CN115652111B - Method for recycling beryllium from beryllium-containing magnesium fluoride slag - Google Patents
Method for recycling beryllium from beryllium-containing magnesium fluoride slag Download PDFInfo
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- CN115652111B CN115652111B CN202211377336.0A CN202211377336A CN115652111B CN 115652111 B CN115652111 B CN 115652111B CN 202211377336 A CN202211377336 A CN 202211377336A CN 115652111 B CN115652111 B CN 115652111B
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- beryllium
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- 229910052790 beryllium Inorganic materials 0.000 title claims abstract description 195
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 195
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 title claims abstract description 156
- 229910001635 magnesium fluoride Inorganic materials 0.000 title claims abstract description 156
- 239000002893 slag Substances 0.000 title claims abstract description 132
- 238000000034 method Methods 0.000 title claims abstract description 67
- 238000004064 recycling Methods 0.000 title description 5
- 239000011324 bead Substances 0.000 claims abstract description 85
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000011084 recovery Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 229950005228 bromoform Drugs 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 18
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- JZKFIPKXQBZXMW-UHFFFAOYSA-L beryllium difluoride Chemical compound F[Be]F JZKFIPKXQBZXMW-UHFFFAOYSA-L 0.000 claims description 5
- 229910001633 beryllium fluoride Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims 4
- 230000005484 gravity Effects 0.000 abstract description 6
- 238000005406 washing Methods 0.000 description 32
- 238000005303 weighing Methods 0.000 description 30
- 238000005070 sampling Methods 0.000 description 20
- 238000002386 leaching Methods 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 239000012074 organic phase Substances 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 7
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a method for recovering beryllium from beryllium-containing magnesium fluoride slag, which comprises the following steps: preparing an intermediate density solution with the density larger than that of the beryllium simple substance and smaller than that of magnesium fluoride, mixing the beryllium-containing magnesium fluoride slag with the intermediate density solution, stirring, and collecting upper-layer floats of the intermediate density solution to realize the recovery of beryllium beads. The method for recovering beryllium from beryllium-containing magnesium fluoride slag is characterized in that an intermediate density solution is prepared according to the specific gravity difference of beryllium beads and magnesium fluoride, so that the specific gravity of the solution is between the beryllium beads and the magnesium fluoride and the solution is not compatible with the beryllium beads and the magnesium fluoride, the purpose of separating the beryllium beads from the magnesium fluoride is achieved.
Description
Technical Field
The invention belongs to the field of solid waste resource and valuable metal recovery, and particularly relates to a beryllium recovery method.
Background
Beryllium is a material with more specific properties, in particular nuclear and physical properties that cannot be replaced by any other metallic material. The production method of the elemental beryllium commonly comprises the step of carrying out reduction reaction on beryllium fluoride and magnesium to obtain the elemental beryllium. The direct yield of the metal simple substance beryllium produced by the magnesian reduction method is very low, and 40-45% of the metal beryllium can enter magnesium reduction slag and smoke dust. The beryllium entering the reducing slag is mostly in the form of beryllium beads (simple substances), and the small part of beryllium beads (simple substances) exists in the magnesium fluoride in the form of beryllium oxide and is mixed with the magnesium fluoride to be in a wrapped state. Aiming at the beryllium-containing magnesium fluoride slag obtained by the magnesian reduction method, high-acid leaching is adopted for recycling beryllium beads in the beryllium-containing magnesium fluoride slag at present, leaching liquid enters a beryllium production process, the process is long, and a large amount of hydrofluoric acid and electric energy are needed in the process, so that the production cost is greatly increased.
Therefore, development of a method for recovering beryllium from beryllium-containing magnesium fluoride slag, which is simple in process and low in cost, is imperative.
Disclosure of Invention
The invention aims to overcome the defects and the defects in the background art, and provides a method for recycling beryllium from beryllium-containing magnesium fluoride slag, which has the advantages of simple process, low cost and high beryllium bead direct yield. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for recovering beryllium from magnesium fluoride slag containing beryllium, comprising the following steps: preparing an intermediate density solution with the density larger than that of a beryllium simple substance and smaller than that of magnesium fluoride, mixing the beryllium-containing magnesium fluoride slag with the intermediate density solution, stirring (normal temperature), and collecting upper-layer floats of the intermediate density solution to realize the recovery of beryllium beads.
In the present invention, the density of magnesium fluoride was 3.148g/cm 3 The density of the magnesium oxide is 3.58g/cm 3 Beryllium density of 1.85g/cm 3 The density of beryllium oxide is 3.025g/cm 3 . Because of a certain difference between the specific gravity of beryllium and the specific gravity of magnesium fluoride, an intermediate density solution is prepared, and beryllium beads can float on the surface of the intermediate density solution, magnesium fluoride and the like sink below the intermediate density solution, so that the purpose of directly recycling the beryllium beads is achieved.
The beryllium beads separated and recovered by the method can be used as industrial-grade beryllium beads for producing beryllium-aluminum alloy after being washed.
In the above method for recovering beryllium from beryllium-containing magnesium fluoride slag, it is preferable to control the density of the intermediate density solution to 2.3 to 2.7g/cm 3 . More preferably, the density of the intermediate density solution is controlled to be 2.4-2.6g/cm 3 . Further preferably, the density of the intermediate density solution is controlled to be 2.5g/cm 3 . We have found that, when separating beryllium beads from magnesium fluoride using an intermediate density solution, the density of the intermediate density solution is in the range of 2.4-2.6g/cm 3 In the process, the separation effect of the beryllium beads and the magnesium fluoride is better, and the direct yield of the beryllium beads is higher.
In the method for recovering beryllium from the beryllium-containing magnesium fluoride slag, preferably, the intermediate density solution is an organic separation solution or an inorganic separation solution, the organic separation solution mainly comprises at least one of methanol, ethanol and carbon tetrachloride and bromoform, and the inorganic separation solution is a zinc chloride solution. In selecting the intermediate density solution, the nature of the solvent itself needs to be considered, and the nature and density of the solvent after combination needs to be considered.
In the above method for recovering beryllium from beryllium-containing magnesium fluoride slag, preferably, the intermediate density solution is composed of bromoform and ethanol and has a density of 2.5g/cm 3 Is used for separating the organic separation solution. Considering the properties and density of the intermediate density solution obtained after solvent combination, we have shown that the more preferred combination of bromoform and ethanol provides better separation of beryllium beads from magnesium fluoride, especially at a density of 2.5g/cm 3 The separation effect is optimal when the separation is performed.
In the above method for recovering beryllium from the beryllium-containing magnesium fluoride slag, preferably, the beryllium beads and the magnesium fluoride are insoluble in the intermediate-density solution, and neither react chemically with the intermediate-density solution. The intermediate density solution is preferably insoluble in and chemically inert to the beryllium beads and magnesium fluoride to minimize loss of beryllium beads in the intermediate density solution.
In the method for recovering beryllium from the beryllium-containing magnesium fluoride slag, preferably, the beryllium-containing magnesium fluoride slag is magnesium fluoride reduction slag with beryllium bead particles (small particles) left after the beryllium fluoride is subjected to magnesian reduction, crushing and screening separation.
In the method for recovering beryllium from the beryllium-containing magnesium fluoride slag, preferably, the mass ratio of beryllium beads in the beryllium-containing magnesium fluoride slag is 1.5-12%, the beryllium beads are visible in different sizes, and the rest is magnesium fluoride slag (containing a small amount of beryllium oxide and magnesium oxide).
In the method for recovering beryllium from the beryllium-containing magnesium fluoride slag, preferably, the magnesium fluoride slag contains 55-60% of F, 35-39% of Mg, 0.1-0.5% of Be and the balance of impurities (such as silicon, calcium, iron, copper and the like, the contents of which are all less than 0.05%) in percentage by mass.
In the method for recovering beryllium from the beryllium-containing magnesium fluoride slag, preferably, collecting magnesium fluoride slag sediment at the bottom layer of the intermediate density solution, leaching the magnesium fluoride slag sediment by utilizing hydrofluoric acid to recover residual beryllium in the magnesium fluoride slag sediment so that the mass content of the beryllium in the magnesium fluoride slag sediment is less than 0.05 percent. The magnesium fluoride slag after separating the beryllium beads contains a small amount of beryllium oxide and fine beryllium beads which are mixed with the beryllium oxide, the recovery rate of the beryllium is obtained by acid leaching and recovery, the influence of the beryllium on the environment is reduced, the solution of the beryllium leached by the acid is returned to the production process, the grade of the washed magnesium fluoride is more than 98%, and the washed magnesium fluoride can be taken as a product for take-out sale.
In the invention, the intermediate density solution can be reused to reduce the process cost of the method as much as possible.
Compared with the prior art, the invention has the advantages that:
1. the method for recovering beryllium from beryllium-containing magnesium fluoride slag is characterized in that an intermediate density solution is prepared according to the specific gravity difference of beryllium beads and magnesium fluoride, so that the specific gravity of the solution is between the beryllium beads and the magnesium fluoride and the solution is not compatible with the beryllium beads and the magnesium fluoride, the purpose of separating the beryllium beads from the magnesium fluoride is achieved.
2. The method for recovering beryllium from the beryllium-containing magnesium fluoride slag can recover more than 90% of beryllium from the beryllium-containing magnesium fluoride slag, is used for matching with a magnesia-thermal reduction method, and can obviously improve the direct yield of beryllium beads by the magnesia-thermal reduction method. Compared with the traditional method, the high acid leaching method can lead to the existence of more beryllium in a non-simple substance form, and the beryllium is recovered through a series of procedures in the follow-up process, so that the direct yield of the beryllium beads is improved, and the profit of enterprises can be obviously improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a process flow diagram of a method of the present invention for recovering beryllium from a beryllium-containing magnesium fluoride slag.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
The magnesium fluoride slag containing beryllium used in the following examples is magnesium fluoride reducing slag which is left after beryllium fluoride is subjected to magnesian reduction, crushing and beryllium bead and magnesium fluoride screening separation and is used for carrying beryllium bead particles, and the particles of the beryllium beads are visible in the magnesium fluoride slag containing beryllium bead and have different sizes.
Typical magnesium reduction process steps may be as follows: mixing beryllium fluoride and magnesium metal to obtain a reduction raw material, and heating the reduction raw material to obtain a material slag cake; crushing the material slag cake, separating beryllium beads and magnesium fluoride, wherein the separation process can be water boiling and screening; the magnesium fluoride obtained is the beryllium-containing magnesium fluoride slag in the following examples. The above process steps and process parameters are those of the prior art, and reference may be made to the technical solutions described in the published patent CN109082540 a. The different beryllium-containing magnesium fluoride slag obtained by the above-mentioned magnesian reduction process steps can be as follows:
slag 1: the mass content of beryllium is 4.02 percent (including beryllium beads and beryllium oxide), the mass content of magnesium fluoride is 84.5 percent, the mass content of moisture and other impurities is 11.48 percent (moisture is the main component and other impurities are trace).
Slag 2: the mass content of beryllium is 8.11 percent (including beryllium beads and beryllium oxide), the mass content of magnesium fluoride is 81.69 percent, the mass content of moisture and other impurities is 10.2 percent (the moisture is the main component and the other impurities are trace).
Example 1:
as shown in fig. 1, a method for recovering beryllium from beryllium-containing magnesium fluoride slag comprises the following steps:
(1) The intermediate density solution is prepared by adopting the tribromomethane and the absolute ethyl alcohol, and the dosage of the tribromomethane and the absolute ethyl alcohol is controlled to be 2.4g/cm 3 ；
(2) Weighing 50g of magnesium fluoride slag (slag 1), pouring the magnesium fluoride slag into the medium-density solution, slowly stirring, standing (normal temperature), and waiting for layering;
(3) Separating beryllium beads (upper layer), organic phase and magnesium fluoride slag (bottom layer), washing the beryllium beads, weighing and sampling, and weighing and sampling the magnesium fluoride slag after washing, acid leaching and washing (controlling the mass content of beryllium in the sample to be less than 0.05 percent, and the same applies below).
In this embodiment, the detailed process steps of washing magnesium fluoride slag with water, acid leaching and washing are known in the art, and reference may be made to the technical solution described in the publication CN109082540 a.
The technical indexes of the process of the embodiment are as follows after measurement:
the weight of the obtained beryllium beads is 1.82g, the direct yield of the beryllium beads is 90.55 percent through calculation, and the beryllium beads can be used as industrial-grade beryllium beads for producing beryllium aluminum alloy; the obtained magnesium fluoride slag had a weight of 41g and contained 98.2% by mass of magnesium fluoride (the same applies hereinafter), 0.034% by mass of silicon, 0.011% by mass of calcium, 0.0167% by mass of iron, 0.0154% by mass of copper, and the magnesium fluoride was directly available for take-out.
Example 2:
a method for recovering beryllium from magnesium fluoride slag containing beryllium, comprising the following steps:
(1) The intermediate density solution is prepared by adopting the tribromomethane and the absolute ethyl alcohol, and the dosage of the tribromomethane and the absolute ethyl alcohol is controlled to be 2.5g/cm 3 ；
(2) Weighing 50g of magnesium fluoride slag (slag 1), pouring the magnesium fluoride slag into the medium-density solution, slowly stirring, standing, and waiting for layering;
(3) Separating beryllium beads (upper layer), organic phase and magnesium fluoride slag (bottom layer), washing the beryllium beads, weighing and sampling, and weighing and sampling the magnesium fluoride slag after washing, acid leaching and washing.
The technical indexes of the process of the embodiment are as follows after measurement:
the weight of the obtained beryllium beads is 1.91g, and the direct yield of the beryllium beads is 95.02% after calculation; the obtained magnesium fluoride slag had a weight of 42.0g and contained 98.8% by mass of magnesium fluoride (the same applies hereinafter), 0.027% by mass of silicon, 0.01% by mass of calcium, 0.011% by mass of iron and 0.0151% by mass of copper.
Example 3:
a method for recovering beryllium from magnesium fluoride slag containing beryllium, comprising the following steps:
(1) The intermediate density solution is prepared by adopting the tribromomethane and the absolute ethyl alcohol, and the dosage of the tribromomethane and the absolute ethyl alcohol is controlled to be 2.6g/cm 3 ；
(2) Weighing 50g of magnesium fluoride slag (slag 1), pouring the magnesium fluoride slag into the medium-density solution, slowly stirring, standing, and waiting for layering;
(3) Separating beryllium beads (upper layer), organic phase and magnesium fluoride slag (bottom layer), washing the beryllium beads, weighing and sampling, and weighing and sampling the magnesium fluoride slag after washing, acid leaching and washing.
The technical indexes of the process of the embodiment are as follows after measurement:
the weight of the obtained beryllium beads is 1.87g, and the direct yield of the beryllium beads is 93.03% after calculation; the obtained magnesium fluoride slag weighed 41.8g and contained 98.5% by mass of magnesium fluoride (the same as described below), 0.03% by mass of silicon, 0.015% by mass of calcium, 0.01% by mass of iron and 0.016% by mass of copper.
Example 4:
a method for recovering beryllium from magnesium fluoride slag containing beryllium, comprising the following steps:
(1) The intermediate density solution is prepared by adopting the bromoform, the carbon tetrachloride and the absolute ethyl alcohol, and the dosage of the bromoform, the carbon tetrachloride and the absolute ethyl alcohol is controlled to be 2.6g/cm 3 ；
(2) Weighing 50g of magnesium fluoride slag (slag 1), pouring the magnesium fluoride slag into the medium-density solution, slowly stirring, standing, and waiting for layering;
(3) Separating beryllium beads (upper layer), organic phase and magnesium fluoride slag (bottom layer), washing the beryllium beads, weighing and sampling, and weighing and sampling the magnesium fluoride slag after washing, acid leaching and washing.
The technical indexes of the process of the embodiment are as follows after measurement:
the weight of the obtained beryllium beads is 1.85g, and the direct yield of the beryllium beads is 92.04 percent after calculation; the obtained magnesium fluoride slag had a weight of 41.8g, and contained 98.5% by mass of magnesium fluoride (the same applies hereinafter) with the other impurities.
Example 5:
a method for recovering beryllium from magnesium fluoride slag containing beryllium, comprising the following steps:
(1) The intermediate density solution is prepared by adopting the tribromomethane and the absolute ethyl alcohol, and the dosage of the tribromomethane and the absolute ethyl alcohol is controlled to be 2.5g/cm 3 ；
(2) Weighing 50g of magnesium fluoride slag (slag 2), pouring the magnesium fluoride slag into the medium-density solution, slowly stirring, standing, and waiting for layering;
(3) Separating beryllium beads (upper layer), organic phase and magnesium fluoride slag (bottom layer), washing the beryllium beads, weighing and sampling, and weighing and sampling the magnesium fluoride slag after washing, acid leaching and washing.
The technical indexes of the process of the embodiment are as follows after measurement:
the weight of the obtained beryllium beads is 3.8g, and the direct yield of the beryllium beads is 93.71% after calculation; the obtained magnesium fluoride slag had a weight of 40g and contained 99.1% by mass of magnesium fluoride (the same applies hereinafter), with the remainder being impurities.
Example 6:
a method for recovering beryllium from magnesium fluoride slag containing beryllium, comprising the following steps:
(1) The intermediate density solution is prepared by adopting the tribromomethane and the absolute ethyl alcohol, and the dosage of the tribromomethane and the absolute ethyl alcohol is controlled to be 2.6g/cm 3 ；
(2) Weighing 50g of magnesium fluoride slag (slag 2), pouring the magnesium fluoride slag into the medium-density solution, slowly stirring, standing, and waiting for layering;
(3) Separating beryllium beads (upper layer), organic phase and magnesium fluoride slag (bottom layer), washing the beryllium beads, weighing and sampling, and weighing and sampling the magnesium fluoride slag after washing, acid leaching and washing.
The technical indexes of the process of the embodiment are as follows after measurement:
the weight of the obtained beryllium beads is 3.74g, and the direct yield of the beryllium beads is 92.23 percent through calculation; the obtained magnesium fluoride slag weighed 39.4g, contained 98.6% by mass of magnesium fluoride (the same applies hereinafter), and the other was impurities.
Example 7:
a method for recovering beryllium from magnesium fluoride slag containing beryllium, comprising the following steps:
(1) The use amount of the tribromomethane and the carbon tetrachloride is controlled to be 2.5g/cm by matching the tribromomethane and the carbon tetrachloride with the intermediate density solution 3 ；
(2) Weighing 50g of magnesium fluoride slag (slag 2), pouring the magnesium fluoride slag into the medium-density solution, slowly stirring, standing, and waiting for layering;
(3) Separating beryllium beads (upper layer), organic phase and magnesium fluoride slag (bottom layer), washing the beryllium beads, weighing and sampling, and weighing and sampling the magnesium fluoride slag after washing, acid leaching and washing.
The technical indexes of the process of the embodiment are as follows after measurement:
the weight of the obtained beryllium beads is 3.7g, and the direct yield of the beryllium beads is 91.25% after calculation; the obtained magnesium fluoride slag weighed 39.1g, contained 98.8% by mass of magnesium fluoride (the same applies hereinafter), and the other was impurities.
Example 8:
a method for recovering beryllium from magnesium fluoride slag containing beryllium, comprising the following steps:
(1) Zinc chloride and water are adopted to prepare a solution with intermediate density, and the density is 2.5g/cm 3 ；
(2) Weighing 50g of magnesium fluoride slag (slag 2), pouring the magnesium fluoride slag into the medium-density solution, slowly stirring, standing, and waiting for layering;
(3) Separating beryllium beads (upper layer), organic phase and magnesium fluoride slag (bottom layer), washing the beryllium beads, weighing and sampling, and weighing and sampling the magnesium fluoride slag after washing, acid leaching and washing.
The technical indexes of the process of the embodiment are as follows after measurement:
the weight of the obtained beryllium beads is 3.58g, and the direct yield of the beryllium beads is 88.29 percent through calculation; the obtained magnesium fluoride slag weighed 39.5g, contained 98.7% by mass of magnesium fluoride (the same applies hereinafter), and the other was impurities.
Example 9:
a method for recovering beryllium from magnesium fluoride slag containing beryllium, comprising the following steps:
(1) The use level of the tribromomethane and the absolute ethyl alcohol is controlled to be 2.3g/cm by adopting the tribromomethane and the absolute ethyl alcohol to be matched with the intermediate density solution 3 ；
(2) Weighing 50g of magnesium fluoride slag (slag 2), pouring the magnesium fluoride slag into the medium-density solution, slowly stirring, standing, and waiting for layering;
(3) Separating beryllium beads (upper layer), organic phase and magnesium fluoride slag (bottom layer), washing the beryllium beads, weighing and sampling, and weighing and sampling the magnesium fluoride slag after washing, acid leaching and washing.
The technical indexes of the process of the embodiment are as follows after measurement:
the weight of the obtained beryllium beads is 3.5g, and the direct yield of the beryllium beads is 86.31 percent after calculation; the obtained magnesium fluoride slag weighed 39g, contained 98.8% by mass of magnesium fluoride (the same applies hereinafter), and the other was impurities. The layered mixed organic phase was slightly cloudy.
Example 10:
a method for recovering beryllium from magnesium fluoride slag containing beryllium, comprising the following steps:
(1) The use amount of the tribromomethane, the carbon tetrachloride and the absolute ethyl alcohol is controlled by adopting the tribromomethane, the carbon tetrachloride and the absolute ethyl alcohol to be matched with the intermediate density solutionDensity of 2.7g/cm 3 ；
(2) Weighing 50g of magnesium fluoride slag (slag 2), pouring the magnesium fluoride slag into the medium-density solution, slowly stirring, standing, and waiting for layering;
(3) Separating beryllium beads (upper layer), organic phase and magnesium fluoride slag (bottom layer), washing the beryllium beads, weighing and sampling, and weighing and sampling the magnesium fluoride slag after washing, acid leaching and washing.
The technical indexes of the process of the embodiment are as follows after measurement:
the weight of the obtained beryllium beads is 3.79g, and the direct yield of the beryllium beads is 93.46 percent after calculation; the obtained magnesium fluoride slag weighed 38.5g, contained 98.9% by mass of magnesium fluoride (the same as described below) and the other impurities. The organic phase was mixed in layers to cloudiness.
Claims (7)
1. A method for recovering beryllium from magnesium fluoride slag containing beryllium, comprising the steps of: preparing an intermediate density solution with the density larger than that of a beryllium simple substance and smaller than that of magnesium fluoride, mixing the beryllium-containing magnesium fluoride slag with the intermediate density solution, stirring, and collecting upper-layer floats of the intermediate density solution to realize the recovery of beryllium beads;
controlling the density of the intermediate density solution to be 2.3-2.7g/cm 3 ；
The intermediate density solution is an organic separation solution or an inorganic separation solution, the organic separation solution mainly comprises at least one of methanol, ethanol and carbon tetrachloride and bromoform, and the inorganic separation solution is a zinc chloride solution;
the beryllium-containing magnesium fluoride slag is magnesium fluoride reducing slag with beryllium bead particles left after beryllium fluoride is subjected to magnesian reduction, crushing and screening separation.
2. The method for recovering beryllium from magnesium fluoride slag containing beryllium according to claim 1, wherein the density of the intermediate density solution is controlled to be 2.4-2.6g/cm 3 。
3. The method for recovering beryllium from magnesium fluoride slag containing beryllium according to claim 1, wherein the intermediate density solution isThe density of the composition consisting of the tribromomethane and the ethanol is 2.5g/cm 3 Is used for separating the organic separation solution.
4. The method of recovering beryllium from magnesium fluoride slag containing beryllium of claim 1, wherein neither the beryllium beads nor the magnesium fluoride are soluble in the intermediate density solution and chemically react with the intermediate density solution.
5. The method for recovering beryllium from a beryllium-containing magnesium fluoride slag as claimed in claim 1, wherein the mass ratio of beryllium beads in the beryllium-containing magnesium fluoride slag is 1.5-12%, and the balance is magnesium fluoride slag.
6. The method for recovering beryllium from magnesium fluoride slag containing beryllium according to claim 5, wherein the magnesium fluoride slag contains 55-60% by mass of F, 35-39% by mass of Mg, 0.1-0.5% by mass of Be and the balance of impurities.
7. The method for recovering beryllium from magnesium fluoride slag containing beryllium according to claim 6, wherein the magnesium fluoride slag precipitate at the bottom layer of the intermediate density solution is collected, and the magnesium fluoride slag precipitate is leached out by hydrofluoric acid to recover the residual beryllium in the magnesium fluoride slag precipitate so that the mass content of beryllium in the magnesium fluoride slag precipitate is less than 0.05%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104195356A (en) * | 2014-04-15 | 2014-12-10 | 西北稀有金属材料研究院 | Smelting and purification method of beryllium beads used for casting pure beryllium ingots |
| CN109082540A (en) * | 2018-09-25 | 2018-12-25 | 陆世强 | A method of it preparing the method for thick beryllium powder and prepares ultra-high purity metal beryllium |
| CN109110789A (en) * | 2018-09-25 | 2019-01-01 | 陆世强 | A method of it preparing the method for beryllium fluoride and prepares ultra-high purity metal beryllium |
| CN113059154A (en) * | 2021-04-12 | 2021-07-02 | 钢研晟华科技股份有限公司 | Preparation method of metallic beryllium bead and metallic beryllium ingot |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104195356A (en) * | 2014-04-15 | 2014-12-10 | 西北稀有金属材料研究院 | Smelting and purification method of beryllium beads used for casting pure beryllium ingots |
| CN109082540A (en) * | 2018-09-25 | 2018-12-25 | 陆世强 | A method of it preparing the method for thick beryllium powder and prepares ultra-high purity metal beryllium |
| CN109110789A (en) * | 2018-09-25 | 2019-01-01 | 陆世强 | A method of it preparing the method for beryllium fluoride and prepares ultra-high purity metal beryllium |
| CN113059154A (en) * | 2021-04-12 | 2021-07-02 | 钢研晟华科技股份有限公司 | Preparation method of metallic beryllium bead and metallic beryllium ingot |
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