CN107803211A - Preparation method of cobalt or/and manganese bromide - Google Patents
Preparation method of cobalt or/and manganese bromide Download PDFInfo
- Publication number
- CN107803211A CN107803211A CN201711030735.9A CN201711030735A CN107803211A CN 107803211 A CN107803211 A CN 107803211A CN 201711030735 A CN201711030735 A CN 201711030735A CN 107803211 A CN107803211 A CN 107803211A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- manganese
- hydroxide
- acid
- carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010941 cobalt Substances 0.000 title claims abstract description 67
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 66
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 52
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 49
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 47
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 13
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 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 abstract description 9
- 235000019253 formic acid Nutrition 0.000 claims abstract description 9
- 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 abstract description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 8
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 8
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 8
- 229930091371 Fructose Natural products 0.000 claims abstract description 7
- 239000005715 Fructose Substances 0.000 claims abstract description 7
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims abstract description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 7
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims abstract description 7
- 239000008103 glucose Substances 0.000 claims abstract description 7
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 6
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 6
- 235000001727 glucose Nutrition 0.000 claims abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 47
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 42
- 229910052794 bromium Inorganic materials 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 22
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 16
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims description 16
- 230000003750 conditioning effect Effects 0.000 claims description 15
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 14
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 13
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 12
- 239000011656 manganese carbonate Substances 0.000 claims description 10
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 10
- 229940093474 manganese carbonate Drugs 0.000 claims description 9
- 235000006748 manganese carbonate Nutrition 0.000 claims description 9
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 8
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 8
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 8
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 7
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical group [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 7
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 4
- HJZMCWKYJQFMPG-UHFFFAOYSA-J cobalt(2+);manganese(2+);dicarbonate Chemical compound [Mn+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HJZMCWKYJQFMPG-UHFFFAOYSA-J 0.000 claims description 4
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 16
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical class Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 13
- 238000010992 reflux Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229910021568 Manganese(II) bromide Inorganic materials 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910019131 CoBr2 Inorganic materials 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229930003268 Vitamin C Natural products 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 2
- 229940006460 bromide ion Drugs 0.000 description 2
- -1 cobalt manganese bromine compound Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- 235000019154 vitamin C Nutrition 0.000 description 2
- 239000011718 vitamin C Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ZBICJTQZVYWJPB-UHFFFAOYSA-N [Mn].[Co].[Br] Chemical compound [Mn].[Co].[Br] ZBICJTQZVYWJPB-UHFFFAOYSA-N 0.000 description 1
- GEIJUOCMDNDDBH-UHFFFAOYSA-L [OH-].[OH-].[Mn].[Co++] Chemical compound [OH-].[OH-].[Mn].[Co++] GEIJUOCMDNDDBH-UHFFFAOYSA-L 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QYTBWVFCSVDTEC-UHFFFAOYSA-N azane;iron Chemical compound N.[Fe] QYTBWVFCSVDTEC-UHFFFAOYSA-N 0.000 description 1
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- BYMAUHXAUBWFOR-UHFFFAOYSA-J cobalt(2+) manganese(2+) tetraacetate Chemical compound [Mn+2].[Co+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O BYMAUHXAUBWFOR-UHFFFAOYSA-J 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011234 economic evaluation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 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 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/27—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a liquid or molten state
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of cobalt or/and manganese bromide, which is characterized in that at least one of carbonate, hydroxide and oxide of cobalt or/and manganese and hydrobromic acid are added into a reactor, and 1-4 of formaldehyde, acetaldehyde, formic acid, phenol, hydrazine hydrate, ascorbic acid, oxalic acid, propionic acid, glucose and fructose are added as regulators to react to prepare an aqueous solution of cobalt or/and manganese bromide, wherein the aqueous solution can be directly used for preparing a catalyst for preparing terephthalic acid by oxidizing paraxylene.
Description
Technical field
The present invention relates to the preparation method field of a kind of cobalt or/and manganese bromide.It is by cobalt or/and manganese in more detail
At least one of carbonate, hydroxide, oxide and hydrobromic acid and formaldehyde, acetaldehyde, formic acid, phenol, hydrazine hydrate, Vitamin C
1 ~ 4 kind in acid, oxalic acid, propionic acid, glucose, fructose carries out the method that reaction prepares cobalt or/and manganese bromide solution.
Background technology
It is compound that cobalt manganese bromine is prepared in carbonate, hydroxide, oxide and hydrobromic acid reaction usually using cobalt or/and manganese
During the aqueous solution, the cobalt and manganese in the carbonate, hydroxide, oxide of used cobalt or/and manganese is typically required to divalent
State form is present, but in actual production, the carbonate and hydroxide of cobalt manganese be all carbonate using alkali metal or ammonia or
Hydroxide is precipitated to obtain, and the oxide of cobalt manganese is obtained by heating or burning to decompose to carbonate or hydroxide.By
In the carbonate and hydroxide of alkali metal be all highly basic, therefore, during precipitation and washing cobalt manganese precipitation, with air contact
Appraising at the current rate for cobalt and manganese ion is easily lead to, causes divalent cobalt and manganese in the carbonate or hydroxide of part cobalt manganese to change into 3
Valency cobalt ions and 4 valency manganese ions, so as to cause during cobalt manganese bromine compound aqueous solution is further prepared with hydrobromic acid reaction, its
In trivalent cobalt ions and 4 valency manganese ions part bromide ion is oxidized to simple substance bromine and existed in solution in the form of free bromine,
Product is caused to be used directly as catalyst, and the presence of free bromine has significantly corrosion to Ti equipment and pipeline
Property.
It is also existing online using sodium carbonate or the report of sodium hydroxide Call Provision manganese in PTA catalyst recovery systems, but
Exist the later stage dissolving not exclusively, the low problem of catalytic activity, using hydrobromic acid as solvent also exist free bromine aggravate equipment corruption
The phenomenon of erosion.It is yellow and bright at it for the recovery from PTA catalyst recovery system cobalt manganese【The skill of recovery of acetic acid Mn catalyst
Art economic evaluation】（2006 Chinese Technology Association's nd Annual Meeting collection（Volume two））Once a kind of recycling method was described in one text, i.e.,
Cobalt carbonate manganese, dilute sulfuric acid or diluted hydrochloric acid dissolution cobalt carbonate manganese, logical ammonia iron removaling are obtained by carbonate deposition, add sulfide（Sulphur
Change sodium）Cobalt sulfide manganese precipitation is obtained, then cobalt acetate manganese is prepared by complex process, technological process is complicated, equipment is more, environment be present
Pollution.
The content of the invention
The purpose of the present invention is exactly to overcome disadvantage existing for prior art, using new technical characteristic, there is provided it is a kind of it is low into
Originally, the pollution-free new method for preparing cobalt or/and manganese bromide solution, the aqueous solution can be directly used for by xylene upon oxidation system
Make phthalic acid and by the oxidized manufacture TMA of trimethylbenzene（Trimellitic anhydride）High activated catalyst.
In order to reach the purpose of the present invention, carbonate, the hydroxide of the invention by adding cobalt or/and manganese in the reactor
At least one of thing, oxide and hydrobromic acid, add formaldehyde, acetaldehyde, formic acid, phenol, hydrazine hydrate, ascorbic acid, oxalic acid,
1 ~ 4 kind in propionic acid, glucose, fructose is reacted as conditioning agent, by controlling reactant ratio, temperature, realizes cobalt
Manganese compound is completely dissolved, and by filtering off the removal of impurity, filtrate is cobalt or/and manganese bromide solution, be can be directly used for
Allocate catalyst.
The present invention is described in detail below：
The present invention is to add at least one of carbonate, hydroxide, oxide of cobalt or/and manganese and and hydrogen in the reactor
Bromic acid, 1 ~ 4 kind added in formaldehyde, acetaldehyde, formic acid, phenol, hydrazine hydrate, ascorbic acid, oxalic acid, propionic acid, glucose, fructose
Reacted as conditioning agent, by controlling the mol ratio, conditioning agent dosage and reaction temperature of cobalt or/and manganese and hydrobromic acid, promoted
Enter solids dissolving and free bromine is converted into bromide ion, filter, filtrate is cobalt or/and manganese bromide solution.
The preparation method of a kind of cobalt or/and manganese bromide solution of the present invention, the carbon of used cobalt or/and manganese
Hydrochlorate, hydroxide, oxide refer to cobalt carbonate or basic cobaltous carbonate, manganese carbonate or basic carbonate manganese, cobalt carbonate manganese, alkali formula carbon
Sour cobalt manganese, cobalt hydroxide (II), cobalt hydroxide (III), manganous hydroxide (II), manganous hydroxide (IV), cobalt hydroxide manganese (II), hydrogen
Cobalt oxide (III) manganese (IV), cobalt oxide (II), cobalt oxide (III), manganese oxide (II), manganese dioxide (IV), cobaltosic oxide, oxygen
Change cobalt manganese, cobalt oxide (III) manganese (IV), the wherein carbonate of cobalt manganese or hydroxide had both included what is purchased on direct market, also wrapped
Include and reclaim what is got by adding sodium hydroxide and sodium carbonate from PTA oxidation residuas.
Carbonate, the hydrogen of the preparation method of a kind of cobalt or/and manganese bromide solution of the present invention, cobalt or/and manganese
The mol ratio of cobalt or/and manganese and hydrobromic acid is 1: 2.1~3 in oxide, oxide, when cobalt manganese total amount and the mol ratio of hydrobromic acid
During more than 1: 2.1, the dissolving of cobalt manganese is incomplete, and solution is easily muddy；When cobalt manganese total amount and the mol ratio of hydrobromic acid are less than 1: 3
When, continue to increase hydrobromic acid amount, on course of dissolution without influence, thus present invention selection cobalt manganese total amount and the mol ratio of hydrobromic acid for
1: 2.1~3, within this range, hydrobromic acid dosage is more, and reaction conversion is rapider and complete；In addition, the feed postition of hydrobromic acid
To be slowly added in batches, a large amount of foam overflow phenomenons otherwise easily occur, in addition, the feed postition of hydrobromic acid can also be according to reaction
Automatic linkage feed postition is taken in solution level change in device.
The preparation method of a kind of cobalt or/and manganese bromide solution of the present invention, be add hydrobromic acid make cobalt or/
Formaldehyde, acetaldehyde, formic acid, phenol, hydrazine hydrate, Vitamin C are added after being completely dissolved with the carbonate, hydroxide, oxide of manganese
In acid, oxalic acid, glucose and fructose it is at least one kind of, at most 4 kinds be used as conditioning agent, the addition of conditioning agent can not only eliminate hydrogen
Because of free bromine caused by ingress of air when bromic acid adds, and a small amount of cobalt manganese sediment can be eliminated because sticky and containing etc. causes
Early stage high price cobalt and manganese conversion not exclusively again with hydrobromic acid reaction caused by free bromine.Send out conditioning agent existing in implementation process
Such as hydrazine hydrate, oxalic acid, phenol then need 2 kinds using a kind of free bromine being completely eliminated in lysate, some conditioning agents
Even 3~4 kinds are applied in combination effect just significantly or stably, continue to increase breed combination influence no longer obvious.In addition, conditioning agent is used
Amount is closely related with conditioning agent self character, temperature, action time length, in the present invention, when conditioning agent total amount and 48% hydrogen bromine
When the mass ratio of acid is less than 0.1: 100, it is found that it is not thorough or unstable free bromine removes；In conditioning agent total amount and 48% hydrobromic acid
Mass ratio be 0.1~5: 100 when, do not detect free bromine.
The preparation method of a kind of cobalt or/and manganese bromide solution of the present invention, it is that normal press control temperature is normal
Temperature~boiling temperature, within this range, improve the dissolving that temperature is advantageous to the carbonate, hydroxide, oxide of cobalt or/and manganese
Free bromine is eliminated with quickening.
The preparation method of a kind of cobalt or/and manganese bromide solution of the present invention, obtained cobalt or/and manganese bromide
The aqueous solution directly by paraxylene is oxidized can prepare terephthalic acid (TPA) or by the oxidized preparation of inclined triphen by pumping allotment
The catalyst of trimellitic anhydride, it is simple to operate.
Embodiment
The present invention is further illustrated below by embodiment：
Embodiment 1：
In the reactor that volume is 500ml, technical grade cobalt carbonate and 80g water that 60g cobalt contents are 46% are added, in stirring shape
165g48% hydrobromic acids are gradually added under state, is gradually heated up being warming up to boiling, adds 1.65g10% hydrazine hydrates, reactor tail gas
By entering exhaust treatment system after reflux condensate device, when solution is clarified and is tested wherein without free bromine, stop reaction, mistake
Filter, obtains the cobaltous bromide aqueous solution, is added with water to gross weight 300g, wherein cobalt content 9.18%, bromine content 27.37%, the cobaltous bromide water
Solution can be directly used for allocating catalyst use.
Embodiment 2：
In the reactor that volume is 500ml, it is 53% to add cobalt hydroxide (II), 21g amounts containing cobalt that 30g amounts containing cobalt are 62%
Cobalt hydroxide (III) and 45g water, are gradually added into 180g hydrobromic acids under stirring, after the completion of addition, are heated to boiling,
Reactor emptying enters exhaust treatment system after passing through reflux condensate device, adds 0.2g industry hydrazine hydrate, acetaldehyde 0.5g, protects
Hold boiling to continue to react, when solution is clarified and is tested wherein without free bromine, stop reaction, filtering, obtain the cobaltous bromide aqueous solution,
Gross weight 280g, wherein cobalt content 10.54%, bromine content 30.16% are added with water to, the cobaltous bromide aqueous solution can be directly used for allotment and urge
Agent uses.
Embodiment 3：
In the reactor that volume is 500ml, 38.7g cobalt contents are added as 73.4% cobaltosic oxide and 20g water, under normal temperature
245g48% hydrobromic acids are gradually added into, reactor tail gas is by entering exhaust treatment system after reflux condensate device, after the completion of addition
8.0g oxalic acid is added immediately, 3.0g acetaldehyde, 0.6g formic acid and 0.7g ascorbic acid, is gradually heated up being warming up to fluidized state continuation instead
Should, when solution is clarified and is tested wherein without free bromine, stop reaction, filtering, obtain the cobaltous bromide aqueous solution, be added with water to gross weight
320g, wherein cobalt content 8.87%, bromine content 36.13%, the cobaltous bromide aqueous solution can be directly used for allocating catalyst use.
Embodiment 4：
In the reactor that volume is 500ml, it is 62% to add cobaltosic oxide, 10g amounts containing cobalt that 10g cobalt contents are 73.4%
The technical grade cobalt carbonate and 25g water that cobalt hydroxide (II), the cobalt hydroxide (III) that 5g amounts containing cobalt are 53%, 30g amounts containing cobalt are 46%,
205g48% hydrobromic acids are gradually added into, reactor tail gas is added and completed by entering exhaust treatment system after reflux condensate device
Afterwards, 6.0g oxalic acid, 2.0g phenol, 0.5g formic acid and 0.1g acetaldehyde are added immediately, and slow heating is warming up to fluidized state and continued instead
Should, when solution is clarified and is tested wherein without free bromine, stop reaction, filtering, obtain the cobaltous bromide aqueous solution, be added with water to gross weight
300g, wherein cobalt content 10.04%, bromine content 32.31%, the cobaltous bromide aqueous solution can be directly used for allocating catalyst use.
Embodiment 5：
In the reactor that volume is 500ml, it is 73.4% to add cobalt hydroxide (II), 20g amounts containing cobalt that 20g amounts containing cobalt are 62%
Cobaltosic oxide and 30g water, 218g48% hydrobromic acids are gradually added under stirring, after the completion of addition, add 5.0g immediately
Oxalic acid, 2.0g phenol, 0.2g ascorbic acid, slow heating is warming up to fluidized state and continues to react, when solution is clarified and tests it
During middle no free bromine, stop reaction, filtering, obtain the cobaltous bromide aqueous solution, be added with water to gross weight 300g, wherein cobalt content 9.04%,
Bromine content 34.39%, the cobaltous bromide aqueous solution can be directly used for allocating catalyst use.
Embodiment 6：
In the reactor that volume is 500ml, technical grade manganese carbonate and 60g water that 60g manganese contents are 45% are added, in stirring shape
180g48% hydrobromic acids and 1.8g10% acetaldehyde solution are gradually added under state, is heated to boiling, reactor tail gas passes through
Enter exhaust treatment system after reflux condensate device, when solution is clarified and is tested wherein without free bromine, stop reaction, filter,
The manganous bromide aqueous solution is obtained, is added with water to gross weight 290g, wherein manganese content is 9.37%, bromine content 29.54%, and the manganous bromide is water-soluble
Liquid can be directly used for allocating catalyst use.
Embodiment 7：
In the reactor that volume is 500ml, it is 60% to add technical grade manganese carbonate, 20g manganese contents that 30g manganese contents are 45%
Manganous hydroxide, industrial electrode manganese dioxide and the 30g water that 3g manganese contents are 60%, are gradually added into 190g48% hydrobromic acids, add and complete
Afterwards, slow heating heating, when temperature rises to 80 DEG C, adds 2.0g10% hydrazine hydrates, 3.0g oxalic acid, 2.3g phenol, 4.0g first
Aldehyde, continue to be heated to seething with excitement, reactor tail gas is by entering exhaust treatment system after reflux condensate device, when solution is clarified and is surveyed
When examination is wherein without free bromine, stops reaction, filtering, obtain the manganous bromide aqueous solution, be added with water to gross weight 280g, wherein manganese content is
9.76%th, bromine content 32.04%, the manganous bromide aqueous solution can be directly used for allocating catalyst use.
Embodiment 8：
In the reactor that volume is 500ml, it is 60% to add technical grade manganese carbonate, 30g manganese contents that 30g manganese contents are 45%
Manganous hydroxide, 290g48% hydrobromic acids are gradually added into, after the completion of addition, add 0.5g formic acid, 0.5g ascorbic acid and 0.5g fruits
Sugar, slow heating are warming up to boiling, and reactor tail gas is by entering exhaust treatment system after reflux condensate device, when solution is clarified
And when testing wherein without free bromine, stop reaction, filtering, obtain the manganous bromide aqueous solution, be added with water to gross weight 350g, wherein manganese contains
Amount 9.02%, bromine content 39.17%, the manganous bromide aqueous solution can be directly used for allocating catalyst use.
Embodiment 9：
In the reactor that volume is 500ml, industrial electrode manganese dioxide and the 10g water that 50g manganese contents are 60% is added, is gradually added
Enter 275g48% hydrobromic acids, after the completion of addition, then 10g oxalic acid is added portionwise, slow heating is warming up to boiling, and reactor tail gas leads to
Enter exhaust treatment system after crossing reflux condensate device, when solution is clarified and is tested wherein without free bromine, stop reaction, mistake
Filter, obtains the manganous bromide aqueous solution, is added with water to gross weight 350g, wherein manganese content 8.56%, bromine content 37.14%, the manganous bromide water
Solution can be directly used for allocating catalyst use.
Embodiment 10：
In the reactor that volume is 500ml, manganous hydroxide and 30g water that 50g manganese contents are 60% are added, is gradually added into
230g48% hydrobromic acids, after the completion of addition, slow heating heating, when temperature rises to 80 DEG C, add 1.0g10% hydrazine hydrates and
5.0g phenol, continue to be heated to seething with excitement, reactor tail gas is by entering exhaust treatment system after reflux condensate device, when solution is clear
When clear and test is wherein without free bromine, stops reaction, filtering, obtain the manganous bromide aqueous solution, be added with water to gross weight 320g, wherein manganese
Content 9.76%, bromine content 32.04%, the manganous bromide aqueous solution can be directly used for allocating catalyst use.
Embodiment 11：
In the reactor that volume is 1000ml, it is 62% to add technical grade cobalt carbonate, 10g amounts containing cobalt that 20g cobalt contents are 46%
Cobalt hydroxide, 5g amounts containing cobalt be 73.4% cobaltosic oxide（The mixture of cobalt sesquioxide and cobalt oxide）, 20g manganese contents
The manganous hydroxide that the industrial electrode manganese dioxide for being 60% for 45% technical grade manganese carbonate, 3.0g manganese contents, 10g manganese contents are 60%
With 100g water, stirring is opened, is gradually added into 320g48% hydrobromic acids, reactor tail gas is by entering tail gas after reflux condensate device
Processing system, after the completion of addition, it is immediately heated and is warming up to boiling, add 10.0g oxalic acid and 2.0 glucose, when solution is clarified
And when testing wherein without free bromine, stop reaction, filtering, obtain the cobaltous bromide manganese aqueous solution, be added with water to gross weight 500g, wherein cobalt
Content 3.82%, manganese content 3.38%, bromine content 30.24%, the cobaltous bromide manganese aqueous solution can be directly used for allocating catalyst use.
Embodiment 12：
In the reactor that volume is 1000ml, it is 62% to add technical grade cobalt carbonate, 10g amounts containing cobalt that 20g cobalt contents are 46%
Cobalt hydroxide, 5g amounts containing cobalt be 73.4% cobaltosic oxide（The mixture of cobalt sesquioxide and cobalt oxide）, 20g manganese contents
The manganous hydroxide that the industrial electrode manganese dioxide for being 60% for 45% technical grade manganese carbonate, 3.0g manganese contents, 10g manganese contents are 60%
With 100g water, stirring is opened, is gradually added into 265g48% hydrobromic acids, reactor tail gas is by entering tail gas after reflux condensate device
Processing system, after the completion of addition, it is immediately heated and is warming up to boiling, adds 6.0g propionic acid, 2.0 fructose, 5.0g acetaldehyde and 0.3g
Ascorbic acid, when solution is clarified and is tested wherein without free bromine, stop reaction, filtering, obtain the cobaltous bromide manganese aqueous solution, add water
Gross weight 450g, wherein cobalt content 4.24%, manganese content 3.75%, bromine content 27.87% are adjusted to, the cobaltous bromide manganese aqueous solution can be direct
Used for allocating catalyst.
Embodiment 13：
In the reactor that volume is 3000ml, 1000kg is added from PTA residues by adding sodium hydroxide and sodium carbonate simultaneously
Through precipitating isolated cobalt manganese mixture, cobalt, manganese content are respectively 8.19% and 8.33%, wherein containing cobalt carbonate, alkali formula carbon
Sour cobalt, manganese carbonate, basic carbonate manganese, cobalt hydroxide, manganous hydroxide and a small amount of cobalt hydroxide (III) and manganous hydroxide (IV)
With 200kg water, it is gradually added into 1030kg48% hydrobromic acids and stirring is opened after solution-wet solids, reactor tail gas passes through
Enter exhaust treatment system after reflux condensate device, after the completion of addition, be immediately heated and be warming up to boiling, be slow added into
10.5kg10% hydrazine hydrates, when solution is clarified and is tested wherein without free bromine, stop reaction, filtering, it is water-soluble to obtain cobaltous bromide manganese
Liquid, it is measured by sampling, wherein cobalt content 3.92%, manganese content 3.97%, bromine content 23.17%, the cobaltous bromide manganese aqueous solution can be returned directly
Return PTA oxidative systems or used after being allocated with fresh catalyst.
Symbol description is used in the present invention：
%：Mass percent；g：Gram；kg：Kilogram；mol：Mole；min：Minute；ml：Milliliter；L：Rise.
The stoichiometric equation of chemical reaction being related in the present invention is：
（1）CoCO3(S)+2HBr(L)=CoBr2(L)+H2O(L)+CO2(g)
（2）Co2(OH)2CO3(S)+4HBr(L)=2CoBr2(L)+2H2O(L)+2CO2(g)
（3）MnCO3(S)+2HBr(L)=MnBr2(L)+H2O(L)+CO2（g）
（4）Mn2(OH)2CO3(S)+4HBr(L)=2MnBr2(L)+2H2O(L)+2CO2(g)
（5) Co(OH)2(S)+2HBr(L)=CoBr2(L)
（6）Mn(OH)2(S)+2HBr(L)=MnBr2(L)
（7) 2Co(OH)3(S)+6HBr(L)=2CoBr2(L)+6H2O(L)+Br2(L)
（8）Mn(OH)4(S)+4HBr(L)=MnBr2(L)+4H2O(L)+Br2(L)
（9) CoO(S)+2HBr(L)=CoBr2(L)+H2O(L)
（10）MnO(S)+2HBr(L)=MnBr2(L)+H2O(L)
（11) Co2O3(S)+6HBr(L)=2CoBr2(L)+3H2O(L)+Br2(L)
（12）MnO2(S)+4HBr(L)=MnBr2(L)+2H2O(L)+Br2(L)
(13) Br2(L)+R=2Br-(L)+R+
(14) Co2++2Br-(L)= CoBr2(L)
(15) Mn2++2Br-(L)=MnBr2(L)
In equation bracket（S）Represent solid；（L）Represent liquid；（g）Represent gas;R represents conditioning agent；R+Represent conditioning agent
Reaction product.
Cobalt, manganese, the measure of bromine use titration in the present invention；Free bromine measure uses KI+starch method.
Claims (5)
1. the preparation method of a kind of cobalt or/and manganese bromide, it is characterised in that add the carbonic acid of cobalt or/and manganese in the reactor
At least one of salt, hydroxide, oxide and hydrobromic acid, add conditioning agent and reacted, cobalt or/and manganese and hydrobromic acid
Mol ratio be 1: 2.1~3, the mass ratio of regulating dosage and 48% hydrobromic acid is 0.1~5: 100, and normal press control temperature is normal
Temperature~boiling temperature, when solution is clarified and is tested wherein without free bromine, stop reaction, filter, that is, obtain the bromine of cobalt or/and manganese
The compound aqueous solution, the aqueous solution can be directly used for allotment by the oxidized catalyst for preparing terephthalic acid (TPA) of paraxylene.
2. the preparation method of a kind of cobalt according to claim 1 or/and manganese bromide, it is characterised in that cobalt or/and manganese
Carbonate, hydroxide, oxide are by Co2+、Mn2+、Co3+、Mn4+As from molecular compound or mixture, depositing substantially
It is cobalt carbonate, basic cobaltous carbonate, manganese carbonate, basic carbonate manganese, cobalt carbonate manganese, basic cobaltous carbonate manganese, cobalt hydroxide in form
(II), cobalt hydroxide (III), manganous hydroxide (II), manganous hydroxide (IV), cobalt hydroxide (II) manganese (II), cobalt hydroxide (III) manganese
(IV), cobalt oxide (II), cobalt sesquioxide (III), cobaltosic oxide (II, III), manganese oxide (II), manganese dioxide (IV), oxidation
Cobalt manganese, cobalt oxide (III) manganese (IV).
3. the preparation method of a kind of cobalt according to claim 1 or/and manganese bromide, it is characterised in that used regulation
Agent is formaldehyde, acetaldehyde, formic acid, phenol, hydrazine hydrate, ascorbic acid, oxalic acid, propionic acid, glucose, fructose.
4. the preparation method of a kind of cobalt or/and manganese bromide according to claim 1 and 4, it is characterised in that add regulation
1 kind be at least added thereto during agent, 4 kinds be at most added thereto, can directly or be made the aqueous solution addition.
5. the preparation method of a kind of cobalt according to claim 1 or/and manganese bromide, it is characterised in that add during normal pressure and temperature
Enter hydrobromic acid, conditioning agent is added in the range of normal temperature to boiling temperature.
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Effective date of registration: 20220520 Address after: 312369 No. 15, Weiwu Road, Hangzhou Bay Economic and Technological Development Zone, Shangyu, Shaoxing City, Zhejiang Province Patentee after: ZHEJIANG SHANGYU LIXING CHEMICAL CO.,LTD. Address before: 312369 No. 15 Wei five road, Hangzhou Bay Economic and Technological Development Zone, Shangyu District, Shaoxing, Zhejiang Patentee before: ZHEJIANG SHANGYU LIXING CHEMICAL CO.,LTD. Patentee before: JINAN ZHAOHUI TECHNOLOGY Co.,Ltd. |
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Address after: 312369 No. 15, Weiwu Road, Hangzhou Bay Economic and Technological Development Zone, Shangyu, Shaoxing City, Zhejiang Province Patentee after: Zhejiang Lixing Technology Co.,Ltd. Address before: 312369 No. 15, Weiwu Road, Hangzhou Bay Economic and Technological Development Zone, Shangyu, Shaoxing City, Zhejiang Province Patentee before: ZHEJIANG SHANGYU LIXING CHEMICAL CO.,LTD. |
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