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公开(公告)号：US07968065B2
公开(公告)日：2011-06-28
申请号：US12216940
申请日：2008-09-29
CPC分类号： C22B23/0461 , C22B3/10 , C22B15/0069 , C22B15/0093 , C22B23/0423 , Y02P10/234 , Y02P10/236
摘要： A process for leaching a value metal from a base metal sulfide ore, comprising the step of leaching the ore with a lixiviant comprising a chloride, an oxidant and hydrochloric acid is disclosed. The leaching is controlled, by use of low concentrations of hydrochloric acid and a redox potential, to effect formation of hydrogen sulfide from the base metal sulfide ore. The hydrogen sulfide is stripped from the leach solution, thereby reducing the amount of sulfate generated in the leach to very low levels. The leaching may also be conducted to limit the co-dissolution of platinum group metals and gold with the base value metals. The leach forms a value metal-rich leachate and a solids residue. The solids residue may be subsequently leached to recover the platinum group metals and gold. The value metal-rich leachate can be oxidized and neutralized to recover the value base metals. In an embodiment, the chloride is magnesium chloride and lixiviant solution is regenerated.
摘要翻译： 公开了一种用于从碱金属硫化物矿石中浸出值金属的方法，其包括用包含氯化物，氧化剂和盐酸的浸液浸出矿石的步骤。 通过使用低浓度的盐酸和氧化还原电位来控制浸出，从而从硫化贱金属矿石中形成硫化氢。 从浸出溶液中汽提硫化氢，从而将浸出液中产生的硫酸盐的量减少到非常低的水平。 还可以进行浸出以限制铂族金属和金与基础金属的共溶解。 浸出液形成富含金属的浸出液和固体残渣。 随后浸出固体残渣以回收铂族金属和金。 价值金属富集的浸出液可以被氧化和中和以回收碱金属的价值。 在一个实施方案中，氯化物是氯化镁，并且溶液被再生。
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公开(公告)号：US20100135878A1
公开(公告)日：2010-06-03
申请号：US12591472
申请日：2009-11-20
IPC分类号： B01D11/04
CPC分类号： C22B23/0461 , C01G51/30 , C01G53/11 , C22B3/08 , C22B3/44 , C22B15/0093 , Y02P10/234 , Y02P10/236
摘要： A production process of a sulfide containing nickel and cobalt by adding a sulfurizing agent under pressurization into an aqueous solution of sulfuric acid containing nickel and cobalt, which is capable of recovering nickel and cobalt as a sulfide in high yield, as well as enhancing the utilization efficiency of hydrogen sulfide gas.A production process of a sulfide containing nickel and cobalt by adding a sulfurizing agent under pressurization into an aqueous solution of sulfuric acid containing nickel and cobalt, characterized by supplying, as the above sulfurizing agent, hydrogen sulfide gas into the vapor phase of inside of a reactor, as a major sulfurizing agent, as well as, by supplying an aqueous solution containing a sodium hydrosulfide, which is recovered by absorbing unreacted hydrogen sulfide gas, which is discharged from inside of the reactor in producing the above sulfide, with an aqueous solution of sodium hydroxide, into the liquid phase.
摘要翻译： 通过在加压下将硫化剂加入到含有镍和钴的硫酸水溶液中的能够以高收率回收镍和钴作为硫化物的硫化物的硫化物的生产方法，以及提高利用率 硫化氢气体的效率。 通过在加压下将硫化剂加入到含有镍和钴的硫酸水溶液中，含有镍和钴的硫化物的制造方法，其特征在于，作为上述硫化剂，将硫化氢气体供给到 反应器，作为主要的硫化剂，以及通过提供含有硫氢化钠的水溶液，该水溶液通过吸收在反应器内部从生产上述硫化物中排出的未反应的硫化氢气体，用水溶液 的氢氧化钠进入液相。
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公开(公告)号：US20090013829A1
公开(公告)日：2009-01-15
申请号：US12216940
申请日：2008-09-29
IPC分类号： C22B3/10
CPC分类号： C22B23/0461 , C22B3/10 , C22B15/0069 , C22B15/0093 , C22B23/0423 , Y02P10/234 , Y02P10/236
摘要： A process for leaching a value metal from a base metal sulfide ore, comprising the step of leaching the ore with a lixiviant comprising a chloride, an oxidant and hydrochloric acid is disclosed. The leaching is controlled, by use of low concentrations of hydrochloric acid and a redox potential, to effect formation of hydrogen sulfide from the base metal sulfide ore. The hydrogen sulfide is stripped from the leach solution, thereby reducing the amount of sulfate generated in the leach to very low levels. The leaching may also be conducted to limit the co-dissolution of platinum group metals and gold with the base value metals. The leach forms a value metal-rich leachate and a solids residue. The solids residue may be subsequently leached to recover the platinum group metals and gold. The value metal-rich leachate can be oxidized and neutralized to recover the value base metals. In an embodiment, the chloride is magnesium chloride and lixiviant solution is regenerated
摘要翻译： 公开了一种用于从碱金属硫化物矿石中浸出值金属的方法，其包括用包含氯化物，氧化剂和盐酸的浸液浸出矿石的步骤。 通过使用低浓度的盐酸和氧化还原电位来控制浸出，从而从硫化贱金属矿石中形成硫化氢。 从浸出溶液中汽提硫化氢，从而将浸出液中产生的硫酸盐的量减少到非常低的水平。 还可以进行浸出以限制铂族金属和金与基础金属的共溶解。 浸出液形成富含金属的浸出液和固体残渣。 随后浸出固体残渣以回收铂族金属和金。 价值金属富集的浸出液可以被氧化和中和以回收碱金属的价值。 在一个实施方案中，氯化物是氯化镁，并且溶液被再生
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4.发明申请公开(公告)号：US20040232084A1
公开(公告)日：2004-11-25
申请号：US10488390
申请日：2004-03-02
IPC分类号： C02F001/52
CPC分类号： C22B15/0093 , C02F1/001 , C02F1/20 , C02F1/5236 , C02F1/66 , C02F2101/20 , C02F2103/16 , C02F2103/346 , C02F2209/265 , C22B3/44 , C22B7/006 , C22B11/042 , Y02P10/214 , Y02P10/234 , Y02P10/236 , Y10S210/912
摘要： A method and apparatus for treating heavy-metal-containing wastewater using a sulfidizing agent. Sulfidizing treatment is carried out by adding a sulfidizing agent to heavy-metal-containing wastewater, while detecting hydrogen sulfide gas generated from the wastewater, such as to maintain a state in which hydrogen sulfide gas is just starting to be generated from the wastewater. When separately recovering each of a plurality of metals from wastewater in which are mixed ions of the plurality of metals, there is repeated for each of the metals a process in which the acidity of the wastewater is adjusted to within a range suitable for the metal to be separated out and recovered, a sulfidizing reaction is carried out on that metal, and the metal sulfide produced is precipitated and filtered off.
摘要翻译： 一种使用硫化剂处理含重金属的废水的方法和装置。 硫化处理是通过在含重金属的废水中加入硫化剂，同时检测由废水产生的硫化氢气体，从而保持从废水开始生成硫化氢气体的状态。 当从其中是多种金属的混合离子的废水中分别回收多种金属中的每一种时，对于每种金属，重复将废水的酸度调节到适合于金属的范围内的方法 分离出并回收，对该金属进行硫化反应，使所生成的金属硫化物析出并过滤。
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公开(公告)号：US20040130076A1
公开(公告)日：2004-07-08
申请号：US10737420
申请日：2003-12-15
发明人： John O. Marsden , Robert E. Brewer , Joanna M. Robertson , David R. Baughman , Philip Thompson , Wayne W. Hazen , Christel M. A. Bemelmans
IPC分类号： C22B003/02 , C22B015/00
CPC分类号： C22B15/0093 , C22B15/0071 , C22B15/0089 , Y02P10/236
摘要： A system and process for recovering copper from a copper-containing ore, concentrate, or other copper-bearing material to produce high quality cathode copper from a leach solution without the use of copper solvent extraction techniques or apparatus. A process for recovering copper from a copper-containing ore generally includes the steps of providing a feed stream containing comminuted copper-containing ore, concentrate, or other copper-bearing material, leaching the feed stream to yield a copper-containing solution, conditioning the copper-containing solution through one or more physical or chemical conditioning steps, and electrowinning copper directly from the copper-containing solution, without subjecting the copper-containing solution to solvent extraction.
摘要翻译： 用于从含铜矿石，浓缩物或其它含铜材料中回收铜的系统和方法，以在不使用铜溶剂萃取技术或设备的情况下从浸出溶液中生产高质量阴极铜。 从含铜矿石中回收铜的方法通常包括提供含有粉碎的含铜矿石，浓缩物或其它含铜材料的进料流的步骤，浸提进料流以产生含铜溶液，调理 通过一个或多个物理或化学调节步骤的含铜溶液，以及直接从含铜溶液中电解提取铜，而不对含铜溶液进行溶剂萃取。
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公开(公告)号：US4428773A
公开(公告)日：1984-01-31
申请号：US454803
申请日：1982-12-30
申请人： Kenneth J. Krotz
发明人： Kenneth J. Krotz
CPC分类号： C01G3/02 , C22B15/0089 , C22B15/0093 , C22B7/008 , Y02P10/234 , Y02P10/236
摘要： A process for recovering copper and copper oxide for spent ammoniacal etchant, electroless and copper persulfate bath fluids used in the manufacture of copper printed wiring boards such that the treated baths contain no ammonia. The spent solutions are placed in a cooking vessel having its inner surface made of titanium and the formaldehyde is added. The ingredients are then stirred while air is bubbled through the ingredients until thoroughly mixed after which the pH of the mixture is adjusted to between 12.0 and 14.0. The adjusted mixture is now heated to a temperature within the range of 200.degree.-210.degree. F. and air is bubbled through the heated mixture until copper and copper oxide precipitates form in the mixture. After the precipitates form the mixture is allowed to cool to permit the precipitates to settle to the bottom of the vessel and the mixture is decanted from the vessel. The copper and copper oxide precipitates are washed and then collected.
摘要翻译： 用于回收用于废氨水蚀刻剂的铜和氧化铜的方法，用于制造铜印刷线路板的无电镀和过硫酸铜浴液，使得处理的浴不含氨。 将废弃的溶液置于具有由钛制成的内表面并加入甲醛的烹饪容器中。 然后将各成分搅拌，同时使空气鼓泡通过成分直到充分混合，之后将混合物的pH调节至12.0至14.0。 调整后的混合物现在被加热到200-210°F的范围内，空气鼓泡通过加热的混合物，直到在混合物中形成铜和氧化铜沉淀。 沉淀物形成后，使混合物冷却，使沉淀物沉淀至容器的底部，并将混合物从容器中倾出。 将铜和氧化铜沉淀物洗涤，然后收集。
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7.发明授权Method of treating electrolytic solution of copper for purification and reuse thereof 失效处理铜的电解液进行纯化和再利用的方法
公开(公告)号：US4404071A
公开(公告)日：1983-09-13
申请号：US372230
申请日：1982-04-26
申请人： Hideki Abe , Kiyomi Yamaguchi , Yuzo Asano
发明人： Hideki Abe , Kiyomi Yamaguchi , Yuzo Asano
CPC分类号： C22B15/0093 , C25C1/12 , C25C7/06 , Y02P10/236
摘要： There is disclosed an improved method of treating a spent electrolyte of copper from a cell for electrolytic refining of copper for the purpose of purification and reuse of the spent electrolyte. The process comprises the steps of: pretreating the spent electrolyte for removing copper therefrom until the copper content is greatly reduced but still remains at a level which is substantially higher than the total content of various metal ion impurities, preferably to a concentration of 10-13 g/l of Cu; blowing a hydrogen sulfide gas into the pretreated solution at a temperature of 40.degree. C. or higher until the redox potential of solution becomes a certain predetermined value to precipitate metal ions; filtering the treated solution to separate the residue available as a raw material for copper smelting from a filtrate which consists essentially of sulfuric acid; and returning the filtrate to the cell for electrolytic refining of copper.
摘要翻译： 公开了一种改进的方法，用于从用于铜的电解精制的电池处理铜的废电解质，以用于废电解质的净化和再利用。 该方法包括以下步骤：对用于除去铜的废电解质进行预处理，直到铜含量大大降低，但仍保持在基本上高于各种金属离子杂质的总含量的水平，优选浓度为10-13 g / l的Cu; 在40℃或更高的温度下将硫化氢气体吹入预处理溶液中，直至溶液的氧化还原电位达到一定的预定值以沉淀金属离子; 过滤处理过的溶液，从基本上由硫酸组成的滤液中分离作为铜熔炼原料可得到的残留物; 并将滤液返回到电解铜的电解精炼。
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公开(公告)号：US4066733A
公开(公告)日：1978-01-03
申请号：US728275
申请日：1976-09-30
申请人： Michael Dubeck , Gordon G. Knapp
发明人： Michael Dubeck , Gordon G. Knapp
CPC分类号： C22B47/0027 , C22B15/0006 , C22B15/0078 , C22B15/0089 , C22B15/0093 , C22B23/005 , C22B34/34 , C22B47/0072 , Y02P10/236 , Y10S423/04
摘要： A process is disclosed for extracting nickel, copper, cobalt and molybdenum from a complex ore containing copper, nickel, cobalt, molybdenum, manganese and iron. The process features treatment of the ore with gaseous compound followed by leaching with an aqueous ammonia/ammonium salt solution into which is additionally introduced sulfite.
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公开(公告)号：US4047940A
公开(公告)日：1977-09-13
申请号：US695389
申请日：1976-06-14
申请人： Alkis S. Rappas , J. Paul Pemsler
发明人： Alkis S. Rappas , J. Paul Pemsler
CPC分类号： C22B15/0089 , C01G3/003 , C07F1/08 , C22B15/0076 , C22B15/0086 , C22B15/0093 , C22B3/0029 , Y02P10/234 , Y02P10/236
摘要： Copper is recovered from solutions containing cupric ammoniacal complexes by reducing copper in the complexes to the cuprous state and thereafter precipitating the copper as cuprous acetylide by passing acetylene through the solution. After the cuprous acetylide is separated from the solution and washed thoroughly, it is reacted with acetonitrile and an acid to form acetylene and a cuprous-acetonitrile complex: Cu(CH.sub.3 CN).sub.2.sup.+. The solution containing this complex is then flash distilled to remove the acetonitrile and to disproportionate unstable cuprous ions into copper metal and cupric ions. Following the disproportionation, the components are separated and copper metal is collected. SUBACKGROUND OF THE INVENTIONThis invention relates to the recovery of copper from ammoniacal solution which may also contain nickel, cobalt, and other ions. In practicing the invention, very pure copper metal is obtained without the need to employ ion exchangers, acid stripping, electrowinning, or electrorefining.It is known that copper (as well as nickel and cobalt) can be leached from the ores with ammoniacal leach liquors. One method of separating the copper values from such leach liquors while leaving the nickel and other metals in the raffinate, is disclosed in U.S. Pat. No. 2,440,612 to M. Lichtenwalter entitled Separation of Copper. In accordance with the process disclosed therein, the copper is recovered from the ammoniacal leach solutions by first reducing the copper values to the cuprous state and then precipitating the reduced copper by reacting it with acetylene to yield insoluble copper actylide which may be separated from the solution by filtration. If silver, mercury, or gold components are present in the leaching solution with the copper, these will also be precipitated out.In addition to the above process, it is known that solutions of cuprous salts can be thermally or electrochemically disproportionated to produce copper and solutions of cupric salts. This method is disclosed in U.S. Pat. No. 3,865,744 to Alan J. Parker et al. In general, this method involves reacting a cuprous salt with a ligand, i.e., an organic nitrile, to form a cuprous nitrile complex such as Cu(CH.sub.3 CN).sub.2.sup.+. The solution containing the complex can then be distilled to produce copper powder, a cupric salt, and an organic nitrile.The present invention provides a method of isolating and purifying copper utilizing a novel combination of the above two known copper recovering processes.SUMMARY OF THE INVENTIONThe process of the present invention produces copper metal from an ammoniacal solution containing cuprous ions. The process comprises the steps of precipitating the cuprous ions from the ammoniacal solution as a cuprous acetylide, separating and washing the cuprous acetylide precipitate, acid hydrolyzing the cuprous acetylide in the presence of a cuprous ion stabilizing ligand, e.g., a nitrile, and disproportionating the resulting cuprous complex to produce copper metal and cupric salt.The process of the present invention is characterized by the use of reactions which take place at or near ambient temperatures and pressures, and thus a system for utilizing the process can be built at a relatively low cost. In addition, many of the reagents in the process can be recycled, allowing further cost savings, and the process is quite energy efficient. Also, upwards of 99% of the available copper can be recovered and the product metal is of very high purity.Accordingly, it is an object of the present invention to provide a process for obtaining pure copper from ammoniacal copper containing solutions which avoids the necessity of electrowinning the copper, is capable of continuous operation on an industrial scale with a relatively low capital outlay, involves reactions which occur at or near ambient temperatures and pressures, and employs reagents which are neither unduly corrosive nor consumed.Another object of the invention is to provide such a copper recovery process which is energy efficient and significantly diminishes the quantities of waste involved when compared with prior art processes by regenerating and recycling reagents.Still another object of the invention is to quantitatively separate copper from ammoniacal solutions containing copper and other metals such as nickel, cobalt, iron, manganese, etc., without using an ion exchanger.Another object of the invention is to produce copper of very high purity by precipitating cuprous ions from solutions as a cuprous acetylide, separating the cuprous acetylide precipitate, reacting the acetylide with an acid and a nitrile to form a cuprous-nitrile complex, and disproportionating the cuprous ion to produce copper metal.
摘要翻译： 通过将络合物中的铜还原为亚铜状态，然后通过使乙炔通过溶液将铜沉淀为乙炔化亚铜，从含有铜铵络合物的溶液中回收铜。 将乙炔化亚铜与溶液分离并彻底洗涤后，与乙腈和酸反应形成乙炔和亚铜 - 乙腈络合物：Cu（CH 3 CN）2。 然后将含有该络合物的溶液快速蒸馏除去乙腈，将不相称的不稳定的亚铜离子转移到铜金属和铜离子中。 在歧化之后，分离组分并收集铜金属。
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公开(公告)号：US4022866A
公开(公告)日：1977-05-10
申请号：US568996
申请日：1975-04-17
申请人： Martin C. Kuhn , Nathaniel Arbiter
发明人： Martin C. Kuhn , Nathaniel Arbiter
CPC分类号： C22B15/0093 , C22B15/0078 , C22B19/24 , C22B23/0446 , Y02P10/234 , Y02P10/236
摘要： Copper, zinc and nickel are recovered from sulfide concentrates prepared from ores of one or more such metals by subjecting such concentrate to a leaching operation which comprises slurrying the concentrate in an aqueous solution containing ammonium sulfate and free ammonia and vigorously agitating the slurry at 50 to 80.degree. C. and below 10 psig. in the presence of free oxygen while vigorously recirculating said oxygen from above the surface of the slurry to a substantial depth below such surface. The resulting pregnant leach solution contains copper, zinc, and/or nickel in dissolved form complexed with ammonia and such solution is treated to recover the dissolved metal. The undissolved sulfidic residue from the leaching operation is subjected to a secondary flotation operation to produce a sulfide concentrate containing the metal values not dissolved in the leaching operation, and such concentrate is treated to recover such values, as by smelting or by releaching.
摘要翻译： 铜，锌和镍从一种或多种这样的金属矿石制备的硫化物浓缩物中回收，通过使这种浓缩物经过浸出操作，包括将浓缩物在含有硫酸铵和游离氨的水溶液中浆化，并在50℃剧烈搅拌该浆液 80℃和低于10psig。 在游离氧的存在下，同时从所述浆料表面上方将所述氧气从所述表面的相当深度剧烈再循环。 所得到的浸出溶液含有与氨络合的溶解形式的铜，锌和/或镍，并处理这种溶液以回收溶解的金属。 来自浸出操作的未溶解的硫化物残余物进行二次浮选操作以产生含有不溶于浸出操作中的金属值的硫化物浓缩物，并且通过熔炼或通过沉淀处理这种浓缩物以回收这些值。
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