CN1273386C - Production technology of optical fiber grade high purity ger manium tetrachloride - Google Patents
Production technology of optical fiber grade high purity ger manium tetrachloride Download PDFInfo
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- CN1273386C CN1273386C CN200410041500.6A CN200410041500A CN1273386C CN 1273386 C CN1273386 C CN 1273386C CN 200410041500 A CN200410041500 A CN 200410041500A CN 1273386 C CN1273386 C CN 1273386C
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- CN
- China
- Prior art keywords
- optical fiber
- germanium tetrachloride
- grade high
- chloride
- germanic
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- 239000013307 optical fiber Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 title claims description 33
- 238000005516 engineering process Methods 0.000 title abstract description 3
- 239000007789 gas Substances 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000012043 crude product Substances 0.000 claims abstract description 6
- 150000004820 halides Chemical class 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 15
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- AEEAZFQPYUMBPY-UHFFFAOYSA-N [I].[W] Chemical group [I].[W] AEEAZFQPYUMBPY-UHFFFAOYSA-N 0.000 claims description 3
- CKQBSDUWDZEMJL-UHFFFAOYSA-N [W].[Br] Chemical compound [W].[Br] CKQBSDUWDZEMJL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 7
- 238000004821 distillation Methods 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 8
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Silicon Compounds (AREA)
Abstract
The present invention discloses production technology of optical fiber-grade high-purity germanic chloride. The present invention has the steps that a rectifying device is made to be in an oxygen free and anhydrous state; under the protection of inert gases, catalyst and crude products of germanic chloride are added, wherein catalyst occupies 1 to 10 percent (weight ratio); halide gas needed in a reaction is led; a light-irradiation reactor or photoinitiator are used for reflux and distillation; a product is transferred under the protection of the inert gases. The present invention has the advantages that the manufacturing process is simple, a plurality of steps are completed in one device, and the defect that the production quality is decreased caused by solution transfer during the treatment course is avoided. The characteristic is quite important to the high-purity germanic chloride solution, for the germanic chloride can be easily decomposed when encounters water. The function of the germanic chloride in the optical fiber can be influenced even by a little water in the air.
Description
One, the technical field
The invention relates to a method for purifying a high-purity compound, in particular to a method for purifying high-purity germanium tetrachloride for producing optical fibers.
Second, background Art
The optical fiber is the basis of optical communication science and technology and industry, high-purity germanium tetrachloride is an indispensable key raw material of high-grade quartz optical fiber, and the germanium tetrachloride is used as a main doping agent in the quartz optical fiber and is used for improving the refractive index of the optical fiber, reducing the optical loss and further improving the transmission distance of the optical fiber. The distribution and content of germanium in the fiber determines the key performance index of the fiber, so the quality of the germanium directly affects the performance and quality of the fiber.
According to DE-AS No.1263730, germanium tetrachloride can be purified from hydrogen chloride. This process can remove arsenic and other similar impurities. Another german patent DE-asno.1948911 reports purification with anhydrous chlorine at a temperature in the range of-30 ℃ to 30 ℃, but this method does not remove hydrogen-containing impurities. According to us patent 4,842,839, it is reported that hydrogen atoms in germanium tetrachloride are chlorinated by chlorine gas into hydrogen chloride at high temperatures of 1000 c, thereby removing hydrogen-containing impurities. Another us patent 6,110,258 reports the use of zeolites to remove water molecules from gases, including germanium tetrachloride, but the effect is not as high as 6N. In combination with the above patents, germanium tetrachloride is treated either with hydrogen chloride gas alone or with chlorine gas alone or at extremely high temperatures, all under certain conditions to remove certain impurities.
Third, the invention
The invention aims to provide a method for purifying high-purity germanium tetrachloride, which can remove hydrogen-containing impurities and metal impurities on Ge-OH bonds and C-H bonds at one time by utilizing the characteristics of the germanium tetrachloride aiming at the defects in the prior art so as to obtain qualified products.
The technical scheme of the invention is as follows: a production process of optical fiber grade high-purity germanium tetrachloride is characterized by comprising the following steps:
1. the rectifying device is in an oxygen-free and water-free state;
2. under the protection of inert gas, adding a catalyst and a crude product of germanium tetrachloride, wherein the catalyst accounts for 1-10% (weight ratio);
3. introducing halide gas required by the reaction;
4. refluxing and distilling by using an illumination reaction kettle or using a photoinitiator;
5. the product is transferred under the protection of inert gas.
Wherein in step 4, refluxing at 50-90 deg.C for 2-8 hr, distilling at 80-100 deg.C, decomposing at a temperature above 300 deg.C, and collecting distillate at a low temperature below 20 deg.C.
In step 2, the catalyst is an aluminum, calcium, phosphorus, or magnesium containing compound.
Germanium tetrachloride is colorless oily liquid, is fuming in air, can be immediately decomposed when meeting water, and has stronger corrosion effect on metals. Aiming at the characteristic, the patent provides a simple purification method. The hydrogen-containing impurities and metal impurities on Ge-OH bonds and C-H bonds can be removed at one time by adding the mixed gas of hydrogen chloride and chlorine into a set of device and using illumination or adding a photoinitiator, so that a qualified product is obtained.
Because germanium tetrachloride can be immediately decomposed when it is in contact with water, when the volume fraction of water contained is greater than 1 × 10-2At mol/L, it will be at 3400cm-1An absorption peak appears in the vicinity. This is due to the following reaction: (when the volume fraction of water is less than 1X 10-2When mol/L); (n-2, 3) (when the volume fraction of water is more than 1X 10)-2At mol/L). In order to obtain high-purity germanium tetrachloride, the system contacted with the germanium tetrachloride must be ensured to be dry, and the method is to vacuumize the whole device under the heating condition and then to obtain the germanium tetrachlorideInert gas is flushed. In order to ensure that the system is dry, the charging and discharging are carried out under the protection of inert gas. The inert gas here may beIs nitrogen or argon. Chlorine is irradiated by light or a photoinitiator is added to generate chlorine free radicals, so that generated hydrogen ions are chlorinated. The hydrogen chloride generated by the chlorination reaction and the added hydrogen chloride gas can convert the hydroxide radical-containing compound into chloride. The light source can be an iodine tungsten lamp or a bromine tungsten lamp, and can irradiate for a long time or intermittently. Refluxing for 2-8 hr at 50-90 deg.c. The refluxed liquid is redistilled, chlorine and hydrogen chloride are continuously introduced during the redistillation, and the gas phase is condensed after high-temperature treatment. The high temperature treatment is to heat the quartz tube to 300-1000 deg.c with resistance wire and to make the distilled gas stay inside the quartz tube for 5 sec-1 min. The condensation temperature is-10 ℃ to 20 ℃. The chloride gas contained in the distillate was evacuated by a vacuum pump at low temperature and replaced with an inert gas. The low temperature is-50 deg.C to-5 deg.C. The required vacuum is 760mmHg to 700 mmHg. The product with the purity of more than 6N can be obtained by the treatment of the steps.
Compared with the prior art, the invention has the following remarkable advantages: the process is simple, and several steps are completed in one set of equipment, so that the problem of product quality reduction caused by solution transfer in the treatment process is avoided. This is particularly important for high purity germanium tetrachloride solutions because it decomposes very readily in the presence of water, even a small amount of moisture in the air can interfere with its use in optical fibers.
Fourth, detailed description of the invention
The invention is further described in detail below with reference to the following examples:
example 1: the production process of the optical fiber grade high-purity germanium tetrachloride comprises the following steps:
1. heating the whole device, blowing hot each part by an electric blower, vacuumizing for a period of time after reaching the limit vacuum, and filling nitrogen to atmospheric pressure; repeated for a total of three times.
2. Under the protection of nitrogen, about 50 g of anhydrous calcium chloride and about 500 g of crude germanium tetrachloride are added.
3. Heating the crude product of germanium tetrachloride to 80 ℃, introducing hydrogen chloride and chlorine, and performing light irradiation by using a tungsten iodine lamp for refluxing for 4 hours.
4. The quartz tube was heated to a temperature of 400 ℃.
5. And (4) preserving the temperature of the fractionating column for distillation, wherein the condensate is low-temperature brine.
6. About 30ml of the previous fraction is obtained, and about 150ml of the middle fraction is obtained.
7. The product was transferred to a 500ml round bottom flask under nitrogen.
8. Hydrogen chloride and chlorine gas were extracted at a low temperature (about-20 ℃) environment made of liquid nitrogen.
Example 2: the invention relates to a production process of optical fiber grade high-purity germanium tetrachloride, which comprises the following steps:
1. heating the whole device, blowing hot each part by electric blower and vacuumizing, vacuumizing for a period of time after reaching the limit vacuum, and filling nitrogen to atmospheric pressure for three times.
2. Under the protection of argon, about 50 g of phosphorus oxide-free and about 1000 g of crude germanium tetrachloride are added.
3. Heating the crude product of germanium tetrachloride to 60 ℃, introducing hydrogen chloride and chlorine, illuminating by a bromine-tungsten lamp, and refluxing for 6 hours.
4. The quartz tube was heated to a temperature of 600 ℃.
5. And (4) preserving the temperature of the fractionating column for distillation, wherein the condensate is tap water.
6. About 50ml of the previous fraction is obtained, and about 400ml of the middle fraction is obtained.
7. The product was transferred to a 1000ml round bottom flask under argon.
8. Hydrogen chloride and chlorine gas were extracted at a low temperature (about-20 ℃) environment made of liquid nitrogen.
Example 3: the invention relates to a production process of optical fiber grade high-purity germanium tetrachloride, which comprises the following steps:
1. heating the whole device, blowing hot each part by an electric blower, vacuumizing for a period of time after reaching the limit vacuum, and filling nitrogen to atmospheric pressure; repeated for a total of three times.
2. Under a nitrogen atmosphere, about 10 g of magnesium compound and about 1000 g of crude germanium tetrachloride were added.
3. Heating the crude product of germanium tetrachloride to 90 ℃, introducing hydrogen chloride and chlorine, using a photoinitiator, and refluxing for 2 hours.
4. The quartz tube was heated to a temperature of 300 ℃.
5. And (4) preserving the temperature of the fractionating column for distillation, wherein the condensate is low-temperature brine.
6. About 50ml of the previous fraction is obtained, and about 400ml of the middle fraction is obtained.
7. The product was transferred to a 1000ml round bottom flask under nitrogen.
8.Hydrogen chloride and chlorine gas were extracted at a low temperature (about-20 ℃) environment made of liquid nitrogen.
Claims (5)
1. A production process of optical fiber grade high-purity germanium tetrachloride is characterized by comprising the following steps:
(1) the rectifying device is in an oxygen-free and water-free state;
(2) under the protection of inert gas, adding catalyst anhydrous calcium chloride or phosphorus pentoxide and a germanium tetrachloride crude product, wherein the catalyst accounts for 1-10% by weight;
(3) introducing halide gas required by the reaction, wherein the halide gas is mixed gas of hydrogen chloride and chlorine;
(4) refluxing and distilling by using an illumination reaction kettle or a photoinitiator, wherein the temperature conditions are as follows: refluxing at 50-90 deg.C for 2-8 hr, distilling at 80-100 deg.C, decomposing at above 300 deg.C, and collecting distillate at low temperature;
(5) transferring the product under the protection of inert gas;
(6) hydrogen chloride and chlorine gas were extracted under a low temperature environment of-20 ℃ made with liquid nitrogen.
2. The process for producing optical fiber grade high-purity germanium tetrachloride according to claim 1, wherein in the step (4), the low temperature is 20 ℃ or less.
3. The process for producing optical fiber grade high-purity germanium tetrachloride according to claim 1, wherein in the step (1), inert gas is repeatedly introduced into the device, and the whole rectification device is in an oxygen-free and water-free state by heating and vacuumizing.
4. The process for the production of fiber-grade high-purity germanium tetrachloride according to claim 1 or 3, wherein the inert gas is nitrogen or argon.
5. The process for producing optical fiber grade high-purity germanium tetrachloride according to claim 1, wherein in (4), the light source is iodine tungsten lamp or bromine tungsten lamp.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410041500.6A CN1273386C (en) | 2004-07-27 | 2004-07-27 | Production technology of optical fiber grade high purity ger manium tetrachloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410041500.6A CN1273386C (en) | 2004-07-27 | 2004-07-27 | Production technology of optical fiber grade high purity ger manium tetrachloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1597533A CN1597533A (en) | 2005-03-23 |
| CN1273386C true CN1273386C (en) | 2006-09-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200410041500.6A Expired - Fee Related CN1273386C (en) | 2004-07-27 | 2004-07-27 | Production technology of optical fiber grade high purity ger manium tetrachloride |
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| Country | Link |
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| CN (1) | CN1273386C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102328951B (en) * | 2011-07-13 | 2014-08-06 | 云南驰宏锌锗股份有限公司 | Method and device for removing hydrogen-containing impurities from germanium tetrachloride |
| CN103387237A (en) * | 2012-05-10 | 2013-11-13 | 深圳市格林美高新技术股份有限公司 | Method for recycling optical fiber wastes |
| 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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- 2004-07-27 CN CN200410041500.6A patent/CN1273386C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1597533A (en) | 2005-03-23 |
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