CN105907994A - Method for achieving germanium precipitation through metallic oxide - Google Patents

Method for achieving germanium precipitation through metallic oxide Download PDF

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Publication number
CN105907994A
CN105907994A CN201610339560.9A CN201610339560A CN105907994A CN 105907994 A CN105907994 A CN 105907994A CN 201610339560 A CN201610339560 A CN 201610339560A CN 105907994 A CN105907994 A CN 105907994A
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Prior art keywords
germanium
oxide
metal
sinks
alkali
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CN201610339560.9A
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CN105907994B (en
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沈建中
韩笑
孙灿
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QUZHOU HUAYOU COBALT NEW MATERIAL CO Ltd
Zhejiang Huayou Cobalt Co Ltd
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QUZHOU HUAYOU COBALT NEW MATERIAL CO Ltd
Zhejiang Huayou Cobalt Co Ltd
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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
    • C22B41/00—Obtaining germanium
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Removal Of Specific Substances (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to a treatment method for comprehensive resource recycling of dissipated metal germanium, in particular to a treatment method for carrying out precipitation recycling on germanium through metallic oxide. According to the treatment method, the metallic oxide is adopted as a neutral precipitation agent, a two-section neutralizing hydrolysis method is adopted, and the germanium is subjected to precipitation recycling from germanium containing material liquid. Compared with an existing germanium precipitation recycling process, the advantages of the method are remarkable, the metallic oxide is adopted as the neutral precipitation agent, and the two-section neutralizing hydrolysis method is adopted for treating germanium pre-precipitation liquid; operation is easy, the residue filtering performance is good, and the quantity of added auxiliary materials is small; and the total germanium precipitation rate can reach 98% or above, the grade of obtained germanium concentrates is about 6%-8%, and extraction and comprehensive recycling of the valuable metal germanium in the germanium containing material liquid can be achieved.

Description

A kind of metal-oxide sinks the method for germanium
Technical field
The present invention relates to the processing method that the comprehensive resource of dissipated metal germanium reclaims, particularly to the processing method of a kind of metal oxide deposits Ti recovery.
Technical background
At present, the major processes precipitating Ti recovery from the germanic feed liquids such as cobalt Copper making leachate includes: the tannin sedimentation method, H2The S sedimentation method and Fe-Ge coprecipitation.The tannin sedimentation method are simple to operate, rate of deposition is high, but tannin is expensive, consumption is big, generally 25～30 times of Ge content, belong to expendable consumed product, and the tannic acid Organic substance contained in tannin can produce certain impact to follow-up cobalt, copper extraction process, and tannin is expensive, tannin supply has limitation.H2Though the S sedimentation method have germanium is enriched with fast, good selective, but operating condition is harsh, is unfavorable for producing, and H2S has toxicity, and operating environment is poor, there is potential safety hazard and the requirement to reaction unit is high in industry actual production.Fe-Ge coprecipitation is to utilize Fe3+Produce co-precipitation Ti recovery during hydrolytic precipitation with Ge, this method environment is preferable, pollution-free, if but Fe in feed liquid3+Concentration is higher, hydrolyzes the Fe (OH) of generation in solution3Colloid amount is more, and in slag, iron-holder is high, germanium grade is low and slag strainability is poor, Fe3+The low germanium of concentration just cannot sink completely, therefore Fe-Ge coprecipitation is higher to ingredient requirement, has certain limitation.
Summary of the invention
It is an object of the invention to overcome the defect of any of the above method, it is provided that a kind of with metal-oxide for neutralization precipitation agent, use two sections of neutralizing hydrolysis methods, from germanic feed liquid, precipitate the processing method of Ti recovery.
To this end, the present invention is by the following technical solutions:
A kind of metal-oxide sinks the method for germanium, comprises the steps:
(1) liquid before the heavy germanium that certain volume contains sulphuric acid and Ge ion is taken, it is heated to 70-75 DEG C, add a certain amount of metal-oxide and water, regulation pH to 4.5-6, carry out one section of heavy germanium reaction 1-2h of alkali, the filtering residue of one section of heavy germanium of alkali prepares germanium product as germanium concentrate, and filtrate goes step (2) to carry out alkali two-stage nitration to sink germanium；
(2) one section of filtrate of alkali is heated to 70-75 DEG C, add a certain amount of metal-oxide and water, regulation pH to 5-7, carry out alkali two-stage nitration sink germanium reaction 1-2h, alkali two-stage nitration sink the filtering residue of germanium be back to the heavy germanium operation of one section of alkali before next group sinks germanium in liquid weight the most molten, alkali two-stage nitration filtrate goes liquid waste processing operation.
As preferably, described metal-oxide is potassium oxide, sodium oxide or calcium oxide.
As preferably, before described heavy germanium, liquid is cobalt Copper making leachate.
As preferably, before described heavy germanium, in liquid, germanium concentration is more than 0.5g/L.
As preferably, described step (1) regulates in regulation pH to 5, described step (2) pH to 6.
The heavy germanium reaction of the present invention is as follows:
Ge(SO4)2+MeO+2H2O=MeO GeO2↓+2H2SO4
H2GeO3+ MeO=MeO GeO2↓+H2O (Me represents metal)
Compared with existing heavy germanium recovery process, advantage of the present invention is obvious, use metal-oxide as neutralization precipitation agent and with liquid before two sections of heavy germanium of neutralizing hydrolysis methods process, the most simple to operate, slag strainability preferably, adjuvant addition few, and the total rate of deposition of germanium can reach more than 98%, the germanium concentrate grade obtained is about 6%-8%, can realize extraction and the synthetical recovery of valuable metal germanium in germanic feed liquid.The inventive method can obtain the germanium concentrate that rate of deposition is higher, grade is higher, available HpGe product after processing further.The present invention enables in particular to realize utilizing the synthesization of valuable metal germanium in cobalt Copper making leachate, prepares HpGe product.
Accompanying drawing explanation
Fig. 1 is that a kind of metal-oxide of the present invention sinks the process chart of germanium method.
Detailed description of the invention
Embodiment 1
Take the sulphuric leachate of 50L cobalt Copper making as liquid before heavy germanium, wherein Cu concentration is 0.73g/L, Fe concentration is 22.97g/L, Ge concentration is 1.09g/L, and other impurity concentrations are shown in Table 1, are heated to 72 DEG C, liquid adds before heavy germanium metal-oxide and water, regulation pH value, to 5.0, filters after carrying out one section of heavy germanium reaction 1h of alkali, one section of residue washing post-drying detection；Adding metal-oxide and water after one section of filtrate is heated to 70 DEG C, regulation pH value, to 6.0, carries out alkali two-stage nitration and sinks and filter after germanium reaction 1h, and two-stage nitration residue washing post-drying detects, and two-stage nitration filtrate is detected.Testing result is shown in Table 1.
Table 1 embodiment 1 testing result
Composition Co Cu Fe Ge As
Liquid/g/L before heavy germanium 12.82 0.73 22.97 1.09 0.47
One section of filtrate/g/L 10.08 0.015 18.56 0.068 0.0077
One section of filtering residue/% 6.26 3.92 24.01 8.07 3.5
One section of rate of deposition/% 21.37 97.95 19.20 93.76 98.36
Two-stage nitration filtrate/g/L 4.85 0.0038 10.73 0.0015 0.0023
Two-stage nitration filtering residue/% 15.05 0.046 20.05 0.21 0.039
Two-stage nitration rate of deposition/% 51.88 84.80 42.19 97.79 70.13
Total rate of deposition/% 62.17 99.48 53.29 99.86 99.51
From testing result, the rate of deposition of one section of Ge reaches 93.76%, and one section of filtering residue is 8.07% containing Ge；In two-stage nitration filtrate, Ge concentration is 0.0015g/L, illustrates that Ge has precipitated completely, and two-stage nitration filtrate goes liquid waste processing operation；Two-stage nitration filtering residue is 0.21% containing Ge, is back to the heavy germanium operation of one section of alkali heavy molten in liquid before next group sinks germanium；Total rate of deposition of Ge is 99.86%, and the grade of germanium concentrate is 8.07%.
Embodiment 2
Take the sulphuric leachate of 50L cobalt Copper making as liquid before heavy germanium, wherein Cu concentration is 0.55g/L, Fe concentration is 24.04g/L, Ge concentration is 1.28g/L, and other impurity concentrations are shown in Table 2, are heated to 75 DEG C, liquid adds before heavy germanium metal-oxide and water, regulation pH value, to 4.5, filters after carrying out one section of heavy germanium reaction 1.5h of alkali, one section of residue washing post-drying detection；One section of filtrate being heated to 72 DEG C, adds metal-oxide and water, regulation pH value, to 5, carries out alkali two-stage nitration and sinks and filter after germanium reaction 2h, and two-stage nitration residue washing post-drying detects, and two-stage nitration filtrate is detected.Testing result is shown in Table 2.
Table 2 embodiment 2 testing result
From testing result, the rate of deposition of one section of Ge is 90.63%, and one section of filtering residue is 6.73% containing Ge；In two-stage nitration filtrate, Ge concentration is 0.025g/L, and two-stage nitration filtrate goes liquid waste processing operation；Two-stage nitration filtering residue is 1.79% containing Ge, is back to the heavy germanium operation of one section of alkali heavy molten in liquid before next group sinks germanium；Total rate of deposition of Ge is 98.05%, and the grade of germanium concentrate is 6.73%.
Embodiment 3
Take the sulphuric leachate of 50L cobalt Copper making as liquid before heavy germanium, wherein Cu concentration is 0.46g/L, Fe concentration is 3.68g/L, Ge concentration is 0.79g/L, other impurity concentrations are shown in Table 3, it is heated to 70 DEG C, adding metal-oxide and water before heavy germanium in liquid, regulation pH value, to 6, filters after carrying out one section of heavy germanium reaction 1h of alkali, one section of residue washing post-drying detection, adding metal-oxide and water after one section of filtrate is heated to 75 DEG C, regulation pH value, to 7, carries out alkali two-stage nitration and sinks and filter after germanium reaction 1h, two-stage nitration residue washing post-drying detects, and two-stage nitration filtrate is detected.Testing result is shown in Table 3.
Table 3 embodiment 3 testing result
From testing result, the rate of deposition of one section of Ge is 99.56%, and one section of filtering residue is 6.38% containing Ge；In two-stage nitration filtrate, Ge concentration is 0.001g/L, illustrates that Ge has precipitated completely, and two-stage nitration filtrate goes liquid waste processing operation；Two-stage nitration filtering residue is 0.25% containing Ge, is back to the heavy germanium operation of one section of alkali heavy molten in liquid before next group sinks germanium；Total rate of deposition of Ge is 99.87%, and the grade of germanium concentrate is 6.38%.

Claims (9)

1. a metal-oxide sinks the method for germanium, it is characterised in that: comprise the steps:
(1) take liquid before the heavy germanium that certain volume contains sulphuric acid and Ge ion, be heated to 70-75 DEG C, add a certain amount of metal-oxide and water, regulate pH to 4.5-6, carry out one section of heavy germanium reaction 1-2 of alkali H, the filtering residue of one section of heavy germanium of alkali prepares germanium product as germanium concentrate, and filtrate goes step (2) to carry out alkali two-stage nitration to sink germanium；
(2) one section of filtrate of alkali is heated to 70-75 DEG C, add a certain amount of metal-oxide and water, regulate pH to 5-7, carry out alkali two-stage nitration and sink germanium reaction 1-2 h, alkali two-stage nitration sink the filtering residue of germanium be back to the heavy germanium operation of one section of alkali before next group sinks germanium in liquid weight the most molten, alkali two-stage nitration filtrate goes liquid waste processing operation.
A kind of metal-oxide the most according to claim 1 sinks the method for germanium, it is characterised in that: described metal-oxide is potassium oxide, sodium oxide or calcium oxide.
A kind of metal-oxide the most according to claim 1 and 2 sinks the method for germanium, it is characterised in that: before described heavy germanium, liquid is cobalt Copper making leachate.
A kind of metal-oxide the most according to claim 1 and 2 sinks the method for germanium, it is characterised in that: before described heavy germanium in liquid germanium concentration more than 0.5g/L.
A kind of metal-oxide the most according to claim 3 sinks the method for germanium, it is characterised in that: before described heavy germanium in liquid germanium concentration more than 0.5g/L.
A kind of metal-oxide the most according to claim 1 and 2 sinks the method for germanium, it is characterised in that: regulation pH to 6 in regulation pH to 5, described step (2) in described step (1).
A kind of metal-oxide the most according to claim 3 sinks the method for germanium, it is characterised in that: regulation pH to 6 in regulation pH to 5, described step (2) in described step (1).
A kind of metal-oxide the most according to claim 4 sinks the method for germanium, it is characterised in that: regulation pH to 6 in regulation pH to 5, described step (2) in described step (1).
A kind of metal-oxide the most according to claim 5 sinks the method for germanium, it is characterised in that: regulation pH to 6 in regulation pH to 5, described step (2) in described step (1).
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107723467A (en) * 2017-09-20 2018-02-23 郴州丰越环保科技有限公司 A kind of method of high efficiente callback germanium

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GB866039A (en) * 1958-09-29 1961-04-26 Gen Electric Co Ltd Improvements in or relating to the recovery of germanium
CN1069524A (en) * 1991-08-22 1993-03-03 沈阳冶炼厂 A kind of method that from offscum containing germanium, reclaims germanium
CN101418373A (en) * 2008-09-16 2009-04-29 云南临沧鑫圆锗业股份有限公司 Method for extracting germanium from chlorinated distillation slag
CN102392144A (en) * 2011-11-07 2012-03-28 云南东昌金属加工有限公司 Process method for recovering indium and germanium from germanium concentrate
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB866039A (en) * 1958-09-29 1961-04-26 Gen Electric Co Ltd Improvements in or relating to the recovery of germanium
CN1069524A (en) * 1991-08-22 1993-03-03 沈阳冶炼厂 A kind of method that from offscum containing germanium, reclaims germanium
CN101418373A (en) * 2008-09-16 2009-04-29 云南临沧鑫圆锗业股份有限公司 Method for extracting germanium from chlorinated distillation slag
CN102392144A (en) * 2011-11-07 2012-03-28 云南东昌金属加工有限公司 Process method for recovering indium and germanium from germanium concentrate
CN104593611A (en) * 2014-12-30 2015-05-06 郴州丰越环保科技有限公司 Method for efficiently recovering germanium

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107723467A (en) * 2017-09-20 2018-02-23 郴州丰越环保科技有限公司 A kind of method of high efficiente callback germanium

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