CN110937622A - Method for preparing 4N gallium oxide from sponge gallium - Google Patents
Method for preparing 4N gallium oxide from sponge gallium Download PDFInfo
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- CN110937622A CN110937622A CN201911105255.3A CN201911105255A CN110937622A CN 110937622 A CN110937622 A CN 110937622A CN 201911105255 A CN201911105255 A CN 201911105255A CN 110937622 A CN110937622 A CN 110937622A
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- C01—INORGANIC CHEMISTRY
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- C01G15/00—Compounds of gallium, indium or thallium
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Abstract
The invention provides a method for preparing 4N gallium oxide from sponge gallium, which mainly comprises the following steps: heating and dissolving sponge gallium by using analytically pure sulfuric acid, nitric acid or hydrochloric acid to obtain a gallium sulfate solution, a gallium nitrate solution or a gallium chloride solution; adding a certain amount of ammonia water or ammonium carbonate or ammonium bicarbonate precipitator, pre-precipitating to form high-activity colloid for impurity removal, and performing solid-liquid separation to obtain a high-purity gallium salt solution; purifying and analyzing pure ammonia water or ammonium carbonate or ammonium bicarbonate precipitator by using a high-purity alumina adsorbent; carrying out precipitation reaction on the high-purity gallium salt solution and a certain amount of purified precipitator, and filtering and washing to obtain high-purity gallium oxide hydrate; and roasting the high-purity gallium oxide hydrate to obtain the high-purity gallium oxide. The purity of the high-purity gallium oxide prepared by the invention is more than or equal to 99.99 percent, and the problems of complex process, high requirements on raw materials and equipment, poor economical efficiency, difficulty in large-scale production and the like of the existing preparation method of the high-purity gallium oxide are solved.
Description
Technical Field
The invention belongs to the technical field of preparation of high-purity gallium oxide powder, and particularly relates to a method for preparing 4N gallium oxide from sponge gallium.
Background
Gallium oxide (Ga)2O3) The material is a multifunctional semiconductor material, has excellent conductivity, luminescent property, gas-sensitive property and better thermal stability, can be used as a raw material or an auxiliary material of a magneto-optical film substrate material, namely gadolinium gallium garnet, an organic catalyst, a transparent conductive oxide, fluorescent powder, a gas sensor, an ultraviolet luminescent material, an ultraviolet filter, a deep ultraviolet photosensitive diode and the like, and is widely applied to the fields of optoelectronic devices, catalysts, luminescent materials, nonlinear optical materials, sensors and the like.
At present, the traditional methods for preparing gallium oxide comprise a neutralization method and a hydrothermal synthesis method, but the prepared gallium oxide has unstable impurity content and purity of less than 4N, and 6N high-purity gallium which is expensive is used as a raw material, so that the preparation method is complicated and low in economy.
The purity of the high-purity gallium oxide product prepared by the prior related technology can reach 5N, 4N metal gallium, analytically pure sulfuric acid and analytically pure ammonium sulfate are used as raw materials, firstly, a gallium ammonium sulfate crystal is synthesized, a high-purity gallium ammonium sulfate precursor is obtained after multiple recrystallization purification operations, and the high-purity gallium oxide is obtained after the precursor is subjected to heat treatment. However, the preparation process adopts expensive 4N metal gallium, analytically pure sulfuric acid and ammonium sulfate as raw materials, is poor in economical efficiency and is not beneficial to industrial mass production.
And the purity of the high-purity gallium oxide product prepared by the related technology can reach 5N, 4N industrial gallium is used as a raw material, a sodium gallate solution is prepared by three-stage electrolysis in 30% sodium hydroxide solution, and the high-purity gallium oxide is obtained by neutralization, washing, drying, roasting and other operations. However, the preparation method is too complicated, and the first-stage electrolytic current density is 3000A/m2-5000A/m2The electrolysis time is 30-60 hours, the preparation period is long, and the price of electrolysis and matched equipment is high, thus being not beneficial to industrialized mass production.
The existing method for preparing high-purity gallium oxide is generally complicated in preparation process, high in requirements on used raw materials and equipment, poor in economical efficiency and not beneficial to large-scale application.
Disclosure of Invention
In view of the above, the invention provides a method for preparing 4N gallium oxide from sponge gallium, which takes sponge gallium as a raw material, and has the advantages of high economy, simple and feasible process, high purity of the synthesized gallium oxide product and stable quality.
The invention provides a method for preparing 4N gallium oxide from sponge gallium, which comprises the following steps:
s1, acid dissolution: dissolving sponge gallium in acid, diluting and filtering to obtain a gallium salt solution;
s2, pre-precipitation and impurity removal: adding a pre-precipitator into the gallium salt solution to form colloidal precipitate, and carrying out solid-liquid separation to obtain a high-purity gallium salt solution; the pre-precipitating agent comprises one or more of ammonia water, ammonium carbonate or ammonium bicarbonate;
s3, chemical homogeneous precipitation: reacting the high-purity gallium salt solution obtained in the step S3 with a precipitator, controlling the reaction temperature to be 5-60 ℃, and reacting for 5-30min to obtain gallium oxide hydrate precipitate; the precipitator comprises one or more of ammonia water, ammonium carbonate or ammonium bicarbonate after adsorption and purification;
s4, roasting: washing, drying, roasting and cooling the gallium oxide hydrate precipitate to obtain the 4N-level high-purity gallium oxide.
Compared with the prior art, the invention has the following advantages:
(1) the process flow is simple and the cost is low. The invention prepares 4N gallium oxide from sponge gallium, the gallium salt preparing process is a simple metal acid dissolving process, the pre-precipitation to generate jelly and the precipitation to generate gallium oxide hydrate is a simple chemical precipitation process, the precipitant solution is purified to be a simple physical adsorption process, and the process is simple. The sponge gallium and the precipitator which are used as raw materials are low in price, and the large-scale application prospect is good.
(2) The purity index is stable. The two purification processes of purifying the gallium salt solution and purifying the precipitant solution in the preparation of the 4N gallium oxide by using the sponge gallium ensure the stability of the purity of gallium oxide powder.
(3) The product has high purity. The purity of the gallium oxide obtained by the method can reach more than or equal to 99.99 percent, and the product has high purity and good quality.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods. The sponge gallium adopted in the invention can be a byproduct of gallium removing process in the production flow of aluminum hydroxide by Bayer process, and can also be obtained by market purchase; the high-purity alumina is prepared by self and can be purchased and obtained from the market, and the following indexes are met: purity of>99.999% of specific surface>50m2(ii)/g; the acid solvent is analytically pure sulfuric acid, nitric acid or hydrochloric acid, and the pre-precipitator is analytically pure ammonia water, ammonium carbonate or ammonium bicarbonate.
The invention realizes the control of the purity index by controlling the precipitation process. The invention takes sponge gallium as gallium source, analytically pure sulfuric acid, nitric acid and hydrochloric acid as acid dissolvent, analytically pure ammonia water, ammonium carbonate and ammonium bicarbonate as precipitant, and high-purity alumina as adsorbent; firstly, forming a gallium salt solution after the sponge gallium is acidized, filtering, and then carrying out colloidal precipitation on the clear liquid by a precipitator, wherein the formed high-activity colloid can effectively remove impurities in the solution; after solid-liquid separation, high-purity gallium salt solution is obtained. And reacting the precipitant purified by the high-purity alumina adsorbent with the high-purity gallium salt solution to prepare gallium oxide hydrate, and roasting to obtain the high-purity gallium oxide. The invention adopts sponge gallium to prepare 4N gallium oxide, and the key point is to control the purity of the product, and the method comprises the following steps:
s1, acid dissolution: dissolving sponge gallium in acid, diluting and filtering to obtain a gallium salt solution;
s2, pre-precipitation and impurity removal: adding a pre-precipitator into the gallium salt solution to form colloidal precipitate, and carrying out solid-liquid separation to obtain a high-purity gallium salt solution; the pre-precipitating agent comprises one or more of ammonia water, ammonium carbonate or ammonium bicarbonate;
s3, chemical homogeneous precipitation: reacting the high-purity gallium salt solution obtained in the step S3 with a precipitator, controlling the reaction temperature to be 5-60 ℃, and reacting for 5-30min to obtain gallium oxide hydrate precipitate; the precipitator comprises one or more of ammonia water, ammonium carbonate or ammonium bicarbonate after adsorption and purification;
s4, roasting: washing, drying, roasting and cooling the gallium oxide hydrate precipitate to obtain the 4N-level high-purity gallium oxide.
Preferably, in step S1, the acid-soluble sponge gallium includes: mixing 10-98% sulfuric acid, 10-68% nitric acid or 10-35% hydrochloric acid with sponge gallium, and reacting at 100-150 deg.C in a pressure container for 2-20 h. The obtained gallium salt solution is gallium sulfate solution, gallium nitrate solution or gallium chloride solution. The reaction equipment used in the acid dissolution process is an autoclave lined with preferably polytetrafluoroethylene or enamel.
Preferably, in step S2, the pre-precipitant is one of ammonia water, ammonium carbonate or ammonium bicarbonate; the molar ratio of the addition amount of the ammonia water as a pre-precipitator to the gallium element is (0.59-0.83): 1; the molar ratio of the addition amount of the ammonium carbonate as a pre-precipitator to the gallium element is (0.16-0.28): 1; the molar ratio of the addition amount of the ammonium bicarbonate as a pre-precipitator to the gallium element is (1.2-1.4): 1. The addition of ammonia water, ammonium carbonate or ammonium bicarbonate precipitant is controlled, part of the precipitant precipitates to form high-activity colloid which can adsorb impurity ions and suspended matters in the solution, thus being beneficial to solid-liquid separation and obtaining high-purity gallium salt solution.
More preferably, in step S2, the amount of gallium element in the colloidal precipitate is controlled to be 2-10% of the total amount of gallium in the gallium salt solution.
Preferably, in step S3, the separated colloidal precipitate is returned to step S1 for acidification and recycling. The acidification can be carried out by analytically pure sulfuric acid, nitric acid or hydrochloric acid.
Preferably, in step S3, analytically pure ammonia, ammonium carbonate or ammonium bicarbonate is used as a precipitant after being purified by adsorption with a high-purity alumina adsorbent. The adding amount of the high-purity alumina adsorbent is 5-10% of the mass of the precipitator, the stirring time is more than or equal to 20min, a high-purity ammonium carbonate solution is obtained after filtration, and a filter cake is returned for recycling.
Preferably, in step S3, the precipitant is one of ammonia water, ammonium carbonate or ammonium bicarbonate after adsorption purification; the molar ratio of the addition amount of the ammonia water as a precipitator to the gallium element is (3.15-4.5): 1; the molar ratio of the addition amount of ammonium carbonate as a precipitant to gallium is (1.6-2.3): 1; the molar ratio of the addition amount of the ammonium bicarbonate as a pre-precipitator to the gallium element is (3.15-4.5): 1.
More preferably, in step S3, during the precipitation reaction between the high-purity gallium salt solution and the purified precipitant, the high-purity gallium salt solution is preferably added to the purified precipitant solution in the order of addition.
Preferably, in step S4, the calcination condition is 900-1200 ℃ for 3-6 hours.
Preferably, in step S4, the drying is performed in an air atmosphere at 80 to 150 ℃ for 5 to 10 hours.
The method for preparing 4N gallium oxide from sponge gallium provided by the invention is described below with reference to specific examples.
Example 1
In the embodiment, sponge gallium is dissolved in concentrated sulfuric acid and filtered to prepare a gallium sulfate solution, and the gallium sulfate solution is pre-precipitated by ammonium carbonate to obtain a high-purity gallium sulfate solution; the ammonium carbonate solution purified by the self-made high-purity alumina adsorbent is used as a precipitator, and non-self-made high-purity alumina can be used as long as the following indexes are met: purity of>99.999% of specific surface>50m2(ii) in terms of/g. Adding high-purity gallium sulfate solution into ammonium carbonate precipitant to perform precipitation reaction to obtain gallium oxide hydrate, and roasting to obtain high-purity gallium oxide. The method comprises the following specific steps:
(1) dissolving sponge gallium: 100g of sponge gallium (the mass fraction of gallium is 90%) and 200mL of an analytical pure sulfuric acid solution with the concentration of 80% are added into an autoclave lined with polytetrafluoroethylene, the mixture reacts for 3 hours at the temperature of 130 ℃, and the gallium sulfate solution is obtained after dilution and filtration.
(2) Pre-precipitation and impurity removal: and adding 100mL of 3mol/L ammonium carbonate solution into the gallium sulfate solution, and filtering to obtain the high-purity gallium sulfate solution. The filtered colloidal precipitate is returned to analytically pure sulfuric acid for acidification and then recycled.
(3) Purifying the ammonium carbonate solution: adding a self-made high-purity alumina adsorbent into an ammonium carbonate solution, wherein the addition amount of the high-purity alumina adsorbent is 8% of the mass of the ammonium carbonate solution, stirring for 25min, filtering to obtain a high-purity ammonium carbonate solution, and returning a filter cake to reuse.
(4) Chemical precipitation: adding high-purity gallium sulfate solution into 900mL of 3mol/L high-purity ammonium carbonate solution at 35 ℃, reacting for 20min, filtering and washing to obtain gallium oxide hydrate.
(5) Drying and roasting: drying the gallium oxide hydrate in 150 ℃ air atmosphere for 5 hours, then roasting in a high-temperature furnace at 1200 ℃ for 3 hours, naturally cooling, and taking out to obtain the 4N-level high-purity gallium oxide.
The purity of the gallium oxide obtained in the example can reach more than or equal to 99.99%, and the data result of a plasma emission spectrometer (ICP) is shown in Table 1:
table 1 results of ICP analysis of the product of example 1
Example 2
Dissolving sponge gallium with nitric acid, filtering to obtain gallium nitrate solution, pre-precipitating with ammonia water to obtain high-purity gallium nitrate solution, purifying ammonia water with self-made high-purity alumina adsorbent, adding high-purity nitric acid solution into ammonia water precipitant to perform precipitation reaction to obtain gallium oxide hydrate, and roasting to obtain high-purity gallium oxide.
The method of the invention is further explained, and the specific steps are as follows:
(1) dissolving sponge gallium: 100g of sponge gallium (the mass fraction of gallium is 90%) and 1L of analytically pure nitric acid solution with the concentration of 35% are added into an autoclave lined with polytetrafluoroethylene, the mixture reacts for 3 hours at the temperature of 105 ℃, and the gallium nitrate solution is obtained after dilution and filtration.
(2) Pre-precipitation and impurity removal: 150mL of 25% ammonia water is added into the gallium nitrate solution, and the high-purity gallium nitrate solution is obtained after filtration. The filtered colloidal precipitate is acidified by analytically pure nitric acid and then recycled.
(3) Purifying ammonia water: adding a self-made high-purity alumina adsorbent into the analytically pure ammonia, wherein the addition amount of the high-purity alumina adsorbent is 10% of the mass of the ammonia solution, stirring for 30min, filtering to obtain a high-purity ammonia water precipitator, and returning a filter cake as the adsorbent for recycling.
(4) Chemical precipitation: adding high-purity gallium nitrate solution into 700ml of 25% high-purity ammonia water at 15 ℃, reacting for 10min, filtering and washing to obtain gallium oxide hydrate. Adding high-purity gallium nitrate solution into 1L and 3mol/L high-purity ammonium carbonate solution.
(5) Drying and roasting: drying the gallium oxide hydrate in an air atmosphere at 80 ℃ for 10 hours, then roasting in a high-temperature furnace at 1200 ℃ for 3 hours, naturally cooling, and taking out to obtain the 4N-level high-purity gallium oxide.
The purity of the gallium oxide obtained in the example can reach more than or equal to 99.99%, and the data result of a plasma emission spectrometer (ICP) is shown in Table 2.
Table 2 product ICP analysis results of example 2
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. A method for preparing 4N gallium oxide from sponge gallium comprises the following steps:
s1, acid dissolution: dissolving sponge gallium in acid, diluting and filtering to obtain a gallium salt solution;
s2, pre-precipitation and impurity removal: adding a pre-precipitator into the gallium salt solution to form colloidal precipitate, and carrying out solid-liquid separation to obtain a high-purity gallium salt solution; the pre-precipitating agent comprises one or more of ammonia water, ammonium carbonate or ammonium bicarbonate;
s3, chemical homogeneous precipitation: reacting the high-purity gallium salt solution obtained in the step S3 with a precipitator, controlling the reaction temperature to be 5-60 ℃, and reacting for 5-30min to obtain gallium oxide hydrate precipitate; the precipitator comprises one or more of ammonia water, ammonium carbonate or ammonium bicarbonate after adsorption and purification;
s4, roasting: washing, drying, roasting and cooling the gallium oxide hydrate precipitate to obtain the 4N-level high-purity gallium oxide.
2. The process for preparing 4N gallium oxide from sponge gallium as claimed in claim 1, wherein: in step S1, the acid-soluble sponge gallium includes: mixing 10-98% sulfuric acid, 10-68% nitric acid or 10-35% hydrochloric acid with sponge gallium, and reacting at 100-150 deg.C in a pressure container for 2-20 h.
3. The process for preparing 4N gallium oxide from sponge gallium as claimed in claim 1, wherein: in step S2, the pre-precipitant is one of ammonia water, ammonium carbonate or ammonium bicarbonate; the molar ratio of the addition amount of the ammonia water as a pre-precipitator to the gallium element is (0.59-0.83): 1; the molar ratio of the addition amount of the ammonium carbonate as a pre-precipitator to the gallium element is (0.16-0.28): 1; the molar ratio of the addition amount of the ammonium bicarbonate as a pre-precipitator to the gallium element is (1.2-1.4): 1.
4. The process for preparing 4N gallium oxide from sponge gallium as claimed in claim 3, wherein: in step S2, the amount of gallium element in the colloidal precipitate is controlled to be 2-10% of the total amount of gallium in the gallium salt solution.
5. The process for preparing 4N gallium oxide from sponge gallium as claimed in claim 1, wherein: in step S3, the separated colloidal precipitate is returned to step S1 for acidification and recycling.
6. The process for preparing 4N gallium oxide from sponge gallium as claimed in claim 1, wherein: in step S3, analytically pure ammonia water, ammonium carbonate or ammonium bicarbonate is adsorbed and purified by a high-purity alumina adsorbent to be used as a precipitator, the addition amount of the high-purity alumina adsorbent is 5-10% of the mass of the precipitator, the stirring time is more than or equal to 20min, a high-purity ammonia water, ammonium carbonate or ammonium bicarbonate solution is obtained after filtration, and a filter cake is returned for recycling.
7. The process for preparing 4N gallium oxide from sponge gallium as claimed in claim 1, wherein: in step S3, the precipitant is one of ammonia water, ammonium carbonate or ammonium bicarbonate after adsorption and purification; the molar ratio of the addition amount of the ammonia water as a precipitator to the gallium element is (3.15-4.5): 1; the molar ratio of the addition amount of ammonium carbonate as a precipitant to gallium is (1.6-2.3): 1; the molar ratio of the addition amount of the ammonium bicarbonate as a pre-precipitator to the gallium element is (3.15-4.5): 1.
8. The process for preparing 4N gallium oxide from sponge gallium as claimed in claim 1, wherein: in step S4, the baking condition is 900-1200 deg.C, and the baking time is 3-6 hours.
9. The process for preparing 4N gallium oxide from sponge gallium as claimed in claim 1, wherein: in step S4, the drying is carried out in an air atmosphere at 80-150 ℃ for 5-10 hours.
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| CN111592033A (en) * | 2020-05-21 | 2020-08-28 | 广东先导稀材股份有限公司 | Preparation method of target-grade gallium oxide |
| CN114715931A (en) * | 2022-04-22 | 2022-07-08 | 珠海经济特区方源有限公司 | Method for preparing high-purity gallium nitrate from sponge gallium |
| CN114715932A (en) * | 2022-04-22 | 2022-07-08 | 珠海经济特区方源有限公司 | Method for preparing high-purity gallium sulfate from sponge gallium |
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Application publication date: 20200331 |