- the ion-exchange purification process is described by the following equations:
- Regeneration of the spent ion exchanger is carried out in two stages: first, with a solution of hydrochloric acid to obtain an “acidic” solution of MgCh and CaCl 2 as the spent regenerate and transfer the ion exchanger to the H-form, then with a NaOH solution to transfer the ion exchanger to the Na-form.
- the regeneration process is described by the following equations:
- the spent regenerates are sent for mixing with the industrial brine (NaCl solution) that has passed the strontium precipitation stage and is supplied to the reagent cleaning operation.
- the NaCl solution is used as a raw material for the production of NaOH solution and chlorine gas by membrane electrolysis. The process is described by the following overall reaction:
- the produced chlorine gas is used as the main reagent in the production of bromides.
- the NaOH solution which is the catholyte of membrane electrolysis, is used as a reagent for the production of productive sodium bromide and sodium carbonate solutions, as well as a reagent for the precipitation of Mg(OH) 2 and the production of neutral calcium hypochlorite.
- Cathodic hydrogen is used as an energy carrier in the production of heating steam used in the evaporation of productive bromide solutions.
- Neutral calcium hypochlorite is obtained by precipitation of the Ca(OC1) 2 phase, from the resulting exchange reaction when mixing saturated aqueous solutions of sodium hypochlorite and calcium hypochlorite, produced by chlorination of a NaOH solution and a suspension of Ca(OH) 2 according to the reactions:
- the Ca(OS1) 2 precipitate is separated from the mother liquor and dried to obtain commercial calcium hypochlorite with an active chlorine content of at least 60% w/w. and containing in its composition water-insoluble impurities in an amount of not more than 6.0% wt.
- the active chlorine mother liquor of the neutral calcium hypochlorite precipitation operation is divided into two streams and, after dosing the appropriate amounts of NaOH and Ca(OH) 2 , is returned to the operations for obtaining hypochlorite solutions (reactions 41, 42).
- Table 1 Composition of the original commercial brine
- the flow of commercial brine purified from impurities entering the processing was 1214.25 dm 3 /h.
- the residual content of impurities in the commercial brine used to obtain samples of bromide salts was: oil products ⁇ 5 mg/dm 3 ; Fe ⁇ 1 mg/ dm3 ; Mp ⁇ 1 mg/dm 3 .
- Table 2 The main indicators of technological processes for obtaining bromides from a purified productive bromine-bearing polycomponent brine are presented in Table 2.
- Table 2 The main indicators of the processes for obtaining samples of bromides from a brine purified from
- the obtained melts were poured onto a rotating cooled drum equipped with scrapers, the shell of which was made of titanium.
- the resulting flake products were weighed.
- the weight of the sample from the productive solution No. 1 was 8.251 kg
- the weight of the sample from the productive solution No. 2 was 7.887 kg.
- the results of the analysis for the content of the main substance and impurities are presented in table 4.
- the results obtained confirm the possibility of obtaining high-quality bromide salts by the proposed method from commercial waters of oil and gas processing enterprises by the proposed method.
- the yield of bromine from the bromine-bearing commercial brine into commercial bromides is at least 93.5% while maintaining the material composition of the brine.
- the experiments also confirm the possibility of obtaining a wide range of bromide salts by the proposed method.
- a pilot plant for the production of lithium products including a sorption-desorption module (SDM) for separating the primary lithium concentrate from the commercial brine, which passed the stage of bromine extraction, which was based on four sorption-desorption columns containing a granular sorbent DGAL-S1 (granule size 0.30 - 3.2 mm) in volume
- the device of the sorption-desorption module of four columns made it possible to conduct the process of obtaining primary lithium concentrate in a continuous mode with minimal downtime of the columns at the stages of the technological operation obtaining a primary lithium concentrate, which included: a stepwise stage of displacement of the brine from the column, which passed the stage of sorption and saturation of the sorbent with lithium chloride, a staged stage of water desorption of lithium from the sorbent, which passed the stage of removal of the brine.
- the resulting primary lithium concentrate was divided into three equal parts, each of which, after purification from impurities and concentration (reverse osmosis concentration in combination with thermal concentration), was brought to productive lithium concentrates from which samples of LigCO3, NCHH2O and LONH2O were produced, the weight of which was respectively 1.387 kg, 2.185 kg and 1.425 kg.
- the main indicators of the technological production of primary lithium concentrate are presented in Table 5.
- the compositions of Li2CO3, LiCl H2O and NOH H2O samples obtained from primary lithium concentrate are presented in Table 6.
- the experiments performed confirm the possibility of separating LiCl from brine in the form of primary lithium concentrate from polycomponent commercial brines of oil and gas producing enterprises and producing high-quality lithium products from it.
- the macro-base of commercial brine after passing through the lithium stage remains unchanged with a decrease in the total salt content by no more than 2% due to dilution of the brine with spent washing brine.
- the primary lithium concentrate was obtained from a multicomponent commercial brine purified from petroleum products, iron and manganese, which was not subjected to bromine extraction.
- the composition of the resulting primary lithium concentrate (g/DM 3 ): Li - 0.529; Ca - 1.33; K + -0.15; Mg 2+ - 0.10; Na - 0.08; Cl - 6.34; Br - 0.08; SO' - 0.01; HCO3 - 0.04; B ⁇ 0.01; pH - 7.0 differed significantly from the composition of the primary lithium concentrate produced in example 2, only the content of bromine (0.08 g/DM 3 in relation to 0.005 g/DM 3 ). However, this did not lead to a significant increase in the bromine content in the lithium carbonate sample produced from the primary lithium concentrate, in which the bromine content did not exceed 0.001% wt.
- the concentration of NaCl in the anolyte at the entrance to the cell maintained at the level of 270 - 280 g/DM 3 when the content of HC1 1 - 2 g/DM 3 .
- the composition of NaCl make-up brine in the anolyte was (g/dm 3 ): NaCl - 300 - 310; C103 ⁇ 15; SO4 2 ' ⁇ 4.0; Ca + Mg + Sr ⁇ 0.5 10' 3 .
- the temperature of the electrolysis was maintained at 70 - 80°C.
- the current efficiency of chlorine was 94 - 96%, the current efficiency of alkali was 75 - 85%.
- Precipitation of Mg(OH)2 from the field solution was carried out in two stages: at the first stage, achieving the maximum degree of Mg(OH)2 content in the sediment, precipitation was carried out with a mixed suspension of Ca(OH)g and Mg(OH)2, removing the formed precipitate by thickening and thick phase filtration.
- the phase of the commercial brine with a residual content of MgCh was brought into contact with the NaOH solution, achieving the introduction of a stoichiometric amount of NaOH in relation to the mass amount of MgCh in the volume of the initial processed commercial solution.
- the precipitate was washed and divided into two unequal parts. Most of the washed cake after drying contained 99.3% Mg(OH)2.
- the obtained products: solid-phase MgO (binder) and Mg(HCOa)2 solution (closing agent) were further used in the preparation of various Sorel cement samples.
- the precipitation was carried out in one stage.
- the Ca(OH)g precipitate was separated from the mother liquor by centrifugation. After washing, the wet precipitate of Ca(OH)g contained up to 0.4% wt. strontium and up to 0.2% sodium.
- the resulting wet precipitate of Ca(OH)g was used as a reagent to obtain a saturated solution of Ca(OC1)g + CaCh by chlorination of an aqueous pulp of Ca(OH)g.
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Abstract
L'invention se rapporte à la production de sels de bromure de métaux à partir de solutions salines bromifères à plusieurs composants lors de leur traitement complexe, et peut être utilisée pour produire des produits commerciaux NaBr, CaBr2Н2О, MgBr22H2O, SrBr22Н2О, LiBrН2О, Li2CO3, LiClH2O, LiOHН2О, MgO, MgCl2, Ca(OCl)2, SrCO3 à partir de solutions salines industrielles de type calcium-magnésium issues d'entreprises d'extraction de gaz et de pétrole. L'invention comprend des mesures consistant à purifier en profondeur une solution saline industrielle pour éliminer les produits pétroliers, le fer et le manganèse, obtenir des solutions de bromure par absorption du brome à partir de produits secondaires selon un procédé de désorption aérienne de mélanges brome-air avec des solutions alcalines ou des pulpes en présence d'agents réducteurs, extraire le chlorure de lithium de la solution saline industrielle ayant subi l'étape d'extraction de brome sur un sorbant granulé sélectif envers le lithium DHAL-C1 afin de produire un concentré de lithium primaire sous forme d'une solution aqueuse de chlorure de lithium à partir de laquelle on produit Li2CO3, LiClН2О et LiOHH2O. Une partie de la solution saline ayant subi l'étape d'extraction de brome et de lithium est utilisée pour la production de Mg(OH)2, MgO, MgCl26H2O, Са(OCl)2 neutre et de concentrée de strontium. L'invention permet également de produire à partie de solutions salines industrielles de solutions de NaOH et Na2CO3, Cl2, Н2, que l'on utilise comme réactifs et fluides énergétiques pour la production de Li2CO3, Mg(OH)2, Са(OCl)2 et SrCO3.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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RU2157339C2 (ru) * | 1998-09-15 | 2000-10-10 | Закрытое акционерное общество "Экостар-Наутех" | Способ получения бромистого лития из рассолов |
RU2189362C2 (ru) * | 2000-06-19 | 2002-09-20 | Общество с ограниченной ответственностью "ЛУКОЙЛ-Коми" | Способ комплексной переработки попутных вод нефтяных месторождений |
RU2190700C1 (ru) * | 2001-01-09 | 2002-10-10 | Государственное унитарное предприятие "Всероссийский научно-исследовательский институт химической технологии" | Способ извлечения иода и брома из природных вод |
RU2724779C1 (ru) * | 2020-01-14 | 2020-06-25 | Публичное акционерное общество «Татнефть» имени В.Д. Шашина | Способ комплексной переработки попутных вод нефтяных месторождений |
US20210087697A1 (en) * | 2019-09-25 | 2021-03-25 | Ecostar-Nautech Co., Ltd. | Method for producing lithium hydroxide monohydrate from brines |
-
2022
- 2022-08-31 WO PCT/RU2022/000265 patent/WO2023038541A1/fr unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2157339C2 (ru) * | 1998-09-15 | 2000-10-10 | Закрытое акционерное общество "Экостар-Наутех" | Способ получения бромистого лития из рассолов |
RU2189362C2 (ru) * | 2000-06-19 | 2002-09-20 | Общество с ограниченной ответственностью "ЛУКОЙЛ-Коми" | Способ комплексной переработки попутных вод нефтяных месторождений |
RU2190700C1 (ru) * | 2001-01-09 | 2002-10-10 | Государственное унитарное предприятие "Всероссийский научно-исследовательский институт химической технологии" | Способ извлечения иода и брома из природных вод |
US20210087697A1 (en) * | 2019-09-25 | 2021-03-25 | Ecostar-Nautech Co., Ltd. | Method for producing lithium hydroxide monohydrate from brines |
RU2724779C1 (ru) * | 2020-01-14 | 2020-06-25 | Публичное акционерное общество «Татнефть» имени В.Д. Шашина | Способ комплексной переработки попутных вод нефтяных месторождений |
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