CN108439459A - A kind of technique using regeneration germanium production germanium tetrachloride - Google Patents
A kind of technique using regeneration germanium production germanium tetrachloride Download PDFInfo
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- CN108439459A CN108439459A CN201810438244.6A CN201810438244A CN108439459A CN 108439459 A CN108439459 A CN 108439459A CN 201810438244 A CN201810438244 A CN 201810438244A CN 108439459 A CN108439459 A CN 108439459A
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- germanium
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- tetrachloride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
- C01G17/04—Halides of germanium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The invention discloses a kind of techniques producing germanium tetrachloride using regeneration germanium, which is containing FeCl2It after regeneration germanium raw material is added in the hydrochloric acid solution of catalyst, is continuously passed through chlorine and carries out chlorination reaction, after the completion of chlorination reaction, be separated by distillation recycling germanium tetrachloride product.This is simple for process, and low energy consumption, at low cost, and effectively realizes spent acid closed cycle use, solves environmental issue, while improving regeneration germanium raw materials recovery rate, generates higher economic value.
Description
Technical field
It is the present invention relates to a kind of preparation process of germanium tetrachloride, more particularly to a kind of to pass through dichloride using regeneration germanium raw material
Iron catalytic chlorination prepares GeCl4New technology, belong to GeCl4Preparing technical field.
Background technology
In the prior art, GeCl4It is mainly prepared using regeneration germanium raw material, is used to prepare GeCl4Germanium to account for annual germanium total
The 70~80% of output.Germanium in reclaiming germanium produces GeCl4Traditional handicraft mainly include it is following two：
1) by piece alkali NaOH and H2O2、H2O, by quality 1：2：1 ratio generates inclined germanium by steam heating melting, oxidation
Sour sodium, then neutralize with sulfuric acid to acidity, add salt acid distillation output germanium tetrachloride.
2) germanium raw material and sodium carbonate are regenerated：By quality 1:3 ratios mix, and in 800 DEG C of roasts one hour, steam calorified
110 DEG C with salt acid distillation output germanium tetrachloride.
The traditional preparation process of both the above has the following disadvantages：(1) the residual acid amount of product is more, and germanium is discharged less than 50mg/L；
(2) the germanium rate of recovery is relatively low, between 90~95%；(3) complex operation, labor intensity is big, and day produces GeCl4Amount
It is few；(4) a large amount of acid pickles discharge, environmental pollution is serious；(5) energy consumption is higher, of high cost, it is difficult to large-scale promotion application.
Chinese patent (publication number CN103183375A) is disclosed using germanium concentrate as raw material, in hydrochloric acid, sulfuric acid, ferric trichloride
Thick germanium tetrachloride is prepared in reaction in system；It is again that thick germanium tetrachloride, hydrochloric acid and manganese dioxide is abundant in multiple steaming reaction kettle
Mixing, distilation obtain the germanium tetrachloride of preliminary purification；It is purified in quartzy rectifying column by the multiple germanium tetrachloride for steaming purification
To high-purity germanium tetrachloride.Although this method can obtain transition metal impurity content by germanium concentrate is less than 3ppb, hydrogen containing foreign
Less than the high-purity germanium tetrachlorides of 1ppm, but its technique is sufficiently complex, high energy consumption, also without solving the problems such as spent acid pollutes.
Invention content
For existing GeCl is prepared using regeneration germanium raw material4Technique, the purpose of the present invention
It is to be to provide a kind of to utilize FeCl2It is catalyzed chlorinated with chlorine regeneration germanium raw material and prepares GeCl4Technique, this is simple for process, energy consumption
It is low, it is at low cost, and spent acid closed cycle use is effectively realized, solve environmental issue, while improving regeneration germanium raw materials recovery
Rate generates higher economic value.
It in order to achieve the above technical purposes, should the present invention provides a kind of technique producing germanium tetrachloride using regeneration germanium
Technique is containing FeCl2After regeneration germanium raw material is added in the hydrochloric acid solution of catalyst, continuously it is passed through chlorine and carries out chlorination reaction, chlorine
After the completion of changing reaction, it is separated by distillation recycling germanium tetrachloride product.
Technical scheme of the present invention dexterously utilizes FeCl2As catalyst, germanium may be implemented as chlorination reagent in chlorine
Efficient chlorination, to improve the rate of recovery of germanium in regeneration germanium, while FeCl2It will not lose and pollute with hydrochloric acid solution, it can be with
It is reused, the pollutants such as no acid pickle generate.
The mass percent concentration of preferred scheme, the hydrochloric acid solution is more than 18%.Preferably 6~7mol/L.Hydrochloric acid
Concentration be less than 18%, be easy to happen the hydrolysis of iron, cause solution in reaction kettle sticky, reaction speed is slow.Reaction kettle inner salt
The concentration of acid generates hydrogen chloride gas by salt acid distillation and supplements, if concentration of hydrochloric acid is excessively high in reaction kettle, tetrachloro when distillation
Hua Germanium influence recycled in its entirety rate with hydrogen chloride tail gas band people's tail gas alkali spray absorber.
Preferred scheme, FeCl2Mass percent concentration of the catalyst in hydrochloric acid solution be 5~15%, preferably 9~
10%.Frerrous chloride mass concentration is too low, and rate of catalysis reaction declines, if frerrous chloride mass concentration is excessively high, frerrous chloride
Opposite concentration of hydrochloric acid is excessive, it may occur that the hydrolysis of iron, solution is sticky in reaction kettle, and reaction speed is slow.FeCl2Primarily serve rush
Into the effect of chlorine oxidation germanium, therefore, the FeCl of a certain concentration ratio2Be conducive to the progress of chlorination reaction.
Preferred scheme, regeneration germanium raw material are the 15~25% of hydrochloric acid solution quality；Preferably 19%~20%.
Preferred scheme, the intake of chlorine are regenerate germanium material quality 20% to 30%.
The temperature of preferred scheme, the chlorination reaction is 20~80 DEG C.
Preferred scheme, it is containing FeCl to be separated by distillation the reaction solution after recycling germanium tetrachloride product2The salt of catalyst
Acid solution is reused.
Preferred scheme is distilled to recover germanium tetrachloride and detaches germanium tetrachloride, hydrochloric acid and tail gas by three bifurcated devices.
The germanium tetrachloride good product purity that technical scheme of the present invention is produced by regenerating germanium, impurity content are low.
The regeneration germanium raw material of the present invention is crushed to granularity 98% (mass percent) of satisfaction and passes through 100 mesh screens.
Following reaction mainly occurs during being converted to germanium tetrachloride for the regeneration germanium raw material of the present invention：
Therefore, in entire reaction system, frerrous chloride plays the role of catalytic action, and hydrochloric acid solution plays medium, the two
Synergistic effect promotes chlorination reaction more successfully to carry out, and the amount kept in balance of frerrous chloride and hydrochloric acid solution.To salt
Acid solution and catalyst have obtained abundant recycling, no waste acid liquor discharge.
Compared with the prior art, the advantageous effects that technical scheme of the present invention is brought：
Present invention firstly provides using frerrous chloride as catalyst, chlorine is oxidant, realizes regeneration in a mild condition
The efficient chlorination of germanium.
Regeneration germanium raw material proposed by the present invention prepares GeCl4Technique can greatly improve regeneration germanium the rate of recovery, recycling
Rate is up to 98%, and relatively traditional method, the rate of recovery for regenerating germanium at least improves 3 percentage points.
Regeneration germanium raw material proposed by the present invention prepares GeCl4Technique realize reaction mother liquor and recycle, no acid pickle
Deng discharge, it is good for the environment.
Regeneration germanium raw material proposed by the present invention prepares GeCl4Technique use catalyst and the raw materials such as acid solution and chlorine
It is easy to get, and catalyst and acid solution free of losses, advantageously reduces cost.
Regeneration germanium raw material proposed by the present invention prepares GeCl4Handicraft product impurity content it is low, the one-pot daily output is big, energy consumption
It is low, be conducive to industrialized production.
Specific implementation mode
Following embodiment is intended to further illustrate the content of present invention, rather than limits scope of the claims.
Embodiment 1
The molten germanium ingot in the areas 20T is produced per year as regeneration germanium raw material using Hengyang Heng Rong Semi Materials Co., Ltd. is used to prepare tetrachloro
Change germanium, is illustrated.
Compound concentration is the hydrochloric acid solution of 6mol/L in reaction kettle, and frerrous chloride is added, and frerrous chloride is molten in hydrochloric acid
Mass percent concentration in liquid is 10%.Regeneration germanium powder is added in reaction kettle, the addition of germanium powder is hydrochloric acid solution quality
20%, the percent of pass that the granularity of germanium powder meets 100 mesh sieve reaches 98% or more, stirs 40 minutes, keeps solution system mixing equal
Even, control reactor temperature is at 30 DEG C, then is continuously passed through chlorine into hydrochloric acid solution and is reacted, and chlorine intake is according to gold
The addition for belonging to germanium calculates, and is the 25% of germanium quality, and the elemental Germanium regenerated in germanium is fully oxidized to Ge4+, react and form GeCl4
Solution.After logical chlorine reaction is complete, by being steam heated to 110 DEG C of distillations, double absorption pipette overflows separation germanium tetrachloride, gained
GeCl4Liquid form product.After distillation, solution continues supplement addition secondary metal germanium powder in reaction kettle, carries out next round chlorination
Reaction.Germanium is not lost substantially, and the rate of recovery reaches 98.5%, the GeCl separated and collected4Product, GeCl4Content is 99.95%.
Embodiment 2
The molten germanium ingot in the areas 20T is produced per year as regeneration germanium raw material using Hengyang Heng Rong Semi Materials Co., Ltd. is used to prepare tetrachloro
Change germanium, is illustrated.
Compound concentration is the hydrochloric acid solution of 7mol/L in reaction kettle, and frerrous chloride is added, and frerrous chloride is molten in hydrochloric acid
Mass percent concentration in liquid is 9%.Regeneration germanium powder is added in reaction kettle, the addition of germanium powder is hydrochloric acid solution quality
40%, the granularity of germanium powder meets the percent of pass that 100 mesh sieve and reaches 98% or more, stirs 60 minutes, solution system is made to be uniformly mixed,
Reactor temperature is controlled at 50 DEG C, then is continuously passed through chlorine into hydrochloric acid solution and is reacted, chlorine intake is according to metal
The addition of germanium calculates, and is the 35% of germanium quality, and the elemental Germanium regenerated in germanium is fully oxidized to Ge4+, react and form GeCl4It is molten
Liquid.After logical chlorine reaction is complete, by being steam heated to 110 DEG C of distillations, double absorption pipette overflows separation germanium tetrachloride, gained
GeCl4Liquid form product.After distillation, solution continues supplement addition secondary metal germanium powder in reaction kettle, carries out next round chlorination
Reaction.Germanium is not lost substantially, and the rate of recovery reaches 98.8%, the GeCl separated and collected4Product, GeCl4Content is 99.97%.
Claims (7)
1. a kind of technique using regeneration germanium production germanium tetrachloride, it is characterised in that：Containing FeCl2In the hydrochloric acid solution of catalyst
After regeneration germanium raw material is added, continuously it is passed through chlorine and carries out chlorination reaction, after the completion of chlorination reaction, be separated by distillation recycling tetrachloro
Change germanium product.
2. a kind of technique using regeneration germanium production germanium tetrachloride according to claim 1, it is characterised in that：The hydrochloric acid
The mass percent concentration of solution is more than 18%.
3. a kind of technique using regeneration germanium production germanium tetrachloride according to claim 1, it is characterised in that：FeCl2Catalysis
Mass percent concentration of the agent in hydrochloric acid solution is 5~15%.
4. a kind of technique using regeneration germanium production germanium tetrachloride according to claim 1, it is characterised in that：It is former to regenerate germanium
Material is the 15%~25% of hydrochloric acid solution quality.
5. a kind of technique using regeneration germanium production germanium tetrachloride according to claim 1, it is characterised in that：Chlorine leads to
It is regenerate germanium material quality 20% to 40% to enter amount.
6. according to a kind of technique producing germanium tetrachloride using regeneration germanium of Claims 1 to 5 any one of them, feature exists
In：The temperature of the chlorination reaction is 20 DEG C~80 DEG C.
7. a kind of technique using regeneration germanium production germanium tetrachloride according to claim 1, it is characterised in that：Pass through distillation
It is containing FeCl to separate and recover the reaction solution after germanium tetrachloride product2The hydrochloric acid solution of catalyst is reused.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109179487A (en) * | 2018-10-30 | 2019-01-11 | 云南驰宏国际锗业有限公司 | A method of utilizing waste acid treatment germanium mud |
| CN115367786A (en) * | 2022-09-05 | 2022-11-22 | 广东先导稀材股份有限公司 | Preparation method of germanium tetrachloride |
| CN115404363A (en) * | 2022-08-29 | 2022-11-29 | 云南驰宏国际锗业有限公司 | Method for recovering germanium from germanium mud by utilizing germanium concentrate distillation waste hydrochloric acid |
| CN115477322A (en) * | 2022-09-29 | 2022-12-16 | 云南驰宏国际锗业有限公司 | Ultra-high purity GeCl 4 Preparation method |
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| CN103183375A (en) * | 2011-12-29 | 2013-07-03 | 北京有色金属研究总院 | Preparation purification method of germanium tetrachloride for optical fiber |
| CN107324376A (en) * | 2017-08-02 | 2017-11-07 | 昆明汇泉高纯半导材料有限公司 | It is a kind of to utilize the method that germanium dioxide is produced containing germanium waste material |
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Patent Citations (2)
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| CN103183375A (en) * | 2011-12-29 | 2013-07-03 | 北京有色金属研究总院 | Preparation purification method of germanium tetrachloride for optical fiber |
| CN107324376A (en) * | 2017-08-02 | 2017-11-07 | 昆明汇泉高纯半导材料有限公司 | It is a kind of to utilize the method that germanium dioxide is produced containing germanium waste material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109179487A (en) * | 2018-10-30 | 2019-01-11 | 云南驰宏国际锗业有限公司 | A method of utilizing waste acid treatment germanium mud |
| CN115404363A (en) * | 2022-08-29 | 2022-11-29 | 云南驰宏国际锗业有限公司 | Method for recovering germanium from germanium mud by utilizing germanium concentrate distillation waste hydrochloric acid |
| CN115367786A (en) * | 2022-09-05 | 2022-11-22 | 广东先导稀材股份有限公司 | Preparation method of germanium tetrachloride |
| CN115367786B (en) * | 2022-09-05 | 2023-10-24 | 广东先导稀材股份有限公司 | Preparation method of germanium tetrachloride |
| CN115477322A (en) * | 2022-09-29 | 2022-12-16 | 云南驰宏国际锗业有限公司 | Ultra-high purity GeCl 4 Preparation method |
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