CN101850995B - Process for preparing 5-20mm high-purity polycrystalline magnesium fluoride by liquid crystallization method - Google Patents
Process for preparing 5-20mm high-purity polycrystalline magnesium fluoride by liquid crystallization method Download PDFInfo
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- CN101850995B CN101850995B CN 201010202805 CN201010202805A CN101850995B CN 101850995 B CN101850995 B CN 101850995B CN 201010202805 CN201010202805 CN 201010202805 CN 201010202805 A CN201010202805 A CN 201010202805A CN 101850995 B CN101850995 B CN 101850995B
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- Prior art keywords
- magnesium fluoride
- polycrystalline
- purity
- growth
- single crystal
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Links
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 title claims abstract description 57
- 229910001635 magnesium fluoride Inorganic materials 0.000 title claims abstract description 57
- 239000007788 liquid Substances 0.000 title claims abstract description 13
- 238000002425 crystallisation Methods 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 239000013078 crystal Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 32
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 30
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 11
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 17
- 230000036571 hydration Effects 0.000 claims description 14
- 238000006703 hydration reaction Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229960001708 magnesium carbonate Drugs 0.000 claims description 9
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 9
- 239000012452 mother liquor Substances 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 4
- 238000005352 clarification Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 13
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005469 granulation Methods 0.000 abstract description 5
- 230000003179 granulation Effects 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 4
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005056 compaction Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 2
- 238000004334 fluoridation Methods 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 238000007747 plating Methods 0.000 abstract 1
- 238000002834 transmittance Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- -1 environmentally safe Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a process for preparing 5-20mm high-purity polycrystalline magnesium fluoride by a liquid crystallization method, which comprises the following steps: adding magnesium carbonate (Mg2CO3) into hydrofluoric acid (HF) to generate hydrated magnesium fluoride crystallite by fluoridation; and allowing the hydrated magnesium fluoride crystallite to be subjected to single crystal growth, then putting in a polycrystal generator to be subjected to polycrystalline growth, and finally putting in a cylindrical three-zone-temperature sintering furnace to be sintered so as to obtain the high-purity polycrystalline magnesium fluoride after cooling. The process of the invention adopts single crystal and polycrystalline growth to replace the steps of washing, drying, mechanical compaction and granulation in the existing process, does not need to add shielding gas and naturally forms the high-purity polycrystalline magnesium fluoride with extremely lower crystal water content and magnesium oxide content, so the pollution is reduced, the cost is reduced, the purity of the product is up to 99.99 percent, the transmittance of crystals is high, the collapse points are few and the input-output ratio is high during membrane plating.
Description
Technical field
The present invention relates to the preparation technology of magnesium fluoride, specifically, is a kind of technique of preparing 5-20 mm high-purity polycrystalline magnesium fluoride by liquid crystallization.
Background technology
Magnesium fluoride is to use optical filming material the earliest, modal, excellent property, yet, difference on the material inside organization structures that cause owing to preparation process is different is the most at last to technique for vacuum coating, Film Optics performance (such as refractive index n) with collapse to count etc. and produce a very large impact.The technical process of present industrial preparation higher degree magnesium fluoride is first hydrofluoric acid and magnesiumcarbonate to be carried out chemosynthesis, then with the step of resultant through washing, filtration, drying, Mechanical Crushing, granulation, again at shielding gas (NH
4HF
2) condition that exists bends down vacuum sintering, can obtain content after the cooling and reach 99% hydration magnesium fluoride (MgF
2X H
2O).But above-mentioned technique also exists a lot of shortcomings: 1. crystal water content is higher in the product, and the magnesium fluoride crystal formation is little, pore is many, has the phenomenons such as specific refractory power departs from after venting, splash and the film forming during plated film; 2. drying process is weightless large, causes product proportion little, and single furnace output is low; 3. the magnesium fluoride particle is mechanical compaction gained but not Nature creating, and pressing process has dust to produce to pollute the environment and human body, and need to add a small amount of binding agent during compacting, will be cracked into powdery when long-term storage or the moisture absorption, and product is unstable; 4. in the process of rough vacuum dehydration, added shielding gas NH
4HF
2, the latter has pollution to environment, has increased simultaneously production cost; 5. the content of magnesium oxide (MgO) is higher in the product, has affected purity and the quality of product, makes the transmitance of magnesium fluoride crystal low, easily splashes during plated film, and generation is collapsed a little many.
The novel magnesium fluoride preparation technology of magnesium oxide impurity and crystal water content has to be developed in reduction cost, minimizing pollution, the minimizing product.
Summary of the invention
The object of the invention is to provide a kind of technique of preparing 5-20 mm high-purity polycrystalline magnesium fluoride by liquid crystallization, and its magnesium fluoride particle is that self-assembling formation but not mechanical compaction get, and preparation process need not to add shielding gas, not only reduces pollution but also reduce cost; Magnesium oxide impurity and crystal water content are extremely low in the magnesium fluoride product that makes, and product purity is high, produce during plated film to collapse a little to lack; Low and the proportion of the specific surface area of product increases, and input-output ratio improves.
Concrete technical scheme of the present invention is:
A kind of technique of preparing 5-20 mm high-purity polycrystalline magnesium fluoride by liquid crystallization adopts magnesiumcarbonate (Mg
2CO
3) the mode in the hydrofluoric acid (HF) of joining fluoridizes and generate hydration magnesium fluoride crystallite, then make first hydration magnesium fluoride crystallite carry out single crystal growing, move into and carry out polycrystalline growth in the polycrystalline maker, move into sintering in the vertical barrel type three-temperature-zone sintering oven at last again, namely obtain content after the cooling and be 99.99% high-purity polycrystalline magnesium fluoride.Concrete processing step is as follows:
(1) be first that 40% hydrofluoric acid adds in the reactor with concentration, add again magnesiumcarbonate (wherein content of magnesia 〉=41%), add hydrofluoric acid and magnesiumcarbonate mass ratio be 1: 1, the uniform stirring (reaction equation: Mg that reacts fully
2CO
3+ HF → MgF
2XH
2O+CO
2+ H
2O), generate hydration magnesium fluoride crystallite behind the reaction terminating, mother liquor is the hydrofluoric acid solution of PH=3～4 after the reaction;
(2) the hydration magnesium fluoride crystallite that generates is incubated 24 hours under 100 ℃～105 ℃ temperature, to carry out liquid single crystal growth, the magnesium fluoride single crystal of generating center particle diameter D50 〉=22 μ m;
(3) mother liquor (mother liquor can reuse) of sucking-off clarification moves into the polycrystalline growth device with the magnesium fluoride single crystal, and polycrystalline growth was carried out in insulation in 20 hours under 140 ℃～150 ℃ temperature, and generating particle diameter is the magnesium fluoride polycrystal of 5～20mm;
(4) with the magnesium fluoride polycrystal in the quartzy sintering oven of three warm areas of vertical barrel type under 500 ℃～550 ℃ temperature atmosphere sintering 24 hours;
(5) cooling is 24 hours, namely gets the high-purity polycrystalline magnesium fluoride that particle diameter is 5～20mm, its purity 〉=99.99%, crystal water content≤0.005%, content of magnesia≤0.001%.
In the existing technique, behind hydrofluoric acid and magnesiumcarbonate generation hydration magnesium fluoride crystallite, adopted and first hydration magnesium fluoride crystallite washed, under 150 ℃ temperature, carried out again dry mode, the crystal water content high (being about 0.5%) of the hydration magnesium fluoride crystallite that generates, pore is many, crystal formation is little, specific surface area is large, dry after weightlessness many (about 11%).And technique of the present invention replaces the liquid single crystal process of growth of step (2) and the polycrystalline growth process of step (3), namely under 100 ℃～105 ℃ temperature, be incubated 24 hours first and carry out the liquid single crystal growth, then without cleaning, directly polycrystalline growth was carried out in insulation in 20 hours under 140 ℃～150 ℃ temperature, the crystal water content low (≤0.005%) of the hydration magnesium fluoride crystallite that therefore generates, crystal formation large (being tetragonal body polycrystalline state structure), specific surface area is little, and in weightlessness after the polycrystalline growth only below 7%, obviously be less than dry rear about 11% weightlessness in the existing technique, product proportion improves, and single furnace output also improves.
In the existing technique, needing after the drying that hydration magnesium fluoride crystallite elder generation machinery is broken for the powder of particle diameter below 100 μ m, add again a small amount of binding agent powder is cold-pressed into sheet (being granulation), but the process of Mechanical Crushing has dust and produces, not only contaminate environment but also cause loss, in a single day binding agent makes moist or because long-term storage lost efficacy, then can cause product again to be cracked into powder, poor stability simultaneously.And technique of the present invention is by the magnesium fluoride single crystal being moved into the polycrystalline growth device, insulation was carried out polycrystalline growth in 20 hours and is directly generated the magnesium fluoride polycrystal that particle diameter is 5～20mm under 140 ℃～150 ℃ temperature, be that particle is self-assembling formation, not only need not Mechanical Crushing but also needn't add binding agent, environmentally safe, product is lossless and good stability, has saved simultaneously artificial and other costs.
In the existing technique, for reducing magnesian generation, the rough vacuum sintering process after the granulation need to add the shielding gas NH that environment is had pollution
4HF
2Only pipe so, also have crystal water content high (about 0.5%) in the product, pore is many, specific surface area is large, the problem that oxidation-resistance is poor, still very easily generate magnesium oxide (about 0.5%), the phenomenons such as the crystal transmitance is low after venting when causing plated film, splash, the film forming, specific refractory power departs from, generation is collapsed a little many during plated film.And technique of the present invention need not to add shielding gas, has not only reduced cost but also non-environmental-pollution; The even internal structure that in monocrystalline and polycrystalline growth process, forms simultaneously, can farthest get rid of pore and remaining crystal water (≤0.005%) for the impact of coating process, on the other hand, because sintering condition is abundant, the content of magnesia extremely low (≤0.001%) that generates, not splash when therefore having plated film, the pre-molten time is short and film refractive index departs from the advantages such as little.
In sum, the technique of preparing 5-20 mm high-purity polycrystalline magnesium fluoride by liquid crystallization of the present invention has the following advantages: 1. adopt monocrystalline and polycrystalline growth process to replace and wash first dry again mode in the existing technique, greatly reduced the content of crystal water in the product; 2. by monocrystalline and the complete tetragonal body crystal formation of polycrystalline growth process Nature creating, the step that need not carry out Mechanical Crushing and granulation, so no dust pollution, product-free loss, must not add binding agent, in protection of the environment, reduced production cost; 3. sintering process need not add the shielding gas that environment is had pollution, has not only reduced cost but also protection of the environment; 4. sintering condition is abundant, generate magnesian may be extremely low.5～20mm high-purity polycrystalline magnesium fluoride of preparing with technique of the present invention has the following advantages: 1. crystal formation is Nature creating, and particle is large and internal structure is even, and remaining crystal water content is few, is difficult for during plated film splashing; 2. specific surface area is little, than great, and the total significant quantity of crystal in the stove in the time of can guaranteeing the crystal growth, single pass yield is high, is 2 times that existing technique is prepared magnesium fluoride output; 3. the crystal formation internal structure of Nature creating is uniform and stable, and anti-adsorption conditions is good, can long storage time, be difficult for oxidation and deliquescence; 4. crystal formation is large, and specific surface area is little, thus little with the surface in contact of air, can be in atmosphere direct sintering and magnesium oxide generates few; 5. purity high (〉=99.99%), impure few (remaining crystal water≤0.005%, magnesium oxide≤0.001%), the crystal transmitance is high, and what produce during plated film collapses a little less, and yield rate is high; 6. product particle is evenly distributed, and particle diameter can directly be supplied with the player whose turn comes next and use between 5～20mm, is widely used in the fields such as magnesium fluoride monocrystal material, Coating Materials, anti-fake material, sensitive materials, far-infrared material.
Embodiment
Below further describe the present invention by embodiment, as known by the technical knowledge, the present invention also can describe by other the scheme that does not break away from the technology of the present invention feature, thus all within the scope of the present invention or the change that is equal in the scope of the invention all be included in the invention.
Embodiment 1
The high-purity polycrystalline magnesium fluoride for preparing 5～20mm according to following technique:
(1) be first that 40% hydrofluoric acid adds in the reactor with concentration, add again magnesiumcarbonate (wherein content of magnesia 〉=41%), add hydrofluoric acid and magnesiumcarbonate mass ratio be 1: 1, the uniform stirring (reaction equation: Mg that reacts fully
2CO
3+ HF → MgF
2XH
2O+CO
2+ H
2O), generate hydration magnesium fluoride crystallite behind the reaction terminating, mother liquor is the hydrofluoric acid solution of PH=3～4 after the reaction;
(2) the hydration magnesium fluoride crystallite that generates is incubated 24 hours under 100 ℃～105 ℃ temperature, to carry out liquid single crystal growth, the magnesium fluoride single crystal of generating center particle diameter D50 〉=22 μ m;
(3) (mother liquor can reuse the mother liquor of sucking-off clarification, and the magnesium fluoride single crystal is moved into the polycrystalline growth device, and polycrystalline growth was carried out in insulation in 20 hours under 140 ℃～150 ℃ temperature, and generating particle diameter is the magnesium fluoride polycrystal of 5～20mm;
(4) with the magnesium fluoride polycrystal in the quartzy sintering oven of three warm areas of vertical barrel type under 500 ℃～550 ℃ temperature atmosphere sintering 24 hours;
(5) cooling is 24 hours, namely gets the high-purity polycrystalline magnesium fluoride that particle diameter is 5～20mm, its purity 〉=99.99%, crystal water content≤0.005%, content of magnesia≤0.001%.
Claims (1)
1. the technique of a preparing 5-20 mm high-purity polycrystalline magnesium fluoride by liquid crystallization is characterized in that, comprises the steps:
(1) be first that 40% hydrofluoric acid adds in the reactor with concentration, add again magnesiumcarbonate, content of magnesia 〉=41% wherein, add hydrofluoric acid and magnesiumcarbonate mass ratio be 1: 1, uniform stirring reacts fully, reaction equation: Mg
2CO
3+ HF → MgF
2XH
2O+CO
2+ H
2O generates hydration magnesium fluoride crystallite behind the reaction terminating, mother liquor is the hydrofluoric acid solution of pH=3～4 after the reaction;
(2) the hydration magnesium fluoride crystallite that generates is incubated 24 hours under 100 ℃～105 ℃ temperature, to carry out liquid single crystal growth, the magnesium fluoride single crystal of generating center particle diameter D50 〉=22 μ m;
(3) mother liquor of sucking-off clarification, described mother liquor can reuse, and the magnesium fluoride single crystal is moved into the polycrystalline growth device, and polycrystalline growth was carried out in insulation in 20 hours under 140 ℃～150 ℃ temperature, and generating particle diameter is the magnesium fluoride polycrystal of 5～20mm;
(4) with the magnesium fluoride polycrystal in the quartzy sintering oven of three warm areas of vertical barrel type under 500 ℃～550 ℃ temperature sintering 24 hours in the atmosphere;
(5) cooling is 24 hours, namely gets the high-purity polycrystalline magnesium fluoride that particle diameter is 5～20mm, its purity 〉=99.99%, crystal water content≤0.005%, content of magnesia≤0.001%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010202805 CN101850995B (en) | 2010-06-18 | 2010-06-18 | Process for preparing 5-20mm high-purity polycrystalline magnesium fluoride by liquid crystallization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010202805 CN101850995B (en) | 2010-06-18 | 2010-06-18 | Process for preparing 5-20mm high-purity polycrystalline magnesium fluoride by liquid crystallization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101850995A CN101850995A (en) | 2010-10-06 |
| CN101850995B true CN101850995B (en) | 2013-02-13 |
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|---|---|---|---|
| CN 201010202805 Expired - Fee Related CN101850995B (en) | 2010-06-18 | 2010-06-18 | Process for preparing 5-20mm high-purity polycrystalline magnesium fluoride by liquid crystallization method |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2708509A1 (en) * | 2012-09-18 | 2014-03-19 | Nanofluor GmbH | Process for the production of magnesium fluoride sol solutions from alkoxides comprising addition of carbon dioxide |
| CN103422170B (en) * | 2013-07-29 | 2016-03-30 | 齐钰 | A kind of disc magnesium fluoride MgF 2crystal coating material and production method thereof |
| CN113955778B (en) * | 2021-11-08 | 2023-02-14 | 大连理工大学 | A kind of preparation method of high-purity magnesium fluoride powder |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3920802A (en) * | 1974-03-04 | 1975-11-18 | Kewanee Oil Co | Process for preparation of hot-pressable magnesium fluoride |
| CN1046511A (en) * | 1989-04-14 | 1990-10-31 | 罗纳-布朗克化学公司 | Preparation of magnesite, its application in magnesium fluoride preparation technology and the magnesium fluoride that makes like this |
| CN101100303A (en) * | 2007-08-14 | 2008-01-09 | 赵益 | Method for preparing high purity magnesium fluoride powder |
| CN101549878A (en) * | 2008-04-03 | 2009-10-07 | 天津市风船化学试剂科技有限公司 | Method for preparing magnesium fluoride powder capable of being hot pressed |
-
2010
- 2010-06-18 CN CN 201010202805 patent/CN101850995B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3920802A (en) * | 1974-03-04 | 1975-11-18 | Kewanee Oil Co | Process for preparation of hot-pressable magnesium fluoride |
| CN1046511A (en) * | 1989-04-14 | 1990-10-31 | 罗纳-布朗克化学公司 | Preparation of magnesite, its application in magnesium fluoride preparation technology and the magnesium fluoride that makes like this |
| CN101100303A (en) * | 2007-08-14 | 2008-01-09 | 赵益 | Method for preparing high purity magnesium fluoride powder |
| CN101549878A (en) * | 2008-04-03 | 2009-10-07 | 天津市风船化学试剂科技有限公司 | Method for preparing magnesium fluoride powder capable of being hot pressed |
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