CN102229436B - Preparation method of gamma-aluminium oxide (Al2O3) nanofiber - Google Patents

Preparation method of gamma-aluminium oxide (Al2O3) nanofiber Download PDF

Info

Publication number
CN102229436B
CN102229436B CN 201110150019 CN201110150019A CN102229436B CN 102229436 B CN102229436 B CN 102229436B CN 201110150019 CN201110150019 CN 201110150019 CN 201110150019 A CN201110150019 A CN 201110150019A CN 102229436 B CN102229436 B CN 102229436B
Authority
CN
China
Prior art keywords
filter cake
preparation
solution
inorganic salt
salt containing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN 201110150019
Other languages
Chinese (zh)
Other versions
CN102229436A (en
Inventor
姚楠
李小年
马成成
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Taide New Material Co ltd
Original Assignee
Zhejiang University of Technology ZJUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN 201110150019 priority Critical patent/CN102229436B/en
Publication of CN102229436A publication Critical patent/CN102229436A/en
Application granted granted Critical
Publication of CN102229436B publication Critical patent/CN102229436B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of gamma-aluminium oxide (Al2O3) nanofiber. The preparation method comprises the following steps of: (a) mixing aluminum-containing inorganic salt solution and alkaline precipitant solution according to the volume ratio of 1:(2-5) and reacting at the temperature of between 30 and 100 DEG C to obtain a suspension; (b) filtering the suspension to obtain a filter cake, and pulping and filtering in deionized water to remove impurities to obtain a filter cake I; (c) treating the filter cake I prepared in the step (b) in an organic solvent, and carrying out filtering and recovering the organic solvent to obtain a filter cake II; and (d) roasting the filter cake II prepared in the step (c) at the temperature of between 300 and 600 DEG C to obtain the gamma-Al2O3 nanofiber material. The preparation method is simple and can be applied to industry. The prepared gamma-Al2O3 has the characteristics of large aperture and large specific surface area.

Description

A kind of γ-Al 2O 3The preparation method of nanofiber
(1) technical field
The present invention relates to a kind of γ-Al 2O 3The material preparation method relates in particular to a kind of γ-Al 2O 3The preparations of nanomaterials method.
(2) background technology
γ-Al 2O 3Be a kind of support of the catalyst commonly used, be widely used in the various loaded catalysts of preparation.γ-Al 2O 3The character such as the specific surface area of carrier, aperture, pore volume and pattern have important impact to the activity and selectivity of catalyzer.To the pay attention to day by day that the bulky molecular catalysis such as biomass, heavy oil and residual oil transform, need urgently γ-Al along with people 2O 3Carrier has larger specific surface area (improving the dispersity of institute's loaded metal component) and aperture (improving the diffusion of macromolecular cpd in the duct), to improve the reactivity worth of catalyzer.But, γ-Al that existing market is on sale 2O 3Can't have simultaneously high specific surface area and larger aperture.Because for the ordinary oxide material, the raising of its specific surface area can be accompanied by aperture decline (A.Mart í nez, G.Prieto, J.Roll á n, J.Catal.263 (2009) 292-305) usually.Adopt the methods such as organic formwork agent, expanding agent can obtain all larger Al of specific surface area and aperture 2O 3Material, but these preparation process exist the shortcomings such as preparation process complexity, raw material costliness.Simultaneously, easily produce the obnoxious flavour of a large amount of sulfur-bearings, nitrogen in organic removal process of touching plate agent or expanding agent, be unfavorable for environment protection.Above these drawbacks limit these methods in industrial application.
(3) summary of the invention
But the technical problem to be solved in the present invention is to provide a kind of preparation of simple industrial application has wide aperture, bigger serface γ-Al 2O 3Novel method.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of γ-Al 2O 3The preparation method of nanofiber comprises the following steps:
(a) inorganic salt containing aluminium solution and alkaline sedimentation agent solution are mixed according to volume ratio 1: 2~5, in described inorganic salt containing aluminium solution, the mass percent of inorganic salt containing aluminium is 5~40%, in described alkaline sedimentation agent solution, the mass percent of water is 80-95%, reacts after mixing to obtain suspension liquid under 30~100 ℃ of conditions;
(b) the suspension liquid filtration is obtained filter cake, and then remove impurity by making beating, filtration step in deionized water, obtain filter cake I;
(c) will be processed in organic solvent again by the filter cake I that step (b) makes, and then filter, reclaim organic solvent and obtain filter cake II;
(d) will carry out calcination process at 300~600 ℃ by the filter cake II that step (c) makes, obtain γ-Al 2O 3Nano-fiber material.
In step of the present invention (a), we find, the temperature of precipitin reaction and the concentration of raw material have important impact to particle diameter and the structure of controlling precursor particle in this step reaction.By controlling these key factors in step (a), can obtain: (1) has the particle of appropriate particle size, thereby is conducive to filter and washing; (2) between particle, water content is lower, reduces roasting process and caves in because the surface tension phenomenon causes the hole.Therefore, the preferred aluminum nitrate of described inorganic salt containing aluminium and Tai-Ace S 150; In described inorganic salt containing aluminium solution, the mass percent of inorganic salt containing aluminium is 5~40%, is preferably 10~30%, more preferably 10~20%.The preferred aqueous sodium carbonate of described alkaline sedimentation agent solution, aqueous sodium hydroxide solution or ammonia soln, more preferably aqueous sodium carbonate.In preferred steps (a), the temperature of precipitin reaction is 60~100 ℃.
In step of the present invention (b), suspension liquid is filtered obtains filter cake, and then in deionized water by repeatedly pull an oar, the washing step such as filtration to be to remove impurity, can make through the specific surface area of roasting rear oxidation aluminium larger.
In step of the present invention (c), with an organic solvent to carrying out replacement Treatment by the water in step (a) and the precipitated filter cakes that (b) obtains, cause the hole to cave in further reduction roasting process due to the surface tension phenomenon and the phenomenon such as particle aggregation.Described organic solvent can be selected from following a kind of or several combination arbitrarily: methyl alcohol, ethanol, propyl alcohol, butanols.
In step of the present invention (d), preferably with filter cake II at 300-600 ℃ of lower roasting 2-6 hour.Preferred roasting condition was: 400 ℃ of roastings 5 hours.
Described γ-the Al of the concrete recommendation of the present invention 2O 3The preparation method of nanofiber carries out in accordance with the following steps:
(a) inorganic salt containing aluminium solution and alkaline sedimentation agent solution are mixed according to volume ratio 1: 2~5, react under 30~100 ℃ of conditions and obtain suspension liquid; Described inorganic salt containing aluminium solution is aluminum nitrate aqueous solution or aluminum sulfate aqueous solution, and in described inorganic salt containing aluminium solution, the mass percent of inorganic salt is 5~40%; Described alkaline sedimentation agent solution is aqueous sodium carbonate, aqueous sodium hydroxide solution or ammonia soln, and in described alkaline sedimentation agent solution, the mass percent of water is 80-95%;
(b) the suspension liquid filtration is obtained filter cake, and then remove impurity by making beating, filtration step in deionized water, obtain filter cake I;
(c) will be processed in organic solvent again by the filter cake I that step (b) makes, and then filter, reclaim organic solvent and obtain filter cake II; Described organic solvent is selected from following a kind of or several combination arbitrarily: methyl alcohol, ethanol, propyl alcohol, butanols;
The filter cake II that (d) will be made by step (c) obtained γ-Al at 300~600 ℃ of roasting 2-6 hours 2O 3Nano-fiber material.
The Al that the present invention makes 2O 3Material, particle are fibrous particle, and its crystal formation is the γ crystal formation; The material specific surface area is not less than 300m 2g -1, pore volume is not less than 1.5cm 3g -1, the aperture is not less than 10nm.
Compared with the prior art, the present invention has the following advantages:
(1) novel method of the present invention report pattern that is conducive to control aluminium oxide particles to form fibrous particle, forms larger aperture, the Al that makes by piling up between these particles 2O 3Material has bigger serface, wide-aperture characteristics.
(2) preparation process of the present invention's report does not need complicated equipment and exacting terms to control, and the raw material that uses is cheap, and the preparation process environmental friendliness is convenient to suitability for industrialized production.
(4) description of drawings
The TEM figure of the aluminum oxide that Fig. 1: embodiment 1 makes.
The XRD figure of the aluminum oxide that Fig. 2: embodiment 1 makes.
(5) embodiment
The below is described further technical scheme of the present invention with specific embodiment, but protection scope of the present invention is not subjected to the restriction of the following example.
Embodiment (1)
With 88 gram Al (NO 3) 39H 2O and 50 gram Na 2CO 3Be dissolved in respectively and be made into 15wt% and 6wt% solution in 250 and 750 ml deionized water, then with Al (NO 3) 3And Na 2CO 3Solution mixes under 95 ℃ of conditions and carries out precipitin reaction.Resulting suspension liquid is filtered obtain filter cake, with deionized water, filter cake is washed, and then filter.Through repeatedly the washing and filtration treatment after, with ethanol, filter cake is processed.After filtration, reclaim ethanol after, resulting filter cake is obtained Al through 400 ℃ of roastings after 5 hours 2O 3Sample.Fig. 1 is TEM figure, shows to exist nanometer fibrous particle.Fig. 2 is XRD figure, shows that this material is γ-Al 2O 3
Embodiment (2)
With 78 gram Al 2(SO 4) 318H 2O and 50 gram Na 2CO 3Be dissolved in respectively and be made into 12wt% and 6wt% solution in 250 and 750 ml deionized water, then with Al 2(SO 4) 3And Na 2CO 3Solution mixes under 95 ℃ of conditions and carries out precipitin reaction.Resulting suspension liquid is filtered obtain filter cake, with deionized water, filter cake is washed, and then filter.After repeatedly washing and filtering, with ethanol, precipitated filter cakes is processed.After filtration, reclaim ethanol after, resulting filter cake is obtained Al through 400 ℃ of roastings after 5 hours 2O 3Sample.
Embodiment (3)
With 17.7 gram Al (NO 3) 39H 2O and 10 gram Na 2CO 3Be dissolved in respectively and be made into 15wt% and 6wt% solution in 50 and 150 ml deionized water, then with Al (NO 3) 3And Na 2CO 3Solution mixes at ambient temperature and carries out precipitin reaction.Resulting suspension liquid is filtered obtain filter cake, with deionized water, filter cake is washed, and then filter.After repeatedly washing and filtering, with ethanol, precipitated filter cakes is processed.After filtration, reclaim ethanol after, resulting filter cake is obtained Al through 400 ℃ of roastings after 5 hours 2O 3Sample.
Embodiment (4)-----F-T building-up reactions
Prepare CoRu/Al take the aluminum oxide of embodiment 1 preparation and commercial aluminum oxide (seeing Table 1) as carrier respectively 2O 3Catalyzer.
Catalyst preparation step: with 4.2 gram Co (NO 3) 26H 2O and 0.14 gram Ru (NO) (NO 3) 3And polyoxyethylene glycol (molecular weight 400 2vol%) joins 120cm under the condition of vigorous stirring 3In methyl alcohol and water mixed solution (the mixed volume ratio is 3: 1).After reaction 2h under 90 ℃, with 3 gram Al 2O 3Carrier joins in formed colloidal sol, and continues vigorous stirring.After evaporating solvent under 100 ℃ of conditions, can make the presoma of cobalt metal and ruthenium load to Al 2O 3On carrier, and obtain the colloidal solid material.The roasting under 400 ℃ of conditions of this colloidal solid material was obtained CoRuO in 4 hours x/ Al 2O 3Catalyzer.At last, pass through H 2Reduction can prepare CoRu/Al 2O 3Catalyzer (Co=22wt.%, (Ru/Co) at.=0.03).
By fixed-bed reactor, the synthetic performance of the F-T of catalyzer has been carried out evaluation test.Reaction conditions is 210 ℃, 2000KPa, H 2/ CO=2.With N 2As interior mark, by gas-chromatography to CO, N 2, CH 4, CO 2Carry out online qualitative and quantitative analysis Deng gas-phase product.Test-results shows, under the chemical constitution prerequisite identical with reaction conditions, the aluminum oxide by embodiment 1 preparation is that the catalyzer of carrier preparation has higher CO conversion rate (h than the catalyzer of the preparation take commercial aluminum oxide as carrier -1).
Table 1: the texture data of alumina material
Figure BDA0000066373690000061
Table 2:CoRu/Al 2O 3The F-T building-up reactions performance of catalyzer
Figure BDA0000066373690000062
CO conversion rate (the per hour CO mole number of every mole metal cobalt conversion)

Claims (7)

1. γ-Al 2O 3The preparation method of nanofiber comprises the following steps:
(a) inorganic salt containing aluminium solution and alkaline sedimentation agent solution are mixed according to volume ratio 1:2 ~ 5, in described inorganic salt containing aluminium solution, the mass percent of inorganic salt containing aluminium is 5 ~ 40%, in described alkaline sedimentation agent solution, the mass percent of water is 80 ~ 95%, reacts after mixing to obtain suspension liquid under 30 ~ 100 ℃ of conditions; Described alkaline sedimentation agent solution is aqueous sodium carbonate;
(b) the suspension liquid filtration is obtained filter cake, and then remove impurity by making beating, filtration step in deionized water, obtain filter cake I;
(c) will be processed in organic solvent again by the filter cake I that step (b) makes, and then filter, reclaim organic solvent and obtain filter cake II;
(d) will be carried out calcination process 2-6 hour at 300 ~ 600 ℃ by the filter cake II that step (c) makes, obtain γ-Al 2O 3Nano-fiber material.
2. γ-Al as claimed in claim 1 2O 3The preparation method of nanofiber is characterized in that: the described inorganic salt containing aluminium solution of step (a) is aluminum nitrate aqueous solution or aluminum sulfate aqueous solution.
3. γ-Al as claimed in claim 2 2O 3The preparation method of nanofiber is characterized in that: in the described inorganic salt containing aluminium solution of step (a), the mass percent of inorganic salt containing aluminium is 10 ~ 30%.
4. γ-Al as claimed in claim 1 2O 3The preparation method of nanofiber is characterized in that: the temperature of reaction in step (a) is 60 ~ 100 ℃.
5. γ-Al as claimed in claim 1 2O 3The preparation method of nanofiber is characterized in that: the described organic solvent of step (c) is selected from following a kind of or several combination arbitrarily: methyl alcohol, ethanol, propyl alcohol, butanols.
6. γ-Al as claimed in claim 1 2O 3The preparation method of nanofiber is characterized in that: the described maturing temperature of step (d) is 400 ℃, and roasting time is 5 hours.
7. γ-Al as claimed in claim 1 2O 3The preparation method of nanofiber is characterized in that: described preparation method carries out in accordance with the following steps:
(a) inorganic salt containing aluminium solution and alkaline sedimentation agent solution are mixed according to volume ratio 1:2 ~ 5, react under 30 ~ 100 ℃ of conditions and obtain suspension liquid; Described inorganic salt containing aluminium solution is aluminum nitrate aqueous solution or aluminum sulfate aqueous solution, and in described inorganic salt containing aluminium solution, the mass percent of inorganic salt containing aluminium is 5 ~ 40%; In described alkaline sedimentation agent solution, the mass percent of water is 80-95%;
(b) the suspension liquid filtration is obtained filter cake, and then remove impurity by making beating, filtration step in deionized water, obtain filter cake I;
(c) will be processed in organic solvent again by the filter cake I that step (b) makes, and then filter, reclaim organic solvent and obtain filter cake II; Described organic solution is selected from following a kind of or several combination arbitrarily: methyl alcohol, ethanol, propyl alcohol, butanols;
The filter cake II that (d) will be made by step (c) obtained γ-Al at 300 ~ 600 ℃ of roasting 2-6 hours 2O 3Nano-fiber material.
CN 201110150019 2011-06-03 2011-06-03 Preparation method of gamma-aluminium oxide (Al2O3) nanofiber Active CN102229436B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201110150019 CN102229436B (en) 2011-06-03 2011-06-03 Preparation method of gamma-aluminium oxide (Al2O3) nanofiber

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201110150019 CN102229436B (en) 2011-06-03 2011-06-03 Preparation method of gamma-aluminium oxide (Al2O3) nanofiber

Publications (2)

Publication Number Publication Date
CN102229436A CN102229436A (en) 2011-11-02
CN102229436B true CN102229436B (en) 2013-06-19

Family

ID=44842059

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201110150019 Active CN102229436B (en) 2011-06-03 2011-06-03 Preparation method of gamma-aluminium oxide (Al2O3) nanofiber

Country Status (1)

Country Link
CN (1) CN102229436B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104096487A (en) * 2014-07-28 2014-10-15 合肥工业大学 Preparation method for Gamma type aluminum oxide nanofiltration membrane
CN106276993B (en) * 2015-05-27 2017-08-11 裕祥化工(大连)有限公司 A kind of nano aluminium oxide thickened pulp and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101182024A (en) * 2007-11-23 2008-05-21 清华大学 Method for preparing one-dimensional aluminum oxide fibre by hydrothermal-flux technique

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101182024A (en) * 2007-11-23 2008-05-21 清华大学 Method for preparing one-dimensional aluminum oxide fibre by hydrothermal-flux technique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
魏蕾.超细γ-Al2O3的制备、表征及其在羰基硫水解反应中的应用.《中国优秀博硕士学位论文全文数据库(硕士) 工程科技I辑》.2006,(第8期),18-20,24-39,45. *

Also Published As

Publication number Publication date
CN102229436A (en) 2011-11-02

Similar Documents

Publication Publication Date Title
CN100494066C (en) Method for preparing ordered mesoporous aluminium oxide
CN102275962B (en) Preparation method and application of nano-alumina
CN103657643B (en) A kind of method preparing nano palladium metal catalyst
CN102941093B (en) Catalyst for decahydronaphthalene preparation by naphthalene hydrogenation, preparation and application thereof
CN102259900B (en) Hydrated alumina and preparation method thereof
CN110586094B (en) Copper-based nanoflower catalyst for producing methanol and ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof
WO2001026805A1 (en) Catalyst for hydrorefining distillate oil, its carrier and preparation thereof
CN101983765B (en) Catalyst for preparing methyl alcohol by catalytic hydrogenation on assistant modified carbon dioxide and preparation method thereof
CN105903484A (en) Nano-catalyst for preparing methyl formate by oxidizing methyl alcohol at one step and preparation method thereof
CN106904632B (en) A kind of HTS and its synthetic method and application and a kind of method for hydroxylation of phenol
CN103601226B (en) A kind of preparation method of boehmite
CN102744085B (en) Catalytic system containing nanometer Ru catalyst and alkali zinc sulfate salt and method for preparing cyclohexene through catalytic benzene selective hydrogenation
WO2020082195A1 (en) Ultra high selective hydrogenation catalyst and preparation thereof
CN114471447B (en) Palladium adsorbent for deeply removing organic sulfur in benzene refining and preparation method thereof
CN102229436B (en) Preparation method of gamma-aluminium oxide (Al2O3) nanofiber
CN101961661B (en) Organo-metallic catalyst for preparing cyclohexane by hydrogenation of benzene and preparation method and application thereof
US7919659B2 (en) Catalyst for cycloolefin production and process for production
CN101318139A (en) Composite solid super acidic catalyst and preparation method thereof
CN107537498B (en) Fischer-Tropsch catalyst and preparation method thereof
CN102974342B (en) Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof
CN111054384B (en) Catalyst for organic liquid hydrogen storage material dehydrogenation and preparation method thereof
CN105713657B (en) Hydrocracking method
CN100411735C (en) Solid super acidic catalyst and its preparing method
CN112093824B (en) Method for regulating and controlling crystal form of iron oxide, iron-based composite oxide prepared by method and application of iron-based composite oxide
CN110586957B (en) Preparation method of porous Pd hollow nanospheres in ionic liquid aqueous solution

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20180130

Address after: No. 335 Green Avenue 323000 Lishui Shuige Industrial Park in Zhejiang Province

Patentee after: ZHEJIANG TAIDE NEW MATERIAL CO.,LTD.

Address before: 310014 Hangzhou city in the lower reaches of the city of Zhejiang Wang Road, No. 18

Patentee before: Zhejiang University of Technology

PE01 Entry into force of the registration of the contract for pledge of patent right
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: one kind g- Preparation method of Al2O3nanofibers

Granted publication date: 20130619

Pledgee: Agricultural Bank of China Limited Lishui Development Zone Sub branch

Pledgor: ZHEJIANG TAIDE NEW MATERIAL CO.,LTD.

Registration number: Y2024330000582