WO1999041198A1 - Procede de production d'argile anionique utilisant deux types de composes d'alumine - Google Patents

Procede de production d'argile anionique utilisant deux types de composes d'alumine Download PDF

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Publication number
WO1999041198A1
WO1999041198A1 PCT/EP1999/000938 EP9900938W WO9941198A1 WO 1999041198 A1 WO1999041198 A1 WO 1999041198A1 EP 9900938 W EP9900938 W EP 9900938W WO 9941198 A1 WO9941198 A1 WO 9941198A1
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WIPO (PCT)
Prior art keywords
aluminium
process according
source
metals
anionic clay
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PCT/EP1999/000938
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English (en)
Inventor
Dennis Stamires
Mike Brady
William Jones
Fathi Kooli
Original Assignee
Akzo Nobel N.V.
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 Akzo Nobel N.V. filed Critical Akzo Nobel N.V.
Priority to EP99904879A priority Critical patent/EP1054838B1/fr
Priority to CA002320438A priority patent/CA2320438C/fr
Priority to JP2000531402A priority patent/JP2003524569A/ja
Priority to DE69919330T priority patent/DE69919330T2/de
Publication of WO1999041198A1 publication Critical patent/WO1999041198A1/fr

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Classifications

    • 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
    • C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • 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
    • B01J21/005—Spinels
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B01J27/236—Hydroxy carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

Definitions

  • This invention involves the preparation of anionic clays and the preparation of Mg-AI solid solutions by heat-treatment of the anionic clay.
  • Anionic clays have a crystal structure which consists of positively charged layers built up of specific combinations of metal hydroxides between which there are anions and water molecules.
  • Hydrotalcite is an example of a naturally occurring anionic clay, in which carbonate is the predominant anion present.
  • Meixnerite is an anionic clay wherein hydroxyl is the predominant anion present.
  • the brucite-like main layers are built up of octahedra alternating with interlayers in which water molecules and anions, more particularly carbonate ions, are distributed.
  • the interlayers may contain anions such as NO 3 -, OH, CI “ , Br, I " , SO 4 2" , SiO 3 2' , CrO 4 2” , BO 3 2" , MnO 4 ' ,
  • a characteristic of anionic clays is that mild calcination at 500 °C results in the formation of a disordered MgO-like product.
  • Said disordered MgO-like product is distinguishable frorrt spinel (which results upon severe calcination) and from anionic clays.
  • frorrt spinel which results upon severe calcination
  • anionic clays in this patent application we refer to said disordered MgO-like materials as Mg-AI solid solutions.
  • these Mg-AI solid solutions contain a well-known memory effect whereby the exposure to water of such calcined materials results in the reformation of the anionic clay structure.
  • European Patent Application 0 536 879 describes a method for introducing pH-dependent anions into the clay.
  • the clay is prepared by the addition of a solution of AI(NO 3 ) 3 and Mg(N0 3 ) 2 to a basic solution containing borate anions.
  • the product is then filtered, washed repeatedly with water, and dried overnight. Additionally mixtures of Zn/Mg are used.
  • the hydrotalcite is made by reacting activated MgO (prepared by activating a magnesium compound such as magnesium carbonate or magnesium hydroxide) with aqueous solutions containing aluminate, carbonate and hydroxyl ions.
  • activated MgO prepared by activating a magnesium compound such as magnesium carbonate or magnesium hydroxide
  • aqueous solutions containing aluminate, carbonate and hydroxyl ions As an example the solution is made from NAOH, Na 2 CO 3 and Al 2 0 3 .
  • the synthesis involves the use of industrial Bayer liquor as the source of Al.
  • the resulting products are washed and filtered before drying at 105 °C.
  • a catalyst for removing sulfur oxides or nitrogen oxides from a gaseous mixture is made by calcining an anionic clay, said anionic clay having been prepared by co-precipitation of a solution of Mg(NO 3 ) 2 , AI(NO 3 ) 3 and Ce(NO 3 ) 3 .
  • the product again is filtered and repeatedly washed with de-ionized water.
  • layered double hydroxide sorbents for the removal of sulfur oxide(s) from flue gases, which layered double hydroxide is prepared by reacting a solution of Al and Mg nitrates or chlorides with a solution of NAOH and Na 2 CO 3 .
  • layered double hydroxides intercalated with polyoxo anions are described, with the parent clay being made by co-precipitation techniques.
  • Our invention includes a process for producing anionic clays using raw materials which are inexpensive and utilizing such raw materials in a simple process which is extremely suitable to be carried out in continuous mode. Said process involves reacting mixtures with or without stirring in water at ambient or elevated temperature at atmospheric or elevated pressure. Such continuous processes can be operated in standard industrial equipment. More specifically, there is no need for washing or filtering, and a wide range of ratios of Mg/AI in the reaction product is possible.
  • an aluminium source and a magnesium source are reacted in aqueous suspension to obtain an anionic clay.
  • the aluminium source comprises two types of aluminium-containing compounds, for instance alumina trihydrate (such as gibbsite, bayerite or nordstrandite) and thermally treated forms thereof.
  • the reaction is carried out at ambient or elevated temperature and ambient or elevated pressure and the reaction mixture results in the direct formation of an anionic clay which can be obtained by simply drying the slurry continuously retrieved from the reactor.
  • the powder X-ray diffraction pattern (PXRD) suggests that the product is comparable to anionic clays made by other standard (batch) methods.
  • the physical and chemical properties of the product are also comparable to those anionic clays made by the other conventional methods.
  • the overall process of this invention is very flexible, enabling a wide variety of anionic clay compositions and anionic clay- like materials involving for example carbonate, hydroxide and other anions to be prepared in an economically and environmental-friendly manner.
  • Figure 1 shows a PXRD pattern of commercially available Mg-AI carbonate anionic clay.
  • Figure 2 shows a PXRD pattern of a Mg-AI carbonate anionic clay prepared by coprecipitation.
  • Figure 3 shows a PXRD pattern of a Mg-AI carbonate anionic clay prepared by using gibbsite, amorphous gel alumina and MgO.
  • Figure 4 shows a PXRD pattern of a Mg-AI carbonate anionic clay prepared by using gibbsite, thermally treated gibbsite and MgO.
  • Figure 5 shows a PXRD pattern of a Mg-AI carbonate anionic clay prepared by using gibbsite, flash calcined alumina and MgO.
  • Figure 6 shows a PXRD pattern of a Mg-AI carbonate anionic clay prepared by using gibbsite, Catapal A ® and MgO.
  • This invention involves the preparation of anionic clays.
  • a process for the preparation of an anionic clay wherein an aluminium source and a magnesium source are reacted in aqueous suspension to obtain an anionic clay, the aluminium source comprising two types of aluminium-containing compounds wherein one type of aluminium- containing compound is aluminium trihydrate or its thermally treated form.
  • Said magnesium source may be composed of a solution of a magnesium salt, a solid magnesium-bearing compound or a mixture of the two. Reaction between the Mg source and aluminium source results in the direct formation of an anionic clay. Said reaction takes place at room temperature or higher. At temperatures higher than 100 °C, the reaction is preferably carried out under 10 autogeneous conditions.
  • carbonate, hydroxyl, or other anions or mixtures thereof are incorporated into the interlayer region as the necessary charge-balancing anion.
  • Anionic clays prepared by this method exhibit the well known properties and characteristics (e.g. chemical analysis, powder X-ray diffraction pattern, FTIR, thermal decomposition characteristics, surface area, pore volume, and pore size distribution) usually associated with anionic clays prepared by the customary and previously disclosed methods.
  • anionic clays Upon being heated, anionic clays generally form Mg-AI solid solutions, and at higher temperatures, spinels.
  • an adsorbent for instance a SO x adsorbent for catalytic cracking reactions
  • the anionic clay according to the invention is usually heated during preparation and is thus in the Mg-AI solid solution form.
  • the catalyst or adsorbent is converted from an anionic clay into Mg-AI solid solutions.
  • the present invention is also directed to a process wherein an anionic clay prepared by the process according to the invention, is heat-treated at a temperature between 300 and 1200 °C to form a Mg-AI-containing solid solution and/or spinel.
  • the anionic clay according to the invention has a layered structure corresponding to the general formula 11 [Mg m 2+ Al n 3+ (OH) 2m+2n .](X n/z z -). bH 2 O
  • X may be CO 3 2" , OH " or any other anion normally present in the interlayers of anionic clays. It is more preferred that m/n should have a value of 2 to 4, more particularly a value close to 3.
  • the product can be spray dried directly to form microspheres or can be extruded to form shaped bodies.
  • the present invention includes the use of two types of aluminium-containing compounds wherein one type of aluminium-containing compound is crystalline aluminium trihydrate (ATH) or its thermally treated form.
  • An example of aluminium trihydrate is gibbsite (for instance provided by Reynolds Aluminium Company RH-20® or JM Huber Micral ® grades).
  • BOC Bosite Ore Concentrate
  • bayerite and nordstrandite are suitable aluminium trihydrates.
  • BOC is the cheapest alumina source.
  • the alumina trihydrate is preferred to have a small particle size. Thermally treated forms of gibbsite can also be used.
  • the thermally treated (calcined) aluminium trihydrate is readily obtained by thermally treating aluminium trihydrate (gibbsite) at a temperature ranging from 100 to 800 °C for 15 minutes to 24 hours.
  • the calcining 12 temperature and time for obtaining calcined aluminium trihydrate should be sufficient to cause a measurable increase of the surface area in view of the surface area of the gibbsite as produced by the Bayer process which is generally between 30 and 50 m 2 /g.
  • flash calcined alumina is also considered to be a thermally treated form of aluminium trihydrate, although generally it is considered a very specific alumina.
  • Flash calcined alumina is obtained by treating aluminium trihydrate at temperatures between 800-1000 °C for very short periods of time in special industrial equipment, as is described in US 4,051,072 and US 3,222,129.
  • aluminium trihydrate other aluminium-containing compounds such as oxides and hydroxides of aluminium, (e.g. sols, thermally treated aluminium trihydrate including flash calcined alumina, gels, pseudo- boehmite, boehmite) aluminium salts such as aluminium nitrate, aluminium chloride, aluminium chlorohydrate and sodium aluminate are added as the second type of aluminium-containing compound.
  • Said other aluminium- containing compounds may be soluble or insoluble in water and may be added to the aluminium trihydrate or it may be added to the reactor separately as a solid, a solution or as a suspension.
  • a thermally treated aluminium trihydrate also other aluminium-containing compounds are added such as the ones described above and of course aluminium trihydrate and other thermally treated forms thereof.
  • Said other aluminium sources may be added to the thermally treated aluminium trihydrate or it may be added to the reactor separately as a solid, a solution or as a suspension.
  • the aluminium source is added to the reactor in the form of a slurry.
  • Mg-bearing sources which may be used include MgO, Mg(OH) 2 , magnesium acetate, magnesium formate, magnesium hydroxy acetate, hydromagnesite (Mg 5 (CO 3 ) 4 (OH) 2 ), magnesium carbonate, magnesium bicarbonate, magnesium nitrate, magnesium chloride, dolomite and sepiolite. Both solid Mg sources and soluble Mg salts are suitable. Also combinations of Mg sources may be used.
  • the magnesium source may be fed to the reactor as a solid, a solution, or, preferably, as a slurry.
  • the magnesium source may also be combined with the aluminium source before it is added to the reactor.
  • this process is particularly suitable to be carried out in a continuous mode.
  • an aluminium source and a magnesium source are fed to a reactor and reacted in aqueous suspension to obtain an anionic clay.
  • the aluminium source and magnesium source are added to the reactor and reacted in aqueous suspension to obtain an anionic clay.
  • a reactor is considered to be any confined zone in which the reaction between the aluminium source and magnesium source takes place.
  • the reactor may be equipped with stirrers, baffles etcetera to ensure homogeneous mixing of the reactants.
  • the reaction can take place with or without stirring, at ambient or at elevated temperature and at atmospheric or elevated pressure.
  • a temperature between 0 and 100 °C is used at or above atmospheric pressure. It is preferred to carry out the process at temperatures above 50 °C rather than at room temperature, because this results in anionic clays with sharper peaks in the x-ray diffraction 14 pattern than anionic clays obtained at room temperature.
  • the reactor may be heated by any heating source such as a furnace, microwave, infrared sources, heating jackets (either electrical or with a heating fluid), lamps, etcetera.
  • Said aqueous suspension in the reactor may be obtained by either feeding slurries of the starting materials, either combined or separate, to the reactor or adding magnesium source to a slurry of alumina source or vice versa and feeding the resulting slurry to the reactor. It is possible to treat, for instance the aluminium source slurry at elevated temperature and then add either the Mg source ger se, or add the Mg source in a slurry or solution either to the reactor or the aluminium source slurry. Given particular facilities which might be available, the process can be conducted hydrothermally. This is particularly advantageous, because it this is faster and a higher conversion is obtained. There is no need to wash or filter the product, as unwanted ions (e.g.-sodium, ammonium, chloride, sulfate) which are frequently encountered when using other preparation methods, are absent in the product.
  • unwanted ions e.g.-sodium, ammonium, chloride, sulfate
  • the process is conducted in a multi-step process, e.g. a slurry of aluminium source and magnesium source is treated thermally in a first reactor at a mild temperature, followed by a hydrothermal treatment in a second reactor.
  • a preformed anionic clay may be added to the reactor.
  • Said preformed clay may be recycled anionic clay from the reaction mixture or anionic clay made separately by the process according to the invention or any other process.
  • organic or inorganic acids and bases may be added to the reactor or added to either the magnesium source or the aluminium source before they are added to the reactor.
  • An example of a preferred pH modifier is an ammonium base, because upon drying no 15 deleterious cations remain in the anionic clay.
  • the anionic clay prepared by the process according to the invention may be subjected to ion exchange.
  • the interlayer charge- balancing anions are replaced with other anions.
  • Said other anions are the ones commonly present in anionic clays and include pillaring anions such as V 10 O 2 Mo 7 O 24 6" , PW 12 O 40 3 -, B(OH) 4 " , B 4 O 5 (OH) 4 2" , HBO 4 2" , HGaO 3 2 ' CrO 4 2 ⁇
  • suitable pillaring anions are given in US 4774212 which is included by reference for this purpose.
  • Said ion exchange can be conducted before or after drying the anionic clay formed in the slurry.
  • the process of the invention provides wide flexibility in preparing products with a wide range of Mg:AI ratios.
  • the Mg:AI ratio can vary from 0.1 to 10 , preferably from 1 to 6, more preferred from 2 to 4, and especially preferred to close to 3.
  • both metals and non- metals such as rare earth metals, Si, P, B, group VI, group VIII, alkaline earth (for instance Ca and Ba) and/or transition metals (for example Mn, Fe, Ti, Zr, Cu, Ni, Zn, Mo, Sn), present.
  • Said metals and non-metals can easily be deposited on the anionic clay or the solid solution according to the invention or they can be added either to the alumina source or magnesium source which are added combined to the reactor or separately.
  • the metals and non-metals can also be added to the aqueous suspension in which the reaction takes place.
  • Suitable sources of metals or non-metals are oxides, halides or any other salt such as chlorides, nitrates etcetera.
  • the metals and non-metals may be added in any of the steps. Is can be especially advantageous for controlling the distribution of the metals and 16 non-metals in the anionic clay.
  • This comparative example illustrates the co-precipitation method where Mg and Al salt solutions are added to a solution of base.
  • Thermogravimetric analysis showed three weight losses: at approximately 100, 250 and 450 °C which are ascribed to loss of physisorbed water, interlayer water and loss of CO 2 and lattice dehydroxylation.
  • Example 1 The product obtained from Example 1 was calcined at 500 °C for 12 h. The product gave broad X-ray diffraction lines at 45 and 63 degrees two theta similar to those obtained for samples of calcined anionic clays prepared by other established methods with a Mg:AI ratio between 2 and 5.
  • Example 2 The product obtained from Example 2 was calcined at 500°C for 12 h. The product gave broad X-ray diffraction lines at 45 and 63 degrees two theta similar to those obtained for samples of calcined anionic clays prepared by other established methods with a Mg:AI ratio between 2 and 5. 18
  • Example 4 0. 15 g of the product from Example 4 was added to water at room temperature and stirred for 12 h. The product was filtered and dried at 80 °C. The PXRD pattern indicated that the product was similar to that for Comparative Example 5 and confirmed that the anionic clay structure had reformed.
  • the anionic clays may be prepared under nitrogen or under carbon dioxide-free atmosphere, so that the anionic clay predominantly comprises hydroxide rather than predominantly carbonate as charge balancing anion. It is also possible to feed carbon dioxide to the reactor so that an anionic clay results with predominantly carbonate as charge balancing anion.
  • the pH was adjusted to 9.96 by the addition of ammonium hydroxide solution.

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  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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Abstract

L'invention concerne un procédé à la fois économique et écologique permettant de synthétiser des argiles anioniques grâce à l'utilisation d'un carbonate et/ou d'anions hydroxyde comme espèces de couche intermédiaire destinées à équilibrer la charge. Ce procédé consiste à faire réagir une boue renfermant une source d'aluminium et une source de magnésium, ladite source d'aluminium comprenant deux types de composés à base d'aluminium, de préférence de l'hydroxyde d'aluminium et/ou de l'hydroxyde d'aluminium calciné traité thermiquement, sans avoir besoin de laver ou de filtrer le produit. Ce produit peut être séché par pulvérisation directement, de manière à former des microsphères, ou être extrudé afin de constituer des pièces profilées. Le produit de cette invention peut en outre être associé à d'autres ingrédients pour fabriquer des catalyseurs, des agents absorbants, des produits pharmaceutiques, des cosmétiques, des détergents, et d'autres biens de consommation.
PCT/EP1999/000938 1998-02-11 1999-02-11 Procede de production d'argile anionique utilisant deux types de composes d'alumine WO1999041198A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP99904879A EP1054838B1 (fr) 1998-02-11 1999-02-11 Procede de production d'argile anionique utilisant deux types de composes d'alumine
CA002320438A CA2320438C (fr) 1998-02-11 1999-02-11 Procede de production d'argile anionique utilisant deux types de composes d'alumine
JP2000531402A JP2003524569A (ja) 1998-02-11 1999-02-11 ２つのタイプのアルミナ化合物を用いるアニオン性クレーの製造方法
DE69919330T DE69919330T2 (de) 1998-02-11 1999-02-11 Verfahren zur herstellung anionischer tonerden unter verwendung zwei verschiedener aluminiumhydroxid verbindungen

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US2183998A 1998-02-11 1998-02-11
US09/021,839 1998-02-11
US23456799A 1999-02-09 1999-02-09
US01/234,567 1999-02-09

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PCT/EP1999/000938 WO1999041198A1 (fr) 1998-02-11 1999-02-11 Procede de production d'argile anionique utilisant deux types de composes d'alumine

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CN (2) CN1194895C (fr)
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6593265B2 (en) 2001-02-09 2003-07-15 Akzo Nobel N.V. Process for the preparation of anionic clay
US6710004B2 (en) 2001-02-09 2004-03-23 Akzo Nobel Nv Process for the preparation of anionic clay and boehmite-containing compositions
US7022304B2 (en) 2001-02-09 2006-04-04 Akzo Nobel N.V. Doped anionic clays
US7303654B2 (en) 2002-11-19 2007-12-04 Akzo Nobel N.V. Cellulosic product and process for its production
US7582202B2 (en) 2003-02-13 2009-09-01 Akzo Nobel N.V. Composition comprising a metal hydroxy salt, its preparation and use as catalyst or sorbent
EP2261177A1 (fr) 2009-06-11 2010-12-15 Akzo Nobel Chemicals International B.V. Hydroxyde à double couche, sa préparation et utilisation
EP2263976A1 (fr) 2009-06-03 2010-12-22 Akzo Nobel Chemicals International B.V. Hydroxyde à double couche avec une morphologie spécifique, sa préparation et utilisation
CN113086998A (zh) * 2021-04-07 2021-07-09 长治学院 一种Mg6Al2(OH)18·4.5H2O纳米片及其制备方法和应用

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US6541409B1 (en) * 1999-01-29 2003-04-01 Akzo Nobel N.V. Process for producing anionic clay using non-peptized boemite and compositions produced therefrom
NO316440B1 (no) † 2000-05-18 2004-01-26 Statoil Asa Hydrotalcitt-basert materiale med forbedret styrke, anvendelse og fremgangsmåte derav, og katalysator omfattende dette materialet
DE102004018336A1 (de) * 2004-04-15 2005-11-10 Albemarle Corporation Flammhemmender Füllstoff für Kunststoffe
KR101396778B1 (ko) * 2013-03-08 2014-05-20 윤석태 스플릿 롤러 베어링 및 그 설치방법

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WO1996005140A1 (fr) * 1994-08-15 1996-02-22 Aluminum Company Of America Synthese d'hydrotalcite et de composes apparentes, a partir de deux poudres

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WO1993022237A1 (fr) * 1992-04-30 1993-11-11 J.M. Huber Corporation Procede de production d'hydrotalcite synthetique
EP0640379A1 (fr) * 1993-08-27 1995-03-01 Engelhard Corporation Méthode pour la décomposition de N2O en utilisant des catalyseurs comprenant des argiles minérales anioniques calcinées
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CAVANI F ET AL: "HYDROTALCITE-TYPE ANIONIC CLAYS: PREPARATION, PROPERTIES AND APPLICATIONS", CATALYSIS TODAY, vol. 11, no. 4, 1 January 1991 (1991-01-01), pages 173 - 301, XP000537043 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6593265B2 (en) 2001-02-09 2003-07-15 Akzo Nobel N.V. Process for the preparation of anionic clay
US6710004B2 (en) 2001-02-09 2004-03-23 Akzo Nobel Nv Process for the preparation of anionic clay and boehmite-containing compositions
US7022304B2 (en) 2001-02-09 2006-04-04 Akzo Nobel N.V. Doped anionic clays
KR100796104B1 (ko) * 2001-02-09 2008-01-21 아크조 노벨 엔.브이. 음이온성 클레이의 제조 방법
US7303654B2 (en) 2002-11-19 2007-12-04 Akzo Nobel N.V. Cellulosic product and process for its production
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EP2261177A1 (fr) 2009-06-11 2010-12-15 Akzo Nobel Chemicals International B.V. Hydroxyde à double couche, sa préparation et utilisation
CN113086998A (zh) * 2021-04-07 2021-07-09 长治学院 一种Mg6Al2(OH)18·4.5H2O纳米片及其制备方法和应用

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CN1290233A (zh) 2001-04-04
CN1194895C (zh) 2005-03-30
CN1176022C (zh) 2004-11-17
WO1999041197A1 (fr) 1999-08-19
CN1290232A (zh) 2001-04-04
JP2003524569A (ja) 2003-08-19

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