US20200377968A1 - Copper precipitation method by iron modification and copper precipitation and preparation apparatus used therefor - Google Patents

Copper precipitation method by iron modification and copper precipitation and preparation apparatus used therefor Download PDF

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US20200377968A1
US20200377968A1 US16/312,069 US201716312069A US2020377968A1 US 20200377968 A1 US20200377968 A1 US 20200377968A1 US 201716312069 A US201716312069 A US 201716312069A US 2020377968 A1 US2020377968 A1 US 2020377968A1
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copper
reactor
iron
reaction
solution
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Kyoung Ok HAN
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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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C22B15/0093—Treating solutions by chemical methods by gases, e.g. hydrogen or hydrogen sulfide
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • 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
    • C22B15/00—Obtaining copper
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • 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
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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

Definitions

  • the present disclosure relates to a copper extraction method including modifying iron to copper. Specifically, the present disclosure relates to a copper extraction method via an iron modification occurring by introducing hydrogen into a mixture formed by mixing iron with an acidic solution containing copper, and to a copper extraction apparatus for performing the method.
  • Iron is used as a main source material in various industries. Iron is also available at a reasonable price. Copper is expensive compared to iron. Thus, an approach in which copper is obtained via iron modification may double an economic value.
  • the prior art will be described.
  • Korean Patent No. 10-0962214 discloses a copper powder producing method.
  • This method includes producing a copper nitrate solution by adding a concentrated nitric acid to a copper ingot and dissolving the nitric acid; replacing the nitric acid copper solution with cupric chloride by adding concentrated hydrochloric acid to the nitric acid copper solution via evaporation and concentration; controlling Ph of the solution by adding sodium hydroxide solution to the cupric chloride; adding dispersing agent; extracting copper powders by attaching an iron plate to an agitator; and filtering, washing and drying the copper powder.
  • there is a disadvantage in that it is necessary to attach the iron plate to the agitator to produce copper powders.
  • the present disclosure provides a copper extraction method via an iron modification using a hollow spherically-structured reactor as shown in FIG. 2 and a copper extraction producing apparatus for performing the method.
  • a mixture of the selected acidic solution and iron is charged into a hollow spherically-structured reactor into which the iron powder is charged, and then oxygen is introduced into the reactor.
  • the iron is modified into an iron oxide.
  • copper and acidic copper are introduced into the hollow spherically structured reactor containing the iron oxide.
  • Hydrogen and hydrogen water are input to the reactor.
  • an agitator is rotated to extract copper powders.
  • the copper powder can be easily produced using only iron powders, without the hassle of placing the iron piece on the agitator as in the prior art.
  • Korean patent No. 10-1539458 disclose an apparatus for producing alloy copper having a simple structure.
  • the apparatus comprises: a first reaction tank dissolving copper; a first aqua regia supply path supplying aqua regia to the first reaction tank; a second reaction tank dissolving iron; a second aqua regia supply path supplying aqua regia to the second reaction tank; a mixing reaction tank receiving a mixing solution of copper chloride and the mixing solution of iron chloride; a first mixing solution supply path enabling the mixing solution of the first reaction tank to flow to the mixing reaction tank; a second mixing solution supply path enabling the mixing solution of the second reaction tank to flow to the mixing reaction tank; a first gas supply path enabling a chlorine gas generated in the first reaction tank to flow to the mixing reaction tank; a second gas supply path enabling the chlorine gas generated in the second reaction tank to flow to the mixing reaction tank; an additive supply path supplying an additive to the mixing reaction tank; a third aqua regia supply path supplying aqua regia to the mixing reaction tank; an electrolytic extraction device receiving
  • the hollow spherically-structured reactor is a copper extraction producing apparatus, which is composed of a single hollow spherically-structured reactor. Until a step of obtaining the result, all the entire process steps are carried out in the single hollow spherically-structured reactor. This is different from the conventional extraction producing apparatus.
  • Patent Document 1 KR Patent No. 10-0962214 (Jun. 1, 2010)
  • Patent Document 2 KR Patent No. 10-1539458 (Jul. 20, 2015)
  • a purpose of the present disclosure is to provide a copper extraction method, which can economically mass produce copper from inexpensive iron by modifying the iron element to a copper element via a hydrogen nuclear fusion reaction.
  • the hydrogens (H) exiting and the hydrogens introduced as the reaction accelerator are combined such that the four hydrogens (H) turn into one helium (He), resulting in a chain reaction between the protons and the neutrons and thus hydrogen fusion reaction occurs.
  • He helium
  • the copper element expands to destroy the iron nucleus, such that the iron element is modified to a copper element.
  • the iron is directly added into the acidic copper solution, the copper is extracted.
  • the reason for including the oxidation of iron to iron oxide is to achieve a time reduction and to promote the iron modification.
  • the addition of the hydrogen is also intended to achieve a time reduction and promote the iron modification.
  • the use of the iron particle having an iron particle diameter of 0.001 mm to 10 mm is to shorten the modification time.
  • Embodiments of the present disclosure for achieving the object of the present invention are as follows.
  • a concentration % means g of solute per 100 g of solution.
  • a copper extraction method via iron modification may include:
  • the copper-containing acidic solution is selected from a group consisting of copper chloride solution, copper sulfate solution, copper nitrate solution, copper acetate solution, copper borate solution, and copper phosphate solution;
  • adding the selected copper-containing acidic solution into the hollow spherically-structured reactor in one example, adding 22.5 g of copper sulfate pentahydrate in 100 ml of distilled water to form a copper sulfate solution and adding the copper sulfate solution into the hollow spherically-structured reactor;
  • the neutralizing agent is selected from a group consisting of sodium carbonate, potassium carbonate, and a surfactant;
  • the copper extraction apparatus may include:
  • a hollow spherically-structured reactor 100 in which iron is input into an acidic solution to change into an iron oxide (FeO) which in turn is added into an acidic copper solution to modify the iron into copper;
  • FeO iron oxide
  • an opening 110 constructed to penetrate a reaction chamber wall of the hollow spherically-structured reactor 100 , wherein a source iron, copper, acidic solution, and acidic copper solution is charged through the opening 110 into a reaction chamber of the hollow spherically-structured reactor 100 , and an extracted copper is discharged through the opening 110 out of the hollow spherically-structured reactor 100 ;
  • a gas inlet 128 constructed to penetrate the reaction chamber wall of the hollow spherically-structured reactor 100 so that oxygen and hydrogen are introduced through the gas inlet into the hollow spherically-structured reactor 100 to promote the oxidation reaction and the modification reaction;
  • a gas outlet 120 constructed to pass through the reaction chamber wall of the hollow spherically-structured reactor 100 such that gases generated in the oxidation reaction and modification reaction are discharged through the gas outlet out of the hollow spherically-structured reactor 100 ;
  • washing-water inlet 130 constructed to penetrate the reaction chamber wall of the hollow spherically-structured reactor 100 so that washing-water for cleaning neutralized copper is injected through the inlet 130 into the reaction chamber of the hollow spherically-structured reactor 100 ;
  • a hot and cold air generator 148 attached to the hollow spherically-structured reactor 100 ;
  • a cold or hot air inlet 140 constructed to pass through the reaction chamber wall of the hollow spherically-structured reactor 100 so that cold air or hot air is introduced through the inlet 140 into the reaction chamber to dry extracted copper using cold air or hot air generated by the hot and cold air generator 148 ;
  • an agitator 108 disposed in the reaction chamber of the hollow spherically-structured reactor 100 so as to facilitate copper washing, copper drying, and oxidation and modification reactions, wherein the agitator 108 includes nine blades 960 at three stages;
  • reaction solution outlet 160 constructed to pass through the reaction chamber wall of the hollow spherically-structured reactor 100 so that reaction solutions are discharged through the outlet 160 out of the reaction chamber;
  • a filtering mesh 162 disposed on an inner wall of the reaction chamber to cover the reaction solution outlet 160 to prevent discharge-out of the extracted copper when the reaction solution and impurities are discharged out of the chamber;
  • a tilting mount plate 200 mounted on the hollow spherically-structured reactor 100 , wherein the tilting mount plate 200 is capable of being inclined at 5° to 180° relative to a ground such that the copper and the solutions can be easily injected into the chamber through the opening 110 , and the obtained copper can be easily discharged through the opening 110 out of the chamber, and the reaction solution and impurities can be easily discharged through the reaction solution outlet 160 out of the chamber.
  • Using the copper extraction apparatus according to the present disclosure may extract a large amount of expensive copper in an economical manner using low cost iron. This may have the same economic effect as obtaining copper mines.
  • FIG. 1 is a schematic representation of a copper extraction process according to the present disclosure.
  • FIG. 2 is a schematic diagram of a copper extraction apparatus according to the present disclosure.
  • FIG. 3 shows an operating state of the copper extraction apparatus according to the present disclosure.
  • FIG. 4 is a photograph of a certified test result according to Present Example 1.
  • FIG. 5 shows a photograph of extracted copper according to Present Example 2.
  • FIG. 6 is a representative figure of KR 10-1539458.
  • reactor 110 opening 120: gas outlet 128: gas inlet 130: washing-water inlet 140: cold or hot air inlet 148: hot and cold air generator 160: reaction solution outlet.
  • 162 filtering mesh 200: tilting mount plate 400: ascending and descending mechanism 500: controller.
  • the copper extraction method according to the present disclosure may include the step of adding iron (Fe) to the acidic solution. Further, the method may include the step of adding oxygen as a reaction promoter into the hollow spherically-structured reactor containing the iron and the acid solution to accelerate the oxidation reaction to produce the iron oxide.
  • iron may be added in the form of iron powder or pieces having a particle diameter of about 0.001 to 10 mm, and the acidic solution may have a concentration of 0.01 to 1570%.
  • the oxidation reaction may be promoted by rotating the blades of the agitator via the engine motor.
  • the time for oxidizing the iron during the oxidation process may vary depending on the concentration of the acidic solution and the amount of iron used.
  • oxygen as a promoter is added to oxidize the iron (Fe) to the iron oxide (FeO), and, then, the acidic copper solution is introduced into the chamber of the reactor.
  • the copper When the iron has been subjected to the modification reaction into the copper, the copper may be contained in a range of from 1 to 40% by weight based on 100% by weight of iron.
  • the process of modifying the iron to the copper by adding the hydrogen or hydrogen as the modification promoter in the hollow spherically-structured reactor is as follows.
  • the method comprises administering the copper-containing acidic solution in the chamber of the hollow spherically-structured reactor containing the iron. Further, in this method, the agitator is rotated to perform the modification reaction to modify the iron element to a copper element.
  • the step of introducing the copper-containing acidic solution may be repeatedly performed.
  • Hydrogen may be added at a dissolution rate 0.001 to 0.01% liter. Further, using hydrogen and hydrogen peroxide may have following advantages: the process of modification of iron to copper occurs rapidly; the yield of copper is improved; and, a large amount of copper having a high purity can be extracted in a relatively short time.
  • Copper added to perform the modification reaction may be added in an amount of 1 to 40 wt % relative to 100 wt % of iron.
  • the method may involve the use of hydrogen water for the modification reaction. Further, when the copper production is high, the method may also include injecting the oxygen and hydrogen directly to the reactor using a hose.
  • the copper extraction method via iron modification may include:
  • the copper-containing acidic solution is selected from a group consisting of copper chloride solution, copper sulfate solution, copper nitrate solution, copper acetate solution, copper borate solution, and copper phosphate solution;
  • adding the selected copper-containing acidic solution into the hollow spherically-structured reactor in one example, adding 22.5 g of copper sulfate pentahydrate (copper content: 5.71g) in 100 ml of distilled water to form a copper sulfate solution and adding the copper sulfate solution into the hollow spherically-structured reactor;
  • the neutralizing agent is selected from a group consisting of sodium carbonate, potassium carbonate, and a surfactant;
  • a copper extraction method via iron modification may include:
  • the copper-containing acidic solution is selected from a group consisting of copper chloride solution, copper sulfate solution, copper nitrate solution, copper acetate solution, copper borate solution, and copper phosphate solution;
  • adding the selected copper-containing acidic solution into the hollow spherically-structured reactor in one example, adding 22.5 g of copper sulfate pentahydrate (copper content: 5.71 g) in 100 ml of distilled water to form a copper sulfate solution and adding the copper sulfate solution into the hollow spherically-structured reactor;
  • the neutralizing agent is selected from a group consisting of sodium carbonate, potassium carbonate, and a surfactant;
  • the method may involve repeatedly injecting the copper-containing acidic solution in the modification reaction of an iron element into a copper element.
  • a test result for the purity of the copper obtained from the present example is shown in FIG. 4 .
  • the test result shows that the purity of the obtained copper is 96.1%.
  • FIG. 5 is a photograph of copper as extracted from copper extraction with the addition of hydrogen.
  • the copper extraction apparatus used in accordance with the present disclosure includes a hollow spherically-structured reactor having a chamber defined therein, and having a chamber wall made of stainless steel for defining the chamber.
  • the reactor is configured to perform material input, reaction, gas discharge, cooling, neutralization, washing, drying, etc. in the single chamber.
  • the inner and outer circumferential surfaces of the chamber wall of the hollow spherically-structured reactor may be coated with a fiber reinforced plastic (FRP) 800 , thereby preventing corrosion.
  • the fiber-reinforced plastic 800 is preferably a heat-resistant material so as to withstand high temperatures.
  • the copper extraction apparatus via the iron modification has the hollow spherically-structured reactor, as shown in FIG. 2 .
  • the hollow spherically-structured reactor 100 has a chamber formed therein. The chamber is defined by the chamber wall.
  • the agitator 108 for evenly mixing the raw materials is disposed on a center of the inner bottom surface of the chamber wall.
  • the agitator 108 has nine blades 960 mounted at three stages on a rotating shaft. The blades rotate rapidly to promote the iron oxidation reaction and rapidly mix the reactants within the hollow spherically-structured reactor.
  • an inner cylinder 600 may be powered via a power transmission 700 and the agitator 108 may be driven by an engine motor 102 .
  • the engine motor 102 Since the engine motor 102 is operated by an electric force, the motor receives separate power.
  • the copper extraction apparatus via the iron modification may include an opening 110 constructed to penetrate a reaction chamber wall of the hollow spherically-structured reactor 100 , wherein a source iron, copper, acidic solution, and acidic copper solution is charged through the opening 110 into a reaction chamber of the hollow spherically-structured reactor 100 , and an extracted copper is discharged through the opening 110 out of the hollow spherically-structured reactor 100 ;
  • the copper extraction apparatus via the iron modification may include a gas inlet 128 constructed to penetrate the reaction chamber wall of the hollow spherically-structured reactor 100 so that oxygen and hydrogen are introduced through the gas inlet into the hollow spherically-structured reactor 100 to promote the oxidation reaction and the modification reaction.
  • the copper extraction apparatus via the iron modification may include a gas outlet 120 constructed to pass through the reaction chamber wall of the hollow spherically-structured reactor 100 such that gases generated in the oxidation reaction and modification reaction are discharged through the gas outlet out of the hollow spherically-structured reactor 100 .
  • the copper extraction apparatus via the iron modification may include a washing-water inlet 130 constructed to penetrate the reaction chamber wall of the hollow spherically-structured reactor 100 so that washing-water for cleaning neutralized copper is injected through the inlet 130 into the reaction chamber of the hollow spherically-structured reactor 100 .
  • the copper extraction apparatus via the iron modification may include a hot and cold air generator 148 attached to the hollow spherically-structured reactor 100 .
  • the copper extraction apparatus via the iron modification may include a cold or hot air inlet 140 constructed to pass through the reaction chamber wall of the hollow spherically-structured reactor 100 so that cold air or hot air is introduced through the inlet 140 into the reaction chamber to dry extracted copper using cold air or hot air generated by the hot and cold air generator 148 .
  • the copper extraction apparatus via the iron modification may include an reaction solution outlet 160 constructed to pass through the reaction chamber wall of the hollow spherically-structured reactor 100 so that reaction solutions are discharged through the outlet 160 out of the reaction chamber.
  • the copper extraction apparatus via the iron modification may include a filtering mesh 162 disposed on an inner wall of the reaction chamber to cover the reaction solution outlet 160 to prevent discharge-out of the extracted copper when the reaction solution and impurities are discharged out of the chamber.
  • the copper extraction apparatus via the iron modification may include a tilting mount plate 200 mounted on the hollow spherically-structured reactor 100 , wherein the tilting mount plate 200 is capable of being inclined at 5° to 180° relative to a ground such that the copper and the solutions can be easily injected into the chamber through the opening 110 , and the obtained copper can be easily discharged through the opening 110 out of the chamber, and the reaction solution and impurities can be easily discharged through the reaction solution outlet 160 , out of the chamber.
  • the hollow spherically-structured reactor 100 is mounted on a tilting mount plate 200 .
  • An ascending and descending mechanism 400 is installed at one end of the tilting mount plate 200 .
  • the tilting mount plate 200 is inclined by the ascending and descending movement of the ascending and descending mechanism 400 .
  • the hollow spherically-structured reactor 100 is correspondingly inclined.
  • the coupling position of the ascending and descending mechanism 400 and the tilting mount plate 200 is controlled such that, when one end of the tilting mount plate 200 is lifted up and tilted and thus a portion of the reaction solution outlet 160 defined in the hollow spherically-structured reactor 100 is tilted downward.
  • the ascending and descending mechanism 400 is connected to one end of the tilting mount plate 200 .
  • the tilting mount plate 200 is tilted by the tilting mount plate 400 .
  • FIG. 3 shows a state in which the tilting mount plate 200 is tilted.
  • the reaction solution outlet 160 has a closed structure by a lid. The lid is removed when the reaction solution is drained.
  • the ascending and descending mechanism 400 comprises an inner cylinder 600 .
  • the hollow spherically-structured reactor may have an inclination of 5° to 180° relative to the ground.
  • the hollow spherically-structured reactor is tilted such that the raw material can be easily injected into the inlet, and the resulting copper can be easily discharged out of the reactor.
  • the copper production is economical because the present method produces expensive copper using cheap iron.
  • the copper extraction method via the iron modification and the copper extraction apparatus which conducts the method may allow the large-scale production of the copper using the iron, which is highly industrially applicable.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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  • Geochemistry & Mineralogy (AREA)
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US16/312,069 2016-06-24 2017-06-26 Copper precipitation method by iron modification and copper precipitation and preparation apparatus used therefor Abandoned US20200377968A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
KR10-2016-0079558 2016-06-24
KR1020160079558A KR20170091488A (ko) 2016-02-01 2016-06-24 신규한 구리 석출방법
KR1020170059546A KR20180001441A (ko) 2016-06-24 2017-05-12 구리 석출 방법 및 이에 사용되는 구리 석출 제조장치
KR10-2017-0059546 2017-05-12
PCT/KR2017/006733 WO2017222357A2 (ko) 2016-06-24 2017-06-26 철 변성에 의한 구리 석출 방법 및 이에 사용되는 구리 석출 제조장치

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KR (1) KR20180001441A (ko)
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KR0141265B1 (ko) * 1995-06-26 1998-06-01 우덕창 고강도 알파-반수 석고의 제조 장치
KR970001572A (ko) * 1995-06-28 1997-01-24 허용태 철의 변성에 의한 동 제조방법
KR20080073038A (ko) * 2007-02-05 2008-08-08 주식회사 태원 인쇄회로기판 제조시 발생하는 폐수를 처리하는 과정 중발생된 슬러지내의 구리를 회수하는 방법
KR20110024849A (ko) * 2009-09-03 2011-03-09 윤인규 염소 또는 염화 제1철과 염산을 혼합용액을 이용하여 순 철 또는 산화철을 변성시켜 염화 동을 제조하는 방법
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CN109642267A (zh) 2019-04-16
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WO2017222357A3 (ko) 2018-02-15

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