CN102597278B - 从复合矿中选择性沥滤回收矿物 - Google Patents
从复合矿中选择性沥滤回收矿物 Download PDFInfo
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- CN102597278B CN102597278B CN201080047176.2A CN201080047176A CN102597278B CN 102597278 B CN102597278 B CN 102597278B CN 201080047176 A CN201080047176 A CN 201080047176A CN 102597278 B CN102597278 B CN 102597278B
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- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 14
- 239000011707 mineral Substances 0.000 title claims abstract description 14
- 238000011084 recovery Methods 0.000 title abstract description 6
- 239000002131 composite material Substances 0.000 title 1
- 238000002386 leaching Methods 0.000 claims abstract description 53
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011575 calcium Substances 0.000 claims abstract description 20
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000011777 magnesium Substances 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- -1 ferric fluoborate Chemical compound 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 2
- 239000011572 manganese Substances 0.000 abstract description 19
- 229910052748 manganese Inorganic materials 0.000 abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 9
- 229910052745 lead Inorganic materials 0.000 abstract description 5
- 238000005065 mining Methods 0.000 abstract description 4
- 239000013528 metallic particle Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011066 ex-situ storage Methods 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 6
- 238000011065 in-situ storage Methods 0.000 abstract 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 3
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 230000035699 permeability Effects 0.000 abstract 1
- 239000011435 rock Substances 0.000 abstract 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 abstract 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 239000000126 substance Substances 0.000 description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 239000011133 lead Substances 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 229910001748 carbonate mineral Inorganic materials 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052569 sulfide mineral Inorganic materials 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 239000001639 calcium acetate Substances 0.000 description 2
- 235000011092 calcium acetate Nutrition 0.000 description 2
- 229960005147 calcium acetate Drugs 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
-
- 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
- C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
-
- 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining 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
- C22B47/00—Obtaining manganese
-
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
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- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Ocean & Marine Engineering (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
可渗透主体、经粉碎的矿、浓缩物或矿山排放尾矿中的钙(Ca)、锰(Mn)和镁(Mg)的碳酸盐以及铅(Pb)和锌(Zn)的硫化物矿物为选择性溶液，其用选定的酸例如醋酸开采(原位或异位)以提取Ca、Mn和Mg，然后通过多价态氧化盐例如铁盐来依次提取Pb和Zn。对于原位沥滤，已确定压力、温度、目标深度和浸出液浓度之间的相互关系，这样，碳酸盐沥滤能够以防止二氧化碳气体(CO2)排放从而堵塞主岩渗透性途径避免进一步沥滤的方式进行。这需要控制步骤中醋酸沥滤的速率，在所述步骤中，可用溶液溶解所得的排放的CO2。随后在碳酸盐耗尽的主体上进行硫化物沥滤。两种所得浸出液经化学处理以选择性回收提取的矿物作为增值的工业准制品。原位方法在制备锂离子电池需要的高纯度锰制品方面特别有利，因为其能够防止制品中出现非常细的金属颗粒，这可在常规开采过程中发生。或者，原位碳酸盐回收步骤可单独采用；全部以环境友好的方式进行。
Description
技术领域
本发明涉及一种矿物回收方法，其采用目标选择性原位或异位沥滤(leach)以回收矿物，其中某些矿物作为碳酸盐存在，而其它作为硫化物出现，并且在前者的情形中，从可渗透主体中回收。通过两个连续的步骤从主体中回收矿物：(1)用例如稀醋酸沥滤提取钙、锰、镁和相关的碳酸盐矿物，然后(2)通过用例如铁盐再次沥滤主体来提取铅、锌和相关的硫化物矿物。在(1)的过程中，根据地下条件调节醋酸的强度，以防止产生过量的CO2气体并避免从而阻断岩床渗透性途径、阻止酸的传递用于后续的矿物消解。浸出剂(leachant)浓度为目标温度和气压(深度)的函数。异位(ex situ)目标不需要调节压力和温度。可能需要使浸出剂再循环以完全提取主体中目标矿物的总量。然后将碳酸盐矿物耗尽的主体用例如铁盐在步骤(2)中再沥滤，以回收其余下的Pb、Zn和相关的硫化物矿物。步骤(1)和(2)的浸出液(leachate)分别经化学处理以选择性地回收其溶解的组分，以获得可以销售的高价值工业制品。本技术在回收锰用于锂离子电池方面具有特定的优势，因为其防止了锰制品中细金属颗粒的形成，这在常规的采矿回收中会发生并因此潜在地令使用了它的电池短路。
背景技术
钙的主要传统工业用途是其碳酸盐形式(CaCO3)，其作为填料用于纸和橡胶。最近，其用途已上升作为填料用于塑料和油漆，其形式为亚纳米范围内越来越小的颗粒，以为其主体提供改进的特性，所述特性由钙物质减少的尺寸所导致。在某些情况下，对主体的改进已足够明显地保证钙物质价格的显著增加。对于用作填料的用途，买方主要关注钙物质的粒径、均匀性和填充密度，这些是性能的主要控制项目。人们还广泛采用钙作为土壤补充剂或肥料，以及在较小程度上用在药物中。
钙主要作为碳酸钙(称为石灰石)存在，或者以钙镁碳酸盐(称为白云石)的形式存在。两者通常为尺寸庞大的海洋沉积物。它们通常是露天进行开采，并且通过机械或化学方法选择性回收各成分。
锰矿的主要形式是二氧化锰(软锰矿)，MnO2。沉积物通常作为矿脉通过地下开采来回收。锰的主要用途是作为钢合金。其以大块回收，被粉碎至可用的尺寸，并与铁矿一起进料到高炉中以炼钢。这种方式不需要非常高的价格。其还可有一些化学用途。然而最近，伴随着价格的上涨，锰作为可充电电池的主成分越来越重要，所述可充电电池用于越来越多的工业、电子和电力设备，延伸至汽车电池。所需的电池形式是称为LMD的锰酸锂(lithiatedmanganese dioxide)。
软锰矿可以并且正用于此目的。将其开采、粉碎、溶于溶液中并经电化学回收为电解质二氧化锰(EMD)。然后，必须将其再粉碎并用锂化合物在高温下进行处理以形成LMD。这种方法是复杂且昂贵的过程。此外，已发现所得的LMD常常包含显然可导致由其制成的电池短路的微小金属颗粒。这些颗粒不能通过电磁方式除去，它们的存在也不能通过扫描电子显微镜(SEM)完全确定。目前解决该问题的方法是测试所有采用LMD的新电池并弃置那些发现有故障的电池。或者，可采用多个处理步骤以纯化MnO2作为前体物质。
我们惊讶地发现，作为碳酸盐矿脉的锰通过原位沥滤开采(ISLM)可有利地回收为生产高纯度LMD的浸出液，所述矿脉一般不能经济地开采，但存在于具有足够渗透性的地质中。这种溶液无金属颗粒，因为其不涉及常规的开采或粉碎，并因此不具有导致采用其的电池中出现电气短路问题的可能性。此外，碳酸钙和通常以这种设置出现的锰的存在也为其与锰的回收提供机会，从而进一步提高该方法的经济性。
专利检索公开了两种方法，一种由Geisler在美国专利5,523,066中提出，另一种由Turner在美国专利6,726,828中提出，其描述了采用醋酸和过氧化氢(用于硫化物的氧化)的混合物的ISLM的用途，以从可渗透地质主体中回收Ca、Mn、Pb和Zn作为组合浸出液。两种方法均依赖单独的氧化剂(即过氧化物)并且没有采取预防措施防范流动通道的逐步地下阻塞，该阻塞会阻止进一步的沥滤。这些方法都没有提示本文提出的方法。
另一专利指出(美国专利号4,500,398)用氟硅酸和氧化剂处理硫化物矿物，以释放金属价值(metal values)。
发明内容
本发明包括从具有金属碳酸盐和金属硫化物成分的矿中沥滤矿物价值的方法，其包括：用选定的酸浸出剂沥滤碳酸盐以溶解碳酸盐但不溶解硫化物，选定其速率以避免原位释放CO2气体，随后用氧化性浸出剂沥滤硫化物以溶解硫化物，然后从各浸出液中选择性地回收需要的金属价值。
从矿中获得的微粒可包括经粉碎的矿、矿浓缩物和矿山排放尾矿(mine dischargetailings)。
可选择不同的酸用于步骤a)的浸出剂，例如醋酸、甲酸、硝酸、硫酸、盐酸、氟硅酸和氟硼酸。
对于步骤b)，氧化性浸出剂包括选定的具有多价态并处于最高价态的金属的盐。
优选用于步骤b)氧化性浸出剂的盐包括氟硅酸铁、氟硼酸铁、硫酸铁和硝酸铁。
如果在步骤a)和b)之间***冲洗步骤，发现步骤b)变得更高效。
在广阔的方面，本发明包括矿体重碳酸盐沥滤(独立于硫化物沥滤)，该沥滤被控制至一沥滤速率，避免CO2气体在矿体中释放并保持矿的渗透性。通过调节浸出剂的压力、温度和酸浓度来控制沥滤速率，以提供低于开始释放CO2气体的沥滤速率。发现这可保持矿体的渗透性。可通过将溶于浸出液中的气体与地下采用的温度和压力条件下的最大溶解度相比较来找到CO2气体释放的阀值。
具体实施方式
在一个实施方案中，采用本领域技术人员熟知的两阶段ISL开采技术，从含有Ca、Mn和Pb的碳酸盐主体中回收Ca、Mn和Pb(以硫化物形式)。开始时通过采用稀醋酸沥滤回收Ca和Mn。该步骤完成后，用水冲洗正被沥滤的井场(wellfield)，以除去醋酸的所有痕迹，并将沉淀用氟硅酸铁溶液再沥滤以回收余下的Pb。两个序贯的沥滤步骤的化学反应在下面描述为(A)和(B)。
初始沥滤(A)
(A)碳酸盐沥滤反应
碳酸钙和碳酸锰与醋酸浸出剂反应，形成可溶的醋酸钙和醋酸锰。
CaCO3+2CH3COOH＝(CH3COO)2Ca+CO2+H2O
MnCO3+2CH3COOH＝(CH3COO)2Mn+CO2+H2O
(A)钙回收反应
采用硫酸选择性地从浸出液中沉淀钙，所述浸出液由醋酸钙和醋酸锰的混合物组成。这是可能的，因为硫酸钙不溶而硫酸锰为可溶性化合物。该步骤还能使浸出剂(醋酸)再生。随后通过使硫酸钙与碳酸铵反应，将硫酸钙转化成沉淀的碳酸钙。在该方法过程中，硫酸铵作为高纯度可出售副制品产生。
(CH3COO)2Ca+H2SO4＝CaSO4+2CH3COOH
CaSO4+(NH4)2CO3＝CaCO3+(NH4)2SO4
(A)锰回收反应
去除了钙的浸出液主要由醋酸锰组成，将其用高锰酸钾处理以选择性地将锰氧化成二氧化锰。由此获得的二氧化锰可用作前体物质，通过将其与碳酸锂在较高温度下加热来制备锰酸锂。锰还可通过溶剂提取选择性地回收。
3Mn2++2KMnO4+2H2O→5MnO2+4H++2K+
将再生的浸出剂注入地下，形成闭环操作。
后续沥滤(B)
(B)用氟硅酸铁浸出剂进行的铅沥滤反应
Fe2(SiF6)3+PbS->2FeSiF6+PbSiF6+S
在优选的方面，通过电解沉积(electrowinning)从所得浸出液中回收铅作为高纯度铅金属。电解沉积方法通过在阳极处将氟硅酸亚铁氧化为氟硅酸铁，使原浸出液再生，并回收氟硅酸铁用于循环。
Claims (5)
1.一种从可渗透矿体或从获自矿的微粒中沥滤矿物价值的方法，所述矿具有碳酸金属盐和金属硫化物成分，所述方法包括：
a）首先用含水浸出剂从矿中沥滤所述碳酸金属盐，并回收金属，所述金属包括锰、钙和镁，同时，对于原位矿，控制所述沥滤的速率以避免CO2气体在矿体中的释放，所述含水浸出剂包括酸，所述酸选自由以下物质组成的组：醋酸、甲酸、硝酸、硫酸、盐酸、氟硼酸和氟硅酸；和
b）用含水浸出剂从矿中沥滤所述金属硫化物，用于将所述硫化物氧化成可溶的氧化产物，并回收金属，所述金属主要包括铅和锌，所述含水浸出剂包括至少一种铁盐，所述铁盐选自由以下物质组成的组：氟硅酸铁、氟硼酸铁、硫酸铁和硝酸铁。
2.根据权利要求1所述的方法，其中所述沥滤步骤在可渗透矿体中原位进行。
3.根据权利要求2所述的方法，其中在步骤a）和b）之间冲洗经沥滤的原位地层，以除去步骤a）留下的酸浸出剂。
4.根据权利要求1所述的方法，其中所述沥滤步骤在从矿中获得的微粒上进行，所述从矿中获得的微粒选自由以下物质组成的组：经粉碎的矿、矿浓缩物和矿山排放尾矿。
5.根据权利要求1所述的方法，其中所述酸是醋酸。
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| CN103757247A (zh) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | 碳酸锰矿的浸出方法 |
| US10815138B1 (en) * | 2018-07-06 | 2020-10-27 | Geokinetics, Llc | Treatment of acid mine drainage by hydrides, and formation of zero valent iron nanoparticles |
| CN108842066A (zh) * | 2018-08-24 | 2018-11-20 | 淄博淦达环保科技有限公司 | 一种铅的浸取液及浸出工艺 |
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| CN111961848A (zh) * | 2020-07-21 | 2020-11-20 | 江西离子型稀土工程技术研究有限公司 | 基于原地浸矿工艺获得高浓度浸出液的稀土开采方法 |
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