CN114702060A - Preparation method of germanium dioxide capable of being rapidly dissolved in ethylene glycol - Google Patents
Preparation method of germanium dioxide capable of being rapidly dissolved in ethylene glycol Download PDFInfo
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- CN114702060A CN114702060A CN202210518815.3A CN202210518815A CN114702060A CN 114702060 A CN114702060 A CN 114702060A CN 202210518815 A CN202210518815 A CN 202210518815A CN 114702060 A CN114702060 A CN 114702060A
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
- C01G17/02—Germanium dioxide
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a preparation method of germanium dioxide quickly dissolved in ethylene glycol, which comprises the following steps: adding germanium tetrachloride and ammonia water into the base solution simultaneously under the stirring condition at the temperature of 0-20 ℃, wherein the adding time is 3-8 h, the pH value of the system is 9.0-11.0, and centrifuging after the reaction is finished to obtain a solid; the base solution is dilute ammonia water with the pH value of 9.0-11.0; and drying the solid and then calcining to obtain the germanium dioxide. The germanium dioxide prepared by the method is amorphous, so that the time for dissolving the germanium dioxide in ethylene glycol is reduced. The experimental results show that: 0.300g of germanium dioxide is dissolved in 60.0g of glycol, and the mixture is dissolved and stirred at the temperature of 200 plus or minus 1 ℃ for reaction, and the dissolution and clarification time is 5-7 min.
Description
Technical Field
The invention belongs to the technical field of preparation of germanium dioxide, and particularly relates to a preparation method of germanium dioxide quickly dissolved in ethylene glycol.
Background
The synthesis methods used for the production of polyethylene terephthalate (PET) are largely divided into the transesterification process (DMT process) and the direct process (PTA process). Currently, the PTA method is basically adopted in PET production in the market, Ethylene Glycol (EG) and terephthalic acid are used as monomers, and the PET material is prepared after esterification and polycondensation. At present, the main catalysts used for industrial production of PET are Sb, Ge and Ti series compounds, and the performances of PET synthesized by different catalysts are slightly different.
The germanium catalyst is germanium dioxide, which has low promotion effect on side reaction in polycondensation reaction, less by-products, and germanium dioxide and stabilizer H3PO4No effect occurs. The polyester chip prepared by using the germanium catalyst has high brightness, high transparency and low yellowness, and a sample shows excellent white color and is favored in high-end application fields of polyester, such as X-ray substrates and the like. However, the most easily existing form of germanium dioxide is a hexagonal crystal form, and the germanium dioxide of the crystal form has low solubility and long dissolution time in EG, which increases the difficulty for preparing various additives by EG in actual production.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing germanium dioxide which is fast soluble in ethylene glycol, the method is simple, and the prepared germanium dioxide has short dissolution time in EG.
The invention provides a preparation method of germanium dioxide quickly dissolved in ethylene glycol, which comprises the following steps:
adding germanium tetrachloride and ammonia water into the base solution simultaneously under the stirring condition at the temperature of 0-20 ℃, wherein the adding time is 3-8 h, the pH value of the system is 9.0-11.0, and centrifuging after the reaction is finished to obtain a solid; the base solution is dilute ammonia water with the pH value of 9.0-11.0;
and drying the solid and then calcining to obtain the germanium dioxide.
In the invention, the drying temperature is 80-120 ℃, and the drying time is 4-8 h; in a specific embodiment, the drying temperature is 80 ℃, 120 ℃ or 100 ℃; the drying time is 8h, 4h or 6 h.
The calcining temperature is 400-600 ℃, and the calcining time is 4-8 h. In specific embodiments, the temperature of the calcination is 500 ℃, 600 ℃, or 400 ℃; the calcination time is 6h, 4h or 8 h.
In the invention, the volume ratio of the germanium tetrachloride to the base solution is 16: 450-550. In the present invention, the feed rate of germanium tetrachloride is related to the volume of the reaction vessel. The mass concentration of the ammonia water added into the base solution is preferably 5-15%, and the base solution is diluted ammonia water with the pH value of 9.0-11.0. The pH value of the system is maintained to be 9.0-11.0 by adding ammonia water.
In the invention, the calcination adopts a continuous feeding mode, and the feeding speed is 1-10 kg/h. In particular embodiments, the feed rate is 1kg/h, or 5kg/h or 10 kg/h. The calcination adopts dynamic calcination, the materials are continuously turned over in the furnace body, continuously fed and continuously discharged, and the volatilization of water, ammonia and chlorine is facilitated.
In the invention, oxygen or filtered air is introduced from the discharge end to the feed end during calcination; the feeding rate is 5-30L/min. H can be decomposed in the process of calcination2O、NH3HCl, which may enter the product if removed from the discharge end, so that oxygen or filtered air needs to be fed from the discharge end to the feed end.
In the present invention, the purity of the germanium tetrachloride is 6N or more.
In the present invention, the germanium dioxide is amorphous germanium dioxide.
The invention provides a preparation method of germanium dioxide quickly dissolved in ethylene glycol, which comprises the following steps: adding germanium tetrachloride and ammonia water into the base solution simultaneously under the stirring condition at the temperature of 0-20 ℃, wherein the adding time is 3-8 h, the pH value of the system is 9.0-11.0, and centrifuging after the reaction is finished to obtain a solid; the base solution is dilute ammonia water with the pH value of 9.0-11.0; and drying the solid and then calcining to obtain the germanium dioxide. The germanium dioxide prepared by the method is amorphous, so that the time for dissolving the germanium dioxide in ethylene glycol is reduced. The experimental results show that: 0.300g of germanium dioxide is dissolved in 60.0g of glycol, and the mixture is dissolved and stirred at the temperature of 200 plus or minus 1 ℃ for reaction, and the dissolution and clarification time is 5-7 min.
Drawings
FIG. 1 is a flow chart of a process for preparing germanium dioxide which is rapidly soluble in ethylene glycol according to the present invention;
FIG. 2 is an XRD spectrum of germanium dioxide prepared in example 1 of the present invention.
Detailed Description
In order to further illustrate the present invention, the following examples are provided to describe the preparation method of germanium dioxide rapidly dissolved in ethylene glycol, but they should not be construed as limiting the scope of the present invention.
Example 1
450L of dilute ammonia water base solution with the pH value of 9.0 is added into the hydrolysis kettle, and the temperature is reduced to 0 ℃. Then under the stirring state, simultaneously adding germanium tetrachloride and ammonia water with the content of 5% into the hydrolysis kettle, adding 16L of germanium tetrachloride for 3h, adjusting the adding speed of the ammonia water, controlling the pH value of the system to be 9.0, and simultaneously controlling the temperature of the reaction system to be 0 ℃. And after the feeding is finished, carrying out solid-liquid separation on the slurry through a centrifugal machine to obtain the germanium oxide. The temperature of the rotary calcining furnace is set to be 80 ℃, germanium oxide is thrown into the quartz tube at the feeding speed of 1kg/h, and the drying time is controlled to be 8 h. And then setting the temperature of the rotary calciner to be 400 ℃, introducing oxygen from the discharge end to the feed end for 5L/min, putting germanium oxide into the quartz tube at the feeding speed of 1kg/h, and controlling the calcination time to be 8h to obtain the germanium dioxide.
The detection result shows that 0.300g of germanium dioxide is dissolved in 60.0g of ethylene glycol, and the mixture is dissolved and stirred at 200 +/-1 ℃ for reaction, the dissolution and clarification time is 5min, the solution is cooled to room temperature, the solution is clear and transparent, and the solution transmittance is 99.7 percent, which is detailed in the attached table 1.
Example 2
Adding 550L of dilute ammonia water base solution with pH of 11.0 into the hydrolysis kettle, and cooling to 20 ℃. Then, under the stirring state, adding germanium tetrachloride and ammonia water with the content of 15% into the hydrolysis kettle simultaneously, adding 16L of germanium tetrachloride for 8h, adjusting the adding speed of the ammonia water to control the pH value of the system to be 11.0, and controlling the temperature of the reaction system to be 20 ℃. And after the feeding is finished, carrying out solid-liquid separation on the slurry through a centrifugal machine to obtain the germanium oxide. The temperature of the rotary calcining furnace is set to be 120 ℃, germanium oxide is put into the quartz tube at the feeding speed of 1kg/h, and the drying time is controlled to be 4 h. And then setting the temperature of the rotary calcining furnace at 600 ℃, introducing oxygen from the discharge end to the feed end for 20L/min, putting the germanium oxide into the quartz tube at the feeding speed of 10kg/h, and controlling the calcining time to be 4h to obtain the germanium dioxide.
The detection result shows that 0.300g of germanium dioxide is dissolved in 60.0g of ethylene glycol, and the mixture is dissolved and stirred at 200 +/-1 ℃ for reaction, the dissolution and clarification time is 7min, the solution is cooled to room temperature, the solution is clear and transparent, and the solution transmittance is 99.8 percent, which is detailed in the attached table 1.
Example 3
Adding 500L of dilute ammonia water base solution with the pH value of 10.0 into the hydrolysis kettle, and cooling to 10 ℃. Then, under the stirring state, adding germanium tetrachloride and ammonia water with the content of 10% into the hydrolysis kettle simultaneously, adding 16L of germanium tetrachloride for 5h, adjusting the adding speed of the ammonia water to control the pH value of the system to be 10.0, and controlling the temperature of the reaction system to be 10 ℃. And after the feeding is finished, carrying out solid-liquid separation on the slurry through a centrifugal machine to obtain the germanium oxide. The temperature of the rotary calcining furnace is set to be 100 ℃, germanium oxide is put into the quartz tube at the feeding speed of 5kg/h, and the drying time is controlled to be 6 h. And then setting the temperature of the rotary calciner to be 500 ℃, introducing oxygen from the discharge end to the feed end for 30L/min, putting germanium oxide into the quartz tube at the feeding speed of 5kg/h, and controlling the calcination time to be 6h to obtain the germanium dioxide.
The detection result shows that 0.300g of germanium dioxide is dissolved in 60.0g of ethylene glycol, and the mixture is dissolved and stirred at 200 +/-1 ℃ for reaction, the dissolution and clarification time is 6min, the solution is cooled to room temperature, the solution is clear and transparent, and the solution transmittance is 99.6 percent, which is detailed in the attached table 1.
TABLE 1 test results for the products of examples 1-3
Wherein the ignition loss is determined according to GB/T11069 and 2017 appendix A of high-purity germanium dioxide volatile matter.
From the above embodiments, the present invention provides a method for preparing germanium dioxide rapidly soluble in ethylene glycol, comprising the following steps: adding germanium tetrachloride and ammonia water into the base solution simultaneously under the stirring condition at the temperature of 0-20 ℃, wherein the adding time is 3-8 h, the pH value of the system is 9.0-11.0, and centrifuging after the reaction is finished to obtain a solid; the base solution is dilute ammonia water with the pH value of 9.0-11.0; and drying the solid and then calcining to obtain the germanium dioxide. The germanium dioxide prepared by the method is amorphous, so that the time for dissolving the germanium dioxide in ethylene glycol is reduced. The experimental results show that: 0.300g of germanium dioxide is dissolved in 60.0g of glycol, and the mixture is dissolved and stirred at the temperature of 200 +/-1 ℃, and the dissolution and clarification time is 5-7 min.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A preparation method of germanium dioxide which is fast dissolved in ethylene glycol comprises the following steps:
adding germanium tetrachloride and ammonia water into the base solution simultaneously under the stirring condition at the temperature of 0-20 ℃, wherein the adding time is 3-8 h, the pH value of the system is 9.0-11.0, and centrifuging after the reaction is finished to obtain a solid; the base solution is dilute ammonia water with the pH value of 9.0-11.0;
and drying the solid and then calcining to obtain the germanium dioxide.
2. The preparation method according to claim 1, wherein the drying temperature is 80-120 ℃ and the drying time is 4-8 h;
the calcining temperature is 400-600 ℃, and the calcining time is 4-8 h.
3. The preparation method according to claim 1, wherein the volume ratio of the germanium tetrachloride to the base solution is 16: 450-550.
4. The preparation method of claim 1, wherein the calcination adopts a continuous feeding mode, and the feeding speed is 1-10 kg/h.
5. The preparation method according to claim 1, characterized in that oxygen or filtered air is introduced from the discharge end to the feed end during calcination; the feeding rate is 5-30L/min.
6. The method according to claim 1, wherein the germanium tetrachloride has a purity of 6N or more.
7. The method of claim 1 wherein the germanium dioxide is amorphous germanium dioxide.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10194737A (en) * | 1997-01-10 | 1998-07-28 | Sumitomo Metal Mining Co Ltd | Production of amorphous germanium dioxide |
| JP2001002416A (en) * | 1999-06-17 | 2001-01-09 | Mitsui Chemicals Inc | Production of ethylene glycol soluble germanium dioxide and dissolving method thereof |
| US20050085381A1 (en) * | 1994-12-17 | 2005-04-21 | Matthias Irgang | Catalysts or carriers which consist essentially of monoclinic zirconium dioxide |
| CN109279646A (en) * | 2018-11-26 | 2019-01-29 | 广东先导稀材股份有限公司 | The production method of catalyst grade germanium dioxide |
| CN109534388A (en) * | 2019-01-10 | 2019-03-29 | 成都中建材光电材料有限公司 | A kind of preparation method of high-purity germanium dioxide |
| CN112830511A (en) * | 2021-03-15 | 2021-05-25 | 广东先导稀材股份有限公司 | Germanium dioxide dechlorinating method |
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2022
- 2022-05-13 CN CN202210518815.3A patent/CN114702060A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050085381A1 (en) * | 1994-12-17 | 2005-04-21 | Matthias Irgang | Catalysts or carriers which consist essentially of monoclinic zirconium dioxide |
| JPH10194737A (en) * | 1997-01-10 | 1998-07-28 | Sumitomo Metal Mining Co Ltd | Production of amorphous germanium dioxide |
| JP2001002416A (en) * | 1999-06-17 | 2001-01-09 | Mitsui Chemicals Inc | Production of ethylene glycol soluble germanium dioxide and dissolving method thereof |
| CN109279646A (en) * | 2018-11-26 | 2019-01-29 | 广东先导稀材股份有限公司 | The production method of catalyst grade germanium dioxide |
| CN109534388A (en) * | 2019-01-10 | 2019-03-29 | 成都中建材光电材料有限公司 | A kind of preparation method of high-purity germanium dioxide |
| CN112830511A (en) * | 2021-03-15 | 2021-05-25 | 广东先导稀材股份有限公司 | Germanium dioxide dechlorinating method |
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