CN101234780A - Method for producing germanium tetrachloride for optical fibre - Google Patents
Method for producing germanium tetrachloride for optical fibre Download PDFInfo
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- CN101234780A CN101234780A CNA2008100581536A CN200810058153A CN101234780A CN 101234780 A CN101234780 A CN 101234780A CN A2008100581536 A CNA2008100581536 A CN A2008100581536A CN 200810058153 A CN200810058153 A CN 200810058153A CN 101234780 A CN101234780 A CN 101234780A
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- germanium tetrachloride
- solution
- optical fibre
- distillation
- hydrochloric acid
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Abstract
The invention discloses a method for producing germanium tetrachloride for optical fibers, which includes the steps: hydrochloric acid and germanium tetrachloride with a volume ratio of 0.25-2.0: 1 are added into a distiller to be distilled; or while separately distilling the germanium tetrachloride, HCI gas is pumped in until the distilling is finished with the distilling temperature of 76-80 DEG C; after the distilled solution is separated by a hydrochloric separator, the germanium tetrachloride solution is stored in a storage tank to be discharged to an empty tower distiller for 36-72 hours of standing; temperature of the germanium tetrachloride solution is raised to 70-75 DEG C; while continuous pumping nitrogen for 12-36 hours, an ultraviolet lamp is adopted for lighting; finally, distillation operation is carried out at 76-80 DEG C and the product is transferred. The method for producing the germanium tetrachloride for optical fibers has the advantages of simple process course and convenient operation which can remove the impurity containing hydrogen in the germanium tetrachloride with high value for industrial use.
Description
Technical field
The invention belongs to the dissipated metal field of metallurgy, relate to a kind of method of purification of high-purity compound, especially for the method for purification of the germanium tetrachloride for optical fibre of optical fiber production.
Background technology
High-purity germanium tetrachloride is that high grade quartz is the indispensable critical materials of optical fiber, is main doping agent in the optical fiber as quartz, and its purposes is to improve the refractive index of optical fiber, reduces optical loss, and then the transmission range of raising optical fiber.Because doping agent enters into fiber core, its content and distribution are determining the important performance indexes of optical fiber, and whether how its quality directly affects can obtain high-quality optical fiber.Therefore, extremely low to the metallic impurity in the germanium tetrachloride (Fe, Co, Cr, Mn, Cu etc.) and the content requirement of hydrogen containing foreign (OH, CH, HCl).
Present widely used rectification process can be removed metallic impurity (Fe, Co, Cr, Mn, Cu etc.) preferably, but can't remove hydrogen containing foreign (OH, CH, HCl) effectively; Adopt hydrogen chloride gas or anhydrous chlorine to come purifying germanium tetrachloride separately, can only remove arsenic and other similar impurity, and can not remove hydrogen containing foreign; PCl
3Or PBr
3Be added to SiCl
4, GeCl
4And POCl
3In and add Cl therein
2Or Br
2, make-reaction of OH group formed HCl (or HBr) and POCl
3(or POBr
3), to remove HCl and HBr then, thereby realize removing OH impurity and HCl impurity in the germanium tetrachloride, this technology also can't be removed CH impurity; Though germanium tetrachloride is handled under the high temperature more than 1000 ℃, make hydrogen atom wherein be become hydrogenchloride by chlorinated with chlorine, the final removal that realizes hydrogen containing foreign, this technology is very high to the requirement of equipment, and complicated operation.
Summary of the invention
The objective of the invention is deficiency, propose a kind of technology that can effectively remove hydrogen containing foreign in the germanium tetrachloride (OH, CH and HCl), thereby obtain to satisfy the germanium tetrachloride for optical fibre of optical fiber production at the prior art existence.
Technical scheme of the present invention is: its step:
(1) with 0.25～2.0: 1 hydrochloric acid and germanium tetrachloride join in the still kettle and distill, or feeding HCl gas in the distillation germanium tetrachloride separately, finish until distillation, and distillation temperature is 76～80 ℃;
(2) the germanium tetrachloride solution of the solution that distills after the salt acid separator separates is deposited in the storage tank, need leave standstill 36h～72h;
(3) the germanium tetrachloride solution in the storage tank is entered in the void tower still kettle, the germanium tetrachloride solution temperature is increased to 70～75 ℃, when constantly feeding nitrogen, adopt ultraviolet lamp to carry out illumination, carry out distillation operation and migrate out product at 76～80 ℃ at last.
Wherein: described hydrochloric acid is analytical pure hydrochloric acid, and described nitrogen is high pure nitrogen, and feeding the nitrogen time is 12h～36h, and described ultraviolet lamp power is 40W, and producing wavelength is the UV-light of 253.7nm.
Germanium tetrachloride is liquid under normal temperature, normal pressure, and easily volatilization, and have very strong corrodibility exposes in that air is medium-term and long-term, can absorb airborne moisture and chemical reaction takes place, and according to the mole number difference of water, following reaction: GeCl takes place
4+ H
2O Ge (OH) Cl
3+ HCl (C
(H2O)＜1 * 10
-2Mol/L); GeCl
4+ nH
2O Ge (OH)
nCl
4-n+ nHCl (n=2,3) (C
(H2O)＞1 * 10
-2Mol/L).Expect the germanium tetrachloride that the OH foreign matter content is less, just should increase the concentration of HCl as much as possible, reduce H
2O content, the method that adopts is that analytical pure hydrochloric acid and germanium tetrachloride are distilled jointly, distills the germanium tetrachloride that obtains thus and leaves standstill 36h～72h, can suppress the generation of OH impurity well, and hydrochloric acid is well separated with germanium tetrachloride, reduce the solubleness of hydrochloric acid in germanium tetrachloride.Adopting ultraviolet lamp to carry out illumination can make the small amount of moisture that exists in the germanium tetrachloride be dissociated into H
2And O
2, it is the 253.7nm UV-light that ultraviolet lamp produces wavelength.Rectification temperature is 76～80 ℃, collects distillate in room temperature.Handle the germanium tetrachloride for optical fibre that can be met optical fiber production through above-mentioned steps.
The present invention has compared with the prior art: technological process is simple, and is easy to operate, can finish institute in steps in a covering device, can remove the hydrogen containing foreign in the germanium tetrachloride well, has higher industrial use value.
Embodiment
Embodiment 1:
(1) 7L hydrochloric acid and 28L germanium tetrachloride are joined in the still kettle distill, distillation temperature is 76 ℃;
(2) the germanium tetrachloride solution of the solution that distills after the salt acid separator separates is deposited in the storage tank, need leave standstill 36h;
(3) the germanium tetrachloride solution in the storage tank is entered in the void tower still kettle, the germanium tetrachloride solution temperature is increased to 70 ℃, when constantly feeding nitrogen 12h, adopt ultraviolet lamp to carry out illumination, ultraviolet lamp power is 40W, and producing wavelength is the UV-light of 253.7nm.Carry out distillation operation at last and migrate out product, rectification temperature is 76 ℃.
Embodiment 2:
(1) 20L hydrochloric acid and 10L germanium tetrachloride are joined in the still kettle distill, distillation temperature is 80 ℃;
(2) the germanium tetrachloride solution of the solution that distills after the salt acid separator separates is deposited in the storage tank, need leave standstill 72h;
(3) the germanium tetrachloride solution in the storage tank is entered in the void tower still kettle, the germanium tetrachloride solution temperature is increased to 75 ℃, when constantly feeding nitrogen 36h, adopt ultraviolet lamp to carry out illumination, ultraviolet lamp power is 40W, and producing wavelength is the UV-light of 253.7nm.Carry out distillation operation at last and migrate out product, rectification temperature is 80 ℃.
Embodiment 3:
(1) 10L hydrochloric acid and 20L germanium tetrachloride are joined in the still kettle distill, distillation temperature is 77 ℃;
(2) the germanium tetrachloride solution of the solution that distills after the salt acid separator separates is deposited in the storage tank, need leave standstill 48h;
(3) the germanium tetrachloride solution in the storage tank is entered in the void tower still kettle, the germanium tetrachloride solution temperature is increased to 72 ℃, when constantly feeding nitrogen 18h, adopt ultraviolet lamp to carry out illumination, ultraviolet lamp power is 40W, and producing wavelength is the UV-light of 253.7nm.Carry out distillation operation at last and migrate out product, rectification temperature is 77 ℃.
Embodiment 4:
(1) 18L hydrochloric acid and 12L germanium tetrachloride are joined in the still kettle distill, distillation temperature is 79 ℃;
(2) the germanium tetrachloride solution of the solution that distills after the salt acid separator separates is deposited in the storage tank, need leave standstill 60h;
(3) the germanium tetrachloride solution in the storage tank is entered in the void tower still kettle, the germanium tetrachloride solution temperature is increased to 74 ℃, when constantly feeding nitrogen 30h, adopt ultraviolet lamp to carry out illumination, ultraviolet lamp power is 40W, and producing wavelength is the UV-light of 253.7nm.Carry out distillation operation at last and migrate out product, rectification temperature is 79 ℃.
Embodiment 5:
(1) distilling germanium tetrachloride 20L separately simultaneously, feeding flow is the HCl gas of 20L/h, finishes until distillation, and distillation temperature is 76 ℃;
(2) the germanium tetrachloride solution of the solution that distills after the salt acid separator separates is deposited in the storage tank, need leave standstill 36h;
(3) the germanium tetrachloride solution in the storage tank is entered in the void tower still kettle, the germanium tetrachloride solution temperature is increased to 70 ℃, when constantly feeding nitrogen 12h, adopt ultraviolet lamp to carry out illumination, ultraviolet lamp power is 40W, and producing wavelength is the UV-light of 253.7nm.Carry out distillation operation at last and migrate out product, rectification temperature is 76 ℃.
Embodiment 6:
(1) distilling germanium tetrachloride 35L separately simultaneously, feeding flow is the HCl gas of 60L/h, finishes until distillation, and distillation temperature is 80 ℃;
(2) the germanium tetrachloride solution of the solution that distills after the salt acid separator separates is deposited in the storage tank, need leave standstill 72h;
(3) the germanium tetrachloride solution in the storage tank is entered in the void tower still kettle, the germanium tetrachloride solution temperature is increased to 75 ℃, when constantly feeding nitrogen 36h, adopt ultraviolet lamp to carry out illumination, ultraviolet lamp power is 40W, and producing wavelength is the UV-light of 253.7nm.Carry out distillation operation at last and migrate out product, rectification temperature is 80 ℃.
Embodiment 7:
(1) distilling germanium tetrachloride 25L separately simultaneously, feeding flow is the HCl gas of 30L/h, finishes until distillation, and distillation temperature is 77 ℃;
(2) the germanium tetrachloride solution of the solution that distills after the salt acid separator separates is deposited in the storage tank, need leave standstill 48h;
(3) the germanium tetrachloride solution in the storage tank is entered in the void tower still kettle, the germanium tetrachloride solution temperature is increased to 72 ℃, when constantly feeding nitrogen 18h, adopt ultraviolet lamp to carry out illumination, ultraviolet lamp power is 40W, and producing wavelength is the UV-light of 253.7nm.Carry out distillation operation at last and migrate out product, rectification temperature is 77 ℃.
Embodiment 8:
(1) distilling germanium tetrachloride 30L separately simultaneously, feeding flow is the HCl gas of 50L/h, finishes until distillation, and distillation temperature is 79 ℃;
(2) the germanium tetrachloride solution of the solution that distills after the salt acid separator separates is deposited in the storage tank, need leave standstill 60h;
(3) the germanium tetrachloride solution in the storage tank is entered in the void tower still kettle, the germanium tetrachloride solution temperature is increased to 74 ℃, when constantly feeding nitrogen 30h, adopt ultraviolet lamp to carry out illumination, ultraviolet lamp power is 40W, and producing wavelength is the UV-light of 253.7nm.Carry out distillation operation at last and migrate out product, rectification temperature is 79 ℃.
Adopt original technology and the present invention, hydrogen containing foreign transmitance (%) sees the following form in the germanium tetrachloride that is obtained:
| The hydrogen containing foreign sequence number | OH | CH | HCl |
| Rectifying product 1 | 2.5 | 57.6 | 45.5 |
| Rectifying product 2 | 4.7 | 51.6 | 37.2 |
| Embodiment 1 | 90.3 | 91.2 | 90.7 |
| Embodiment 2 | 96.1 | 97.9 | 96.7 |
| Embodiment 3 | 91.5 | 92.6 | 92.0 |
| Embodiment 4 | 93.6 | 95.5 | 94.6 |
| Embodiment 5 | 90.8 | 92.1 | 91.6 |
| Embodiment 6 | 96.8 | 98.2 | 97.1 |
| Embodiment 7 | 92.2 | 93.4 | 92.6 |
| Embodiment 8 | 95.0 | 96.8 | 95.3 |
As can be seen from the above table, adopt this to invent described method and all can obtain the germanium tetrachloride for optical fibre of hydrogen containing foreign transmitance more than 90%, and adopt in the first step feeding HCl gas in the distillation germanium tetrachloride separately, can obtain the higher product of hydrogen containing foreign transmitance.
Claims (6)
1, a kind of production method of germanium tetrachloride for optical fibre, its step:
(1) with 0.25-2.0: 1 hydrochloric acid and germanium tetrachloride join in the still kettle and distill, or feeding HCl gas in the distillation germanium tetrachloride separately, finish until distillation, and distillation temperature is 76-80 ℃;
(2) the germanium tetrachloride solution of the solution that distills after the salt acid separator separates is deposited in the storage tank, need leave standstill 36h-72h;
(3) the germanium tetrachloride solution in the storage tank is entered in the void tower still kettle, the germanium tetrachloride solution temperature is increased to 70-75 ℃, when constantly feeding nitrogen, adopt ultraviolet lamp to carry out illumination, carry out distillation operation and migrate out product at 76-80 ℃ at last.
2, the production technique of germanium tetrachloride for optical fibre according to claim 1 is characterized in that described hydrochloric acid can be analytical pure hydrochloric acid.
3, the production technique of germanium tetrachloride for optical fibre according to claim 1 is characterized in that described HCl gas is produced by the thermal analysis pure hydrochloric acid.
4, the production technique of germanium tetrachloride for optical fibre according to claim 1 is characterized in that described nitrogen can be high pure nitrogen.
5, the production technique of germanium tetrachloride for optical fibre according to claim 1, it is characterized in that feeding the nitrogen time is 12h-36h.
6, the production technique of germanium tetrachloride for optical fibre according to claim 1 is characterized in that ultraviolet lamp, and power is 40W, and producing wavelength is the UV-light of 253.7nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100581536A CN101234780A (en) | 2008-03-05 | 2008-03-05 | Method for producing germanium tetrachloride for optical fibre |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100581536A CN101234780A (en) | 2008-03-05 | 2008-03-05 | Method for producing germanium tetrachloride for optical fibre |
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| Publication Number | Publication Date |
|---|---|
| CN101234780A true CN101234780A (en) | 2008-08-06 |
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ID=39918723
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|---|---|---|---|
| CNA2008100581536A Pending CN101234780A (en) | 2008-03-05 | 2008-03-05 | Method for producing germanium tetrachloride for optical fibre |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102328951A (en) * | 2011-07-13 | 2012-01-25 | 云南驰宏锌锗股份有限公司 | Method and device for removing hydrogen-containing impurities from germanium tetrachloride |
| CN114653085A (en) * | 2022-03-07 | 2022-06-24 | 广东长信精密设备有限公司 | Germanium tetrachloride production device and method |
-
2008
- 2008-03-05 CN CNA2008100581536A patent/CN101234780A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102328951A (en) * | 2011-07-13 | 2012-01-25 | 云南驰宏锌锗股份有限公司 | Method and device for removing hydrogen-containing impurities from germanium tetrachloride |
| 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 |
| CN114653085A (en) * | 2022-03-07 | 2022-06-24 | 广东长信精密设备有限公司 | Germanium tetrachloride production device and method |
| CN114653085B (en) * | 2022-03-07 | 2023-12-01 | 广东长信精密设备有限公司 | Germanium tetrachloride production device and method |
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Open date: 20080806 |