CN102020298A - Al2O3 with double-mesoporous distribution and preparation method thereof - Google Patents
Al2O3 with double-mesoporous distribution and preparation method thereof Download PDFInfo
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- CN102020298A CN102020298A CN201010519425.5A CN201010519425A CN102020298A CN 102020298 A CN102020298 A CN 102020298A CN 201010519425 A CN201010519425 A CN 201010519425A CN 102020298 A CN102020298 A CN 102020298A
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Abstract
The invention discloses Al2O3 with double-mesoporous distribution and a preparation method thereof. The aperture of the small mesopore of Al2O3 is 3.4 to 3.8nm; the aperture of the big mesopore is 9.8 to 24.5nm; the specific surface area of the Al2O3 is 239 to 347m<2>/g; and the pore volume of the Al2O3 is 0.48 to 1.14cm<3>/g. The Al2O3 with double-mesoporous distribution has relatively large pore volume and has double-mesoporous distribution in an aperture range of 2 to 100nm. The method disclosed by the invention has a mild reaction condition, is simple, convenient and feasible in operation, is flexible and can adjust and control the double-mesoporous distribution structure of a synthesized Al2O3 material. The Al2O3 with double-mesoporous distribution, which is provided by the invention, can serve as a catalyst, an adsorbent, a catalyst carrier or an adsorbent carrier.
Description
Technical field
The invention belongs to the inorganic porous material technical field, be specifically related to a kind of Al of two mesoporous distributions
2O
3And preparation method.
Background technology
Aluminum oxide is a kind of porous, high dispersive, have the material than bigger serface, good adsorption properties, based on its heat, chemistry, the stability of mechanical aspects, anti-oxidant and lower-price characteristic can be widely used in fields such as catalysis, absorption, separation, material.And often need have the alumina particle of nano-scale in the practical application, and the pore size of aluminum oxide and distribute the scattering nature of reactant in the catalytic process in granules of catalyst inside had material impact.Two meso-porous aluminas can improve the diffusivity of material and the dispersiveness of carrier metal simultaneously, are a kind of desirable multifunctional materials.There is the meso-hole structure of two kinds of different pore sizes in this material, mesoporously can allow larger-diameter molecule to enter wherein greatly, and its passage as mass transfer has littler diffusional resistance simultaneously; Littlely mesoporously provide bigger active area as the adsorption site of material and the place of reaction, have the dispersiveness that the ability of shape selective catalysis preferably improves active component simultaneously, therefore have broad application prospects.
CN101700900A discloses a kind of preparation method of ordered dual-pore alumina.Take the alkoxide of aluminium as raw material, the aqueous solution that absolute ethyl alcohol, water, acid source, alkali source are made into certain pH value by a certain percentage adds the surfactant reaction that is hydrolyzed, and is centrifugal finally by crossing washing, drying, and soxhlet's extraction, calcining is because the difference of calcining heat can obtain γ-Al
2O
3, α-Al
2O
3, δ-Al
2O
3Three kinds of crystal formations.The aluminum oxide of this prepared is macropore-mesopore distributed architecture, and big bore dia is 0.3～2 μ m, and median pore diameter is 2～20nm.
Bai etc. (Microporous and Mesoporous Materials, 2009,118:288-295) utilize the two-way hydrolytic process of zwitterion to prepare and have the aluminum oxide of two mesoporous distributions.Utilize aluminum nitrate and sodium metaaluminate, add template P123, obtained having the aluminium oxide of two mesoporous distributions, little mesoporous about 3nm, big mesoporous about 6nm, wherein aperture is that the bayerite hydrolysis obtains, macropore is unbodied aluminium hydroxide, and diaspore and gibbsite are in conjunction with formation.The chemosynthesis system plays crucial effects for final solid product, and this method synthesis condition is comparatively harsh, and resulting two kinds of pore size distributions are nearer.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of relatively large pore volume that has is provided, large and small mesoporous layering significantly has the Al of two mesoporous distributions
2O
3
Second purpose of the present invention provides a kind of Al with two mesoporous distributions simple to operate
2O
3The preparation method.
Technical scheme of the present invention is summarized as follows:
A kind of Al with two mesoporous distributions
2O
3, described Al
2O
3Little mesoporous being distributed between 3.4～3.8nm, big mesoporous being distributed between 9.8～24.5nm, specific area is 239～347m
2/ g, pore volume are 0.48～1.14cm
3/ g.
A kind of Al with two mesoporous distributions
2O
3The preparation method, comprise the steps:
(1) be that to join concentration expressed in percentage by volume be in 55.6%～66.7% the aqueous ethanolic solution for 4.54～20.45: 1 cetyl trimethylammonium bromide and nonionogenic tenside with mol ratio, make mixture, the mass ratio of described cetyl trimethylammonium bromide and described aqueous ethanolic solution is 0.02～0.025: 1;
(2) with described mixture after 40～50 ℃ of following supersound process are treated to dissolve fully, add aluminum isopropylate, the mol ratio of described aluminum isopropylate and described cetyl trimethylammonium bromide is 1: 0.13～0.15, continue supersound process 0.5～1h again, regulate pH=10, water-bath, under 50～60 ℃, aging 8～24h gets wet gel;
(3) remove supernatant liquor, get xerogel at 80 ℃ of lower dry 10～15h, then with the xerogel roasting, obtain having the Al of two mesoporous distributions
2O
3, described Al
2O
3Little mesoporous being distributed between 3.4～3.8nm, big mesoporous being distributed between 9.8～24.5nm, specific area is 239～347m
2/ g, pore volume are 0.48～1.14cm
3/ g.
Described nonionogenic tenside is PEG4000, PEG20000 or PEG-PPG-PEG.
Preferred 550～650 ℃ of the temperature of xerogel roasting, the speed that heats up during roasting is 5 ℃/min, the time 2～6h of roasting.
Described step (2) is preferably: with described mixture after 40～50 ℃ of following supersound process are treated to dissolve fully, add aluminum isopropylate, the mol ratio of described aluminum isopropylate and described cetyl trimethylammonium bromide is 1: 0.13～0.15, continue supersound process 0.5～1h again, regulate pH=10, the expanding agent of adding and nonionogenic tenside equimolar amount, water-bath, under 50～60 ℃, aging 8～24h gets wet gel.
Described expanding agent is trimethylbenzene, hexane, benzene or whiteruss.
Al with two mesoporous distributions of the present invention
2O
3Have relatively large pore volume, in the pore diameter range of 2～100nm, have two mesoporous distributions.Method of the present invention has the reaction conditions gentleness, easy to operation and flexible and changeable characteristics, and can be to institute's synthetic alumina material diplopore pore distribution structure regulating.By changing Template Types, template mol ratio and add different expanding agents, littlely mesoporous can be stabilized in 3.4～3.8nm in several apertures, big mesoporous can in the scope of 9.8～24.5nm, adjusting in several apertures.Al with two mesoporous distributions provided by the present invention
2O
3Can be used as catalyst, adsorbent, catalyst carrier or adsorbing agent carrier.
Description of drawings
Fig. 1 is the graph of pore diameter distribution of embodiment 1,2,3.
Fig. 2 is the graph of pore diameter distribution of embodiment 3,4,5.
Fig. 3 is the graph of pore diameter distribution of embodiment 6,7,8,9.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
It is in 66.7% the ethanol water that 0.56g softex kw (CTAB) is added the 30ml volumetric concentration, wait to dissolve rear adding 1.49g PEG4000, under 40 ℃, carry out ultrasonic processing to fully dissolving, the aluminium isopropoxide that adds then 2.36g, ultrasonic processing 30min again, last dropping ammonia is transferred its pH=10, forms the precursor gel, should elder generation's body gel in 50 ℃ of water-baths aging 8h complete to gel, get wet gel; The supernatant liquor of gained wet gel is removed, at 80 ℃ of lower dry 10h, got xerogel then, last 550 ℃ of lower roasting 6h in Muffle furnace, heating rate is 5 ℃/min, obtains the Al of two mesoporous distributions
2O
3, its character sees Table 1.
Embodiment 2
It is in 66.7% the alcohol-water mixing solutions that 0.56g CTAB is added the 30ml volumetric concentration, wait to dissolve the PEG20000 that the back adds 1.50g, in the dissolving extremely fully of 50 ℃ of supersound process, the aluminum isopropylate that adds 2.36g then, supersound process 30min again, dropping ammonia is transferred its pH=10, forms the precursor gel, and is should elder generation's body gel aging 8h in 50 ℃ of water-baths complete to gel.The supernatant liquor of gained gel is removed, got xerogel at 80 ℃ of lower dry 12h then, be warmed up to 600 ℃ of roasting 3h at the Muffle furnace Program at last, heating rate is 5 ℃/min, obtains having the Al of two mesoporous distributions
2O
3, its character sees Table 1.
Embodiment 3
It is in 55.6% the alcohol-water mixing solutions that 0.64g CTAB is added the 28ml volumetric concentration, the PEG-PPG-PEG that adds 2g after waiting to dissolve again, 50 ℃ of supersound process are to dissolving fully, the aluminum isopropylate that adds 2.36g then, supersound process 1h again, dropping ammonia 7ml forms the precursor gel, and is should elder generation's body gel aging 12h in 50 ℃ of water-baths complete to gel.The supernatant liquor of gained gel is removed, got xerogel at 80 ℃ of lower dry 15h then, be warmed up to 650 ℃ of roasting 2h at the Muffle furnace Program at last, heating rate is 5 ℃/min, obtains having the Al of two mesoporous distributions
2O
3, its character sees Table 1.
Embodiment 4
It is in 55.6% the alcohol-water mixing solutions that 0.64g CTAB is added the 28ml volumetric concentration, the PEG-PPG-PEG that adds 1.04g after waiting to dissolve again, 50 ℃ of supersound process are to dissolving fully, the aluminum isopropylate that adds 2.36g then, supersound process 1h again, dropping ammonia 7ml forms the precursor gel, and is should elder generation's body gel aging 12h in 50 ℃ of water-baths complete to gel.The supernatant liquor of gained gel is removed, got xerogel at 80 ℃ of lower dry 15h then, be warmed up to 650 ℃ of roasting 2h at the Muffle furnace Program at last, heating rate is 5 ℃/min, obtains having the Al of two mesoporous distributions
2O
3, its character sees Table 1.
Embodiment 5
It is in 55.6% the alcohol-water mixing solutions that 0.64g CTAB is added the 28ml volumetric concentration, the PEG-PPG-PEG that adds 0.53g after waiting to dissolve again, 50 ℃ of supersound process are to dissolving fully, the aluminum isopropylate that adds 2.36g then, supersound process 1h again, dropping ammonia 7ml forms the precursor gel, and is should elder generation's body gel aging 12h in 50 ℃ of water-baths complete to gel.The supernatant liquor of gained gel is removed, got xerogel at 80 ℃ of lower dry 15h then, be warmed up to 650 ℃ of roasting 2h at the Muffle furnace Program at last, heating rate is 5 ℃/min, obtains having the Al of two mesoporous distributions
2O
3, its character sees Table 1.
Embodiment 6
It is in 55.6% the alcohol-water mixing solutions that 0.64g CTAB is added the 28ml volumetric concentration, the PEG20000 that adds 1.46g after waiting to dissolve again, 50 ℃ of supersound process are to dissolving fully, the aluminum isopropylate that adds 2.36g then, supersound process 1h again, dropping ammonia 7ml adds the trimethylbenzene of 1ml again, form the precursor gel, should elder generation's body gel aging 24h in 60 ℃ of water-baths complete to gel.The supernatant liquor of gained gel is removed, got xerogel at 80 ℃ of lower dry 12h then, be warmed up to 600 ℃ of roasting 3h at the Muffle furnace Program at last, heating rate is 5 ℃/min, obtains having the Al of two mesoporous distributions
2O
3, its character sees Table 1.
Embodiment 7
It is in 55.6% the alcohol-water mixing solutions that 0.63g CTAB is added the 28ml volumetric concentration, the PEG20000 that adds 1.45g after waiting to dissolve again, 50 ℃ of following supersound process are to dissolving fully, the aluminum isopropylate that adds 2.36g then, it is complete that supersound process 1h makes its hydrolysis again, and dropping ammonia 7ml adds the hexane of 1ml again, form the precursor gel, should elder generation's body gel aging 24h in 60 ℃ of water-baths complete to gel.The supernatant liquor of gained gel is removed, got xerogel at 80 ℃ of lower dry 12h then, be warmed up to 600 ℃ of roasting 3h at the Muffle furnace Program at last, heating rate is 5 ℃/min, obtains having the Al of two mesoporous distributions
2O
3, its character sees Table 1.
Embodiment 8
It is in 55.6% the alcohol-water mixing solutions that 0.63g CTAB is added the 28ml volumetric concentration, the PEG20000 that adds 1.44g after waiting to dissolve again, 50 ℃ of supersound process are to dissolving fully, the aluminum isopropylate that adds 2.36g then, supersound process 30min again, dropping ammonia 7ml adds the benzene of 0.66ml again, form the precursor gel, should elder generation's body gel aging 24h in 60 ℃ of water-baths complete to gel.The supernatant liquor of gained gel is removed, got xerogel at 80 ℃ of lower dry 12h then, be warmed up to 600 ℃ of roasting 3h at the Muffle furnace Program at last, heating rate is 5 ℃/min, obtains having the Al of two mesoporous distributions
2O
3, its character sees Table 1.
Embodiment 9
It is in 55.6% the alcohol-water mixing solutions that 0.63g CTAB is added the 28ml volumetric concentration, the PEG20000 that adds 1.46g after waiting to dissolve again, 50 ℃ of supersound process are to dissolving fully, the aluminum isopropylate that adds 2.36g then, supersound process 30min again, dropping ammonia 7ml adds the whiteruss of 1ml again, form the precursor gel, should elder generation's body gel aging 24h in 60 ℃ of water-baths complete to gel.The supernatant liquor of gained gel is removed, got xerogel at 80 ℃ of lower dry 12h then, be warmed up to 600 ℃ of roasting 3h at the Muffle furnace Program at last, heating rate is 5 ℃/min, obtains having the Al of two mesoporous distributions
2O
3, its character sees Table 1.
The structural parameter of the aluminum oxide that table 1 obtains for embodiment 1,2,3,4,5,6,7,8,9.
Change as can be known template by embodiment in the table 11,2, data and Fig. 1 of 3, big mesoporous aperture becomes big, and it is big that pore volume becomes.Increase as can be known the mol ratio of template by embodiment in the table 13,4,5 data and Fig. 2, that big mesoporous aperture becomes is big, pore volume becomes big, specific area and also becomes big.
By 2,6,7,8,9 data of embodiment in the table 1 and Fig. 3 as can be known, add expanding agent after pore volume become big, and specific surface area decreases, big mesoporous aperture becomes big.The pore volume of the sample of trimethylbenzene and benzene all is greatly increased.
Table 1
Claims (6)
1. Al with two mesoporous distributions
2O
3, it is characterized in that described Al
2O
3Little mesoporous being distributed between 3.4～3.8nm, big mesoporous being distributed between 9.8～24.5nm, specific area is 239～347m
2/ g, pore volume are 0.48～1.14cm
3/ g.
2. a kind of Al with two mesoporous distributions according to claim 1
2O
3The preparation method, its feature comprises the steps:
(1) be that to join concentration expressed in percentage by volume be in 55.6%～66.7% the aqueous ethanolic solution for 4.54～20.45: 1 cetyl trimethylammonium bromide and nonionogenic tenside with mol ratio, make mixture, the mass ratio of described cetyl trimethylammonium bromide and described aqueous ethanolic solution is 0.02～0.025: 1;
(2) with described mixture after 40～50 ℃ of following supersound process are treated to dissolve fully, add aluminum isopropylate, the mol ratio of described aluminum isopropylate and described cetyl trimethylammonium bromide is 1: 0.13～0.15, continue supersound process 0.5～1h again, regulate pH=10, water-bath, under 50～60 ℃, aging 8～24h gets wet gel;
(3) remove supernatant liquor, get xerogel at 80 ℃ of lower dry 10～15h, then with the xerogel roasting, obtain having the Al of two mesoporous distributions
2O
3, described Al
2O
3Little mesoporous being distributed between 3.4～3.8nm, big mesoporous being distributed between 9.8～24.5nm, specific area is 239～347m
2/ g, pore volume are 0.48～1.14cm
3/ g.
3. the Al with two mesoporous distributions according to claim 2
2O
3The preparation method, it is characterized in that described non-ionic surface active agent is PEG4000, PEG20000 or PEG-PPG-PEG.
4. the Al with two mesoporous distributions according to claim 2
2O
3The preparation method, it is characterized in that the temperature of xerogel roasting is 550～650 ℃, the speed that heats up during roasting is 5 ℃/min, the time 2～6h of roasting.
5. the Al with two mesoporous distributions according to claim 2
2O
3The preparation method, it is characterized in that in described step (2) being: with described mixture after 40～50 ℃ of lower ultrasonic processing are treated to dissolve fully, add aluminium isopropoxide, the mol ratio of described aluminium isopropoxide and described softex kw is 1: 0.13～0.15, continues ultrasonic processing 0.5～1h again, regulates pH=10, add the expanding agent with the non-ionic surface active agent equimolar amounts, water-bath, under 50～60 ℃, aging 8～24h gets wet gel.
6. the Al with two mesoporous distributions according to claim 5
2O
3The preparation method, it is characterized in that at described expanding agent be trimethylbenzene, hexane, benzene or atoleine.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106348326A (en) * | 2016-08-23 | 2017-01-25 | 山东国瓷功能材料股份有限公司 | Gamma alumina, preparation method and application thereof and device |
| CN110882683A (en) * | 2019-11-26 | 2020-03-17 | 青岛庄信恒瑞催化剂有限公司 | Dechlorination deoxidation catalyst and preparation method and application thereof |
| CN113247930A (en) * | 2021-06-30 | 2021-08-13 | 上海交通大学 | Alpha-alumina and preparation method thereof |
| CN113332969A (en) * | 2021-04-27 | 2021-09-03 | 东南大学 | Preparation method of catalyst capable of improving deactivation resistance in carbonyl sulfide hydrolysis reaction |
| CN114195164A (en) * | 2020-09-17 | 2022-03-18 | 中国石油天然气股份有限公司 | Composite material with step pore structure distribution and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060147364A1 (en) * | 2004-12-30 | 2006-07-06 | Council Of Scientific And Industrial Research | Process for synthesising porous crystalline aluminophosphate molecular sieves |
| CN101704537A (en) * | 2009-11-09 | 2010-05-12 | 中国海洋石油总公司 | Method for preparing aluminum oxide with bimodal pore distribution |
-
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- 2010-10-26 CN CN201010519425A patent/CN102020298B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060147364A1 (en) * | 2004-12-30 | 2006-07-06 | Council Of Scientific And Industrial Research | Process for synthesising porous crystalline aluminophosphate molecular sieves |
| CN101704537A (en) * | 2009-11-09 | 2010-05-12 | 中国海洋石油总公司 | Method for preparing aluminum oxide with bimodal pore distribution |
Non-Patent Citations (1)
| Title |
|---|
| 《Materials Research Bulletin》 20041231 Younghun Kim et al. Synthesis of tailored porous alumina with a bimodal pore size distribution 2106-2109 1 第39卷, 2 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106348326A (en) * | 2016-08-23 | 2017-01-25 | 山东国瓷功能材料股份有限公司 | Gamma alumina, preparation method and application thereof and device |
| CN110882683A (en) * | 2019-11-26 | 2020-03-17 | 青岛庄信恒瑞催化剂有限公司 | Dechlorination deoxidation catalyst and preparation method and application thereof |
| CN114195164A (en) * | 2020-09-17 | 2022-03-18 | 中国石油天然气股份有限公司 | Composite material with step pore structure distribution and preparation method thereof |
| CN114195164B (en) * | 2020-09-17 | 2023-09-26 | 中国石油天然气股份有限公司 | Composite material with step hole structure distribution and preparation method thereof |
| CN113332969A (en) * | 2021-04-27 | 2021-09-03 | 东南大学 | Preparation method of catalyst capable of improving deactivation resistance in carbonyl sulfide hydrolysis reaction |
| CN113247930A (en) * | 2021-06-30 | 2021-08-13 | 上海交通大学 | Alpha-alumina and preparation method thereof |
| CN113247930B (en) * | 2021-06-30 | 2022-04-01 | 上海交通大学 | Alpha-alumina and preparation method thereof |
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