CN113584319B - Method for extracting germanium from smoke dust - Google Patents

Method for extracting germanium from smoke dust Download PDF

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Publication number
CN113584319B
CN113584319B CN202110889216.8A CN202110889216A CN113584319B CN 113584319 B CN113584319 B CN 113584319B CN 202110889216 A CN202110889216 A CN 202110889216A CN 113584319 B CN113584319 B CN 113584319B
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germanium
smoke dust
reaction
pressure
ccl
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CN113584319A (en
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邵雨萌
普世坤
张红潇
熊浩
柴皓茗
尹国文
罗中旭
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YUNNAN LINCANG XINYUAN GERMANIUM INDUSTRY CO LTD
Yunnan University YNU
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YUNNAN LINCANG XINYUAN GERMANIUM INDUSTRY CO LTD
Yunnan University YNU
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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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • 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
    • C22B41/00—Obtaining germanium
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to the technical field of germanium extraction, and particularly discloses a method for extracting germanium from smoke dustThe method comprises the following steps: taking germanium-containing smoke dust generated in a rotary volatilizing furnace, adding the smoke dust into a pressure kettle, placing the smoke dust in a suspended manner for oxygen pressure oxidation, and introducing CCl4The solution enters a pressure kettle for reaction, volatile gas is collected and cooled, and the cooled GeCl is added4Chlorine is introduced into the solution for chlorination, distillation and purification, and then GeO is collected by hydrolysis and filtration2Heating the waste liquid, collecting the dissipated gas, cooling in ice brine, and recovering the residual CCl4Recycling and reusing GeO2The method has the advantages that the gaseous reaction is carried out under the condition of high-temperature pressure chlorination, the reaction recovery efficiency is high, the reaction speed is high, and the problem of overlong reaction time of the traditional process is solved.

Description

Method for extracting germanium from smoke dust
Technical Field
The invention relates to the technical field of germanium extraction, in particular to a technology for extracting germanium from low-grade germanium-containing smoke dust generated by brown coal mine enrichment.
Background
Germanium is an important strategic resource and is widely applied to a plurality of national defense military industry and civil fields such as infrared optics, optical fiber communication, aerospace, solar cells, nuclear physics detection and the like. The method belongs to the strategic storage of metals in China, along with the exploitation of germanium ores, the grade of the germanium ores is continuously reduced in recent years, high-quality brown coal ores are less and less, the germanium content of the germanium ores is continuously reduced, the germanium enrichment ratio of a pyrogenic process enrichment furnace is certain, and the grade of obtained smoke dust is also continuously reduced. In the prior art, a large amount of hydrochloric acid is still needed for chlorination after primary enrichment of smoke dust by a pyrogenic process, and a large amount of generated waste acid needs to be neutralized, so that the cost cannot be reduced. The method abandons the conventional mode of treating germanium smoke dust, and the reaction product can be recycled for the second time, thereby reducing the influence on the environment to the minimum and ensuring the production cost to be about the highest. The invention can greatly save the use amount of raw materials in later industrial production. Can reduce the cost of industrial production, and relates to a novel method for extracting germanium.
Disclosure of Invention
The invention aims to provide a method for extracting germanium from smoke dust, which solves the problems in the prior art.
In order to solve the problems, the invention adopts the following technical scheme:
a method for extracting germanium from smoke dust comprises the following steps:
s1: taking germanium-containing smoke dust generated in the rotary volatilizing furnace, and then adding the smoke dust into a pressure kettle for suspension placement for oxygen pressure oxidation;
s2: introduction of CCl4The solution enters a pressure kettle for reaction;
s3: collecting the volatilized gas, and cooling;
s4: cooling the GeCl4Cooling the solution, hydrolyzing and collecting GeO2Heating the waste liquid, collecting the dissipated gas, cooling in ice brine, and recovering the residual CCl4Recycling and reusing;
s5: will collect GeO2And reducing by hydrogen to obtain a germanium simple substance.
The grade of the germanium smoke dust enriched by the pyrogenic process is improved to a certain extent, wherein the content of germanium in the germanium-containing smoke dust is 9.5-44.1%.
Preferably, the oxygen pressure oxidation is carried out in a mechanical stirring pressure kettle, and the temperature is increased to 250 ℃ and the pressure is increased by 10 kpa. The following reactions occur:
2GeO+O2＝2GeO2
preferably, CCl4With GeO2The reaction condition is that phosgene is generated at 500 ℃ to generate lightGas can further react with GeO2The chlorination is carried out under the reaction conditions of 600 ℃. The following reactions occur in particular:
GeO2+2CCl4＝GeCl4↑+2COCl4
GeO2+CCl4＝GeCl4↑+COCl4
GeO2+2COCl2＝GeCl4↑+2CO2↑
then the phosgene with low boiling point is collected and recycled.
The invention has the advantages that:
the method adopts the gaseous reaction under the condition of high temperature and pressure, and has high reaction efficiency and high reaction speed. The problem of long reaction time of the traditional process is avoided. The gas reaction is more thorough, and compared with the traditional hydrochloric acid leaching, the high-grade germanium still remains in the residue, so that the problem of recycling a large amount of residue can be solved. Simultaneous CCl4The content of the chloride ions is high, and the raw materials are saved in the chlorination process, so that less waste is generated. Compared with the prior art, the method has less influence on the environment. Meanwhile, a mode different from the traditional hydrochloric acid leaching mode is adopted, and waste acid does not need to be treated, so that a large amount of cost is saved. Using CCl4GeCl produced by nature4Nearly does not contain other impurities, omits a fussy impurity removal process, generates little waste and is easy to treat, and can carry out pollution-free treatment on the waste. Compared with the traditional process, the pressure on the environment is greatly reduced. The production process adopts a closed mode to minimize the safety problem.
Detailed Description
Example 1:
a method for extracting germanium from smoke dust selects the same batch of smoke dust containing germanium in the implementation case, and verifies the feasibility of the method under the condition that the germanium content is approximately the same. The method comprises the following steps:
the first step is as follows: 500g of germanium-containing smoke volatilized from the rotary volatilizing furnace is collected, and the germanium content in the germanium-containing smoke is firstly determined to be 15 wt% and then the smoke is sent into a pressure kettle to be suspended.
The second step is that: controlling the pressure of the pressure kettle to be increased to 10kpa, and carrying out oxygen pressure oxidation treatment on the smoke dust in the kettle at the temperature of 250 ℃ for 30 min.
The third step: adding CCl4And (4) reacting the solution. The amount added was 1000 ml. Heating the pressure kettle to 500 ℃ to ensure that CCl in the kettle4The inner phase is converted into a vapor form. React with the smoke dust. The reaction time is 1h, and the pressure is released after the reaction is finished to collect the gas for cooling.
The fourth step: and placing the collected and cooled solution at room temperature, collecting phosgene generated by reaction by utilizing the property of low boiling point of phosgene, and recycling the phosgene.
The fifth step: and (3) distilling and rectifying the residual solution by using chlorine gas. Purification was carried out, and the resulting refined germanium tetrachloride solution was hydrolyzed to germanium dioxide and reduced to germanium using hydrogen and subjected to ICP-OES analysis and resistivity test. By calculating the method for recovering the germanium, the recovery efficiency is 98.4 percent, and the purity of the germanium can reach 99.9999 percent.
Example 2:
a method for extracting germanium from smoke dust selects the same batch of smoke dust containing germanium in the implementation case, and verifies the feasibility of the method under the condition that the germanium content is approximately the same. The method comprises the following steps:
the first step is as follows: 500g of germanium-containing smoke volatilized from the rotary volatilizing furnace is collected, and the germanium content in the germanium-containing smoke is firstly determined to be 15 wt% and then the smoke is sent into a pressure kettle to be suspended.
The second step: controlling the pressure of the pressure kettle to be increased to 10kpa, and carrying out oxygen pressure oxidation treatment on the smoke dust in the kettle at the temperature of 250 ℃ for 30 min.
The third step: adding CCl4And (4) reacting the solution. The amount added was 1000 ml. Heating the pressure kettle at 550 ℃ to ensure that CCl in the kettle4The inner phase is converted into a vapor form. React with the smoke dust. The reaction time is 2h, and the pressure is released after the reaction is finished, and the collected gas is cooled.
The fourth step: and placing the collected and cooled solution at room temperature, collecting phosgene generated by reaction by utilizing the property of low boiling point of phosgene, and recycling the phosgene.
The fifth step: and (4) carrying out chlorine gas distillation and rectification on the residual solution. Purification was carried out, and the resulting refined germanium tetrachloride solution was hydrolyzed to germanium dioxide and reduced to germanium using hydrogen and subjected to ICP-OES analysis and resistivity test. By calculating the method for recovering the germanium, the recovery efficiency is 99.1 percent, and the purity of the germanium can reach 99.9999 percent.
Example 3:
a method for extracting germanium from smoke dust selects the same batch of smoke dust containing germanium in the implementation case, and verifies the feasibility of the method under the condition that the germanium content is approximately the same. The method comprises the following steps:
the first step is as follows: 500g of germanium-containing smoke dust volatilized from the rotary volatilizing furnace is collected, the germanium content in the germanium-containing smoke dust is firstly measured to be 16 wt%, and the germanium-containing smoke dust is sent into a pressure kettle to be suspended and placed.
The second step is that: controlling the pressure of the pressure kettle to be increased to 10kpa, and carrying out oxygen pressure oxidation treatment on the smoke dust in the kettle at the temperature of 300 ℃ for 30 min.
The third step: adding CCl4And (4) reacting the solution. The amount added was 1000 ml. Heating the pressure kettle at 600 deg.C to make CCl in the kettle4The inner phase is converted into a vapor form. React with the smoke dust. The reaction time is 3h, and the pressure is released after the reaction is finished to collect the gas for cooling.
The fourth step: and placing the collected and cooled solution at room temperature, collecting phosgene generated by reaction by utilizing the property of low boiling point of phosgene, and recycling the phosgene.
The fifth step: and (4) carrying out chlorine gas distillation and rectification on the residual solution. Purification was carried out, and the resulting refined germanium tetrachloride solution was hydrolyzed to germanium dioxide and reduced to germanium using hydrogen and subjected to ICP-OES analysis and resistivity test. By calculating the method for recovering the germanium, the recovery efficiency is 98.8 percent, and the purity of the germanium can reach 99.9999 percent.
Experiments show that the reaction time and the material ratio are finally determined. The content of germanium in the smoke dust has certain influence on the final recovery rate of the method, and phosgene generated by reaction at the temperature of 600 ℃ can improve the recovery rate of germanium.

Claims (3)

1. A method for extracting germanium from smoke dust is characterized by comprising the following steps:
s1: taking germanium-containing smoke dust generated in the rotary volatilizing furnace, and then adding the smoke dust into a pressure kettle for suspension placement for oxygen pressure oxidation;
s2: introduction of CCl4The solution enters a pressure kettle for reaction;
s3: collecting the volatilized gas and cooling;
s4: cooling the GeCl4Distilling and purifying the solution by introducing chlorine gas, hydrolyzing and collecting GeO2Heating the waste liquid, collecting the dissipated gas, cooling in ice brine, and recovering the residual CCl4Recycling and reusing;
s5: will collect GeO2Carrying out hydrogen reduction to obtain germanium metal;
in the step S1, the pressure of the pressure kettle is controlled to be increased to 10kPa, and the smoke dust in the kettle is subjected to oxygen pressure oxidation treatment at 250 ℃;
in the step S2, the temperature of the pressure kettle is 500-600 ℃.
2. A method as claimed in claim 1, wherein said germanium-containing soot is mixed with added CCl4The solution-to-liquid ratio is 1: 2.
3. A method for extracting germanium from smoke according to any one of claims 1-2, wherein the germanium content of said germanium-containing smoke is 9.5% to 44.1%.
CN202110889216.8A 2021-08-04 2021-08-04 Method for extracting germanium from smoke dust Active CN113584319B (en)

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CN114606401B (en) * 2022-01-26 2024-04-30 株洲科能新材料股份有限公司 Chlorine-free dry germanium recovery method

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DE3635450A1 (en) * 1986-10-18 1988-04-21 Metallgesellschaft Ag METHOD FOR SELECTIVE PRODUCTION OF GERMANIUM AND / OR ARSEN FROM AQUEOUS SOLUTIONS
US5919964A (en) * 1994-03-02 1999-07-06 Viva America Marketing, Inc. Method for the preparation of pure carboxyethyl germanium sesquioxide
CN102181653B (en) * 2011-04-26 2012-10-17 临沧韭菜坝煤业有限责任公司 Method for recovering germanium from germanium-containing smoke dust
CN104789785B (en) * 2015-05-19 2017-01-25 河北工程大学 Method for extracting germanium from germanium-containing smoke dust
CN104911363A (en) * 2015-06-24 2015-09-16 上海交通大学 Method for recovering germanium in lignite smoke
CN106521193B (en) * 2016-07-15 2018-10-16 深圳市深投环保科技有限公司 A method of the enriching and recovering germanium from germanium-containing solution

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