CN1171295A - Method for fabricating porous composite oxide - Google Patents

Method for fabricating porous composite oxide Download PDF

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Publication number
CN1171295A
CN1171295A CN97103418A CN97103418A CN1171295A CN 1171295 A CN1171295 A CN 1171295A CN 97103418 A CN97103418 A CN 97103418A CN 97103418 A CN97103418 A CN 97103418A CN 1171295 A CN1171295 A CN 1171295A
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CN
China
Prior art keywords
porous composite
composite oxide
oxide
solution
manufacturing porous
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Granted
Application number
CN97103418A
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Chinese (zh)
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CN1074303C (en
Inventor
权镐真
洪舜教
白桂东
金惠真
朴东坤
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Samsung Electronics Co Ltd
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Samsung Electronics Co Ltd
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Publication of CN1171295A publication Critical patent/CN1171295A/en
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Publication of CN1074303C publication Critical patent/CN1074303C/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Abstract

The invention provides a method for making a porous composite oxide, which includes the steps of: (a) preparing a solution including a silicon oxide source and a solution including an aluminium oxide source; (b) slowly pouring one of the solutions from step (a) into the other solution while stirring; (c) adding hydrochloric acid to the mixed solution prepared in step (b) to obtain a sol and then adding sodium hydroxide to the sol to obtain a gel; and (d) reacting the silicon oxide source and aluminium oxide source in the gel at high temperature and high pressure. The porous composite oxide so formed has an abundance of fine pores and a relatively uniform distribution of pore sizes, making it suitable for use as a carrier or catalytic support.

Description

Method for fabricating porous composite oxide
The present invention relates to a kind of method of making porous composite oxide, more particularly, relate to the porous composite oxide of a kind of manufacturing, on this porous composite oxide, be formed with a large amount of pores, and pore-size distribution is even relatively as carrier.
Follow the present development of chemical relevant industries, various catalyst are also in development.Usually, catalyst is mainly used in the synthetic of material, cracking and reformation.
Such catalyst comprises the particle of metal or other composition.Catalyst has multiple application process, yet, should main method be catalyst soakage on carrier.
The carrier that is used for the impregnated catalyst particle does not have reactivity, and it has a large amount of pores.In order to activate catalytic reaction, the enough spaces that provide catalyst component to contact with reactant are necessary.As general carrier silica, aluminium oxide, alumino-silicate, zeolite and active carbon arranged.Particularly, because alumino-silicate has the hole in different apertures, it is extensively used as carrier.
On the other hand, for more effective catalytic reaction, the sort of carrier that can further improve reactant and catalyst contact area is needed.Generally can heat the solution that obtains then and can make alumino-silicate by dissolving soluble alumina and soluble silica.But can not provide abundant hole for the impregnated catalyst particle according to the alumino-silicate that said method makes.The hole that forms on the carrier is the space that is used for the impregnated catalyst particle, and catalytic reaction takes place in this space.Therefore, if there is not big metering-orifice, catalytic reaction just can not effectively be carried out.Therefore having the carrier that enriches the hole needs.
In addition, a large amount of hole with different-diameter should evenly distribute in whole carrier, so that various catalyst granules is easy to dipping.But the alumino-silicate pore size that makes according to a conventional method is not evenly distributed.
The purpose of this invention is to provide a kind of method of making porous composite oxide, this porous composite oxide has a large amount of micropores thereby can be used as carrier, and has pore-size distribution relatively uniformly.
For achieving the above object, a kind of manufacturing porous composite oxide method is provided here, comprise following steps:
(a) preparation contains the solution and the solution that contains aluminum oxide (aluminum oxide source) of Si oxide (silicon oxid source);
(b) a kind of solution in the step (a) is slowly poured in another solution, stirred simultaneously;
(c) in the mixed solution that step (b) obtains, add hydrochloric acid and obtain colloidal sol, then in colloidal sol, add NaOH and obtain gel;
(d) under the HTHP, make that Si oxide and aluminum oxide react in the gel.
Above-mentioned purpose of the present invention and advantage are passed through more detailed description preferred embodiment with reference to the accompanying drawings, will be more clear.
Fig. 1 represents porous composite oxide pore volume and the pore size relation curve that one preferred embodiment makes according to the present invention.
Fig. 2 represents the porous composite oxide pore volume and the pore size relation curve that make according to conventional methods.
According to the present invention, in the alumino-silicate forming process, use hydrochloric acid to form and have different big or small equally distributed holes in a large number with NaOH.
At first, respectively with soluble silicon oxide and soluble aluminum oxide dissolution in water.
According to the present invention, silicate, especially sodium metasilicate are as preferred Si oxide.And aluminate particularly sodium aluminate as preferred aluminum oxide.In addition, because under the room temperature condition, the solubility of Si oxide in water is low, therefore preferably add hydrothermal solution with the dissolves silicon oxide.Heating-up temperature can change according to solubility and reactant character.Yet general 50～60 ℃ is preferred range.
Prepare after the Si oxide and the aluminum oxide aqueous solution, two solution are mixed.Here, preferably control Si oxide and aluminum oxide concentration ratio, the mol ratio that makes silicon and aluminium is 1 to 3.
On the other hand, in order evenly to mix Si oxide and aluminum oxide, a kind of solution should be joined in another solution, and add this solution of thermal agitation simultaneously.
After two kinds of solution mix fully, add hydrochloric acid, up to obtaining transparent colloidal sol.Add NaOH then, and keep a scheduled time, make colloidal sol be converted into gel.Here, NaOH stimulates activity and the reaction uniformly between Si oxide and aluminum oxide.Preferred hydrochloric acid and NaOH use in weak solution, and reacting solution pH value is 3～12.
At last, heat gel, obtain having the alumino-silicate of pore.Heating is at 100～300 ℃, carries out 1～10 hour under 100～1200 pounds of/square inch (psi) conditions of pressure.Here, 100～150 ℃ of temperature ranges, pressure limit is an optimum condition for 100～200 pounds/square inch.
Hereinafter, will the present invention be described in detail with reference to preferred embodiment and comparative example, yet, will be appreciated that the particular form shown in the invention is not restricted to.
＜embodiment 1 〉
At first, in 150ml55 ℃ of distilled water with 98.4g sodium metasilicate (Na 2SiO 3) dissolving fully, with 152.5g sodium aluminate (NaAlO 2) also be dissolved in the 700ml distilled water.Then, sodium aluminate solution is slowly poured in the sodium silicate solution.In mixed process, mixed liquor is 55 ℃ of heating and stirrings simultaneously continuously.After two kinds of solution mixed fully, adding 6N HCl was transparent until reactant mixture.In clear solution, add 6N NaOH then and reach 10, keep obtaining in 60 minutes gel then until solution PH.Gel is put into reative cell and keep 100 ℃ of pressure 100psi of temperature.After one hour, product filters with vacuum equipment, is deposited in 100 ℃ of dryings and obtains the powdery alumino-silicate in 24 hours.
The surface area, pore volume and the pore size relation that make powder are measured, and obtain the result: recording surface area with the BET method is 135m 2/ g, size distribution relatively evenly (referring to the curve of accompanying drawing 1 a).
＜embodiment 2 〉
The shape alumino-silicate method that makes powder is described identical with embodiment 1, but different is, adds 6N NaOH and adjusts pH value of solution to 7, is reflected at 150 ℃ and 150psi condition and carries out.
To making the surface area of powder, pore volume and pore size relation are measured, and obtain the result: recording surface area with the BET method is 135m 2/ g, size distribution is even relatively.(referring to the curve b of accompanying drawing 1).
＜embodiment 3 〉
The shape alumino-silicate method that makes powder is described identical with embodiment 1, but difference is: add 6N NaOH and transfer molten pH value to 3, be reflected under 265 ℃ and the 1100PSi condition and carry out.
To making the surface area of powder, pore volume and pore size relation are measured, and obtain the result and be: the surface area that records with the BET method is 135m 2/ g changes according to pore size, and the degree of distribution in hole is fully uniform (referring to accompanying drawing 1 curve c).
＜comparative example 〉
The shape alumino-silicate method that makes powder is described identical with embodiment 1, but difference is: do not use hydrochloric acid and NaOH.The BET surface area and the pore-size distribution of the powder that measurement makes.
Obtain from embodiment and Comparative Examples measurement result: the alumino-silicate BET surface area that makes according to the present invention is greater than 100m 2/ g, and the alumino-silicate BET surface area that makes according to conventional method is less than 3.3m 2/ g.And aspect pore-size distribution, the pore volume of alumino-silicate of the present invention changes along with pore size and relatively evenly distributes by (referring to accompanying drawing 1), and is uneven (referring to accompanying drawing 2) according to the alumino-silicate pore volume distribution that conventional method makes
Porous composite oxide constructed in accordance has a large amount of micropores above it, and pore-size distribution is even relatively, so porous composite oxide of the present invention is suitable as carrier.

Claims (9)

1, makes the method for porous composite oxide, comprise the steps:
(a) preparation contains the solution and the solution that contains aluminum oxide of Si oxide;
(b) the described a kind of solution of step (a) is slowly poured in another solution, stirred simultaneously;
(c) add hydrochloric acid in the described mixed solution of step (b) preparation and obtain colloidal sol, then hydro-oxidation sodium obtains gel in described colloidal sol;
(d) described Si oxide and aluminum oxide are reacted.
2, the method for manufacturing porous composite oxide as claimed in claim 1, wherein, the silicon of above-mentioned mixed solution and al mole ratio are 1～3.
3, the method for manufacturing porous composite oxide as claimed in claim 1, wherein Si oxide is a silicate.
4, the method for manufacturing porous composite oxide as claimed in claim 3, wherein said silicate is sodium metasilicate.
5, the method for manufacturing porous composite oxide as claimed in claim 1, wherein said aluminum oxide is an aluminate.
6, the method for manufacturing porous composite oxide as claimed in claim 5, wherein said aluminate is a sodium aluminate.
7, the method for manufacturing porous composite oxide as claimed in claim 1 wherein adds described NaOH and reaches 3～12 up to the pH of colloidal sol value.
8, the method for manufacturing porous composite oxide as claimed in claim 1, wherein, reaction is to be 100～300 ℃ in temperature, pressure is to carry out under the condition of 100～1200psi.
9, the method for manufacturing porous composite oxide as claimed in claim 8, wherein said temperature are 100～150 ℃, and pressure is 100～200psi.
CN97103418A 1996-07-19 1997-02-28 Method for fabricating porous composite oxide Expired - Fee Related CN1074303C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR29309/1996 1996-07-19
KR29309/96 1996-07-19
KR1019960029309A KR100195111B1 (en) 1996-07-19 1996-07-19 Method for manufacturing porous composite oxide

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CN1171295A true CN1171295A (en) 1998-01-28
CN1074303C CN1074303C (en) 2001-11-07

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JP (1) JP2928189B2 (en)
KR (1) KR100195111B1 (en)
CN (1) CN1074303C (en)
BR (1) BR9701084A (en)
GB (1) GB2315430B (en)
IT (1) IT1289954B1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101388414B (en) * 2004-11-05 2011-01-26 财团法人工业技术研究院 Heat resistance construction on plastic substrate
US8029890B2 (en) 2004-11-04 2011-10-04 Industrial Technology Research Institute Structure of thermal resistive layer and the method of forming the same
WO2022151828A1 (en) 2021-01-15 2022-07-21 百瑞全球有限公司 Membrane-shaped immobilized cell, polypeptide, oligopeptide or protein, and preparation method therefor

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* Cited by examiner, † Cited by third party
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KR100761452B1 (en) * 2006-11-06 2007-10-04 한양대학교 산학협력단 Method for manufacturing cement having minute particle by chemical synthesis and method for manufacturing concrete using thereof
KR101142398B1 (en) * 2009-08-17 2012-05-08 (주)한천자원 Manufacturing method of molding coal using coal dust
CN103055891A (en) * 2012-12-03 2013-04-24 天津大学 Method for preparing nano porous titanium dioxide thin film doped with Pd by constant voltage dealloying method on amorphous alloy stripe

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GB1413874A (en) * 1973-01-10 1975-11-12 Atlantic Richfield Co Process for hydrotreating high nitrogen feedstocks and a catalyst for use therein
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JPH0655276B2 (en) * 1990-02-28 1994-07-27 富田製薬株式会社 Method for producing ammonium ion-selective adsorbent
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EP0783371B1 (en) * 1994-09-22 1998-06-24 F. Hoffmann-La Roche Ag Heterogeneous catalysts

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8029890B2 (en) 2004-11-04 2011-10-04 Industrial Technology Research Institute Structure of thermal resistive layer and the method of forming the same
CN101388414B (en) * 2004-11-05 2011-01-26 财团法人工业技术研究院 Heat resistance construction on plastic substrate
WO2022151828A1 (en) 2021-01-15 2022-07-21 百瑞全球有限公司 Membrane-shaped immobilized cell, polypeptide, oligopeptide or protein, and preparation method therefor

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CN1074303C (en) 2001-11-07
KR980009114A (en) 1998-04-30
BR9701084A (en) 1998-12-15
GB2315430B (en) 1999-04-07
GB2315430A (en) 1998-02-04
JP2928189B2 (en) 1999-08-03
GB9701614D0 (en) 1997-03-19
KR100195111B1 (en) 1999-06-15
ITMI970382A1 (en) 1998-08-21
JPH1036111A (en) 1998-02-10
IT1289954B1 (en) 1998-10-19

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C53 Correction of patent for invention or patent application
CB03 Change of inventor or designer information

Inventor after: Quan Gaozhen

Inventor after: Hong Shunjiao

Inventor after: Bai Guidong

Inventor after: Jin Huizhen

Inventor after: Pu Dongkun

Inventor before: Quan Gaozhen

Inventor before: Hong Shunjiao

Inventor before: Bai Guidong

Inventor before: Jin Huizhen

Inventor before: Pu Dongkun

Inventor before: Nan Xiangcheng

COR Change of bibliographic data

Free format text: CORRECT: INVENTOR; FROM: GAOZHEN KWON; HONG SHUNJIAO; BAI GUIDONG; JIN HUIZHEN; PARK DONG-KUN; NAN XIANGCHENG TO: GAOZHEN KWON; HONG SHUNJIAO; BAI GUIDONG; JIN HUIZHEN; PARK DONG-KUN

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