CN101284679B - Preparation method for anion pillared hydrotalcite - Google Patents
Preparation method for anion pillared hydrotalcite Download PDFInfo
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- CN101284679B CN101284679B CN2008100644431A CN200810064443A CN101284679B CN 101284679 B CN101284679 B CN 101284679B CN 2008100644431 A CN2008100644431 A CN 2008100644431A CN 200810064443 A CN200810064443 A CN 200810064443A CN 101284679 B CN101284679 B CN 101284679B
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- hydrotalcite
- houghite
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Abstract
The invention provides a method for preparing anion column support houghite, which comprises the steps of weighing M(II)(NO3)2*6H2O and M(III)(NO3)3*9H2O to prepare a nitrate aqueous solution; weighing NaOH and Na2CO3 to prepare a solution; adding the alkali solution and the salt solution into a three-necked bottle simultaneously, drop by drop and at a uniform speed till the pH value is 11.0 plusor minus 0.5; quickly transferring the mixed serous fluid into a high-pressure reactor through supercritical fluid; controlling the temperature and the pressure conditions to reach a supercritical state at constant temperature and pressure; releasing the supercritical fluid within 10 to 60s, communicating with the atmosphere and obtaining the mesoporous houghite compound; and baking the houghite toform the mesoporous oxide with the aperture of 5 to 15nm. The method introduces the supercritical fluid technology into the hydrothermal synthesis method, effectively prevents the formation of absorp tion layers and diffusion layers during the growth of crystals, and prepares houghite three-dimensional crystals.
Description
(1) technical field
That the present invention relates to is a kind of preparation method of anion pillared hydrotalcite, specifically a kind of preparation method who supercritical fluid technology is used for anion pillared hydrotalcite.
(2) background technology
The special structure of hydrotalcite material (LDHs) is given its diversified physicochemical property, makes it demonstrate wide application prospect in fields such as catalysis, intercalation, slow releasing pharmaceutical, er material, fire-retardant, sewage disposal, function luminescent material and semi-conductors.In addition, the laminate structure that hydrotalcite is special makes it demonstrate the potential advantage in various inorganic, the organic hybrid functional material fields of design and assembly.As the preparation method of hydrotalcite compound, known method has coprecipitation method, hydrothermal method, roasting restoring method etc. both at home and abroad at present.Coprecipitation method is to prepare the most frequently used method of hydrotalcite compound at present, though this method can the one-step synthesis product, reaction requires to carry out (H.C.Zeng, Z.P.Xu, M.Qian, Chem.Mater.10,2277 (1998) under the nitrogen protection of strictness; J.Qiu, G.Villemure, J.Electroanal.Chem.428,165 (1997); I.Carpani, M.Berrettoni, M.Giorgetti, D.Tonelli, J.Phys.Chem.B.110,7265 (2006)).Owing to be subject to CO in the air in the building-up process
2Pollution and LDHs-CO appears
3Crystalline phase, CO is avoided in whole process need strictness
2Contact, reaction conditions is relatively harsh, the actually operating difficulty is very big, therefore is unfavorable for the industrialization promotion and the application of this method.In addition, this method synthetic anion pillared hydrotalcite degree of crystallinity is low, and structurally ordered property is poor, and laminate structure is imperfect.In addition, the hydrotalcite crystal of coprecipitation method preparation found that by TEM " lamella reunion " phenomenon easily takes place the platy shaped particle of hydrotalcite.The traditional water thermal synthesis method is to utilize the aqueous solution as reaction medium, and throw out is put into the aged process of autoclave (F.Kovanda, D.
Z.C í lov á, V.
Appl.Clay Sci.28,101 (2005); J.Theo Kloprogge, L.Hickey, Ray L.Frost, J.Solid State Chem.177,4047 (2004); S.K.Sharma, P.K.Kushwaha, V.K.Srivastava, S.D.Bhatt, R.V.Jasra, Ind.Eng.Chem.Res.46 (14), 4856 (2007)).The characteristics of this method are that the nucleation of hydrotalcite and crystallization process are kept apart, and promote crystallization process by improving temperature and pressure.Yet the prepared hydrotalcite compound of this method is irregular single laminated structure, and the degree of order of laminate structure is poor.The roasting restoring method is a kind of preparation method (the Odair P.Ferreira that is based upon on " structure memory effect " characteristic basis of hydrotalcite, Oswaldo L.Alves, Daniel X.Gouveia, Antonio G.Souza Filho, Jos é A.C.de Paiva, Josu é Mendes Filho, J.Solid State Chem.177,3058 (2004); H.Nakayama, N.Wada, M.Tsuhako, Int.J.Pharm.269,469 (2004)).Adopt this method can synthesize inorganic, the organic anion intercalated houghite of some complexity, still the veneer structure owing to hydrotalcite can only obtain the part recovery, so be difficult to obtain pure crystal phase structure.
Although Chinese scholars is done a lot of work to the basic theory and the applied research of hydrotalcite,, assemble the preparation of hydrotalcite three-dimensional crystal in order and the research of correlation theory still belongs to blank by the two-dimensional layer precursor.
(3) summary of the invention
The object of the present invention is to provide and a kind ofly can when improving the hydrotalcite layered structure integrity, improve the preparation method of the anion pillared hydrotalcite of application powers such as its catalysis, absorption, intercalation.
The object of the present invention is achieved like this: under the room temperature, be 1～4 according to the mol ratio of M (II)/M (III), take by weighing M (II) (NO respectively
3)
26H
2O and M (III) (NO
3)
39H
2O is mixed with nitrate aqueous solution 300mL, and other gets a certain amount of NaOH and Na
2CO
3Be mixed with solution 300mL, wherein n (OH
-)/[n (Ni
2+)+n (Al
3+)]=2.2, n (CO
3 2-)/[n (Ni
2+)+n (Al
3+)]=0.667.With above-mentioned alkali lye, saline solution simultaneously dropwise constant speed join in the 1000mL three-necked bottle, drip to pH be 11.040.5, obtain mixed serum;
Change over to above-mentioned mixed serum in the autoclave rapidly, feed in the supercutical fluid, condition is controlled to be: temperature 80～240C, pressure 8～10MPa, make supercutical fluid reach supercritical state, constant temperature and pressure 1～10h, communicate with supercutical fluid release and in atmosphere in the time at 10～60s, obtain hydrotalcite compound.
The present invention can also comprise:
1, wherein M (II) is a divalent-metal ion, can be Mg
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+Or Mn
2+
2, described M (III) is a trivalent metal ion, can be Al
3+, Fe
3+Or Cr
3+
3, described supercutical fluid is selected from a kind of of carbonic acid gas, water, alcohol or their mixture.
4, described hydrotalcite compound is made the mesoporous metal composite oxides at 300～800 ℃ of roasting temperatures.
The present invention utilizes supercritical fluid technology, and the three-dimensional anion pillared hydrotalcite of a kind of high-crystallinity and high-sequential is provided, and when improving the hydrotalcite layered structure integrity, improves application powers such as its catalysis, absorption, intercalation.
The present invention has explored the gordian technique that realizes that two-dimensional layer precursor hydrotalcite is assembled orderly three-dimensional crystal, the relation of research packaging technology and structure and performance.
The present invention is the action rule of research supercutical fluid to two-dimensional layer hydrotalcite precursor integrity, and supercutical fluid is to the synthesis mechanism of two-dimensional layer precursor assembling three-dimensional crystal.
Technical characterictic of the present invention is that supercritical fluid technology is incorporated in the hydrothermal synthesis method.Supercutical fluid has the flowability of similar liquids and the penetration power characteristic of gas, can effectively prevent adsorption layer and diffusion layer formation in the crystal growing process, thereby realize preparing the hydrotalcite three-dimensional crystal by two-dimentional precursor is effectively assembled.
Method of the present invention makes it obtain better application in fields such as catalysis, absorption, intercalations for the application performance of improving hydrotalcite provides theoretical support.
The hydrotalcite that adopts method of the present invention to obtain comprises binary and ternary anion pillared hydrotalcite material.The hydrotalcite layers negatively charged ion can be inorganic anion such as Cl
-, NO
3 -, CO
3 2-, SO
4 2-, [Fe (CN)
6]
3-Deng; Also can be for same many or heteropolyanion, as V
10O
28 6-, Mo
9O
24 6-, [PMo
12O
40]
3-, [PW
12O
40]
3-Deng.The stratum water talc compound is a high-crystallinity, and porous two dimension lamella is the three-dimensional crystalline structure of assembling in order.Its pore size distribution is 2～6nm, is mesoporous material.
(4) description of drawings
Fig. 1 is Ni/Al-CO
3Hydrotalcite is through supercritical CO
2The scanning electron microscope pattern picture of the two-dimensional layer precursor after fluid technique is handled.
Fig. 2 is two-dimentional sheet Ni/Al-CO
3Hydrotalcite is at the transmission electron microscopy pattern picture of 300 ℃ of maturing temperatures, and wherein Fig. 2-a is the part figure of Fig. 2-b.
Fig. 3 is two-dimentional sheet Ni/Al-CO
3Hydrotalcite is at the transmission electron microscopy pattern picture of 450 ℃ of maturing temperatures, and wherein Fig. 3-a is the part figure of Fig. 3-b.
Fig. 4 is two-dimentional sheet Ni/Al-CO
3Hydrotalcite is at the transmission electron microscopy pattern picture of 550 ℃ of maturing temperatures, and wherein Fig. 4-a is the part figure of Fig. 4-b.
Fig. 5 is two-dimentional sheet Ni/Al-CO
3Hydrotalcite is at the transmission electron microscopy pattern picture of 700 ℃ of maturing temperatures, and wherein Fig. 5-a is the part figure of Fig. 5-b.
(5) embodiment
For example the present invention is done in more detail below and describes:
Embodiment 1:
Under the room temperature, be to take by weighing a certain amount of Ni (NO at 3: 1 by the Ni/Al mol ratio
3)
26H
2O and Al (NO
3)
39H
2O is mixed with nitrate aqueous solution 300mL, and other gets a certain amount of NaOH and Na
2CO
3Be mixed with the 300mL alkaline solution, wherein n (OH
-)/[n (Ni
2+)+n (Al
3+)]=2.2, n (CO
3 2-)/[n (Ni
2+)+n (Al
3+)]=0.667.With above-mentioned alkali lye, saline solution simultaneously dropwise constant speed join in the 1000mL three-necked bottle, drip to pH be 11.040.5.Above-mentioned mixed serum is changed over to rapidly in the autoclave, under 240 ℃ of temperature and 8MPa pressure, raw material and supercritical CO
2The fluid contact is taken out product behind the reaction 10h, and repetitive scrubbing is to neutral, and product is in 60 ℃ of dry 24h.
Embodiment 2:
Change Ni (NO
3)
26H
2O and Al (NO
3)
39H
2The mol ratio of O, other experiment condition can make the hydrotalcite material of different Ni/Al mol ratio with embodiment 1.
Embodiment 3:
Other experiment condition is with embodiment 1, and (temperature range is 100～200 ℃, and pressure range can make the Ni/Al hydrotalcite material of different crystallinity 3～10MPa) to change hydrothermal temperature and pressure.
Embodiment 4:
With the nickel aluminum hydrotalcite sample of embodiment 1 preparation in retort furnace respectively at 300 ℃, 450 ℃, 550 ℃, 700 ℃, 900 ℃, 1100 ℃ of following roasting 5h finally obtain mesoporous composite oxides.
Embodiment 5:
Under the room temperature, take by weighing n (Zn
2+)/n (Ni
2+)/n (Al
3+) than the Zn (CH that is 3: 3: 2
3COO)
22H
2O, Ni (NO
3)
26H
2O, Al (NO
3)
39H
2O is mixed with mixed-cation salts solution 250mL; Other gets a certain amount of NaOH and Na
2CO
3Be mixed with solution 250mL.Above-mentioned solution is added drop-wise in the three-necked bottle simultaneously, and regulating the pH value is 12.0 ± 0.5, continues to stir 30min.With in the slurries impouring autoclave in the there-necked flask, set certain temperature and time and proceed reaction again, in reactor, feed supercritical CO simultaneously
2Fluid is kept pressure at 8～10MPa.Take out the slurries repetitive scrubbing to neutral by the time reaction finishes the back, product is in 60 ℃ of dry 24h.Through 200 ℃, 300 ℃, 500 ℃, 700 ℃, 900 ℃, 1100 ℃ of roasting 5h finally obtain composite oxides to above-mentioned sample in retort furnace.
Embodiment 6:
Under the room temperature, take by weighing n (Co
2+)/n (Ni
2+)/n (Al
3+) be 3: 3: 2 Co (NO
3)
26H
2O, Ni (NO
3)
26H
2O, Al (NO
3)
39H
2O is mixed with salts solution 250mL; Other gets a certain amount of NaOH and Na
2CO
3Be mixed with solution 250mL.Above-mentioned solution is added drop-wise in the three-necked bottle simultaneously, and regulating the pH value is 12.0 ± 0.5, continues to stir 30min.With in the slurries impouring autoclave in the there-necked flask, set certain temperature and time and proceed reaction again, in reactor, feed supercritical CO simultaneously
2Fluid is kept pressure at 8～10MPa.Take out the slurries repetitive scrubbing to neutral by the time reaction finishes the back, product is in 60 ℃ of dry 24h.Through 200 ℃, 300 ℃, 500 ℃, 700 ℃, 900 ℃, 1100 ℃ of roasting 5h finally obtain composite oxides to above-mentioned sample in retort furnace.
Claims (1)
1. the preparation method of an anion pillared hydrotalcite is characterized in that: under the room temperature, according to Ni
2+/ Al
3+Mol ratio be 1～4, take by weighing Ni (NO respectively
3)
26H
2O and Al (NO
3)
39H
2O is mixed with nitrate aqueous solution 300mL, and other gets a certain amount of NaOH and Na
2CO
3Be mixed with solution 300mL, wherein n (OH-)/[n (Ni
2+)+n (Al
3+)]=2.2, n (CO
3 2-)/[n (Ni
2+)+n (Al
3+)]=0.667; With above-mentioned alkali lye, saline solution simultaneously dropwise constant speed join in the 1000mL three-necked bottle, drip to pH be 11.0 ± 0.5, obtain mixed serum; Above-mentioned mixed serum is changed over to rapidly in the autoclave, feed supercritical CO
2In the fluid, condition is controlled to be: 80～240 ℃ of temperature, pressure 8～10MPa, and make supercutical fluid reach supercritical state, constant temperature and pressure 1～10h communicates with supercutical fluid release and in atmosphere in the time at 10～60s, obtains hydrotalcite compound.
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| CN101507917B (en) * | 2009-04-02 | 2011-01-19 | 北京化工大学 | Solid base catalyst for synthesizing alkanolamide type compound and preparation method thereof |
| CN104162419A (en) * | 2014-07-02 | 2014-11-26 | 昆明理工大学 | Preparing method and applications of hydrogen cyanide hydrolyst |
| CN107858035A (en) * | 2017-11-14 | 2018-03-30 | 上海荣富新型材料有限公司 | A kind of halogen-free flame retardants, its preparation method and the anti-flaming dope with its preparation |
| CN108479687A (en) * | 2018-06-12 | 2018-09-04 | 中国工程物理研究院激光聚变研究中心 | A kind of stratiform calcium aluminium hydroxide aeroge and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050238569A1 (en) * | 2002-11-29 | 2005-10-27 | Council Of Scientific And Industrial Research | Process for preparing and self-assembling property of nanobinary and ternary oxy/hydroxides |
| CN101049953A (en) * | 2007-01-12 | 2007-10-10 | 北京化工大学 | Microballons of laminar dual hydroxy composite metal oxide and preparation method |
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2008
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050238569A1 (en) * | 2002-11-29 | 2005-10-27 | Council Of Scientific And Industrial Research | Process for preparing and self-assembling property of nanobinary and ternary oxy/hydroxides |
| CN101049953A (en) * | 2007-01-12 | 2007-10-10 | 北京化工大学 | Microballons of laminar dual hydroxy composite metal oxide and preparation method |
Non-Patent Citations (3)
| Title |
|---|
| B. M. Choudary et al..Synthesis, Characterization, Ion Exchange, and CatalyticProperties of Nanobinary and Ternary Metal Oxy/Hydroxides.Chemistry of Materials17.2005,172740-2743. * |
| 景晓燕 等.水滑石类化合物的研究现状及进展.应用科技31 10.2004,31(10),41-42. * |
| 郑崇辉 等.阴离子柱撑磁性镍铝水滑石的制备及表征.应用化学24 8.2007,24(8),883-887. * |
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