TW200932669A - Purified powder of nanometric particles - Google Patents

Abstract

Process for synthesizing a powder, comprising the following successive steps: (A) preparation of a mother liquor comprising: i. an oxide base constituent or a precursor of the said base constituent and an additional constituent of formula MC, the said additional constituent being composed of: an agent M chosen from the group of oxo anions, anions of elements from column 17 of the Periodic Table of the Elements, hydroxide OH-, and mixtures thereof, and a complement C, this complement being inorganic when the agent is hydroxide OH-; or ii. an oxide base constituent or a precursor of the said base constituent incorporating an agent M chosen from the group of oxo anions, anions of elements from column 17 of the Periodic Table of the Elements, and mixtures thereof; (B) preparation, hydrothermally from the said mother liquor, of a sol whose crude particles have a maximum size of greater than 10 nm and less than 250 nm and even of less than 100 nm; (C) washing of the sol so as to obtain, after an optional drying step, a powder comprising more than 99.3% of the said base constituent, as mass percentage on the basis of dry matter.

Description

200932669 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to nano catalytic particles and systems for catalytic chemical reactions, and also to methods for their synthesis. Catalysis involves multiple reactions in various technical fields, especially in environmental, petrochemical or fine chemical applications. It adjusts the chemical reaction rate by contacting the reagent of this reaction with a catalyst (e.g., platinum) that does not appear in the equilibrium of the reaction. In general, the catalyst is deposited in advance on a support, for example in the form of a nanopowder Φ having a particle size of less than 100 nm. [Prior Art] The paper "Surface studies of supported model catalysts" - C.R. Henry - Surface science reports 31 (1998) 231-325 describes the use of a single crystal as a carrier of a noble metal in a catalytic reaction. X. ''Effect of the interface structure on the high-temperature morphology of supported metal clusters'' - H. Graoui, S. Giorgio, CR Henry - Philosophical Magazine φ B, 2001, Vol. 81, No. 1, 1649 -1658 also describes the use of micronized magnesium oxide (MgO) having a cubic or exposed crystal face {〇, 〇, 1} and {1, 1, 1} as a palladium support. Finally, lw X. ''Some recent results on metal / support interaction effects in NM/Ce02 catalysts''-S. Bernal, JJ Calvino, MA Cauqui, JM Gatica, JA Perez Omil, JM Pintado - Catalysis today 50 (1999) 175-206 describes the use of a Ce02 single crystal having a cubic structure as a carrier for platinum, palladium or rhodium in a catalytic reaction, 136600.doc 200932669. In particular, its effect on the nature of the interaction between the support and the catalyst is investigated. Further, the use of substantially spherical zirconia particles as a catalyst carrier is known. ^ X. ''Synthesis and crystallization of anisotropic shaped ' Zr〇2 nanocrystalline powders by hydrothermal process"-

Materials 丨etters 57 (2003) pp. 2425-2431 describe a hydrothermal process for obtaining nano zirconia powders whose particles have an anisotropic shape. The shape of the particles φ is not smooth. Information on the purity of the resulting powder is not given. Hydrothermal method for obtaining nano zirconia and titanium oxide powder is also described in "Synthesis of Zr02 and Ti〇2 nanocrystallirie powders /lyi/roi/zerma/ process" - Material Science and Engineering C23 (2003) 1033-1038 (The catalytic reaction is not mentioned.) The particles are in the form of a rod and a needle. Further, the sol of the particles obtained by the hydrothermal method is only centrifuged in a conventional manner and washed with distilled water, whereby a powder purity of less than 0.7% cannot be obtained. SUMMARY OF THE INVENTION One object of the present invention is to propose a catalytic powder or catalytic system for enhancing the efficacy of a catalytic reaction and a method for industrially preparing the catalytic powder or catalytic system. According to the present invention, the object is achieved by a synthesis A powder method is achieved, the method comprising the following consecutive steps: A) preparing a mother liquor comprising: i. an oxide base component or a base component precursor and an additional component of formula MC, the additional component being The following are composed of: 136600.doc 200932669 - a group selected from the group consisting of oxyanions, anionic hydroxide OH of the elements of the 17th line of the periodic table, and mixtures thereof Agent M, and • Formulation C, when the agent is hydroxide 〇Η _, the compound is an inorganic substance; or - and has the active ingredient of the bismuth oxide or the basic component The agent is selected from the group consisting of oxyanions, anions of the elements of the elements of the periodic table, and mixtures thereof; Β) hydrothermally preparing a sol from the mother liquor, the granules of the sol having a particle size of less than 250 nm Preferably, the maximum size is less than i〇〇nm; C) washing the sol to obtain 99.3% or more, preferably 99.5% or more, and more preferably 99.7% or more based on the mass percentage of the dry matter after the optional drying step More preferably 99.9 %. The powder of the above basic component. Preferably, the remaining material constituting 1% by weight is composed of impurities. The hydrothermal method is prepared to prepare particles having a maximum size of less than 250 nm or even less than 100 nm. The purity of the powder is generally limited by the specificity of β. The impurity content of less than 1% is not considered to be obvious. The inventors have now found that the maximum size is less than 250 nm and preferably less than 100 nm and has less than 〇_7%. The initial particle set of the impurity content The resulting powders are particularly suitable for use as catalysts in catalyst systems or as catalyst supports. More specifically, the inventors have discovered that when the level of impurities is low, the efficacy of such powders decreases very slowly over time, regardless of purity. How, as long as it is made, this effect is generally uniform. Therefore, 'the powder prepared according to the method of 136600.doc 200932669 according to the present invention can be presented as compared with the catalytic performance (reaction rate and/or selectivity) of the powder of the prior art. Better catalytic performance to maintain time. The present invention is also directed to a powder prepared according to the synthesis method of the present invention. Preferably, step c) comprises at least one knee-washing operation selected from the group consisting of: - transitioning in advance of re-suspending the sol or re-suspending the sol in advance, - re-suspending the sol in advance or not pre-solding Resuspension of the brothers. Dialysis, - in the case of resuspending the sol in advance or without resuspending the sol in advance Φ using ion exchange resin purification, - rinsing, - acid neutralization, and - a combination of these techniques. When appropriate, the washing operation is repeated as many times as necessary until the desired degree of purity is achieved. When additional components of formula MC are introduced into the mother liquor, a single overshoot or single rinse is insufficient to achieve an impurity content of less than 〇.7%. & acid-base neutralization is a preferred washing operation. Preferably, it comprises: depending on whether the impurity to be removed is a cation or an anion, and the suspended MpH is less than or greater than the zero charge point of the basic component; the suspension is below its bar Maintain a period of more than 1 minute at the temperature of the lower boiling point; and filter. Preferably, the pH is less than or greater than the zero charge point by at least 2 unit units, and if so, preferably at least 4 units greater than or even greater than the zero charge point. Still preferably, this temperature is maintained for less than 3 minutes. The pH can be controlled, inter alia, by the addition of hydrochloric acid and/or nitric acid and/or high gas or by the addition of aqueous ammonia (nh4oh) by 136600.doc •10·200932669. Several acid test neutralization operations can be performed consecutively. Preferably, the final operation for removing cationic impurities is performed in a ruler/liquid mixture using a mixture of organic or organic acids to control the P value and/or the final operation for removing anionic impurities is to use an organic test. Or an organic test mixture to control the water solubility of the bay, to perform. 'In-shooting, step C) comprising at least one rinsing operation comprising rinsing the product obtained in the previous step in a solvent for a period of more than 10 minutes at a temperature below its boiling point , then filter. The flushing is preferably carried out in water having a purity at least equal to the purity of the permeated water or in an alcohol towel having a purity of more than 98% by volume. The rinse time is preferably between 丨^min and the clock. The rinsing can be carried out in particular between the scouring operations, in particular between two operations for removing % ions or anionic impurities. Performing the washing step C) allows the skilled artisan to obtain the desired purity by repeating the above operations as many times as necessary. The method of the present invention may further comprise one or more of the following steps: D) drying; E) calcining the powder to remove residual moisture and any organic matter present in the particle powder; F) step C) or step D) or After step E), the powder is depolymerized to fragment any agglomerates in the final powder. The calcining step E) advantageously removes residual moisture and further increases the powder purity by removing the organic components. Preferably, the powder is calcined at least for a while. More preferably, the calcination temperature is higher than 3 Torr. Preferably, it is less than 5 ° C. Favorable 136600.doc 200932669 Maintain the proportion of exposed crystal faces. Preferably, in the step A), the essential component and/or the basic component precursor are respectively contained in an amount of 99.5% or more, preferably 99.8% or more and more preferably 99.9% or more (based on the mass percentage based on the dry matter). The precursor component and/or the precursor of the base component. This advantageously simplifies the purification. In the absence of a washing step, the selection of a very pure starting material which provides the basic component and/or the basic group is the precursor is not hydrothermally produced.

A powder of the invention having a low content of impurities. In other words, the method of the present invention still needs to include a washing step. In one embodiment, the base component added to the mother liquor and/or the precursor of the basic set of knives are selected such that the essential component of the powder has 95% or more, preferably 97, based on the mass percent of the dry matter. More than %, more preferably (four) or more and more preferably 100°/. Single oblique crystal structure. The base component added to the mother liquor or the base component is selected such that the base component is selected from the group consisting of: ζγο2, ε=

Sm2〇3, Mo〇3, w〇3, preferably selected from the group consisting of Hf〇2, Μ〗, 广W03, more preferably selected from the oxides of ton and/or reinforced 2, and more preferably the basic component is oxidized. Wrong Zr02. If the essential component to be considered is selected from the group consisting of Hfo2, Zr02, and Sm2〇3, the ipH value of the mother liquor may be adjusted to be less than 4, or, if the basic component considered in 3 is selected from Hf〇2, Zr〇2, Eu2h, s is called, Mo03, W〇3, (d) adjusting the pH of the mother liquor to be less than 2; 3 large methods of the invention may also include the following 1 optional features 136600.doc 200932669 in step A) The mother liquor may comprise at least 〇.5 based on the percentage by weight of the mother liquor. /. It has a monoclinic structure of ^ A , , v soil component (especially oxidized) and / or the precursor of the basic component. The oxidized precursor is a sulphur oxide or a partially hydrolyzed yttrium derivative. , Social Label - The mother liquor contains a solvent other than water, such as ethanol. The content of the other solvent is less than 5 (four) based on the mass of the liquid phase.

- in step A)t, the source of the precursor having the monoclinic structure and/or the precursor of the basic component having a monoclinic structure based on the mass percentage of dry matter (ie, The component and/or the starting material introduced by the precursor) respectively comprise 99.5% or more, preferably more than 10 parts and more preferably 99.9. /. The above-mentioned basic component having a monoclinic structure and/or the precursor of the essential component having a monoclinic structure. This advantageously simplifies the purification. _ In step A), at least one anion which is soluble in an aqueous medium selected from the group consisting of an oxyanion, an element of the 17th row of the periodic table, a hydroxide 〇H_ (if the pH of the mother liquor is alkaline), and a mixture thereof The group of agents is added to the mother liquor. In particular, the agent that is soluble in the aqueous medium can be selected from the group consisting of sulfate (s〇42-), carbonate (c〇32·), phosphate (PCV·), fluoride ion. (F-), gas ion (C1·), high acid acid (cio4·), borate (Β〇33·), nitrate (Ν〇3·), and hydroxide (〇H) and mixtures thereof, or If the pH value is less than 4, it can be selected from the group consisting of: gas ion (C1·), high acid acid (cl〇4_) and nitrate (NO〇 and its mixture. 136600.doc 13 200932669 -action The content of the agent is more than l〇-4 mol/l, preferably more than i〇-3 m〇1/1 and more preferably more than 10_2 mol/1. - The pH of the mother liquor is selected from the group consisting of organic acids and inorganic acids and mixtures thereof. The acid of the group is adjusted using a base selected from the group consisting of an organic base and an inorganic base and a mixture thereof. - In one embodiment, the mother liquor is composed of: water; an agent; the basic group having a monoclinic structure And/or the pre-e 驱 drive of the base component; other optional melts; optional acid or test; optional surfactant and optional deflocculant - in step B) The liquid is heated in a closed vessel to a temperature above the point of the crucible, preferably between 1 Torr and 3 Torr. - In step B), the rate of temperature increase is less than 2 耽 / hr or even less than 200 ° C / hour. The temperature is preferably maintained for at least i hours and more preferably less - in step B) for 200 hours. In step B), the boiling pressure of the pressure mother liquor in the vessel or reactor, in the reactor, is sealed. - In step D) the drying temperature is lower than the c and preferably less than 2 generations. _ ; 2D) The drying time is adjusted so that the particle powder is here (4), -. The bundle has a residual moisture content of less than 1% by mass. • The ^ method consists of an additional step after step (4), in which free oxyanion is used, and the dopant in the 17th row is selected from the group consisting of A ^ t 1 仃% ion and its chelate. It can be selected from the group consisting of citrate, phosphate, sulfur, especially gas ion, fluoride ion, platinum 136600.doc 200932669 and potassium. When the pH of the mother liquor is less than 4 and when the agent is introduced in the form of an additive of the formula mc, the additive consists of: - the agent Μ; and - is selected from the group consisting of: Agent C: 'A group of positively charged organic molecules whose organic group consists of a group of atoms selected from the group consisting of carbon, helium, oxygen and nitrogen; - element 1 and / or 2 a cation, preferably a φ cation of the first lanthanum element; - a cation of the following elements: aluminum (Α1), manganese (Μη), iron (Fe), yttrium (Y), copper (Cu), silver (Ag), yttrium ( Ce); - ammonium (nh4+). When the pH of the mother liquor is greater than 10 and when the agent is introduced as an additive, the MC additive is composed of: - the agent Μ; and - is selected from the group consisting of: Agent C: a group of positively charged organic molecules whose organic group consists of a group of atoms selected from the group consisting of carbon, hydrogen, oxygen and nitrogen; • cations of the first row of elements; - ammonium (νη4+ ). The parameters of the synthesis method of the invention are preferably adjusted such that: - the primary particles have a largest dimension greater than 10 nm, and/or - the impurities are as follows, in terms of mass percent dry matter: -Si〇2 &lt;〇. 1% ' Preferably, SiO2 &lt; 200 ppm, more preferably Si〇2 <l〇〇136600.doc -15- 200932669 ppm, and/or -Al2〇3&lt;〇.l%, preferably Al2〇3&lt;200 ppm, more preferably Α12〇3&lt;100 ppm, and/or -MgO&lt;0.1%&gt;车交佳MgO&lt;200 ppm, 佳佳MgO&lt;100 ppm, better MgO&lt;50 ppm, and/or

- CaO &lt; 0.1%, preferably CaO &lt; 200 ppm, more preferably CaCKlOO ppm, and / or -Na2 〇 &lt; %. 1%, preferably Na20 &lt; 500 ppm, preferably Na2O &lt; 200 10 ppm and more preferably Na20&lt; 100, and / or - Cl_ &lt; 0.1%, preferably Cr &lt; 500 ppm, preferably C &lt; 200 ppm, more preferably Cl_ &lt; 100 ppm, and / or -N〇3_ &lt; 0.1%, preferably Ν 03 · &lt; 500 ppm, preferably Ν03·&lt;200 ppm, more preferably _3_&lt;100 ppm, and/or -SO42-&lt;0.1%, preferably S〇42-&lt;500 ppm, preferably S042-&lt; 200 ppm, better S〇42_&lt;100 ppm, and/or

Fe2〇3&lt;〇1%, preferably Fe2〇3&lt;200 ppm, preferably Fe2〇3&lt;l00® ppm, more preferably Fe2O3&lt;50 ppm, and/or -TiO2&lt;0.1%, preferably TiO2&lt;200 ppm Preferably, TiO2 &lt; 100 ppm 'better TiO2 &lt; 50 ppm. In particular, the preparation comprises the exposure of a large number of crystal faces belonging to the family of crystal faces {1, 1, 1}, based on the percentage of the total exposed surface area, in particular more than 50% or even more than 80% and even more than 85% and/or 90% In a first specific embodiment of the powder of the invention of the following rod-shaped cerium oxide particles belonging to the crystal face of the crystal face family {1, 1, 1}, the step A) has the following characteristics: 136600.doc -16- 200932669 - mother liquor The ph value is less than 4. The mother liquor thus comprises a group selected from the group consisting of an oxyanion, an anion (halide ion) of the 17th row element, and mixtures thereof, preferably selected from the group consisting of a gas ion (cr), a perchlorate (Cl〇4_) and a nitrate (N).改3·) A modifier of the group consisting of a mixture thereof. - when the modifier is introduced in the form of an additive of the formula MC, the additive preferably consists of: - the modifier Μ, and

a complementing agent c selected from the group consisting of a group of positively charged organic molecules, the organic group of which consists of a group of atoms selected from the group consisting of carbon, hydrogen, oxygen and nitrogen; The cation of the element of the 1st row and the 2nd row, preferably the cation of the element of the first row; - the following 70 cations: aluminum bismuth), manganese (Mn), iron (Fe), Ji (7), steel (Cu), silver ( Ag), cerium (Ce); - ammonium (NH4+). Still preferably, the concentration of the modifier in the mother liquor is between 1 〇·4 忉 and 忉 mol/1. In particular, the preparation of the sentence 〇a ^ I « « The enamel contains a large number of crystal faces belonging to the crystal face family {u, 〇}, based on the total exposure, the percentage of the product, especially more than 35% or even 50% or more and/or 7〇0/. In the first special embodiment of the powder of the present invention in which the rod-shaped oxidized particles belonging to the crystal face of the Japanese family {1, 1, 〇} are lacking, the step A) has the following characteristics: ) 136600.doc 17 200932669 • The pH of the mother liquor is greater than i〇. - the mother liquor comprises an oxyanion selected from the group consisting of boric acid removal (B〇33-), carbonate (c〇32-), nitrate (n〇3_) and perchlorate (Ci〇4·) and mixtures thereof A group of modifiers preferably selected from the group consisting of sulfate (S042.) and phosphate (P043.) and mixtures thereof. - When the modifier is introduced in the form of a formula MC additive, the additive preferably consists of: - the modifier Μ and e

a complementing agent c selected from the group consisting of a group of positively charged organic molecules, the organic group of which consists of a group of atoms selected from the group consisting of carbon, hydrogen, oxygen and nitrogen; a cation of a row of elements; - ammonium (νη4+). The concentration of the modifier in the mother liquor is greater than 1〇1 m〇1/1, and the value of ρΗ is between 1〇 and 14. In particular, the preparation comprises the exposure of a plurality of crystal faces belonging to the crystal face family {1, 〇, 〇), based on the percentage of the total exposed surface area, especially 35% or more or even 50% or more I or 60% or less. In a third specific embodiment of the powder of the invention of the ingot of the crystal face of the familia {1〇〇}, step A has the following characteristics: - The pH of the mother liquor is greater than 1 Torr. - the mother liquor comprises a group selected from the group consisting of an oxyanion, an anion of the 17th row of elements, a hydroxide (OH.), and mixtures thereof, preferably selected from the group consisting of 136600.doc 200932669 hydroxide (OH), carbonate (c〇32·), fluoride ion (F·), gas ion (cr), perchlorate (CUV), borate (B〇33·), and nitrate (N〇3) and mixtures thereof More preferably, the modifier is hydroxide (OH-). _ When the modifier is introduced as an additive, the MC additive is preferably composed of: • - Modifier

- a complementary agent selected from the group consisting of C ® _ a group of positively charged organic molecules whose organic group consists of a group of atoms selected from the group consisting of carbon, hydrogen, oxygen and nitrogen; The cation of the element in row 1; - ammonium (νη4+). - still preferably 'if the modifier is selected from the group consisting of borate (BO3), carbonate (C032·), indeed 'acidate (Ν03-), high acid acid (cl〇4-), hydroxide (〇Η -), the group of anions (drawn ions) of the 17th line and the mixture of the mixture, the modifier of the mother liquor is less than 10 mo 1 / 1. Even more preferably, if the modifier is selected from the group consisting of boric acid (Β〇33·), carbonate (C〇32-), nitrate (ν〇3.) and high oxy-acid (Cl〇4·) outside the oxyanion and its mixture, then the modifier The concentration is less than 10·3 mol/ι. In general, the present invention is also a powder synthesized according to the synthesis method of the present invention or capable of being synthesized according to the synthesis method of the present invention. The particles of the powder are referred to as &quot;particles of the present invention The specific example of the method of the present invention just described can prepare the powder of the present invention 136600.doc -19- 200932669, the initial particles of the powder of the present invention have: - exposure of more than 35%, preferably more than 5% by weight, Preferably, it is preferably 8 % or more, preferably 85% or more, and preferably 9 % or less, which belongs to the crystal face of the crystal face family {^, the crystal face of the crucible, and the initial particles are called "Bar granules", and/or - a sheet shape of a crystal face belonging to a scorpion 〇, 〇, 〇 曝, which is exposed to more than 35%, preferably more than 5% by weight, and preferably less than 6% by weight The initial particles are thus referred to as &quot;grain U,0,0}&quot;; and/or-exposure of more than 35%, preferably more than 5%, and preferably less than 7% by weight. The rod shape of the crystal plane of 1,1,〇), the initial particles are thus called "bar particles {i, i, 〇}", based on the percentage of total exposed surface area. The initial particles are advantageously exposed to a high percentage" Rare &quot; crystal faces (that is, crystal faces other than the thermodynamically most stable crystal faces), and especially a high percentage of the facets and the crystal faces of π, 〇, 〇}. The crystal faces are suitable for use as a catalyst or catalyst support so that the catalyst exposes the reaction sensitive surface to be catalyzed. Preferably, the primary particles of the powder of the present invention are exposed to at least 90% 'preferably at least 95% and preferably substantially 1% of the crystal face family {11〇}, U, M} and {1, regardless of their morphology. , 〇} crystal face. The particles of the powder may be primary particles. It may also be at least partially in the form of secondary particles. The maximum size of the particles of the powder is less than 250 nm, preferably less than 2 〇〇 nm, preferably less than 150 nm, preferably less than 100 nm, preferably less than 9 〇 nm, preferably less than 80 nm and/or greater than 1 〇 nm. It is preferably greater than 20 nm. 136600.doc 200932669 The powder of the invention is especially intended to act as a catalyst or as a catalyst support for constituting the catalytic system of the invention. Therefore, the powder of the present invention itself can act as a catalyst (particles are not coated by a catalyst), especially for catalyzing a reaction sensitive to the crystal face families U, U}, {1, 〇 〇} and {1, 1〇}. It is also possible to use particles coated with a catalyst to form a catalytic system, especially for catalyzing the reaction sensitive to the crystal face family {M, 〇} and {1, 1, 1}. The present invention is also directed to a catalytic system comprising a carrier particle powder 黏 to which a catalyst crystal grain is adhered, which powder is a powder of the present invention. &gt; In particular, the inventors have discovered that this catalytic system advantageously exposes a percentage of &quot;rare&quot; crystal faces (i.e., crystal faces other than the thermodynamically most stable crystal faces), and especially in the catalyst When selected from the 8th row, the 9th row, and the 1st row metal and having a cubic structure, the crystal face of the crystal face family {1,0,0} exposed to a high percentage is selected from the 8th row. Further, in the case of the metal having a cubic structure in the 9th row and the 10th row, it is particularly advantageous to include a catalytic system in which the crystal faces of the main exposed crystal face {1, 00} are in the form of pellets. The catalytic system of the present invention is particularly advantageous. There may be one or more of the following features: - the initial particles are preferably single crystals. The catalyst deposited on the surface of the support may be a metal, preferably selected from the eighth, fifth and first rows of the periodic table and having a cubic structure. a group of metals and mixtures thereof. The metal is preferably platinum. The catalyst may also be an oxide, preferably selected from the group consisting of oxidized steel and/or transition metal oxides (e.g., V2〇5 or (4)3) and/or i4 and I5 row element 136600.doc •21 · 200932669 element oxide, preferably An oxide of tin (sn), lead (Pb) and/or bismuth (Bi). The catalyst may also be a carbide, preferably selected from transition metal carbides such as molybdenum carbide and/or carbonized towns. a sulfide, preferably selected from transition metal sulfides, preferably molybdenum sulfide and tungsten sulfide, optionally doped with cobalt or nickel (eg

CoMoS). Preferably, the catalyst is a metal selected from the group consisting of the 8th, 9th and 10th rows of metals of the Periodic Table of the Elements and is selected such that it is at least 80. /. Preferably, it is: &gt;, 90/β and more preferably at least 95% by number and more preferably substantially all of the catalyst grains have a truncated cubic octahedron or dome shape. - In the case of the metal having a cubic structure in the 8th row, the 9th row or the 1st row, the size of the crystal grains is preferably between 丨5 11111 and 1 〇 nm and preferably between 3 nm and 10 nm. Therefore, it is advantageous to obtain mainly the crystal grains of the metal (especially platinum) which are mainly one of the truncated cubic octahedron shape and one of the two shapes or two shapes β &amp; _ in the eighth row, In the case of a metal having a cubic structure in the 9th row or the 10th row, the truncated cubic octahedral grain system is formed on the carrier particles, and the exposed crystals {{, 1, G} and {i, i, 1} Jl, a post-formed grain system is formed on the exposed crystal faces {1, 〇, ()} of the particles, especially when the particles have a monoclinic crystal structure. Preferably, the catalyst is selected such that at least 8%, preferably at least 90% and more preferably at least 95%, and more preferably substantially all of the catalyst grains in the catalytic system are not spherical or not Carrier contact flat 136600.doc -22- 200932669 The shape of the spherical shape of the face truncation. This advantageously increases the effectiveness of the catalytic system. The size of the catalyst grains is preferably between 1.5 nm and 1 〇 nm and preferably between 3 nm and 10 nm. Preferably, the catalyst comprises less than 1% by mass of the mass of the catalytic system, preferably 7 〇 / 〇 , and more preferably 5% or less. The content of 1% catalyst is generally suitable. The powder of the granules comprising the crystal faces of the main exposed crystal face group and the granules of the main exposed crystals of the face group {1, 〇, 〇} are particularly advantageous. The invention is therefore also directed to a method of catalyzing a chemical reaction using the powder of the invention. In particular, when the morphology of the particles of the powder of the present invention is not spherical, for example, when the particles are rods or pellets, the powder of the present invention can be advantageously used to catalyze a structurally sensitive reaction. The invention thus also relates to a method of using the powder of the invention: The primary particles are not coated with a catalyst, and the powder of the invention can be used to catalyze a reaction selected from a hydrocarbon conversion reaction, including a selective oxidation reaction, a hydrogenation reaction, a dehydrogenation reaction, Hydrogenolysis reaction, isomerization reaction, dehydrocyclization reaction and recombination reaction; or, after the initial particles are at least partially covered by the catalyst, when the catalyst is selected from the eighth row of the periodic table, In the case of groups 9 and 10 and having a cubic structure of a metal and a mixture thereof, and especially when the essential component of the carrier particles is zirconia, the powder of the present invention can be used to catalyze a reaction selected from the group consisting of: 136600. Doc 23· 200932669 a. More than 26% or even more than 35% or even 51°/% based on the total exposed surface area of the catalyst. The above exposed crystal faces belonging to the crystal face family {1,0,0} and/or 35% or more or even 45% or more or even 66% or more or even 70% or more belong to the crystal face family {1,1,1} The reaction of exposing the crystal face; and/or b. the reaction selected from the hydrocarbon conversion reaction, including selective oxidation reaction, hydrogenation reaction, dehydrogenation reaction, hydrogenolysis reaction, isomerization reaction, dehydrocyclization reaction and Recombination reaction; reference c. selective hydrogenation reaction, and selective hydrogenation reaction of a molecule containing at least one functional group CO, and selective hydrogenation of a molecule containing at least two double bonds; d. methane formation reaction &quot;decaneization reaction&quot;); Fischer-Tropsch synthesis reaction (including methanol synthesis reaction), in other words, by carbon monoxide (CO), hydrogen (h2) and/or Organic molecules (such as biomass) form oxygenated hydrocarbons; ® - regardless of the catalyst 'as long as the basic components of the carrier particles are monoclinic, the powders of the invention can be used to catalyze reactions selected from hydrocarbon conversion reactions' including selectivity Oxidation reaction, hydrogenation reaction, Argon reaction, hydrogenolysis reaction, an isomerization reaction, the dehydrocyclization reaction and recombination reactions. In particular, when the catalyst is a metal having a cubic structure from the 8th row, the 9th row, and the 10th row, the present invention comprises the primary particles (the essential components thereof are selected from the group consisting of strontium oxide (Zr〇2), oxidation Catalytic powders and catalytic systems of ruthenium (Hf〇2), zirconia and oxidized 136600.doc -24· 200932669 混合物 mixture, molybdenum oxide and tungsten oxide are suitable for catalyzing the crystal face family {1,1,1 The percentage-sensitive reaction of the exposed crystal faces of } and / or {1,0,0}.

The catalytic system of the invention is also particularly suitable for use in catalysis below 500. (: a reaction occurring at a temperature. When the reaction occurs at a temperature lower than 500 Torr, the maximum size of the initial carrier particles can be advantageously maintained below 250 nm and preferably below 100 nm, and carried by the carrier The size of the catalyst crystallites can be maintained below 10 nm. In addition, during the entire reaction period, the crystal grains can be exposed to crystal planes other than the thermodynamically most stable crystal plane of the crystal face group. In the specific case of a metal with a cubic structure in rows 9 and 10, the thermodynamically most stable family of crystal faces is the lattice family {1, U}. The definition of the term 'catalytic system' means that it is in powder form. a carrier and a combination of catalysts immobilized on the carrier. For the sake of clarity, the term &quot;grain&quot; is used in this specification to refer to a catalyst crystal that has been formed on a support, and the term &quot;particle&quot; Used to refer to the carrier powder. However, the carrier primary particles may be crystalline in structure. For convenience, the term &quot;crystal, is used without preference to represent the initial particles or grains of the carrier. The grain Or a grain may be said to be generally a "single crystal" when the particle or grain system is composed of a single homogeneous homogeneous volume throughout its entire volume. The particle is substantially as long as at least 90% of the particle volume has a monoclinic structure. The composition may be referred to as &quot;having a monoclinic crystal structure. 136600.doc •25· 200932669 When the top view of the particle is allowed to appear at a ratio of about 10 nm/cm, the line of sight is thus substantially in the observation plane along the length of the particle. When defining the edge of the particle shape with little or no steps (staggered edges) and/or sharp corners (rough), the particles may be said to have a &quot;smooth shape&quot;. For example, in a bar with a hexagonal cross section In the case of granules, this means that each of the six sides of the cross section is substantially linear. The smooth shape can also be attributed to the group of de-granular faces U, M}, {1, 1, 0} and { Preferably, the ratio of the exposed crystal face of the crystal face group other than 1, 〇, 〇} is less than 10% of the total surface area of the exposed crystal face. Preferably, according to the present invention, the ratio is less than 5% and preferably substantially zero. &quot;Powder&quot; for particle combinations. These The child may be an "initial particle" (ie, not associated with other particles), or a &quot;secondary particle&quot; (ie, consisting of agglomerates or aggregates of primary particles). In &quot; agglomerates, Let the combination of the initial particles result from a combination of weak intensities, for example via a charge effect or a polar bond. In the aggregate, the combination between the initial particles is stronger than in the case of a combination of agglomerates. For example, the primary particles can be chemically bonded to each other. Therefore, splitting the agglomerates into smaller agglomerates or initial particles is easier than splitting the aggregate into smaller ® aggregates or primary particles. In the present specification, the term "carrier" means a carrier in the form of a powder. The basic component of the carrier particles is a main component, preferably more than 90% by mass and preferably more than 99%. Preferably, the carrier particles of the present invention are composed of essential components and impurities. "Quality agent" is a component of a mother liquor which is soluble in an aqueous medium and chemically interacts with a solid element oxide forming a basic component or with an oxide precursor present in the mother liquor, the chemical interaction It is strong enough that 136600.doc -26- 200932669 can be used in the presence or absence of a modifier in the mother liquor (especially in relation to its pH and the pH of the mother liquor) to affect the morphology of the particles obtained after hydrothermal treatment. The nature of the modification depends on the following: the nature of the solid element oxide or the precursor of the oxide or even the crystal structure; the i-degree of the agent in the mother liquor, and the pH of the mother liquor. For example, As long as the solid element oxide or the precursor of this oxide has a monoclinic structure and is within the concentration and pH range described below, it is selected from the oxyanion, the anion of the element of the 17th line of the periodic table. The agent φ of the group of hydroxide 0H- and its mixture is &quot;modifier&quot;. The maximum size of the initial particle of the powder is defined as generally performed by electron microscopy in the observation plane. Measure its maximum size. &quot;Maximum size of the initial particle combination (or powder)&quot; corresponds to the &quot;maximum size&quot; of the particles in this combination with the largest size. The &quot;size&quot; of the catalyst grains deposited on the surface of the carrier particles is defined as its average surface size. When the catalyst belongs to a group of metals having a cubic structure from the 8th row, the 9th row, and the 1st row, the average surface size of the catalyst can be determined by the dispersion value thereof, particularly by hydrogen chemisorption. Especially when the catalyst belongs to the group of carbides, sulfides and oxides identified as catalysts. (detailed in & detailed) 'average surface size can be measured by electron microscopy observation. The percentile or &quot;percentile&quot;50(D5G) and 90(0^) are the powder particles of the mass particle size distribution curve corresponding to the mass ratio of 5〇% and 9% by mass, respectively, on the cumulative particle size distribution curve of the powder particle size. Size, particle size is sorted in ascending order. For example, 90% by mass of the powder particles have a size smaller than ο" and 1〇% by mass 136600.doc • 27- 200932669 The particles have a size larger than Dm. The particle size distribution generated by the Bai Ba analyzer can be borrowed. :: using the "median size" of the sedimentation granularity, that is, dividing the group corresponding to the first group of particles and the particles of the first-hetero-amp; σ into the size of the first group and the first group of equal mass, The granules and the second-groups that are greater than or less than the average size respectively contain only the size of the quotient. The usual 媢囍 媢囍 媢囍 术 术 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子The particle size of the granules of the granules of the MiCr〇merities® company can be used, for example, for 8 kg.

_ Settling particle size analyzer lamp 0 &quot; crystal face family&quot; or "crystal form" (written as {h, k, 1}) usually refers to a crystal plane with a specific atomic arrangement (that is, a specific arrangement of specified atoms) combination. Therefore this definition does not include the arrangement of atoms extending along the surface. The term &quot;crystal face&quot; (usually represented by its Miller index (10) )) refers to the crystal face of the family of crystal faces {h, k, l} characterized by the specific orientation defined by its Miller index (hk, l). The crystal face family {h,k,l} thus contains a set of crystal faces: (hk,i), (9)丨(4), (k'h'l), (k,l,h), (l,h,k , (l, k, h), and combinations obtained by changing the sign of one, two or three Miller indices. For example, the family of crystal faces {1, 0, 0} is a set of crystal faces: ( 10 0), (〇1〇), (〇〇1), (1), 〇, 〇), (0,-1,0) and (0,0,_1) 〇 crystal&quot;exposed crystal face&quot; The crystal face that is in contact with the outside, for example, is opposite to the crystal face adjacent to the carrier. When referring to the exposed crystal face of the particle, only the initial particle is considered. When referring to the carrier particle in the catalytic system, the exposed crystal face is considered to be included. At least a portion of the crystallized surface of the structuring agent. In other words, to evaluate the percentage of the crystal face exposed by the particles 136600.doc -28- 200932669, the catalyst is not considered to have an exposed crystal face on the surface of the specific particle. {h,k,1} is the group exposure of the crystal face family Crystal plane. For example, Lu's exposed crystal family {i, M} is in the crystal plane (im), (〇1〇), (0,0,1), (-1,0,0), (〇, 〇) (〇, 〇, -1) one of the groups exposed to the crystal face and only exposed to the crystal face. When the exposed crystal face contacts the reagent roll contact to promote chemical reaction, it can be called "favorable" ".

When the crystal face family contains at least one favorable crystal face, it can be called V, which is advantageous. When the crystal face family contains the most favorable crystal face, it can be called &quot;the most favorable.&quot; The growth axis is the main growth direction of the crystal. The growth axis does not have to be associated with the exposed crystal plane of the crystal. β When the initial particle satisfies the following three conditions, it has a &quot;stick&quot; shape: 1) 1&lt;L/Wy0' where L represents the length of the initial particle, that is, its longest Dimensions, and W = (W1 + W2) / 2, where the sand and the sand are the smaller axes of the smallest possible ellipse of the cross-section of the intrinsic primary particles (also (4) the cross section perpendicular to the length of the initial particles) The length of the longer axis; and 2) W2 &lt; 1.5 W1, and a 3) The cross section is substantially constant over the entire length of the rod, is generally polygonal and contains at least 4 sides. The cross-section of the rod-shaped initial particles of the present invention preferably has less than 8 sides. More preferably, the rod-shaped primary particles are iWL/WU and preferably 2$L/wq. Figure 1 is a graphical representation of primary particles in the form of rods. 136600.doc -29- 200932669 When the initial particle satisfies the following three conditions, it has a &quot;slice" shape: 1) 5&lt;L/W1S10 and l^L/W2y, where [indicates the length of the initial particle, ie its The longest dimension, and W1 and W2 are the shorter axis and the longer axis of the smallest possible ellipse of the cross-section of the intrinsic primary particle (ie, the cross section perpendicular to the length of the initial particle); and 2) W221 .5 W1 'and preferably W2&gt;2 W1, and 3) The cross section is substantially constant over the entire length of the pellet, generally polygonal and comprising at least 4 sides. Φ Cross section of the tabular particle of the present invention Preferably, the sheet has less than 8 sides. More preferably, the sheet-shaped initial particles are 6SL/W1S8 and 2SL/W2S4. Figure 2 is an illustration of the primary particles in the form of pellets. Thus, the sheet or rod-shaped particles are particularly different from Spherical or fibrous, yarn, filament, needle or cube. The dome corresponds to a flat shape in which the cross section is generally substantially constant throughout its thickness (eg, always octahedron regardless of the cross section considered). In other words, when the grain satisfies the following four conditions, it has筏&quot;Form: ^ 1} 3£W/E' 'where £ represents the thickness of the grain, ie its minimum size, and W=( W i + W2)/2, where W! and W2 are respectively The smaller axis of the smallest possible ellipse of the cross section of the inscribed grain (ie, the cross section perpendicular to the grain thickness direction) and the length of the larger axis; and 2) W2 &lt; 1.5 W1 ' and preferably W2 &lt; 1.2 W1 , and 3) the thickness is generally hate, and 4) the cross-section of the 筏-shaped grain is generally prepared to be ww eight bottles of the main moon shape and contains at least four sides. Preferably, it comprises less than 8 sides. 136600.doc -30- 200932669 More preferably, the 筏-shaped grain is 乜W/Es6. Figure 7 is a graphical representation of several shaped grains. The cubic octahedron is an intrinsic w 肜 曰 曰 ( ( ( ( ( ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ 优先 优先 优先 优先 优先 优先 优先The truncated cube octahedron is incomplete. It is just a cubic octahedron cut along the thousand faces that come into contact with the carrier. 6a and 6b are truncated top views and side view photographs and illustrations, respectively. Cubic octahedron

Containing a milk anion•, an oxide anion of the form muscle η. Q is a metal (such as Shi Xi) or a non-metal (such as carbon, scale or sulfur), n is greater than or equal to an integer and X is equal to (n+W ) / 2, is the price of the metal or non-metal considered. The term &quot;impurity&quot; means an unavoidable component that is inadvertently and necessarily introduced with the starting material or is caused by reaction with the components. Impurities are not essential components, but are only permissible. For example, If the presence of a compound belonging to the group of the following substances is not required, it is an impurity: sodium and other alkali metals, iron, vanadium and chromium oxides, nitrides, oxynitrides, carbides, oxycarbides, Carbonitrides and metal materials. When the desired product is oxidized or based on products of zirconia and yttria, yttrium oxide is not considered as an impurity. Similarly, if Mo 〇 3 is an essential component of particles, uranium oxide M 〇 〇2 and Μ] are not considered as impurities. Finally, similarly, if WO3 is an essential component of the particles, the tungsten oxides W〇2 and W〇3 are not regarded as impurities. In the powder of the present invention, the impurities may be The initial particles of the powder of the present invention may be combined to form independent particles. In the present specification, the two types of impurities are not distinguished. 136600.doc •31 · 200932669 Purpose and intentionally add &quot;dopant&quot; In the group that becomes the final product Divided into components. :::, &quot;hydrothermal&quot; method is to heat the aqueous solution to a temperature at the boiling point of the door at atmospheric pressure in a closed vessel and at a pressure greater than or equal to the minimum pressure required for the Guluo 'Furton' Well known methods. 'Glue generally refers to colloidal particles that are dispersed or suspended in a liquid phase (eg, an aqueous medium). The particles in the sol generally do not coalesce or coalesce.

The zero charge point ZCP is defined as follows. The surface charge of the suspended oxide. Generated by the balance of =. Therefore, it depends on the pH of the solution and the ion concentration. Depending on the condition of the quality, σ can be positive, negative or zero. The zero charge point defines the enthalpy of the medium that the charge 得以 is able to cancel. At PH&lt;ZCP, the charge σ is positive. At pH&gt;ZCP, σ is negative. The zcp value is directly related to the nature of the oxide. The hourly space velocity of the gas (written as HSV) is defined as the volume of gas per unit volume of reactor and unit time. It is represented by y. The reaction can be referred to as &quot;structural sensitivity&quot; depending on the nature of the catalyst and the amount of catalyst surface area accessible to the reagent&apos; and depending on the morphology of the catalyst and the exposed crystal plane. Unless otherwise mentioned, 'the percentage of the ratio used to characterize the exposed facet always means the percentage of the total surface area (expressed in m2) relative to the exposed facet. 0 Unless otherwise mentioned, the percentage used to characterize the composition always means Based on the mass percentage of dry matter. When referring to the line number of the authentication element, the line number of the periodic table of elements is indicated. [Embodiment] 136600.doc -32- 200932669 Other features and advantages of the present invention can also be present by reading the following embodiments and inspections. The above steps A) to F) will now be described in detail. Step A) In the step A), an aqueous stock solution or an aqueous stock suspension (hereinafter referred to as mother liquor) containing the solid element oxide to be prepared or the precursor of the oxide is prepared. This solution is determined according to the parameters of step B) so that the desired initial particles can be obtained. e

Typically, the mother liquor typically contains a solid (elemental oxide or precursor of the oxide) in an amount between 5% and 5% by weight. The synthesis method can be specifically performed to prepare a monoclinic oxide, especially a monoclinic oxide selected from the group consisting of brain 2, Zr 〇 2, Eu 2 〇 3, Sm 2 〇 3, M 〇〇 3, w 〇 3. Preferably, the monoclinic oxide is selected from the group consisting of Hf 〇 2, Zr 〇 2, W03 (preferably selected from the group consisting of Zr 〇 2 and HfCM 甘, 9 * * 口. 2) and mixtures thereof. The monoclinic oxide is preferably oxidized Zr02. The mother liquor may contain a monoclinic oxide to be prepared. It may also contain such oxide precursors. The liquid phase of the mother liquor can be water. Autumn, however, however, other water-miscible agents such as ethanol may be included in the liquid phase. The liquid phase is less than 5% by weight. The amount of f and other solvents are preferably additional components of the formula MC. The additional hydrophobic mother liquor also comprises at least a sub-system consisting of: - selected from the group consisting of oxyanions, meta-, scent &amp; ± &amp; ΜΟΗ-μ α ^ , the anion of the element of the 17th line of the periodic table, the hydroxide of the hydroxide and the mixture of the mixture, and 136600.doc • 33 - 200932669

- Formulation c, when the agent is a oxime OH., the compound is an inorganic substance. The pH of the mother liquor can be adjusted by means of organic acids or inorganic acids and/or organic or inorganic bases. When the field agent is a modifier, the positive value of the mother liquor and the nature and amount of the modifier can illuminate the shape of the last-transmitted elementary particles and the nature and ratio of the exposed crystal faces. Step Β) ❻ In step Β) 'heat the mother liquor in a closed vessel and at a pressure greater than or equal to the boiling pressure of the mother liquor to a temperature above the boiling point of the bar, preferably between 1 and 3 . Advantageously, this method directly obtains the primary particles of the oxide of the element under consideration. The hydrothermal treatment can be carried out in a batch reactor or in a continuous reactor. The residence time in a continuous reactor is generally shorter and the temperature is generally higher compared to a batch reactor. The reducer adds #to the desired temperature&apos; and then maintains the i degree for at least i&lt;0&gt; hours and preferably less than 200 hours. The hold time of the temperature stabilization phase can vary with the reactor temperature and the concentration in the mother liquor. It can be determined by routine testing. The choice of temperature/sustainment time combination during the stabilization phase will also affect the size of the initial particles. This combination is therefore selected to achieve a maximum initial particle size of less than 25 Å and preferably less than 100 nm. The pressure in the reactor is greater than or equal to the boiling pressure of the mother liquor. This pressure may be self-generated (i.e., corresponding to the vapor pressure of water at the reactor temperature), hydraulic 136600.doc • 34·200932669 or may result from the addition of an inert gas such as nitrogen. The pressure is selected such that the resulting final product is in the desired crystalline phase. The reactor is then cooled to a temperature below the boiling point at 1 bar. The resulting sol was separated. It contains a liquid fraction and "coarse" particles having a high impurity content. The inventors have found that such impurities impair the efficacy of the particles, whether they are used as catalyst supports or as catalysts. Step C) Step A And B) are known for the preparation of crude particles by hydrothermal method. © According to the invention, in step C), the solid phase consisting of crude particles in the sol is purified 'so that its impurity content is the mass of the dry matter The percentage is less than 0.7%, preferably less than 〇5%, preferably less than 〇·3% and more preferably less than 0.1%. The purification of the crude particles in the sol preferably comprises the following steps C1 to C3: Step C1 (which is optional) The step) is to reduce the amount of the liquid phase of the sol and/or to purify the liquid phase of the sol. The expression &quot;reducing the amount of the liquid phase of the sol&quot; means any operation for removing all or part of the liquid phase of the sol. Such methods are well known to those skilled in the art and may include: - filtration in the case of resuspending the sol in advance or without resuspending the sol; - resuspending the sol in advance or resuspending the sol without prior Dialysis in the case; - at Purification using an ion exchange resin without resuspending the sol in advance or without resuspending the sol; 136600.doc -35- 200932669 - Flushing, and - a combination of these techniques. Expression &quot; Purifying the liquid phase of the sol&quot; Any operation that reduces the concentration of ionic species in a liquid solution of a sol. These methods are well known to those skilled in the art and may include the following methods: dialysis, purification using ion exchange resins, or • rinsing by dilution. C1 cannot achieve the desired purity of the final powder by a general method, so it is preferred to use an additional purification step C2 and/or step C3. β Step C2 removes cationic impurities. The term &quot;cation impurity&quot; means containing carbon removal (C a molecule other than hydrogen (Η), oxygen (〇), and nitrogen (Ν), a molecule that is positively charged and contained in the liquid phase of the sol and/or attached to the sol. The liquid phase of the sol and the sol The crude particles may not contain cationic impurities, for example in the case of hydrochloric acid (HC1), thus eliminating the need for step C2. The product from the previous method step (step Β) or step C1) Suspended in an aqueous solution having a pH lower than the zero point of charge (ZCP) of the last oxide of the element under consideration. Preferably, the pH is 2 pH lower than the ZCP and is preferably better. 4 pH units lower than the ZCP. The ZCP value of the main oxide and its determination method can be found, for example, in the book uDe la Solution a VOxyde^ &gt; J.-P. Jolivet, CNRS^ » Paris (1994) No. 255 to Page 308. The pH of the suspension is controlled by the addition of organic and/or inorganic acids. Among the acids, 'nitrogen and/or high acidity is preferred. Preferably, the suspension is maintained at a temperature below its boiling point at the bar (preferably at room temperature) for preferably more than 丨〇 minutes and preferably less than 3 〇136600.doc - 36- 200932669 minutes period. This suspension is then filtered by any means known to those skilled in the art. Step C2 can be repeated several times if the desired purity of the cationic material is desired. Step C3 removes anionic impurities. The term &quot;anionic impurity&quot; means an element other than carbon (C), hydrogen (H), oxygen (〇) and nitrogen (N), negatively charged and contained in the liquid phase of the sol and/or attached The molecule of the crude particles of the sol. The liquid phase of the sol and the coarse particles of the sol may not contain anionic impurities, for example in the case of ammonia (NH4〇H). Thus no steps are required. The product obtained from the previous process step (B) or C14C2) is suspended in an aqueous solution having a pH greater than the zero charge point of the last oxide of the element under consideration. If the ZCP is less than 1 〇, the pH value is preferably more than the ZCJ^2 pH unit, and more preferably 4 pH units higher than the zcp. The pH of the suspension is controlled by the addition of an organic base and/or an inorganic base. Among these bases, ammonia water NH4OH is preferably used. Preferably, the suspension is maintained at a temperature below its boiling point at 1 bar (preferably at room temperature) for preferably more than 丨0 minutes and preferably less than 3 〇-minutes. period. This suspension is then transferred by any means known to those skilled in the art. Step C3 can be repeated several times if the desired purity of the anionic material is desired. Steps C2 and C3 can be performed alternately or in reverse. 136600.doc -37· 200932669 Since the crude particles still contain at least some cationic or anionic impurities, at least one of steps C2 and C3 is performed to reduce the impurity content to less than 0.7% 各 at each step C1, C2 and/or C3 The optional rinsing step C4 can be carried out in a solvent, preferably in water having a purity at least equal to the purity of the permeate water or in an alcohol having a purity greater than 98% by volume and preferably greater than 99% by volume. The product from the previous step is preferably suspended in the solvent in a solvent at a temperature below its boiling point at 1 bar (preferably at room temperature) preferably for more than ❹ minutes and preferably less than 30. The period of minutes. This suspension is then filtered through any means known to those skilled in the art. After step C), the resulting product consists of wet purified particles. Step D) In step D), after purification, the liquid fraction is removed by drying. Next, the purified particle powder of the present invention is obtained. Any method known to those skilled in the art can be used. The drying temperature is generally below 500. (: and preferably less than 2 〇〇. (:.) Adjust the drying time so that the powder of purified particles has a residual moisture content of less than 1% by mass at the end of this step. Step E) In optional step E) The powder is calcined, preferably calcined at least! hour. The calcination temperature is preferably higher than 300 ° C and preferably lower than 500. (: to avoid converting the exposed crystal into the thermodynamically most stable crystal face. This step E) removes residual moisture and any organic matter present in the purified particles obtained after step D). 136600.doc -38- 200932669 The final depolymerization step can also be added after step E) or step D) to fragment any agglomerates in the final powder. Specific Method for Preparing Ammonium Oxide Particles The above-described synthetic methods (Steps A) to E)) of the present invention are advantageously carried out to prepare a powder of the primary particles of the present invention. In the case of zirconia, the method has the following specific characteristics: Step A)

The hydrothermal preparation (steps A) and B)) of sols of particles smaller than 250 nm or even less than 1 〇〇 nm are well known to those skilled in the art and are described, for example, in the book &quot;£)e /α仏/mHo" a , j._p j〇iivet CNRS edition, Paris (1994). In step A), an aqueous stock solution or aqueous stock suspension containing zirconia or lead oxide precursors is prepared (hereinafter referred to as &quot;mother liquor&quot;). This solution is determined according to the parameters of step B) in order to obtain the desired initial particles. The mother liquor contains at least 5% zirconia or equivalent precursors based on the mass percentage of the mother liquor. The material may be a cerium salt or a partially hydrolyzed zirconium derivative. Fortunately, the precursor is a basal oxidation fault, also known as hydration oxidation error &quot; or "clear::&" (not limited thereto). This compound can be obtained by making the wrong salt alkaline or &quot; Appropriate warp-based oxidized powders can be found. Example 1 mHO is available from SEPR Saint G〇ba ’. These powders have a microμ median diameter. The liquid phase of the mother liquor can be water. However, a liquid phase solvent such as ethanol. In the liquid phase: including other water mixed streams, the amount of solvent is better, j 136600.doc -39- 200932669 50% The aqueous mother liquor may contain a modifier. The agent for which the agent may be added in the form of an additive or which may be soluble in the aqueous medium by the cerium oxide precursor may be selected from the group consisting of an oxyanion, an anion of a first element (halide ion), and a hydroxide (〇H). -) and its mixture, = preferably selected from the group consisting of: sulfate (s〇42·), carbonate ❹ (C〇32·), phosphate (P〇43-), fluoride ion ( F), gas ions (C1), high gas radicals (Cl〇〇, indeed, acid (N〇3-), folate (10)?.) and gas oxygen (and mixtures thereof. The agent may be corrosive and Therefore, special equipment is required. The pH value of the mother liquor and the nature and amount of the modifier can affect the morphology of the resulting basic particles and the nature and proportion of the exposed crystal faces. The inventors have unexpectedly discovered that regardless of the preparation conditions used, The pH of the mother liquor between 4 and 10 does not provide the primary particles in the form of pellets or pellets of the invention. The pH of the mother liquor can be adjusted by the addition of organic or inorganic acids and/or organic or inorganic bases. Preparation of a rod-shaped and exposed a large number of crystal faces belonging to the crystal face family {ι, ^ In particular, the zirconia particles of the present invention having 50% or more, or even more than 8% by weight and even more than ❶ and less than 5% by weight, make the pH of the mother liquid acidic and less than 4. The modifying agent used. Preferably, it is selected from the group consisting of oxyanions, argon ions of the 17th row element, and mixtures thereof, preferably selected from the group consisting of gas ions 136600.doc 200932669 (cr), high gas radicals (C104_), and nitrates (Ν03· ) and a mixture of its mixtures. When the modifier is introduced in the form of an additive of the formula MC, the additive preferably consists of: - the modifier and

'- a complementary agent C selected from the group consisting of a group of positively charged organic molecules whose organic groups are composed of a group of atoms selected from the group consisting of carbon, hydrogen, oxygen and nitrogen. - the cation of the element of the first row and the second row, preferably the cation of the element of the first row; - the cation of the following element: aluminum (Α1), manganese (Μη), iron (Fe), (Y), copper ( Cu), silver (Ag), cerium (Ce); - ammonium (NH4+). The proportion of the exposed crystal faces belonging to the crystal face family {1, 11} is adjusted by the pH value and the amount of the modifier. If the maximum size is greater than 10 nm, the ratio of exposed crystal faces has a benefit that does not depend on the maximum size of the initial particles. If the content of the modifier is fixed, the amount of the crystal face of the crystal face group is reduced as the pH value increases. The concentration of the modifier in the mother liquor is between 10·4 mol/1 and 10 mol/1. This intensity can change the proportion of exposed crystal faces of different crystal face families. Regular tests can adjust the concentration according to the desired ratio. For the preparation of a rod shape and exposure a large number of crystal face family {^, (^ crystal face, especially 35 ° / above or even more than 5 〇% and / or 7 〇% or less belongs to the crystal face family 136600.doc • 41 · 200932669 {1'1, 〇} of the crystal face of the cerium oxide particles of the present invention, the pH of the mother liquor is alkaline and greater than 1 〇. Thus the modifier used is selected from the removal of borate (B〇33-) The group of carbonate (C032·), acidified root (NO〇 and oxyanion outside the high gas radical (cl〇4·) and a mixture thereof is preferably selected from the group consisting of sulfate (so42-) and phosphate (p〇). 43-) and its mixture • Group of substances. When the modifier is introduced in the form of additive MC, the additive consists of the following: ❹ · The modifier Μ

a complementing agent C selected from the group consisting of a group of positively charged organic molecules, the organic group of which consists of a group of atoms selected from the group consisting of carbon, hydrogen, oxygen and nitrogen; a cation of a row of elements; - ammonium (ΝΗ4+). The ratio of the crystal face of the crystal face is adjusted by the amount of the pH modifier, and the ratio of the exposed facets of 1〇} is taken as an example. If the maximum size is greater than 1 〇 nm, the relative proportions of the different exposed crystal faces are independent of the maximum size of the initial particles. For a fixed pH value, if the concentration of the modifier increases, the proportion of the exposed crystal faces belonging to the crystal face family {1, 1, 0} increases. In order to obtain a large particle powder in the form of the rods, the concentration of the modifier is greater than 10_1 mol/1 and the pH is between 10 and 14. However, if the pH is increased, the concentration of the modifier can be lower, so a concentration of 0.01 m〇m is suitable for the pH of 13. If the amount of the modifier is insufficient, the sheet of the present invention will be obtained 136600.doc -42- 200932669 granules, in fact, exposed crystal family μ,! , (the grain of the crystal face of the crystal face and the crystal grain 4 of the crystal face of the exposed crystal face family {1,0,0} are continuous. In other words, there is a limit value for a given pH value, low At this limit value, μ particles will be obtained and above this limit value will be obtained. In order to prepare a crystal face having a sheet shape and exposing a large amount of crystal group {1, 〇, 〇}, especially (10) or even 5 〇% The above cerium oxide particles of the present invention belonging to the crystal face of the crystal face group U, 0, 0} above and/or 6〇% or less make the pH of the mother liquid alkaline and greater than 1 〇. The modified (4) used is selected from The group consisting of an oxyanion, an anion of the element of the 17th row (tooth ion), a hydroxide (OH-), and a mixture thereof is preferably selected from the group consisting of hydroxide (OH·), carbonate (c〇32·), and fluorine. a group of ions (n, gas ions (C1·), high gas acid (dev), borate (Bo), and nitrate (N(v) and mixtures thereof. More preferably, the modifier is hydrogen and oxygen Root (〇Η·). When the modifier is introduced in the form of an additive of the formula MC, the additive consists of: - the modifier Μ and - selected from the group consisting of: Agent c - one a positively charged organic molecule whose organic group consists of a group of atoms selected from the group consisting of carbon, hydrogen, oxygen and nitrogen; - a cation of the element in the first row; - ammonium (νη4+). The adjustment of the amount of the granule belongs to the ratio of the exposed crystal face of the crystal face family. The right dimension is larger than 1 G nm, and the relative ratio of the different exposed crystal faces is 136600.doc -43- 200932669. The case does not depend on the size of the initial particle. If the content of the modifier is fixed, the proportion of the exposed crystal face belonging to the crystal face group increases with the increase of the pH value. If the pH value is fixed, and if the modifier is selected from the group consisting of boric acid removal and carbonate ( C03), nitric acid (N〇3-), high oxygen acid (ci〇4.), oxygen-containing anion + and mixtures thereof, such as p and 43, belong to the crystal family &quot;, 〇 〇} • The proportion of exposed crystal faces or even the shape of the particles will vary with the amount of modifier. In particular, when the concentration of the modifier increases, the ratio decreases. The A is completely in the form of the pellets. In the form of particle powder, the concentration of the above modifier must always be less than 1〇_3 m〇1/1. Furthermore, in general, between 1〇14 Within the pH range, for the modifier concentration between 1〇-&gt;1 (Γΐ..., the conventional test can adjust the modifier concentration to adjust the ratio and morphology of the exposed crystal face (grain or pellet). The pH value is fixed, and if the modifier is selected from the group consisting of borate (b〇33_), carbonate (CO32·), nitrate (NCV), high carbonate (cl〇4-), element 17 of the periodic table The group of anions and mixtures thereof, the modifier concentration does not change the proportion of the exposed crystal faces belonging to the crystal face family {1, 0, 0}. However, the modifier concentration is preferably less than 10 mol/1. In step B), the mother liquor is heated in a closed vessel to a temperature above the boiling point at 1 bar, preferably at 1 Torr. (: between 30 and rc. The shape of the initial particles, the nature and proportion of the exposed crystal faces are not dependent on the temperature of the hydrothermal treatment, but the temperature values allow for short-term processing (to obtain the desired size and morphology), thereby enabling The invention is utilized on an industrial scale. 136600.doc • 44· 200932669 The reactor is heated to the desired temperature and then maintained at a temperature of at least j hours and preferably less than 200 hours. The choice of temperature/maintenance time combination for the stabilization phase is also This will affect the size of the initial particles. This combination is therefore chosen to achieve a maximum initial particle size of less than 25 〇 nm and preferably less than 100 nm. • The pressure in the reactor is greater than or equal to the boiling pressure of the mother liquor. This pressure can be self-generated (i.e., corresponding to the vapor pressure of water at the reactor temperature), hydraulic, or may be caused by the addition of an inert gas such as nitrogen. ® The pressure is determined so that the resulting final product is in the desired crystalline phase. Thus the final product It is monoclinic. The hydrothermal treatment can be carried out in a &quot;batch&quot; reactor or in a continuous reactor. Compared with batch reactors, The residence time in the read reactor is generally short and the temperature is generally high. At the constant pressure and the strange temperature, the maintenance time of the extended stabilization phase causes the size of the initial particles to increase. If the maintenance time of the stabilization phase is constant, the temperature rises. The size of the initial particles is increased. m The reactor is then cooled to a temperature below the boiling temperature at 1 bar. The resulting sol is then separated. It contains a liquid portion and a 'thickness' with a high impurity content. Crystal cerium oxide particles. The inventors have discovered that, regardless of whether the particles are used as catalyst supports or as catalysts, such impurities are detrimental to the efficacy of the particles. By observation under a microscope, the primary particles are larger than their size. It also has a smooth shape at 5 〇 nm, thereby advantageously improving the selectivity of the catalytic reaction. The present inventors have illustrated this advantageous feature by the fact that the temperature of the reactor used for the hydrothermal method 136600.doc -45-200932669 is raised. The high rate is less than 25 每小时 per hour, and preferably less than 200 ° C per hour. Step C) According to the invention, in step C), the sol is from monoclinic oxygen Solid particles of the wrong phase purified subcomponents, such that the impurity content of the dry mass percentage less than 〇.7%, preferably less than 0.5%, preferably less than%, and more preferably less 〇.3. Billion to 1%. Known purification methods can be used in step C). Purification of the crude particles in the sol comprises the following steps (^ to - or φ multiple steps: Step C1 (which is an optional step) is to reduce the amount of liquid phase in the sol and/or purify the liquid phase in the sol. The expression &quot;reducing the amount of liquid phase in the sol&quot; means any operation which removes all 4 parts of the liquid phase in the sol. These methods are well known to those skilled in the art and may include: ... Resuspension or filtration without resuspending the sol; 纟帛 Resuspension of the sol or dialysis without prior sol; use in the case of resuspending the sol in advance or without resuspending the sol in advance Ion exchange resin purification; rinsing; - and a combination of these techniques. The expression of the liquid phase of the purified sol means any operation that reduces the ionic species in the liquid solution of the sol, such as those skilled in the art. Well known as 136600.doc • 46· 200932669 and may include dialysis, purification using ion exchange resins, or rinsing by dilution. Step C2 removes cationic impurities. The term &quot;cation &quot; means a crude particle containing elements other than carbon (C), hydrogen (H), oxygen (〇), and nitrogen (N), positively charged and contained in the liquid phase of the sol and/or fixed to the sol Molecular. 'The product obtained from the previous method step (B) or C1) is suspended in an aqueous solution having a pH of less than 7 • and more preferably less than 5. The suspension is controlled by the addition of organic and/or inorganic acids. The pH value is better than nitric acid, high gas acid and/or hydrochloric acid (HC1). It is better to use the suspension under the mixing degree of the Buddha point below 1 bar. Preferably, at room temperature, the duration is longer than 1 minute and preferably less than minutes. The suspension is then passed through any means known to those skilled in the art. If the desired purity of the cationic material is desired, then Step C2 can be repeated several times. The number of repetitions of step C2 can be determined by routine testing. Preferably, step C2 is not repeated, and only one step C2 is sufficient for zirconia. Step C3 is to remove anionic impurities. The term &quot;anionic impurities&quot; Means an element other than carbon (c), hydrogen (H), oxygen (〇) and nitrogen (N) a molecule which is negatively charged and contained in the liquid phase of the sol and which is fixed to the crude particles of the sol. The product obtained from the previous method step (B) or (:1 or (:2) is suspended in having greater than 11 The pH value of the aqueous solution. 136600.doc •47- 200932669 The value of the {11] of the suspension is controlled by the addition of an organic test and/or an inorganic base. Among these tests, ammonia water NH4〇H is preferably used. The suspension is maintained at a temperature below its boiling temperature at 1 bar (preferably at room temperature) for a period of preferably more than 10 minutes and preferably less than 30 minutes. This suspension is then passed through any means known to those skilled in the art. If the desired purity of the anionic material is required, step C3 can be repeated several times. The number of repetitions of step C3 can be determined by routine testing. Preferably, step C3 is not repeated, and only one step C3 is sufficient for cerium oxide. Steps C2 and C3 can be performed alternately or in reverse. These steps C2 and C3 are commonly referred to as acid-base neutralization steps. Typically, the acid and base neutralize the operation of removing the cationic impurities and/or removing the anionic impurities. In a preferred embodiment, the final operation for removing cationic impurities is controlled using a mixture of organic or organic acids. The final operation performed in an aqueous solution of 11 values and/or for the removal of anionic impurities is carried out in an aqueous solution using an organic base or an organic test mixture to control the pH. The use of organic or organic bases is believed to be necessary to achieve extremely high purity. Between steps C1, C2 and or C3, an optional rinsing step can be carried out in a solvent, preferably in water having a purity at least equal to the purity of the permeate water or in an alcohol having a purity greater than 98% by volume and preferably greater than 99% by volume. C4. This operation will be obtained from the product of the previous step in this solvent, preferably under stirring, at a temperature below 136600.doc -48. 200932669 at a temperature of 1 bar (preferably at room temperature). More than 1 minute and preferably less than 30 minutes duration. The suspension is then filtered by any means known to those skilled in the art, 0

After step C), the resulting purified product consists essentially of monoclinic zirconia particles. Preferably, the 'purification is sufficient to obtain, after step D), from 99.3% or more, preferably 99.5% or more, preferably 99.7% or more, and more preferably 99.9% or more, based on the mass percentage of the dry matter. 1%% of the remaining material is a powder composed of impurities). Step D) In step D), after purification, the liquid fraction is removed by drying. Thus, the purified particle powder of the present invention is obtained. Any method known to those skilled in the art can be used. The drying temperature is generally below 5 〇〇〇c and preferably below 2 。. The dry material is adjusted so that the purified particle powder has a residual moisture content of less than 1% by mass in this step (4). Step E) In this optional step, calcining the oxidized material is preferably carried out for at least i hours. The calcination temperature is preferably higher than 3 〇 (TC and preferably lower than 5 〇〇〇 c. This step can remove the residual moisture present in the powder towel obtained after the step D) and any organic matter remaining in the powder towel. Without changing the shape or nature of the particles or the proportion of exposed crystal faces. The aggregate of the primary particles of the obtained cerium oxide powder has a pore volume of generally between 0.1 cm 3 and 0.2 cm 3 per gram of the powder. In order to fragment the agglomerates of this powder, a depolymerization step f) can be carried out. 136600.doc • 49- 200932669 The maximum size of the primary particles is less than 250 nm, preferably less than 200 nm, preferably less than 150 nm, preferably less than 10 0 nm, preferably less than 90 nm and preferably less than 80 nm, and Greater than 10 nm, preferably greater than 20 nm. Advantageously, when the powder is used as a catalyst support, this feature allows for regular alignment of the catalyst grains and allows for uniform growth of the exposed crystal faces. • The impurity content of the powder of the present invention is preferably less than 0.7%, preferably less than 0.5%, preferably less than 0.3% and more preferably less than 0.1% by weight of the dry matter. Φ impurities are preferably as follows, dry matter The mass percentage is: -Si〇2 &lt; 0.1%, preferably Si〇2 &lt; 200 ppm, more preferably Si〇2 &lt; 100 ppm, and / or -A12〇3 &lt; 0.1%, preferably A12〇3 &lt; 200 ppm More preferably, A12〇3&lt;100 ppm, and/or -MgO&lt;0.1%, preferably MgO&lt;200 ppm, preferably MgCK100 ppm, more preferably MgO&lt;50 ppm, and/or -CaO&lt;0.1%, preferably CaO&lt; 200 ppm, more preferably CaO&lt;100 ppm, ® and/or -Na2〇&lt;〇. 1%, preferably Na2〇&lt;500 ppm, preferably Na2〇&lt;200 ppm, more preferably Na2〇&lt;l 〇〇ppm, and/or -cr&lt;0.10/〇, preferably cr&lt;500 ppm, preferably cr&lt;200 ppm, more preferably Cr&lt;100 ppm, and/or -Norco"%, preferably N〇3_&lt;500 Ppm, preferably N03-&lt;200 ppm, more preferably ·03·&lt;100 ppm, and/or -SO42-&lt;0.1%, preferably S〇42-&lt;500 ppm, preferably S042-&lt;200 136600 .doc -50- 200932669 ppm 'better s〇42-&lt;i〇〇ppm, and/or -Fe2O3&lt;0.1%' preferably Fe2〇3&lt;2〇〇ppm, preferably Fe2O3&lt;100 ppm' better Fe2〇3&lt;5〇ppm, and/or _Tl〇2&lt;01%, preferably Ti〇2&lt; 200 ppm, preferably TiO2 &lt; 100 ppm 'better Ti〇2 &lt; 5 〇 ppm. Each of the primary particles is composed of a crystal other than the impurities, and the crystal has a mass of 95% or more, preferably 97% or more, more preferably 99% or more, and more preferably

The body is 100% monoclinic. In addition to monoclinic zirconia, it is a stable square or cubic yttrium oxide. The powder has the following characteristics: - The specific surface area of the particles is greater than 1 〇 m 2 /g, preferably greater than 2 〇 m / g, preferably greater than 5 〇 m 2 /g and preferably greater than 7 〇 and / or less than calculated by the BET method. 100 m2 / g ; and / or the pore volume of the agglomerates of the primary particles of the powder is between 0.1 cm 3 and 0.2 cm 3 per gram of the powder; and / or - percentage points 5 〇 (D5.) corresponds to about 1 The median size of μΓΗ, and the percentage point is zero. , μιη, size measurement is performed by sedimentation particle size analysis and the percentage is mass percentage; and/or - the loss on ignition of the powder after calcination at mrc: &lt; 3% 丨 - about 1 g/cm3 density. Further, in the powder, the number of 95 〇 / 〇 is ^, and the amount of the initial particles has a form different from the spherical opening 5 or the truncated spherical shape. More ^ ^ ^ ^ Wen Shuo cut, the number of dry matter _, at least 90%, preferably at least tens of ' powder.. „ and better at least 99% and more The shape of the sheet and / or the rod of the general body and S, for the powder obtained directly after the step D) of 136600.doc 200932669, the percentages only relate to one of the two forms of the order of ''different powders can change the pellets And the respective percentages of the rods. The inventors have surprisingly discovered that the sheet-shaped and/or rod-shaped oxidized particles #露稀f crystal face family 0,1 take U,M), in addition, it has also been found that The granules are exposed to the crystal face family {11,1} and (1,〇〇}, and the metal grain growth of the cubic structure from the 8th row, the 9th row, and the 10th row. Other methods can also be used for preparation. A nano-powder with monoclinic crystal, single crystal structure and exposure selected from {1,0,0}, &quot;mountain (a) and," crystal plane family. Specific and ly, sol-gel method, metal Salt burning or metal oxidation, or high temperature calcination of the precursor of the product under consideration. Then according to the exposed crystal face or shape of the desired initial particles Adjusting the parameters of the methods. Similarly, the present invention specifically covers the initial particles of (Hf〇2) oxidized. Generally speaking, the present invention covers the initial particles composed of oxidation and oxidation, in addition to impurities, and the proportion of oxidation is given. Further, the invention may be between 0 and 1. In addition, the present invention covers a powder which can be obtained hydrothermally in addition to the oxidation anchor (Zr〇2) single crystal powder (especially oxidized (Μ-powder and/or oxidized crane (W03) The use of the powders is a monoclinic powder, a nano powder, and a single crystal powder. The morphology and crystal plane of the oxidized key primary particles and the oxidized crane primary particles are the same as those of the zirconia of the present invention. The primary particles of cerium oxide, the primary particles of cerium oxide and zirconium oxide, the primary particles of oxidized oxidized and oxidized may be prepared in a manner similar to the above-described synthetic method for oxidized erroneous particles. Furthermore, the inventors have/intended to Some dopants can also be modified to perform structurally sensitive reactions (eg, dehydration reactions, elimination reactions, amination reactions) using a 136600.doc •52·200932669 or basic catalyst to perform hydrocarbon conversion. The catalytic performance quality in the hydrogenation reaction or the alkylation reaction. Preferably, the dopant is selected from the group consisting of an oxyanion, an anion (halide ion) of the 17th lampin, and an element (alkali metal) More preferably, the oxyanion is selected from the group consisting of citrate, phosphate and sulfate, and the genus is selected from the group consisting of a gas ion cerium ion, and the genus is selected from the group consisting of sodium hydride and hydrazine. Therefore, it is a mixture of the powder of the present invention (the particles of which are associated with the binder) (hereinafter referred to as "particle mixture"). The dopant may be located on the surface of the particle and partially or partially covered. The particles in the particle mixture of the present invention do not necessarily all contain a dopant. Preferably, the amount of molybdenum of the dopant is determined to account for 40 / of the mass of the particle mixture. The following is preferably 20% or less, preferably 丨〇% or less, preferably 5% or less or even 3% or less. The dopant can be combined with the powder of the present invention by any method known to those skilled in the art, such as via an impregnation method. The present invention relates to a method for preparing a particle mixture of the present invention, wherein a dopant (especially a suspension of a dopant) is mixed with the powder of the present invention. The invention also relates to a porous body comprising the particles of the invention, and in particular to the following three embodiments: According to a first embodiment of the three embodiments, the invention relates to the treatment of the powder of the invention The obtained porous body was subjected to a consolidation heat treatment to obtain a porous body (1). The present invention is also directed to the crude body, which itself may be a porous body. Preferably, the porous body has a porosity of greater than 3% and/or less than 136,600.doc -53.200932669 90%. According to a second embodiment of the three embodiments, the invention relates to a porous body in which the surface of the invention is accessible or &quot;open&quot; It may relate to all accessible pores of the porous body (2) or only a single pore thereof in a surface layer of the porous body (for example, a surface layer extending in a depth range not less than 丨〇0/〇 of the thickness of the porous body) a single pore located at the core of the porous body (for example, at least 50% of the thickness of the porous body from the outer surface of the porous body). In the porous body, the proportion of the pores enthalpy carrying the particles of the present invention may be uniform, but may also vary with the distance from the outer surface of the porous body. Preferably, the material of the porous body is not obtained from the powder or mixture of particles of the present invention. More preferably, the porous body contains 5% by mass or more and preferably 80% by mass or more of alumina. Preferably, the porous body has a porosity of greater than 30% and/or less than 90%. According to a third embodiment of the three embodiments, the present invention relates to a porous body (3) composed of a material in which the particles of the present invention are intimately mixed with particles other than the present invention (e.g., alumina particles). More preferably, the porous body contains 5 Å by mass or more and preferably 80% by mass or more of alumina. Preferably, the porous body has a porosity of greater than 30% and/or less than 90%. To prepare the porous bodies (1) and (3) 'The present invention proposes a method for preparing a porous body' which comprises the following consecutive steps: (a) Preparation of a starting filler by the following steps: a powder or a present invention The powder mixture of the invention is on the one hand and the powder according to the invention on the one hand and one or more selected from the group consisting of organic and/or inorganic binders, organic and/or inorganic extrudates, organic and/or inorganic dispersants and mixtures thereof. Doc-54-200932669 The additive of the group consisting of the composition is dispersed in a liquid and mixed to obtain a paste; (b) the paste is shaped to constitute the crude body of the present invention; and (c) the crude body is subjected to Consolidation heat treatment to obtain a porous body; and (d) depositing a dopant on the outer surface of the porous body and/or on the surface of the porous body as needed; (e) depositing a catalyst on the porous body as needed On the outer surface and/or on the surface of the aperture.

In step (a), the liquid may in particular comprise an aqueous solution, and in particular comprises water. The binder may in particular promote extrusion and/or enhance the mechanical properties in the form of a crude body and after consolidation of the porous body and/or improve its structural properties (specific surface area, porosity). In the step (b), the crude body can be formed by extrusion, compression atomization, coalescence molding or condensation. The coarse body can be produced in particular by extrusion, in particular in the form of granules or "pellets". In the embodiment, the granules have a distance between 4 and 4.5 mm (for example 42 x straight and 3 and 10 mm) The length of the process. The method can thus be used to simultaneously prepare a plurality of crude bodies and thus can be used to prepare the porous body (1) or (7). In the step (4), by less than 6 〇 (rc, preferably less than 5 and less than 500 volts) , w 上 上 上 上 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The yin handyman does not set a group of cations and mixtures of elements in the first row. 136600.doc -55- 200932669 The dopant may especially be selected from the group consisting of citrate, phosphate, sulfate, gas ion, fluorine. Ions, sodium and potassium. In step (e), the catalyst may in particular be selected from the group consisting of: metals from the 8th, 9th and 10th rows of the periodic table and having a cubic structure, mixtures thereof, Oxide ore, transition metal oxides, oxides in the 14th and 15th elements, transition metals Carbide and Transition Metal Sulfide. For the preparation of the porous body (2), a conventional method of preparing a porous ceramic body can be used. The porous body can then be impregnated with the suspension of the powder of the present invention. The © suspension is thus permeable. The porous body and the accessible pores in the porous body. The particles of the present invention can thus be deposited on the outer surface of the porous body and/or on the surface of all accessible pores of the porous body. The particles of the present invention can advantageously be in the catalytic system. The use of a catalyst crystallite is known. Preferably, the support is impregnated with an aqueous solution or a non-aqueous solution containing a catalyst precursor. Next, the impregnated support undergoes a ripening step to allow impregnation The solution enters the pores of the support by capillary action. This step lasts for more than 5 hours. It is then impregnated by any drying means known to those skilled in the art (for example, baking under vacuum or other means). Carrier dry • # m degree - generally less than 5G () t ' adjust the drying time so that the dipped carrier has less than 丨 quality at the end of this step. 4 residual moisture Then, the planting experience after being immersed and dried and dried up is generally higher than 3 〇〇. 低于 低于 低于 低于 低于 500 500 』 』 』 』 选 选 选 选 选 选 选 选 选 选 选 选 选 选 选 选 选More than one hour of stable phase time. The gunping + environment step removes any binder contained in the carrier and is derived from the 136600.doc .56-200932669 &solution; preferably, the drying step and the calcining step Performing in a single operation. The impregnated support that is dried and optionally calcined is then subjected to an optional activation operation known to those skilled in the art. This step is under controlled atmosphere (which is adjusted for the selected catalyst) (eg, for Sulfide-based catalysts, in a sulfur-saturated mixture atmosphere, typically run at a temperature between 10 (TC and 50 (TC) for a period of more than one hour. After activation, the carrier can be referred to as &quot;catalytic system&quot;. This activation step can be performed directly in the catalytic reaction, as needed. Optional additional passivation steps known to those skilled in the art can be performed after activation, which is particularly advantageous for the transport of catalytic systems. In general, this step is carried out in an oxidizing medium at a temperature below T 1 (Tc, under a gas stream. The reactivation step must then be performed in the reactor. To avoid excessive growth of the grains, it is preferred to limit The amount of the catalyst deposited on the carrier particles. In particular, the excess of the catalyst causes a change in the nature and amount of the crystal face exposed by the crystal grains. Preferably, the catalyst accounts for less than 10% of the mass of the catalytic system, preferably 7 % or less and more preferably 5% or less. The content of 1% catalyst is generally suitable. - Preferably, the method is determined such that the size of the catalyst crystal grains is larger than 1.5 nm. In particular, the inventors have found that especially when When the catalyst is a metal having a cubic structure in the 8th, 9th, and 10th rows of the periodic table, and especially platinum, a size larger than 1.5 nm prevents the crystal grains from appearing spherical or exhibiting a truncated plane in contact with the carrier particles. Spherical. A specific method for preparing a catalytic system 136600.doc -57- 200932669 Preferably, for the preparation of the catalytic system of step iii), a preparation process comprising the following steps is carried out: I) preparation based on a catalyst or a solution of the catalyst precursor; II) impregnating the carrier powder with the solution prepared in step I); ΙΠ) aging to allow the impregnation solution to enter the pores of the carrier by capillary action; 'IV) will be impregnated The carrier is dried; V) calcining the dried support; O VI) activating the catalyst; VII) passivating the catalyst as needed; νιπ), if necessary, before being used for the catalytic reaction, preferably under the same conditions as in step VI) Under conditions, it is activated in the reactor. In the step I), in the case of platinum as a catalyst, a solution of a platinum precursor (e.g., tetraammineplatinum PtWhMNO3) 2 (e.g., Sigma_Aldrich) can be prepared. In step II), the impregnation can be carried out according to standard procedures in the event that the solution is not excessive.

In the step IV), drying is preferably carried out in an oven at U0 ° C for 12 hours so that the residual moisture of the carrier is less than 〗 〖% by mass.

Preferably, the calcination is preferably carried out in air and is preferably carried out in at least pJ, and preferably at a temperature between 3 Torr and 500 Torr. I36600.doc • 58 · 200932669. The rate of temperature increase is preferably less than 1 (rc/min and more preferably about 2 〇c/min. Preferably the 'satin burning system is carried out under a gas stream. In step vi) 'the catalyst is preferably by hydrogen (h2) The activation is reduced by reduction, preferably for at least 1 hour, preferably for about 6 hours, and more preferably at 1 Torr.进行 With a temperature between 5 ° ° C. The rate of temperature increase is preferably less than • 1 〇 ° C/min and more preferably about St/min. Activation is preferably carried out under a stream of hydrogen. The activation temperature is preferably between 3 Torr. 〇 with 5 〇〇. Between 〇. In step VH), under an inert gas stream containing several ppm of oxygen, preferably under nitrogen containing several ppm of oxygen, preferably at a temperature below 100 ° C, more preferably at room temperature and more The catalyst was passivated in about 1 hour. After step VI) and / or VIII), the catalytic system of the invention is obtained. This method of preparation is not the only method that can be used to prepare the catalytic system of the present invention. In particular, it is very suitable to deposit a catalyst by chemical vapor deposition (CVD). The catalyst may also be deposited by selective impregnation so that the catalyst is only deposited on one or more of the specific exposed crystal faces of the support particles or on the exposed crystal faces of the particular crystal face of the support particles. All known selective impregnation methods are conceivable, and the parameters of the selective impregnation method depend on the nature of the support. In general, the selective impregnation system &quot;shadows&quot; certain crystal faces of the carrier particles so that the catalyst cannot access the crystal faces during its deposition, thus allowing only the crystal faces of the carrier particles to allow grain growth to remain Upon exposure, the grain exposure is beneficial to the crystal face or crystal face family of the reaction to be catalyzed. Thereby the efficiency of the catalyst is advantageously optimized. When the amount of the catalyst is the same, since the percentage of the surface area of the catalyst which exposes the crystal face is large, the performance of the 136600.doc -59-200932669 system is improved. Conversely, when the catalytic performance is the same, the catalyst consumption is reduced. The catalyst deposited on the surface of the support may be a metal, preferably selected from the group consisting of metals having a cubic structure and mixtures thereof in rows 8, 9 and 10 of the Periodic Table of Elements. The metal is more platinum than platinum. The catalyst may also be an oxide, preferably selected from the group consisting of ruthenium oxide and/or transition metal oxides (e.g., V2〇5 or 〇2〇3) and/or oxides of the 14th and 15th elements, preferably tin ( An oxide of Sn), lead (Pb) and/or bismuth (Bi). • The catalyst may also be a carbide, preferably selected from transition metal carbides such as molybdenum carbide and/or carbonized cranes. The catalyst may also be a sulfide&apos; preferably selected from the group consisting of transition metal sulfides, preferably sulfonate and tungsten sulfide, optionally doped with cobalt or nickel (e.g., C〇m〇s). Preferably, the catalyst is selected such that at least 8%, preferably at least 90%, more preferably at least 95%, and more preferably substantially all of the catalyst grains in the catalytic system are not spherical or in contact with the support. The shape of the spherical shape of the plane truncation. Thereby advantageously improving the performance of the catalytic system. The size of the catalyst grains is preferably between 1.5 nm and 10 nm and preferably between 3 nm and 10 nm. Preferably, the catalyst is generally present in an amount of less than 1% by mass, preferably less than 7%, and more preferably less than 5% by mass of the catalyst system. Preferably, the catalyst is a metal selected from the group consisting of Groups 8, 8 and 10 of the Periodic Table of the Elements and is selected such that at least 8%, preferably at least 90% and more preferably at least 95% More preferably, substantially all of the catalyst grains have a truncated cubic octahedron or dome shape. 136600.doc -60 - 200932669 In the case of a metal with a cubic structure on the 8th, 9th or ι line, the size of the grain is preferably between 15 nm and 10 nm and preferably between 3 nm. Between 10 nm. It is therefore advantageous to obtain predominantly grains of the metal, in particular platinum, which are predominantly in the shape of one or both of a truncated cubic octahedron and a dome. • In the case of a metal having a cubic structure on the 8th, 9th, or 10th line, the truncated cubic octahedral grain is formed on the exposed crystal faces of the carrier particles {1, 1, 0} and { On 1,1,1}, the 筏-shaped crystallites are formed on the exposed crystal faces of the particles {1'0,0丨, especially when the particles have a monoclinic crystal structure. Characterization Methods The following methods can be used to characterize the invention and the tests below, which are provided by way of non-limiting illustration. Morphology and exposed crystal face After the sample is dispersed by ultrasonic processing, the morphology of the crystal can be determined by observation performed by high-resolution transmission electron microscopy (HRTEM). The morphology of the initial particles and grains is determined by the following methods, and the exposed crystal faces are measured and the ratio of the crystal faces is quantified: After the sample to be characterized is dispersed by ultrasonic processing, the initial particles or crystals are obtained by using a transmission electron microscope. High resolution image of the grain. A large number of images are required, generally 50 or more. These images are used to measure the crystal plane of each of the original particles or grains observed in the observation plane. Since the orientation of each of the primary particles or each of the grains is irregular #, it can be assumed that all of the observed initial particles or grains have the same morphology and the same exposed surface properties for the determination of each primary particle or crystal. The orientation of the particles relative to the plane of observation. Under the assumption made by 136600.doc • 61 - 200932669, the image can then be compared to different views taken in different directions along the same initial particle or grain. Therefore, the morphology of the observed primary particles or grains can then be determined. Since each image is viewed as being in the exact direction, after determining the morphology of the grains or particles, it is then possible to select at least one image that is perpendicular to the exposed surface of the viewing plane. This exposed surface is in the form of an edge in the image. The corresponding exposed facets can then be determined. This procedure is used for all exposed faces of the grains or particles to determine all of their exposed faces. The ratio of the exposed crystal faces of the crystal face family {h, k, i} is equal to the total number of exposed surfaces of the crystal face family {h, k, 1} divided by the total number of exposed surfaces. Finally, after measuring the features, verifying that the different images do correspond to different views of the same elementary particle or grain produced along the specified orientation by measuring the two-dimensional projection to verify that all of the observed initial particles or grains do have the same The assumption of form. Performing the same method to confirm the exposure of the crystal face by verifying that the properties and proportions of the exposed crystal faces of the original particles or grains having the specified morphology observed in different directions are consistent with those of the different images acquired in the same direction. The assumptions made by the nature and proportions. Chemical analysis After the metal content was determined by ICP (induced coupling plasma method), thermal hydrolysis was carried out, and the gas ion chromatography was performed by ion chromatography. The carbon and crushed (converted to sulfate S042·) content was measured using a c, s_MAT 5500 carbon sulfur analyzer (sold by the company strShleim Inst.). Measurement of Specific Surface Area and Porosity Accumulation Structural properties were determined by A physical adsorption/desorption at -196 °C. 136600.doc -62· 200932669 A sample of the calcined carrier was desorbed under vacuum for 2 hours at 400 ° C, and a sample of the uncalcined carrier was desorbed at 10 ° C for 10 hours. The specific surface area is calculated by a BET (Brunauer Emmet Teller) method as described in Journal of American Chemical Society 60 (Ί93), 3091 I, page 31. The pore volume VP was determined by the BJH method applied to the isotherm desorption branch [described in E.P. - Barrett, L.G. Joyner, P.H. Halenda, J. Am. Chem. Soc., 73 (1951) 373]. #Measure the uncomplexed density The undensified density was determined by the following method: A powder having a volume between 240 and 250 cm3 was poured into a 250 cm3 cylinder having a mass Mo (in g) using a funnel. The volume Vo (in cm3) of the powder poured into the cylinder is then read and the cylinder thus filled is weighed to measure the mass M1 (in g). The uncomplexed density (expressed in g/cm3) was determined according to the following relationship: Undensed density = (Ml-Mo)/Vo Determination of crystal structure (DRX analysis) ® ffiBruker D5005 diffractometer, obtained with copper Κ alpha radiation (1.54060 A) Powder X-ray diffraction images. The intensity data of the interval of 3-80° is recorded in increments of 0.02° and increments of 1 s per time. The crystal phase is identified by comparison with a standard JCPDS file. The crystal structure can be confirmed by other well-known methods such as Raman spectroscopy, or by transmission electron microscopy for local confirmation of the initial particles. The cells belonging to the 8th, 9th, and 10th rows have a cubic shape. The Group of Metals of Structures 136600.doc -63 - 200932669 Measurement of the Dispersion of Catalysts The degree of dispersion of such catalysts was determined by hydrogen chemisorption and analyzed by chemisorption using an ASAP 2010 machine (sold by Micromeritics). The amount of chemisorbed hydrogen (HCirr) is determined by extrapolation of the linear branch of the entire and reversible adsorption isotherm at zero pressure, such as [G. Bergeret, P. Gallezot, Handbook of Heterogeneous Catalysis, G. Ertl, H. Knijzinger, J. Weitka^mp, Wiley-VCH, Weinheim, Vol. 2 (1997)].

It is assumed that hydrogen dissociation is adsorbed on a catalyst belonging to the group of metals having a cubic structure in the eighth row, the ninth row, and the first one, and the degree of dispersion is determined by the following relationship: D = l〇〇x2x^in, o, For chemical adsorption, the molar number and ~t are the total number of atoms of the catalyst belonging to the group of metal having a cubic structure in the 8th row, the 9th row, and the 10th row. Determination of the size of the catalyst grains The ruler of the catalyst grains is the average surface size of the catalyst grains. It can be measured by observations performed by electron microscopy (especially for catalysts belonging to the group of carbides, sulfides or oxides) and/or by measuring the dispersion of the catalyst on the surface of the support (4) (for example, for ^

Row, line 9, and method of catalyst for a group of metals having a cubic structure). J The average surface size was determined by electron microscopy as follows: The sample of the gentleman to be observed was dispersed by Super B treatment in ethanol by I36600.doc -64-200932669. The suspension is then placed on a carbon coated copper grid. Get a large number of still-resolution images of the grain, generally more than 50. Through these images, if the number of grains having the largest size 怂 in the 1st observation plane, the flat 矣 and the J 岣 surface size is determined by the following formula:

Assuming that the grains are in the form of a cube of five, T and D, the average surface size of the catalyst is measured by the following formula:

PCaaCa^DD is the dispersion of catalyst Ca on the surface of the carrier (expressed in %), which is the density of the catalyst (expressed in g/m3), aca is the area occupied by the atoms of the catalyst &amp;amplitude (expressed in m2), MCa is the catalyst . The molar mass (expressed in g/m )) and Na is the Avogadro number (AV0gadro, s number). The aca value can be found, for example, in [G. Bergeret, p. Gallez〇t, Dan Milk Office, σ/Heterogeneous Catalysis, G. Ertl, H. Knozinger, J. Weitkamp, ed. Wiley-VCH, Weinheim, Vol. 2 (1997). )]in. The inventors verified the average surface size of the crystal sample of the metal having the cubic structure in the eighth row, the ninth row or the i-th row for the above two methods to verify the same as described in the present specification. The cube shape assumption is true in the background of the form (ie, the cubic shape of the night shape and the truncated cube). Measuring the intrinsic rate (conversion rate) of each surface catalyst atom for a given catalytic reaction using a given reagent r in the case of a catalytic system (by 136600.doc •65- 200932669 moUw.s'g" We say that writing vi) is determined by the following relationship:

Kf-1QQ^

D _ V catalysis "(moUw.s'g "agent-1") indicates the specific rate:

_ 100F Catalyzed % 傕化侧 where: - indicates the mass percentage of the catalyst based on the catalytic system; and ❹

-V represents the reaction rate calculated by the following formula (expressed as m〇u #1 s-〗g·丨): γ = ^±ί m F〇 is the molar rate of the reagent entering the reactor (m〇lj&lt; w Si) ; τ is the degree of conversion 'less than 20% in the case of the catalytic reaction used in the example; and m is the mass (g) of the catalytic system; and D represents the degree of dispersion of the catalyst as determined by hydrogen chemisorption ( % indicates). The molar rate F 〇 of the reagent entering the reactor is calculated according to the following equation: f = - ° 22400X &amp; G always indicates the total flow rate of the reagent under standard temperature and pressure conditions (expressed in cm3.s 1); pr indicates reagent The partial pressure (expressed in pa) and Pjs represents the total pressure (in Pa). In the context of evaluating the catalytic properties of different powders for the selective hydrogenation of crotonaldehyde (2-butenal) to crotyl alcohol CrOH (executed as described below), for a given degree of conversion for 136600.doc-66-200932669, The selectivity of crotonol CrOH is determined by the following expression: [CrOH\

Cr〇H ~ [cr〇]0 - [cro], where [cro]〇 is the concentration of crotonaldehyde entering the reactor; leaving the crotonaldehyde concentration of the reactor and [CrOH]t is the croton leaving the reactor at time t Alcohol concentration. Measuring the porosity of a porous body The porosity of a porous body is defined as the following ratio:

Porosity = 100 X (absolute density) - (apparent density) Absolute density The absolute density (expressed in g/cm3) was measured using an ACCUPYC 1330 helium pycnometer sold by Micromeritics. Apparent density (expressed in g/cm3) was measured using a GEOPIC Model 1360 machine sold by Micromeritics. Test example 1

In a 100 ml Teflon® PTFE beaker, 7.4 g of zirconia oxyhydroxide containing 50% by weight of cerium oxide was suspended in 70 ml of deionized water with stirring. This mother liquor was then introduced into a 100 ml Teflon® PTFE high pressure bottle, which was then sealed in a stainless steel high pressure dad and placed in an oven set at 200 °C. It takes 1 hour to reach a nominal temperature of 200 °C in a high pressure bottle. The mother liquor was maintained at 200 ° C for 100 hours and then cooled to room temperature. At this time, the high pressure bottle was removed from the stainless steel autoclave. This procedure produces a sol consisting of a solid phase and a liquid supernatant. A portion of the liquid in the sol is removed by siphoning. 136600.doc -67· 200932669 On the Buchner type filter, the remainder of the sol was filtered and then washed with 200 ml of deionized water. The resulting filter cake was then dried in an oven for at least an hour and then comminuted in a spider. The crude solid particles were satin-fired in air at 55 (TC for 2 hours (2 t:/min temperature increase rate; 100 mL/min air flow rate, that is, 3 〇〇hi hourly space velocity HSV) The main physicochemical properties of the powder thus obtained are listed in the table. This powder has a specific surface area of 80 mVg after calcination at 55 (TC) and has a &quot;% or more as shown in the diffraction diagram of the ®® line The slant crystal phase. The initial particles are quasi-spherical. This powder exposes 30% of the crystal face family {1 mountain 1} crystal face, 1〇% crystal face family {1,1,〇} crystal face, 10% crystal The crystal face of the face family {1〇〇} and the other facet of the crystal face family of 5 〇% with a Miller index greater than 1. Example 2 (Piece {1, 〇, 〇〇 in 70 ml of deionized water, And then, under stirring, 74 g of the base oxidized error containing the weight of the curse/〇 oxidization is suspended therein. The concentration of the reagent 〇Η· is 0.5 mol/1 and then the mother liquor is introduced into the 〇〇(4)(10)8pTFE high pressure. In the bottle, the high-dust bottle is then sealed in the non-mineral steel dad and placed in an oven set at 200 C. The high-pressure bottle reaches 2 〇〇. • 1 hour. The mother liquor is maintained at 20 (rc for 100 hours and then cooled to room temperature. At this point, the high pressure bottle is removed from the stainless steel autoclave. This procedure produces a sol consisting of a solid phase and a liquid supernatant. Remove a portion of the liquid by siphoning. Then resuspend the remainder of the kick and add the N hydrochloric acid to I36600.doc •68· 200932669 to adjust the pH to 8. Then on the Buchner filter, suspend The liquid was transferred and then washed with 200 ml of deionized water. The filter cake thus obtained was then resuspended in 500 ml of deionized water and the pH was adjusted to 5 by the addition of 0.1 N hydrochloric acid. Then in the Buchner type filter The suspension was filtered and then washed with 200 ml of deionized water. The resulting filter cake was resuspended in 5 〇〇ml of deionized water and the pH was adjusted to 11 by the addition of 1 N aqueous ammonia (NHUOH). On a Buchner type filter, the suspension was filtered and then washed twice with 2 mL of deionized water. # The resulting filter cake was then dried in an oven at liot for at least 12 hours, and then in a Makan Institute. Crushing. The resulting powder is in the air At 4 〇〇, the temperature rise rate of the satin burned for 2 hours pt/min; the air flow rate of 1 〇〇mi/min, that is, the space velocity fjSV per hour of 300 hi). The main physicochemical properties are listed in Table 1. The obtained powder had a monoclinic phase of 99% or more as shown in the χ-ray diffraction pattern. The powder morphology is shown in Table 2. The initial particles exhibited a crystal face family exposed to 5% by weight. The granule form of the crystal face of {1'〇'〇}. The other crystal faces that are exposed by the particles are: a crystal face of a crystal face family of 15%, a crystal face of a crystal face group of 1%, and a crystal face of a crystal face group of {1, 1, 1}, and A ratio of 5% of the crystal faces of the crystal face family having a Miller index greater than one. Example 3 (Bars {1,1,〇}) In a 100 ml Teflon® PTFE beaker, 14·2 g of sodium sulphate Na2S〇4 and 4 g of sodium hydroxide NaOH were sequentially dissolved in 70 ml of deionized water, and then Under stirring, 7.4 g of cerium oxyhydroxide containing 50% by weight of zirconia was suspended therein. The concentration of the modifier SO42· is 〇.5 mol/1 and the concentration of hydroxide (〇Η·) is 136600.doc •69· 200932669 degrees is 0.5 mol/l. This mother liquor was then introduced into a 1 〇〇 ml Teflon® PTFE vial. The high pressure crucible was then sealed in a non-mineral steel high pressure crucible and placed in an oven set at 200 °C. It takes 1 hour to reach a nominal temperature of 2 °C in a high pressure bottle. The mother liquor is at 200. (: Maintain for 100 hours and then cool to room temperature. At this time, remove the high pressure bottle from the stainless steel high pressure dad. This procedure produces a sol consisting of solid phase and liquid supernatant. Part of the liquid is removed by siphoning On a Buchner-type filter, the remainder of the sol was filtered and then washed twice with 200 ml of deionized water. The filter cake thus obtained was resuspended in 500 ml of deionized water and added with 〇1. n Hydrochloric acid to adjust the pH to 5. The suspension was then filtered on a Buchner filter followed by 200 ml of deionized water. The resulting filter cake was resuspended in 5 Torr (7) deionized water with Add 丨]^ ammonia to adjust the pH to 11 〇 then filter the suspension on a Buchner filter and wash the squid twice with 2 〇〇ml of deionized water. The resulting filter cake is then ovend at n 〇° Dry at c for at least 12 hours, then pulverize in an agate mortar. The resulting powder is satined in air at 4 〇 (rc for 2 hours) (2 °C/min temperature increase rate; 1 〇〇 ml/ Min air flow rate, that is, 300 1Γ1 per hour Speed HSV) The main physicochemical properties of the powder thus obtained are listed in the table. The obtained powder has a monoclinic phase of 99% or more as shown in its X-ray diffraction pattern. The powder form is listed in Table 2. Initial The particles are in the form of rods exposing the crystal faces of the crystal face family {1,1,〇} of 75%. The other crystal faces exposed by the particles are: a family of crystal faces {1,0,0} with a ratio of 5%. The facet of the crystal face is 15% of the crystal face 136600.doc -70-200932669 family {1,1,1} crystal face, and the ratio of 5% of the facet of the crystal face family with a Miller index greater than 1 Example 4 (Bars {1,1,0}) In a 100 ml Teflon® PTFE beaker, 5 g of sodium sulphate Na2S〇4 and 4 g of sodium hydroxide NaOH were sequentially dissolved in 70 ml of deionized water, and then Distracting 'mixing' suspended 7·4 g of zirconium oxyhydroxide containing 50% by weight of zirconia. The concentration of the modifier SCU2· was 0.25 mol/1 and the concentration of hydroxide (〇η·) was 0.5 mol. /1. Then introduce this mother liquor! 〇〇ml Tefi〇n® PTFE high pressure • In the bottle' Then seal the high pressure bottle in the unrecorded high pressure dad and place it in an oven set at 200 ° C. Up to 2 中 (1 hour for TC nominal temperature. Keep the mother liquor at 20 (TC for 1 hr and then cool to room temperature. At this point ' remove the autoclave from the stainless steel autoclave. This procedure produces A sol consisting of a solid phase and a liquid supernatant. A portion of the liquid was removed by siphoning. On a Buchner type filter, the remainder of the sol was filtered and then washed twice with 200 ml of deionized water. The filter cake thus obtained was then resuspended in 500 deionized water and adjusted to a value of 5 by the addition of 〇1 N hydrochloric acid. The suspension was then filtered on a Buchner filter and the strips were washed with 200 ml of deionized water. The obtained filter cake was resuspended in μ deionized water and added by adding 1 hydrazine aqueous solution. Only adjust to 丨〗. Then at

On a Buchner type substrate, the suspension was filtered and then washed twice with 2 Torr of deionized water. The resulting cake was dried in an oven at a crucible for at least 12 hours and then comminuted in an agate mortar. The temperature of the obtained powder was calcined in air at 136600.doc -71 - 200932669 for 2 hours pt/min; the air flow rate of 1 〇〇ml/min, that is, the hourly space velocity Hsv of 300 1Γ1) . The main physicochemical properties of the powder thus obtained are listed in the Table. The obtained powder had a monoclinic phase of 99% or more as shown in its X-ray diffraction pattern. The powder morphology is shown in Table 2, "The initial particles exhibit a rod form of the crystal face of the crystal face family {1, 1, 0} which is exposed to 6 %. The other crystal faces exposed by the particles are: a crystal face of the crystal face group {1, 〇, 〇} with a ratio of 25%, and a crystal face of the crystal face group {1, 1, 1} with a ratio of 10%. And a ratio of 5% of the crystal faces of the family of crystal faces having a Miller index greater than i. Example 5 (Bars {1,1,1}) In a 100 ml Teflon® PTFE beaker, 7.4 g of a basal oxidative solution containing 50 wt/〇 of an oxidized oxide was suspended in a 7 〇mi 5 n hydrochloric acid solution. The concentration of the modifier C1 is 1 m〇i/i. This mother liquor was then introduced into a 1 〇〇 ml Teflon® PTFE high pressure bottle, which was then sealed in stainless steel and placed at 200. (3; I: in the common box. It takes 1 hour to reach the nominal temperature in the high pressure bottle. Keep the mother liquid at 20 °C for 1 且h and @ then cool to room temperature. At this time 'high pressure 槪 from stainless steel Removed from high pressure dad. This procedure produces a sol consisting of a solid phase and a liquid supernatant. A portion of the liquid is removed by siphoning. The pH of the sol is then adjusted to 8^ by adding 1 water.

On a Buchner type filter, the suspension was filtered and then washed twice with 2 Torr of deionized water. The resulting filter cake was resuspended in 500 ml of deionized water and the pH was adjusted to hydrazine by the addition of 1 N aqueous ammonia. The suspension was then filtered on a Buchner type filter and then washed with 200 mi of deionized water for 136600.doc -72 - 200932669 times. The resulting filter cake was then dried in an oven at 110 t for at least 12 hours and then comminuted in an agate mortar. The resulting powder was at 4 Torr in air. 〇I calcination for 2 hours (2t/min temperature increase rate; 100 ml/min air &quot;IL dynamic rate, that is, 3 空间 hourly space velocity. The main physical chemistry of the powder thus obtained The characteristics are listed in the table. The results are as shown in the X-ray diffraction diagram with a monoclinic phase above 99°/. The powder morphology is listed in Table 2. The initial particles exhibit a crystal face family exposed to 65%. The rod form of the crystal plane of M, U. The other crystal planes exposed by the particles are the ratio of the crystal face of the crystal face, 〗, 〇}, and the ratio is 2〇0/. The crystal face of the crystal face family {1'〇,〇}, and the crystal face of the crystal face family with a ratio of 5% and a Miller index larger than 丨. Example 6 (舆 Example 3 is a bar with higher impurity content) Granules {11, 〇}) In a 100 ml Teflon® PTFE beaker, 14.2 g of sodium sulphate Na2S04 and 4 g of sodium hydroxide NaOH were sequentially dissolved in 70 ml of deionized water, and then 7.4 g of 50 weight was added with stirring. The cerium hydroxide zirconia is suspended therein. The concentration of the modifier SO42- is 0.5 mol/Ι and the concentration of hydroxide (〇Η·) is 〇·5 mol/丨. This mother liquor was introduced into a 100 ml Teflon® PTFE high pressure bottle. The pressure vessel was then sealed in a stainless steel autoclave and placed in an oven set at 200 ° C. The nominal temperature of 2 〇〇〇c was required in the high pressure bottle. 1 hour. The mother liquor was maintained at 2 〇〇 for 1 且 and then cooled to room temperature. At this time, the high pressure bottle was removed from the stainless steel high pressure crucible. This procedure produced a solid phase and liquid supernatant. Sol. Remove a portion of the liquid by siphoning 0 136600.doc -73· 200932669 The remainder of the sol is passed through a Buchner-type crucible, and the thus obtained cake is resuspended in 500 ml of deionized water with 〇1 N hydrochloric acid was added to adjust the pH to 5. The suspension was then filtered through a Buchner-type transition vessel and then washed on a Buchner-type filter with 2 liters of deionized water, followed by a Buchner-type filter. The suspension was passed through and • washed twice with 200 ml of deionized water. • These operations reduced the impurity content to less than 〇·7% to form Example 6 in accordance with the present invention. Evaluate impurities as described below The effect was to maintain the impurity content at a level higher than the impurity content of Examples 1 to 5. The resulting filter cake was then dried in an oven at 11 (TC for at least 12 hours, and then pulverized in an agate mortar. Simmer in air for 4 hours (2 °C / min temperature increase rate; 1 〇〇 ml / min air flow rate, that is, 300 h · 1 hourly space velocity HSV) . The main physicochemical properties of the powder thus obtained are listed in the Table. The content of anionic impurities (such as Cr&amp;S〇42_) is higher than that of the same impurities experienced in Example 3 which has undergone sufficient washing: step ® 豸. The obtained powder had a monoclinic phase of 99% or more. The powder morphology is listed in Table 2. The primary particles exhibited a rod form that exposed the crystal face of the crystal face family {1, 1, 0} of 75%. The other crystal faces exposed by the particles are: a crystal face of a crystal face group {1, 〇, 〇} with a ratio of 5%, a crystal face of a crystal face family of 15%, and a crystal face of {1, 1, 1}, and A ratio of 5% of the crystal faces of the crystal face family having a Miller index greater than 丨. Example 7 (Bars that have not undergone a rigorous purification step in a 100 ml Teflon® PTFE beaker, 14.2 g of sodium sulphate Na2S〇4 136600.doc -74- 200932669 and 4 g of sodium hydroxide NaOH are sequentially dissolved in 70 ml of deionized water And then, under the mixing, '7.4 g of hydroxy group containing 50% by weight of cerium oxide is oxidized and suspended. The concentration of the modifying agent SCU2· is 〇.5 mol/1 and the concentration of hydroxide (〇H_) is 0.5 mol/1. This mother liquor was then introduced into a 1 〇〇ml Teflon® PTFE high pressure bottle'. The high pressure bottle was then sealed in a non-mineral steel high pressure crucible and placed in an oven set at 200 ° C. Up to 20 (the nominal temperature of TC takes 1 hour. The mother liquor is maintained at 20 (TC for 100 hours and then cooled to room temperature. At this point, the high pressure bottle is removed from the stainless steel autoclave. This procedure produces Φ by solid Phase and liquid sol consisting of a sol. Part of the liquid is removed by siphoning. The remainder of the sol is filtered through a Buchner type filter. The filter cake thus obtained is resuspended in 5 〇〇mi deionized water.

The suspension was filtered through a Buchner type filter and then washed on 200 liters of deionized water on a Buchner type filter. On a Buchner type filter, the suspension was filtered and then washed twice with 200 ml of deionized water. This filtration washing operation failed to achieve the high purity Φ (&lt;0.7〇/〇) of the powder of the present invention. The resulting filter cake was then dried in an oven at 11 Torr for at least 2 hours, and then comminuted in a mortar. The resulting powder was at 40 Torr in air. The crucible was calcined for 2 hours (temperature increase rate of 2 ° C / min; air flow rate of 10 〇 ml / min, that is, hourly space velocity HSV of 300 h · 1). The main physicochemical properties of the powder thus obtained are shown in Table 1. The content of ionic impurities such as Na+ (expressed as Na2〇 form) and s〇42-) is higher than the content of such identical impurities as claimed in Example 3. The obtained powder had a monoclinic 136600.doc -75·200932669 crystal phase of 99% or more. The powder morphology is listed in Table 2. The primary particles exhibited a rod form that exposed the crystal face of the crystal family {1, 1, 0} of 75%. The other crystal faces exposed by the particles are: a crystal face of a crystal face group of {1, 0, 0} in a ratio of 5%, a crystal face of a crystal face group having a ratio of 15%, and a ratio of 5 °/. A family of crystal faces having a Miller index greater than one. Table 1 Example Na20 (ppm) Si02 (ppm) Fe2〇3 (ppm) CaO (ppm) Al2〇3 (ppm) Ti02 (PPm) MgO (ppm) N〇3· (ppm) cr (ppm) S〇42' (ppm) specific surface area (m2/g) content of monoclinic phase (% by mass) 1 &lt;100 &lt;100 &lt;50 &lt;50 &lt;50 &lt;50 &lt;50 &lt;50 &lt;100 &lt;100 &lt; 100 80 &gt;99 2 &lt;100 &lt;100 &lt;50 &lt;50 &lt;50 &lt;50 &lt;50 &lt;100 &lt;100 &lt;100 50 &gt;99 3 &lt;100 &lt;100 &lt;50 &lt;50 &lt;50 &lt;50 &lt;50 &lt;100 &lt;100 &lt;100 65 &gt;99 4 &lt;100 &lt;100 &lt;50 &lt;50 &lt;50 &lt;50 &lt;50 &lt;50 &lt;100 &lt;100 &lt;100 60 &gt;99 5 &lt;100 &lt;100 &lt;50 &lt;50 &lt;50 &lt;50 &lt;50 &lt;100 &lt;100 &lt;100 100 &gt;99 6 &lt;100 &lt;;100&lt;50&lt;50&lt;50&lt;50&lt;50&lt;100 500 2000 65 &gt;99 7 5000 &lt;100 &lt;50 &lt;50 &lt;50 &lt;50 &lt;50 &lt;100 &lt;;100 2500 65 &gt;99 Example 1 shows that when the mother liquor does not contain an agent selected from the group consisting of oxyanions, π anions, hydroxides H_ and mixtures thereof, hydrothermal method can achieve less than 0.7% The impurity content does not require sufficient washing. This result can be illustrated by not adding a modifier. Under a single wash, an impurity content of less than 0.7% cannot be achieved even with the use of an extremely pure oxide base component. However, the invention does not relate to products obtained from such mother liquors. Table 2 Example morphology Maximum size of initial particles (nm) Exposure crystal family property 5 f and ratio G Good surface %) 11,1,1} 0,1,0} {1,0,0} Other 1 quasi-spherical 15 30 10 10 50 2 pellets 80 10 35 50 5 3 pellets 50 15 75 5 5 4 pellets 60 10 60 25 5 • 76· 136600.doc 200932669 5 pellets 15 65 10 20 5 6 pellets 50 15 75 5 5 7 Bars 50 15 75 5 5 Preparation of catalytic system: The powders of Examples 1, 2, 3, 5 and 6 were used to prepare a catalytic system using platinum as a catalyst and having a mass content of about 1%. It is prepared by impregnating the powder of each example with a solution of tetraamine nitrate starting from Pt(NH3)4(N03)2 (obtained from Sigma-Aldrich) under the condition that the solution is not excessively simple. Those skilled in the art are familiar with this technology. After the powder φ was immersed, it was aged at room temperature for 8 hours to allow the solution to enter the pores via capillary action. The impregnated various powders were dried in an oven at 110 ° C for a stable period of 12 hours. The dried and impregnated powders were calcined in air at a temperature of 400 ° C for 2 hours (2 〇 c / min temperature increase rate; 1 〇 0 mL / min air flow rate, ie 3 〇每小时h·1 hourly space velocity fjSV). The catalyst was then taken at &amp; At the activation temperature of hydrazine, the temperature increase rate of 2t&gt;c/min is activated by the reduction reaction; the flow rate of Hz in the reactor used is 1 〇〇mL/min, that is, the hourly space of ❿300 P Speed HSV). The thus activated catalyst was then passivated for a few hours at room temperature under N2 (containing several ppmi〇2). The size of the grains is greater than 1.5 run and less than 1 〇 nm. O-benzamide (1,2-monodecylbenzene) is catalyzed by a chlorination reaction in an open reactor with a Pyrex fixed bed (operated at A with a low conversion rate). The test was carried out according to the following procedure: 汕mg catalytic system (in the present case, oxidized powder coated with examples 1, 2, 3, 5 and 6) and 5 石英 quartz powder (8〇-125 _) In the reactor and at 300. (: 136600.doc •77- 200932669 (temperature increase rate of 4 °C/min), activated under H2 (flow rate of 27 cm3/min, ie hourly space velocity of 80 h_1). The hydrogen/o-diphenylbenzene reaction mixture was introduced into the reactor at 200 ° C. The partial pressure of o-xylene was 4 kPa (condenser temperature of 50 ° C). After 2 hours, the activity of the catalytic system was stable. The reaction temperature was set at 100 ° C. - The amount of the catalytic system measured was measured 200 minutes after the introduction of the reagent. The results are shown in Table 3 below: φ Table 3 Structural insensitivity reaction: hydrogenation of o-diphenylbenzene Example (Catalytic System) Powder size of the catalyst used as a catalyst carrier (nm) Vi(mol»dimethyl _s^.g surface platinum 8 Example 1 1.7 2.0x10'7 9 Example 2 3.8 1·8χ10·7 10 Example 3 1.5 2.1χ10·7 11 Example 5 2.1 1.7x10'7 These results show that the catalytic performance is not significantly improved by the morphology of the carrier particles. Next, the selective hydrogenation of crotonaldehyde (2-butenal) to Croton Catalytic properties of the reaction of alcohol CrOH. Study of crotonaldehyde in fixed bed open micro In a type reactor, a gas phase hydrogenation reaction at 100 ° C under atmospheric pressure, hydrogen gas is bubbled through a liquid crotonaldehyde contained in a saturator at room temperature, and then the reaction mixture is maintained in a constant temperature maintenance bath. A condenser at 0 ° C to set the partial pressure of crotonaldehyde to 1.1 X 103 Pa. Typically, 50 mg of the catalytic system to be tested prepared as described above was placed in the reactor with 50 mg of quartz powder (80-125). (μιη) dilution. The catalyst 136600.doc -78- 200932669 is then activated at 300 ° C under H 2 for 6 hours (2 ° C / min heating rate; 100 mL / min H 2 flow rate, ie 900 h_1 each Hourly space velocity (HSV). The temperature is then set at 10 ° C and the reaction mixture is introduced into the reactor. Temperature regulation is achieved by a thermocouple positioned in the finger sleeve in the catalytic bed. Phase chromatography (HP 4890) analyzes the composition of the mixture leaving the reactor. The chromatograph is equipped with flame ionization on a CP-SIL 5CB column (length 25 m, .0 mm internal diameter, and film thickness 0.5 μπι). Detector (FID). The analysis conditions are as follows: column temperature: 40 ° C; carrier gas: nitrogen; Column head overpressure: 3xl〇4pa. Measure the intrinsic rate Vicr of each surface catalyst atom and the selectivity SCr0H for crotyl alcohol. Table 4 provides the results: Table 4 Structural Sensitivity Reaction: Hydrogenated Anti-Deer Example of Crotonaldehyde (Catalytic system) Powder used as a catalyst carrier Vi (molEie.s'gi surface)] ScrOH (%) 8 Example 1 4.5x1 (Τ* 18 9 Example 2 9.6x1ο-4 28 10 Example 3 3.9x1ο-4 14 12 Example 6 2.5χ1〇·4 8 Thus Example 9 greatly improved the catalytic properties, doubling the intrinsic rate % and making the selectivity sCr0H 55% higher than the reference powder selectivity. Currently, as described above, the carrier powder of Example 2 differs from the carrier powder of the example crucible in the form of the primary particles. A comparison of these examples (catalyst systems of Examples 8 and 9) shows that anisotropic morphology yields better results. However, a comparison of catalytic systems 9, 1 and 12 indicates that not all anisotropic whites are suitable for a given structurally sensitive reaction. Thus, the catalytic system 10 obtained from the rod 136600.doc-79·200932669 shaped carrier powder of Example 3 exposed little reaction-sensitive crystal face, and its catalytic performance was similar to that of Example 8. "Comparison of Examples 9 and 10 shows that In the present case, the morphological morphology is the only effective form in the anisotropic morphology tested. The inventors have also noted that the difference in efficacy is due to the exposed crystal faces of the initial particles of the carrier. The inventors have therefore found that it is advantageous to selectively select particles that are exposed to a particular crystal plane. In the present case, 'in the context of the hydrogenation reaction of crotonaldehyde', it is advantageous to select the initial Lu carrier particles which are exposed to the crystal face of the crystal face family {1, 〇, 〇}, which are favorable for the formation of the particles themselves. The surface area belongs to the 筏-shaped crystal grains of the crystal face of the crystal face family {1, 〇, 〇}. A comparison of the catalytic performance of the catalytic system of Example 1 using the powder of Example 3 as a carrier and the catalytic performance of the catalytic system of Example 2 using a powder of Example 6 having a lower purity indicates that the purity of the carrier powder is higher, The better the catalytic performance. Example 1 〇 demonstrates the value of the purification step by sufficient washing. In particular, the intrinsic rate is increased by 56°/. And the crotonol selectivity is increased by 75%. 〇 ® It is now apparent that the present invention provides particles which can improve the catalytic efficacy of a structurally sensitive reaction either directly or in a catalytic system by sufficient purification. • Of course, the invention is not limited to the described and illustrated embodiments. In particular, the powder of the present invention can be used, for example, as an inorganic filler, an abrasive, or in the field of transition. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing initial particles in the form of rods. Figure 2 is a graphical representation of the primary particles in the form of pellets. 136600.doc •80· 200932669 Figures 3a and 3b show top and side views of the bar, respectively. Figure 3a shows the bar with a smooth shape. Fig. 4a and Fig. 4b are a group of granules and a granule image of a crystal face mainly exposed to the crystal face group {1〇 〇}, respectively. The bar image of the 1 } crystal face is shown in Fig. 5a and Fig. 5b as the main exposed crystal face.

Fig. 6a and Fig. 6 are respectively a cut-off vertical view and a side view photo and illustration. Figure 7 is a graphical representation of a grain in the shape of a back. The octahedral shape of the grain is overlooked 136600.doc

Claims (1)

200932669 X. Patent application scope: 1. A method for synthesizing powder, which comprises the following consecutive steps: A) preparing a mother liquor comprising the following: 1. 1 basic component or basic component &lt; precursor and formula , an additional component consisting of: _ selected from the group consisting of an oxyanion, an anion of the element of the 17th line of the periodic table, a hydroxide hydrazine, and a mixture thereof, And ❹ _ compensator C, when the agent is hydroxide ΟΗ _, the compound is inorganic; or η. and has the active agent Μ of the oxide basic component or the basic component precursor, The agent is selected from the group consisting of an oxyanion, an anion of the element of the 17th row of the periodic table, and a mixture thereof; Β) a sol is prepared hydrothermally from the mother liquor, the granulated coarse particles having a particle size greater than 10 nm and less than 25最大nm and even less than the maximum size of 1〇〇nm; ® C) washing the sol to obtain a powder comprising 99.3% or more of the essential component based on the mass percentage of dry matter after the optional drying step; )package At least one operation selected from the group consisting of: - dialysis in the case of resuspending the sol in advance or without resuspending the sol, - in the case of resuspending the sol in advance or without resuspending the sol in advance Purification using ion exchange resin, 136600.doc 200932669 • Acid neutralization, - combination of such techniques, and, if desired, - filtration in the case of resuspending the sol in advance or without resuspending the sol in advance, and / Or - rinse. 2. The method of claim 1, wherein step c) comprises at least one acid-base neutralization operation. ❹ 3. The method of the above claim, wherein the final operation for removing cationic impurities is controlled by using a mixture of organic or organic acids. The first operation in the 1% aqueous solution and/or the removal of the anionic impurities is carried out in an aqueous solution using a neutral or organic mixture to control the pH. The method of any one of the preceding claims, wherein the acid-base neutralization operation comprises: depending on whether the impurity to be removed is a cation or an anion, the suspended piano value: at or above the zero charge point of the basic component In the aqueous solution; the suspension is maintained at a temperature below its boiling point at the bar for a period of more than 1 minute; and filtered. :: Method of describing the μ terminology where the positive value is smaller or larger than the zero charge point &gt; 2 pH units. 6' Method of finding 'where the positive value is less than or greater than the zero charge point by at least 4 pH units. 7: One of the three claims just mentioned is maintained for less than 3 minutes. &amp; U U 8 · The method of the four claims as just described, where the pH value of 136600.doc 200932669 to control the addition of hydrochloric acid and / or nitric acid and / or high gas or by adding ammonia The method of any one of the preceding claims, wherein the powder comprises the essential component based on the quality of the dry matter. • The method of claiming, wherein the powder comprises more than 99% of the essential component based on the mass percentage of the dry matter. The method of the preceding claim, wherein the powder comprises more than 99 9% of the base component based on the mass percentage based on the dry matter. The method of any one of the preceding claims, wherein in the step A), the amount of the agent is greater than l〇-4m()1/1. 13. The method of claim 6, wherein the amount of the agent in step a) is greater than 1 〇 -3 mol/i. 14. For example, the method of the present invention, wherein the amount of the agent in the step ... is greater than 1 〇 -2 mol / l. 15. The method of any of the preceding claims, wherein the step comprises at least one rinsing operation comprising: suspending the rinsing operation in a solvent at a temperature below 1 bar at 1 bar. In the period, it was followed by evidence. 16. The method of claim </ RTI> wherein the rinsing operation is performed in water having a purity at least equal to the purity of the water permeable or greater than 98 vol. Executed in the alcohol. 17. In the method of any of the two claims mentioned earlier, the flushing time is between 10 minutes and 30 minutes. 18. The method of any of the preceding clauses, wherein in step A), the precursor component and/or the precursor of the base component 136600.doc 200932669 are respectively included in a mass percentage based on the dry matter. More than 99.5% of the base component and/or the precursor of the base component. 19. The method of claim 1, wherein in step A), the base component and/or the precursor of the base component comprise 99.8% or more of the base component, respectively, based on the mass percentage of dry matter. And/or the precursor of the basic component. 20. The method of claim 2, wherein in step A), the precursor component and/or the precursor component of the base component comprise 99.9% or more of the basic component, respectively, based on the mass percentage of the dry matter. The precursor of the component and/or the base component. The method of any one of the preceding claims, wherein the base component added to the mother liquor and/or the precursor of the base component is selected such that the powder is based on the mass percentage based on the dry matter The basic component has a monoclinic structure of 95% or more. 22. The method of claim 1, wherein the essential component of the powder has a monoclinic structure of 97% or more. The method of claim 1, wherein the essential component of the powder has a monoclinic structure of 99% or more. 24. The method according to the above claim, wherein the essential component of the powder has a monoclination of more than 100%. Crystal structure. The method of any one of the preceding claims, wherein the base component or the precursor of the base component added to the mother liquor is selected such that the base component is an oxide selected from the group consisting of : Hf02, Zr02, Eu2〇3, Sm2〇3, Mo03, W03. 136600.doc 200932669 26. A method for citing a whistle, wherein the basic component or the hydrazine of the basic component added to the mother liquor is selected such that the component is selected from the group consisting of The oxides of the following: Zr 〇 2, W 〇 3. 27' The method of claim π wherein the base component or the precursor of the base component added to the mother liquor is selected such that the base component is selected from the group consisting of Zr02 and/or Hf〇2. Oxide. The method of claim 2, wherein the base component or the precursor of the base component added to the mother liquor is selected such that the base component is φ oxidized Zr02. The method according to any one of the preceding claims, wherein the agent is selected from the group consisting of sulfate s〇42_, carbonate CO/·, phosphate PO′, fluoride ion F·, gas Ionic cr, high oleate Cl 〇 4 ·, borate BO, nitrate N (V, hydrazine 〇 H. and mixtures thereof; or if the pH is less than 4, it is selected from the gas ion cr, high gas The method of claim 30, wherein the basic component is selected from the group consisting of Ζ2 Ζι:02 Eu2〇3, Sm2〇3, The pH of the mother liquor is adjusted to be less than 4; or greater than 1 〇. 3. The method of claim 29, wherein the essential component is selected from the group consisting of Hf〇2, Zr〇2, Eu2〇3, Sm2. 〇3, m〇〇3, then the pH of the mother liquor is adjusted to be less than 2. 32. The method of any of the three claims, wherein the pH of the mother liquor is less than 4 and When the agent is introduced in the form of an additive (in the form of an additive, the additive is composed of the following: 136600.doc 200932669 _ the agent Μ, and - selected from Complementing agent c of the group consisting of: 'a group of positively charged organic molecules whose organic group consists of a group of atoms selected from the group consisting of carbon, hydrogen, helium and nitrogen; - line 1 And the cation of the element of the second row; the cation of the following elements: Ming A1, mammoth η, iron Fe, Ji Y, copper Cu, silver Ag, 钸Ce; -ammonium NH4+. φ 33. Ο 34. 35. And the method of any one of 30, wherein when the mother liquor has a value of 11 greater than 10 and when the agent is introduced as an additive, the MC additive is composed of the following: Complementing agent C is selected from the group consisting of: • a group of positively charged organic molecules whose organic group consists of a group of atoms selected from the group consisting of carbon 'hydrogen, oxygen and nitrogen; The method of any one of the preceding claims, wherein in the step Β), the mother liquor is heated in a closed vessel to a boiling point above 1 bar and is in the range of 1 〇 The temperature between 〇 ° C and 3 ° ° C, the temperature is maintained for at least one hour and the rate of temperature increase is small 250 ° C / h. The method according to any one of the preceding claims, wherein the prepared powder has an impurity content of -Si02 &lt; 136600.doc 200932669 -Al2〇3&lt;0.1%, and/or -MgO&lt;0.1%, and/or -CaCKO.l%, and/or -Na2O&lt;0.1°/., and/or -cr&lt;oi°/ . And/or -no3-&lt;o.i%, and/or -SO42-&lt;0.1%, and/or -TiO2&lt;0.10/〇. 36. The method of claim 1, wherein the impurities are as follows, mass percentages: 丨〇 • 物质 丨〇 & & & 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 ppm, and / or -CaO &lt; 200 ppm, and / or -Na2 〇 &lt; 500 ppm, and / or -Cr &lt; 500 ppm, and / or - Ν〇 3 · &lt; 500 ppm, and / or -S 〇 42_ &lt; 500 ppm, and / or - Ti 〇 2 &lt; 200 ppm. 37. The method of claim 37, wherein the impurities are as follows: -Si〇2 &lt;100 ppm, and/or -Al2〇3<l〇〇ppm, and/or -MgO&lt;50 Ppm, and/or 136600.doc 200932669 -CaO&lt;100 ppm, and/or -Na2〇&lt;100 ppm, and/or -Cr&lt;l〇〇ppm, and/or -N03_&lt;1〇〇ppm, and/or Or -S〇42_&lt;1〇〇ppm, and/or•Fe2O3&lt;50 ppm, and/or -Ti〇2&lt;50 ppm. 38. The method of any of the preceding claims, comprising an additional step after step c), in which the particles of the powder are selected from an anion selected from the group consisting of an oxyanion, a 17th line, and a ruthenium A suspension of dopants of the group of cations of the elements and their mixtures is mixed. 39. The method of claim 1, wherein the dopant is selected from the group consisting of citrate, phosphate, sulfate, gas ions, fluoride ions, sodium and potassium. 40. A method of synthesizing a powder, the method comprising the following steps: A) preparing a mother liquor comprising: an oxide base component or a precursor of the base component and an additional group of the formula is 'the additional component It is composed of the following: an agent selected from the group consisting of an oxyanion, an anion of the element of the 17th line of the periodic table, a group of hydroxide OH and a mixture thereof, and a compound C, when the action is In the case of hydroxide, the compound is an inorganic substance; or the essential component or the basic agent is selected from the group consisting of oxyanions and elements 136600.doc -8- 200932669, an anion of the 17th element a group of mixtures thereof; = method for preparing a sol from the mother liquor, the crude particles of the sol having a maximum size of less than 250 nm and containing as, to less than 100 nm; C) washing the sol, obtained after an optional drying step Based on the mass percentage of =, the base component of _ above, _ from Si: ί to t - acid neutralization operation, which is used to remove yang, after which the operation is based on the use of organic or organic acids Mixture to adjust pH It was performed, and / or an aqueous solution for the removal of anionic impurities in the final operating system using a mixture of an organic or organic inspection test of the pH control is performed. 41. A powder prepared according to the method of any of the preceding claims. 42. A method of using a powder as described above, and money is used to catalyze a chemical reaction. 43. The method of claim 1, wherein the primary particles of the powder are not coated with a catalyst, and are used to catalyze a reaction selected from a hydrocarbon conversion reaction, including a selective oxidation reaction, a hydrogenation reaction, a dehydrogenation reaction, a hydrogenolysis reaction, Isomerization reaction, dehydrocyclization reaction and recombination reaction. 136600.doc 200932669 VII. Designation of Representative Representatives (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please reveal the characteristics that can best show the invention. Chemical formula: (no) 136600.doc