[go: up one dir, main page]

WO2001074713A1 - Catalyseurs mesoporeux ameliores - Google Patents

Catalyseurs mesoporeux ameliores Download PDF

Info

Publication number
WO2001074713A1
WO2001074713A1 PCT/AU2001/000371 AU0100371W WO0174713A1 WO 2001074713 A1 WO2001074713 A1 WO 2001074713A1 AU 0100371 W AU0100371 W AU 0100371W WO 0174713 A1 WO0174713 A1 WO 0174713A1
Authority
WO
WIPO (PCT)
Prior art keywords
surfactant
catalyst
aluminium hydroxide
activated alumina
alumina
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.)
Ceased
Application number
PCT/AU2001/000371
Other languages
English (en)
Inventor
Gao Qing Lu
Huai Yong Zhu
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.)
University of Queensland UQ
Original Assignee
University of Queensland UQ
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 University of Queensland UQ filed Critical University of Queensland UQ
Priority to AU2001243954A priority Critical patent/AU2001243954A1/en
Publication of WO2001074713A1 publication Critical patent/WO2001074713A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • 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
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/14—Aluminium oxide or hydroxide from alkali metal 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • 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
    • C01P2006/12—Surface area
    • C01P2006/13—Surface area thermal stability thereof at high temperatures
    • 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

Definitions

  • the invention relates to a method of preparing improved catalysts having high surface area and defined pore structure.
  • activated alumina Materials such as activated alumina are widely used as catalysts, catalyst supports and adsorbents.
  • Activated alumina is currently produced by thermal decomposition of hydrated aluminas.
  • the main uses of activated alumina are for drying gases (air, He, H 2 , natural gas, etc), drying liquids (hydrocarbons, petroleum products, alcohols, etc), Claus catalyst (for sulfur recovery from H 2 S), dehydration of alcohols, isomerization, cracking and reforming of hydrocarbons, autoexhaust catalysts, and chromatography.
  • the world production of activated alumina exceeds a few million tons a year.
  • the pore structure of the activated alumina affects the performance of the catalysts or adsorbents. It is desirable to have controllable average pore size and a controllable pore size distribution. Control of these properties has not been possible with the known techniques for producing catalysts. The inventors are aware of United States patent number
  • Basmadjian process works in a similar manner as the Sieg US Patent.
  • Basmadjian and Sieg produce catalysts with a broad pore size distribution and less controllability.
  • the invention resides in a method of preparing activated alumina including the steps of: forming an aqueous aluminium hydroxide precipitate from mixing an acidic solution and a basic solution; mixing the aqueous aluminium hydroxide precipitate with a low molecular weight, water dispersable surfactant; forming a homogeneous composite of aluminium hydroxide and surfactant by keeping the aluminium hydroxide and surfactant in a closed environment at approximately 100°C; calcining the aluminium hydroxide alumina precipitate and surfactant mixture at greater than 100°C to eliminate the surfactant and form the activated alumina (AI 2 O 3 ).
  • the surfactant is a short chain polyethylene oxide having a molecular weight in the range 400-730.
  • the water dispersable surfactant forms irregular micelles within the aqueous aluminium hydroxide precipitate.
  • the acidic solution has glycerol added to assist in the precipitation of smaller particles of aluminium hydroxide.
  • the step of calcining is preferably at a temperature of greater than 200°C.
  • the method may further include the step of collecting and recycling surfactant eliminated in the drying step and the calcining step.
  • a feature of the resultant catalyst from the above method is not only more controllable pore size and pore size distribution but also that the catalyst can withstand treatment, use or regeneration under high temperatures without any significant affect to the catalyst structure or activity.
  • an activated alumina catalyst or catalyst support having a mesoporous structure, formed from particles of alumina, which are arranged to create interstices, wherein the particles of alumina have their largest dimension in the nanometer range.
  • the interstices of the activated alumina catalyst or catalyst support have a diameter in the range of 10 to 400 A. More preferably the interstices have a mean diameter in the range of 80 to 160 A.
  • the activated alumina catalyst or catalyst support suitably has interstices with a mean diameter in the range of 120 to 220A, when subjected to heat treatment at temperatures greater than 900°C.
  • the activated alumina catalyst or catalyst support has a surface area equal or greater than 200 m 2 /g and/or has porosity between 1.4 and 2 cm 2 /g.
  • FIG 1 is a flowchart showing a method of forming an activated alumina
  • FIG 2 is a plot of pore size distribution for a first example of the method of FIG 1 ;
  • FIG 3 is a plot of pore size distribution for a second example of the method of FIG 1 ;
  • FIG 4 is a TEM photo of the alumina catalyst of the example
  • FIG 5 is a sketch of the first stage in the production of an activated alumina.
  • FIG 6 is a sketch of a later stage in the production of an activated alumina.
  • FIG. 1 there is shown a flowchart that outlines the steps for producing an activated alumina with a well-controlled pore size distribution.
  • Aluminium hydroxide is precipitated in the conventional manner from an acid and a base, but not dried.
  • a suitable amount of the wet aluminium hydroxide precipitate is mixed with a surfactant and stirred until a high degree of mixing is achieved.
  • the mix is the kept in a closed environment at 100°C to form a homogeneous composite of the aluminium hydroxide and the surfactant.
  • the closed environment is a sealed container.
  • a supernatant liquid of mainly surfactant and water remains after this stage. It may be collected and recycled.
  • the resultant aluminium hydroxide and surfactant cake is then calcined at above 100°C to eliminate surfactant from the aluminium hydroxide and convert the aluminium hydroxide to activated alumina, thus forming a catalyst.
  • the catalyst of this process is found to have a larger average pore size and narrower pore size distribution than prior art catalysts. Furthermore, the pore size and pore size distribution can be controlled by careful control of the base, acid and surfactant combination.
  • catalyst is used to generically describe the resultant activated alumina. It would also be appreciated that the final product of activated alumina (the catalyst) can be used as a catalyst per se or a catalyst support.
  • Example 1 A series of catalysts were prepared from NaAIO 2 and acetic acid with varying quantities of polyethylene oxide as the surfactant.
  • a base solution was prepared by dissolving 37.6g of NaAIO 2 in 100ml of water.
  • An acid solution was prepared by adding 20g of glycerol into 100ml of 5N acetic acid solution. The base solution was added dropwise to the acid solution under vigorous stirring. White precipitate (alumina) was formed during the addition. The pH of the final solution was 8.8.
  • the precipitate was separated by centrifugation at 2500rpm for 15 minutes. To remove Na + ions, the precipitate was washed three times by dispersion in deionised water and centrifugation. The washed precipitate was divided into five equal portions and each portion was mixed with a different amount of low molecular weight polyethylene oxide surfactant.
  • the surfactant used is known as Tergitol 15-TS-7 and is available from Aldrich Chemical Company. It is a polyethylene oxide (PEO) material having a molecular weight about 500.
  • the precipitate and surfactant were stirred for one hour and then transferred to an autoclave and kept at 100°C for two days. Supernatant liquid was collected and the remaining white cake allowed to dry in atmosphere. The supernatant liquid is primarily surfactant with some water content. The liquid can be collected and reused in the process. This feature has advantage in industrial-scale applications by reducing reagent costs.
  • the dried white cake is calcined at 500°C for 20 hours.
  • the calcination temperature was raised from ambient to 500°C at a rate of
  • the PEO surfactant is evaporated in the temperature range between 150°C and 250°C.
  • the surfactant can be collected in a cooling trap during this phase and reused.
  • Table 1 These samples were then heated at 900°C for three hours.
  • the surface area and porosity data of the products is shown in the following table.
  • Table 2 As can be seen from the two tables, the addition of the surfactant results in a controlled increase in the peak of the pore size distribution. The width of the pore size distribution is also well controlled as can be seen from FIG 2.
  • FIG 2 shows the pore size distribution as a function of pore diameter for a subset of the preparations in Table 1.
  • MR is the molar ratio of surfactant used in preparing the samples.
  • a base solution was prepared from 26.0g of NaAIO 2 dissolved in 500ml of water.
  • An acid solution was prepared by dissolving 241.5g of AICI 3 »6H 2 O in 500ml of water.
  • 10g of glycerol was added to 70ml of the acid solution and 350ml of the base solution was added drop-wise under stirring. White precipitate was formed during the addition.
  • the final pH of the suspension was controlled to about 6. The precipitate was then separated by centrifugation at 2500rpm for 15 minutes.
  • the precipitate was washed three times by dispersing in deionised water and separating by centrifugation to remove Na + and Cl " ions.
  • the washed cake was mixed with polyethylene oxide surfactant, Tergitol 15-TS-7.
  • the amount of surfactant was varied from Og to 214g to obtain a range of samples.
  • After prolonged stirring of one hour the mixture was transferred into an autoclave and kept at 100°C for two days. Supernatant liquid was poured out and the white cake at the bottom was dried in atmosphere.
  • the dried white cake is calcined at 500°C for 20 hours.
  • the calcination temperature was raised at a rate of 2°C/min from ambient to 500°C.
  • FIG 3 shows the pore size distribution as a function of pore diameter for a subset of the preparations in Table 1. As with FIG 2, it can be seen that a desired pore size distribution can be achieved by careful selection of the molar ratio of surfactant to aluminium.
  • a number of alumina catalyst samples were produced in a similar manner to Example 1 and heated to 1200°C to determine the effect of calcining temperature on the pore size of the resultant catalyst. The results are summarized in the table below.
  • Table 5 It can be seen from Table 5, when heated to 1200°C, the sample prepared with the surfactant retained significantly larger specific surface area and porosity, when compared with those samples prepared without surfactant, ie the surface area and pore volume of an alumina prepared with surfactant are over 10 times of those samples prepared without surfactant.
  • the samples prepared with surfactant have significant resistance to high temperature heating. This is very important when the solids are used as the supports of catalysts working at high temperatures, for instance, combustion catalysts. Materials with this property are rare and normally difficult to make and therefore are expensive.
  • the mesoporous structure of the alumina catalysts of examples 1 to 3 is shown in the TEM photo of FIG 4.
  • a desired pore size distribution and total pore volume can be achieved by control of the quantity of surfactant used. Control of catalyst characteristics is achieved to a greater degree than has been possible with prior art methods. The inventors believe that this is due to the mechanism of formation of the catalyst.
  • the white precipitate forms particles in the nanometer range that stack together to form small interstices that are filled with water as shown in FIG 5.
  • Adding surfactant forces the interstices to enlarge as they fill with surfactant and water as shown in FIG 6.
  • the aluminium hydroxide particles set in the positions during the heating step thereby forming a composite meso-structure of aluminium hydroxide.
  • the subsequent heating at higher temperatures eliminated the surfactant and strengthens and forms the catalyst or mesoporous alumina structure.
  • the pore size and total pore volume is determined by the quantity of surfactant rather than the size of the surfactant molecules, as is the case in the prior art techniques that utilise high molecular weight polymers.
  • the dispersable surfactant forms micelles of irregular shape within the dispersed phase of a solution. These micelles are unevenly dispersed and incorporated within the hydrogel framework of the aluminium hydroxide and surfactant mixture. In the aluminium hydroxide precipitate and surfactant mixture, the aluminium hydroxide is aligned or orientated around the surfactant micelles. This arrangement also traps within it some water. After forming the homogeneous mixture of aluminium hydroxide and surfactant at 100°C over two days, most of the trapped water is driven out of the aluminium hydroxide-surfactant mixture.
  • the physical structure of the aluminium hydroxide is stabilised due to the support provided by a number of the smaller surfactant molecules incorporated into the aluminium hydroxide precipitate and surfactant mixture.
  • the surfactant is finally removed in the calcining stage the aluminium hydroxide is converted to alumina, which maintains it's structural arrangement achieved after drying with minimal or no collapsing of its structure.
  • the use of glycerol in the acidic solution, to precipitate the aluminium hydroxide, is to form small particles of precipitate.
  • the aluminium hydroxide has a strong affinity to the glycol and tends to be adsorbed onto the surface of the aluminium hydroxide particles.
  • the resultant precipitate has a larger surface area and pore volume.
  • An additional advantage and result of the current process is to produce a catalyst, which can withstand treatment, use and regeneration at high temperatures, between about 700 - 900°C, without any significant affect to the catalyst structure or activity.
  • the resultant catalyst of mesoporous alumina, produced by the above method, has large porosity and greater surface area.
  • the surface area is typically equal to or greater than 200m 2 /g, whilst the porosity is between 1.4 and 2cm 3 /g. This larger porosity is maintained after heat treatment at very high temperatures, typically 900 °C. This is in comparison to conventional prepared ⁇ alumina with porosity of less than 0.5cm 3 /g and surface area of between 50 and 60m 2 /g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé permettant de préparer des catalyseurs à base d'alumine activée, ayant des pores de grande dimension et présentant une résistance accrue aux effets de températures élevées. Ce procédé comprend les étapes suivantes : former un précipité aqueux d'hydroxyde d'aluminium, à partir d'un mélange de solution acide et de solution basique ; mélanger ledit précipité à un tensioactif dispersible dans l'eau, de faible poids moléculaire ; former un composite homogène d'hydroxyde d'aluminium et de tensioactif par maintien de l'hydroxyde d'aluminium et du tensioactif dans un environnement fermé, à approximativement 100 °C ; puis calciner le mélange de précipité d'alumine d'hydroxyde d'aluminium et de tensioactif, à plus de 100 °C, afin d'éliminer le tensioactif et de former de l'alumine activée (Al2O3). L'invention concerne également un catalyseur à base d'alumine de structure mésoporeuse, formé à partir de particules d'alumine de l'ordre du nanomètre, disposées de manière à former des interstices.
PCT/AU2001/000371 2000-04-03 2001-04-03 Catalyseurs mesoporeux ameliores Ceased WO2001074713A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001243954A AU2001243954A1 (en) 2000-04-03 2001-04-03 Improved mesoporous catalysts

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPQ6650A AUPQ665000A0 (en) 2000-04-03 2000-04-03 Improved catalyst
AUPQ6650 2000-04-03

Publications (1)

Publication Number Publication Date
WO2001074713A1 true WO2001074713A1 (fr) 2001-10-11

Family

ID=3820746

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2001/000371 Ceased WO2001074713A1 (fr) 2000-04-03 2001-04-03 Catalyseurs mesoporeux ameliores

Country Status (2)

Country Link
AU (1) AUPQ665000A0 (fr)
WO (1) WO2001074713A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2836067A1 (fr) * 2002-02-15 2003-08-22 Rhodia Chimie Sa Compose mesostructure homogene comprenant une phase minerale d'alumine et des particules au moins partiellement cristallines d'un compose de cerium, de titane ou de zirconium, son procede de preparation et ses utilisations
WO2003068678A3 (fr) * 2002-02-15 2004-03-25 Rhodia Chimie Sa Compose mesoporeux comprenant une phase minérale d'alumine et des particules d'oxyde de cérium, de titane ou de zirconium, et éventuellement un élément en solution solide dans ces particules, procédés de préparation et ses utilisations
CN100484877C (zh) * 2006-03-22 2009-05-06 中国科学院大连化学物理研究所 一种具有高热稳定性和大比表面积氧化铝的制备方法
CN103754913A (zh) * 2014-01-28 2014-04-30 复旦大学 一种氢氧化铝纳米颗粒材料的简易制备方法
CN115259195A (zh) * 2022-09-01 2022-11-01 杭州智华杰科技有限公司 一种提高活性氧化铝孔径分布的方法
CN117142503A (zh) * 2023-08-28 2023-12-01 山东奥维新材料科技有限公司 一种复合活性氧化铝粉及其制备方法
CN117985748A (zh) * 2024-04-03 2024-05-07 山东吉润纳米新材料有限公司 一种高纯度氧化铝及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU232219A1 (ru) * 1966-12-10 1978-04-30 Пикалевский Глиноземный Комбинат Способ получени активной окиси алюмини
US5622684A (en) * 1995-06-06 1997-04-22 Board Of Trustees Operating Michigan State University Porous inorganic oxide materials prepared by non-ionic surfactant templating route
US5840271A (en) * 1996-02-09 1998-11-24 Intevep, S.A. Synthetic material with high void volume associated with mesoporous tortuous channels having a narrow size distribution
WO1998056499A1 (fr) * 1997-06-10 1998-12-17 Institut Français Du Petrole Extrudes d'alumine, leurs procedes de preparation et leur utilisation comme catalyseurs ou supports de catalyseurs
US5863515A (en) * 1996-02-20 1999-01-26 California Institute Of Technology Mesoporous alumina and process for its preparation
US5911966A (en) * 1997-07-14 1999-06-15 Basf Aktiengesellschaft High surface area alumina solid
US6027706A (en) * 1998-05-05 2000-02-22 Board Of Trustees Operating Michigan State University Porous aluminum oxide materials prepared by non-ionic surfactant assembly route

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU232219A1 (ru) * 1966-12-10 1978-04-30 Пикалевский Глиноземный Комбинат Способ получени активной окиси алюмини
US5622684A (en) * 1995-06-06 1997-04-22 Board Of Trustees Operating Michigan State University Porous inorganic oxide materials prepared by non-ionic surfactant templating route
US5840271A (en) * 1996-02-09 1998-11-24 Intevep, S.A. Synthetic material with high void volume associated with mesoporous tortuous channels having a narrow size distribution
US5863515A (en) * 1996-02-20 1999-01-26 California Institute Of Technology Mesoporous alumina and process for its preparation
WO1998056499A1 (fr) * 1997-06-10 1998-12-17 Institut Français Du Petrole Extrudes d'alumine, leurs procedes de preparation et leur utilisation comme catalyseurs ou supports de catalyseurs
US5911966A (en) * 1997-07-14 1999-06-15 Basf Aktiengesellschaft High surface area alumina solid
US6027706A (en) * 1998-05-05 2000-02-22 Board Of Trustees Operating Michigan State University Porous aluminum oxide materials prepared by non-ionic surfactant assembly route

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; Class E33, AN 92400A/51 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2836067A1 (fr) * 2002-02-15 2003-08-22 Rhodia Chimie Sa Compose mesostructure homogene comprenant une phase minerale d'alumine et des particules au moins partiellement cristallines d'un compose de cerium, de titane ou de zirconium, son procede de preparation et ses utilisations
WO2003068678A3 (fr) * 2002-02-15 2004-03-25 Rhodia Chimie Sa Compose mesoporeux comprenant une phase minérale d'alumine et des particules d'oxyde de cérium, de titane ou de zirconium, et éventuellement un élément en solution solide dans ces particules, procédés de préparation et ses utilisations
CN100484877C (zh) * 2006-03-22 2009-05-06 中国科学院大连化学物理研究所 一种具有高热稳定性和大比表面积氧化铝的制备方法
CN103754913A (zh) * 2014-01-28 2014-04-30 复旦大学 一种氢氧化铝纳米颗粒材料的简易制备方法
CN115259195A (zh) * 2022-09-01 2022-11-01 杭州智华杰科技有限公司 一种提高活性氧化铝孔径分布的方法
CN115259195B (zh) * 2022-09-01 2023-09-22 杭州智华杰科技有限公司 一种提高活性氧化铝孔径分布的方法
CN117142503A (zh) * 2023-08-28 2023-12-01 山东奥维新材料科技有限公司 一种复合活性氧化铝粉及其制备方法
CN117142503B (zh) * 2023-08-28 2024-02-23 山东奥维新材料科技有限公司 一种复合活性氧化铝粉及其制备方法
CN117985748A (zh) * 2024-04-03 2024-05-07 山东吉润纳米新材料有限公司 一种高纯度氧化铝及其制备方法
CN117985748B (zh) * 2024-04-03 2024-06-04 山东吉润纳米新材料有限公司 一种高纯度氧化铝及其制备方法

Also Published As

Publication number Publication date
AUPQ665000A0 (en) 2000-05-04

Similar Documents

Publication Publication Date Title
Charkhi et al. Fabrication of granulated NaY zeolite nanoparticles using a new method and study the adsorption properties
US4514511A (en) Preparation of spheroidal alumina particulates
AU603231B2 (en) Ceric oxide with a large specific surface at high temperatures and method of manufacture
US3520654A (en) Process for the preparation of low density alumina gel
Zhang et al. Designed synthesis of sulfonated polystyrene/mesoporous silica hollow nanospheres as efficient solid acid catalysts
Sun et al. Synthesis of porous zirconia spheres for HPLC by polymerization-induced colloid aggregation (PICA)
CN110550638B (zh) 一种单分散大孔径的介孔二氧化硅纳米粒子的制备方法
KR101820064B1 (ko) 촉매 지지체, 촉매 및 이들의 제조 및 용도
CN102958833A (zh) 包含氧化铁纳米粒子的介孔碳的制备方法
Razani et al. Development of new organic-inorganic, hybrid bionanocomposite from cellulose nanowhisker and Mg/Al-CO3-LDHfor enhanced dye removal
Gopalan et al. Evolution of pore and phase structure of sol-gel derived lanthana doped titania at high temperatures
Freyria et al. Effects of the Brookite Phase on the Properties of Different Nanostructured TiO2 Phases Photocatalytically Active Towards the Degradation of N‐Phenylurea
WO2001074713A1 (fr) Catalyseurs mesoporeux ameliores
CN108579705A (zh) 一种介孔二氧化硅微球的制备方法
KR970002895B1 (ko) 산화 알루미늄 응집체의 제조방법 및 수득한 응집체
CA1276003C (fr) Silice spheroidal
CN1353008A (zh) 一种中孔硅铝催化材料的制备方法
CN117380172B (zh) 具有双亲性结构的光催化自清洁金属氢氧化物/TiO2水溶胶及其制备方法与应用
CN114426300B (zh) 一种大孔氧化铝载体的制备方法
CN108201884A (zh) γ-Al2O3载体的制备方法以及烷烃异构化催化剂的制备方法
WO2006135339A1 (fr) Particules de mousse mesocellulaires
CN107159279A (zh) 一种裂解汽油一段选择性加氢催化剂及其制备方法
CN115677923A (zh) 一种新型预交联凝胶颗粒型堵剂及其制备方法和应用
CN107189812A (zh) 一种裂解c6‑c8馏分选择性加氢的方法
CN117457249B (zh) 一种气凝胶珠在含铀废水处理中的应用

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP