CN104789777A - Method for recovering germanium and bismuth from bismuth germinate crystal processing wastes - Google Patents

Method for recovering germanium and bismuth from bismuth germinate crystal processing wastes Download PDF

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Publication number
CN104789777A
CN104789777A CN201410023369.4A CN201410023369A CN104789777A CN 104789777 A CN104789777 A CN 104789777A CN 201410023369 A CN201410023369 A CN 201410023369A CN 104789777 A CN104789777 A CN 104789777A
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China
Prior art keywords
bismuth
germanium
hydrochloric acid
crystal processing
vinasse
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CN201410023369.4A
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张发
孟力民
杨武斌
王波
张建伟
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Hanergy New Material Technology Co Ltd
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Hanergy New Material Technology Co Ltd
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    • 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

Abstract

The invention relates to a method for recovering germanium and bismuth from bismuth germinate crystal processing wastes. The method comprises the following steps: a, mixing bismuth germinate crystal processing wastes and hydrochloric acid in a reaction vessel, adding potassium permanganate, introducing steam for heating and initiating a reaction so as to convert germanium to germanium tetrachloride, distilling germanium tetrachloride to obtain distillation residue containing Bi<3+>; b, diluting the distillation residue containing Bi<3+> by adding water until concentration of hydrochloric acid is 1-3 mol/L; and c, carrying out a replacement reaction by adding iron powder into the diluted distillation residue containing Bi<3+> so as to obtain sponge bismuth. According to the method, germanium and bismuth can be recovered at high recovery rate. In addition, the technological process is simple, and amounts of wastewater and waste residue are small.

Description

A kind of method of Ti recovery and bismuth from bismuth-germanium-oxide crystal processing waste material
Technical field
The invention belongs to bismuth germanium oxide waste recovery and utilize field.
Background technology
Bismuth germanium oxide chemical formula is Bi 4ge 3o 12, be called for short BGO, in BGO, the valency of bismuth is+3 valencys, and the valency of germanium is+4 valencys.Early 1980s, Shanghai Inst. of Silicate, Chinese Academy of Sciences adopts falling crucible method successfully to grown large size bismuth germanium oxide (Bi 4ge 3o 12) monocrystalline.Because this crystal stops that energetic ray ability is strong, resolving power is high, thus the detection of high energy particle and energetic ray is particularly suitable for, be widely used in research fields such as ultimate particle, space physics and high energy physics, and be extremely successfully used on the electromagnetic calorimeter of CERN L3 electron-positron collider.Due to the physicals of bismuth germanium oxide (BGO) crystal uniqueness, it is made to be widely used in high energy physics, space science, nuclear medicine etc.
BGO crystal loss ratio in the postorder course of processing is comparatively large, about has the loss of 20-40%.In addition, because the polishing grinding wheel of BGO crystal carries out, the chip on bruting process medium plain emery wheel can enter in waste material, in waste material, introduce silicon-dioxide.
The output of current domestic BGO crystal is 6-8 ton/year, and the BGO crystal pro cessing waste material of generation has 2-3 ton/year containing about BGO, and in current domestic BGO waste material, main component is:
Title Ge，％ Bi，％ SiO 2，％ Other
BGO waste material 2--5 7--20 70--85 3-5
Can be found out by above analytical results, inside these BGO waste materials, the value of germanium, bismuth is all very high, needs synthetical recovery.For the recovery of germanium in BGO waste material, domestic generally have two kinds of methods:
First method adds hydrochloric acid by liquid-solid ratio 2: 1-3: 1, adds appropriate potassium permanganate, distills, steamed by germanium with the form of germanium tetrachloride under the condition of temperature 105-110 DEG C; Bismuth-containing solution limestone vegetation after distillation obtains in bismuth-containing and slag.
Bi 4Ge 3O 12+12Cl -+24H +＝4Bi 3++3GeCl 4↑+12H 2O
Bi 3++3OH -＝Bi(OH) 3↓
Germanium in BGO waste material leaches under the condition of temperature about 100 DEG C by liquid-solid ratio 3: 1-4: 1 by the alkali lye of second method containing sodium hydroxide 200-300g/l, and the germanic alkali lye obtained salt adding acid distillation after acidifying obtains germanium tetrachloride; Leached mud Leaching in Hydrochloric Acid bismuth, then neutralization obtains bismuth slag.
Bi 4Ge 3O 12+6OH -＝3GeO 3 2-↑+2Bi 2O 3+3H 2O
GeO 3 2+2H +＝GeO 2+H 2O
GeO 2+4H ++4Cl -＝GeCl 4↑+2H 2O
Bi 2O 3+6H +＝2Bi 3++3H 2O
Bi 3++3OH -＝Bi(OH) 3↓
Comprehensive condition is as following table:
* the Ge rate of recovery and the Bi rate of recovery all refer to the rate of recovery in bismuth-germanium-oxide crystal processing waste material removal process.
Visible, the rate of recovery of first method germanium is higher, very low with bismuth in slag in obtaining.Analysis reason is that the raffinate acidity after distillation is higher, uses limestone vegetation, produces the very large quantity of slag, so the content of bismuth is low in slag.If so low bi content will carry out recovery to be needed first to carry out to leach-be hydrolyzed-and retailoring just can obtain thick bismuth, and energy consumption is high, and enter bismuth smelting system at follow-up bismuth slag and reclaim in the process of bismuth, the comprehensive yield of bismuth only has about 50%.
Also visible, the rate of recovery of second method germanium is lower, and in the bismuth-containing slag obtained, bi content increases.Analyzing reason is containing SiO inside BGO waste material 2, in basic solution leaching process, not only BGO structure is not sufficiently damaged but also SiO 2existence need to consume alkali greatly, cause the leaching yield of germanium low; Leach the bismuth-containing hydrochloric acid for dreg after germanium to leach, then with ash neutralization, the quantity of slag of generation is still very large, so the content of bismuth improves not obvious in slag.Reclaiming bismuth needs first to carry out to leach-be hydrolyzed-and retailoring just can obtain thick bismuth, and energy consumption is high, and enter at follow-up bismuth slag in the process of bismuth smelting system recovery bismuth, the comprehensive yield of bismuth also only has about 70%.
Can be found out by above analysis, this this raw material effect of two kinds of mode process is all bad, there is the problem that comprehensive recovery is low, bismuth-containing item position is low, and especially second method energy consumption, subsidiary material consumption are larger, cost remains high, and the rate of recovery of precious metal germanium is very low.And in above-mentioned two kinds of methods, be all neutralize containing Bi with lime 3+acidleach raffinate generate in hydrogeneous bismuth oxide and slag, the take-back model of bismuth does not have substantial improvements.In order to solve the problem, inventor developed the technology of new Ti recovery and bismuth from BGO waste material, so that can simultaneously with high-recovery Ti recovery and bismuth from BGO waste material.
Summary of the invention
The present invention relates to a kind of method of Ti recovery and bismuth from bismuth-germanium-oxide crystal processing waste material, comprise the steps:
A. mixed in a kettle. with hydrochloric acid by bismuth-germanium-oxide crystal processing waste material, and add potassium permanganate, heating also initiation reaction, make germanium change into germanium tetrachloride, this germanium tetrachloride is distilled away, remaining containing Bi 3+vinasse;
B. add water described containing Bi 3+the vinasse concentration of hydrochloric acid be diluted to wherein be 1-3mol/L;
C. to after dilution containing Bi 3+vinasse in add iron powder there is replacement(metathesis)reaction, obtain sponge bismuth.
In preferred embodiments, method of the present invention also comprises carries out further rectification process to the germanium tetrachloride distilled away, obtains the germanium tetrachloride of having purified, then makes it be hydrolyzed in pure water, obtains pure germanium dioxide product.
In preferred embodiments, method of the present invention also comprises the waste liquid limestone vegetation will produced after displacement reduction in step b, to make Fe wherein 2+and/or Fe 3+there is flocculation sediment, self-purification is carried out to waste liquid simultaneously.
In method of the present invention, the rate of recovery of germanium is greater than 98%, and the rate of recovery of bismuth is greater than 96%.
Summary of the invention
In step a, mixed in a kettle. by bismuth-germanium-oxide crystal processing waste material, and add potassium permanganate with hydrochloric acid, heating also initiation reaction, make germanium change into germanium tetrachloride, this germanium tetrachloride is distilled away, remaining containing Bi 3+vinasse.Wherein the add-on of potassium permanganate depends on the number of organism in waste material (grease etc. be mixed in the such as course of processing) and determines, and object is removed by these oxidation operations under sour environment.Heating can adopt any type of heating, and the mode adopted in a kind of practice in the chuck of reactor, passes into steam heat, and after being heated to certain temperature, causing and reacts as follows:
Bi 4Ge 3O 12+12Cl -+24H +＝4Bi 3++3GeCl 4↑+12H 2O
Wherein germanium tetrachloride is distilled away as steam under this steam heating condition, remaining containing Bi 3+vinasse, also containing unreacted excessive hydrochloric acid in this vinasse.Wherein, still-process will control temperature well, carries out: initial stage temperature is too high, controls at 85-90 DEG C according to step below; Mid-term, temperature slightly raised, and controlled at 90-100 DEG C; Latter temperature continues to raise, control 105-110 DEG C.
In preferred embodiments, the germanium tetrachloride steam distilled away is cooled to thick germanium tetrachloride and is recovered in water cooler, then through further rectification process to obtain high-purity germanium tetrachloride, such as, rectification temperature can control at 83-90 DEG C.This high-purity germanium tetrachloride itself can be used as commodity selling.Or following hydrolysis can be there is in this high-purity germanium tetrachloride in pure water:
GeCl 4+2H 2O＝GeO 2+4HCl
This hydrolysis reaction can obtain germanium dioxide, sells after drying, oven dry with the form of high-purity germanium dioxide product.
In step b, add water described containing Bi 3+the vinasse concentration of hydrochloric acid be diluted to wherein be 1-3mol/L; Such as, the concentration of hydrochloric acid in vinasse is diluted to 1-3mol/L from about 6mol/L, is preferably diluted to 2mol/L.
In step c, to after dilution containing Bi 3+vinasse in add iron powder there is replacement(metathesis)reaction, obtain sponge bismuth.To the Bi be under above-mentioned concentration of hydrochloric acid 3+vinasse in when adding iron powder, only observe little bubble (i.e. hydrogen) and produce, this illustrates the most and Bi of the iron powder added 3+there is replacement(metathesis)reaction, and only have very little a part of iron powder and hydrochloric acid to react.This exceed those skilled in the art expect because being generally expected to is that first the iron powder added can react with hydrochloric acid, this be also those skilled in the art for a long time unexpected iron powder replace reduce Bi 3+to reclaim the reason of Bi.Bi in the amount of the iron added and solution 3+mass ratio, can be controlled in (0.6-0.7): 1.And the generation promoting replacement(metathesis)reaction is stirred to raffinate.The bismuth cemented out is loose porous shape, therefore is referred to as sponge bismuth.This sponge bismuth can be passed through filters and cleaning, obtains sponge bismuth product, is directly used in and sells or directly carry out caustic fusion, refining and obtain smart bismuth.Waste liquid after displacement, containing Fe 2+and/or Fe 3+(Fe 2+after contacting with air in whipping process, be easy to partially or completely be oxidized to Fe 3+, therefore there is Fe in waste liquid 2+and/or Fe 3+), then drop into lime wherein, then Fe wherein 2+and/or Fe 3+become corresponding oxyhydroxide and flocculation sediment, because ironic hydroxide or ferrous hydroxide are all good flocculation agents, therefore, it is possible to carry out self-purification process to waste liquid simultaneously.Therefore, in method of the present invention, only discharge of wastewater can be realized with lime treatment waste liquid up to standard, without the need to extra wastewater treatment process.Waste water after treatment, all neither go discharge, the amount of wherein 2/3rds may be used for diluting aforementioned vinasse, only about 1/3rd goes discharge, This further reduces wastewater discharge.
Compare with the method for bismuth with traditional Ti recovery from bismuth-germanium-oxide crystal processing waste material, the present invention has the following advantages: the rate of recovery of this technology germanium ensures more than 98%, the rate of recovery of bismuth is more than 96%, the sponge bismuth grade more than 80% obtained, obtains the bi content with the 5-10% of slag in bismuth-containing far above traditional method.Sponge obtains smart bismuth after refining, and in follow-up Bi refining removal process, the comprehensive yield of Bi is more than 92%, and more originally improve 42 percentage points, efficiency significantly declines.Obtain sponge bismuth product in the present invention, can be directly used in and sell or directly carry out caustic fusion, refining and obtain smart bismuth, and need not as traditional method, also need in bismuth-containing and slag carry out acidleach-hydrolysis-reducing and smelting and just can obtain thick bismuth.Which greatly simplifies the recovery process of bismuth.In addition, the wastewater discharge that method of the present invention produces is fewer than traditional method a lot, and does not produce in a large amount of bismuth-containings and slag, therefore, and environmental friendliness more.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of an embodiment of method of the present invention.

Claims (5)

1. the method for Ti recovery and bismuth from bismuth-germanium-oxide crystal processing waste material, comprises the steps:
A. mixed in a kettle. with hydrochloric acid by bismuth-germanium-oxide crystal processing waste material, and add potassium permanganate, heating also initiation reaction, make germanium change into germanium tetrachloride, this germanium tetrachloride is distilled away, remaining containing Bi 3+vinasse;
B. add water described containing Bi 3+the vinasse concentration of hydrochloric acid be diluted to wherein be 1-3mol/L;
C. to after dilution containing Bi 3+vinasse in add iron powder there is replacement(metathesis)reaction, obtain sponge bismuth.
2. method according to claim 1, its described germanium tetrachloride also comprised distilling away carries out further rectification process, obtains the germanium tetrachloride of having purified, then makes it be hydrolyzed in pure water, obtains pure germanium dioxide product.
3. method according to claim 1, it also comprises the waste liquid limestone vegetation will produced after displacement reduction in described step b, to make Fe wherein 2+and/or Fe 3+there is flocculation sediment, self-purification is carried out to waste liquid simultaneously.
4. method according to claim 1, in wherein said step a by heating material to the temperature being no more than 110 DEG C.
5. method according to claim 1, the Bi in the iron powder added in wherein said step c and solution 3+mass ratio be (0.6-0.7): 1.
CN201410023369.4A 2014-01-16 2014-01-16 Method for recovering germanium and bismuth from bismuth germinate crystal processing wastes Pending CN104789777A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2660444C1 (en) * 2017-05-30 2018-07-06 Федеральное государственное бюджетное учреждение науки Институт металлургии Уральского отделения Российской академии наук (ИМЕТ УрО РАН) Method of processing germanium containing materials
CN111647760A (en) * 2020-06-16 2020-09-11 中南大学 Method for selectively recovering germanium, bismuth and silicon from bismuth-doped silica optical fiber

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2660444C1 (en) * 2017-05-30 2018-07-06 Федеральное государственное бюджетное учреждение науки Институт металлургии Уральского отделения Российской академии наук (ИМЕТ УрО РАН) Method of processing germanium containing materials
CN111647760A (en) * 2020-06-16 2020-09-11 中南大学 Method for selectively recovering germanium, bismuth and silicon from bismuth-doped silica optical fiber
CN111647760B (en) * 2020-06-16 2021-03-23 中南大学 Method for selectively recovering germanium, bismuth and silicon from bismuth-doped silica optical fiber

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Application publication date: 20150722