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WO2008129034A1 - Composition à base d'hydroxyde double lamellaire (hdl) de type hydrotalcite et son procédé de fabrication - Google Patents

Composition à base d'hydroxyde double lamellaire (hdl) de type hydrotalcite et son procédé de fabrication Download PDF

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Publication number
WO2008129034A1
WO2008129034A1 PCT/EP2008/054805 EP2008054805W WO2008129034A1 WO 2008129034 A1 WO2008129034 A1 WO 2008129034A1 EP 2008054805 W EP2008054805 W EP 2008054805W WO 2008129034 A1 WO2008129034 A1 WO 2008129034A1
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Prior art keywords
hydrotalcite
reflections
magnesium
region
layered double
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Olga Gonsiorova
Renee Van Yperen
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EURO SUPPORT CATALYST GROUP BV
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EURO SUPPORT CATALYST GROUP BV
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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
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
    • C01B13/363—Mixtures of oxides or hydroxides by precipitation
    • 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, with or without oxygen or hydrogen, and containing two or more other elements
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • 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, with or without oxygen or hydrogen, and containing two or more other elements
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C01F7/785—Hydrotalcite
    • 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

  • the invention is directed to a novel Layered Double Hydroxide (LDH) or hydrotalcite-like anionic clay and its production and use in various applications.
  • LDH Layered Double Hydroxide
  • hydrotalcite-like anionic clay hydrotalcite-like anionic clay
  • Anionic clays or otherwise called Layered Double Hydroxide (LDH) represent a class of ionic lamellar materials with positive charged metal hydroxide sheets with the negative charge balance provided by the intercalated anions.
  • LDH Layered Double Hydroxide
  • These layered synthetic inorganic solids are related to the mineral classes of hydrotalcite-sjogrenite-pyroaurite. They are represented with the generic composition of:
  • M 2+ and M 3+ can be divalent and trivalent metals occupying lattice positions in the brucite-like sheets and A *v is an exchangeable anion located in the gallery between the layers along with water molecules.
  • x is the ratio of M 3+ Z(M 2+ + M 3+ ).
  • M 2+ is Mg 2+
  • M 34 is Al 3+ .
  • A" ' is CO.3 2" and typically x is 1 A, and m is Vi.
  • LDHs Layered Double Hydroxides
  • M 2 VM 3i 2 (OH) !6 A n 2/n ® 4H 2 G wherein M ⁇ represents divalent cations, M J* represents trivalent cations and A " represents monovalent anions that are exchangeable with organic or inorganic anions.
  • the divalent M 2+ cation can be selected from the groups of alkaline earth or transition metals or mixtures thereof. For example, one or more OfMg 2+ , Fe 2+ , Co 2+ . Cu 2f , 5 Ni , Zn , Ca , Sr , Ba , and Mn may he used.
  • the trivalent M 3+ cation can be selected from the group of one or more of Al 3+ , Cr 3+ , Ga 3+ , La 3+ , Mn 3+ , Co 3+ , Ni 3+ , B 3+ , V 3+ , Ti 34 , and In 3 ⁇
  • the anion A can be selected from one or more from the group of inorganic and organic anions, such as F “ , Cl “ , T 5 ClO 4 “ , NO 3 " , ClOj “ , OH; CO 3 2” , HVO 4 2 ; SO 4 2” , WO 4 2” , ⁇ O CrO,, 2" , [Fe(CN) 6 J 4 ; [SiO(OH) 3 ]; MnO 4 " , heteropolyacids such as (PMo 12 O 40 ) 3 ; (PWi 2 O 40 ) 3" , as well as polyoxometalates such as [WZn 3 (H 2 O)(ZnW 9 O 34 )J 12" .
  • A can be an organic anion from an acid.
  • hydrotalcite and hydroialcite-like compositions can be prepared by different 15 M 2+ M 3+ A n" combinations as well as by varying the M 2 V M 3 ' " metal ratio,
  • the lattice hydroxy! groups condense and leave as water and the mixed metal oxide solid-solution/spinel is formed.
  • the spinel formation can be initiated at above 600 0 C. Further, the presence of other than Mg 2f and Al 3+ cations 5 can alter the temperature of spinel formation.
  • hydrotalcite is the active component for catalytic applications of the hydrotalcite precursor.
  • hydrotalcite can be used in non-catalytic applications such as in medicines, as antacid, stabilizer, also as sorbents, in PVC stabilizers, in wastewater purifiers, halogen scavengers, ion exchangers, flame retardants, etc.
  • the hydrotalciie compositions exhibit the so called "memory effect" when the hydrotalcite is calcined at temperatures above 400 0 C to 600 0 C, preferably about 500 0 C, to form the solid solution of the mixed metal oxides, and subsequently is rehydrated in water, usually at 65 0 C to 95 0 C for 6 to 18 hours and optionally with the aid of some sodium carbonate solution to reconstruct the original structure of the hydrotalciie as evidenced by the powder X-ray diffraction patterns (PXRD).
  • PXRD powder X-ray diffraction patterns
  • these salts are added simultaneously to the reaction vessel while the ⁇ il is kept constant by the addition of NaOH.
  • the precipitation is followed by aging at temperatures below K)O 0 C, mostly at 65 to 85°C for up to two days or more, or aged in autoclave hydrothermally at temperatures above 100 0 C for a few hours to several days, followed by extensive washing to remove unwanted salts.
  • the precipitation process requires additional chemicals such as sodium hydroxide, sodium carbonate, ammonium hydroxide, urea, etc., which further increases the cost of production.
  • the filtration and washing process steps are difficult due to the small particles of the anionic clay which make filtration and washing a slow process. Further, these processes are not environmenially friendly as they require disposal of the nitrates, chlorides, and sulphates in the washings which require special disposal.
  • the aging process is very long and this decreases the through-put capacity of the plant.
  • the precipitation takes place using very dilute solutions, so the final concentration of the solids in the slurry is quite low.
  • the low concentration of solids in the slurry requires large plant equipment to obtain a cost-effective production rate, which, in turn, requires larger capital investment for the large volume equipment.
  • U.S. Patent 6,800,578 describes a process using boehmite alumina which is first treated with an acid and then neutralized by the addition of a base such as sodium or ammonium hydroxide in a slurry form, to which a magnesium source is subsequently added and the slurry then aged at temperatures in the range of 55 0 C to 250 0 C.
  • the magnesium source can be derived from MgO, MgCO 3 , Mg 3 (OHCO 3 J 2 , Mg(NOs) 2 , Mg(acetate)2, Mg(OH) 2 , etc.
  • This process like the precipitation process, has the disadvantage that it requires filtrations and washings to remove the salts (such as NaNO 3 , NH 4 NO 3 . NaCl, (NHu) 2 SO 4 , etc., formed by the neutralization of the acid-treated boehniite with a strong base.
  • U.S. Patent 6,541,409 describes a process in which pseudoboehmite types of alumina are used as sources of aluminium, which are reacted with magnesium oxide (MgO) in water slurry and aged at temperatures in the range of 65°C to 85°C for 18 to 48 hours.
  • MgO magnesium oxide
  • the preparation conditions and the quality of the products are not suitable and consistent to be able to produce a high quality hydrotalcite-type anionic clay without being contaminated and diluted with substantial quantities of unreacted magnesia and pseudoboehmite alumina.
  • These products are, in essence, mixtures of anionic clays and unreacted magnesium and aluminium sources, which make the products inferior in quality as compared to those produced by the precipitation processes.
  • U.S. Patent 6,171,991 describes a process for producing an anionic clay composition, using a gibbsite as the source of aluminium and MgO as the source of magnesium.
  • the process conditions are such that only a part of the gibbsite and magnesium oxide were converted to hydrotalciie, as shown in examples 7 to 10, indicating the products were mixtures. Therefore, this process is not suitable to produce pure anionic clays from gibbsite and magnesium oxide.
  • hydrotalcite-type anionic clays When hydrotalcite-type anionic clays are prepared in the absence of carbonate anions or in CO 2 -free atmosphere, the intercalated anion in the hydrotalcite structure may be predominantly hydroxy 1 anions, and the crystal structure of this anionic clay is that of a hydrotalcite-like clay, otherwise referred to as meixnerite-like anionic clays.
  • E. Dirnotakis and T. Pinnavaia produced hydroxy hydrotalcite (meixnerite) using the same procedures as W. Jones, by calcining (at 500 0 C for 3 hours) a synthetically produced Carbonate Hydrotalcite (Hydrotalcite) in CO 2 -free atmosphere and rehydrating, the mixed metal oxide solid solution, in a distilled water free of CO ? , and CO 3 2" at 25°C for 16 hours (Inorganic Chemistry, Comm. Vol. 29, Number 13, June 27, 1990) using this process they were able to produce pure hydroxy hydrotal cites (raeixnerites).
  • Patented related technology first appeared in U.S. Patent 5,112,784 of M. Atkins, W. Jones and M. Chibwe wherein catalytically active materials where produced by calcining an anionic Double Hydroxide clay; rehydrating the resulting material in water free of dissolved ions; and calcining the rehydrated material. Accordingly, meixnerite or hydroxy hydrotalc ⁇ tes were produced by this process.
  • U.S. Patent 5,514,361 describes a process of preparing a meixnerite-type material from flash calcined gibbsite (a transition, activated or rehydratable alumina) and magnesium oxide. The preparation was done at boiling temperatures (98°C) and hydrothermally at 150 0 C. As shown in the examples of this patent, the two reactants, the magnesium oxide and the flash calcined gibbsite (Alcoa's CP-2 grade) were stirred in water and the temperatures raised, either to 98 0 C or to 15O 0 C and kept at these temperatures for several hours,
  • US patent 5,728,363 and 5,645,810 and 5,750,453 were also directed to the production of meixnerite type of materials by reacting magnesium oxide and transition alumina (an activated or rehydratable alumina) in aqueous suspension.
  • the main intercalated charge balancing ions of the material as synthesised are hydroxy! anions.
  • the material according to the invention is, therefore, substantially free of nitrate, sulphate, and chloride.
  • the wording "substantially free of "substantially” means that these components may the present in amounts the presence of which cannot realistically be avoided in commercial scale production. More in particular, the composition contains less than 3 wt.%, in particular less than 2 wt.%, even more in particular less that 1 wt%, still more in particular less than 0.5 wt.% of nitrate, sulphate, and chloride.
  • the composition of the present invention is substantially free of anions other than hydroxides and carbonates. More specifically, the composition contains less than 3 wt.%, in particular less than 2 wt.%, even more in particular less that 1 wt%, still more in particular less than 0.5 wt.% of anions other than hydroxides and carbonates.
  • the peak heights are taken to represent the intensities, and are used for measuring the ratio (R) of the sum of the intensities of the hydrotalcite reflections in the region of 8 to 28° 2 ⁇ to the sum of the hydrotalcite reflections in the region of 25 to 55 ° 2 ⁇ (PXRD determined in reflection geometry on a flat plate sample using Cu Ka radiation ( ⁇ is 1,5418A)), wherein R is at least 3, in particular at least 4, more in particular more than 5, still more in particular more than 6.
  • the region of 8 to 28° 2 ⁇ may be further specified to the region of 10 to 25° 2 ⁇ .
  • the region of 25 to 55° 2 ⁇ may be further specified to the region of 28 to 55° 2 ⁇ , or to the region of 25 to 50° 2 ⁇ , It is noted that these further specifications of the 8-28° 2 ⁇ and the 25-55° 2 ⁇ region also apply to other embodiments of the present invention, whether or not this is explicitly indicated. Whether or not such further specifications are appropriate will depend on the exact location of the hydrotalcite-reflections in the PXRD pattern. This can easily be determined by the skilled person for a pattern at hand.
  • the major crystallographic characteristics specific to this new type of meixnerite which are different from the XRPD of the well known in prior art synthetic meixnerite, are represented by the high intensities of the ⁇ 003>, ⁇ 006> reflections, in the region of 8 to 28° 2 ⁇ , as compared to the very low intensities of the ⁇ 012>, ⁇ 015>, ⁇ 018> reflections in the region of 25 to 55° 2 ⁇ .
  • the region of 8 to 28° 2 ⁇ may be further specified to the region of 10 io 25° 2 ⁇ and the region of 25 to 55° 2 ⁇ may be further specified to the region of 28 to 55° 2 ⁇ , or to the region of 25 to 50° 2 ⁇ .
  • the present invention is accordingly characterized by a composition of a hydrotalcite-like Layered Doubled Hydroxide (LDH) comprising divalent M 2+ and trivalent M + metals and having hydroxyl ions as the major charge balancing anions and having an X-ray powder diffraction pattern wherein the ratio (R) of the sum of the relative intensities of the X-ray reflections (IQ UL and W) is such that:
  • LDH Hydrotalcite-like Layered Doubled Hydroxide
  • S.P. Newman et al. Synthesis of the 3R2 polytype of a hydrotalcite-Hke mineral, J. Mater. Chem., 2002, 12, 153-155).
  • Still another embodiment involves a composition of 3R 2 type hydrotalcite-like Layered Double Hydroxide (LDH) comprising divalent (M 2"" ) and trivalent (M 3+ ) metals and having hydroxyl ions as charge balancing anions, and having an X-ray powder diffraction pattern wherein the ratio (R) of the sum of the relative intensities of the X-ray reflections (IQ OI . and Ihu) is such that:
  • the ratio (R) is about 1.5.
  • Other carbonate hydrotalcites and hydrotalcite-like materials known in the prior art prepared by reacting aluminium oxides or aluminium hydroxides with magnesium oxides exhibit a ratio (R) in the range of 1.4 to 1.8.
  • compositions of carbonate hydrotalciles were synthesized through co ⁇ reeipitation, thermally and hydrothermally, which also exhibit ratios (R) above 2 or 3 which compositions of said hydrotalcitc-like materials contain mostly carbonate/nitrate ions as a negative charge balancing anions, and are thus distinguished from the present invention.
  • Figure 1 illustrates the difference in PXRD spectrum between a material according to the invention and a commercial hydrotalcite material, obtainable from Reheis.
  • the commercial material has an R value of 1.4, while the material according to the invention has an R value of 17.
  • the materials according to the invention have an R value of at least 3, in particular at least 4, still more in particular more than 5, still more in particular more than 6, In some embodiments, R values of at least 8 may be obtained, or even at least 10. Sometimes values of at least 12. or at least 14 mav be obtained.
  • the present composition principally contains interlayer hydroxy! principally ions as charge balancing anions. More in particular, the hydroxyl groups make up at least at least 20%, preferably more than 40% and more preferably more than 60% , still more preferably more than 80% of the total intercalated anion concentration, with the balance being carbonate anions.
  • the charge-balancing anions in the material as synthesized, it is preferred for the charge-balancing anions to consists for at least 90% of OH ' , the balance being CO 3 "" , more in particular at least 95% of OH " , the balance being CO 3 2" . Still more in particular, in the as synthesised material the intercalated anions substantially consists of OH " , wherein the wording "substantially consists of” means that minor amounts of other components the presence of which cannot realistically be avoided in commercial scale production may still be present.
  • the charge-balancing anions in the material as synthesised, it is preferred for the charge-balancing anions to consists for at least 90% of OH " , the balance being CO 3 2" , more in particular at least 95% of OH " , the balance being CO 3 2" . Still more in particular, in the as synthesised material the intercalated anions substantially consists of OH " , wherein the wording "substantially consists of means that minor amounts of other components the presence of which cannot realistically be avoided in commercial scale production may still be present. As will be explained in more detail below, it is one of the features of the present invention that during synthesis the contact Of CO 2 from the air with the reaction medium should be minimized. As the material is exposed to carbon dioxide in the air, the amount Of CO 3 2" will increase, until a balance value obtained.
  • the material of the present invention meets the formula
  • M ⁇ /' represents a divalent cation
  • M 3+ represents a trivalent cation
  • a n" represents an anion
  • M 2+ is selected from the groups of alkaline earth and transition metals, and mixtures thereof
  • M 3+ is selected from Al 3+ , Cr 3+ , Ga 3+ , La 3+ , Mn 3+ , Co ' + , Ni ' ' " , B ' + , V “ + , Tr + , In 3+ , and mixtures thereof
  • A" " is selected from OH " and mixtures of OH " with CO 3 2" .
  • M 2+ is selected from one or more Of Mg 2+ , Fe 2+ , Co 2+ , Cu 2+ , Ni 2+ , Zn 2+ , Ca 2+ , Sr 2+ , Ba 2 i" , and MnT .
  • M 2+ Is Mg 2 ".
  • M 3 is Al 3"1" .
  • the material of the present invention meets the formula
  • a n" is selected from OH “ and mixtures of OH “ with CO 3 2" . More in particular, and this also goes for the more general formula above, in the material as synthesised, the A n" consists for at least 90% of OH “ , the balance being CO 3 2" , more in particular at least 95% of OH " , the balance being CO 3 2" . Still more in particular, in the as synthesised material A n" substantially consists of OH " , wherein the wording '"substantially consists of means that minor amounts of other components the presence of which cannot realistically be avoided in commercial scale production may still be present. As the material is exposed to carbon dioxide in the air, the amount OfCO 3 2" will increase, until a balance value obtained.
  • the material according to the invention is characterised in that it consists of thicker sheets in the [001] direction thicker than materia! which is synthesised in other ways, e.g., by precipitation from salt solutions. More in particular, the platelets are thicker than those obtained conventionally. This can be seen, e.g., by microscopical evaluation of the samples. Additionally, in the material of the present invention, the crystallite size in the [001] direction as derived from the full width at half maximum of the reflections via the Seherrer formula is greater than 200A . more preferable greater than 250A and even more preferably greater than 30OA. For more information on this manner of calculating crystallite sizes, reference is made to Kovanda et al. (F.
  • composition according to the invention is preferably substantially free from u ⁇ reaeted starting material sources. It is, however, possible to add, e.g., aluminium trihydrate to the final composition, as will be elucidated below.
  • a PANaiytical® X-ray diffractom ⁇ ter with Ni filter Cu radiation was used. (Model number PW3040/60 X' Pert PRO®).
  • the X-ray tube was a PANaiytical® PW3373/00 Cu LFF tube operating at 4OkV and 4OmA.
  • sample stage model PW3071/60 Bracket®; sample not spun and measured Bragg-Brentano geometry
  • a PANaiytical scanning RTMS (Real Time Multiple Strip ) X'Celerator® detector was used with an active length of 9mm covering ca 2.127 ° 2-theta. Samples were typically analysed between 2 and 80 ° 2-theta with a Step Size of 0.01675, Time per step of 50 seconds and total scan time of 30 minutes.
  • the materials prepared according to this invention exhibit a preferred particle orientation when placed in a compacted flat-bed sample holder for the XRD measurements that produced the XRD patterns characterizing the new hydroxy hydrotalcite or new meixnerite described in this invention.
  • Typical X-ray-diffraction patterns of the hydroxy hydrotalcite or meixnerite anionic clays produced by this invention are characterized by reflections with d (spacings) in A at 7.52, 3.79, 2.56, 2.28, 1.93, 1.52 and 1.49.
  • the position of the 003, d (7.52), reflection varies somewhat e.g., with the conditions of preparation, reactant materials, and the water content. Typical values range between 7.4 and 7.6. It is well within the scope of the skilled person to determine the exact d (spacings) for the various peaks on a case by case basis.
  • the new meixnerite-type anionic clay of this invention is preferably produced by homogenizing in a water slurry a solid divalent metal source and a solid trivalent metal source, of which one at least is water insoluble, and with pH higher than 11 and at temperatures in the range of 6O 0 C to 100 0 C, or hydrothermally under autogenous pressures at a temperature above 100 0 C, the reaction being carried out in the absence of salts of nitrate, sulphate, or chloride, and under such conditions that the contact between the reaction medium and carbon dioxide from the air is minimised.
  • the material according to the invention is synthesised in the absence of substantial amounts of carbon dioxide and carbonate ions. Still more in particular, the reaction is carried out in the absence of salts other than oxides or hydroxides.
  • the slurry is subsequently aged at temperatures below K)O 0 C or elevated temperatures hydrothermally under autogenous pressures.
  • the materials of the present invention characterized by the specific PXRD pattern as defined by the ratio R, show advantageous properties in terms of particle size, dispersability. high porosity, binding properties and attridon resistance. This makes the material extremely suitable for use as catalysts, catalyst support, adsorbants and polymer additives.
  • the material may be used as such after production, filtration and drying. It is also possible to spray dry the material or to extrude it in the presence of an additional binder
  • the solid divalent metal source and the solid trivalent metal source are dispersed in water at a pH of over 11 having a temperature of between 60 and 100 0 C, preferably between 65 and 95 °C and more preferred between 85 and 95 Q C. This is in contrast with conventional synthesis methods where the metal sources are brought into water at room temperature, after which the mixture is heated to reaction temperature,
  • the solid divalent metal source is added to water having the specified temperature, followed by addition of the trivalent metal source.
  • the solid trivalent metal source is added to water having the specified temperature, followed by addition of the divalent metal source.
  • the reaction is carried out under such conditions that the atmosphere above the slurry consists primarily of water vapour (steam). This was found to lead to a product with better properties.
  • the slurry is preferably at least partially heated by steam injection.
  • the dispersion is mixed vigorously. Subsequently the dispersion may be aged for a suitable period of time, such as between 1 and 10 hours, preferably between 2 and 10 hours, at a temperature in the same range of between 60 and 100 0 C, preferably between 65 and 95°C and more preferred between 85 and 95 0 C, Again, this aging step is preferably carried out under such conditions that the contact between the reaction medium and carbon dioxide from the air is minimized.
  • the dispersion may be used as such in further processing.
  • the LDH may be filtered and spray dried, or extruded.
  • hydrotalcite-like material after formation with other metals, such as metal salts and other metal compounds, including transition and/or noble metals. This may either be done directly after formation or in any further stage, such as after (re)calcinalion, rehydration, drying, etc.
  • metals such as metal salts and other metal compounds, including transition and/or noble metals.
  • This may either be done directly after formation or in any further stage, such as after (re)calcinalion, rehydration, drying, etc.
  • the meixnerite type layered double hydroxide of the present invention can advantageously be prepared using a solid magnesium source and a solid aluminium source. While the present invention will be described referring in particular to magnesium as the divalent metal ion and aluminium as the trivalent metal ion. ii should be understood that other divalent and trivalent metal ions are also envisaged within the scope of the present invention, as are combinations of magnesium with one or more other divalent metal ions and aluminium with one or more other trivalent metal ions.
  • aluminium oxide or hydroxide is used as solid aluminium source. More in particular, the solid aluminium source is selected from the group consisting of aluminium hydroxide, boehmite, pseudoboehmite, gibbsit ⁇ , gel alumina, calcined aluminium hydroxide, and mixtures thereof.
  • activated/active alumina is interchangeably used with the term “"transition” alumina. Both of these terms refer to the same material, Briefly, when aluminum hydroxides such as boehmites, gibbsite, hydrous gel alumina are calcined, they transform to "transition' " or '"activated/active” forms of alumina. Depending on the severity of calcination (i.e., temperature, time, atmosphere and particle size of the starting alumina source) different 18
  • transition forms of alumina are formed which have different PXRD patterns, physical, and chemical properties. Another characteristic property of these transition forms of alumina is that during the process of calcination, dehydration and dehydroxylation takes place, thus the produced transition forms contain minimal or no hydroxyl groups and water. Further, when gibbsite is "flash calcined," the transition/activated form of aluminum oxide formed shows a very broad PXRD pattern, and, when contacted with water under thermal or hydrothermal conditions, it reacts with the water and this oxide form of transition alumina forms hydroxyl groups.
  • transition form Under the appropriate hydration conditions (i.e., temperature, time, pH, etc), this kind of transition form can be reconverted to a crystalline or semi-crystalline type of boehmite or gibbsite. Due to this property, these kinds of transition aluminum oxides sometimes are referred to in the prior art, as rehydratable aluminium oxides.
  • Commercial examples of these "transition/activated,” or “rehydratable oxide alumina” are the Alcoa's CP 1, 2, 3 and 7 and used grades and described in patents US 4,579, 839, and 4,120,942.
  • transition (activated) alumina as products formed by calcining or flash calcining aluminum hydroxides (ATH, boehmites. gel alumina) sufficiently that their original crystalline structure (based on PXRD) has substantially disappeared, and/or that the associated hydroxyl groups have been d ⁇ hydroxylated. This definition is consistent with the teachings of prior art and established scientific nomenclature.
  • the activated, transition and rehydratable forms of alumina are, in essence, aluminum oxides since which have been produced by the calcination treatments and are essentially dehydrated and dehydroxylated, and have different XRD patents and different physical and chemical properties from their precursor alumina hydroxides. A clear distinction in this patent application is made between aluminum oxides and aluminum hydroxides.
  • activated/active alumina oxides are equivalent and refer to the same materials as the term “transition” alumina oxides or simply "aluminum metal oxides” or “metal oxides.”
  • rehydratable alumina oxides is one kind of the activated/active alumina oxides which exhibits the property, that when contacted with water reforms hydroxyl groups and may be transformed to aluminum hydroxides such as gibbsite, boehmite, bayerite, etc. L7
  • the solid magnesium source is selected from magnesium oxide, magnesium hydroxide, calcined forms of magnesium carbonate or magnesium hydroxy! carbonate. In a preferred embodiment of the present invention, the solid magnesium source is selected from magnesium oxide and magnesium hydroxide.
  • the material of the invention has the advantage that it can be calcined under conventional condition as indicated above, while retaining the memory of the original, which means that after rehydrating, it still possesses a ratio R within the range of the invention.
  • the layers of the LDH can be pillared with organic, inorganic or mixtures of pillaring ions.
  • the material may be used as such, as a shaped body further optionally comprising a organic or inorganic binder, preferably aluminium trihydrate (ATH), more preferred gibbsite.
  • aluminium trihydrate (ATHj is applied as a low cost effective binder for the preparation of extrudates or other forms of shaped bodies.
  • Such shaped bodies are obtained by combining the material of the present invention with a binder or matrix (if used), and subjecting the material to a shaping step, e.g., an extrusion step, pelletising step, beading step, or any other shaping step known in the art.
  • the aging step is carried out after the formation of shaped bodies. It is also possible to age the material partially in the slurry, shape it, and subject the shaped bodies to a further aging step.
  • shaped anionic clay according to the invention is calcined, rehydrated, and again calcined, wherein if so desired at any point in time the material may or may not be subjected to a shaping step.
  • the material as formed, or the calcined form thereof comprises a composite containing a M 2+ ZM 3+ spinel.
  • the material can also have the form of a matrix, comprising an organic, inorganic or combined organic-inorganic matrix material, and the composition of the present invention.
  • the matrix material is preferably selected from polymer, resin, paint, bo ⁇ hmite, pseudoboelimiie, gibbsite, amorphous alumina, calcined forms of or mixtures thereof, anionic or catiomc clay, synthetic or natural zeolite.
  • the clay material of the present invention may be present in a suspension using water or other solvents, optionally with the aid of an organic additive, such as surfactant, dispersing agent, and so on. It is also possible to apply the material to the surface of a preformed body, for example as a washcoat on a structured material (monolith).
  • the materials of the invention, and the calcined forms thereof, can advantageously be used in various applications in the chemical industry, including the use as catalyst, catalyst support and as additives in various applications, such as paper, polymers, and
  • the materia! of the invention can also suitably be used as polymer additive in PA 7 C 5 polyester packaging (PET), other thermoplastics, for example to impart flame retardant properties.
  • PET PA 7 C 5 polyester packaging
  • other thermoplastics for example to impart flame retardant properties.
  • Radio-active metal scavenging e.g. Fe
  • the invention is further elucidated on the basis of the following, non-limiting, examples.
  • boehmite alumina e.g., Versal 700
  • the resulting slurry is piped to a second closed tank in such a manner as to minimize the introduction of air/carbon dioxide.
  • This slurry is further aged at 95°C for six hours. Again the steam purge minimizes the introduction of air/carbon dioxide into the slurry during this crystallization phase.
  • the PIiXD spectrum of this material is given in Figure 1.
  • the material has an R- value of 17.
  • Example 1 The slurry from Example 1 is spray dried into the form of microspheres with an average particle size of 80 to 100 microns and an LOl(IOOO 0 C) of about 40%.
  • Example 1 To the resulting slurry from Example 1. sufficient acetic acid is added to lower the pH to about 10. This slurry was spray dried into the form of microspheres with an average particle size of 80 to 100 microns and an LOI(I OOO 0 C) of about 40%, The addition of acetic acid results in a material with improved physical properties, such as an improved average bulk density and improved attrition properties,
  • Example 2 To the resulting slurry from Example 1, sufficient aluminum trihydrate (ATH) was added such that weight percentage (dry basis) was 20% based of the overall weight of the product. To this suspension was added sufficient acetic acid to lower the pH to 10 , The resulting slurry was spray dried into the form of microspheres with an average particle size of 80 to 100 microns and an LOI(IOOO 0 C) of about 40%,
  • the spray dried product from Example 4 was calcined at 600 0 C for one hour followed by rehydration in aluminium sulfate solution (equivalent to 6% A12O3 on the final product) at 90 0 C for one hour, The slurry is filtered and dried at 100 0 C. This calcinations/rehydration process improves the mechanical strength of the microspheres.
  • Example 2 The slurry from Example 1 was filtered on a pressure filter without washing. To the resulting filtercake were added 1 to 10% aluminum trihydrate (ATH) and 5% citric acid, both based on the dry weight of the final product. This mixture was further mixed in a kneader-type mixer to produce a uniform "paste" that was processed in a standard extruder to produce 3 mm diameter extrudates . The resulting extrudates were then dried at 150 0 C for twelve hours in a stationary dryer and calcined at 600°C in a muffle furnace.
  • ATH aluminum trihydrate
  • citric acid citric acid
  • Example 4 The spray dried product from Example 4 was calcined at 600 0 C for one hour followed by rehydration in zinc sulfate solution (equivalent to 6% zinc oxide on the final product) at 9O 0 C for one hour. The slurry is filtered and dried at 100 0 C. This calcinations/rehydration process improves the mechanical strength of the microspheres.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Materials Engineering (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
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Abstract

La présente invention concerne un hydroxyde double lamellaire (HDL) de type hydrotalcite comprenant un métal divalent (M2+) et un métal trivalent (M3+) avec des ions hydroxyle intermédiaires constituant des anions équilibreurs de charge. La composition, se présentant sous la forme d'une poudre compactée, présente un diagramme de diffraction des rayons X sur poudre tel que le rapport R entre la somme des intensités des réflexions de l'hydrotalcite dans la région de 8 à 28° 2Θ et la somme des réflexions de l'hydrotalcite dans la région de 25 à 55° 2Θ est au moins égal à 3, ledit matériau étant essentiellement exempt de nitrate, de sulfate et de chlorure. La présente invention concerne également un procédé de fabrication de ce matériau et son utilisation dans diverses applications.
PCT/EP2008/054805 2007-04-20 2008-04-21 Composition à base d'hydroxyde double lamellaire (hdl) de type hydrotalcite et son procédé de fabrication Ceased WO2008129034A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2011015859A1 (fr) 2009-08-03 2011-02-10 Ineos Healthcare Limited Procédé
US8106250B2 (en) * 2008-07-28 2012-01-31 Petroleo Brasileiro S.A.-Petrobras Process for removing silicon compounds from hydrocarbon streams
WO2012020210A3 (fr) * 2010-08-09 2012-05-03 Gtl.F1 Ag Catalyseurs de fischer-tropsch
US8969231B2 (en) 2009-09-01 2015-03-03 Gtl.Fi Ag Fischer-Tropsch catalysts
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US9242869B2 (en) 1997-09-19 2016-01-26 Opko Ireland Global Holdings, Ltd. Metal compounds mixed or sulphated, as phosphate binders
US9566302B2 (en) 2010-02-04 2017-02-14 Opko Ireland Global Holdings, Ltd. Composition comprising mixed metal compounds and xanthan gum
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US9907816B2 (en) 2006-01-31 2018-03-06 Opko Ireland Global Holdings, Ltd. Water-insoluble, iron-containing mixed metal, granular material
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US10155040B2 (en) 2007-10-16 2018-12-18 Opko Ireland Global Holdings, Ltd. Mixed metal compounds for treatment of hyperphosphataemia
US10201501B2 (en) 2007-07-27 2019-02-12 Opko Ireland Global Holdings, Ltd. Mixed metal compounds used as antacids
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CN112978779A (zh) * 2021-04-25 2021-06-18 北京化工大学 一种利用白云石制备纳米碳酸钙和纳米水滑石的方法
CN113718249A (zh) * 2021-09-17 2021-11-30 深圳大学 一种混凝土中钢筋表面层状双金属氢氧化物抗腐蚀膜的自适应生长方法
CN114477317A (zh) * 2022-03-07 2022-05-13 东北石油大学 针状纳米铁基双金属氢氧化物及其应用
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CN114873622A (zh) * 2022-05-12 2022-08-09 南京大学 一种以碱式碳酸镁为原料制备层状双氢氧化物的方法
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5514361A (en) * 1994-04-29 1996-05-07 Aluminum Company Of America Method for making a synthetic meixnerite product
US5645810A (en) * 1995-06-07 1997-07-08 Aluminum Company Of America High surface area meixnerite from hydrotalcites

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5514361A (en) * 1994-04-29 1996-05-07 Aluminum Company Of America Method for making a synthetic meixnerite product
US5645810A (en) * 1995-06-07 1997-07-08 Aluminum Company Of America High surface area meixnerite from hydrotalcites

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
F. PRINETTO, G. GHIOTTI, D. TICHIT: "Study of relevant properties influencing the catalytic activity of Layered Double Hydroxides in the Meixnerite-like form.", STUDIES IN SURFACE SCIENCE AND CATALYSIS, vol. 130, 2000, Elsevier Science B.V., pages 3243 - 3248, XP009088790 *
PAUSCH I ET AL: "Synthesis of disordered and Al-rich hydrotalcite-like compounds", CLAYS AND CLAY MINERALS, CLAY MINERALS SOCIETY, US, vol. 34, no. 5, 1986, pages 507 - 510, XP002101577, ISSN: 0009-8604 *

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US9907816B2 (en) 2006-01-31 2018-03-06 Opko Ireland Global Holdings, Ltd. Water-insoluble, iron-containing mixed metal, granular material
US10201501B2 (en) 2007-07-27 2019-02-12 Opko Ireland Global Holdings, Ltd. Mixed metal compounds used as antacids
US10155040B2 (en) 2007-10-16 2018-12-18 Opko Ireland Global Holdings, Ltd. Mixed metal compounds for treatment of hyperphosphataemia
US8106250B2 (en) * 2008-07-28 2012-01-31 Petroleo Brasileiro S.A.-Petrobras Process for removing silicon compounds from hydrocarbon streams
US9314481B2 (en) 2009-08-03 2016-04-19 Opko Ireland Global Holdings, Ltd. Method
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US9066917B2 (en) 2009-08-03 2015-06-30 Cytochroma Development Inc. Mixed metal compound
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US10040054B2 (en) 2009-11-18 2018-08-07 Gtl.Fi Ag Fischer-Tropsch synthesis
US9566302B2 (en) 2010-02-04 2017-02-14 Opko Ireland Global Holdings, Ltd. Composition comprising mixed metal compounds and xanthan gum
US9242229B2 (en) 2010-08-09 2016-01-26 Gtl.F1 Ag Fischer-tropsch catalysts
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US11873230B2 (en) 2017-12-25 2024-01-16 Toda Kogyo Corp. Hydrotalcite particles, method for producing hydrotalcite particles, resin stabilizer containing hydrotalcite particles, and resin composition containing hydrotalcite particles
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