CN102031397A - Method for reducing high-purity germanium dioxide into germanium ingots continuously - Google Patents
Method for reducing high-purity germanium dioxide into germanium ingots continuously Download PDFInfo
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- CN102031397A CN102031397A CN 201010517799 CN201010517799A CN102031397A CN 102031397 A CN102031397 A CN 102031397A CN 201010517799 CN201010517799 CN 201010517799 CN 201010517799 A CN201010517799 A CN 201010517799A CN 102031397 A CN102031397 A CN 102031397A
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Abstract
The invention belongs to the field of dissipated metal metallurgy, in particular to a new method for reducing high-purity germanium dioxide into germanium ingots continuously. The method comprises the following steps of: adding germanium dioxide of which the purity is more than 99.99 percent into graphite boats, pushing the graphite boats from a preheating section of a quartz tube, and performing three-section heating, wherein the heating temperature of the preheating section is between 550 and 650 DEG C, the heating temperature of a reduction section is between 700 and 750 DEG C, and the heating temperature of an ingot casting section is between 980 and 1,000 DEG C; and allowing hydrogen of which the purity is more than 99 percent to enter from the ingot casting section in the flow of between 0.2 and 0.3 M<3>/H, pushing one boat of GeO2 at intervals of 30 minutes, reducing for 10 hours, and taking the germanium ingots in the graphite boats out. In the method, the process flow is simple, a reduction reaction is easy to control, and intermediate operating links can be reduced; and the method has the advantages of reducing energy consumption, improving production capacity and reducing the using amount of the hydrogen.
Description
Technical field
The invention belongs to the field of metallurgy of dissipated metal, be specifically related to reduce a kind of novel method of germanium ingot continuously with high-purity germanium dioxide.
Background technology
When high-purity germanium dioxide is reduced into the germanium ingot, generally all use pure hydrogen to make its chemical reaction of reductive agent to be:
GeO
2+H
2＝GeO+H
2O
GeO+H
2＝Ge+H
2O
The reduction process of prior art is divided into two above-mentioned stages, and because of GeO vapour pressure height, difficulty is controlled, and when processing parameter was unreasonable slightly, GeO is volatilization loss in a large number.Method commonly used is that a certain amount of germanium dioxide is packed in the quartz boat, is placed in the quartz heating-pipe, feeds hydrogen, drives the air in the silica tube away, heat up at times, not open closely go into hydrogen, through certain hour, outage, cooling after near room temperature, are taken out the germanium ingot.Therefore, adopt traditional method to exist production capacity little, power consumption is big, the deficiency of complicated operation.
Summary of the invention
The objective of the invention is to propose a kind of continuous reductive technology, thereby control easily, cut down the consumption of energy, improve production capacity, reduce hydrogen usage at existing commonly used method of reducing.
Realize that the technical scheme that the object of the invention adopted is: the purity of packing in graphite boat is greater than 99.99% germanium dioxide, graphite boat pushes from the preheating section of silica tube and carries out three sections heating, the preheating section Heating temperature is 550～650 ℃, the reduction section Heating temperature is 700～750 ℃, ingot casting section Heating temperature is 980～1000 ℃, purity is entered by the ingot casting section greater than 99% hydrogen, and the hydrogen flowing quantity that enters is 0.2～0.3M
3/ H pushed a boat GeO every 30 minutes
2, after reduction in 10 hours, take out germanium ingot in the graphite boat.
Described silica tube is to pack into to heat in the high alumina threaded pipe that twines resistance wire, adopts closed loop proportional-integration-differential control, resistive heating with the thyristor voltage regulation heater voltage in 160～200V interval.
Wall thickness of quartz tube 3～4mm, silica tube length 5～6m, silica tube external diameter are 100mm, and preheating section length is 1～1.5m, and reduction section length is 2.5～3m, and the ingot casting segment length is 1～1.5m, the high alumina threaded pipe internal diameter of heating is 110mm; The graphite boat cross section is the lonely type in half garden, long 250～300mm, in adorn 500～600g GeO
2
The end cap of silica tube preheating section and ingot casting section is a stainless steel, interior dress water jacket, water flowing cooling.
Beneficial effect of the present invention: because therefore the heating of silica tube contiguous segmentation controls reduction reaction easily, reduce GeO volatilization loss, also reduced energy consumption; Have easy to operately, production capacity is changeable, saves the advantage of hydrogen usage and power consumption effectively.
Embodiment
Embodiment 1: by feeding hydrogen 15 minutes in the ingot casting district, adopt closed loop proportional-integral-derivative controller to make resistive heating voltage be adjusted at 160～200V, energising heats up and makes each heating zone of silica tube after reaching design temperature, begin charging, pushed the GeO of a boat 500g purity 99.99% every 30 minutes
2, by the hydrogen of ingot casting section feeding purity 99%, hydrogen flowing quantity is 0.2M simultaneously
3/ H after 10 hours, takes out graphite boat, obtains qualified germanium ingot 337g.
Embodiment 2: the 600g purity of packing in graphite boat is 99.995% GeO
2, the hydrogen of feeding purity 99.1%, hydrogen flowing quantity is 0.3m
3/ H pushed boat footpath after 10 hours every 30 minutes, take out graphite boat, obtained qualified germanium ingot 403g.
Embodiment 3: the 500g purity of packing into is 99.998% GeO
2, the preheating section temperature is decided to be 550 ℃, and the reduction section temperature is set at 700 ℃, and ingot casting section temperature is decided to be 980 ℃, hydrogen purity 99.5%, flow is 0.2m
3/ H pushed away boat once every 30 minutes, obtained germanium ingot 335g after 10 hours.
Claims (4)
1. a high-purity germanium dioxide is reduced to the method for germanium ingot continuously, it is characterized in that: the purity of packing in graphite boat is greater than 99.99% germanium dioxide, graphite boat pushes from the preheating section of silica tube and carries out three sections heating, the preheating section Heating temperature is 550～650 ℃, the reduction section Heating temperature is 700～750 ℃, ingot casting section Heating temperature is 980～1000 ℃, and purity is entered by the ingot casting section greater than 99% hydrogen, and the hydrogen flowing quantity that enters is 0.2～0.3M
3/ H pushed a boat GeO every 30 minutes
2, after reduction in 10 hours, take out germanium ingot in the graphite boat.
2. be reduced to the method for germanium ingot continuously by the described high-purity germanium dioxide of claim 1, it is characterized in that: silica tube is to pack into to heat in the high alumina threaded pipe that twines resistance wire, adopt closed loop proportional-integration-differential control, resistive heating uses the thyristor voltage regulation heater voltage in 160～200V interval.
3. be reduced to the method for germanium ingot continuously by the described high-purity germanium dioxide of claim 2, it is characterized in that: wall thickness of quartz tube 3～4mm, silica tube length 5～6m, the silica tube external diameter is 100mm, preheating section length is 1～1.5m, reduction section length is 2.5～3m, and the ingot casting segment length is 1～1.5m, and the high alumina threaded pipe internal diameter of heating is 110mm; The graphite boat cross section is the lonely type in half garden, long 250～300mm, in adorn 500～600g GeO
2
4. be reduced to the method for germanium ingot continuously by the described high-purity germanium dioxide of claim 1, it is characterized in that: the end cap of silica tube preheating section and ingot casting section is a stainless steel, interior dress water jacket, water flowing cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010517799 CN102031397A (en) | 2010-10-25 | 2010-10-25 | Method for reducing high-purity germanium dioxide into germanium ingots continuously |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010517799 CN102031397A (en) | 2010-10-25 | 2010-10-25 | Method for reducing high-purity germanium dioxide into germanium ingots continuously |
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| CN102031397A true CN102031397A (en) | 2011-04-27 |
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| CN 201010517799 Pending CN102031397A (en) | 2010-10-25 | 2010-10-25 | Method for reducing high-purity germanium dioxide into germanium ingots continuously |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108048672A (en) * | 2018-02-06 | 2018-05-18 | 云南临沧鑫圆锗业股份有限公司 | The extraction stove and extracting method of germanium in low-grade germanium concentrate are extracted in thermal reduction volatilization |
| CN108239784A (en) * | 2018-03-23 | 2018-07-03 | 韶关保绿环保科技股份有限公司 | Zone melting furnace system |
| CN108546832A (en) * | 2018-05-09 | 2018-09-18 | 衡阳恒荣高纯半导体材料有限公司 | A kind of continuous hydrogen reduction method of germanium dioxide |
| CN110093517A (en) * | 2018-11-22 | 2019-08-06 | 云南驰宏国际锗业有限公司 | A kind of method that germanium dioxide continuously restores ingot casting |
| CN110842211A (en) * | 2019-12-17 | 2020-02-28 | 云南驰宏国际锗业有限公司 | Method for controlling particle size of superfine germanium powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186974A (en) * | 2006-11-15 | 2008-05-28 | 云南临沧鑫圆锗业股份有限公司 | Reclamation of germanium from germanium waste material by wet method |
| CN101698908A (en) * | 2009-10-20 | 2010-04-28 | 南京中锗科技股份有限公司 | Method for producing metal germanium ingots by continuous reduction |
-
2010
- 2010-10-25 CN CN 201010517799 patent/CN102031397A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186974A (en) * | 2006-11-15 | 2008-05-28 | 云南临沧鑫圆锗业股份有限公司 | Reclamation of germanium from germanium waste material by wet method |
| CN101698908A (en) * | 2009-10-20 | 2010-04-28 | 南京中锗科技股份有限公司 | Method for producing metal germanium ingots by continuous reduction |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108048672A (en) * | 2018-02-06 | 2018-05-18 | 云南临沧鑫圆锗业股份有限公司 | The extraction stove and extracting method of germanium in low-grade germanium concentrate are extracted in thermal reduction volatilization |
| CN108048672B (en) * | 2018-02-06 | 2023-09-15 | 云南临沧鑫圆锗业股份有限公司 | Extraction furnace and extraction method for extracting germanium in low-grade germanium concentrate by thermal reduction and volatilization |
| CN108239784A (en) * | 2018-03-23 | 2018-07-03 | 韶关保绿环保科技股份有限公司 | Zone melting furnace system |
| CN108546832A (en) * | 2018-05-09 | 2018-09-18 | 衡阳恒荣高纯半导体材料有限公司 | A kind of continuous hydrogen reduction method of germanium dioxide |
| CN110093517A (en) * | 2018-11-22 | 2019-08-06 | 云南驰宏国际锗业有限公司 | A kind of method that germanium dioxide continuously restores ingot casting |
| CN110842211A (en) * | 2019-12-17 | 2020-02-28 | 云南驰宏国际锗业有限公司 | Method for controlling particle size of superfine germanium powder |
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Application publication date: 20110427 |