CN106032284B - A kind of preparation method that temperature hexa-aluminate is formed with low phase - Google Patents
A kind of preparation method that temperature hexa-aluminate is formed with low phase Download PDFInfo
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Abstract
The present invention relates to a kind of hexa-aluminate preparation method that temperature is formed with low phase, specific preparation process is that barium salt and aluminium salt are placed in organic solvent, under heating condition, stirring is up to after salt dissolving, salt dissolving, reaction system is set to be cooled to 30~100 DEG C under agitation, and continue to stir with this understanding, mixing time is not less than 3h, adds water and is co-precipitated, ethanol elution, dry, temperature-programmed calcination obtains the hexa-aluminate of single crystalline phase.Compared to other preparation methods, the preparation method reaction condition is gentle, simple to operate and time-consuming few, and what is obtained is the hexa-aluminate of single crystalline phase, while can largely be synthesized.
Description
Technical field
The invention belongs to prepare hexa-aluminate field, and in particular to a kind of preparation that temperature hexa-aluminate is formed with low phase
Method.
Background technology
Hexa-aluminate composite oxides as novel inorganic functional material, since being produced from 20 century 70s,
It is widely used research in many fields.For example, superconductor, fluorescent material, laser material etc. can be done.Particularly make
For the catalysis material of high temperature catalytic combustion reaction has obtained more extensive research.But hexa-aluminate mutually formation temperature high (>
1200 DEG C) caused by low specific surface area (<20m2/ g) turn into its key constraints applied.Therefore, hexa-aluminate is reduced
Mutually forming temperature turns into an important content of hexa-aluminate research.
The primary synthetic methods of current hexa-aluminate include solid reaction process, alkoxide hydrolysis, ammonium carbonate coprecipitation with
And microemulsion method.By grinding come the uniform metal ion mixed in presoma, this mechanical mix techniques are obtained solid reaction process
The sample mixture homogeneity for arriving is not high, therefore the mutually formation temperature of hexa-aluminate is usual at 1400-1500 DEG C.Ammonium carbonate is co-precipitated
For method is compared to solid reaction process, mutually generates temperature and be reduced to 1200 DEG C or so, but hexa-aluminate compares table at this temperature
Area is still very low.By alkoxide hydrolysis and microemulsion method, the mutually formation temperature of hexa-aluminate is minimum drop to 1000 DEG C~
Between 1100 DEG C, this is also the minimum for mutually generating temperature of current document report.Exactly it is with this low mutually formation temperature
Premise, the hexa-aluminate specific surface area highest synthesized using microemulsion method can be more than 100m2/g.But alkoxide hydrolysis need
Carried out under conditions of inert atmosphere isolation steam, severe reaction conditions.Microemulsion method is except facing above mentioned problem, while closing every time
Too low into the end-product amount for obtaining, when the total amount of reaction system is 50g, the final product of synthesis is less than 0.1g, it is difficult to carry out
Extensive synthesis.Therefore, explore a kind of more simple preparation method becomes one to reduce the mutually formation temperature of hexa-aluminate
Plant inevitable choice.
The content of the invention
Mutually form temperature and relatively low specific surface area for higher when preparing hexa-aluminate, and harshness reaction condition
The problems such as, the purpose of the present invention is to provide a kind of with the low hexa-aluminate preparation method for mutually forming temperature, six described aluminium
Hydrochlorate is a kind of hexa-aluminate with low crystalline formation temperature and not comprising other dephasigns, the method reaction condition temperature
With operating process is simple.
The technical scheme is that：
1) barium salt and aluminium salt are placed in organic solvent, under heating condition, stirring is until salt dissolving；
2) after salt dissolving, reaction system is made to be cooled to 30~100 DEG C under agitation, and continue to stir with this understanding
Mix, mixing time is not less than 3h, adds water and is co-precipitated, ethanol elution, dry, temperature-programmed calcination obtains single crystalline substance
The hexa-aluminate of phase.
Described barium salt is barium nitrate, and described aluminium salt is aluminium isopropoxide and/or aluminium secondary butylate, step 1) in, aluminium ion
It is 9.15~12 with the mol ratio of barium ions；
Described organic solvent is DMF (DMF), and the addition of organic solvent is every addition 12mmol
Aluminium ion, DMF add 10~90ml.
Step 1) in, heating-up temperature is 110 DEG C~130 DEG C, and mixing time is 2~4h.
Step 2) in, mixing time is 3~4h.
Precipitating reagent in this reaction is dimethylamine (C2H7N), it is to be decomposed to produce by organic solvent DMF
Raw, decomposition reaction formula is C2H7NCO→C2H7N+CO, the reaction is alkali catalyzed and accelerates, and base catalyst refers to different reactant
Aluminium propoxide or aluminium secondary butylate.
Step 2) in, the amount of water (mole) during co-precipitation is [nBa×2+nAl× 3] 1.0~1.3 times.
Step 2) in, the condition of temperature-programmed calcination is：In moving air, risen to the heating rate of 5~10 DEG C/min
1100~1300 DEG C, 2~6h of roasting time.
Beneficial effects of the present invention are：
1. the preparation method reaction condition is gentle, simple to operate and time-consuming few, prepares mutually formation temperature during hexa-aluminate
It is relatively low, it is 1000-1100 DEG C.Sample crystalline phase than ammonium carbonate Co deposited synthesis the most frequently used at present generates temperature (1200 DEG C)
It is low more than 100 DEG C；
2. what is obtained is the hexa-aluminate of single crystalline phase, while surface area is from less than 20m2/ g is improved to 40-60m2/g；
3. compared to other preparation methods, the preparation method reaction condition is gentle, simple to operate and time-consuming few, and what is obtained is
The hexa-aluminate of single crystalline phase, while can largely be synthesized.
Brief description of the drawings
Fig. 1 is XRD spectra of the hexa-aluminate obtained in the embodiment of the present invention 1 after different temperatures roasting；
Fig. 2 is the TEM spectrograms after the hexa-aluminate obtained in the embodiment of the present invention 1 is calcined at 1200 DEG C.
Specific embodiment
Technical scheme is expanded on further below by specific embodiment.
The key reaction condition of table 1.
Note：①:N (Al)=12mmol；②:Surface area is to be tested after sample is calcined 4h at 1200 DEG C.
Embodiment 1
First, by 0.522g Ba (NO3)2With 4.896g Al (C3H7O)3Add to 60ml N,N-dimethylformamides
(DMF) in, 3h is stirred vigorously at being positioned over 130 DEG C.30 DEG C are cooled to, and continue to be stirred vigorously 4h at this temperature；It is rapid to add
Enter 1.505g water to be co-precipitated.The precipitation for obtaining uses ethanol to clean to filtrate as colourless.Filter cake is taken out, 60 DEG C of bakings are placed in
12h is dried in case.The solid for obtaining rises to 1200 DEG C of roasting 4h in moving air with the heating rate of 5 DEG C/min, obtains most
Whole hexa-aluminate.
Embodiment 2
First, by 0.522g Ba (NO3)2With 5.912g Al (C4H9O)3Add to 60ml N,N-dimethylformamides
(DMF) in, 3h is stirred vigorously at being positioned over 130 DEG C.30 DEG C are cooled to, and continue to be stirred vigorously 4h at this temperature；It is rapid to add
Enter 1.505g water to be co-precipitated.The precipitation for obtaining uses ethanol to clean to filtrate as colourless.Filter cake is taken out, 60 DEG C of bakings are placed in
12h is dried in case.The solid for obtaining rises to 1200 DEG C of roasting 4h in moving air with the heating rate of 5 DEG C/min, obtains most
Whole hexa-aluminate.
Embodiment 3
First, by 0.398g Ba (NO3)2With 4.896g Al (C3H7O)3Add to 60ml N,N-dimethylformamides
(DMF) in, 3h is stirred vigorously at being positioned over 130 DEG C.30 DEG C are cooled to, and continue to be stirred vigorously 4h at this temperature；It is rapid to add
Enter 1.505g water to be co-precipitated.The precipitation for obtaining uses ethanol to clean to filtrate as colourless.Filter cake is taken out, 60 DEG C of bakings are placed in
12h is dried in case.The solid for obtaining rises to 1200 DEG C of roasting 4h in moving air with the heating rate of 5 DEG C/min, obtains most
Whole hexa-aluminate.
Embodiment 4
First, by 0.435g Ba (NO3)2With 5.912g Al (C4H9O)3Add to 60ml N,N-dimethylformamides
(DMF) in, 3h is stirred vigorously at being positioned over 130 DEG C.30 DEG C are cooled to, and continue to be stirred vigorously 4h at this temperature；It is rapid to add
Enter 1.505g water to be co-precipitated.The precipitation for obtaining uses ethanol to clean to filtrate as colourless.Filter cake is taken out, 60 DEG C of bakings are placed in
12h is dried in case.The solid for obtaining rises to 1200 DEG C of roasting 4h in moving air with the heating rate of 5 DEG C/min, obtains most
Whole hexa-aluminate.
Embodiment 5
First, by 0.522g Ba (NO3)2With 4.896g Al (C3H7O)3Add to 60ml N,N-dimethylformamides
(DMF) in, 3h is stirred vigorously at being positioned over 110 DEG C.30 DEG C are cooled to, and continue to be stirred vigorously 4h at this temperature；It is rapid to add
Enter 1.505g water to be co-precipitated.The precipitation for obtaining uses ethanol to clean to filtrate as colourless.Filter cake is taken out, 60 DEG C of bakings are placed in
12h is dried in case.The solid for obtaining rises to 1200 DEG C of roasting 4h in moving air with the heating rate of 5 DEG C/min, obtains most
Whole hexa-aluminate.
Embodiment 6
First, by 0.522g Ba (NO3)2With 4.896g Al (C3H7O)3Add to 60ml N,N-dimethylformamides
(DMF) in, 3h is stirred vigorously at being positioned over 120 DEG C.30 DEG C are cooled to, and continue to be stirred vigorously 4h at this temperature；It is rapid to add
Enter 1.505g water to be co-precipitated.The precipitation for obtaining uses ethanol to clean to filtrate as colourless.Filter cake is taken out, 60 DEG C of bakings are placed in
12h is dried in case.The solid for obtaining rises to 1200 DEG C of roasting 4h in moving air with the heating rate of 5 DEG C/min, obtains most
Whole hexa-aluminate.
Embodiment 7
First, by 0.522g Ba (NO3)2With 4.896g Al (C3H7O)3Add to 20ml N,N-dimethylformamides
(DMF) in, 3h is stirred vigorously at being positioned over 130 DEG C.30 DEG C are cooled to, and continue to be stirred vigorously 4h at this temperature；It is rapid to add
Enter 1.505g water to be co-precipitated.The precipitation for obtaining uses ethanol to clean to filtrate as colourless.Filter cake is taken out, 60 DEG C of bakings are placed in
12h is dried in case.The solid for obtaining rises to 1200 DEG C of roasting 4h in moving air with the heating rate of 5 DEG C/min, obtains most
Whole hexa-aluminate.
Embodiment 8
First, by 0.522g Ba (NO3)2With 4.896g Al (C3H7O)3Add to 120ml N,N-dimethylformamides
(DMF) in, 3h is stirred vigorously at being positioned over 130 DEG C.30 DEG C are cooled to, and continue to be stirred vigorously 4h at this temperature；It is rapid to add
Enter 1.505g water to be co-precipitated.The precipitation for obtaining uses ethanol to clean to filtrate as colourless.Filter cake is taken out, 60 DEG C of bakings are placed in
12h is dried in case.The solid for obtaining rises to 1200 DEG C of roasting 4h in moving air with the heating rate of 5 DEG C/min, obtains most
Whole hexa-aluminate.
Embodiment 9
First, by 0.522g Ba (NO3)2With 4.896g Al (C3H7O)3Add to 180ml N,N-dimethylformamides
(DMF) in, 3h is stirred vigorously at being positioned over 130 DEG C.30 DEG C are cooled to, and continue to be stirred vigorously 4h at this temperature；It is rapid to add
Enter 1.505g water to be co-precipitated.The precipitation for obtaining uses ethanol to clean to filtrate as colourless.Filter cake is taken out, 60 DEG C of bakings are placed in
12h is dried in case.The solid for obtaining rises to 1200 DEG C of roasting 4h in moving air with the heating rate of 5 DEG C/min, obtains most
Whole hexa-aluminate.
Claims (7)
1. it is a kind of with low phase formed temperature hexa-aluminate preparation method, it is characterised in that：
1) barium salt and aluminium salt are placed in organic solvent, under heating condition, heating-up temperature is 110 DEG C~130 DEG C, and stirring is until salt
Dissolving；
2) after salt dissolving, reaction system is cooled to 30~100 DEG C under agitation, and continue to stir with this understanding, stir
The time is mixed not less than 3h, water is added and is co-precipitated, ethanol elution is dried, and temperature-programmed calcination obtains the six of single crystalline phase
Aluminate；
Described barium salt is barium nitrate, and described aluminium salt is aluminium isopropoxide and/or aluminium secondary butylate, and described organic solvent is N, N-
Dimethylformamide (DMF).
2. according to the preparation method described in claim 1, it is characterised in that：
Step 1) in, the mol ratio of aluminium ion and barium ions is 9.15~12；
The addition of organic solvent is the aluminium ion of every addition 12mmol, and DMF adds 10~90ml.
3. according to the preparation method described in claim 1, it is characterised in that：
Step 1) in, mixing time is 2~4h.
4. according to the preparation method described in claim 1, it is characterised in that：
Step 2) in, mixing time is 3~4h.
5. according to the preparation method described in claim 1, it is characterised in that：
Precipitating reagent in this reaction is dimethylamine (C2H7N), it is to be decomposed to produce by organic solvent DMF, point
Solution reaction equation is C2H7NCO→C2H7N+CO, the reaction is alkali catalyzed and accelerates, and base catalyst refers to reactant isopropanol
Aluminium or aluminium secondary butylate.
6. according to the preparation method described in claim 1, it is characterised in that：
Step 2) in, the amount of water (mole) during co-precipitation is [nBa×2+nAl× 3] 1.0~1.3 times.
7. according to the preparation method described in claim 1, it is characterised in that：
Step 2) in, the condition of temperature-programmed calcination is：In moving air, 1100 are risen to the heating rate of 5~10 DEG C/min
~1300 DEG C, 2~6h of roasting time.
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| CN100445208C (en) * | 2006-12-21 | 2008-12-24 | 天津大学 | Preparing process of mesoprous composite Ba-Al oxide with great specific surface area |
| CN100497177C (en) * | 2007-01-26 | 2009-06-10 | 北京化工大学 | Method of preparing hexaaluminate inorganic material by burning urea |
| CN101108340B (en) * | 2007-07-27 | 2010-05-19 | 广东工业大学 | Preparation method of zirconium manganese doped hexa- aluminate catalyzer |
| CN101225301B (en) * | 2008-01-15 | 2010-11-10 | 西安理工大学 | Method for preparing nano hexa-aluminate based luminescent material |
| CN102008954A (en) * | 2010-10-14 | 2011-04-13 | 北京石油化工学院 | Hexaaluminate metal oxide catalyst, preparation methods and application thereof |
| CN104528799B (en) * | 2014-12-10 | 2016-08-24 | 中国地质大学（武汉） | A kind of preparation method of magnesio rare earth hexa-aluminate superfine powder |
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