CN111777039A - Germane production process - Google Patents

Abstract

The invention discloses a germane production process, which comprises the steps of preparing NaOH solution, preparing solution A, preparing solution B, charging concentrated sulfuric acid solution, mixing the solution A, the solution B and concentrated sulfuric acid to perform chemical reaction to synthesize germane, wherein the synthesis of germane adopts DSC automatic synthesis. The invention uses GeO₂、NaOH、NaBH₄And H₂SO₄The raw material is reacted to produce germane, and only germane gas and a small amount of H are generated in the whole process₂Other products are all liquid, so that the purity and the conversion rate of the produced germane are high, and H is₂The process of converting hydrogen germanide into elemental germanium is slightly affected, so that impurity separation is not needed, the cost is saved, and the method is suitable for mass production. In addition, the preparation of the corresponding raw material solution is firstly completed, and then the DSC automatic operation is adopted to synthesize the germane, so that the whole production process is accurately controlled, the operation is simple, and the direct contact between an operator and NaBH is avoided₄The solution is contacted with concentrated sulfuric acid, so that safe production is realized.

Description

Germane production process

Technical Field

The invention relates to the technical field of chemical gas production, in particular to a germane production process.

Background

Germane has the chemical formula GeH₄The germanium is one of important sources of high-purity simple substance germanium, is mainly used for the aspects of semiconductors, infrared technology and the like, is mainly used for a metal organic compound vapor deposition process in the electronic industry, is used as an important precursor gas of a solar cell and the like, and is also used for preparing a heterojunction bipolar transistor. In the prior art, germane is produced by reducing germanium chloride, reacting hydrochloric acid on a germanium-magnesium alloy and oxidizing germanium by an electrode in concentrated sulfuric acid.

In germane synthesis process and use summary (2013.12) published in journal, volume 31, No. 6, of "Low temperature and Special gas", a chemical reduction method, an electrochemical reduction method and a plasma synthesis method are introduced to prepare germane, wherein the chemical reduction method has the advantages of simple raw material source, simple reaction process and equipment, low reaction pressure, simple flow control, good safety performance, mature production process and suitability for production of small and medium-sized enterprises, and the chemical reduction method generally adopts a reducing agent to reduce germanium alloy, germanium dioxide and germanium tetrachloride to prepare germane. However, the method still has some problems in the aspects of comprehensive cost, purification, conversion rate and the like, such as high content of by-products, difficult separation of impurities and the like.

Disclosure of Invention

In view of the above-mentioned disadvantages, the present invention provides a process for producing germane, which can produce germane with high purity and high conversion rate, and is suitable for mass production.

In order to achieve the purpose, the technical scheme provided by the invention is as follows:

a germane production process comprises the following steps:

s1: preparing NaOH solution;

s2: adding NaBH into the NaOH solution prepared in the step S1₄Preparing a solution A;

s3: CeO was added to the NaOH solution prepared in step S1₂Preparing a solution B;

s4: charging a concentrated sulfuric acid solution;

s5: and mixing the solution A, the solution B and concentrated sulfuric acid to perform chemical reaction to synthesize germane.

Preferably, the step S5 is performed by DSC automation.

Preferably, the process of preparing the NaOH solution in step S1 is as follows:

s11: adding deionized water into the NaOH tank;

s12: starting stirring;

s13: slowly adding solid NaOH from a feed inlet of the NaOH tank;

s14: the addition port was sealed and deionized water was added again.

Preferably, the process of preparing the solution a in step S2 is as follows:

s21: adding NaOH solution;

s22: adding deionized water;

s23: starting stirring;

s24: slowly adding solid NaBH from the feeding port of the mixed solution A tank body₄；

S25: and sealing the feed inlet, and adding deionized water into the solution A tank body again.

Preferably, the process of preparing the solution B in step S3 is as follows:

s31: adding NaOH solution;

s32: adding deionized water;

s33: starting stirring;

s34: slowly adding solid GeO from a feeding port of a solution B tank body₂；

S35: and sealing the feed inlet, and adding deionized water into the solution B tank again.

Preferably, the specific process of step S4 is as follows:

s41: inserting a liquid guiding tetrafluoride pipe of a concentrated sulfuric acid tank into a concentrated sulfuric acid raw material barrel to suck concentrated sulfuric acid into the concentrated sulfuric acid tank;

s42: after the concentrated sulfuric acid tank is filled, the surface of the tetrafluoride pipe is cleaned by water and then sealed and collected.

Preferably, the DSC automatically synthesizes germane by a specific process:

s51: confirming that all valves are in a closed state;

s52: adjusting the pressure of the pressure reducing valve;

s53: placing a receiving bottle for collecting the exhaust;

s54: starting a vacuum pump, opening a receiving bottle valve after replacing a pipeline, and then automatically switching to collect gas exhaust;

s55: setting parameters, and automatically adding the NaOH solution prepared in the step S1;

s56: setting parameters, and automatically adding concentrated sulfuric acid in the step S4;

s57: setting parameters, and automatically adding the solution A prepared in the step S2 and the solution B prepared in the step S3;

s58: setting parameters and starting to synthesize germane.

The invention has the beneficial effects that: the invention uses GeO₂、NaOH、NaBH₄And H₂SO₄The raw material is reacted to produce germane, and only germane gas and a small amount of H are generated in the whole process₂All other products are liquid, and GeO₂Completely converted into germane, thereby producing germane with high purity and conversion rate, and H₂The process of converting hydrogen germanide into elemental germanium is slightly affected, so that impurity separation is not needed, the cost is saved, and the method is suitable for mass production. In addition, the preparation of the corresponding raw material solution is firstly completed, and then the DSC automatic operation is adopted to synthesize the germane, so that the whole production process is accurately controlled, the operation is simple, and the direct contact between an operator and NaBH is avoided₄The solution is contacted with concentrated sulfuric acid, so that safe production is realized.

Detailed Description

Example 1:

waste water that produces in the germane production process has very big harm to the environment, consequently need discharge after handling waste water, need prepare large-scale waste liquid bucket before beginning germane production, and the waste liquid pipeline of germane production facility is placed in the waste liquid bucket, and then waste water is unified to get into in the waste liquid bucket through the waste liquid pipeline and is handled the back and discharge.

The germane production steps are as follows:

s1: preparing NaOH solution;

s2: adding NaBH into the NaOH solution prepared in the step S1₄Preparing a solution A;

s3: CeO was added to the NaOH solution prepared in step S1₂Preparing a solution B;

s4: charging a concentrated sulfuric acid solution;

s5: and mixing the solution A, the solution B and concentrated sulfuric acid to perform chemical reaction to synthesize germane.

The gas generated by the invention only contains germane and H₂Without the presence of other impurity gases, germane is used primarily for the production of high purity elemental germanium，H₂The influence on the germanium is small, so that the impurity gas is not required to be separated additionally when the elemental germanium is prepared, the production cost is reduced, the purity and the conversion rate of the obtained germane are high, and the germanium-containing preparation method is suitable for mass production.

Example 2:

the step S5 adopts DSC automatic operation to accurately control the production process and avoid direct contact between the operator and NaBH₄The solution is contacted with concentrated sulfuric acid, safe production is realized, and the operation is simple.

Before the solution preparation, the vacuum pumping is needed, the pressure of the pressure reducing valve is adjusted by opening a replacement gas source, and then the solution preparation is carried out. The specific production process comprises the following steps:

s1: preparation of NaOH solution

S11: adding deionized water into the NaOH tank;

s12: starting stirring;

s13: slowly adding solid NaOH from a feed inlet of the NaOH tank;

s14: and sealing the feed inlet, and adding deionized water again to completely dissolve the solid NaOH in the deionized water.

S2: preparation of solution A

S21: adding the NaOH solution prepared in the step S1;

s22: adding deionized water;

s23: starting stirring;

s24: slowly adding solid NaBH from the feeding port of the solution A tank body₄；

S25: and sealing the feed inlet, and adding deionized water into the solution A tank body again.

S3: preparation of solution B

S31: adding the NaOH solution prepared in the step S1;

s32: adding deionized water;

s33: starting stirring;

s34: slowly adding solid GeO from the feeding port of the solution B tank body₂；

S35: and sealing the feed inlet, and adding deionized water into the solution B tank again.

S4: charging of concentrated sulfuric acid

S41: inserting a liquid guiding tetrafluoride pipe of a concentrated sulfuric acid tank into a concentrated sulfuric acid raw material barrel to suck concentrated sulfuric acid into the concentrated sulfuric acid tank;

s42: after the concentrated sulfuric acid tank is filled, the surface of the tetrafluoride pipe is cleaned by water and then sealed and collected.

S5: DSC automatic synthesis of germane

S51: confirming that all valves are in a closed state;

s52: adjusting the pressure of the pressure reducing valve;

s53: placing a receiving bottle for receiving gas generated in the synthesis process;

s54: starting a vacuum pump, then replacing a pipeline, opening a receiving bottle valve after the pipeline is replaced, and then automatically switching and collecting according to system setting parameters;

s55: setting corresponding parameters, starting a key to automatically prepare the liquid, and adding a certain amount of NaOH solution into the NaOH solution in the NaOH tank body in the reaction tank A according to the set liquid level value;

s56: setting corresponding parameters, starting a key to automatically prepare liquid, and adding a certain amount of acid and water into the reaction tank B according to a set value;

s57: setting corresponding parameters, starting a key to automatically prepare the liquid, and adding a certain amount of mixed solution A, solution B and water into a reaction tank C according to a set value;

s58: setting parameters, starting synthesis, and adding a proper amount of reactants in the reaction tank A, the reaction tank B and the reaction tank C into the synthesis tank to synthesize germane according to the set parameters.

In the invention, the liquid flow in the whole production process is completed by pressure drop, and the whole device has good tightness.

The working principle of the invention is as follows:

main reaction: GeO₂+NaOH+NaBH₄+H₂SO₄＝GeH₄+Na₂SO₄+H₃BO₃

Side reaction: 2NaBH₄+H₂SO₄+6H₂O＝Na₂SO₄+8H₂+2H₃BO₃

The germane obtained contains only a small amount of H₂Therefore, it has high purity and is suitable for mass production.

Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention.

Claims (7)

1. A germane production process is characterized by comprising the following steps:

s1: preparing NaOH solution;

s2: adding NaBH into the NaOH solution prepared in the step S1₄Preparing a solution A;

s3: adding GeO to the NaOH solution prepared in step S1₂Preparing a solution B;

s4: charging a concentrated sulfuric acid solution;

s5: and mixing the solution A, the solution B and concentrated sulfuric acid to perform chemical reaction to synthesize germane.

2. The process of claim 1 for the production of germane, wherein: the step S5 adopts DSC automation operation.

3. A germane production process according to claim 1 or 2, wherein: the process of preparing the NaOH solution in the step S1 is as follows:

s11: adding deionized water into the NaOH tank;

s12: starting stirring;

s13: slowly adding solid NaOH from a feed inlet of the NaOH tank;

s14: the addition port was sealed and deionized water was added again.

4. A germane production process according to claim 1 or 2, wherein: the process of preparing the solution A in the step S2 is as follows:

s21: adding NaOH solution;

s22: adding deionized water;

s23: starting stirring;

s24: slowly adding solid NaBH from the feeding port of the solution A tank body₄；

S25: and sealing the feed inlet, and adding deionized water into the solution A tank body again.

5. A germane production process according to claim 1 or 2, wherein: the process of preparing the solution B in the step S3 is as follows:

s31: adding NaOH solution;

s32: adding deionized water;

s33: starting stirring;

s34: slowly adding solid GeO from the feeding port of the solution B tank body₂；

S35: and sealing the feed inlet, and adding deionized water into the solution B tank again.

6. A germane production process according to claim 1 or 2, wherein: the specific process of step S4 is as follows:

s41: inserting a liquid guiding tetrafluoride pipe of a concentrated sulfuric acid tank into a concentrated sulfuric acid raw material barrel to suck concentrated sulfuric acid into the concentrated sulfuric acid tank;

s42: after the concentrated sulfuric acid tank is filled, the surface of the tetrafluoride pipe is cleaned by water and then sealed and collected.

7. A germane production process according to claim 2, wherein: the specific process for automatically synthesizing germane by DSC is as follows:

s51: confirming that all valves are in a closed state;

s52: adjusting the pressure of the pressure reducing valve;

s53: placing a receiving bottle for collecting the exhaust;

s54: starting a vacuum pump, opening a receiving bottle valve after replacing a pipeline, and then automatically switching to collect gas exhaust;

s55: setting parameters, and automatically adding the NaOH solution prepared in the step S1;

s56: setting parameters, and automatically adding concentrated sulfuric acid in the step S4;

s57: setting parameters, and automatically adding the solution A prepared in the step S2 and the solution B prepared in the step S3;

s58: and setting parameters and starting synthesis.