Process and apparatus for purifying silicon tetrachloride or germanium tetrachloride containing hydrogen compounds
View Patent ↗The invention relates to a process for the purification's of silicon tetrachloride or germanium tetrachloride contaminated with at least one hydrogen-containing compound, in which the silicon tetrachloride or germanium tetrachloride to be purified is treated in a targeted manner by means of a cold plasma and purified silicon tetrachloride or germanium tetrachloride is isolated from the phase which has been treated in this way. The present invention further relates to an apparatus for carrying out the process of the invention, which comprises a stock and vaporization unit for silicon or germanium tetrachloride ( 4.1 or 5.1 ) which is connected via a connecting line with the inlet of the reactor ( 4.3 or 5.3 ) with control unit ( 4.4 or 5.4 ) for producing the dielectrically hindered discharges whose outlet leads via a pipe either directly or indirectly via at least one further reactor ( 5.5 ) to a condensation unit ( 4.5 or 5.11 ) with downstream collection vessel ( 4.6 or 5.12 ) which is connected via an offtake line ( 4.6.2 or 5.12.1 ) to a distillation unit ( 4.8 or 5.13 ) and, if appropriate, is equipped with a feed line ( 4.6.1 ) to the unit ( 4.1 ).
1. A process for the treatment of silicon tetrachloride or germanium tetrachloride contaminated with at least one hydrogen-containing compound, in which the contaminated silicon tetrachloride or germanium tetrachloride to be purified is treated with a cold plasma in a discharge zone of a reactor and a purified silicon tetrachloride or germanium tetrachloride is isolated from the treated silicon tetrachloride or germanium tetrachloride.
2. The process as claimed in claim 1 ,wherein the cold plasma is generated by a dielectrically hindered discharge, a capacitively coupled discharge, a radiofrequency discharge, a microwave discharge, a corona discharge, a (high- to low-pressure) glow discharge or a mixed form thereof.
3. The process as claimed in claim 2 , wherein the cold plasma is generated by a dielectrically hindered discharge produced using an AC voltage or a DC pulse voltage from 1 V to 1 ×10 6 V.
4. The process as claimed in claim 2 , wherein the cold plasma is generated by a dielectrically hindered discharge produced at a frequency of from 50 Hz to 100 MHz.
5. The process as claimed in claim 2 , wherein the cold plasma is generated by the dielectrically hindered discharge produced at a temperature in a gas phase of from −40 to 200° C.
6. The process as claimed in claim 1 , wherein the contaminated silicon tetrachloride or germanium tetrachloride to be treated passes through the discharge zone at a flow velocity of from 0.01 to 100 m/s.
7. The process as claimed in claim 1 , wherein an exposure time of the contaminated silicon tetrachloride or germanium tetrachloride to the cold plasma per discharge of AC voltage or pulsed voltage in the discharge zone is from 10 ns to 1 s.
8. The process as claimed in claim 1 , wherein the contaminated silicon tetrachloride or germanium tetrachloride is treated for 1 ms to 10 min in the discharge zone.
9. The process as claimed in claim 1 , wherein at least one inert buffer gas selected from the group consisting of at least one noble gas and nitrogen is added to the contaminated silicon tetrachloride or germanium tetrachloride to be treated at one or more points in the process.
10. The process as claimed in claim 1 , wherein chlorine and/or hydrogen chloride are/is added to the contaminated silicon tetrachloride or germanium tetrachloride to be treated.
11. The process as claimed in claim 1 , wherein the treatment is carried out at a pressure of from 0.1 mbar to 10 bar abs., and a temperature of from −40 to 200° C.
12. The process as claimed in claim 1 , wherein the process is operated continuously or batchwise.
13. The process as claimed in claim 1 , wherein the process is accompanied continuously by analytical measurements on a treated liquid silicon tetrachloride fraction or germanium tetrachloride fraction.
14. The process as claimed in claim 1 , wherein the treated phase is cooled and the purified silicon tetrachloride fraction or germanium tetrachloride fraction is discharged.
15. The process as claimed in claim 1 , wherein
the contaminated silicon tetrachloride or germanium tetrachloride is circulated through a cycle, comprising: vaporization, cold plasma treatment and condensation, wherein
an analytical guide parameter is monitored in the treated silicon tetrachloride or germanium tetrachloride,
a substream is optionally taken off from the condensed treated silicon tetrachloride or germanium tetrachloride, and fed to a distillation unit, and
an amount of the condensed treated silicon tetrachloride or germanium tetrachloride taken from the cycle in the substream is replaced by a corresponding quantity of contaminated silicon tetrachloride or germanium tetrachloride to be purified, which is fed to the cycle for vaporization.
16. The process as claimed in claim 15 , wherein the contaminated silicon tetrachloride or germanium tetrachloride to be treated is converted into a gas phase,
an inert gas and/or chlorine is optionally added,
the gas phase is exposed at least once to the cold plasma treatment,
the treated silicon tetrachloride or germanium tetrachloride is monitored using the analytical guide parameter, and
a fraction consisting of high-purity silicon tetrachloride or germanium tetrachloride is obtained from the condensed treated substream by distillation.