CN101688267A - 从矿石中回收金属有价物的方法 - Google Patents
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 21
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- 238000001556 precipitation Methods 0.000 claims abstract description 14
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- 239000011572 manganese Substances 0.000 claims abstract description 6
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
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- 239000011651 chromium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
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- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
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- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 239000004317 sodium nitrate Substances 0.000 description 1
- 229940001516 sodium nitrate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0438—Nitric acids or salts thereof
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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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
- C22B3/06—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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- 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
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Abstract
一种用于加工含镍的腐泥土和褐铁矿矿石以回收其中所含的有价值矿物的改进方法，所述方法包括：用硝酸浸提所述矿石以形成浆液；通过沉淀分离铁有价物，从而移出铁有价物；形成液体/固体残余物，其中镍、钴和镁在溶液中，而锰和铝是氧化物形式的固体残余物；进行液固分离，并且移除固体；和从液体－金属浓缩物中回收镍、钴和锰。回收浸出物，并且将浸出物中的硝酸再循环。
Description
发明领域
本发明涉及用于加工含金属的矿石，特别是用于回收镍和其它金属的方法，并且更具体地涉及用于回收腐泥土和褐铁矿矿石中的铁、镍、钴、镁、铝、铬和其它有价值的组分的方法。
发明背景
即使当从相同的采矿地点取得时，矿石的组成也极大地不同。褐铁矿和腐泥土矿石通常含有铁、镍、钴、镁、锰、铬和/或铝。已知的用于处理高镁腐泥土矿石或高铁褐铁矿型矿石的方法通常是高成本方法，而本发明是能够处理全部范围的矿石，包括过渡矿石(transitional ore)的改进的成本有效方法。如本文中使用的，术语“矿石”意在表示氧化物和硫化物矿石、冶金废料以及含金属的物质，应理解为金属可以与其它元素结合。
发明概述
本发明是用于加工含镍的腐泥土和褐铁矿矿石以回收其中所含的有价值矿物的方法。本方法作用于任何氧化物或硫化物矿石、冶金废料和含金属的物质，应理解为在这样的物质中，金属可以与其它元素结合。如果需要，可以将矿石研磨或粉碎，或可以与其它含金属的物质混合。用硝酸浸提矿石，然后通过热水解或pH平衡来沉淀铁。任选地，通过回收沉淀或结晶回收来回收铝。将氢氧化镁加入到溶液中，从而使得pH平衡以形成以沉淀物形式回收的镍氢氧化物和钴氢氧化物。
有利地，用于浸提的硝酸通过在美国专利6,264,909中描述的方法提供，该美国专利名称为硝酸制备和再循环(Nitric Acid Production andRecycle)，授权于2001年7月24日，并且通过引用结合在此。
本发明特别可用于回收镍、钴、铝、铁、铬、锰和镁。
发明目的
本发明的主要目的是提供从腐泥土和褐铁矿矿石中回收镍和钴的改进方法。
本发明的另一个目的是提供从矿石、冶金废料和其它含金属的物质中回收金属有价物(values)的方法。
本发明的另一个目的是提供制备硝酸盐，比如硝酸铵、硝酸钠、硝酸钾、硝酸钙或硝酸镁的方法。
附图简述
通过参照以下详细描述和后附附图，前述和其它目的将变得更显而易见，在附图中：
图1是本发明方法以其最基本形式表示的示意性流程图。
详细描述
现在参照附图，图1显示基本形式的本发明方法。本方法从矿山腐泥土或褐铁矿矿石10或其它含金属的物质的熔化(run)开始。
用HNO3浸提矿石充分的时间以形成浆液。尽管可以将矿石粉碎，但是这样做不是必须的，因为硝酸将有效地起作用，而与矿石颗粒的尺寸无关。在低于160C，通常约70C至130C，但是优选约120C的温度，用硝酸20将矿石浸提18矿石约30分钟至约3小时的时间。所述的酸可以是10至90％(重量％)的硝酸溶液，但是优选为约30至67％硝酸，并且最适宜为约45至55％酸溶液。
用于浸提工艺的硝酸20优选由根据以上引用的美国专利6,264,909的硝酸再循环方法得到。
通过加热22将浸提溶液的温度升高至约125至200C范围内的温度，优选至约165C，以形成液体/固体残余物，其中镍、钴和镁在溶液中，而铁、锰和铝是氧化物形式的固体残余物。加热在封闭体中进行，从该封闭体回收逸出气体(主要为NOx)用于进一步处理。浸提和加热步骤可以在同一容器中进行，或在分离的容器中进行。
在22处通过热水解或溶液的pH平衡来发生沉淀，使铁以Fe2O3的形式沉淀。
浆液经历固液分离，脉石物质以固体的形式移除。将剩余的液体溶液加热，通过热水解或溶液的pH平衡来发生沉淀，使铁以Fe2O3的形式沉淀。
通过液固分离(过滤)将Fe2O3以固体的形式移除，从而留下含有铝、镍和钴有价物的溶液。
在24处通过沉淀将铝移除。备选地，铝以硝酸盐形式的结晶使得可以通过过滤或通过离心来分离。在任一种情况下，留下镍-钴溶液。
将Mg(OH)2与镍-钴溶液混合，然后其经历pH平衡(改变)以形成固体形式的Ni(OH)2和Co(OH)2，在26处将它们以沉淀物的形式移除(通过过滤)。还可以通过溶剂萃取，将镍和钴有价物从溶液中移除。
通常经过多次进行蒸发将滤液浓缩，直至剩余的Mg(NO3)2几乎为无水。然后在28处将硝酸镁热分解，以形成MgO、HNO3和NOx，并且将硝酸和氮氧化化再循环。所得到的MgO可以用在本发明方法中的其它地方。
采用在美国专利6,264,909中描述的硝酸再循环方法，在30处将含NOx的气体重新形成硝酸。
通过加入或移除硝酸，或通过向溶液中加入碱土金属来完成溶液pH的改变。
铁的沉淀通常在pH 2至3完成；
氧化铝的沉淀通常在pH 4-5完成；
镍的沉淀通常在pH 6-7完成；
锰的沉淀通常在pH 8-9完成；
MgO的沉淀通常在pH 10-11完成；
Ca的沉淀通常在pH 12-13完成。
沉淀物通过过滤移除，或可以通过其它已知方法如离心来分离。
在整个方法中的任何位置，在将硝酸或氮的氧化物移除的情况下，都可以将其再循环至硝酸再循环工序中以进一步使用。
本发明对象的成果总结
从前述内容中，显而易见的是，本发明人发明了一种从腐泥土和褐铁矿矿石中回收镍和钴的改进方法，所述方法还用于从矿石、冶金废物和其它含金属的物质中回收金属有价物，比至今可行的方法更经济。
应当理解，前述说明和具体实施方案仅仅为了示出本发明的最佳方式及其原理，并且本领域技术人员可以在不偏离本发明的精神和范围的情况下对设备进行各种修改和添加，因此应理解本发明的精神和范围仅由后附权利要求的范围限定。
Claims (8)
1.一种从含铁、镍、钴和铝的矿石中回收金属有价物的方法，所述方法包括：
a)用HNO3浸提所述矿石充分的时间以形成浆液；
b)使铁以Fe2O3的形式从所述浆液中沉淀；
c)使铝以Al2O3的形式沉淀，从而留下含镍和钴有价物的溶液；
d)将Mg(OH)2与所述镍-钴溶液混合，然后进行热水解、pH平衡(改变)或溶剂萃取，以形成固体形式的Ni(OH)2和Co(OH)2，并且将所述镍-钴有价物以沉淀物的形式移出；
e)从工艺中回收HNO3和NOx；和
f)将所述移出的含NOx的气体重新形成硝酸，用于进一步使用。
2.根据权利要求1所述的方法，其中所述浸提在70C至160C的温度进行约30分钟至约3小时的时间。
3.根据权利要求1所述的方法，其中在所述浸提中的所述硝酸是10至90％硝酸的溶液。
4.根据权利要求3所述的方法，其中在所述浸提中的所述硝酸是30至67％硝酸的溶液。
5.根据权利要求1所述的方法，其中所述浸提步骤之后加热至约125C至约200C的温度，以形成液体/固体残余物，其中所述镍、钴和镁有价物在溶液中，而所述铁、锰和铝有价物是氧化物形式的固体残余物。
6.根据权利要求1所述的方法，其中铁的沉淀通过热水解实现。
7.根据权利要求1所述的方法，其中铁的沉淀通过所述溶液的pH平衡实现。
8.根据权利要求1所述的方法，其中所述矿石在浸提之前被粉碎。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US92739107P | 2007-05-03 | 2007-05-03 | |
| US60/927,391 | 2007-05-03 | ||
| PCT/US2008/005600 WO2008137022A1 (en) | 2007-05-03 | 2008-05-01 | Method of recovering metal values from ores |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101688267A true CN101688267A (zh) | 2010-03-31 |
| CN101688267B CN101688267B (zh) | 2012-12-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2008800142927A Active CN101688267B (zh) | 2007-05-03 | 2008-05-01 | 从矿石中回收金属有价物的方法 |
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| Country | Link |
|---|---|
| US (1) | US8038767B2 (zh) |
| EP (1) | EP2171108A4 (zh) |
| CN (1) | CN101688267B (zh) |
| AU (1) | AU2008248196C1 (zh) |
| BR (1) | BRPI0810751A2 (zh) |
| CA (1) | CA2685369C (zh) |
| MY (1) | MY144463A (zh) |
| WO (1) | WO2008137022A1 (zh) |
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| CN104520454A (zh) * | 2012-08-09 | 2015-04-15 | 迪普格林工程有限公司 | 含锰材料的处理 |
| CN106636654A (zh) * | 2016-12-31 | 2017-05-10 | 山东飞源科技有限公司 | 从含氟电解熔盐中回收金属镍的方法 |
| CN114645140A (zh) * | 2022-04-02 | 2022-06-21 | 宁波容百新能源科技股份有限公司 | 一种制取镍中间品的方法 |
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| US8814980B2 (en) * | 2007-05-03 | 2014-08-26 | Drinkard Metalox, Inc | Method of recovering metal values from nickel-containing ores |
| AU2008253545B2 (en) | 2007-05-21 | 2012-04-12 | Orbite Aluminae Inc. | Processes for extracting aluminum and iron from aluminous ores |
| EP2686458A4 (en) | 2011-03-18 | 2015-04-15 | Orbite Aluminae Inc | METHODS FOR RECOVERING RARE EARTH ELEMENTS FROM ALUMINUM-CONTAINING MATERIALS |
| EP3141621A1 (en) | 2011-05-04 | 2017-03-15 | Orbite Aluminae Inc. | Processes for recovering rare earth elements from various ores |
| RU2013157943A (ru) | 2011-06-03 | 2015-07-20 | Орбит Элюминэ Инк. | Способ получения гематита |
| CA2848751C (en) | 2011-09-16 | 2020-04-21 | Orbite Aluminae Inc. | Processes for preparing alumina and various other products |
| BR112014016732A8 (pt) | 2012-01-10 | 2017-07-04 | Orbite Aluminae Inc | processos para tratar lama vermelha |
| MX360705B (es) * | 2012-01-31 | 2018-11-14 | Deepgreen Eng Pte Ltd | Tratamiento para materiales que contienen manganeso. |
| WO2013142957A1 (en) | 2012-03-29 | 2013-10-03 | Orbite Aluminae Inc. | Processes for treating fly ashes |
| MY175471A (en) | 2012-07-12 | 2020-06-29 | Orbite Tech Inc | Processes for preparing titanium oxide and various other products |
| JP2015535886A (ja) | 2012-09-26 | 2015-12-17 | オーバイト アルミナ インコーポレイテッドＯｒｂｉｔｅ Ａｌｕｍｉｎａｅ Ｉｎｃ． | 種々の材料のＨＣｌ浸出によるアルミナおよび塩化マグネシウムを調製するためのプロセス |
| AU2013325098B2 (en) * | 2012-09-28 | 2017-12-14 | Direct Nickel Pty Ltd | Method for the recovery of metals from nickel bearing ores and concentrates |
| US9284627B2 (en) * | 2012-10-23 | 2016-03-15 | Deepgreen Engineering, Pte. Ltd. | Process for recovering metal values from oxides of manganese-containing materials |
| CN105189357A (zh) | 2012-11-14 | 2015-12-23 | 奥佰特氧化铝有限公司 | 纯化铝离子的方法 |
| RU2583224C1 (ru) * | 2015-01-12 | 2016-05-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Сибирский государственный индустриальный университет" | Способ химического обогащения полиметаллических марганецсодержащих руд |
| CN107338357B (zh) * | 2017-07-07 | 2019-01-22 | 金川集团股份有限公司 | 一种低镍高铁合金粉的硝酸选择性浸出方法 |
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| US2746856A (en) | 1952-02-28 | 1956-05-22 | Bethlehem Steel Corp | Processes for treating materials containing nickel and iron |
| US3876748A (en) * | 1971-10-06 | 1975-04-08 | Int Nickel Co | Extraction of metals from iron oxide materials |
| US3888748A (en) * | 1972-06-28 | 1975-06-10 | Du Pont | Recovery of metal values from ore concentrates |
| FR2259913B1 (zh) * | 1974-02-05 | 1976-11-26 | Nickel Le | |
| US3989886A (en) * | 1975-06-05 | 1976-11-02 | Taylor Industries, Inc. | Wiring duct cover mounting assembly |
| US4261737A (en) * | 1979-10-31 | 1981-04-14 | Uop Inc. | Recovery of cobalt values |
| US4312841A (en) * | 1980-06-25 | 1982-01-26 | Uop Inc. | Enhanced hydrometallurgical recovery of cobalt and nickel from laterites |
| US4670051A (en) * | 1985-03-19 | 1987-06-02 | Hydrochem Developments Ltd. | Oxidation process for releasing metal values in which nitric acid is regenerated in situ |
| US6264909B1 (en) * | 1996-02-29 | 2001-07-24 | Drinkard Metalox, Inc. | Nitric acid production and recycle |
| CN100402679C (zh) * | 2004-08-02 | 2008-07-16 | 斯凯资源有限公司 | 从红土矿中回收镍和钴的方法 |
| AU2006236085C1 (en) * | 2005-11-28 | 2014-02-27 | Vale S.A. | Process for extraction of nickel, cobalt, and other base metals from laterite ores by using heap leaching and product containing nickel, cobalt, and other metals from laterite ores |
| EA200971016A1 (ru) * | 2007-05-02 | 2010-04-30 | Дринкард Металокс, Инк. | Способ переработки никель-латеритных руд |
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2008
- 2008-05-01 US US12/451,233 patent/US8038767B2/en active Active
- 2008-05-01 MY MYPI20094586 patent/MY144463A/en unknown
- 2008-05-01 BR BRPI0810751 patent/BRPI0810751A2/pt not_active IP Right Cessation
- 2008-05-01 AU AU2008248196A patent/AU2008248196C1/en not_active Ceased
- 2008-05-01 WO PCT/US2008/005600 patent/WO2008137022A1/en active Search and Examination
- 2008-05-01 CN CN2008800142927A patent/CN101688267B/zh active Active
- 2008-05-01 CA CA 2685369 patent/CA2685369C/en not_active Expired - Fee Related
- 2008-05-01 EP EP08754166A patent/EP2171108A4/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104520454A (zh) * | 2012-08-09 | 2015-04-15 | 迪普格林工程有限公司 | 含锰材料的处理 |
| CN104520454B (zh) * | 2012-08-09 | 2016-05-11 | 迪普格林工程有限公司 | 含锰材料的处理 |
| CN106636654A (zh) * | 2016-12-31 | 2017-05-10 | 山东飞源科技有限公司 | 从含氟电解熔盐中回收金属镍的方法 |
| CN106636654B (zh) * | 2016-12-31 | 2019-04-26 | 山东飞源科技有限公司 | 从含氟电解熔盐中回收金属镍的方法 |
| CN114645140A (zh) * | 2022-04-02 | 2022-06-21 | 宁波容百新能源科技股份有限公司 | 一种制取镍中间品的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2685369C (en) | 2014-08-19 |
| CA2685369A1 (en) | 2008-11-13 |
| AU2008248196A1 (en) | 2008-11-13 |
| WO2008137022A1 (en) | 2008-11-13 |
| CN101688267B (zh) | 2012-12-05 |
| BRPI0810751A2 (pt) | 2014-10-21 |
| US20100126313A1 (en) | 2010-05-27 |
| AU2008248196C1 (en) | 2011-02-10 |
| EP2171108A4 (en) | 2011-03-30 |
| US8038767B2 (en) | 2011-10-18 |
| AU2008248196B2 (en) | 2010-09-16 |
| EP2171108A1 (en) | 2010-04-07 |
| MY144463A (en) | 2011-09-30 |
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