CN105948082B - The preparation method of method, beryllium fluoride and the metallic beryllium of ammonium fluoberyllate is prepared with basic carbonate beryllium - Google Patents
The preparation method of method, beryllium fluoride and the metallic beryllium of ammonium fluoberyllate is prepared with basic carbonate beryllium Download PDFInfo
- Publication number
- CN105948082B CN105948082B CN201610265158.0A CN201610265158A CN105948082B CN 105948082 B CN105948082 B CN 105948082B CN 201610265158 A CN201610265158 A CN 201610265158A CN 105948082 B CN105948082 B CN 105948082B
- Authority
- CN
- China
- Prior art keywords
- beryllium
- basic carbonate
- concentrate
- strip liquor
- minutes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F3/00—Compounds of beryllium
- C01F3/005—Fluorides or double fluorides of beryllium with alkali metals or ammonium; Preparation of beryllium compounds therefrom
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to the preparation method technical field of ammonium fluoberyllate, beryllium fluoride and metallic beryllium, it is a kind of preparation method for method, beryllium fluoride and the metallic beryllium that ammonium fluoberyllate is prepared with basic carbonate beryllium, this prepares the method for ammonium fluoberyllate with basic carbonate beryllium, carries out as follows：The first step, mixed liquor is obtained after basic carbonate beryllium and hydrofluoric acid are carried out into hybrid reaction；Second step, concentrate is obtained after mixed liquor is concentrated；3rd step, liquefied ammonia is passed through into concentrate until the pH value of concentrate is 7 to 9.The impurity content for the ammonium fluoberyllate that the method for the present invention for preparing ammonium fluoberyllate with basic carbonate beryllium is obtained is lower than the impurity content using the existing ammonium fluoberyllate prepared with technique, so as to improve the purity for the ammonium fluoberyllate that the method for the present invention for preparing ammonium fluoberyllate with basic carbonate beryllium is obtained, in addition, the technological process of the method for the present invention that ammonium fluoberyllate is prepared with basic carbonate beryllium is simple.
Description
Technical field
The present invention relates to the preparation method technical field of ammonium fluoberyllate, beryllium fluoride and metallic beryllium, be one kind with basic carbonate
Beryllium prepares the preparation method of method, beryllium fluoride and the metallic beryllium of ammonium fluoberyllate.
Background technology
The density of beryllium is similar to magnesium, and its rigidity is suitable with tungsten, and fusing point has very strong thermal neutron scattering up to 1285 DEG C
Ability, and when the change of hundreds of degree occurs for temperature, beryllium part remains to keep original size.The radiotransparen ability of beryllium is most strong,
There is the title of " glassy metal ".Its alloy is the irreplaceable strategy metal material in the fields such as Aeronautics and Astronautics, military project, electronics and nuclear energy
Material.The beryllium of high-purity is the important sources of rapid neutron again.It can be used as the neutron moderator of nuclear reactor.These excellent performances
Beryllium is set to turn into a kind of special functional structure material and strategic goods and materials, its application field and national defence system are closely bound up.Nearly 20
Nian Lai, metallic beryllium and material containing beryllium achieve many new progress, but these in terms of technology, the research and development of new material
Achievement is concentrated mainly on the U.S., Russia and Japan, and the research of China's metallic beryllium and the material containing beryllium is concentrated in traditional handicraft optimization,
It is less to new material and technology research.And in all beryllium materials, metallic beryllium consumption is minimum but most important, the powder of metallic beryllium
Last metallurgical technology needs development badly.Beryllium hydroxide is industrially prepared by sulfuric acid process at present, beryllium hydroxide is refined（Recrystallization）, then use
Hydrofluoric acid dissolution, then salting-out crystallization prepare ammonium fluoberyllate intermediate, and beryllium fluoride, metallic beryllium are then prepared again, the technological process compared with
For complexity, in the process, the increase of step can introduce more impurity, need the purity of ammonium fluoberyllate, beryllium fluoride and beryllium
Improve.
The content of the invention
The invention provides a kind of preparation side for method, beryllium fluoride and the metallic beryllium that ammonium fluoberyllate is prepared with basic carbonate beryllium
Method, overcomes the deficiency of above-mentioned prior art, its can effectively solve existing process prepare ammonium fluoberyllate presence impurity content compared with
High the problem of.
One of technical scheme is realized by following measures：It is a kind of that fluorine beryllium acid is prepared with basic carbonate beryllium
The method of ammonium, is carried out as follows：The first step, mixed liquor is obtained after basic carbonate beryllium and hydrofluoric acid are carried out into hybrid reaction,
Wherein, in basic carbonate beryllium beryllium and the mass ratio of hydrofluoric acid is 1:5 to 15；Second step, is concentrated after mixed liquor is concentrated
Liquid, in concentrate, the concentration of beryllium ion is 60g/L to 150g/L；3rd step, liquefied ammonia is passed through into concentrate until concentrate
PH value be 7 to 9；4th step, the concentrate that the 3rd step is obtained sequentially obtains fluorine beryllium after crystallisation by cooling and separation of solid and liquid
Sour ammonium.
Here is the further optimization and/or improvements to one of foregoing invention technical scheme：
Above-mentioned basic carbonate beryllium is obtained in the steps below：The first step, phosphoric acid kind of extractants, alcohol and sulfonated kerosene are blended in
It is configured to extractant afterwards together, the solution containing beryllium and extractant for being 1 to 3 by pH value are 1 by volume:0.5 to 6 progress is multistage inverse
Stream extraction, obtains extraction organic phase and raffinate aqueous phase, multi-stage counter current extraction is into extraction organic phase after multi-stage counter current extraction
The concentration of beryllium ion be 1.8g/L to 3.6g/L, wherein, the volume ratio of phosphoric acid kind of extractants, alcohol and sulfonated kerosene for 10 to
40:4 to 15:50 to 90；Second step, by mass percent for 5% to 25% oxalic acid aqueous solution and extraction organic phase by volume
For 1：3 to 6 carry out multi-stage countercurrent washing, and organic phase and scrub raffinate are extracted after multi-stage countercurrent is washed, multistage inverse
The total concentration that stream washing extracts the iron aluminium impurity in organic phase to after washing is 10-3G/L to 10-2g/L；3rd step, is matched somebody with somebody with ammonium carbonate
Concentration processed is 100g/L to 150g/L ammonium carbonate solution, and extracting organic phase by ammonium carbonate solution and after washing is by volume
1:1 to 2 carries out multi-stage countercurrent back extraction, and countercurrent reextraction obtains lean organic phase and strip liquor containing beryllium after taking, back extraction is anti-to beryllium is contained
The concentration for extracting the beryllium ion in liquid is 1.8g/L to 3.6g/L；4th step, in temperature is 65 DEG C to 75 DEG C by strip liquor containing beryllium
Under the conditions of hydrolyze 10 minutes to 40 minutes, with depth remove strip liquor containing beryllium in iron aluminium, then by the iron in strip liquor containing beryllium
Removal of impurities strip liquor containing beryllium is obtained after the separation of aluminum precipitation thing；5th step, EDTA is added into removal of impurities strip liquor containing beryllium to removal of impurities containing beryllium
The mass ratio of EDTA and beryllium ion in strip liquor are 0.1% to 1.0%, are added after EDTA, and the removal of impurities containing EDTA is anti-containing beryllium
Extraction liquid is hydrolyzed under the conditions of temperature is 80 DEG C to 105 DEG C and precipitated for 10 minutes to 40 minutes, and then precipitation and separation obtains alkali formula
Beryllium carbonate is precipitated；6th step, is deposited in temperature to use pure water under the conditions of 70 DEG C to 100 DEG C 10 minutes extremely by basic carbonate beryllium
40 minutes, basic carbonate beryllium is obtained after separation.
The two of technical scheme are realized by following measures：A kind of preparation method of beryllium fluoride, is pressed
State method progress：The first step, mixed liquor is obtained after basic carbonate beryllium and hydrofluoric acid are carried out into hybrid reaction, wherein, basic carbonate
The mass ratio of beryllium and hydrofluoric acid in beryllium is 1:5 to 15；Second step, concentrate is obtained after mixed liquor is concentrated, in concentrate,
The concentration of beryllium ion is 60g/L to 150g/L；3rd step, liquefied ammonia is passed through into concentrate until the pH value of concentrate is 7 to 9；
4th step, the concentrate that the 3rd step is obtained sequentially obtains ammonium fluoberyllate after crystallisation by cooling and separation of solid and liquid, by fluorine beryllium acid
Ammonium sequentially obtains beryllium fluoride after drying and calcining, wherein, the temperature of drying is 80 DEG C to 120 DEG C, and the temperature of calcining is 400
DEG C to 800 DEG C, the time of calcining is 120 minutes to 180 minutes.
Here is two further optimization and/or improvements to foregoing invention technical scheme：
Above-mentioned basic carbonate beryllium is obtained in the steps below：The first step, phosphoric acid kind of extractants, alcohol and sulfonated kerosene are blended in
It is configured to extractant afterwards together, the solution containing beryllium and extractant for being 1 to 3 by pH value are 1 by volume:0.5 to 6 progress is multistage inverse
Stream extraction, obtains extraction organic phase and raffinate aqueous phase, multi-stage counter current extraction is into extraction organic phase after multi-stage counter current extraction
The concentration of beryllium ion be 1.8g/L to 3.6g/L, wherein, the volume ratio of phosphoric acid kind of extractants, alcohol and sulfonated kerosene for 10 to
40:4 to 15:50 to 90；Second step, by mass percent for 5% to 25% oxalic acid aqueous solution and extraction organic phase by volume
For 1：3 to 6 carry out multi-stage countercurrent washing, and organic phase and scrub raffinate are extracted after multi-stage countercurrent is washed, multistage inverse
The total concentration that stream washing extracts the iron aluminium impurity in organic phase to after washing is 10-3G/L to 10-2g/L；3rd step, is matched somebody with somebody with ammonium carbonate
Concentration processed is 100g/L to 150g/L ammonium carbonate solution, and extracting organic phase by ammonium carbonate solution and after washing is by volume
1:1 to 2 carries out multi-stage countercurrent back extraction, and countercurrent reextraction obtains lean organic phase and strip liquor containing beryllium after taking, back extraction is anti-to beryllium is contained
The concentration for extracting the beryllium ion in liquid is 1.8g/L to 3.6g/L；4th step, in temperature is 65 DEG C to 75 DEG C by strip liquor containing beryllium
Under the conditions of hydrolyze 10 minutes to 40 minutes, with depth remove strip liquor containing beryllium in iron aluminium, then by the iron in strip liquor containing beryllium
Removal of impurities strip liquor containing beryllium is obtained after the separation of aluminum precipitation thing；5th step, EDTA is added into removal of impurities strip liquor containing beryllium to removal of impurities containing beryllium
The mass ratio of EDTA and beryllium ion in strip liquor are 0.1% to 1.0%, are added after EDTA, and the removal of impurities containing EDTA is anti-containing beryllium
Extraction liquid is hydrolyzed under the conditions of temperature is 80 DEG C to 105 DEG C and precipitated for 10 minutes to 40 minutes, and then precipitation and separation obtains alkali formula
Beryllium carbonate is precipitated；6th step, is deposited in temperature to use pure water under the conditions of 70 DEG C to 100 DEG C 10 minutes extremely by basic carbonate beryllium
40 minutes, basic carbonate beryllium is obtained after separation.
The three of technical scheme are realized by following measures：A kind of preparation method of metallic beryllium, is pressed
State method progress：The first step, mixed liquor is obtained after basic carbonate beryllium and hydrofluoric acid are carried out into hybrid reaction, wherein, basic carbonate
The mass ratio of beryllium and hydrofluoric acid in beryllium is 1:5 to 15；Second step, concentrate is obtained after mixed liquor is concentrated, in concentrate,
The concentration of beryllium ion is 60g/L to 150g/L；3rd step, liquefied ammonia is passed through into concentrate until the pH value of concentrate is 7 to 9；
4th step, the concentrate that the 3rd step is obtained sequentially obtains ammonium fluoberyllate after crystallisation by cooling and separation of solid and liquid, by fluorine beryllium acid
Ammonium sequentially obtains beryllium fluoride after drying and calcining, wherein, the temperature of drying is 80 DEG C to 120 DEG C, and the temperature of calcining is 400
DEG C to 800 DEG C, the time of calcining is 120 minutes to 180 minutes；5th step, beryllium fluoride and magnesium ingot are occurred to obtain after reduction reaction
To metallic beryllium.
Here is three further optimization and/or improvements to foregoing invention technical scheme：
Above-mentioned basic carbonate beryllium is obtained in the steps below：The first step, phosphoric acid kind of extractants, alcohol and sulfonated kerosene are blended in
It is configured to extractant afterwards together, the solution containing beryllium and extractant for being 1 to 3 by pH value are 1 by volume:0.5 to 6 progress is multistage inverse
Stream extraction, obtains extraction organic phase and raffinate aqueous phase, multi-stage counter current extraction is into extraction organic phase after multi-stage counter current extraction
The concentration of beryllium ion be 1.8g/L to 3.6g/L, wherein, the volume ratio of phosphoric acid kind of extractants, alcohol and sulfonated kerosene for 10 to
40:4 to 15:50 to 90；Second step, by mass percent for 5% to 25% oxalic acid aqueous solution and extraction organic phase by volume
For 1：3 to 6 carry out multi-stage countercurrent washing, and organic phase and scrub raffinate are extracted after multi-stage countercurrent is washed, multistage inverse
The total concentration that stream washing extracts the iron aluminium impurity in organic phase to after washing is 10-3G/L to 10-2g/L；3rd step, is matched somebody with somebody with ammonium carbonate
Concentration processed is 100g/L to 150g/L ammonium carbonate solution, and extracting organic phase by ammonium carbonate solution and after washing is by volume
1:1 to 2 carries out multi-stage countercurrent back extraction, and countercurrent reextraction obtains lean organic phase and strip liquor containing beryllium after taking, back extraction is anti-to beryllium is contained
The concentration for extracting the beryllium ion in liquid is 1.8g/L to 3.6g/L；4th step, in temperature is 65 DEG C to 75 DEG C by strip liquor containing beryllium
Under the conditions of hydrolyze 10 minutes to 40 minutes, with depth remove strip liquor containing beryllium in iron aluminium, then by the iron in strip liquor containing beryllium
Removal of impurities strip liquor containing beryllium is obtained after the separation of aluminum precipitation thing；5th step, EDTA is added into removal of impurities strip liquor containing beryllium to removal of impurities containing beryllium
The mass ratio of EDTA and beryllium ion in strip liquor are 0.1% to 1.0%, are added after EDTA, and the removal of impurities containing EDTA is anti-containing beryllium
Extraction liquid is hydrolyzed under the conditions of temperature is 80 DEG C to 105 DEG C and precipitated for 10 minutes to 40 minutes, and then precipitation and separation obtains alkali formula
Beryllium carbonate is precipitated；6th step, is deposited in temperature to use pure water under the conditions of 70 DEG C to 100 DEG C 10 minutes extremely by basic carbonate beryllium
40 minutes, basic carbonate beryllium is obtained after separation.
The impurity content ratio for the ammonium fluoberyllate that the method for the present invention for preparing ammonium fluoberyllate with basic carbonate beryllium is obtained
Impurity content using the existing ammonium fluoberyllate prepared with technique is low, so as to improve of the present invention with the preparation of basic carbonate beryllium
The purity for the ammonium fluoberyllate that the method for ammonium fluoberyllate is obtained, in addition, of the present invention prepare ammonium fluoberyllate with basic carbonate beryllium
Method technological process it is simple；The impurity content ratio for the beryllium fluoride that the preparation method of beryllium fluoride of the present invention is obtained is used
The impurity content of the beryllium fluoride now prepared with technique is low, so that what the preparation method for improving beryllium fluoride of the present invention was obtained
The purity of beryllium fluoride, in addition, the technological process of the preparation method of beryllium fluoride of the present invention is simple；Metal of the present invention
The impurity content for the metallic beryllium that the preparation method of beryllium is obtained is lower than the impurity content using the existing metallic beryllium prepared with technique, so that
The purity for the metallic beryllium that the preparation method of metallic beryllium of the present invention is obtained is improved, in addition, metallic beryllium of the present invention
Preparation method technological process it is simple；Therefore, method, the beryllium fluoride of the present invention that ammonium fluoberyllate is prepared with basic carbonate beryllium
Preparation method and the preparation method of metallic beryllium have broad application prospects, the research and development for beryllium material provides new hand
Section.
Embodiment
The present invention is not limited by following embodiments, can technique according to the invention scheme and actual conditions it is specific to determine
Embodiment.
With reference to embodiment, the invention will be further described：
Embodiment 1：This prepares the method for ammonium fluoberyllate with basic carbonate beryllium, carries out as follows：The first step, by alkali formula
Beryllium carbonate obtains mixed liquor after carrying out hybrid reaction with hydrofluoric acid, wherein, the mass ratio of beryllium and hydrofluoric acid in basic carbonate beryllium
For 1:5 to 15；Second step, concentrate is obtained after mixed liquor is concentrated, in concentrate, the concentration of beryllium ion for 60g/L extremely
150g/L；3rd step, liquefied ammonia is passed through into concentrate until the pH value of concentrate is 7 to 9；4th step, the 3rd step is obtained
Concentrate sequentially obtains ammonium fluoberyllate after crystallisation by cooling and separation of solid and liquid.Described in the present embodiment with basic carbonate beryllium system
In the method for standby ammonium fluoberyllate, using basic carbonate beryllium as raw material, the impurity content of the basic carbonate beryllium used in the present embodiment（Quality
Percentage/%）As shown in table 1, in traditional handicraft, the impurity content of the refined beryllium hydroxide obtained after beryllium hydroxide is recrystallized
（Mass percent/%）As shown in table 1, the content of Fe, Al and B in basic carbonate beryllium are can be seen that by the data in table 1
Respectively less than the content of each self-corresponding element in refined beryllium hydroxide, therefore, fluorine beryllium acid is prepared by raw material of basic carbonate beryllium
During ammonium, because the impurity content in raw material declines, it can make to prepare ammonium fluoberyllate described in the present embodiment with basic carbonate beryllium
The impurity content of ammonium fluoberyllate made from method declines therewith, so that being prepared with basic carbonate beryllium according to the present embodiment
The purity of ammonium fluoberyllate is improved made from the method for ammonium fluoberyllate, and it is prepared relative to the refined beryllium hydroxide of use
The purity of ammonium fluoberyllate has been lifted.Because the impurity content of the basic carbonate beryllium in the present embodiment is low, therefore without tying again again
Brilliant removal of impurities, can be directly added into HF and lysate is made（Mixed liquor）, with fluorine beryllium acid is prepared in traditional handicraft by raw material of beryllium hydroxide
For ammonium, step and raw material are greatlyd save.In addition, by preparing ammonium fluoberyllate described in the present embodiment with basic carbonate beryllium
Method can be seen that for the traditional handicraft of ammonium fluoberyllate is prepared at present, described in the present embodiment with basic carbonate beryllium
The method processing step for preparing ammonium fluoberyllate is simple, on the one hand, can simplify the technique for preparing ammonium fluoberyllate, on the other hand, by
In the simplification of technique, it is to avoid the impurity of the cumbersome introducing of processing step, the purity of ammonium fluoberyllate is further improved.
Embodiment 2：This prepares the method for ammonium fluoberyllate with basic carbonate beryllium, carries out as follows：The first step, by alkali formula
Beryllium carbonate obtains mixed liquor after carrying out hybrid reaction with hydrofluoric acid, wherein, the mass ratio of beryllium and hydrofluoric acid in basic carbonate beryllium
For 1:5 or 15；Second step, concentrate is obtained after mixed liquor is concentrated, in concentrate, the concentration of beryllium ion for 60g/L or
150g/L；3rd step, liquefied ammonia is passed through into concentrate until the pH value of concentrate is 7 or 9；4th step, the 3rd step is obtained
Concentrate sequentially obtains ammonium fluoberyllate after crystallisation by cooling and separation of solid and liquid.
Embodiment 3：This prepares the method for ammonium fluoberyllate with basic carbonate beryllium, carries out as follows：The first step, by alkali formula
Beryllium carbonate obtains mixed liquor after carrying out hybrid reaction with hydrofluoric acid, wherein, the mass ratio of beryllium and hydrofluoric acid in basic carbonate beryllium
For 1:5；Second step, concentrate is obtained after mixed liquor is concentrated, in concentrate, and the concentration of beryllium ion is 60g/L；3rd step,
Liquefied ammonia is passed through into concentrate until the pH value of concentrate is 7；4th step, the concentrate that the 3rd step is obtained is sequentially through supercooling
Ammonium fluoberyllate is obtained after crystallization and separation of solid and liquid.In the method that ammonium fluoberyllate is prepared with basic carbonate beryllium described in the present embodiment
In, using basic carbonate beryllium as raw material, the impurity content of the basic carbonate beryllium used in the present embodiment（Mass percent/%）Such as the institute of table 1
Show, the content of Fe, Al and B in basic carbonate beryllium are can be seen that respectively less than refined beryllium hydroxide by the data in table 1
In each self-corresponding element content, therefore, when preparing ammonium fluoberyllate by raw material of basic carbonate beryllium, because the impurity in raw material contains
Amount declines, and can make the impurity that ammonium fluoberyllate made from the method for ammonium fluoberyllate is prepared with basic carbonate beryllium described in the present embodiment
Content declines therewith, so that preparing fluorine beryllium made from the method for ammonium fluoberyllate according to the present embodiment with basic carbonate beryllium
The purity of sour ammonium is improved, and it has been lifted relative to the purity of the ammonium fluoberyllate prepared using refined beryllium hydroxide.
Because the impurity content of the basic carbonate beryllium in the present embodiment is low, therefore without recrystallizing removal of impurities again, HF can be directly added into and be made
Lysate（Mixed liquor）, for preparing ammonium fluoberyllate as raw material using beryllium hydroxide in traditional handicraft, greatly save step and original
Material.In addition, be can be seen that by the method for preparing ammonium fluoberyllate with basic carbonate beryllium described in the present embodiment relative to current
For the traditional handicraft for preparing ammonium fluoberyllate, the method technique for preparing ammonium fluoberyllate with basic carbonate beryllium described in the present embodiment is walked
It is rapid simple, on the one hand, the technique for preparing ammonium fluoberyllate can be simplified, on the other hand, due to the simplification of technique, it is to avoid technique step
The impurity of rapid cumbersome introducing, further improves the purity of ammonium fluoberyllate.
Embodiment 4：This prepares the method for ammonium fluoberyllate with basic carbonate beryllium, carries out as follows：The first step, by alkali formula
Beryllium carbonate obtains mixed liquor after carrying out hybrid reaction with hydrofluoric acid, wherein, the mass ratio of beryllium and hydrofluoric acid in basic carbonate beryllium
For 1:15；Second step, concentrate is obtained after mixed liquor is concentrated, in concentrate, and the concentration of beryllium ion is 150g/L；3rd
Step, liquefied ammonia is passed through into concentrate until the pH value of concentrate is 9；4th step, the concentrate that the 3rd step is obtained sequentially passes through
Ammonium fluoberyllate is obtained after crystallisation by cooling and separation of solid and liquid.In the side that ammonium fluoberyllate is prepared with basic carbonate beryllium described in the present embodiment
In method, using basic carbonate beryllium as raw material, the impurity content of the basic carbonate beryllium used in the present embodiment（Mass percent/%）Such as table 1
It is shown, the content of Fe, Al and B in basic carbonate beryllium are can be seen that respectively less than refined hydroxide by the data in table 1
The content of each self-corresponding element in beryllium, therefore, when preparing ammonium fluoberyllate by raw material of basic carbonate beryllium, due to the impurity in raw material
Content declines, and can make to prepare the miscellaneous of ammonium fluoberyllate made from the method for ammonium fluoberyllate described in the present embodiment with basic carbonate beryllium
Matter content declines therewith, so that preparing fluorine made from the method for ammonium fluoberyllate according to the present embodiment with basic carbonate beryllium
The purity of beryllium acid ammonium is improved, and it has been carried relative to the purity of the ammonium fluoberyllate prepared using refined beryllium hydroxide
Rise.Because the impurity content of the basic carbonate beryllium in the present embodiment is low, therefore without recrystallizing removal of impurities again, HF systems can be directly added into
Into lysate（Mixed liquor）, for preparing ammonium fluoberyllate as raw material using beryllium hydroxide in traditional handicraft, greatly save step and
Raw material.In addition, be can be seen that by the method for preparing ammonium fluoberyllate with basic carbonate beryllium described in the present embodiment relative to mesh
For the preceding traditional handicraft for preparing ammonium fluoberyllate, the method technique that ammonium fluoberyllate is prepared with basic carbonate beryllium described in the present embodiment
Step is simple, on the one hand, can simplify the technique for preparing ammonium fluoberyllate, on the other hand, due to the simplification of technique, it is to avoid technique
The impurity that complex steps are introduced, further improves the purity of ammonium fluoberyllate.
Embodiment 5：The preparation method of the beryllium fluoride, is carried out as follows：The first step, by basic carbonate beryllium and hydrofluoric acid
Mixed liquor is obtained after carrying out hybrid reaction, wherein, the mass ratio of beryllium and hydrofluoric acid in basic carbonate beryllium is 1:5 to 15；Second
Step, concentrate is obtained after mixed liquor is concentrated, in concentrate, and the concentration of beryllium ion is 60g/L to 150g/L；3rd step, to
Liquefied ammonia is passed through in concentrate until the pH value of concentrate is 7 to 9；4th step, the concentrate that the 3rd step is obtained is sequentially through supercooling
But ammonium fluoberyllate is obtained after crystallization and separation of solid and liquid, ammonium fluoberyllate is sequentially obtained into beryllium fluoride after drying and calcining, wherein,
The temperature of drying is 80 DEG C to 120 DEG C, and the temperature of calcining is 400 DEG C to 800 DEG C, and the time of calcining is 120 minutes to 180 points
Clock.In the preparation method of the beryllium fluoride described in the present embodiment, using basic carbonate beryllium as raw material, the alkali formula carbon used in the present embodiment
The impurity content of sour beryllium（Mass percent/%）As shown in table 2, in traditional handicraft, what is obtained after beryllium hydroxide is recrystallized is refined
The impurity content of beryllium hydroxide（Mass percent/%）As shown in table 2, it can be seen that basic carbonate beryllium by the data in table 2
In Fe, Al and B content respectively less than the content of each self-corresponding element in refined beryllium hydroxide, therefore, with basic carbonate
When beryllium is that raw material prepares beryllium fluoride, because the impurity content in raw material declines, the system of the beryllium fluoride described in the present embodiment can be made
The impurity content of beryllium fluoride made from Preparation Method declines therewith, so that the preparation method of the beryllium fluoride according to the present embodiment
The purity of obtained beryllium fluoride is improved, and it has refined the purity for the beryllium fluoride that beryllium hydroxide is prepared relative to use
Lifting.Because the impurity content of the basic carbonate beryllium in the present embodiment is low, therefore without recrystallizing removal of impurities again, HF can be directly added into
Lysate is made（Mixed liquor）, for preparing beryllium fluoride as raw material using beryllium hydroxide in traditional handicraft, greatly save step and
Raw material.In addition, be can be seen that by the preparation method of the beryllium fluoride described in the present embodiment relative to preparing beryllium fluoride at present
For traditional handicraft, the preparation method processing step of the beryllium fluoride described in the present embodiment is simple, on the one hand, can simplify and prepare fluorine
The technique for changing beryllium, on the other hand, due to the simplification of technique, it is to avoid the impurity of the cumbersome introducing of processing step, is further improved
The purity of beryllium fluoride.The impurity analysis result such as table for the beryllium fluoride that the preparation method of beryllium fluoride according to the present embodiment is obtained
Shown in 3, the beryllium fluoride of domestic certain factory production（Prior art）Impurity analysis result it is as shown in table 3.It can be seen from Table 3 that,
Fe, Al of the beryllium fluoride that the preparation method of beryllium fluoride according to the present embodiment is obtained content are respectively less than certain domestic factory
The content of each self-corresponding element in the beryllium fluoride of production, illustrates that the preparation method of the beryllium fluoride according to the present embodiment is obtained
The impurity content of beryllium fluoride is than low in the prior art.
Embodiment 6：The preparation method of the beryllium fluoride, is carried out as follows：The first step, by basic carbonate beryllium and hydrofluoric acid
Mixed liquor is obtained after carrying out hybrid reaction, wherein, the mass ratio of beryllium and hydrofluoric acid in basic carbonate beryllium is 1:5 or 15；Second
Step, concentrate is obtained after mixed liquor is concentrated, in concentrate, and the concentration of beryllium ion is 60g/L or 150g/L；3rd step, to
Liquefied ammonia is passed through in concentrate until the pH value of concentrate is 7 or 9；4th step, the concentrate that the 3rd step is obtained is sequentially through supercooling
But ammonium fluoberyllate is obtained after crystallization and separation of solid and liquid, ammonium fluoberyllate is sequentially obtained into beryllium fluoride after drying and calcining, wherein,
The temperature of drying is 80 DEG C or 120 DEG C, and the temperature of calcining is 400 DEG C or 800 DEG C, and the time of calcining is 120 minutes or 180 points
Clock.
Embodiment 7：The preparation method of the beryllium fluoride, is carried out as follows：The first step, by basic carbonate beryllium and hydrofluoric acid
Mixed liquor is obtained after carrying out hybrid reaction, wherein, the mass ratio of beryllium and hydrofluoric acid in basic carbonate beryllium is 1:5；Second step, will
Concentrate is obtained after mixed liquor concentration, in concentrate, the concentration of beryllium ion is 60g/L；3rd step, liquid is passed through into concentrate
Ammonia is until the pH value of concentrate is 7；4th step, the concentrate that the 3rd step is obtained is sequentially after crystallisation by cooling and separation of solid and liquid
Ammonium fluoberyllate is obtained, ammonium fluoberyllate is sequentially obtained into beryllium fluoride after drying and calcining, wherein, the temperature of drying is 80 DEG C,
The temperature of calcining is 400 DEG C, and the time of calcining is 120 minutes.In the preparation method of the beryllium fluoride described in the present embodiment, with alkali
Formula beryllium carbonate is raw material, the impurity content of the basic carbonate beryllium used in the present embodiment（Mass percent/%）As shown in table 2, pass through
The content that data in table 2 can be seen that Fe, Al and B in basic carbonate beryllium is respectively respective less than in refined beryllium hydroxide
The content of corresponding element, therefore, when preparing beryllium fluoride by raw material of basic carbonate beryllium, because the impurity content in raw material declines,
The impurity content of beryllium fluoride made from the preparation method of the beryllium fluoride described in the present embodiment can be made to decline therewith, so that according to
The purity of beryllium fluoride is improved made from the preparation method of beryllium fluoride described in the present embodiment, and it is relative to using refined hydrogen-oxygen
The purity for changing the beryllium fluoride that beryllium is prepared has been lifted.Because the impurity content of the basic carbonate beryllium in the present embodiment is low, because
This can be directly added into HF and lysate is made without recrystallizing removal of impurities again（Mixed liquor）, with traditional handicraft using beryllium hydroxide as original
Material is prepared for beryllium fluoride, greatlys save step and raw material.In addition, passing through the preparation method of the beryllium fluoride described in the present embodiment
As can be seen that for the traditional handicraft of beryllium fluoride is prepared at present, the preparation method work of the beryllium fluoride described in the present embodiment
Skill step is simple, on the one hand, can simplify the technique for preparing beryllium fluoride, on the other hand, due to the simplification of technique, it is to avoid technique
The impurity that complex steps are introduced, further improves the purity of beryllium fluoride.The preparation side of beryllium fluoride according to the present embodiment
The impurity analysis result for the beryllium fluoride that method is obtained（Mass percent/%）As shown in table 3, the beryllium fluoride of domestic certain factory production（It is existing
Technology）Impurity analysis result（Mass percent/%）As shown in table 3.It can be seen from Table 3 that, according to the present embodiment
Fe, Al of the beryllium fluoride that the preparation method of beryllium fluoride is obtained content are respectively respective less than in the beryllium fluoride of domestic certain factory production
The content of corresponding element, illustrates the impurity content ratio for the beryllium fluoride that the preparation method of the beryllium fluoride according to the present embodiment is obtained
It is low in the prior art.
Embodiment 8：The preparation method of the beryllium fluoride, is carried out as follows：The first step, by basic carbonate beryllium and hydrofluoric acid
Mixed liquor is obtained after carrying out hybrid reaction, wherein, the mass ratio of beryllium and hydrofluoric acid in basic carbonate beryllium is 1:15；Second step,
Concentrate is obtained after mixed liquor is concentrated, in concentrate, the concentration of beryllium ion is 150g/L；3rd step, leads into concentrate
Enter liquefied ammonia until the pH value of concentrate is 9；4th step, the concentrate that the 3rd step is obtained is sequentially by crystallisation by cooling and solid-liquid point
Ammonium fluoberyllate is obtained from after, ammonium fluoberyllate is sequentially obtained into beryllium fluoride after drying and calcining, wherein, the temperature of drying is
120 DEG C, the temperature of calcining is 800 DEG C, and the time of calcining is 180 minutes.In the preparation method of the beryllium fluoride described in the present embodiment
In, using basic carbonate beryllium as raw material, the impurity content of the basic carbonate beryllium used in the present embodiment（Mass percent/%）Such as the institute of table 2
Show, the content of Fe, Al and B in basic carbonate beryllium are can be seen that respectively less than refined beryllium hydroxide by the data in table 2
In each self-corresponding element content, therefore, when preparing beryllium fluoride by raw material of basic carbonate beryllium, due to the impurity content in raw material
Decline, the impurity content of beryllium fluoride made from the preparation method of the beryllium fluoride described in the present embodiment can be made to decline therewith, so that
It is improved the purity of beryllium fluoride made from the preparation method of the beryllium fluoride according to the present embodiment, it is relative to using essence
The purity for the beryllium fluoride that hydrogen manufacturing beryllium oxide is prepared has been lifted.Due to the impurity content of the basic carbonate beryllium in the present embodiment
It is low, therefore without recrystallizing removal of impurities again, HF can be directly added into lysate is made（Mixed liquor）, with traditional handicraft with beryllium hydroxide
For preparing beryllium fluoride for raw material, step and raw material are greatlyd save.In addition, passing through the preparation of the beryllium fluoride described in the present embodiment
Method can be seen that for the traditional handicraft of beryllium fluoride is prepared at present, the preparation side of the beryllium fluoride described in the present embodiment
Method processing step is simple, on the one hand, can simplify the technique for preparing beryllium fluoride, on the other hand, due to the simplification of technique, it is to avoid
The impurity of the cumbersome introducing of processing step, further improves the purity of beryllium fluoride.The system of beryllium fluoride according to the present embodiment
The impurity analysis result for the beryllium fluoride that Preparation Method is obtained（Mass percent/%）As shown in table 3, the beryllium fluoride of domestic certain factory production
（Prior art）Impurity analysis result（Mass percent/%）As shown in table 3.It can be seen from Table 3 that, according to the present embodiment
Fe, Al of the beryllium fluoride that the preparation method of described beryllium fluoride is obtained content are respectively less than the beryllium fluoride of domestic certain factory production
In each self-corresponding element content, illustrate the impurity for the beryllium fluoride that the preparation method of the beryllium fluoride according to the present embodiment is obtained
Content is than low in the prior art.
Embodiment 9：The preparation method of the metallic beryllium, is carried out as follows：The first step, by basic carbonate beryllium and hydrofluoric acid
Mixed liquor is obtained after carrying out hybrid reaction, wherein, the mass ratio of beryllium and hydrofluoric acid in basic carbonate beryllium is 1:5 to 15；Second
Step, concentrate is obtained after mixed liquor is concentrated, in concentrate, and the concentration of beryllium ion is 60g/L to 150g/L；3rd step, to
Liquefied ammonia is passed through in concentrate until the pH value of concentrate is 7 to 9；4th step, the concentrate that the 3rd step is obtained is sequentially through supercooling
But ammonium fluoberyllate is obtained after crystallization and separation of solid and liquid, ammonium fluoberyllate is sequentially obtained into beryllium fluoride after drying and calcining, wherein,
The temperature of drying is 80 DEG C to 120 DEG C, and the temperature of calcining is 400 DEG C to 800 DEG C, and the time of calcining is 120 minutes to 180 points
Clock；5th step, metallic beryllium is obtained after beryllium fluoride and magnesium ingot into reduction reaction occur.In the preparation of the metallic beryllium described in the present embodiment
In method, using basic carbonate beryllium as raw material, the impurity content of the basic carbonate beryllium used in the present embodiment（Mass percent/%）Such as
Shown in table 4, in traditional handicraft, the impurity content of the refined beryllium hydroxide obtained after beryllium hydroxide is recrystallized（Quality percentage
Than/%）As shown in table 4, the content that can be seen that Fe, Al and B in basic carbonate beryllium by the data in table 4 is respectively less than
The content of each self-corresponding element in refined beryllium hydroxide, therefore, when preparing metallic beryllium by raw material of basic carbonate beryllium, due to raw material
In impurity content decline, can make the impurity content of metallic beryllium made from the preparation method of metallic beryllium described in the present embodiment with
Decline so that the purity of metallic beryllium is improved made from the preparation method of metallic beryllium according to the present embodiment, its
Purity relative to the metallic beryllium prepared using refined beryllium hydroxide has been lifted.Due to the basic carbonate in the present embodiment
The impurity content of beryllium is low, therefore without recrystallizing removal of impurities again, can be directly added into HF and lysate is made（Mixed liquor）, with traditional handicraft
In metallic beryllium is prepared as raw material using beryllium hydroxide for, greatly save step and raw material.In addition, by described in the present embodiment
The preparation method of metallic beryllium can be seen that for the traditional handicraft of metallic beryllium is prepared at present, the gold described in the present embodiment
The preparation method processing step for belonging to beryllium is simple, on the one hand, can simplify the technique for preparing metallic beryllium, on the other hand, due to technique
Simplification, it is to avoid the impurity of the cumbersome introducing of processing step, further improve the purity of metallic beryllium.
Embodiment 10：The preparation method of the metallic beryllium, is carried out as follows：The first step, by basic carbonate beryllium and hydrogen fluorine
Acid obtains mixed liquor after carrying out hybrid reaction, wherein, the mass ratio of beryllium and hydrofluoric acid in basic carbonate beryllium is 1:5 or 15；The
Two steps, concentrate is obtained after mixed liquor is concentrated, in concentrate, and the concentration of beryllium ion is 60g/L or 150g/L；3rd step,
Liquefied ammonia is passed through into concentrate until the pH value of concentrate is 7 or 9；4th step, the concentrate that the 3rd step is obtained sequentially passes through
Ammonium fluoberyllate is obtained after crystallisation by cooling and separation of solid and liquid, ammonium fluoberyllate is sequentially obtained into beryllium fluoride after drying and calcining, its
In, the temperature of drying is 80 DEG C or 120 DEG C, and the temperature of calcining is 400 DEG C or 800 DEG C, and the time of calcining is 120 minutes or 180
Minute；5th step, metallic beryllium is obtained after beryllium fluoride and magnesium ingot into reduction reaction occur.
Embodiment 11：The preparation method of the metallic beryllium, is carried out as follows：The first step, by basic carbonate beryllium and hydrogen fluorine
Acid obtains mixed liquor after carrying out hybrid reaction, wherein, the mass ratio of beryllium and hydrofluoric acid in basic carbonate beryllium is 1:5；Second step,
Concentrate is obtained after mixed liquor is concentrated, in concentrate, the concentration of beryllium ion is 60g/L；3rd step, is passed through into concentrate
Liquefied ammonia is until the pH value of concentrate is 7；4th step, the concentrate that the 3rd step is obtained sequentially passes through crystallisation by cooling and separation of solid and liquid
After obtain ammonium fluoberyllate, ammonium fluoberyllate is sequentially obtained into beryllium fluoride after drying and calcining, wherein, the temperature of drying is 80
DEG C, the temperature of calcining is 400 DEG C, and the time of calcining is 120 minutes；5th step, beryllium fluoride and magnesium ingot are occurred after reduction reaction
Obtain metallic beryllium.In the preparation method of the metallic beryllium described in the present embodiment, using basic carbonate beryllium as raw material, used in the present embodiment
Basic carbonate beryllium impurity content（Mass percent/%）As shown in table 4, it can be seen that alkali formula carbon by the data in table 4
The content of Fe, Al and B in sour beryllium are respectively less than the content of each self-corresponding element in refined beryllium hydroxide, therefore, with alkali formula
When beryllium carbonate is that raw material prepares metallic beryllium, because the impurity content in raw material declines, the metallic beryllium described in the present embodiment can be made
Preparation method made from the impurity content of metallic beryllium decline therewith so that the preparation of the metallic beryllium according to the present embodiment
The purity of metallic beryllium made from method is improved, and it is relative to using the purity for refining the metallic beryllium that beryllium hydroxide is prepared
Lifted.Because the impurity content of the basic carbonate beryllium in the present embodiment is low, therefore without recrystallizing removal of impurities again, can directly it add
Enter HF and lysate is made（Mixed liquor）, for preparing metallic beryllium as raw material using beryllium hydroxide in traditional handicraft, greatly save step
Rapid and raw material.In addition, be can be seen that by the preparation method of the metallic beryllium described in the present embodiment relative to preparing metal at present
For the traditional handicraft of beryllium, the preparation method processing step of the metallic beryllium described in the present embodiment is simple, on the one hand, can simplify system
The technique of standby metallic beryllium, on the other hand, due to the simplification of technique, it is to avoid the impurity of the cumbersome introducing of processing step, is further carried
The purity of metallic beryllium is risen.
Embodiment 12：The preparation method of the metallic beryllium, is carried out as follows：The first step, by basic carbonate beryllium and hydrogen fluorine
Acid obtains mixed liquor after carrying out hybrid reaction, wherein, the mass ratio of beryllium and hydrofluoric acid in basic carbonate beryllium is 1:15；Second
Step, concentrate is obtained after mixed liquor is concentrated, in concentrate, and the concentration of beryllium ion is 150g/L；3rd step, into concentrate
Liquefied ammonia is passed through until the pH value of concentrate is 9；4th step, the concentrate that the 3rd step is obtained sequentially passes through crystallisation by cooling and solid-liquid
Ammonium fluoberyllate is obtained after separation, ammonium fluoberyllate is sequentially obtained into beryllium fluoride after drying and calcining, wherein, the temperature of drying is
120 DEG C, the temperature of calcining is 800 DEG C, and the time of calcining is 180 minutes；5th step, occurs reduction reaction by beryllium fluoride and magnesium ingot
After obtain metallic beryllium.In the preparation method of the metallic beryllium described in the present embodiment, using basic carbonate beryllium as raw material, the present embodiment institute
The impurity content of basic carbonate beryllium（Mass percent/%）As shown in table 4, it can be seen that alkali formula by the data in table 4
The content of Fe, Al and B in beryllium carbonate are respectively less than the content of each self-corresponding element in refined beryllium hydroxide, therefore, with alkali
When formula beryllium carbonate is that raw material prepares metallic beryllium, because the impurity content in raw material declines, the metal described in the present embodiment can be made
The impurity content of metallic beryllium declines therewith made from the preparation method of beryllium, so that the system of the metallic beryllium according to the present embodiment
The purity of metallic beryllium made from Preparation Method is improved, and it is pure relative to the metallic beryllium prepared using refined beryllium hydroxide
Degree has been lifted., can be direct because the impurity content of the basic carbonate beryllium in the present embodiment is low, therefore without recrystallizing removal of impurities again
Add HF and lysate is made（Mixed liquor）, for preparing metallic beryllium as raw material using beryllium hydroxide in traditional handicraft, greatly save
Step and raw material.In addition, can be seen that by the preparation method of the metallic beryllium described in the present embodiment gold is prepared relative to current
For the traditional handicraft for belonging to beryllium, the preparation method processing step of the metallic beryllium described in the present embodiment is simple, on the one hand, can simplify
The technique for preparing metallic beryllium, on the other hand, due to the simplification of technique, it is to avoid the impurity of the cumbersome introducing of processing step, further
Improve the purity of metallic beryllium.
Embodiment 13：As the optimization of above-described embodiment, basic carbonate beryllium is obtained in the steps below：The first step, by phosphoric acid
Kind of extractants, alcohol and sulfonated kerosene are configured to extractant after mixing, by the solution containing beryllium and extractant that pH value is 1 to 3
It is 1 by volume:0.5 to 6 carries out multi-stage counter current extraction, and extraction organic phase and raffinate water are obtained after multi-stage counter current extraction
Phase, multi-stage counter current extraction to extract organic phase in beryllium ion concentration for 1.8g/L to 3.6g/L, wherein, phosphoric acid class extraction
The volume ratio of agent, alcohol and sulfonated kerosene is 10 to 40:4 to 15:50 to 90；Second step, by the grass that mass percent is 5% to 25%
Aqueous acid and extraction organic phase are 1 by volume：3 to 6 carry out multi-stage countercurrent washing, after multi-stage countercurrent is washed
Organic phase and scrub raffinate are extracted, the total concentration that multi-stage countercurrent washs to after washing the iron aluminium impurity in extraction organic phase is 10-3g/L
To 10-2g/L；3rd step, with the ammonium carbonate solution that ammonium carbonate compound concentration is 100g/L to 150g/L, by ammonium carbonate solution
With wash after extraction organic phase by volume be 1:1 to 2 carry out multi-stage countercurrent back extraction, countercurrent reextraction obtained after taking lean organic phase and
Strip liquor containing beryllium, the concentration of the beryllium ion in back extraction to strip liquor containing beryllium is 1.8g/L to 3.6g/L；4th step, will contain beryllium anti-
Extract liquid to hydrolyze 10 minutes to 40 minutes under conditions of temperature is 65 DEG C to 75 DEG C, the iron in strip liquor containing beryllium is removed with depth
Aluminium, then will obtain removal of impurities strip liquor containing beryllium after the iron aluminum precipitation thing separation in strip liquor containing beryllium；5th step, it is anti-containing beryllium to removal of impurities
The mass ratio for extracting EDTAs and beryllium ion of the addition EDTA into removal of impurities strip liquor containing beryllium in liquid is 0.1% to 1.0%, adds EDTA
Afterwards, the removal of impurities strip liquor containing beryllium containing EDTA is hydrolyzed under the conditions of temperature is 80 DEG C to 105 DEG C and obtained for 10 minutes to 40 minutes
Precipitate, then precipitation and separation obtains basic carbonate beryllium precipitation；6th step, temperature is deposited in for 70 DEG C to 100 by basic carbonate beryllium
Pure water is used under the conditions of DEG C 10 minutes to 40 minutes, basic carbonate beryllium is obtained after separation.The lean organic phase that 3rd step is obtained
Carried out that the first step can be returned after acidifying regeneration with 5% to 15% aqueous sulfuric acid and recycled as extractant.Phosphoric acid class extracts
It can be two-(2- ethylhexyls) phosphoric acid class and the hexyl alcohol -6 of 3,9- diethyl three and 2,6,8- front threes nonyl alcohol -4 to take agent
The heptadecyl phosphoric acid(HDPA) class or dodecylphosphoric acid class or two-(normal-butyl) phosphoric acid class or first of synthesis are acted on phosphorus pentoxide
P- spy-octyl group-phosphenylic acid the class of base.
In summary, the ammonium fluoberyllate that the method for the present invention for preparing ammonium fluoberyllate with basic carbonate beryllium is obtained it is miscellaneous
Matter content is lower than the impurity content using the existing ammonium fluoberyllate prepared with technique, so as to improve of the present invention with alkali formula carbon
The purity for the ammonium fluoberyllate that the method that sour beryllium prepares ammonium fluoberyllate is obtained, in addition, of the present invention prepared with basic carbonate beryllium
The technological process of the method for ammonium fluoberyllate is simple；The impurity for the beryllium fluoride that the preparation method of beryllium fluoride of the present invention is obtained contains
Measure than using the impurity content of the existing beryllium fluoride prepared with technique low, so as to improve the preparation side of beryllium fluoride of the present invention
The purity for the beryllium fluoride that method is obtained, in addition, the technological process of the preparation method of beryllium fluoride of the present invention is simple；Institute of the present invention
The impurity content for the metallic beryllium that the preparation method for the metallic beryllium stated is obtained contains than the impurity using the existing metallic beryllium prepared with technique
Amount is low, so that the purity for the metallic beryllium that the preparation method for improving metallic beryllium of the present invention is obtained, in addition, of the present invention
Metallic beryllium preparation method technological process it is simple；Therefore, the side of the present invention that ammonium fluoberyllate is prepared with basic carbonate beryllium
The preparation method of method, the preparation method of beryllium fluoride and metallic beryllium has broad application prospects, and is the research and development of beryllium material
There is provided new tool.
Above technical characteristic constitutes embodiments of the invention, and it has stronger adaptability and implementation result, can basis
The non-essential technical characteristic of increase and decrease is actually needed, to meet the demand of different situations.
Claims (6)
1. a kind of method that ammonium fluoberyllate is prepared with basic carbonate beryllium, it is characterised in that carry out as follows：The first step, by alkali
Formula beryllium carbonate obtains mixed liquor after carrying out hybrid reaction with hydrofluoric acid, wherein, the quality of beryllium and hydrofluoric acid in basic carbonate beryllium
Than for 1:5 to 15；Second step, concentrate is obtained after mixed liquor is concentrated, in concentrate, the concentration of beryllium ion for 60g/L extremely
150g/L；3rd step, liquefied ammonia is passed through into concentrate until the pH value of concentrate is 7 to 9；4th step, the 3rd step is obtained
Concentrate sequentially obtains ammonium fluoberyllate after crystallisation by cooling and separation of solid and liquid.
2. the method according to claim 1 that ammonium fluoberyllate is prepared with basic carbonate beryllium, it is characterised in that basic carbonate beryllium
Obtain in the steps below：The first step, is configured to extractant after phosphoric acid kind of extractants, alcohol and sulfonated kerosene are mixed, will
The solution containing beryllium that pH value is 1 to 3 and extractant are 1 by volume:0.5 to 6 carries out multi-stage counter current extraction, extracts by multi-stage countercurrent
Extraction organic phase and raffinate aqueous phase are obtained after taking, multi-stage counter current extraction to the concentration for extracting the beryllium ion in organic phase is 1.8g/L
To 3.6g/L, wherein, the volume ratio of phosphoric acid kind of extractants, alcohol and sulfonated kerosene is 10 to 40:4 to 15:50 to 90；Second step,
The oxalic acid aqueous solution and extraction organic phase for being 5% to 25% by mass percent are 1 by volume：3 to 6 progress multi-stage countercurrents are washed
Wash, organic phase and scrub raffinate are extracted after multi-stage countercurrent is washed, multi-stage countercurrent is washed extracts organic phase to after washing
In iron aluminium impurity total concentration be 10-3G/L to 10-2g/L；3rd step, is 100g/L to 150g/L with ammonium carbonate compound concentration
Ammonium carbonate solution, by ammonium carbonate solution and after washing, extraction organic phase is 1 by volume:1 to 2 carries out multi-stage countercurrent back extraction
Take, countercurrent reextraction obtains lean organic phase and strip liquor containing beryllium after taking, the concentration of the beryllium ion in back extraction to strip liquor containing beryllium is
1.8g/L to 3.6g/L；4th step, will contain beryllium strip liquor and be hydrolyzed 10 minutes to 40 points under conditions of temperature is 65 DEG C to 75 DEG C
Clock, the iron aluminium in strip liquor containing beryllium is removed with depth, then will obtain removal of impurities after the iron aluminum precipitation thing separation in strip liquor containing beryllium
Strip liquor containing beryllium；5th step, EDTAs and beryllium ion of the EDTA into removal of impurities strip liquor containing beryllium are added into removal of impurities strip liquor containing beryllium
Mass ratio be 0.1% to 1.0%, add after EDTA, by the removal of impurities strip liquor containing beryllium containing EDTA temperature be 80 DEG C to 105 DEG C
Under the conditions of hydrolyze and precipitated for 10 minutes to 40 minutes, then precipitation and separation obtains basic carbonate beryllium precipitation；6th step, by alkali formula
Beryllium carbonate is deposited in temperature to use pure water under the conditions of 70 DEG C to 100 DEG C 10 minutes to 40 minutes, and alkali formula carbon is obtained after separation
Sour beryllium.
3. a kind of preparation method of beryllium fluoride, it is characterised in that carry out as follows：The first step, by basic carbonate beryllium and hydrogen fluorine
Acid obtains mixed liquor after carrying out hybrid reaction, wherein, the mass ratio of beryllium and hydrofluoric acid in basic carbonate beryllium is 1:5 to 15；The
Two steps, concentrate is obtained after mixed liquor is concentrated, in concentrate, and the concentration of beryllium ion is 60g/L to 150g/L；3rd step,
Liquefied ammonia is passed through into concentrate until the pH value of concentrate is 7 to 9；4th step, the concentrate that the 3rd step is obtained sequentially passes through
Ammonium fluoberyllate is obtained after crystallisation by cooling and separation of solid and liquid, ammonium fluoberyllate is sequentially obtained into beryllium fluoride after drying and calcining, its
In, the temperature of drying is 80 DEG C to 120 DEG C, and the temperature of calcining is 400 DEG C to 800 DEG C, and the time of calcining is 120 minutes to 180
Minute.
4. the preparation method of beryllium fluoride according to claim 3, it is characterised in that basic carbonate beryllium is obtained in the steps below：
The first step, extractant is configured to after phosphoric acid kind of extractants, alcohol and sulfonated kerosene are mixed, by pH value for 1 to 3 containing beryllium
Solution is 1 by volume with extractant:0.5 to 6 carries out multi-stage counter current extraction, extraction is obtained after multi-stage counter current extraction organic
Mutually and raffinate aqueous phase, multi-stage counter current extraction to extract organic phase in beryllium ion concentration for 1.8g/L to 3.6g/L, wherein, phosphorus
The volume ratio of acids extractant, alcohol and sulfonated kerosene is 10 to 40:4 to 15:50 to 90；Second step, is 5% by mass percent
Oxalic acid aqueous solution and extraction organic phase to 25% are 1 by volume：3 to 6 carry out multi-stage countercurrent washing, are washed by multi-stage countercurrent
Wash and organic phase and scrub raffinate are extracted after being washed, multi-stage countercurrent washs to after washing the total dense of the iron aluminium impurity in extraction organic phase
Spend for 10-3G/L to 10-2g/L；3rd step, with the ammonium carbonate solution that ammonium carbonate compound concentration is 100g/L to 150g/L, is incited somebody to action
Ammonium carbonate solution and extraction organic phase is 1 by volume after washing:1 to 2 carries out multi-stage countercurrent back extraction, and countercurrent reextraction is obtained after taking
To lean organic phase and strip liquor containing beryllium, the concentration of the beryllium ion in back extraction to strip liquor containing beryllium is 1.8g/L to 3.6g/L；The
Four steps, will contain beryllium strip liquor and be hydrolyzed 10 minutes to 40 minutes under conditions of temperature is 65 DEG C to 75 DEG C, and be removed with depth and contain beryllium
Iron aluminium in strip liquor, then will obtain removal of impurities strip liquor containing beryllium after the iron aluminum precipitation thing separation in strip liquor containing beryllium；5th step,
Added into removal of impurities strip liquor containing beryllium EDTAs and beryllium ion of the EDTA into removal of impurities strip liquor containing beryllium mass ratio for 0.1% to
1.0%, add after EDTA, the removal of impurities strip liquor containing beryllium containing EDTA is hydrolyzed 10 minutes under the conditions of temperature is 80 DEG C to 105 DEG C
Precipitated to 40 minutes, then precipitation and separation obtains basic carbonate beryllium precipitation；6th step, temperature is deposited in by basic carbonate beryllium
To use pure water under the conditions of 70 DEG C to 100 DEG C 10 minutes to 40 minutes, basic carbonate beryllium is obtained after separation.
5. a kind of preparation method of metallic beryllium, it is characterised in that carry out as follows：The first step, by basic carbonate beryllium and hydrogen fluorine
Acid obtains mixed liquor after carrying out hybrid reaction, wherein, the mass ratio of beryllium and hydrofluoric acid in basic carbonate beryllium is 1:5 to 15；The
Two steps, concentrate is obtained after mixed liquor is concentrated, in concentrate, and the concentration of beryllium ion is 60g/L to 150g/L；3rd step,
Liquefied ammonia is passed through into concentrate until the pH value of concentrate is 7 to 9；4th step, the concentrate that the 3rd step is obtained sequentially passes through
Ammonium fluoberyllate is obtained after crystallisation by cooling and separation of solid and liquid, ammonium fluoberyllate is sequentially obtained into beryllium fluoride after drying and calcining, its
In, the temperature of drying is 80 DEG C to 120 DEG C, and the temperature of calcining is 400 DEG C to 800 DEG C, and the time of calcining is 120 minutes to 180
Minute；5th step, metallic beryllium is obtained after beryllium fluoride and magnesium ingot into reduction reaction occur.
6. the preparation method of metallic beryllium according to claim 5, it is characterised in that basic carbonate beryllium is obtained in the steps below：
The first step, extractant is configured to after phosphoric acid kind of extractants, alcohol and sulfonated kerosene are mixed, by pH value for 1 to 3 containing beryllium
Solution is 1 by volume with extractant:0.5 to 6 carries out multi-stage counter current extraction, extraction is obtained after multi-stage counter current extraction organic
Mutually and raffinate aqueous phase, multi-stage counter current extraction to extract organic phase in beryllium ion concentration for 1.8g/L to 3.6g/L, wherein, phosphorus
The volume ratio of acids extractant, alcohol and sulfonated kerosene is 10 to 40:4 to 15:50 to 90；Second step, is 5% by mass percent
Oxalic acid aqueous solution and extraction organic phase to 25% are 1 by volume：3 to 6 carry out multi-stage countercurrent washing, are washed by multi-stage countercurrent
Wash and organic phase and scrub raffinate are extracted after being washed, multi-stage countercurrent washs to after washing the total dense of the iron aluminium impurity in extraction organic phase
Spend for 10-3G/L to 10-2g/L；3rd step, with the ammonium carbonate solution that ammonium carbonate compound concentration is 100g/L to 150g/L, is incited somebody to action
Ammonium carbonate solution and extraction organic phase is 1 by volume after washing:1 to 2 carries out multi-stage countercurrent back extraction, and countercurrent reextraction is obtained after taking
To lean organic phase and strip liquor containing beryllium, the concentration of the beryllium ion in back extraction to strip liquor containing beryllium is 1.8g/L to 3.6g/L；The
Four steps, will contain beryllium strip liquor and be hydrolyzed 10 minutes to 40 minutes under conditions of temperature is 65 DEG C to 75 DEG C, and be removed with depth and contain beryllium
Iron aluminium in strip liquor, then will obtain removal of impurities strip liquor containing beryllium after the iron aluminum precipitation thing separation in strip liquor containing beryllium；5th step,
Added into removal of impurities strip liquor containing beryllium EDTAs and beryllium ion of the EDTA into removal of impurities strip liquor containing beryllium mass ratio for 0.1% to
1.0%, add after EDTA, the removal of impurities strip liquor containing beryllium containing EDTA is hydrolyzed 10 minutes under the conditions of temperature is 80 DEG C to 105 DEG C
Precipitated to 40 minutes, then precipitation and separation obtains basic carbonate beryllium precipitation；6th step, temperature is deposited in by basic carbonate beryllium
To use pure water under the conditions of 70 DEG C to 100 DEG C 10 minutes to 40 minutes, basic carbonate beryllium is obtained after separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610265158.0A CN105948082B (en) | 2016-04-26 | 2016-04-26 | The preparation method of method, beryllium fluoride and the metallic beryllium of ammonium fluoberyllate is prepared with basic carbonate beryllium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610265158.0A CN105948082B (en) | 2016-04-26 | 2016-04-26 | The preparation method of method, beryllium fluoride and the metallic beryllium of ammonium fluoberyllate is prepared with basic carbonate beryllium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105948082A CN105948082A (en) | 2016-09-21 |
| CN105948082B true CN105948082B (en) | 2017-10-17 |
Family
ID=56916008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610265158.0A Active CN105948082B (en) | 2016-04-26 | 2016-04-26 | The preparation method of method, beryllium fluoride and the metallic beryllium of ammonium fluoberyllate is prepared with basic carbonate beryllium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105948082B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112794343B (en) * | 2021-02-10 | 2022-12-16 | 钢研晟华科技股份有限公司 | Method for purifying and preparing ammonium beryllium fluoride from beryllium fluoride-containing mixture |
| CN113059154B (en) * | 2021-04-12 | 2022-09-16 | 钢研晟华科技股份有限公司 | Preparation method of metallic beryllium bead and metallic beryllium ingot |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2356963C2 (en) * | 2008-02-05 | 2009-05-27 | Государственное образовательное учреждение высшего профессионального образования "Уральский государственный технический университет-УПИ" | Extraction method of beryllium from beryllium-bearing spodumene concentrate |
| CN103088206B (en) * | 2012-12-25 | 2014-04-23 | 戴元宁 | Chemical metallurgy method for extracting beryllium oxide from chrysoberyl |
| CN103601222B (en) * | 2013-11-25 | 2016-01-20 | 中国科学院上海有机化学研究所 | A kind of preparation method of high-purity ammonium fluoroberyllate and application thereof |
| CN103818937B (en) * | 2013-12-30 | 2016-01-13 | 新疆有色金属研究所 | From containing the method producing beryllium oxide or high-purity beryllium oxide beryllium solution |
-
2016
- 2016-04-26 CN CN201610265158.0A patent/CN105948082B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105948082A (en) | 2016-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2023528091A (en) | Carboxylic acid compound, preparation method and use thereof | |
| CN110002509B (en) | Ferric trichloride crystal and preparation method and application thereof | |
| CN106611841B (en) | A method of nickel-cobalt-manganese ternary material precursor is prepared using nickel cobalt slag charge | |
| CN102603000B (en) | Process for preparing high-purity vanadium pentoxide by adopting ammonium metavanadate as raw material | |
| CN106048257B (en) | A kind of method of extraction and recovery scandium titanium in leachate from metatitanic acid containing scandium | |
| CN102010991A (en) | Method for extracting lithium salt and removing potassium from lithium mica raw material | |
| CN114318008B (en) | Method for extracting lithium by secondary reverse leaching of spodumene with nitric acid | |
| CN101552346A (en) | Method of preparing electrolyte of vanadium ion redox flow battery | |
| CN101880768B (en) | Method for extracting high-purity manganese dioxide from manganese slag | |
| CN105907962B (en) | The preparation method of high-purity strip liquor containing beryllium and preparation method thereof, ammonium fluoberyllate, beryllium fluoride and metallic beryllium | |
| CN105948082B (en) | The preparation method of method, beryllium fluoride and the metallic beryllium of ammonium fluoberyllate is prepared with basic carbonate beryllium | |
| Wang et al. | A novel process on separation of manganese from calcium and magnesium using synergistic solvent extraction system | |
| CN110902703A (en) | Method for producing alumina and recovering rare earth elements by using coal ash hydrochloric acid method | |
| CN105129851B (en) | A kind of preparation method of high purity niobium oxide | |
| CN106756023A (en) | The method that depth separates calcium and magnesium impurity in manganese sulfate | |
| CN113122725A (en) | Method for improving metal recovery rate and purity of waste lithium battery | |
| CN105161746A (en) | Method for preparing vanadium battery electrolyte from acid vanadium-enriched liquid | |
| CN113697790A (en) | Method for preparing phosphoric acid by hydrochloric acid wet process combining organic solvent extraction and water back extraction | |
| CN111137869A (en) | Preparation method of lithium iron phosphate | |
| CN107739825B (en) | A method of vanadium product is prepared using containing vanadium leachate | |
| CN112342407B (en) | Back extraction method of lithium extraction liquid | |
| CN107794383B (en) | A method of producing fluorine beryllium acid and fluorine beryllium ammonium from sulfur acid beryllium solution | |
| CN106399685A (en) | Uranium, iron, thorium and rare earth extraction and separation process | |
| CN111945001B (en) | Treatment method of monazite optimal slag | |
| CN102126756B (en) | Method for producing industrial grade ammonium paramolybdate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |