阅读说明：本技术 一种制备电子级锗烷联产电子级四氟锗烷的方法及装置 (Method and device for preparing electronic-grade germane and co-producing electronic-grade tetrafluorogermane ) 是由 蔡江 曾宪友 于 2020-12-18 设计创作，主要内容包括：本发明涉及一种制备电子级锗烷联产电子级四氟锗烷的方法及装置。将二氧化锗溶解到酸中,然后加入硼氢化钠；二氧化锗和硼氢化钠在酸性环境中进行反应；得到锗烷粗品气；将锗烷粗品气在压力0.3～0.8MPa、-70～-35℃操作条件下进行精制,得到纯度≥99.999％的电子级锗烷产品和粗乙锗烷；将得到的粗乙锗烷与氟气进行反应；得到四氟锗烷粗品气；将四氟锗烷粗品气在压力0.2～0.7MPa、-20.4～16.7℃操作条件下进行精制,得到纯度≥99.999％的电子级四氟锗烷产品。本发明不使用有机溶剂,原料成本低,过程简单易于实现。锗烷精制采用低温双效精馏工艺,节约能耗≥30％。(The invention relates to a method and a device for preparing electronic-grade germane and co-producing electronic-grade tetrafluorogermane. Dissolving germanium dioxide into acid, and then adding sodium borohydride; reacting germanium dioxide and sodium borohydride in an acid environment; obtaining germane crude product gas; refining the germane crude product gas under the operating conditions of the pressure of 0.3-0.8 MPa and the temperature of-70-35 ℃ to obtain an electronic grade germane product with the purity of more than or equal to 99.999 percent and crude digermane; reacting the obtained crude digermane with fluorine gas; obtaining crude tetrafluorogermane gas; and refining the crude tetrafluorogermane product gas under the operating conditions of pressure of 0.2-0.7 MPa and temperature of-20.4-16.7 ℃ to obtain an electronic-grade tetrafluorogermane product with the purity of more than or equal to 99.999 percent. The method does not use organic solvent, has low raw material cost and simple and easily realized process. The germane is refined by adopting a low-temperature double-effect rectification process, so that the energy consumption is saved by more than or equal to 30 percent.)

1. A method for preparing electronic grade germane and co-producing electronic grade tetrafluorogermane; the method is characterized by comprising the following steps:

(1) dissolving germanium dioxide into acid, and then adding sodium borohydride; reacting germanium dioxide and sodium borohydride in an acid environment, wherein the reaction pressure is 0.12-0.3 MPa, and the temperature is 20-90 ℃; obtaining germane crude product gas;

(2) refining the crude germane gas prepared in the step (1) under the operating conditions of the pressure of 0.3-0.8 MPa and the temperature of-70-35 ℃ to obtain an electronic grade germane product with the purity of more than or equal to 99.999 percent and crude digermane;

(3) reacting the crude digermane obtained in the step (2) with fluorine gas under the conditions of 0.12-0.3 MPa and 0-40 ℃; obtaining crude tetrafluorogermane gas;

(4) and (4) refining the crude tetrafluorogermane gas prepared in the step (3) under the operation conditions of pressure of 0.2-0.7 MPa and temperature of-20.4-16.7 ℃ to obtain an electronic-grade tetrafluorogermane product with purity of more than or equal to 99.999%.

2. The method as set forth in claim 1, wherein the molar ratio of the acid to the germanium dioxide in the step (1) is 2-5: 1; the molar ratio of the sodium borohydride to the germanium dioxide is 3-7: 1.

3. The method as set forth in claim 1, wherein the acid used in the step (1) is preferably one of hydrofluoric acid, acetic acid and oxalic acid.

4. The method according to claim 1, wherein the molar ratio of fluorine gas to digermane in the step (3) is 4 to 6: 1.

5. A device for preparing electronic grade germane and co-producing electronic grade tetrafluorogermane is characterized by comprising a germane reactor R101, a germane light removing tower T101, a germane refining tower T102, a heat exchanger E103, a tetrafluorogermane reactor R201, a tetrafluorogermane light removing tower T201 and a tetrafluorogermane refining tower T202 which are connected in sequence; wherein the germane lightness-removing tower T101 is provided with a T101 reboiler E101, the germane refining tower T102 is provided with a T102 condenser E102, the tetrafluorogermane lightness-removing tower T201 is provided with a T201 condenser E201 and a T201 reboiler E202, and the tetrafluorogermane refining tower T202 is provided with a T202 condenser E203 and a T202 reboiler E204.

6. The device as claimed in claim 5, wherein the device comprises a germane reactor R101, a germane lightness removing tower T101, a T101 reboiler E101, a germane refining tower T102, a T102 condenser E102 and a heat exchanger E103; the upper part of the germane reactor R101 is provided with a material inlet, the top part is provided with a reaction gas outlet, the bottom part is provided with a mixed salt solution outlet, and the reaction gas outlet is connected with a germane light-ends removal tower T101; the middle part of a germane lightness removing tower T101 is provided with a material inlet, the top part is provided with a tower top extraction outlet, the upper part is provided with a reflux port, the bottom part is provided with a tower kettle extraction outlet, wherein the material inlet is connected with a germane reactor R101, the reflux port is connected with a heat exchanger E103, the tower top extraction outlet is divided into two paths, one path is connected with the heat exchanger E103, and the other path is used for extracting light components; the extraction outlet of the tower kettle is divided into two paths, one path is connected with a germane refining tower T102, and the other path is connected with a T101 reboiler E101; the T101 reboiler E101 is provided with a material inlet and a material outlet which are connected with the germane lightness removing tower T101; the heat exchanger E103 is provided with a germane lightness-removing tower T101 top material inlet, a germane lightness-removing tower T101 top material outlet, a germane refining tower T102 tower kettle material inlet and a germane refining tower T102 tower kettle material outlet, wherein the germane lightness-removing tower T101 top material inlet and the germane lightness-removing tower T101 top material outlet are connected with the germane lightness-removing tower T101, the germane refining tower T102 tower kettle material inlet and the germane refining tower T102 tower kettle material outlet are connected with the germane refining tower T102; the middle part of a germane refining tower T102 is provided with a material inlet, the top part is provided with a tower top extraction outlet, the upper part is provided with a reflux port, the lower part is provided with a material return port, the bottom part is provided with a tower kettle extraction outlet, the material inlet is connected with a germane lightness removing tower T101, the tower top extraction outlet and the reflux port are both connected with a T102 condenser E102, the material return port is connected with a heat exchanger E103, the tower kettle extraction outlet is divided into two paths, one path is connected with the heat exchanger E103, and the other path is connected with a tetrafluorogerman; the T102 condenser E102 is provided with a material inlet, a liquid phase material outlet and a gas phase material outlet, wherein the material inlet and the liquid phase material outlet are both connected with the germane refining tower T102, and the gas phase material outlet is used for extracting an electronic grade germane product.

7. The device as claimed in claim 5, wherein the device comprises a tetrafluorogermane reactor R201, a tetrafluorogermane light component removing tower T201, a T201 condenser E201, a T201 reboiler E202; the tetrafluorogermane reactor R201 is provided with a material inlet, an F2 inlet and a reaction gas outlet, wherein the material inlet is connected with a germane refining tower T102, and the reaction gas outlet is connected with a tetrafluorogermane light-removing tower T201; the middle part of a tetrafluorogermane light-removing tower T201 is provided with a material inlet, the top part is provided with a tower top extraction outlet, the upper part is provided with a reflux port, the bottom part is provided with a tower kettle extraction outlet, the material inlet is connected with a tetrafluorogermane reactor R201, the tower top extraction outlet and the reflux port are both connected with a T201 condenser E201, the tower kettle extraction outlet is divided into two paths, one path is connected with a T201 reboiler E202, and the other path is connected with a tetrafluorogermane refining tower T202; the T201 reboiler E202 is provided with a material inlet and a material outlet which are connected with the tetrafluorogermane light-removing tower T201; the T202 condenser E201 is provided with a material inlet, a liquid phase material outlet and a gas phase material outlet, wherein the material inlet and the liquid phase material outlet are both connected with the tetrafluorogermane light-removing tower T201, and the gas phase material outlet extracts light impurities.

8. The apparatus according to claim 5, wherein the apparatus comprises a tetrafluorogermane refining column T202, a T202 condenser E203, a T202 reboiler E204; the middle part of a tetrafluorogermane refining tower T202 is provided with a material inlet, the top part is provided with a tower top extraction outlet, the upper part is provided with a reflux port, the bottom part is provided with a tower kettle extraction outlet, the material inlet is connected with a tetrafluorogermane lightness removing tower T201, the tower top extraction outlet and the reflux port are both connected with a T202 condenser E203, the tower kettle extraction outlet is divided into two paths, one path is connected with a T202 reboiler E204, and the other path is connected with the tetrafluorogermane lightness removing tower T201; the T202 reboiler E204 is provided with a material inlet and a material outlet which are both connected with the tetrafluorogermane refining tower T202; the T202 condenser E203 is provided with a material inlet, a liquid phase material outlet and a gas phase material outlet, wherein the material inlet and the liquid phase material outlet are both connected with the tetrafluorogermane refining tower T202, and the gas phase material outlet is used for extracting light impurities.

9. The device as claimed in any one of claims 5 to 8, wherein the germane reactor R101 has a reaction pressure of 0.12 to 0.3MPa and a reaction temperature of 20 to 90 ℃; the operating pressure of a germane light component removal tower T101 is 0.4-0.8 MPa, and the operating temperature is-60 to-35 ℃; the operating pressure of a T102 of the germane refining tower is 0.3-0.7 MPa, and the operating temperature is-70 to-45 ℃; the temperature of the top of the germane lightness removing tower T101 is more than or equal to 10 ℃ than the temperature of the bottom of the germane refining tower T102.

10. The apparatus as claimed in any one of claims 5 to 8, wherein the reaction pressure of R201 in the tetrafluorogermane reactor is 0.12 to 0.3MPa, and the reaction temperature is 0 to 40 ℃; the operating pressure of the T201 of the tetrafluorogermane light-removing tower is 0.3-0.7 MPa, and the operating temperature is-9.6-16.7 ℃; the T202 operation pressure of the tetrafluorogermane refining tower is 0.2-0.6 MPa, and the operation temperature is-20.4-11.5 ℃.

Technical Field

The invention relates to a preparation method of electronic grade gas, in particular to a method and a device for preparing electronic grade germane and co-producing electronic grade tetrafluorogermane.

Background

Germane (GeH)₄) It is colorless toxic gas with unpleasant odor at normal temperature and pressure. Germane is used as an important raw material gas for the electronic industry, and plays an important supporting role in the sustainable development of the whole industry. The germanium prepared by decomposing germane has low impurity content, high purity and low energy consumption,the material is mainly used for infrared optical materials, space efficient batteries of spacecrafts and the like; as a source material of the solar thin film battery, various amorphous germanium-silicon batteries are prepared together with silane.

Tetrafluogermane (GeF4) is a colorless gas with garlic odor at normal temperature and pressure. The tetrafluorogermane is used to produce silicon germanium crystallites directly on a glass substrate in combination with disilane gas. Germanium and silicon nanocrystals can emit strong visible light, and are receiving much attention due to their potential application value in optoelectronic devices.

Chinese patent CN200910095214.0 proposes a method for preparing germane, which uses magnesium germanate and ammonium chloride as raw materials and liquid ammonia as a reaction medium to prepare germane.

Chinese patent CN200910155708.3 proposes a method for preparing germane, in which a tetrahydrofuran solution of germanium tetrachloride is dripped into a sodium hydroxide solution of sodium borohydride to react to prepare germane.

Chinese patent CN201110132107.8 proposes a preparation method of germane gas, which comprises the steps of firstly preparing sodium hydroxide solution of sodium borohydride, adding polyether according to the proportion of 0.5-5% of the volume of the solution, and dropwise adding tetrahydrofuran solution of germanium tetrachloride into the solution to prepare germane.

US4668502 proposes a method for synthesizing germane, which comprises dissolving germanium dioxide with strong alkali solution, adding sodium borohydride, and adding sulfuric acid to react to prepare germane.

Chinese patent CN200910095215.5 discloses a method for purifying germane, which makes crude germane pass through an adsorption column filled with 4A and 5A molecular sieves in turn according to related physical parameters of gas molecules contained in the germane with the purity of 92-96% and the adsorption characteristics of the molecular sieves, so as to obtain pure germane with the purity of 99-99.99%.

Chinese patent CN200980138501.3 discloses a method for preparing germanium tetrafluoride, which is a method for preparing germanium tetrafluoride by reacting fluorine gas with metal germanium at high temperature.

Certain digermane can be generated in the germane production process to cause germanium waste, and no report related to the preparation of electronic grade germane and the co-production of electronic grade germanium tetrafluoride exists. The production of germanium tetrafluoride not only uses fluorine gas, but also has high-temperature reaction and has considerable danger. Germane and germanium tetrafluoride are used as source materials in the industries of semiconductors, photovoltaic solar energy and integrated circuits, key technologies of synthesis and refining of germane and germanium tetrafluoride are broken through, and the method has important significance on the health, stability and sustainable development of the electronic industry in China.

Disclosure of Invention

According to the problems of the prior art, the invention provides a method and a device for preparing electronic-grade germane and co-producing electronic-grade tetrafluorogermane. The invention takes germanium dioxide and sodium borohydride as raw materials, and prepares crude germane by reaction in an acid environment, wherein the conversion rate of germanium is more than or equal to 95 percent; and refining the crude germane by a low-temperature double-effect rectification process to obtain germane with the purity of more than or equal to 99.999 percent and crude digermane, further reacting the crude digermane with fluorine gas to prepare tetrafluorogermane, and then refining to obtain the tetrafluorogermane with the purity of more than or equal to 99.999 percent. The method can prepare two products of electronic-grade germane and electronic-grade tetrafluorogermane simultaneously, so that the benefit of germanium is maximized; the energy can be saved by more than or equal to 30 percent by using the low-temperature double-effect rectification process. The invention has simple process and is easy to realize the stable industrial production of germane and tetrafluorogermane.

The invention is realized by adopting the following technical scheme:

a method for preparing electronic grade germane and co-producing electronic grade tetrafluorogermane; the method comprises the following steps:

(1) dissolving germanium dioxide into acid, and then adding sodium borohydride; reacting germanium dioxide and sodium borohydride in an acid environment at the reaction pressure of 0.12-0.3 MPa and the temperature of 20-90 ℃; obtaining germane crude product gas;

(2) refining the crude germane gas prepared in the step (1) under the operating conditions of the pressure of 0.3-0.8 MPa and the temperature of-70-35 ℃ to obtain an electronic grade germane product with the purity of more than or equal to 99.999 percent and crude digermane;

(3) reacting the crude digermane obtained in the step (2) with fluorine gas under the conditions of 0.12-0.3 MPa and 0-40 ℃; obtaining crude tetrafluorogermane gas;

(4) and (4) refining the crude tetrafluorogermane gas prepared in the step (3) under the operation conditions of pressure of 0.2-0.7 MPa and temperature of-20.4-16.7 ℃ to obtain an electronic-grade tetrafluorogermane product with purity of more than or equal to 99.999%.

The molar ratio of the acid to the germanium dioxide in the step (1) is 2-5: 1.

The molar ratio of the sodium borohydride to the germanium dioxide in the step (1) is 3-7: 1.

The acid adopted in the step (1) is preferably one of hydrofluoric acid, acetic acid and oxalic acid.

The molar ratio of the fluorine gas to the digermane in the step (3) is 4-6: 1.

A device for preparing electronic grade germane and co-producing electronic grade tetrafluorogermane comprises a germane reactor R101, a germane light removing tower T101, a germane refining tower T102, a heat exchanger E103, a tetrafluorogermane reactor R201, a tetrafluorogermane light removing tower T201 and a tetrafluorogermane refining tower T202 which are connected in sequence; wherein the germane lightness-removing tower T101 is provided with a T101 reboiler E101, the germane refining tower T102 is provided with a T102 condenser E102, the tetrafluorogermane lightness-removing tower T201 is provided with a T201 condenser E201 and a T201 reboiler E202, and the tetrafluorogermane refining tower T202 is provided with a T202 condenser E203 and a T202 reboiler E204.

The device comprises a germane reactor R101, a germane light component removal tower T101, a T101 reboiler E101, a germane refining tower T102, a T102 condenser E102 and a heat exchanger E103; the upper part of the germane reactor R101 is provided with a material inlet, the top part is provided with a reaction gas outlet, the bottom part is provided with a mixed salt solution outlet, and the reaction gas outlet is connected with a germane light-ends removal tower T101; the middle part of a germane lightness removing tower T101 is provided with a material inlet, the top part is provided with a tower top extraction outlet, the upper part is provided with a reflux port, the bottom part is provided with a tower kettle extraction outlet, wherein the material inlet is connected with a germane reactor R101, the reflux port is connected with a heat exchanger E103, the tower top extraction outlet is divided into two paths, one path is connected with the heat exchanger E103, and the other path is used for extracting light components; the extraction outlet of the tower kettle is divided into two paths, one path is connected with a germane refining tower T102, and the other path is connected with a T101 reboiler E101; the T101 reboiler E101 is provided with a material inlet and a material outlet which are connected with the germane lightness removing tower T101; the heat exchanger E103 is provided with a germane lightness-removing tower T101 top material inlet, a germane lightness-removing tower T101 top material outlet, a germane refining tower T102 tower kettle material inlet and a germane refining tower T102 tower kettle material outlet, wherein the germane lightness-removing tower T101 top material inlet and the germane lightness-removing tower T101 top material outlet are connected with the germane lightness-removing tower T101, the germane refining tower T102 tower kettle material inlet and the germane refining tower T102 tower kettle material outlet are connected with the germane refining tower T102; the middle part of a germane refining tower T102 is provided with a material inlet, the top part is provided with a tower top extraction outlet, the upper part is provided with a reflux port, the lower part is provided with a material return port, the bottom part is provided with a tower kettle extraction outlet, the material inlet is connected with a germane lightness removing tower T101, the tower top extraction outlet and the reflux port are both connected with a T102 condenser E102, the material return port is connected with a heat exchanger E103, the tower kettle extraction outlet is divided into two paths, one path is connected with the heat exchanger E103, and the other path is connected with a tetrafluorogerman; the T102 condenser E102 is provided with a material inlet, a liquid phase material outlet and a gas phase material outlet, wherein the material inlet and the liquid phase material outlet are both connected with the germane refining tower T102, and the gas phase material outlet is used for extracting an electronic grade germane product.

The device comprises a tetrafluorogermane reactor R201, a tetrafluorogermane light-removing tower T201, a T201 condenser E201 and a T201 reboiler E202; the tetrafluorogermane reactor R201 is provided with a material inlet, an F2 inlet and a reaction gas outlet, wherein the material inlet is connected with a germane refining tower T102, and the reaction gas outlet is connected with a tetrafluorogermane light-removing tower T201; the middle part of a tetrafluorogermane light-removing tower T201 is provided with a material inlet, the top part is provided with a tower top extraction outlet, the upper part is provided with a reflux port, the bottom part is provided with a tower kettle extraction outlet, the material inlet is connected with a tetrafluorogermane reactor R201, the tower top extraction outlet and the reflux port are both connected with a T201 condenser E201, the tower kettle extraction outlet is divided into two paths, one path is connected with a T201 reboiler E202, and the other path is connected with a tetrafluorogermane refining tower T202; the T201 reboiler E202 is provided with a material inlet and a material outlet which are connected with the tetrafluorogermane light-removing tower T201; the T202 condenser E201 is provided with a material inlet, a liquid phase material outlet and a gas phase material outlet, wherein the material inlet and the liquid phase material outlet are both connected with the tetrafluorogermane light-removing tower T201, and the gas phase material outlet extracts light impurities.

The device comprises a tetrafluorogermane refining tower T202, a T202 condenser E203 and a T202 reboiler E204; the middle part of a tetrafluorogermane refining tower T202 is provided with a material inlet, the top part is provided with a tower top extraction outlet, the upper part is provided with a reflux port, the bottom part is provided with a tower kettle extraction outlet, the material inlet is connected with a tetrafluorogermane lightness removing tower T201, the tower top extraction outlet and the reflux port are both connected with a T202 condenser E203, the tower kettle extraction outlet is divided into two paths, one path is connected with a T202 reboiler E204, and the other path is connected with the tetrafluorogermane lightness removing tower T201; the T202 reboiler E204 is provided with a material inlet and a material outlet which are both connected with the tetrafluorogermane refining tower T202; the T202 condenser E203 is provided with a material inlet, a liquid phase material outlet and a gas phase material outlet, wherein the material inlet and the liquid phase material outlet are both connected with the tetrafluorogermane refining tower T202, and the gas phase material outlet is used for extracting light impurities.

The method for preparing the electronic grade germane and co-producing the electronic grade tetrafluorogermane by using the device comprises the following steps:

the reaction pressure of the germane reactor R101 is 0.12-0.3 MPa, and the reaction temperature is 20-90 ℃.

The operating pressure of a germane light component removal tower T101 is 0.4-0.8 MPa, and the operating temperature is-60 to-35 ℃; the operating pressure of the T102 of the germane refining tower is 0.3-0.7 MPa, and the operating temperature is-70 to-45 ℃.

The temperature of the top of the germane lightness removing tower T101 is more than or equal to 10 ℃ than the temperature of the bottom of the germane refining tower T102.

The reaction pressure of the R201 tetrafluorogermane reactor is 0.12-0.3 MPa, and the reaction temperature is 0-40 ℃.

The operating pressure of the T201 of the tetrafluorogermane light-removing tower is 0.3-0.7 MPa, and the operating temperature is-9.6-16.7 ℃; the T102 operation pressure of the germane refining tower is 0.2-0.6 MPa, and the operation temperature is-20.4-11.5 ℃.

The concrete description is as follows:

(1) germanium dioxide is dissolved in acid and then added into a germane reactor R101, and then sodium borohydride is added. Germanium dioxide and sodium borohydride react in an acid environment to obtain germane crude gas (containing impurities such as nitrogen, hydrogen, CO2, digermane and the like), and the germane crude gas is extracted to a germane lightness-removing tower T101.

The reaction pressure of the germane reactor R101 is 0.12-0.3 MPa, the temperature is 20-90 ℃, and the reaction time is 1-5 h.

The molar ratio of the acid to the germanium dioxide is 2-5: 1.

The molar ratio of the sodium borohydride to the germanium dioxide is 3-7: 1

The acid is preferably one of hydrofluoric acid, acetic acid and oxalic acid.

(2) One path of the light component is extracted from the top of the germane lightness removing tower T101 and enters a heat exchanger E103 for heat exchange, the other path of the light component is extracted, and the light component is extracted from the bottom of the tower and enters a germane refining tower T102. The top of the germane refining tower T102 extracts electronic grade germane with the purity of more than or equal to 99.999 percent, one path of the tower kettle enters a heat exchanger E103 for heat exchange, and the other path of the tower kettle extracts crude digermane to a tetrafluorogermane reactor R201.

The operating pressure of the T101 of the germane lightness removing tower is 0.4-0.8 MPa, and the operating temperature is-60 ℃ to-35 ℃.

The operating pressure of the T102 of the germane refining tower is 0.3-0.7 MPa, and the operating temperature is-70 ℃ to-45 ℃.

The temperature of the top of the germane lightness removing tower T101 is more than or equal to 10 ℃ than the temperature of the bottom of the germane refining tower T102.

(3) Fluorine gas is added into a tetrafluorogermane reactor R201, digermane reacts with the fluorine gas to obtain a tetrafluorogermane crude product gas (containing impurities such as nitrogen, hydrogen fluoride, fluorine gas, digermane and the like), and the tetrafluorogermane crude product gas is extracted to a tetrafluorogermane light-removing tower T201.

The reaction pressure of the R201 of the tetrafluorogermane reactor is 0.12-0.3 MPa, the temperature is 0-40 ℃, and the reaction time is 1-5 h.

The molar ratio of the fluorine gas to the digermane is 4-6: 1.

(4) Light impurities are extracted from the top of the tetrafluorogermane light-removing tower T201, and the light impurities are extracted from the bottom of the tower and enter a tetrafluorogermane refining tower T202. The top of the T102 tower of the tetrafluorogermane refining tower extracts electronic-grade tetrafluorogermane with the purity of more than or equal to 99.999 percent, and the bottom of the tower extracts heavy impurities.

The operating pressure of the T201 of the tetrafluorogermane light-removing tower is 0.3-0.7 MPa, and the operating temperature is-9.6-16.7 ℃.

The operating pressure of the T202 of the tetrafluorogermane refining tower is 0.2-0.6 MPa, and the operating temperature is-20.4 to-11.5 ℃.

The beneficial results of the invention are:

1. the reaction raw materials are germanium dioxide and sodium borohydride, an organic solvent is not used, the raw material cost is low, and the process is simple and easy to realize.

2. Meanwhile, the electronic grade germane with the purity of more than or equal to 99.999 percent and the electronic grade tetrafluorogermane with the purity of more than or equal to 99.999 percent are produced, the generation of digermane is avoided, the benefit of germanium is maximized, and the conversion rate of germanium is more than or equal to 95 percent.

3. The germane is refined by adopting a low-temperature double-effect rectification process, so that the energy consumption is saved by more than or equal to 30 percent.

Drawings

FIG. 1: a method and a device schematic diagram for preparing electronic grade germane and co-producing electronic grade tetrafluorogermane are provided:

r101: germane reactor, T101: germane lightness-removing column, E101: t101 reboiler, T102: germane refining column, E102: t102 condenser, E103: heat exchanger, R201: tetrafluorogermane reactor, T201: tetrafluorogermane light component removal tower, E201: t201 condenser, E202: t201 reboiler, T202: tetrafluorogermane refining tower, E203: t202 condenser, E204: t202 reboiler

Detailed Description

The method and the device for preparing the electronic-grade germane and co-producing the electronic-grade tetrafluorogermane take germanium dioxide and sodium borohydride as raw materials, and react in an acid environment to prepare the crude germane, wherein the conversion rate of the germanium is more than or equal to 95 percent; and refining the crude germane by a low-temperature double-effect rectification process to obtain germane with the purity of more than or equal to 99.999 percent and crude digermane, further reacting the crude digermane with fluorine gas to prepare tetrafluorogermane, and then refining to obtain the tetrafluorogermane with the purity of more than or equal to 99.999 percent. The method can prepare two products of electronic-grade germane and electronic-grade tetrafluorogermane simultaneously, so that the benefit of germanium is maximized; the energy can be saved by more than or equal to 30 percent by using the low-temperature double-effect rectification process. The invention has simple process and is easy to realize the stable industrial production of germane and tetrafluorogermane.

As shown in fig. 1, an apparatus for preparing electronic grade germane and co-producing electronic grade tetrafluorogermane: the device comprises a germane reactor R101, a germane light removal tower T101, a T101 reboiler E101, a germane refining tower T102, a T102 condenser E102, a heat exchanger E103, a tetrafluorogermane reactor R201, a tetrafluorogermane light removal tower T201, a T201 condenser E201, a T201 reboiler E202, a tetrafluorogermane refining tower T202, a T202 condenser E203 and a T202 reboiler E204.

The upper part of the germane reactor R101 is provided with a material inlet, the top of the germane reactor R101 is provided with a reaction gas outlet, the bottom of the germane reactor R101 is provided with a mixed salt solution outlet, and the reaction gas outlet is connected with the germane lightness-removing tower T101. The middle part of a germane lightness removing tower T101 is provided with a material inlet, the top part is provided with a tower top extraction outlet, the upper part is provided with a reflux port, the bottom part is provided with a tower kettle extraction outlet, wherein the material inlet is connected with a germane reactor R101, the reflux port is connected with a heat exchanger E103, the tower top extraction outlet is divided into two paths, one path is connected with the heat exchanger E103, and the other path is used for extracting light components; the extraction and outlet of the tower kettle are divided into two paths, one path is connected with a germane refining tower T102, and the other path is connected with a T101 reboiler E101. The T101 reboiler E101 is provided with a material inlet and a material outlet which are connected with the germane lightness removing tower T101. The heat exchanger E103 is provided with a germane lightness-removing tower T101 top material inlet, a germane lightness-removing tower T101 top material outlet, a germane refining tower T102 tower kettle material inlet and a germane refining tower T102 tower kettle material outlet, wherein the germane lightness-removing tower T101 top material inlet and the germane lightness-removing tower T101 top material outlet are connected with the germane lightness-removing tower T101, the germane refining tower T102 tower kettle material inlet and the germane refining tower T102 tower kettle material outlet are connected with the germane refining tower T102; the middle part of a germane refining tower T102 is provided with a material inlet, the top part is provided with a tower top extraction outlet, the upper part is provided with a reflux port, the lower part is provided with a material return port, the bottom part is provided with a tower kettle extraction outlet, the material inlet is connected with a germane lightness-removing tower T101, the tower top extraction outlet and the reflux port are both connected with a T102 condenser E102, the material return port is connected with a heat exchanger E103, the tower kettle extraction outlet is divided into two paths, one path is connected with the heat exchanger E103, and the other path is connected with a tetrafluoro. The T102 condenser E102 is provided with a material inlet, a liquid phase material outlet and a gas phase material outlet, wherein the material inlet and the liquid phase material outlet are both connected with the germane refining tower T102, and the gas phase material outlet is used for extracting an electronic grade germane product.

The tetrafluorogermane reactor R201 is provided with a material inlet, an F2 inlet and a reaction gas outlet, wherein the material inlet is connected with a germane refining tower T102, and the reaction gas outlet is connected with a tetrafluorogermane light-removing tower T201. The middle part of the tetrafluorogermane light-removing tower T201 is provided with a material inlet, the top part is provided with a tower top extraction outlet, the upper part is provided with a reflux port, the bottom part is provided with a tower kettle extraction outlet, the material inlet is connected with the tetrafluorogermane reactor R201, the tower top extraction outlet and the reflux port are both connected with a T201 condenser E201, the tower kettle extraction outlet is divided into two paths, one path is connected with a T201 reboiler E202, and the other path is connected with a tetrafluorogermane refining tower T202. The T201 reboiler E202 is provided with a material inlet and a material outlet which are connected with the tetrafluorogermane light-removing tower T201. The T202 condenser E201 is provided with a material inlet, a liquid phase material outlet and a gas phase material outlet, wherein the material inlet and the liquid phase material outlet are both connected with the tetrafluorogermane light-removing tower T201, and the gas phase material outlet extracts light impurities.

The middle part of the tetrafluorogermane refining tower T202 is provided with a material inlet, the top part is provided with a tower top extraction outlet, the upper part is provided with a reflux port, the bottom part is provided with a tower kettle extraction outlet, the material inlet is connected with the tetrafluorogermane lightness-removing tower T201, the tower top extraction outlet and the reflux port are both connected with a T202 condenser E203, the tower kettle extraction outlet is divided into two paths, one path is connected with a T202 reboiler E204, and the other path is connected with the tetrafluorogermane lightness-removing tower T201. The T202 reboiler E204 is provided with a material inlet and a material outlet which are connected with the tetrafluorogermane refining tower T202. The T202 condenser E203 is provided with a material inlet, a liquid phase material outlet and a gas phase material outlet, wherein the material inlet and the liquid phase material outlet are both connected with the tetrafluorogermane refining tower T202, and the gas phase material outlet is used for extracting light impurities.

The specific implementation mode is as follows:

(1) germanium dioxide is dissolved in acid and then added into a germane reactor R101, and then sodium borohydride is added. Germanium dioxide and sodium borohydride react in an acid environment to obtain germane crude gas (containing impurities such as nitrogen, hydrogen, CO2, digermane and the like), and the germane crude gas is extracted to a germane lightness-removing tower T101.

The reaction pressure of the germane reactor R101 is 0.12-0.3 MPa, the temperature is 20-90 ℃, and the reaction time is 1-5 h.

The molar ratio of the acid to the germanium dioxide is 2-5: 1.

The molar ratio of the sodium borohydride to the germanium dioxide is 3-7: 1

The acid is preferably one of hydrofluoric acid, acetic acid and oxalic acid.

(2) One path of the light component is extracted from the top of the germane lightness removing tower T101 and enters a heat exchanger E103 for heat exchange, the other path of the light component is extracted, and the light component is extracted from the bottom of the tower and enters a germane refining tower T102. The top of the germane refining tower T102 extracts electronic grade germane with the purity of more than or equal to 99.999 percent, one path of the tower kettle enters a heat exchanger E103 for heat exchange, and the other path of the tower kettle extracts crude digermane to a tetrafluorogermane reactor R201.

The operating pressure of the T101 of the germane lightness removing tower is 0.4-0.8 MPa, and the operating temperature is-60 ℃ to-35 ℃.

The operating pressure of the T102 of the germane refining tower is 0.3-0.7 MPa, and the operating temperature is-70 ℃ to-45 ℃.

The temperature of the top of the germane lightness removing tower T101 is more than or equal to 10 ℃ than the temperature of the bottom of the germane refining tower T102.

(3) Fluorine gas is added into a tetrafluorogermane reactor R201, digermane reacts with the fluorine gas to obtain a tetrafluorogermane crude product gas (containing impurities such as nitrogen, hydrogen fluoride, fluorine gas, digermane and the like), and the tetrafluorogermane crude product gas is extracted to a tetrafluorogermane light-removing tower T201.

The reaction pressure of the R201 of the tetrafluorogermane reactor is 0.12-0.3 MPa, the temperature is 0-40 ℃, and the reaction time is 1-5 h.

The molar ratio of the fluorine gas to the digermane is 4-6: 1.

(4) Light impurities are extracted from the top of the tetrafluorogermane light-removing tower T201, and the light impurities are extracted from the bottom of the tower and enter a tetrafluorogermane refining tower T202. The top of the T102 tower of the tetrafluorogermane refining tower extracts electronic-grade tetrafluorogermane with the purity of more than or equal to 99.999 percent, and the bottom of the tower extracts heavy impurities.

The operating pressure of the T201 of the tetrafluorogermane light-removing tower is 0.3-0.7 MPa, and the operating temperature is-9.6-16.7 ℃.

The operating pressure of the T202 of the tetrafluorogermane refining tower is 0.2-0.6 MPa, and the operating temperature is-20.4 to-11.5 ℃.

Example 1

The present invention will be further described with reference to fig. 1 and the following detailed description.

Adding 2mol of germanium dioxide solvent into 4mol of acetic acid water solution, adding into a germane reactor R101 and adding 6mol of sodium borohydride, and reacting for 1 h. In the reaction process, the pressure of the R101 of the germane reactor is kept at 0.12MPa, the temperature is kept at 20 ℃, and the generated crude germane gas is extracted to a germane light component removal tower T101. The operating pressure of the germane lightness-removing tower T101 is 0.8MPa, the operating temperature is-35 ℃, one path of the top of the germane lightness-removing tower T101 enters a heat exchanger E103 for heat exchange, the other path of the top of the germane lightness-removing tower extracts light components, and the tower bottom of the germane lightness-removing tower extracts light components to a germane refining tower T102. The operating pressure of a germane refining tower T102 is 0.7MPa, the operating temperature is-45 ℃, electronic grade germane with the purity of more than or equal to 99.999 percent is extracted from the top of the germane refining tower T102, one path of the tower bottom enters a heat exchanger E103 for heat exchange, and the other path of the tower bottom is extracted to a tetrafluorogermane reactor R201. According to the molar weight of digermane added into the tetrafluorogermane reactor R201, 4 times of fluorine gas is added for reaction, the pressure of the tetrafluorogermane reactor R201 is controlled to be 0.12MPa, the temperature is controlled to be 0 ℃, and the reaction time is controlled to be 1 h. And (3) extracting a crude tetrafluorogermane product gas generated by the tetrafluorogermane reactor R201 to a tetrafluorogermane light-removing tower T201. The T201 operation pressure of the tetrafluorogermane light-ends removal tower is 0.7MPa, and the operation temperature is 16.7 ℃. Light impurities are extracted from the top of the tetrafluorogermane light-removing tower T201, and the light impurities are extracted from the bottom of the tower to a tetrafluorogermane refining tower T202. The operating pressure of the T202 of the tetrafluorogermane refining tower is 0.6MPa, the operating temperature is 11.5 ℃, electronic-grade tetrafluorogermane with the purity of more than or equal to 99.999 percent is extracted from the top of the T202 of the tetrafluorogermane refining tower, and heavy impurities are extracted from the bottom of the tower.

Dissolving germanium dioxide into acetic acid water solution according to the molar ratio of the germanium dioxide to the acetic acid being 1:2, and then dissolving the germanium dioxide into the acetic acid water solution

After the addition, add to germane reactor R101, then add sodium borohydride. Germanium dioxide and sodium borohydride react in an acid environment to obtain germane crude gas (containing impurities such as nitrogen, hydrogen, CO2, digermane and the like), and the germane crude gas is extracted to a germane lightness-removing tower T101.

The reaction pressure of the germane reactor R101 is 0.12-0.3 MPa, the temperature is 20-90 ℃, and the reaction time is 1-5 h.

The molar ratio of the acid to the germanium dioxide is 2-5: 1.

The molar ratio of the sodium borohydride to the germanium dioxide is 3-7: 1

The acid is preferably one of hydrofluoric acid, acetic acid and oxalic acid.

(2) One path of the light component is extracted from the top of the germane lightness removing tower T101 and enters a heat exchanger E103 for heat exchange, the other path of the light component is extracted, and the light component is extracted from the bottom of the tower and enters a germane refining tower T102. The top of the germane refining tower T102 extracts electronic grade germane with the purity of more than or equal to 99.999 percent, one path of the tower kettle enters a heat exchanger E103 for heat exchange, and the other path of the tower kettle extracts crude digermane to a tetrafluorogermane reactor R201.

The operating pressure of the T101 of the germane lightness removing tower is 0.4-0.8 MPa, and the operating temperature is-60 ℃ to-35 ℃.

The operating pressure of the T102 of the germane refining tower is 0.3-0.7 MPa, and the operating temperature is-70 ℃ to-45 ℃.

The temperature of the top of the germane lightness removing tower T101 is more than or equal to 10 ℃ than the temperature of the bottom of the germane refining tower T102.

(3) Fluorine gas is added into a tetrafluorogermane reactor R201, digermane reacts with the fluorine gas to obtain a tetrafluorogermane crude product gas (containing impurities such as nitrogen, hydrogen fluoride, fluorine gas, digermane and the like), and the tetrafluorogermane crude product gas is extracted to a tetrafluorogermane light-removing tower T201.

The reaction pressure of the R201 of the tetrafluorogermane reactor is 0.12-0.3 MPa, the temperature is 0-40 ℃, and the reaction time is 1-5 h.

The molar ratio of the fluorine gas to the digermane is 4-6: 1.

(4) Light impurities are extracted from the top of the tetrafluorogermane light-removing tower T201, and the light impurities are extracted from the bottom of the tower and enter a tetrafluorogermane refining tower T202. The top of the T102 tower of the tetrafluorogermane refining tower extracts electronic-grade tetrafluorogermane with the purity of more than or equal to 99.999 percent, and the bottom of the tower extracts heavy impurities.

The operating pressure of the T201 of the tetrafluorogermane light-removing tower is 0.3-0.7 MPa, and the operating temperature is-9.6-16.7 ℃.

The operating pressure of the T202 of the tetrafluorogermane refining tower is 0.2-0.6 MPa, and the operating temperature is-20.4 to-11.5 ℃.

Example 2

Adding 2mol of germanium dioxide solvent into 10mol of hydrofluoric acid water solution, adding into a germane reactor R101 and adding 14mol of sodium borohydride, and reacting for 5 h. In the reaction process, the pressure of a germane reactor R101 is kept at 0.2MPa and the temperature is kept at 40 ℃, and the generated crude germane gas is extracted to a germane light component removal tower T101. The operating pressure of the germane lightness-removing tower T101 is 0.6MPa, the operating temperature is-50 ℃, one path of the top of the germane lightness-removing tower T101 enters a heat exchanger E103 for heat exchange, the other path of the top of the germane lightness-removing tower extracts light components, and the tower bottom of the germane lightness-removing tower extracts light components to a germane refining tower T102. The operating pressure of a germane refining tower T102 is 0.5MPa, the operating temperature is-60 ℃, electronic grade germane with the purity of more than or equal to 99.999 percent is extracted from the top of the germane refining tower T102, one path of the tower bottom enters a heat exchanger E103 for heat exchange, and the other path of the tower bottom is extracted to a tetrafluorogermane reactor R201. According to the molar weight of digermane added into the tetrafluorogermane reactor R201, fluorine gas of 6 times is added for reaction, the pressure of the tetrafluorogermane reactor R201 is controlled to be 0.2MPa, the temperature is controlled to be 20 ℃, and the reaction time is controlled to be 5 hours. And (3) extracting a crude tetrafluorogermane product gas generated by the tetrafluorogermane reactor R201 to a tetrafluorogermane light-removing tower T201. The T201 operation pressure of the tetrafluorogermane light-ends removal tower is 0.5MPa, and the operation temperature is 5.6 ℃. Light impurities are extracted from the top of the tetrafluorogermane light-removing tower T201, and the light impurities are extracted from the bottom of the tower to a tetrafluorogermane refining tower T202. The operating pressure of the tetrafluorogermane refining tower T202 is 0.4MPa, the operating temperature is-1.7 ℃, electronic-grade tetrafluorogermane with the purity of more than or equal to 99.999 percent is extracted from the top of the tetrafluorogermane refining tower T202, and heavy impurities are extracted from the bottom of the tower.

Example 3

Adding 2mol of germanium dioxide solvent into 7mol of hydrofluoric acid water solution, adding into a germane reactor R101 and adding 10mol of sodium borohydride, and reacting for 3 hours. In the reaction process, the pressure of a germane reactor R101 is kept at 0.3MPa and the temperature is kept at 90 ℃, and the generated crude germane gas is extracted to a germane light component removal tower T101. The operating pressure of the germane lightness-removing tower T101 is 0.4MPa, the operating temperature is-60 ℃, one path of the top of the germane lightness-removing tower T101 enters a heat exchanger E103 for heat exchange, the other path of the top of the germane lightness-removing tower extracts light components, and the tower bottom of the germane lightness-removing tower extracts light components to a germane refining tower T102. The operating pressure of a germane refining tower T102 is 0.3MPa, the operating temperature is-70 ℃, electronic grade germane with the purity of more than or equal to 99.999 percent is extracted from the top of the germane refining tower T102, one path of the tower bottom enters a heat exchanger E103 for heat exchange, and the other path of the tower bottom is extracted to a tetrafluorogermane reactor R201. According to the molar weight of digermane added into the tetrafluorogermane reactor R201, fluorine gas of 6 times is added for reaction, the pressure of the tetrafluorogermane reactor R201 is controlled to be 0.3MPa, the temperature is controlled to be 40 ℃, and the reaction time is controlled to be 3 hours. And (3) extracting a crude tetrafluorogermane product gas generated by the tetrafluorogermane reactor R201 to a tetrafluorogermane light-removing tower T201. The T201 operation pressure of the tetrafluorogermane light-ends removal tower is 0.3MPa, and the operation temperature is-9.6 ℃. Light impurities are extracted from the top of the tetrafluorogermane light-removing tower T201, and the light impurities are extracted from the bottom of the tower to a tetrafluorogermane refining tower T202. The operating pressure of the tetrafluorogermane refining tower T202 is 0.2MPa, the operating temperature is-20.4 ℃, electronic-grade tetrafluorogermane with the purity of more than or equal to 99.999 percent is extracted from the top of the tetrafluorogermane refining tower T202, and heavy impurities are extracted from the bottom of the tower.

While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.