CN106745111B - A kind of preparation method of high-specific area nano crystalline substance magnesium fluoride - Google Patents
A kind of preparation method of high-specific area nano crystalline substance magnesium fluoride Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of high-specific area nano crystalline substance magnesium fluoride.It is to solve the problems such as that there are high temperature specific surface areas is small, thermostabilization is poor, existing preparation method is costly, complicated in prepared by magnesium fluoride, pollution weight.The high-specific surface area of the present invention, the preparation method of nanocrystalline magnesium fluoride include the following steps：(1) prepare the presoma of source containing magnesium, polyol solvent and coagulant component solution, flow back at 20~80 DEG C；(2) fluorination reagent is added to the solution that (1) obtains to be fluorinated, the aging acquisition lyosol at 100~160 DEG C；(3) lyosol at 140~200 DEG C is dried to obtain solid gel, is finally roasted at 350 DEG C~450 DEG C and nano magnesium fluoride is made.
Description
Technical field
The present invention relates to a kind of Gao Bibiao to accumulate magnesium fluoride, and in particular to large specific surface area, nanocrystalline fluorination under a kind of high temperature
Mild, the simple and environmental-friendly preparation method of magnesium.
Background technology
Magnesium fluoride (MgF2) have been widely used as a kind of important chemical industry, optics and catalysis material, tool.It can be used as
The additive of electrolytic aluminium, the fluxing agent of smelting magnesium, titanium pigment apply agent, cathode-ray screen fluorescent material.While it
Be also a kind of infrared optical material of water white transparency, have it is wider through range and high transmitance, for making infrared light
Optical element in system.In addition, MgF2Being one kind existing steadily in the long term under corrosivity HF, HCl atmosphere can be catalyzed material
Material, it is often more important that, its surface alkalinity is weak, with SiO2It is similar to tend to chemical inertness, it is easy to by introducing different metal
Ion accurate modulation MgF in wider range2Catalyst surface acid-base property, thus catalyst or carrier are can be used as corrosivity
Catalysis reaction under atmosphere.For example, at present would generally during industrial production hydrofluorocarbon (HFCs), HF hydrocarbon (HFOs)
It is related to gas phase fluorination or de-hydrogen halide, usually uses MgF2Loaded catalyst.Because it has weaker soda acid
Property, side reaction is few in above-mentioned reaction, stability is good, shows preferable application prospect.
MgF2As catalytic carrier, it is necessary to have big specific surface area, considerable catalytic activity could be obtained.In addition, mesh
Preceding major part gas phase fluorination or de-hydrogen halide are carried out at 300~500 DEG C, therefore MgF2It must when as catalytic carrier
There must be certain high high-temp stability that can smoothly use.Domestic and international correlation prepares bigger serface MgF2Document, patent
It is less, it is more than 60m more particularly to specific surface area2/ g and the high-specific surface area MgF that can be stabilized at high temperature2Preparation.Base
In this, high-specific surface area, nanocrystalline M gF are prepared2It is very great to exploitation high activated catalyst or coating material meaning.
In only report, Germanization scholar Kemnitz seminars are source metal with metal alkoxide, such as magnesium methoxide, anhydrous
Alcohol, the ether solvents of HF are Fluorine source, and specific surface area, which can be made, by anhydrous sol-gel fluoride process is more than 100m2The Gao Bibiao of/g
Area, amorphous MgF2(Erhard Kemnitz, Catal.Sci.Technol., 2015,5,786).Chinese patent
CN104437567 discloses a kind of specific surface area and is more than 140m2The MgF of/g2The preparation method of base catalyst is to not soluble in water
Metal magnesium salts carry out back flow reaction in the presence of surfactants, then perfluorinated processing obtains.Chinese patent CN103482661
It discloses a kind of specific surface area and is more than 150m2The MgF of/g2Preparation method, be in the presence of acetate that soluble magnesium salt is water-soluble
Liquid mutually mixes with ammonium fluoride aqueous solution and obtains MgF2Presoma, then fired obtained nanometer MgF2.Chinese patent CN104071814 is public
It has opened a kind of specific surface area and has been more than 70m2The MgF of/g2Preparation method, be in the presence of carbon source by soluble magnesium saline solution
It is mutually mixed with ammonium fluoride aqueous solution and obtains MgF2Presoma, then be carbonized in advance through high temperature, high temperature cabonization and high temperature are except carbon obtains MgF2。
The MgF of above-mentioned report2Preparation method still at least has problems with：(1) anhydrous sol-gel fluoride process be with
Expensive organic metal is that the organic solvent of source metal and anhydrous HF is Fluorine source, and this method must be grasped in anhydrous conditions
Make, process is complicated, it is difficult to be applicable in industrial production, while gained MgF2Unstable under high temperature for impalpable structure, easy crystallization is low
Specific surface area fluoride；(2) although carbonization fluoride process raw material is easy to get, technological process is complicated, need to be repeated high temperature cabonization and
Except carbon process, high energy consumption, and when temperature is higher than 350 DEG C, magnesium fluoride specific surface area is dropped rapidly to 30m2/ g or so；(3)
Acetate method is although easy to operate, but required acetate concentration is high, dosage is big, and cost is higher, is unsuitable for industrial production.(4) it returns
Stream reaction is using magnesium source not soluble in water, and product is lost in seriously, and back flow reaction energy consumption is higher.
Invention content
In view of the defects existing in the prior art with deficiency, simple, operation that the object of the present invention is to provide a kind of preparation methods
Mildly, environmental-friendly, the low nano magnesium fluoride of production cost preparation method.This magnesium fluoride of the present invention has specific surface area
Greatly, pore passage structure is adjustable, mesopore orbit is abundant, grain size is in nanoscale, is easy to be doped catalyst, be modified, to obtain
Obtain the catalytic performance of high activity, high stability.
Sol-gel method under polyol systems is that high-specific surface area, nanoscale fluorination are prepared under a kind of temperate condition
The high efficiency method of magnesium.In this mild fluorination process, with magnesium source ion ligand complex effect occurs for polyol solvent, it is suppressed that institute
It generates the growth of fluoride crystal grain, reunite, the generation for preventing fluoride to precipitate, to generate sol-gel process, most throughout one's life
At grain size within nanometer range magnesium fluoride particle.In addition, by the modulation to polyalcohol, the coordination of magnesium source ion therewith can be made
Ability changes, and the magnesium fluoride of generation is made to be grown by various grain sizes, to obtain with different specific surfaces, pore passage structure
Magnesium fluoride crystallite.In addition, different magnesium source is not significantly affected by the sol gel in preparing in this sol-gel process
Process has more wide in range use scope.
In order to realize above-mentioned technical assignment, the present invention is realised by adopting the following technical scheme：
A kind of preparation method of high-specific area nano crystalline substance magnesium fluoride, includes the following steps：
(1) magnesium source, coagulant and polynary alcohol phase are mixed, flow back 6h or more at 20 DEG C~80 DEG C, obtains reaction solution A；
The magnesium source is magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium methoxide, one kind in magnesium acetate or arbitrary several combination
Composition；
Polyalcohol is a kind of in ethylene glycol, tirethylene glycol, 1,3- propylene glycol, 1,2- propylene glycol, glycerine or arbitrary several
The group of kind is combined into；
Coagulant is polyethylene glycol, polyvinylpyrrolidone, peregal, citric acid, cyclodextrin, polyvinyl alcohol, epoxy second
A kind of or arbitrarily several group is combined into alkane, and the mass ratio of magnesium source and coagulant is 1:0.5~10；
(2) under stiring, fluorination reagent is added to and carries out fluorination treatment in reaction solution A, continue to stir 6h after addition
More than, obtain lyosol；
The fluorination reagent is hydrogen fluoride, one kind in ammonium fluoride aqueous solution, the molar ratio in fluorination reagent and magnesium source is 3~
6:1；
(3) lyosol is stood to aging for 24 hours or more at 100 DEG C~160 DEG C, obtains solid gel；
(4) by solid gel at 140 DEG C~200 DEG C it is dry for 24 hours more than, finally roasted at 350 DEG C~450 DEG C 4h with
On, high-specific surface area, nanocrystalline magnesium fluoride is made.
Further, in step (2), a concentration of 20wt.%~90wt.% of the fluorination reagent；It is described in step (4)
Roasting is to carry out under an oxygen-containing atmosphere；The magnesium fluoride has crystal form, and specific surface area is 60~200m after roasting2/ g, aperture point
Cloth concentrates on 15~30nm, and centralized particle diameter is in 27~68nm.
Beneficial effects of the present invention：Compared with prior art, the present invention with following beneficial technique effect：
1. compared with anhydrous sol-gel fluoride process, carbonization fluoride process, acetate fluoride process and back flow reaction fluoride process,
A kind of high-specific surface area that the present invention provides raw materials to be easy to get, easy to operate, preparation condition is mild, low energy consumption, environmental-friendly is received
The preparation method of the brilliant magnesium fluoride of rice；2. preparation method provided by the invention can be easily achieved to made magnesium fluoride specific surface area,
Duct, particle size, crystal form modulation, can be made specific surface area be more than 60m2/ g, crystallite dimension are nanocrystalline within 70nm
Magnesium fluoride, and magnesium fluoride obtained by anhydrous sol-gel fluoride process is amorphous, high-temperature roasting specific surface area can decline rapidly, carbon
Changing fluoride process need to roast through multiple high temp, high energy consumption, and acetate fluoride process is big to acetate dosage, of high cost, back flow reaction
There is also products to be lost in serious, high energy consumption problem for method；3. the present invention has no special requirements to magnesium source used, applicability is wide, cost
It is low；4. made magnesium fluoride colloidal sol of the invention has the characteristics that corrosivity is small, it is easy to carry out material surface coating；5. using Gao Bibiao
Area nanometer crystalline substance magnesium fluoride does catalytic carrier, it can be achieved that catalysis of the reaction temperature more than 350 DEG C is reacted.
Description of the drawings
Fig. 1 is the X-ray diffractogram of high-specific area nano crystalline substance magnesium fluoride
Fig. 2 is the adsorption isothermal curve figure of high-specific area nano crystalline substance magnesium fluoride
Specific implementation mode
Embodiment 1：Prepare high-specific surface area, nanocrystalline magnesium fluoride
1.0M magnesium source is dissolved in 50mL polyol solvents, reflow treatment 6h under being stirred at 20~80 DEG C, then fluorination is tried
Agent is added drop-wise under stiring in above-mentioned solution, and time for adding 30min is stirred for 6h after being added dropwise, obtains lyosol；So
Afterwards more than static aging for 24 hours solid gel is obtained at 100~160 DEG C；Again at 140~200 DEG C more than drying for 24 hours, finally
4h or more is roasted at 350~450 DEG C of air atmosphere, and high-specific area nano crystalline substance magnesium fluoride under high temperature is made.It is different magnesium sources, polynary
Magnesium fluoride texture property obtained is shown in Table 1 under alcoholic solvent, coagulant, fluorination reagent, calcination temperature.
The magnesium fluoride physico-chemical property result of 1 embodiment 1 of table
Embodiment 2：Prepare high-specific area nano crystalline substance magnesium fluoride
1.0M magnesium nitrates and polyethylene glycol are dissolved in 50mL ethylene glycol, reflow treatment 6h under being stirred at 30 DEG C, then by HF
Aqueous solution (40wt.%) is added drop-wise under stiring in above-mentioned solution, and time for adding 30min is stirred for 6h after being added dropwise, obtains
To lyosol；Then more than static aging for 24 hours solid gel is obtained at 100 DEG C；Again at 140 DEG C more than drying for 24 hours,
4h or more is finally roasted at 400 DEG C, and high-specific area nano crystalline substance magnesium fluoride under high temperature is made.Different polyethylene glycol dosages are made
Magnesium fluoride texture be shown in Table 2.
The magnesium fluoride physico-chemical property result of 2 embodiment 2 of table
Embodiment 3：Prepare high-specific area nano crystalline substance magnesium fluoride
By 1.0M magnesium nitrates and polyethylene glycol, (Mg/ gelling agent mass ratioes are 1:3) it is dissolved in 50mL ethylene glycol, is stirred at 30 DEG C
Lower reflow treatment 6h is mixed, then HF aqueous solutions are added drop-wise under stiring in above-mentioned solution, time for adding 30min is added dropwise
After be stirred for 6h, obtain lyosol；Then more than static aging for 24 hours solid gel is obtained at 100 DEG C；Again at 140 DEG C
More than drying for 24 hours, 4h or more is finally roasted at 400 DEG C, high-specific area nano crystalline substance magnesium fluoride under high temperature is made.Different HF are dense
Degree magnesium fluoride texture obtained is shown in Table 3.
The magnesium fluoride physico-chemical property result of 3 embodiment 3 of table
Embodiment 4：Prepare high-specific area nano crystalline substance magnesium fluoride
By 1.0M magnesium nitrates and polyethylene glycol, (Mg/ gelling agent mass ratioes are 1:3) it is dissolved in 50mL ethylene glycol, is stirred at 30 DEG C
Lower reflow treatment 6h is mixed, then HF aqueous solutions (40wt.%) are added drop-wise under stiring in above-mentioned solution, time for adding 30min,
It is stirred for 6h after being added dropwise, obtains lyosol；Then more than static aging for 24 hours solid gel is obtained at 100 DEG C；Again
At 140 DEG C more than drying for 24 hours, 4h or more is finally roasted at 400 DEG C, and high-specific area nano crystalline substance under high temperature is made and is fluorinated
Magnesium.Magnesium fluoride texture is shown in Table 4 made from different Mg/HF molar ratios.
The magnesium fluoride physico-chemical property result of 4 embodiment 4 of table
Embodiment 5：Prepare high-specific area nano crystalline substance magnesium fluoride
By 1.0M magnesium nitrates and polyethylene glycol, (Mg/ gelling agent mass ratioes are 1:3) it is dissolved in 50mL ethylene glycol, is stirred at 30 DEG C
Lower reflow treatment 6h is mixed, then HF aqueous solutions (40wt.%) are added drop-wise under stiring in above-mentioned solution, time for adding 30min,
It is stirred for 6h after being added dropwise, obtains lyosol；Then more than static aging for 24 hours solid gel is obtained at 100 DEG C；Again
At 140 DEG C more than drying for 24 hours, 4h or more is finally roasted at 400 DEG C, and high-specific area nano crystalline substance under high temperature is made and is fluorinated
Magnesium.Magnesium fluoride texture obtained is shown in Table 5 under different atmosphere.
The magnesium fluoride physico-chemical property result of 5 embodiment 5 of table
Claims (4)
1. a kind of preparation method of high-specific area nano crystalline substance magnesium fluoride, includes the following steps：
(1) magnesium source, coagulant and polynary alcohol phase are mixed, flow back 6h or more at 20 DEG C~80 DEG C, obtains reaction solution A；
The magnesium source is that magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium methoxide, one kind in magnesium acetate or arbitrary several group are combined into；
Polyalcohol is a kind of in ethylene glycol, tirethylene glycol, 1,3- propylene glycol, 1,2- propylene glycol, glycerine or arbitrary several
Group is combined into；
Coagulant is in polyethylene glycol, polyvinylpyrrolidone, peregal, citric acid, cyclodextrin, polyvinyl alcohol, ethylene oxide
A kind of or arbitrary several group is combined into, and the mass ratio of magnesium source and coagulant is 1:0.5~10；
(2) under stiring, fluorination reagent is added to and carries out fluorination treatment in reaction solution A, continue to stir 6h or more after addition,
Obtain lyosol；
The fluorination reagent is hydrogen fluoride, one kind in ammonium fluoride aqueous solution, and the molar ratio in fluorination reagent and magnesium source is 3~6:1；
(3) lyosol is stood to aging for 24 hours or more at 100 DEG C~160 DEG C, obtains solid gel；
(4) solid gel more than drying for 24 hours, is finally roasted into 4h or more at 140 DEG C~200 DEG C at 350 DEG C~450 DEG C,
High-specific area nano crystalline substance magnesium fluoride is made.
2. the preparation method of high-specific area nano crystalline substance magnesium fluoride as described in claim 1, which is characterized in that the fluorination examination
A concentration of 20wt.%~90wt.% of agent.
3. the preparation method of high-specific area nano crystalline substance magnesium fluoride as described in claim 1, which is characterized in that the step
(4) roasting is to carry out under an oxygen-containing atmosphere in.
4. the preparation method of high-specific area nano crystalline substance magnesium fluoride as described in claim 1, which is characterized in that the magnesium fluoride
With crystal form, specific surface area is 60~200m after roasting2/ g, pore-size distribution concentrate on 15~30nm, and centralized particle diameter is in 27
~68nm.
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| CN108941610B (en) * | 2018-09-19 | 2021-07-16 | 西京学院 | Method for preparing hydrogen storage magnesium-nickel alloy nano powder based on polyol method |
| CN109718813B (en) * | 2018-12-17 | 2022-02-22 | 西安近代化学研究所 | Chromium-free environment-friendly catalyst for gas-phase fluorination synthesis of 3,3, 3-trifluoropropene |
| CN109499589B (en) * | 2018-12-17 | 2021-11-23 | 西安近代化学研究所 | Chromium-free environment-friendly catalyst for gas-phase fluorination synthesis of 1,1,1,3,3, 3-hexafluoro-2-butene |
| CN109718814B (en) * | 2018-12-17 | 2022-02-22 | 西安近代化学研究所 | Low-temperature ultrahigh-activity environment-friendly catalyst for synthesizing trans-1, 3,3, 3-tetrafluoropropene through gas phase isomerization |
| CN109485080A (en) * | 2018-12-17 | 2019-03-19 | 西安近代化学研究所 | The low cost preparation method of high-specific surface area aluminum fluoride |
| CN109746006A (en) * | 2018-12-20 | 2019-05-14 | 西安近代化学研究所 | Gas phase dehydrofluorination synthesizes 1,3,3,3- tetrafluoropropene with long-life, environmental protection catalyst |
| CN109499590A (en) * | 2018-12-25 | 2019-03-22 | 西安近代化学研究所 | 1,1,1,3,3- pentafluoropropane dehydrofluorination prepares 1,3,3,3- tetrafluoropropene magnesium-base catalyst |
| CN114082386B (en) * | 2021-12-06 | 2022-09-06 | 大连理工大学 | Device and method for semi-continuously synthesizing high-purity magnesium fluoride |
| CN115920932A (en) * | 2022-11-28 | 2023-04-07 | 中船(邯郸)派瑞特种气体股份有限公司 | Preparation method of catalyst for fluorine-chlorine exchange |
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| CN102674411A (en) * | 2012-04-13 | 2012-09-19 | 中国人民解放军第二炮兵工程学院 | Direct precipitation synthesis method of spherical nano magnesium fluoride |
| CN103482661A (en) * | 2013-09-30 | 2014-01-01 | 浙江工业大学 | Synthetic method of nanometer magnesium fluoride with high specific surface area |
| CN104071814A (en) * | 2014-02-28 | 2014-10-01 | 浙江工业大学 | Preparation method of magnesium fluoride with high specific surface area |
| CN104437567A (en) * | 2014-11-20 | 2015-03-25 | 西安近代化学研究所 | Magnesium fluoride-based catalyst and application of magnesium fluoride-based catalyst |
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| CN102674411A (en) * | 2012-04-13 | 2012-09-19 | 中国人民解放军第二炮兵工程学院 | Direct precipitation synthesis method of spherical nano magnesium fluoride |
| CN103482661A (en) * | 2013-09-30 | 2014-01-01 | 浙江工业大学 | Synthetic method of nanometer magnesium fluoride with high specific surface area |
| CN104071814A (en) * | 2014-02-28 | 2014-10-01 | 浙江工业大学 | Preparation method of magnesium fluoride with high specific surface area |
| CN104437567A (en) * | 2014-11-20 | 2015-03-25 | 西安近代化学研究所 | Magnesium fluoride-based catalyst and application of magnesium fluoride-based catalyst |
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