CN107794383B - A method of producing fluorine beryllium acid and fluorine beryllium ammonium from sulfur acid beryllium solution - Google Patents
A method of producing fluorine beryllium acid and fluorine beryllium ammonium from sulfur acid beryllium solution Download PDFInfo
- Publication number
- CN107794383B CN107794383B CN201611014052.XA CN201611014052A CN107794383B CN 107794383 B CN107794383 B CN 107794383B CN 201611014052 A CN201611014052 A CN 201611014052A CN 107794383 B CN107794383 B CN 107794383B
- Authority
- CN
- China
- Prior art keywords
- beryllium
- extraction
- acid
- solution
- organic phase
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B35/00—Obtaining beryllium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Extraction Or Liquid Replacement (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The method that the invention discloses a kind of to produce fluorine beryllium acid and fluorine beryllium ammonium from sulfur acid beryllium solution, comprising the following steps: (1) after the pH value of adjustment sulfur acid beryllium solution, with extraction chalybeate extraction, obtain liquid and load iron organic phase after extraction iron；(2) it uses extraction beryllium agent to extract liquid after the extraction iron, obtains liquid and load beryllium organic phase after extraction beryllium；(3) it is washed with the mixed solution of oxalic acid and sodium sulfite to beryllium organic phase multi-stage countercurrent is carried, obtains washing rear organic phase and wash water；(4) it is stripped with hydrofluoric acid solution to rear organic phase is washed, obtains fluorine beryllium acid solution；This method shortens the process flow of beryllium production, improves the rate of recovery of beryllium, reduces production cost, stablizes the quality of beryllium.
Description
Technical field
The method that the present invention relates to a kind of to produce fluorine beryllium acid and fluorine beryllium ammonium from sulfur acid beryllium solution.
Background technique
Beryllium is important strategic rare metal, in fields such as military project, aerospace, nuclear industry, accurate high-precision instrument, optics
Using very extensive.For metallic beryllium since atomic weight is small, thermal capture face is small, and neutron scattering coefficient is high, makees to radiation and high temperature
It can make neutron moderator and reflecting layer in atomic reactor with stable performance, in thermonuclear fusion reactor (ITER)
It is used as the first wall of the Shield blanket towards plasma in design.
The beryllium sulfate solution that the production of metallic beryllium obtains after mainly being leached by the melting of ingredient containing beryllium, acidification at present passes through
Except aluminium, neutralization remove iron, hydrolytic precipitation obtains beryllium hydroxide, beryllium hydroxide obtains exquisite hydrogen through heavy molten, removal of impurities, neutralization precipitation for evaporation
Beryllium oxide, the reaction of filling liquid ammonia, crystallisation by cooling obtain fluorine beryllium ammonium after exquisite beryllium hydroxide hydrofluoric acid dissolution, and fluorine beryllium ammonium is in height
Lower decompose of temperature obtains beryllium fluoride, and metallic beryllium is obtained after magnesium-reduced.Long, at high cost, production process the direct yield of its process and total
Yield is low, and removal of impurities is not clean also to will affect beryllium pearl quality.
Summary of the invention
The present invention provides a kind of to extract the new method that beryllium produces fluorine beryllium acid, fluorine beryllium ammonia from beryllium sulfate solution, makes a living
It produces metallic beryllium pearl and develops a shortcut, while overcoming the shortcoming of existing procedure.
The technical scheme is that provide one kind produces fluorine beryllium acid H from sulfur acid beryllium solution2BeF4Method, including
Following steps:
(1) after the pH value of adjustment sulfur acid beryllium solution, with extraction chalybeate extraction, liquid and load iron organic phase after extraction iron are obtained；
(2) it uses extraction beryllium agent to extract liquid after the extraction iron, obtains liquid and load beryllium organic phase after extraction beryllium；
(3) it is washed with the mixed solution of oxalic acid and sodium sulfite to beryllium organic phase multi-stage countercurrent is carried, obtains washing rear organic phase
And wash water；
(4) it is stripped with hydrofluoric acid solution to rear organic phase is washed, obtains fluorine beryllium acid solution.
Further, step (3), the mass fraction 5~8% of mixed solution mesoxalic acid, Na2SO3Concentration be 1-2g/L.
Further, in the step (1), the pH value of adjustment sulfur acid beryllium solution is 1.2 ~ 2.0.
Further, which is characterized in that based on volumn concentration, the extraction chalybeate is composed of the following components:
N-235 40~50%
Sec-octyl alcohol 10~25%
Kerosene 25~50%.
Further, when the extraction chalybeate extracts, the volume ratio of organic phase and water phase is 1:0.8-1.2, series 4-6
Grade stops 5~10min in every grade of mixing chamber.
Further, the sulfur acid beryllium solution is that beryllium is obtained through ingredient melting, sulfuric acid leaching or the miscellaneous material containing beryllium is used
Sulfuric acid leaching recycles to obtain.
Further, the hydrofluoric acid solution is the hydrofluoric acid solution that mass fraction is 30-50%.
Further, hydrofluoric acid solution carries out in stripping steps to rear organic phase is washed, and the volume ratio of organic phase and water phase is
2.0-2.5:1。
Further, extract iron after liquid pH value be 1.5~2.0, or by extract iron after liquid pH value be adjusted to 1.5~2.0 after,
Step (2) are carried out again.
Further, based on volumn concentration, the extraction beryllium agent is composed of the following components:
P204 30~40%
Isoamyl alcohol 5~10%
Sulfonated kerosene 50~65%.
Further, the present invention provides one kind and produces fluorine beryllium acid (NH from sulfur acid beryllium solution4)2BeF4Method, upper
It states in the fluorine beryllium acid solution of method acquisition and is passed through liquefied ammonia, fluorine beryllium ammonium is obtained after reaction.
The purpose that step (1) extracts iron is to reduce or eliminate Fe3+Content finds after study, with P204 from beryllium sulfate
The sequencing that cation is extracted in solution is Fe3+> Be2+> AL3+> Fe2+, under ph control, to keep beryllium preferential
Extraction enters in organic phase, must just eliminate Fe3+Or make Fe3+Switch to Fe2+, inhibit the effect of extracting of impurity.The present invention is by touching
Rope is realized the extracting impurities iron ion from beryllium sulfate solution, is realized ferric by a kind of formula of new extraction chalybeate
Separation.
The purpose of step (3) washing is except ferrous iron and aluminium, and the combination of oxalic acid and sodium sulfite is best except iron aluminium tries
Agent combination, iron aluminium is washable to 10- 3g/L.The present invention, which has further been found that, can also be stripped organic phase by hydrofluoric acid
In beryllium, and effect of extracting is very good.Hydrofluoric acid can rush pure water with anhydrous hydrofluoric acid and be made, and the back extraction of hydrofluoric acid liquid is supported on organic
Beryllium in phase forms fluorine beryllium acid, and hydrofluoric acid can be stripped repeatedly, and the beryllium concentration in fluorine beryllium acid is made to reach 65~80g/L.
The present invention is slowly 40~56h towards the time of liquefied ammonia into fluorine beryllium acid, is continuously stirred, and control endpoint pH and be
7.2~8.7.It is cooling, it precipitates crystal, obtains fluorine beryllium ammonium.
The increasing situation of demand for military project and civilian goods to beryllium pearl, requirement of the present invention to beryllium content in raw material is not
Height can handle low beryllium (such as beryllium content is no more than 2% beryllium), naturally it is also possible to handle the molten of the beryllium sulfate of low concentration
Liquid (such as 1-5g/L) can also handle the higher beryllium of the impurity such as fluorine-containing, silicon and phosphorus, have stronger adaptability and can be according to life
It produces and needs and adjust.This method shortens the process flow of beryllium production, improves the rate of recovery of beryllium, reduces production cost, stablizes beryllium
Quality.
Detailed description of the invention
Fig. 1 shows the process flow charts of embodiment 1.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
The embodiment of the present invention is related with the ingredient of the stoste containing beryllium, therefore can be not limited to the embodiment in the specific implementation.
Embodiment 1
The present embodiment provides the production method for extracting beryllium compound and beryllium from the solution of sulfur acid beryllium, sulfur acid beryllium it is molten
Liquid main component is (g/L) Be 5.43, Fe 3.76, Al 14.55, Si 0.09.The following steps are included:
(1) extract iron
The pH value of sulfuric acid solution is transferred to 1.2~2.0 with NaOH, as extraction iron stoste.Extract chalybeate by 40~50%N-235
+ 25~50% kerosene of+10~25% sec-octyl alcohol is formed by percentage by volume.The extraction chalybeate newly matched need to be handled with the hydrochloric acid solution of 2N.
Compared to O:A(organic phase: water phase)=1:1, series is 5 grades, time of contact: 5~10min is stopped in mixing chamber, de-ferrous effect can
With 10% ammonium thiocyanate (or potassium rhodanide) identification outflow water phase, until showing colourless or blush.Iron stripping agent is 5%
Sulfuric acid liquid (or organic phase regenerated liquid after extraction beryllium) is comparably 1:1, and series is three-level, and time of contact is 5~10min.
(2) extract beryllium
Extracting beryllium stoste is after extracting iron without ferric water phase, and pH value is 1.5~2.0.Extract beryllium agent to form: 30~40%
+ 50~65% sulfonated kerosene of the isoamyl alcohol of P204+5~10%.O/A=2:1, extraction series are 6~8 grades, 10~20min of incorporation time.
(3) washing of beryllium organic phase is carried
Carry 5~8%% oxalic acid+1.5g/L Na of beryllium organic phase2SO3The washing of solution multi-stage countercurrent, is comparably 1:1, time 5
~10min, until the iron content in organic phase is less than 1 × 10- 3G/L, aluminium content are less than 1 × 10- 3g/L。
(4) it is stripped to obtain fluorine beryllium acid with hydrofluoric acid.Hydrofluoric acid of the water phase for mass fraction 40%, O/A=2.0-2.5:
1, time 15-20min, three-level continuous flow upstream.
(5) anti-rear organic phase is washed with the dilute sulfuric acid of 2.0-2.5%, is comparably 1:1, time 5min, three-level countercurrent washing.
(6) it is slowly passed through liquefied ammonia into fluorine beryllium acid, it is made to generate fluorine beryllium ammonia, crystallisation by cooling is precipitated.It is obtained after being centrifuged
Fluorine beryllium ammonium.
(7) fluorine beryllium ammonium obtains metallic beryllium pearl after pyrolytic, magnesium-reduced.
Embodiment 2
The main component of the sulfur acid beryllium solution of the present embodiment is (g/L) Be 2.8, Fe 4.11, Al 12.75, Si
1.05.Processing method is same as Example 1, and difference is only that comparing when step (2) are extracted beryllium is adjusted to O/A=1.5:1,
Remaining step is the same.
Embodiment 3
The sulfur acid beryllium main component in solution of the present embodiment is (g/L) Be 1.95, Fe 3.58, Al 13.8, Si
1.12.Processing method is same as Example 1, and difference is only that comparing when step (2) are extracted beryllium is adjusted to O/A=1:1,
Remaining step is the same.
To the fluorine beryllium ammonium obtained according to embodiment 1-3, through chemical examination detection, to obtain ingredient as follows: Be > 7.0%, Fe <
0.0045%, Al < 0.003%, Si < 0.001% can reach the quality requirement for producing high-purity beryllium pearl.The rate of recovery is mentioned than prior art
It is high by 8~10%.
Claims (8)
1. a kind of method for producing fluorine beryllium acid from sulfur acid beryllium solution, which comprises the following steps:
(1) after the pH value of adjustment sulfur acid beryllium solution, with extraction chalybeate extraction, liquid and load iron organic phase after extraction iron are obtained；
(2) it uses extraction beryllium agent to extract liquid after the extraction iron, obtains liquid and load beryllium organic phase after extraction beryllium；
(3) it is washed, obtain washing rear organic phase and washed to beryllium organic phase multi-stage countercurrent is carried with the mixed solution of oxalic acid and sodium sulfite
Water；
(4) it is stripped with hydrofluoric acid solution to rear organic phase is washed, obtains fluorine beryllium acid solution；
In the step (1), the pH value of adjustment sulfur acid beryllium solution is 1.2 ~ 2.0；
The extraction chalybeate is composed of the following components:
N-235 40~50%
Sec-octyl alcohol 10~25%
Kerosene 25~50%.
2. the method as described in claim 1, which is characterized in that when the extraction chalybeate extracts, the volume ratio of organic phase and water phase
For 1:0.8-1.2, series is 4-6 grades, and 5~10min is stopped in every grade of mixing chamber.
3. the method as described in claim 1, which is characterized in that the sulfur acid beryllium solution is beryllium through ingredient melting, sulphur
Ore Leaching obtains or the miscellaneous material containing beryllium recycles to obtain with sulfuric acid leaching.
4. the method as described in claim 1, which is characterized in that the hydrofluoric acid solution is the hydrogen that mass fraction is 30-50%
Fluorspar acid solution.
5. the method as described in claim 1, which is characterized in that hydrofluoric acid solution carries out in stripping steps to rear organic phase is washed,
The volume ratio of organic phase and water phase is 2.0-2.5:1.
6. the method as described in claim 1, which is characterized in that the pH value of liquid is 1.5~2.0 after extraction iron, or will be after extraction iron
After the pH value of liquid is adjusted to 1.5~2.0, then carry out step (2).
7. the method as described in claim 1, which is characterized in that based on volumn concentration, the extraction beryllium agent is by following components
Composition:
P204 30~40%
Isoamyl alcohol 5~10%
Sulfonated kerosene 50~65%.
8. a kind of method for producing ammonium fluoberyllate from sulfur acid beryllium solution, which is characterized in that any in such as claim 1-7
It is passed through liquefied ammonia in the fluorine beryllium acid solution that method described in obtains, fluorine beryllium ammonium is obtained after reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611014052.XA CN107794383B (en) | 2016-11-18 | 2016-11-18 | A method of producing fluorine beryllium acid and fluorine beryllium ammonium from sulfur acid beryllium solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611014052.XA CN107794383B (en) | 2016-11-18 | 2016-11-18 | A method of producing fluorine beryllium acid and fluorine beryllium ammonium from sulfur acid beryllium solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107794383A CN107794383A (en) | 2018-03-13 |
| CN107794383B true CN107794383B (en) | 2019-08-27 |
Family
ID=61530204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611014052.XA Active CN107794383B (en) | 2016-11-18 | 2016-11-18 | A method of producing fluorine beryllium acid and fluorine beryllium ammonium from sulfur acid beryllium solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107794383B (en) |
Families Citing this family (3)
| 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 |
| CN115074539B (en) * | 2022-07-20 | 2022-11-22 | 中南大学 | Method for recycling and detoxifying beryllium in beryllium-containing sludge |
| CN115927883A (en) * | 2022-12-13 | 2023-04-07 | 核工业北京化工冶金研究院 | Method for separating and recovering beryllium element |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103556186A (en) * | 2013-11-05 | 2014-02-05 | 浙江科菲冶金科技股份有限公司 | Selective separation method for copper and beryllium in sulfuric acid system |
| CN103695671A (en) * | 2014-01-13 | 2014-04-02 | 江西泛美亚材料有限公司 | Method for recycling and purifying scandium oxide powder from waste acid in zirconium salt production |
| CN105907962A (en) * | 2016-04-26 | 2016-08-31 | 新疆有色金属研究所 | High-purity beryllium-containing strip liquor, preparation method thereof and preparation methods of ammonium fluoroberyllate, beryllium fluoride and metallic beryllium |
| CN106011485A (en) * | 2016-07-14 | 2016-10-12 | 潮州三环（集团）股份有限公司 | Method for extracting scandium oxide from scandium-containing waste residue |
-
2016
- 2016-11-18 CN CN201611014052.XA patent/CN107794383B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103556186A (en) * | 2013-11-05 | 2014-02-05 | 浙江科菲冶金科技股份有限公司 | Selective separation method for copper and beryllium in sulfuric acid system |
| CN103695671A (en) * | 2014-01-13 | 2014-04-02 | 江西泛美亚材料有限公司 | Method for recycling and purifying scandium oxide powder from waste acid in zirconium salt production |
| CN105907962A (en) * | 2016-04-26 | 2016-08-31 | 新疆有色金属研究所 | High-purity beryllium-containing strip liquor, preparation method thereof and preparation methods of ammonium fluoroberyllate, beryllium fluoride and metallic beryllium |
| CN106011485A (en) * | 2016-07-14 | 2016-10-12 | 潮州三环（集团）股份有限公司 | Method for extracting scandium oxide from scandium-containing waste residue |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107794383A (en) | 2018-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107794383B (en) | A method of producing fluorine beryllium acid and fluorine beryllium ammonium from sulfur acid beryllium solution | |
| Thorat et al. | Extraction of beryllium from Indian beryl by ammonium hydrofluoride | |
| CN108165747A (en) | A kind of abstraction purification method recycled for uranium in fluorination reaction lime-ash | |
| CA1185097A (en) | Process for preparing metals from their fluorine- containing compounds | |
| CN108193058B (en) | A method of extracting the ion liquid abstraction of lithium from salt lake | |
| CN105907962B (en) | The preparation method of high-purity strip liquor containing beryllium and preparation method thereof, ammonium fluoberyllate, beryllium fluoride and metallic beryllium | |
| CN110747357B (en) | Method for extracting and separating zirconium and hafnium by using biphosphoric acid extracting agent | |
| CN115710645B (en) | Method for preparing nuclear-grade zirconium and nuclear-grade hafnium through extraction separation under hydrochloric acid system | |
| CN102952951A (en) | Method for extracting tantalum and niobium and producing potassium fluosilicate from tungsten smelting slag | |
| Jantunen et al. | Separation of zinc and iron from secondary manganese sulfate leachate by solvent extraction | |
| CN106399685B (en) | A kind of uranium, iron, thorium, rare-earth extraction separating process | |
| Fang et al. | Recovery of valuable metals from anode material of hydrogen-nickel battery | |
| CN106854706B (en) | A kind of HF-H2SO4System separation of U and Nb method | |
| CN104651619A (en) | Method for separating and recovering scandium in stable zirconia ceramic wastes containing scandium and rare earth | |
| CN104630489B (en) | The method for reclaiming Scia from zirconium oxychloride mother solution | |
| CN109136996A (en) | A method of Mg-Nd base intermediate alloy is prepared using neodymium iron boron waste material | |
| Abrão et al. | Preparation of highly pure thorium nitrate via thorium sulfate and thorium peroxide | |
| EP0055486B1 (en) | Process for producing aluminum oxide | |
| CN108517426A (en) | The method that the CRT fluorescent powder middle rare earth that gives up under a kind of temperate condition efficiently separates recycling | |
| CN108441637A (en) | The method that valuable metal is recycled in giving up chip from copper indium gallium selenium solar hull cell | |
| CN103451452A (en) | Method for recovering tin from tin-containing waste liquid | |
| CN103738982B (en) | Technology for separating alkaline earth metal impurities in lithium chloride by employing quasi fractional distillation extraction method | |
| CN106319229A (en) | Method for recovering silver from silver particles in silver production waste liquid | |
| CN109182765A (en) | A method of star metal is prepared with antimony cigarette ash | |
| CN115418503B (en) | Method for selectively extracting scandium from leaching solution based on microemulsion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |