TW201435091A - 用於從含錳材料之氧化物回收價値金屬之方法 - Google Patents
用於從含錳材料之氧化物回收價値金屬之方法 Download PDFInfo
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- TW201435091A TW201435091A TW102138049A TW102138049A TW201435091A TW 201435091 A TW201435091 A TW 201435091A TW 102138049 A TW102138049 A TW 102138049A TW 102138049 A TW102138049 A TW 102138049A TW 201435091 A TW201435091 A TW 201435091A
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- manganese
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- 239000011572 manganese Substances 0.000 title claims abstract description 53
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 52
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 title claims description 33
- 239000002184 metal Substances 0.000 title claims description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002386 leaching Methods 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005065 mining Methods 0.000 claims abstract description 5
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 4
- 150000002739 metals Chemical class 0.000 claims description 18
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- 229910052793 cadmium Inorganic materials 0.000 claims description 11
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052787 antimony Inorganic materials 0.000 claims description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000011133 lead Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 4
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- 239000003337 fertilizer Substances 0.000 claims description 3
- 201000008827 tuberculosis Diseases 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 7
- 238000001556 precipitation Methods 0.000 claims 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 2
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 claims 2
- 235000014413 iron hydroxide Nutrition 0.000 claims 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims 2
- 238000000227 grinding Methods 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 22
- 229910021529 ammonia Inorganic materials 0.000 abstract description 10
- 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 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052758 niobium Inorganic materials 0.000 abstract description 2
- 239000010955 niobium Substances 0.000 abstract description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- -1 zinc-carbon Chemical compound 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- BPKGOZPBGXJDEP-UHFFFAOYSA-N [C].[Zn] Chemical compound [C].[Zn] BPKGOZPBGXJDEP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229910001655 manganese mineral Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
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- C22B47/00—Obtaining manganese
- C22B47/0018—Treating ocean floor nodules
- C22B47/0045—Treating ocean floor nodules by wet processes
- C22B47/0054—Treating ocean floor nodules by wet processes leaching processes
- C22B47/0063—Treating ocean floor nodules by wet processes leaching processes with acids or salt solutions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
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- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
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- C22B15/0089—Treating solutions by chemical methods
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- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/065—Nitric acids or salts thereof
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- 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
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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Abstract
本發明揭示一種用於處理含錳材料，諸如藉由海底採礦回收之結核的改良方法，其包括使該等材料與氨反應，及用無機酸瀝濾；及用於從該等結核回收有價值成分，尤其錳、鈷、鎳、鐵、銅、鈦、釩、鈰及鉬之方法。本發明亦揭示一種用於生產硝酸鹽產物之方法。
Description
本發明係關於一種藉由利用氨氣處理含錳材料，諸如氧化物、碳酸鹽及礦石之方法。本發明非常適合於處理藉由海底採礦回收之多金屬含錳結核，且特定言之，用於從該等結核回收有價值成分，尤其錳、鈷、鎳、銅及鐵之方法。
多金屬或錳結核由核心周圍之鐵及錳氫氧化物之同心層形成之岩石結核。
在海底之海底結核其組成中包括錳(Mn)，且通常含有Ni、Co、Cu、Zn及Fe，具有少量鈦、釩、鉬及鈰。另外常常存在一或多種以下金屬：鎂、鋁、鈣、鎘、鉀、鈉、鋯、鈦、鉛、磷及鋇。深海結核一般含有約28% Mn、約10% FeO、約1% Cu及約1.2% Ni。
錳結核中大多數所需之有價值金屬與不溶性氧化錳，諸如MnO2密切相關。結核中所含之少於10%之錳為酸溶性的。因此，必需由適合還原劑還原MnO2作為第一步驟，以回收金屬成分。歷史上，SO2已用於此目的，且一氧化碳(CO)已用於銅回收方法中。然而，該等先前技術方法常常無法回收適合的錳產物且僅能夠回收約80%至約92%之初級價值金
屬，且常常產生大量廢物，其可能包括未完全移出之金屬組分。
由本發明處理之含錳材料可不僅包括礦石或深海結核，而且包括帶有氧化錳之電池，諸如鋅-碳、鹼性及鋰(LMO或LiMn2O4)電池，或呈任何形式之其他含錳礦物或材料。
本發明為一種藉由用氨處理含錳材料而從包括深海錳結核之海底含錳材料回收錳及其他價值金屬(「有價金屬(pay metal)」)(若存在)之方法。氣態NH3與礦石反應7MnO2(s)+2NH3(g)->7MnO(s)+3H2O(l)+2NO2(g)
釋放截留之所需有價值金屬。一噸NH3比8噸SO2更有效。
用氨氣還原MnO2之後，可使用任何無機酸從起始含錳材料瀝濾並回收錳及其他金屬。硝酸為較佳瀝濾材料，因為一些硝酸在氨反應中由H2O及NO2形成。
本發明尤其適用於製造硝酸鹽產物，諸如炸藥、肥料或其他硝酸鹽。
本發明之主要目標為提供一種從帶有錳之材料，包括從海底錳結核回收錳之改良方法。
本發明之另一目標為提供一種用於從帶有錳之材料回收價值金屬之有效方法，該等價值金屬包括(若存在)任何鎳、鈷、銅、鎂、鋁、鐵、鈣、鎘、鉀、鈉、鋯、鈦、鋅、鉛、鈰、鉬、磷、鋇及釩。
本發明之另一目標為提供一種從海底含錳材料，包括深海錳
結核回收其他價值金屬之有效方法。
本發明之另一目標為生產硝酸鹽產物。
藉由參考以下【實施方式】及隨附圖式，前述及其他目標將變得更顯而易見，在圖式中：唯一圖式為本發明方法之一個較佳具體實例的圖解流程圖。
現參考圖式，該方法以諸如深海錳結核之含錳材料10開始，其可獲自海洋、海或其他水體。有時該等結核存在於大湖中。深海結核含有超過20%之錳，通常為約28%。
除錳以外，該等深海結核可含有至少一種以下金屬：鎳、鈷、銅、鎂、鋁、鐵、鈣、鎘、鉀、鈉、鋯、鈦、鋅、鈰、鉬、磷、鋇、鉛及釩。本發明方法包括許多此等價值金屬之有效瀝濾及回收。
視情況，將結核或其他含錳材料壓碎或研磨以為稍後反應增加表面積。有利地，藉由任何適宜方法，諸如洗滌，較佳用水洗滌來移除結核中之任何氯化物。可在任何壓碎之前、期間或之後，但較佳在壓碎之後進行此步驟。
在12中結核與氨在高溫下反應。氣態NH3與氧化錳礦石根據以下反應式反應：7MnO2+2NH3->7MnO+3H2O+2NO2
在步驟14中NH3與MnO2反應形成MnO、水及NO2且從結核釋放其他金屬。可以氣體形式移除NO2或使其反應形成硝酸。
用氨還原MnO2之後，在瀝濾步驟16中可使用任何無機酸從起始含錳材料瀝濾並回收錳及其他金屬鹽18。硝酸為較佳瀝濾材料，因為一些硝酸在氨反應中形成。
在20中從瀝濾步驟中形成之金屬鹽沈澱並回收有價金屬。在瀝濾之後，隨後將溶液之pH值改變至約2.2-2.3以使水合氧化鐵(FeOOH．H2O)沈澱。藉由過濾溶液來移出沈澱之價值鐵。可依各種方式達成此pH值改變，包括添加氨或諸如Mg(OH)2或Ca(OH)2之鹼土金屬氫氧化物、諸如MgO或CaO之鹼土金屬氧化物或諸如Mg(CO3)2或Ca(CO3)2之鹼土金屬碳酸鹽至溶液中。
亦從溶液移出存在於溶液中之任何銅、鉛、鎘及鋅。一旦處於溶液中，價值金屬即可以氧化物或硫化物形式沈澱。較佳地，將溶液調節至低pH值，將硫化氫(H2S)或NaHS引入溶液中以使存在於溶液中之任何銅、鉛、鎘及鋅以硫化物形式沈澱，且藉由過濾移除沈澱之價值金屬。
隨後升高溶液之pH值，再次添加硫化氫或NaHS至溶液中以使鈷及鎳以硫化物形式沈澱。亦可在此步驟中使鋁及一些剩餘鋅以硫化物形式沈澱。
較佳地，隨後將溶液之pH值升至約9以在22中沈澱並回收錳氧化物及氫氧化物。過濾殘餘物之後，剩餘溶液為硝酸鹽產物26，其可用作肥料，或作為在該方法中再使用之硝酸鹽的來源。
或者，含錳材料可來源於工業廢物或化學處理，或來自土地採礦操作之礦石，該等礦石含有由處理該等礦石而產生之錳或含錳材料。
含錳材料可藉由預先化學或冶金處理獲自任何水體之多金屬結核來獲得。
可加熱NH3或含錳材料或兩者來增強反應。此外，可在該方法中使用液態氨，但氣態氨較佳。
由前文顯而易見，吾人已發明一種改良方法，該方法用於處理含錳材料，其包括處理藉由海底採礦回收之海底錳結核，以使該材料與氨有效反應，從而產生氧化錳產物且釋放任何有價值金屬；及用於有效回收結核中所含之價值金屬。吾人亦已發明一種從帶有錳之材料回收錳，包括從帶有錳之材料回收其他價值金屬之改良方法，該等價值金屬包括(若存在)鎳、鈷、銅、鎂、鋁、鐵、鈣、鎘、鉀、鈉、鋯、鈦、鋅、鉛、鈰、鉬、磷、鋇及釩；以及從包括深海錳結核之海底含錳材料回收價值金屬，及用於生產硝酸鹽產物之有效方法。
應瞭解，以上描述及特定具體實例僅說明本發明之最佳模式及其原理，且在不背離本發明之精神及範疇的情況下可由熟習此項技術者對裝置作出各種修改及添加。
Claims (18)
- 一種從含錳材料回收價值金屬之方法，其包含以下步驟：a.獲得亦含有其他金屬之含錳材料；b.使該等含錳材料與NH3反應形成MnO且釋放該等其他金屬；c.用無機酸瀝濾該等反應之材料，形成金屬鹽；d.從該等金屬鹽沈澱並回收有價金屬；及e.沈澱並回收錳氧化物及氫氧化物。
- 根據申請專利範圍第1項之方法，其中該等含錳材料為獲自任何水體之多金屬結核。
- 根據申請專利範圍第2項之方法，其中該等含錳材料為深海錳結核。
- 根據申請專利範圍第1項之方法，其中該等含錳材料為藉由海底採礦回收之含錳結核。
- 根據申請專利範圍第1項之方法，其中該等含錳材料係藉由化學或冶金處理獲自任何水體之多金屬結核而獲得。
- 根據申請專利範圍第5項之方法，其進一步包含壓碎或研磨該等結核。
- 根據申請專利範圍第1項之方法，其進一步包含藉由洗滌該等含錳材料而從該等材料移除氯化物。
- 根據申請專利範圍第1項之方法，其中步驟b在高溫下進行。
- 根據申請專利範圍第1項之方法，其中該等含錳材料亦含有由以下組成之群組中的至少一種金屬：鎳、鈷、鐵、銅、鎂、鋁、鈣、鎘、鉀、鈉、鋯、鈦、鋅、鉛、鈰、鉬、磷、鋇及釩，該方法進一步包含：a.添加鹼土金屬氧化物、氫氧化物或碳酸鹽至溶液中以使任何鐵以 氫氧化鐵形式沈澱；b.從該溶液過濾殘餘物；c.使存在於該溶液中之任何銅、鉛及鎘以硫化物形式沈澱；及d.使任何鈷及鎳硫化物沈澱，從而留下鹼土金屬硝酸鹽。
- 根據申請專利範圍第1項之方法，其中任何銅、鉛或鎘從溶液中沈澱係藉由將該溶液調節至低pH值且將H2S或NaHS引入該溶液中且形成硫化物來實現。
- 根據申請專利範圍第1項之方法，其中鈷及鎳硫化物之沈澱係藉由升高溶液之pH值且向其中引入額外H2S或NaHS來進行。
- 根據申請專利範圍第1項之方法，其中錳氧化物及氫氧化物之沈澱係藉由將溶液之pH值升至約9來進行。
- 一種硝酸鹽產物，其係根據申請專利範圍第1項之方法生產。
- 一種可再循環硝酸鹽，其係根據申請專利範圍第1項之方法生產。
- 一種硝酸鹽肥料產物，其係根據申請專利範圍第1項之方法生產。
- 根據申請專利範圍第1項之方法，其中該等含錳材料亦含有鐵，該方法進一步包含：a.添加鹼土金屬氧化物、氫氧化物或碳酸鹽至溶液中以使氫氧化鐵沈澱；及b.從該溶液過濾殘餘物。
- 根據申請專利範圍第1項之方法，其中該等含錳材料亦含有銅、鉛及鎘，該方法進一步包含使存在於溶液中之銅、鉛及鎘以硫化物形式沈澱。
- 根據申請專利範圍第1項之方法，其中該等含錳材料亦含有鈷及鎳，該方法進一步包含使鈷及鎳硫化物沈澱，從而留下鹼土金屬硝酸鹽之步驟。
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| CN104263955B (zh) * | 2014-10-09 | 2017-02-15 | 中国有色集团（广西）平桂飞碟股份有限公司 | 一种钨冶炼除钼渣中钼和铜的回收方法 |
| CN105779784B (zh) * | 2016-03-18 | 2017-02-08 | 广州有色金属研究院 | 一种常温常压下从被锰包裹金银矿中浸出金银的方法 |
| CN105755282A (zh) * | 2016-05-14 | 2016-07-13 | 北京矿冶研究总院 | 一种同时处理海底钴锰氧化物资源与多金属硫化物的方法 |
| CN106282535B (zh) * | 2016-08-24 | 2018-08-14 | 北京矿冶研究总院 | 一种钴锰多金属氧化矿选冶联合回收锰的方法 |
| CN111286605B (zh) * | 2018-12-06 | 2021-09-03 | 深圳市金航深海矿产开发集团有限公司 | 一种海底多金属结核有价金属回收以及联产ncm前驱体的方法 |
| CN111455171B (zh) * | 2019-01-22 | 2021-10-08 | 深圳市金航深海矿产开发集团有限公司 | 一种海底多金属结核提取有价金属并联产锂电正极材料前驱体及掺钛正极材料的方法 |
| CN110306056B (zh) * | 2019-06-20 | 2020-09-22 | 厦门大学 | 一种从锰矿渣中提取高纯度锰的方法 |
| WO2022221653A1 (en) * | 2021-04-15 | 2022-10-20 | University Of Miami | Methods for oxidizing a nitrogen oxide to nitrate |
| CN115842186A (zh) * | 2022-11-22 | 2023-03-24 | 广东邦普循环科技有限公司 | 一种废锂电池的回收处理方法 |
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| JP6182216B2 (ja) | 2017-08-16 |
| RU2015108064A (ru) | 2016-12-20 |
| CN104603858A (zh) | 2015-05-06 |
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