TW201026387A - Shell catalyst, process for its preparation and use - Google Patents

Abstract

The present invention relates to a shell catalyst, comprising a ZrO2-containing catalyst support with a shell in which Pd and Au are contained, wherein the Au/Pd atomic ratio of the shell catalyst is 0.2 to 1.2. To provide a shell catalyst which has a relatively high alkenyl acetate activity, it is proposed that the proportion of Pd in the shell catalyst is less than/equal to 0.75 wt%.

Description

201026387 VI. Description of the Invention: [Technical Field] The present invention relates to a shell catalyst comprising a catalyst carrier containing Zr〇2 and a shell layer containing Pd and Au, “drying the shell layer The atomic ratio of Au/Pd of the medium is 0.2 to 1.2. [Prior Art], 6 acid vinegar is an important monomer building block in the synthesis of plastic polymers. The main field of β-indole acetic acid vinegar is theoretically to prepare polyacetic acid. B (IV), polyvinyl alcohol and polyvinyl acetal, and copolymerization with other monomers such as ethylene, ethylene acrylate, maleate, fumarate and vinyl laurate Tripolymerization. Acetyl acetate can be prepared, for example, by reacting acetic acid and ethylene in the gas phase with oxygen, wherein the catalyst used in the synthesis preferably contains ? (1 as an active metal, containing Au as a promoter and containing a surplus The component is a co-promoting agent, preferably potassium in the form of an acetate. In the Pd/Au system of the catalyst, the metals Pd and Au are not present in the form of metal particles of respective pure metals, but Pd/Au alloy particle form with possibly different composition However, the presence of non-alloy particles cannot be excluded. As an alternative to Au, for example, cd or Ba can also be used as a co-promoter. Currently, 'acetic acid esters are mainly prepared by means of so-called shell catalysts, in which the shells are prepared. In the layer catalyst, the noble metals Pd and Au do not completely penetrate the catalyst carrier, but only in the outer region (shell) of the catalyst carrier width or larger (refer to EP 565 952 A1, EP 634 for this) 214 A1, EP 634 209 A1 3 201026387 and EP 634 208 A1), while the catalyst carrier region located further inside is free of precious metals. In many cases, by means of the shell catalyst, the active component is compared to the carrier. The catalyst immersed in the core of the support ("impregnated through") may be more selective for reaction control. The shell catalyst known in the prior art for preparing ruthenium acetate S may be, for example, ruthenium oxide. A catalyst carrier based on alumina, aluminosilicate, titanium oxide or zirconia (for this, please refer to EP 839 793 Al, WO 1998/018553 Al, WO 2000/058008 A1 and WO 2005/061107 A1). However, titanium oxide is rarely used at present. Oxidation hammer-based catalyst carrier, because the catalyst carrier does not exhibit long-term acetic acid resistance and is relatively expensive. Most of the catalysts currently used in the preparation of acetate are in porous amorphous Mingshi acid carrier a shell catalyst having a Pd/Au shell layer formed by a natural layered tantalate-based sphere in which potassium acetate is impregnated as a co-promoter. The enester shell catalyst is typically prepared by a so-called chemical route in which a catalyst carrier is immersed in a solution of the corresponding metal precursor compound, for example by dipping the support in solution, or by means of incipient wetness impregnation. An incipient wetness method (pore-filling method) is prepared in which a carrier is loaded with a volume of solution corresponding to the pore volume. For example, the Pd/Au shell layer of the catalyst is generated as follows: first, in the first step, the catalyst carrier is immersed in the vaporized palladium solution, and then the Pd component is Pd-hydrogen in the _ step with the NaOH solution. The oxide compound form is immobilized on a catalyst carrier. In a subsequent independent third step, the coil detacher dipped the catalyst carrier 201026387 into the vaporized gold solution, and then fixed the Au component by means of Na〇H. After the precious metal component is immobilized in the outer shell layer of the catalyst support, the support is subsequently washed to be substantially free of gas ions and sodium ions, followed by drying, calcination and finally reduction in the liquid or gas phase. The thickness of the thus obtained pd/Au shell layer is usually from about 100 μm to 500 Å to 111. Typically, after the final fixation or reduction step, the probe loaded with the precious metal is loaded with acetic acid oblique, wherein the catalyst carrier is completely saturated with the co-promoter' rather than only the potassium acetate loaded in the outer layer loaded with the precious metal. . The catalyst carrier mainly uses a spherical carrier called rKA_16(R), which is from SOD. Chemie AG of Munich, Germany, and is mainly composed of natural layered sulphate and has a BET surface area of about 160 m2/g. The selectivity of the acetate ester obtained by using the pd and Au and ΚΑ-16〇-based acetophenone-based catalysts known in the prior art is about 90 m〇 with respect to the supplied ethylene. %, wherein the remaining 1 〇m 〇 1% of the reaction product is substantially formed by the total oxidation of the soil organic educt/product. ❿ 1 provides a acetic acid vinegar catalyst having an activity relative to (iv) acetic acid. To this end, the prior art is attempting to further increase the proportion of active metal Pd in known shell catalysts. The Pd content of the vinyl acetate catalyst currently used in the prior art is 0.9% by weight or more. SUMMARY OF THE INVENTION It is an object of the present invention to provide a shell catalyst having a relatively high activity of acetic acid vinegar. The object is achieved by a catalyst carrier comprising a catalyst carrier containing Zr〇2 and a shell layer catalyst containing 5 and a layer of 201026387, and the Au/Pd atomic ratio of the shell catalyst is 〇2 to 1: and the shell thereof The proportion of pd in the layer catalyst is less than / equal to Ο"% by weight. Surprisingly, it has been confirmed that although the shell catalyst of the present invention has a relatively small active metal content compared to the corresponding shell catalyst of the prior art. However, it also has a relatively high acetate activity. In addition, it has been confirmed that although the activity of the acetate of the catalyst of the present invention is high, it is characterized in that the selectivity of the acetate is relatively high. The shell catalyst is particularly inexpensive because it requires less Pd to provide the same acetic acid vinegar activity and at least the same acetate selectivity as the corresponding catalysts of the prior art. Shell catalysts are known in the art. It is known that in the case of a shell catalyst, there is a difference between "egg-shell" and "egg_white" shell catalyst. The "egg shell" catalyst is a shell catalyst in which a catalytically active material is present in the outer layer of the catalyst carrier, wherein the shell layer extends inwardly from the outer surface of the carrier - and the core of the catalyst carrier does not contain a catalytically active material. On the other hand, in the "protein" shell catalyst, the inner shell layer is loaded with a catalytically active substance in a region near the surface of the catalyst carrier and substantially below the outer surface of the carrier, wherein it is not occupied by the catalytic active material. The outer shell layer is intended to trap catalyst poisons and thus prevent poisoning of the catalytically active material located thereunder. Further, in the case of a "protein" type shell catalyst, the core of the catalyst carrier does not contain a catalytically active substance. The shell catalyst of the present invention is an "egg shell" or "protein" type shell catalyst, preferably an "egg shell" type shell catalyst. [Embodiment] 6

❹ 201026387 The ratio of the shell layer catalyst to the preferred medium in the preferred embodiment of the present invention is from 75755% by weight to the weight of the shell layer = 0.4% by weight and preferably (10)% by weight. Preferably, the shell layer of the present invention is in the above range of 0.70. · 5 wt%. The properties of the shell layer catalyst according to the invention are particularly high. Another preferred and catalyst for the 'sister' is the ratio. .75 wt% to 〇5〇, two:: shell weight Μ 55 wt% and a heavier ratio of Pd in the shell catalyst of the present invention is less than/equal to 〇·重f two "this hair (four) money material pd set ^ In the case of the media, f Pn L ^ " knows that the Pd weight is less than the reset of the shell catalyst', that is, the ratio of the catalyst carrier, the noble metal p-agent or the co-promoter compound (for example, cesium acetate = layer catalyst) Before the weight, it is preferred to dry the shell-free layer at a temperature of 1 hour under a nitrogen atmosphere to substantially remove any moisture, followed by analysis. According to another preferred embodiment of the present shell-forming catalyst, The atomic ratio of Au/Pd of the shell catalyst is specified to be 〇3 to 丨〇, preferably 〇4 to 〇7. Within the above range, the shell catalyst of the present invention is characterized by relatively high selectivity of acetate. At the same time, relatively less Au is used. According to another preferred embodiment of the shell catalyst of the present invention, it is specified that at least part of the Zr〇2 contained in the catalyst carrier is modified by a tetragonal shape (to play "(10) heart modification) The existence of Zr〇2 in the form of a tetragonal crystal modification is such that the shell catalyst of the present invention is characterized by being relatively A long period of dilute acetic acid is relatively high activity.

There are three variants of Zr〇2. Zr〇2 is stored in a monoclinic crystal at room temperature. 7 201026387 In the case of temperatures above 1170 ° C, it is present in a tetragonal modification, but at 237 〇. (: above to 269 (the melting point of TC exists in a cubic crystal modification. According to a preferred embodiment of the shell catalyst of the present invention, it is specified that at least 5 〇% by weight of Zr〇2 contained in the catalyst carrier is square The crystal modification type exists. Since the ratio of the tetragonal modified Zr〇2 contained in the catalyst carrier is determined by means of X-ray diffraction (XRD), the ratio only refers to the X-ray winding contained in the catalyst carrier of the present invention. Active Zr02. It has been confirmed that in the case of the shell catalyst of the present invention, the higher the proportion of ruthenium 2 present in the tetragonal modification of the carrier, the Zr released (i.e., washed) in the synthesis of acetate. Therefore, according to a preferred embodiment of the shell catalyst of the present invention, it is specified that the catalyst carrier contains at least 5% by weight, preferably 50% by weight to 1 in the form of a tetragonal modification. 〇〇% by weight, more preferably from 70% by weight to 100% by weight, still more preferably from 85% by weight to 1% by weight, still more preferably from 90% by weight to 100% by weight, more preferably from 92% by weight to 1% Weight / 〇 and more preferably from 93% by weight to 丨〇〇 weight ❶ / ◦. The above ratio is contained in the carrier The X-ray diffraction activity is related to Zr〇2. The tetragonal crystal of the invention is particularly preferred.

The Zr〇2 ratio of 1 〇〇% by weight means that only the number of the tetragonal crystal Zr〇2 can be identified in the corresponding XRD diffraction pattern without the signal of the monoclinic modification or the cubic modification. . According to another preferred embodiment of the catalyst of the present invention, it is defined as 28 2 in the XRD diffraction pattern of the carrier. The signal strength of the time is ^3. The ratio of the signal intensity at time is less than / equal to 丨, preferably less than 〇5, preferably less than 〇·3' is better than 0.05 and more preferably equal to b. The better the xrd diffraction pattern of the carrier is no cubic Ba Zr〇2 Signal. The maximum intensity peak of monoclinic Zr〇2 (201026387 111) is located at 20 of 28.2. Where, the maximum intensity peak of the tetragonal square 2 (at 1 101 ) is 20.2 at 2Θ. At the office. The XRD diffraction pattern is a so-called XRD difference diffraction pattern. The XRD differential diffraction pattern is obtained by recording the XRD diffraction pattern of the Zr〇2-containing catalyst carrier and the xrd diffraction pattern of the reference catalyst carrier under the same conditions and XRD diffraction from the catalyst carrier containing Zr〇2. The XRD diffraction pattern of the reference catalyst carrier is subtracted from the figure to generate. The reference catalyst carrier is prepared analogously to the catalyst carrier containing .2, except that Zr is not added to the reference catalyst carrier. The XRD diffraction pattern is preferably measured on a D4 endeav〇r X® ray powder diffractometer from Bruker AXS using Bragg_Brentano geometry. The device parameters are preferably: Cu Κα : 丨 54 〇 6 a, voltage · 40 kV, current intensity: 4 〇 mA; and the scanning parameters are: continuous scanning, 20 is 5 to 90, step length = 〇.03. 20, Each step time = 〇 58, divergence - slit = 12 mm (variable), anti-scatter slit = 12 mm (variable), sample rotation: 30 rpm. ..... This surface area of the tetragonal crystal is relatively high. However, it is stable at room temperature: the phase is monoclinic zirconium dioxide, and its specific surface area is relatively low. The surface-rich (s-like) tetragonal Zr〇2 phase is produced and stabilized in a high yield by simply f-injecting ruthenium hydroxide in the carrier matrix containing the layered salt and X undoped, followed by calcination. Thus, relatively inexpensive ruthenium is used to provide a relatively commensurate dioxin ratio surface area in the catalyst support. The catalyst carrier known in the prior art is prepared by impregnating a catalyst carrier with a salt solution, followed by satin burning, which is a x-ray amorphous state in the case of a hammer. This generally means that zirconium is present in the form of nanocrystalline particles and/or in amorphous form. According to another preferred embodiment of the shell catalyst of the present invention, it is provided that 9 201026387 is present in the form of a particulate. If Zr〇2 is present in the catalyst carrier in a tetragonal modification, Zr〇2 is contained in the carrier in the form of particles. Further, in principle, Zr〇2 may also be incorporated into, for example, individual Zr〇2 in the carrier structure. The unit form is contained in the carrier. Preferably, however, Zr〇2 is present in the form of particles in the catalyst carrier. Thereby ensuring that the Zr 〇 2 solid is incorporated into the support, and thus the catalyst support releases substantially less Zr 〇 2 in the acetic acid. If Zr〇2 is contained in the form of particles in the catalyst carrier of the catalyst of the present invention, according to another preferred embodiment of the catalyst of the present invention, it is preferred that the average particle diameter dw of the palpitations 2 is at most 50 " m, preferably The average particle diameter is at most 3 〇" ❹ m, and the average particle diameter is preferably at most 2 〇em. The average particle diameter d5〇 was determined by means of electron microscopy (EDX). To this end, the random selection of the edx spectrum of the catalyst carrier is selected from 5 1 in the 1 mm x 1 mm region to identify the maximum size of the largest Zr 〇 2 particle, and the seven ❶ value is calculated therefrom. EDX measurements are preferably performed on a LE〇 43〇vp scanning electron microscope equipped with an energy dispersive spectrometer from Bruker AXS. During the measurement, the cut catalyst carrier was glued to the aluminum sample holder and subsequently vaporized with carbon. The detector preferably uses a gas-free drift chamber finder (nitrogen seven ee siHc〇n secret 仏 ❹ ctor) (41 〇), and its energy resolution of the L-line is (2) ^. The d5° value thus determined is usually significantly greater than the actual "value of the Zr 〇 2 particle in the human catalyst carrier. If the ton particle can be removed from the carrier and measured, the actual d5 J value of J quant / then corresponds... 8 to 2 times the ruthenium oxide used in the method for preparing the catalyst carrier. This value and the intensity of the xrd & reflection of the tetragonal crystal (10) can be inferred from the size of the Zr 〇 2 particles in the catalyst carrier. More than 50 angstroms) and having a ratio of ray-ray diffraction activity. 10 201026387 According to another preferred embodiment of the shell layer catalyst of the present invention, it is specified that Zr 〇 2 is contained in the catalyst carrier in a uniformly distributed or randomly distributed manner. It has been confirmed that the more uniform the distribution of Zr〇2 in the matrix, the less Zr〇2 released by the catalyst carrier in acetic acid. The matrix means the carrier solid matter around the pores. Therefore, it is contained in the shell catalyst of the present invention. When the catalyst carrier is not composed of Zr〇2, according to another preferred embodiment of the shell catalyst of the present invention, Zr〇2 is specified to be contained in the matrix of the carrier in a uniformly distributed, preferably homogeneously distributed manner. Another preferred embodiment of the shell catalyst The ratio of Zr〇2 contained in the catalyst carrier is from 1% by weight to 30% by weight based on the weight of the catalyst carrier. If the ratio of Zr〇2 contained in the catalyst carrier is less than i% by weight, then the hair • The activity of the acetate ester of the bright shell catalyst is only slightly increased, and when the ratio is above 25 wt. /〇, the selectivity of the acetate is significantly impaired as the activity of the catalyst increases. Therefore, the catalyst according to the present invention Another preferred embodiment of the invention stipulates that the ratio of _Z: 〇2 contained in the catalyst-load-body is Λ by weight q% to 25% by weight relative to the weight of the vehicle carrier, preferably 5 wt% to 20 wt%, and more preferably 8 wt% to 15 wt%. The catalyst carrier contained in the shell catalyst of the present invention may consist of Zr〇2 or may contain other components in addition to Zr〇2. , such as one or more metal oxides selected from the group consisting of SiO 2 , MgO, Al 2 〇 3, aluminosilicates, Ti 〇 2, smog-type sulphur dioxide (fumed chuan (8)), and Nh gt. In another preferred embodiment of the inventive shell catalyst, it is provided that the catalyst carrier comprises a natural layered bismuth salt. Natural sheet silicate )" (also referred to in the literature as 11 201026387 by the term "phyllosilicate") means, within the scope of the present invention, an untreated or treated silicate mineral from a natural source, wherein The Si04 tetrahedron constituting the basic structural unit of all phthalates is cross-linked to each other in each layer, and has the general formula [Si205]2·. The tetrahedral layers alternate with so-called octahedral layers in which the cations (mainly A1 and Mg) are surrounded by OH or 0 octahedrons. For example, there is a difference between a two-layered phyllosilicate and a three-layered citrate. Preferred layered sulphate salts within the scope of the present invention are clay minerals, in particular kaolinite, beidellite, hectorite, saponite, pouch dislocation Nontronite, mica, vermiculite, and smectite, of which smectite and especially montmorillonite are preferred. The definition of the term "sheet silicate" can be found, for example, in "Lehrbuch der anorganischen Chemie j, Hollemann Wiberg, de Gruyter, 102nd edition, 2007 (ISBN 978-3-11-017770-1). Or can be found in the "R6mpp Lexikon Chemie", 10th edition, within the title of "Gelylosilikat" by Georg Thieme Verlag. Typical aspects of natural layered phthalates that are experienced prior to use as carrier materials include, inter alia, treatment with an acid, in particular with a mineral acid such as hydrochloric acid, and/or calcination. A preferred natural layered niobate within the scope of the present invention is smectite, which is preferably used in the form of bentonite. The expanded soil is a mixture of different clay minerals containing montmorillonite as a main component (about 50% by weight to 90% by weight). Other companion minerals may theoretically be quartz, mica and feldspar 〇 12 201026387 According to another preferred embodiment of the shell catalyst of the present invention, the natural layered niobate is defined as an acid activated layered niobate. The hydrazine-activated layered decanoate is known in the art (cf. R5mpp Lexikon Chemie, 10th edition, Georg Thieme Verlag, heading "Bentonite"). In order to increase the adsorption of the catalyst carrier, the natural layered phthalate is preferably present in the carrier in the form of an acid activated layered silicate. More preferably, the acid activated layered niobate is an acid activated montmorillonite, and in accordance with the present invention, the acid activated montmorillonite is more preferably contained in the carrier in the form of an acid activated bentonite. The proportion of the natural layered acid salt in the preferred catalyst carrier according to the invention is greater than/equal to 5% by weight, preferably from 55% to 95% by weight, preferably 60% by weight, relative to the weight of the catalyst carrier. It is up to 9% by weight, more preferably from 65% by weight to 85% by weight and still more preferably from 70% by weight to 8% by weight. According to another preferred embodiment of the shell catalyst of the present invention, the content of the Si〇2 content of the natural layered niobate contained in the catalyst carrier is at least 65% by weight, at least 80% by weight and particularly preferably 90% by weight. % to % t %. From the protection of the catalyst carrier in the synthesis of vinyl acetate and under the right, there is chemical resistance. In the gas phase synthesis of acetic acid from acetic acid and ethylene, decyl phthalate is a natural layered tannin.

The relatively low content of Al2〇3 in the salt has a small T θ private A boat has a strong J adverse effect, while Al2〇3 contains a relatively long-term, it will be expected to be the carrier carrier, to the hardness (indentation hardness) Significantly reduced. Therefore, it is preferred that one of the catalysts of the present invention has a weight ratio of Ai n + .3 contained in the natural layered niobate relative to the natural slippery tantalate contained in the carrier of less than 5 times. The /weight/〇' is preferably from 0.1% by weight to 3.5% by weight and preferably from 0.3% by weight to 3% by weight. According to another preferred and/or example of the catalyst of the present invention, the acidity of the catalyst carrier 13 201026387 is specified from 1//val/g to 1 50/z val/g. For the gas phase synthesis of acetate from acetic acid and ethylene, the acidity of the catalyst carrier can advantageously affect the activity of the catalyst of the present invention. Therefore, according to another preferred embodiment of the catalyst of the present invention, the acidity of the catalyst carrier is specified to be val/g to 150 v val/g. The acidity is preferably from 5 // val/g to 130 μ val/g. The acidity is preferably from 10 // val/g to 100 μ val/g, and the acidity is preferably from 20 " val/g to 60 from val/g. The acidity of the carrier can be increased, for example, by impregnating the catalyst or carrier with an acid. The acidity of the catalyst carrier was determined by adding 100 ml of water (pH blank value) to 1 g of the fine powder catalyst carrier and extracting for 15 minutes with stirring. Then, titrate with a 0.01 n NaOH solution to at least pH 7.〇, wherein the titration step is repeated; firstly, 1 ml of NaOH solution (1 drop/second) is added dropwise to the extract, and then wait for 2 minutes to read the pH value. Then add 1 ml of Na〇H and the like. Determine the blank value of the water used and calculate the acidity accordingly. The titration curve (0.01 ml of NaOH vs. pH) is then plotted and the intersection of the titration curves at pH 7 is determined. Calculate the molar equivalent (1 eq/g carrier) which is obtained from the NaOH consumption at the intersection of pH 7: Total acid: \0* ml O.OlnNaOH . ~~ίϋ - ival/g Another catalyst according to the invention In a preferred embodiment, the catalyst carrier is defined to have an average pore diameter of from 8 nm to 30 nm. In order to keep the pore diffusion limit of the catalyst of the present invention substantially small, according to the touch-preferable embodiment of the present invention, the average pore diameter of the support is from 8 nm to 30 nm, preferably from 1 〇 1 ^ to 2 〇 nm. And especially good 201026387 is l〇nmi 15nm. The average pore diameter is determined by mN66i34 (by the nitrogen adsorption (Barreu, J. Surface area) determination. According to another preferred embodiment of the catalyst of the present invention, the specific surface area of the catalyst carrier is specified to be less than/equal to 18 〇 m 2 /g.

It has been confirmed that the smaller the specific surface area of the catalyst carrier, the higher the selectivity of the catalyst of the present invention, and the higher the selectivity of the catalyst H (four). According to the catalyst of the present invention, a specific embodiment, the catalyst carrier is specified. The specific surface area is less than / equal to 180 m 2 /g, preferably less than / equal to 16 〇 m 2 / g, preferably less than / equal to 14 〇 m 2 / g, more preferably less than / equal to 137 m 2 / g, more preferably less than / equal to i35 m 2 / g, more Preferably less than / equal to 133 mVg, and particularly preferably less than / equal to 13 〇 m2 / g. The specific surface area of the support is determined according to DIN 66131 (by Bmnauer, Emmett and Teller (BET) gas adsorption to determine the specific surface area of the solid) and _ DIN 6.6132. According to the present invention, the preferred catalyst carrier has a specific surface area of from 6 μm 2 /g to 180 m 2 /g, preferably from 65 mVg to 16 μm 2 /g, preferably from 7 to 100 m / g, more preferably It is preferably from 70 m2/g to 120 m2/g, more preferably from 70 m2/g to 110 m2/g, and most preferably from 80 m2/g to 1〇〇m2/g. When the catalyst carrier comprises a natural layered niobate, the specific surface area, average pore diameter and overall pore volume of the catalyst carrier are determined, in particular, depending on the quality of the natural layered niobate used and the acid treatment method (also That is, for example, relative to the nature and quality of the layered niobate and the concentration of the mineral acid used, the duration of the acid treatment and the temperature, the molding pressure and the duration of the calcination and the temperature 15 201026387 and the deflagration atmosphere. According to another preferred embodiment of the catalyst of the present invention, the hardness of the catalyst carrier is specified to be greater than or equal to 55 N, the hardness is preferably from 55 N to 65 N, and the hardness is particularly preferably from 57 N to 63 N. With the help of him (four) w

Phannatron AG (Switzerland) 8" Bond Hardness Tester measures spherical samples (diameter · 5mn 硬度 hardness (indentation hardness). Before measurement. (: Temperature at room temperature for 2 hours. Hardness is calculated as (10) Sub-measurement

The average value. For the measurement, the following optional parameters of the 8M tablet hardness tester are set as follows: °X

N 5.00 mm 0.80 s 6 D Hardness (size): Distance from the sample: Time delay: Feeding type: υ·60 mm/s According to another preferred embodiment of the catalyst of the present invention, the overall pore of the catalyst (4) is specified The volume is from 0.25 ml/g to 〇.7 mi/g.

It has been found that the catalyst of the present invention is based on the volume of the pores of the acetic acid-selective photocatalyst carrier; Therefore, the overall pore volume of the preferred catalyst carrier is from 25 rm/g to 0.7 ml/g', preferably from 〇3 to 〇55 _, and the shoulder is preferably from 0.35 nU/g to 〇.5 ml/g. . The overall pore volume was determined according to the surface of the surface (by the nitrogen adsorption (Brent's Jonah/Halda (Bm) method); the pore size distribution and specific surface area of the mesoporous solid). Another overall pore volume of the catalyst according to the present invention is at least 8 Å/β. Preferably, the catalyst carrier is preferably at least 90% and preferably at least 95%. 16 201026387 is formed by mesopores and macropores. This counteracts the reduction in activity of the catalyst of the present invention, especially the relatively thick shell layer of the shell due to diffusion limitations. "Micropore", "mesopore" and "macropore" mean pores with a diameter of less than 2 nm, pores with a diameter of 2 nm to 50 nm, and pores with a diameter of more than 50 nm. The volume fraction of mesopores and macropores in the overall pore volume uses the pore volume distribution of the catalyst carrier of the present invention

(Pore-volume distribution) determined that the pore volume distribution according to DIN 66134 (by the nitrogen adsorption (Brent-Jonathan/Halenda (bjh) square method) determination of pore size distribution and specific surface area of mesoporous solids ) Determination. According to another preferred embodiment of the catalyst of the present invention, it is specified that the ratio of the pores of the carrier having a diameter of 6 nm to 50 nm to the total pore volume is greater than 66 Å/〇, • preferably from 66% to 80%, and particularly preferably 68% to 75°/. . The percentage is calculated from the pore size distribution's pore size distribution according to DIN 66134 (the pore size of the mesoporous solids is determined by nitrogen adsorption (Brent-Jonathan-Halunda (BJH) method). Determination. ____ _ According to another preferred embodiment of the catalyst of the present invention, the carrier density of the catalyst carrier is specified to be greater than 3.3 g/ml, preferably greater than 〇35 g/m, and the bulk density is preferably 〇35 g/ml to 〇6. According to another preferred embodiment of the catalyst of the present invention, the catalyst carrier is defined to be formed into a shaped body. In principle, the catalyst carrier can be in any form known to those skilled in the art to be suitable for the present invention. For example, the catalyst carrier can be formed into a sphere, a cylindrical porous cylinder, a trilobal, a ring, a torus or a chain, preferably a rib chain or a star bond. . 17 201026387 According to another preferred embodiment of the catalyst of the present invention, the size of the catalyst carrier is specified to be at most 1 mm to 25 mm', preferably 3 mm to μ mm. According to another preferred embodiment of the catalyst of the present invention, the catalyst carrier is defined to be formed into a sphere. According to another preferred embodiment of the catalyst of the present invention, the diameter of the sphere is specified to be 2 mm to 10 mm, and the diameter is preferably 4 mm to 8 mm. According to another preferred embodiment of the catalyst of the present invention, the catalyst carrier is modified to have at least one metal oxide selected from the group consisting of Hf, Ding, Si,

The group of La, Nb, Ta, W, Mg, Re, Y and Fe is preferably doped with ❹Hf〇2. The activity of the catalyst of the present invention may increase due to doping. It is especially preferred that the catalyst carrier is doped with HfOy and/or Zr〇2 doped with γ2〇3,

La2〇3 and/or Si〇2. The Zr〇2 doping makes the acetic acid resistance of Zr02 relatively high. Doping Hf〇2 increases the activity of the catalyst of the present invention. According to an alternative embodiment, it is specified that Zr〇2 contained in the catalyst carrier does not contain a matrix oxide which stabilizes the tetragonal phase of Zr〇2, preferably not containing La2〇3,

Si〇2 and Y2〇3. The tetragonal Zr〇2 in the carrier may be stabilized without corresponding doping.另一 Another preferred embodiment of the catalyst according to the invention 'specifies that the proportion of doped oxide in the catalyst carrier is between 重量·i% by weight and 20% by weight, preferably 1 weight, relative to the weight of the catalyst carrier. 〇/. It is up to 1% by weight, and preferably 3% by weight to 8% by weight. Doping can be carried out, for example, by surface doping (such as is known in the art), or the metal oxide can be incorporated into the matrix of the catalyst carrier. According to another preferred embodiment, it is provided that the water absorption of the catalyst carrier is calculated to be 40% to 75%, preferably 50% 18 201026387 ^ 7 〇 ° / °, based on the weight increase due to water absorption. The water absorption was determined by soaking 10 g of the carrier sample in deionized water for 3 minutes until no more bubbles escaped from the carrier sample. The excess water was then decanted and the soaked sample was blotted with a cotton towel to remove the adhering moisture from the sample. Then weigh the water carrier... seven core carriers, and calculate the water absorption rate as follows: (the amount after the effluent (g) - the amount before the water (g)) xl 〇 = the water absorption rate (%) 壳 according to the present invention shell Another preferred embodiment of the layer catalyst, wherein the thickness of the shell layer is 30 to 5 m, preferably 5 G "m to · heart, preferably 75 em to l5 〇 em. It has been found that within the above range The acetic acid-thin vinegar of the layer catalyst of the present invention has a relatively high selectivity, and the activity of the catalyst is relatively high. The thickness of the shell layer can be measured, for example, using an optical microscope or by means of a coffee amount. The present invention further relates to a method In detail, the method for preparing the shell catalyst of the present invention _,. The method 9 includes: Q a fluidized bed for generating a catalyst carrier by means of a gas, wherein the catalyst carrier is in an elliptical or circular orbit in the fluidized bed Trace movement; - a catalyst carrier sprayed in an elliptical or circular path in a fluidized bed with a first solution in which a Pd precursor is dissolved; 'spraying in a fluidized bed with a second solution in which an Au precursor is dissolved A catalyst carrier that moves in a circular or circular trajectory. It has been confirmed that 'the method according to the present invention is prepared. The shell catalyst may have a relatively thin shell layer and a relatively uniform thickness and a relatively uniform precious metal distribution, which allows the catalyst to have a relatively high acetic acid dilute vinegar selectivity. 19 201026387 The method of the present invention is by medium The carrier is in the shape of an ellipse or a ring: the crucible is in the fluidized bed 'touch μ m ψ mm ^ ' , or in other words, the catalyst carrier is == ring-shaped helium ring. To illustrate how the catalyst carrier is in the "oval" Circulation (一一_)" 〇 and: Axis: The large catalyst carrier moves in a fluidized bed in a vertical plane with a long axis and a very small elliptical trajectory. In the case of "circular loop to^cndal clrcuiati〇n)", the catalyst carrier changes in the fluidized bed in the straight plane by the size of the major axis and the minor axis, and the variation in the radius of the radius is minimal. The circular trajectory moves. On average, 'in the case of the "elliptical cycle", the catalyst carrier moves in a circular trajectory in a vertical plane. In the case of a "circular loop", it moves in a circular trajectory, that is, the catalyst carrier is covered. A ring-shaped surface having a torus with a vertical elliptical cross section. In the prior art, the particles in the bed are transformed into a state in which the particles can move completely freely (fluidized bed) is called a 1 〇〇sening p〇int (incipient fluidization point) and corresponding The fluidization speed is called the loose speed (l〇osening vel〇city). According to the present invention, it is preferred that the fluidization rate (gas) in the method of the present invention is four times the loose speed, preferably three times the loose speed, and more preferably two times the loose speed. Instead of a specific example according to one of the methods of the present invention, it is possible to specify that the fluidization speed is up to 4 times the usual logarithm of the loose speed, preferably 1.3 times the common logarithm of the loose speed, and more preferably the common logarithm of the loose speed. Unlike when operating in a conventional fluidized bed, the combination of a sprayed catalyst carrier and a fluidized-bed-like elliptical or toroidal cyclical movement 20 201026387 should be in the individual contact body. Pass through the nozzle at approximately the same frequency. In addition, the cyclic process also causes the individual catalyst carriers to rotate about their own axis, whereby the catalyst carrier is particularly uniformly immersed in the solution. ❹ In the process of the present invention, a catalyst carrier which is first sprayed in a fluidized bed in an elliptical or circular trajectory with a first solution containing a Pd precursor is subsequently sprayed: followed by spraying with a second solution containing the Au precursor. Alternatively, the catalyst carrier can be first sprayed with the second solution and subsequently sprayed with the first solution. Alternatively, it may be provided to use both the first solution and the second solution to support the carrier, for example by means of two single product nozzles or by means of a dual product nozzle. According to the invention, it is especially preferred to first spray the catalyst carrier with the first solution and subsequently with the second solution nozzle. In the method of the present invention, the catalyst carrier is circular or annular in the fluidized bed. However, it is preferred that the catalyst carrier be moved in the fluidized bed. Difficult Tracks In another preferred embodiment, the method of the present invention further comprises - drying the catalyst carrier sprayed through the first solution and/or the second solution. Within the scope of the method of the invention, the catalyst carrier impregnated with the solution is preferably continuously dried by means of a gas-generating fluidized bed, whereby a relatively thin shell layer can be obtained in a simple manner in terms of process engineering. It is specified that a separate step is carried out after sneezing and accompanied by continuous drying or no drying. For example, in the first case, the drying speed can be set according to the μ degree of the gas or the catalyst carrier, and thus the thickness of the shell layer, for example, can be used by those skilled in the art. Any drying method = dry 0 21 201026387 According to the invention, the preferred drying temperature is between 20 ° C and 2 ° C, preferably between 4 ° C and 150 ° C, and particularly preferably 7 Hey. 12; and 12 (TC, wherein drying can be carried out in normal pressure and vacuum. Drying can be carried out in air and inert gas. According to another preferred embodiment, the method of the present invention further comprises - spraying The catalyst carrier sprayed through the first solution and/or the second solution is calcined at a temperature at which the metal component of the metal precursor on the catalyst carrier is converted into an oxide form. As a result of the stewing, first, Pd, The Au or pd and Au components are fixed to the catalyst carrier, and secondly, the metals can be relatively easily converted from the oxide form to the metal state. Within the scope of the present invention, the temperature range in which the calcination is carried out can be, for example, 2〇〇C to i〇〇〇°c, the temperature range is preferably 3〇(rc to 8〇〇t>c, and the temperature range is more preferably 350. (: to 750. (:, and the temperature range is particularly preferably 4〇〇〇c to 5〇〇〇c. The calcination duration is usually in the range of 1 minute to 48 hours, preferably in the range of 30 minutes to 12 hours, and more preferably in the range of i hours to 7 hours, wherein forging The duration of the burning is particularly preferably from 2 hours to 5 hours. ❹ According to the invention, if the metal precursor ( For example, a metal which is decomposed into a zero oxidation state due to amoreduction is preferably calcined with a catalyst carrier sprayed by a metal precursor under a helium gas, thereby eliminating an independent reduction step. The shielding gas is particularly preferably a gas selected from the group consisting of a rare gas, c〇2, disordered gas, and a mixture of two or more of the above gases. The protective gas means a gas or gas mixture which can be used as an inert protective atmosphere 22 201026387 For example, in order to avoid unwanted chemical reactions, the protective gas may especially be a noble gas helium, neon, argon, helium or gas or a mixture of two or more of the above gases, Argon gas is particularly preferred as the shielding gas. In addition to the rare gas, it is also possible to use or additionally use, for example, nitrogen as a shielding gas. The protective gas atmosphere according to the method of the present invention preferably contains a rare gas argon gas and nitrogen gas. In an example, the method of the present invention further comprises converting the Pd component of the Pd precursor and the Au component of the Au precursor to an oxime oxidation state. Preferably, the metal component of the metal precursor is preferably converted to the 0 oxidation state by means of a reducing agent. 'It is preferred to use a gaseous or vaporizable reducing agent such as ruthenium 2, CO, ruthenium, formaldehyde, methanol and hydrocarbons, wherein the gaseous state The reducing agent may also be diluted with an inert gas such as carbon monoxide, nitrogen or argon. It is preferred to use a reducing agent diluted with an inert gas - followed by a mixture of hydrogen and nitrogen or gas; a hydrogen content of 0 is preferred. Between 1 vol.% and 50 vol.%. The amount of reducing agent is preferably selected so as to pass through the catalyst during processing; the equivalent of the metal is completely converted. However, it is preferred to pass through the catalyst. Excess reducing agent to ensure rapid and complete conversion. It is preferred to convert the metal to a ruthenium oxidation state under pressureless (i.e., at an absolute pressure of about 1 bar). For the preparation of industrial quantities of catalyst, a rotary tube oven or a fluidized bed reactor is preferably used to ensure uniform reduction. According to the invention, it is preferred to convert the metal to a oxidation state of from 0 〇〇〇C to 45 (at the temperature of rc. 23 201026387 In principle, any metal known to the person skilled in the art to be suitable for the purpose of the invention may be used. The temperature is converted to the ruthenium oxidation state. Within the scope of the present invention, the temperature at which the metal can be converted to the ruthenium oxidation state is 1 〇 (rc to 5 〇〇. 〇, the temperature range is preferably 150 t to 450 ° C, and The temperature range is preferably 2 〇 (rc to 400 〇 C. Pd and can also be applied in situ (in the process reactor) or externally (exsUu) (ie in a special reduction reactor). Au is converted to the ruthenium oxidation state. The external conversion can be, for example, a nitrogen mixture of 5 v 〇 1% hydrogen (for example by means of a mixed gas), preferably 15 〇. 〇 to 4 〇〇t> It is preferably carried out at a temperature of 5 hours. It is preferred to convert Pd and Au into an oxime oxidation state by a wet chemical route (for example by means of an aqueous solution of an alkali metal hypophosphite). Another preferred method according to the invention In a specific example, the first solution is defined as the same solution as the first solution. ^ Right in the method of the present invention The catalyst carrier is sprayed with a cold liquid in which both the Pd precursor and the Au" body are dissolved, and the precursor can be applied to the carrier in a particularly simple manner in terms of process engineering. ❹ According to another preferred embodiment of the method of the present invention, The Pd precursor is defined as Pd(NH3)4(〇H)2. In principle, the 'Pd precursor may be any Pd-containing material known to those skilled in the art to be suitable for the purpose of the present invention. According to the present invention, preferred pd The precursor system is selected from the group consisting of Pd(NH3)4(〇H)2, Pd(NH3)4(OAc)2, 2PdCl4 Pd(NH3)4(HC〇3)2, Pd(NH3)4(HP04 ), Pd(NH3)4Cl2, tetraamine oxalate ° (Π), oxalic acid, Pd(N03)2, Pd(NH3)4(N〇3)2, 24 201026387 K2Pd(OAc)2(〇H)2 , Na2Pd(OAc)2(OH)2, Pd(NH3)2(N02)2, K2Pd(N02)4, Na2Pd(N02)4, Pd(OAc)2, K2PdCl4, (NH4)2Pd Cl4, PdCl2 and Na2PdCl4 Among them, Pd(NH3)4(OH)2 is particularly preferred. In addition to NH3, it is also possible to use the corresponding wrong salt with ethylenediamine or ethanolamine as a ligand. In addition to Pd(OAc)2, other palladium may be used. a carboxylate, preferably a salt of an aliphatic monocarboxylic acid having 3 to 5 carbon atoms, such as propionate or butyl According to another preferred embodiment of the method of the present invention, a palladium nitrite precursor may also be preferred. Preferably, the palladium nitrite precursor is obtained, for example, by dissolving Pd(OAc) 2 in a NaNO 2 solution. By. According to another preferred embodiment of the method of the present invention, the Au precursor is defined as KAu〇2. In principle, the Au precursor can be any Au-containing material known to those skilled in the art for the purposes of the present invention. According to the present invention, the preferred Au precursor system is selected from the group consisting of KAu02, HAuC14, KAu(NQ2)4, AuC13., KAuC14, NaAuCl4, KAuC14, KAu(OAc)3(OH), HAu(N03)4, ® NaAu〇2, NMe4Au〇2, RbAu〇2, CsAu02, NaAu(OAc)3(OH), RbAu(OAc)3OH, CsAu(OAc)3OH, NMe4Au(OAc)3OH and Au(OAc)3, of which KAu02 Especially good. In each case, it is preferable to prepare Au(OAc)3 freshly by precipitating oxide/hydroxide from a gold acid solution, washing and separating the precipitate, and dissolving the latter in acetic acid or KOH, respectively. Or KAu〇2. According to another preferred embodiment of the method of the present invention, the first solution and the second solution are defined as aqueous solutions. 25 201026387 A pure solvent or solvent mixture of the selected precursor which is soluble therein and which can be easily removed from the catalyst carrier by application to the dry and then self-catalytic carrier is suitable as a solvent for the precursor. The preferred solvent for the metal acetate as the precursor is, for example, acetone or an unsubstituted carboxylic acid, especially acetic acid, and the preferred solvent for the metal hydride is water or dilute hydrochloric acid. If the precursor is not sufficiently soluble in a pure solvent such as acetamidine acetic acid, water or dilute hydrochloric acid or a mixture thereof, other solvents or solvent additives may be used instead of or in addition to the solvent. In a particularly preferred embodiment, the process of the invention is carried out using a device set up to generate a fluidized bed of cerium particulate matter by means of a gas, wherein the particles of the material move in a fluidized bed in a sugar circular or circular trajectory. Such devices are described, for example, in WO 2006/027009 DE DE 102 48 116 Β 3, 〇 〇 370 167 A1. ΕΡ 0 436 787 B1 ^ DE 199 04 147 A1 ^ DE 20 2005 791 U1, the contents of which are incorporated by reference. Into the present invention. The device according to the invention is preferably named by jnn〇jet Technologies

Innojet® Ventilus or Innojet® AirCoater for sale. The package includes a cylindrical container, the bottom of which is fixedly mounted, and a nozzle is mounted in the center of the bottom. The bottom is formed by an annular plate that is progressively raised from each other to form a process that eccentrically flows between the individual plates in the container at an eccentrically level 1 outwardly toward the container wall. The so-called entrained flow bed is formed to 'the carrier carrier on the gas flow bed is first transported outward toward the container wall. The vertically oriented process air stream that deflects the catalyst carrier upwardly deflects outwardly along the vessel wall. Upon reaching the top, the catalyst carrier moves back toward the center of the bottom in a generally tangential manner, during which it passes through the nozzle spray. After the 26 201026387 spray, the moving process resumes. The direction of the process air provides the basis for a substantially homogeneous annular fluidized bed-like cyclic movement of the catalyst support. In another preferred embodiment, device 2 has an offset 180. a nozzle connected to the inner ring (circular-segment nozzle), wherein the inner ring separates the two fluidized beds in an annular circulation from each other. This preferred embodiment enables, for example, separate feeding of the solution (eg Au solution and pd solution)' allows Pd and Au to be simultaneously coated from separate stock solutions.

A catalytic carrier fluidized bed for producing a catalyst carrier in an elliptical or toroidal cycle in a manner that is simple and therefore inexpensive in terms of process engineering. According to another preferred embodiment of the method of the invention, the device comprises a bottom and a side wall. Processing the chamber to a horizontally moving component in which the gas is radially outwardly directed through the bottom of the processing chamber into the processing chamber to produce a catalyst carrier fluidized bed, wherein the bottom of the processing chamber is preferably comprised of a plurality of each other An overlapping annular guide plate that is stacked one on top of the other and that forms an annular gap therebetween is constructed. Since the gas is fed into the processing chamber with a horizontally moving component of the radially outwardly gripping column, the catalyst carrier is caused to circulate in an elliptical shape in the fluidized bed. If the structure is intended to be in a circular loop in the fluidized bed, then the catalyst carrier must also undergo another circumferentially moving component to force the carrier to move in a circular trajectory. Thus, the method of the present invention comprises subjecting a gas fed into a processing chamber to a characteristic of a circumferential flow component. The catalyst carrier is subjected to a circumferentially moving component by attaching a suitable S-arranged rail to the sidewall to deflect the catalyst carrier. Thus, in accordance with a preferred embodiment of the method of the present invention, it is provided that the gas fed into the processing chamber is subjected to a circumferential flow component. This ensures that it is simple in terms of process engineering. 27 201026387 A fluidized bed in which the catalyst carrier is in a toroidal circulation. In order to subject the gas fed into the processing chamber to a circumferential flow component, in accordance with another preferred embodiment of the method of the present invention, it may be provided to position suitably shaped and aligned gas guiding elements between the annular guide plates. As an alternative or in addition, it may be provided that the gas fed into the processing chamber is subjected to a circumferential flow component, which is fed into the processing chamber through the bottom of the processing chamber by moving the additional gas in a diagonally upwardly directed moving component. Preferably, it is in the sidewall region of the processing chamber.

It may be provided that the carrier circulating in the fluidized bed is used by means of an annular gap nozzle of a spray cioud (surface _ _ s): liquid irrigating, the symmetry plane of the spray cloud in the raft is parallel to the plane of the bottom of the device or It flows out in parallel. Due to the spray cloud. On the circumference, the catalyst carrier moving downward in the middle can be squirted with a solution in a particularly uniform manner. The annular gap nozzle (i.e., its spout) is preferably completely embedded in the fluidized bed.

According to another preferred embodiment of the method of the invention, the inter-annular β is defined: the mouth is placed in the middle of the bottom of the container, and the nozzle of the annular gap nozzle is embedded in the bed. Thereby ensuring that the distance of the spray cloud droplets before the collision with the catalyst carrier is relatively short' and correspondingly the droplets coalesce into larger droplets, leaving less time, larger droplets hinder the formation of the basic The upper layer - the shell layer month according to another preferred embodiment of the method of the present invention, can be specified in the spray, the surface produces chaotic support 纠 (纠8 Qing. " (3) also (10)). The bottom crucible retaining liquid does not contain a spray solution, which means that almost all sprays dissolve into the k-bed, so that the spray has almost no loss. According to another preferred embodiment of the process of the invention, the gas system for producing a fluidized bed of 28 201026387 is selected from the group consisting of air, oxygen, nitrogen and a rare gas and a mixture of the above gases. According to another embodiment of the method of the present invention, the temperature at which the catalyst carrier is sprayed with the first solution and/or the second solution is 5 (TC to 12 ° C, preferably 55) (: to 90). (: and the temperature is preferably 6 (TC to 80 ° C. In order to prevent the spray cloud droplets from drying in advance, it may be specified that the gas passes through the first solution, the second solution or the first solution and the second solution before being fed into the device) Dissolve

The agent enrichment is preferably in the range of from 1% to 50% saturated vapor pressure (at process temperature). The solvent added to the gas can be separated from the gas by means of a suitable cooling unit, condenser and separator, and the solvent formed by drying the catalyst carrier' and pumped back to the enricher by means of a pump. The invention further relates to a shell catalyst of the invention which is obtainable by means of the method of the invention. The invention further relates to the use of the shell catalyst of the present invention or the gambling layer catalyst which can be obtained by means of the method of the present invention. To illustrate the invention, the preferred embodiment of the method of the invention is described below in conjunction with the drawings and describes the movement trajectory of the catalyst carrier.

The apparatus for carrying out the method of the invention is shown in FIG. 1A as having a container 20 having a container 20 having a vertical cylindrical side wall surrounding the processing chamber 15 . The processing chamber 15 has a bottom 16 and a bottom 16 Below the bottom Qiu is the blowing chamber 30 〇 low division 16 consists of a total of seven as the guiding aligning plate of each other up and down # annular plate 29 201026387. The seven annular plates are stacked one on another, stacked in such a way that the outermost annular plate 25 forms the lowest annular plate on which the other six inner annular plates are placed, each portion overlapping one of the lower ones. For the sake of clarity, only a portion of the total of seven annular plates are numbered with reference numerals, such as two heavy annular plates 26 and 27. Due to this overlap and spacing, in each of the It cases, an annular gap 28 is formed between the two annular plates, and the process air 40 is moved through the slit 28 into a gas passing through the bottom portion 16 in a predominantly horizontally arranged moving component.

The Q-annular gap nozzle 50 is inserted into the central opening of the central highest inner annular plate 29 from below. The annular gap nozzle 5 () has a spout 55, a spout 55 and a total of three orifice gaps 52, 53 & All three orifice gaps 1 W and 54 are arranged to smear substantially parallel to the bottom 16 (and therefore substantially horizontal), covering 36 inches. The angle. Alternatively, the nozzle can be designed such that the spray flows out obliquely. The spray air is forced out as a spray gas, and the solution to be sprayed through the upper gap W and the lower gap 54 is pressed out through the center gap μ. a annular gap nozzle 50 has a rod-shaped body 56 with a rod-shaped body extending downwardly with a respective passageway known per se and thus not shown in the drawings and a feed annular gap nozzle 5 can be formed, for example, with a so-called rotation The walls of the channel of the annular two-out solution are rotated relative to each other to avoid nozzle plugs, so that I is sufficient for the entire 36 turns. Within the range, the gap is uniformly ejected. The annular gap nozzle 50 has a tapered head 5 above the orifice gap 52 and is a truncated wall 58 having a plurality of small holes 59 in the region below the orifice gap 54. As can be seen in Figure 1B, the bottom surface of the frustoconical wall 58 rests on the innermost annular plate 29 such that a narrow surface is formed between the bottom surface of the frustoconical wall 58 and the annular plate 29 located at 30 201026387 and partially overlapping therewith. The slit 60, the treatment void 40, can pass through the slit 60. The outer ring 25 is spaced from the wall 18 such that the process air 40 can enter the process chamber 15 in the direction of the arrow indicated by reference numeral 61 in a predominantly vertical component, thereby imparting access to the process chamber is through the slot 28 Processing null = 40 is a component that is arranged relatively steeply upwards. t rolling 右 The right half of Fig. 1A shows the relationship formed in the device 10 after entering. The solution spray cloud 7 流出 which is horizontally mirrored substantially parallel to the bottom surface is ejected from the gap 53. The air passing through the small holes 59 in the tapered wall 58 is formed as a treatment air = 40 on the bottom surface of the spray cloud 7 (). The process air 40 passes through a plurality of slits 28 to form a radial flow in the direction of the wall 18 (which is thereby deflected upwardly), as indicated by reference numeral 74: head. The catalyst carrier is deflected by the arrow in the region of the wall 18. , rational air 4. And the catalyst carrier to be treated with each other: 22 理 ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ Go down. The catalyst of the falling load was sent to the spray emperor on the 70th, and the work was carried out at 57. .... The top of the dragon was treated with the spray medium. The sprays are moved because they are far apart from each other in the process because the annular space is available after the spray cloud 70 has left. In the region of the spray cloud 70, there is a larger solution to the spray and moved toward the wall 18, and the heated process air 4 均 is = this: dry). Ground processing (ie dry 31 201026387 Figure 2A shows two possible movement trajectories of the catalyst carrier indicated by reference numerals 21 〇 and 22 不 not by two elliptical cycles. The elliptical movement trajectory 210 shows The ideal elliptical trajectory changes relatively larger than the major axis and the minor axis. On the other hand, as seen from Fig. 2b, the circular trajectory 220 shows that the major axis and the minor axis vary relatively little in size and the description is close to no circumference. The ideal elliptical trajectory of the (horizontal) moving component. The shape of the curve indicated by reference numeral 31 图 in Fig. 3A shows the possible movement trajectory of the catalyst carrier in a circular loop. The circular movement trace 31 〇 describes the almost uniform torus The cross section of the surface has a vertical cross section of a heart-shaped cross section and a horizontal cross section of a ring shape. Fig. 3B shows a plan view of the movement locus 31. The following examples are intended to illustrate the invention. Embodiments 1 and 2: 'will be 500.0 g with a main component of montmorillonite as a layered citrate acid treated dry powdery bentonite (acid-activated bentonite) and equivalent to 61 875 g Zr〇2 (implementation = 1) or equivalent to 132 g Zr〇 2 (Example 2) The amount of commercially available Zr(〇H)4 (seven. The value is about 1 " m, the d5〇 value is about 5 " m and d9. The value is 7 β m ) and 1 习g conventional organic binder, pore former mixing. Water is added to the obtained mixture, and processed into a dough by means of a mixer, which is pressed into a spherical body by means of a tablet machine (d = 5 mm) For hardening, the spheres were dried and calcined at a temperature of 650 ° C for 5 hours. After calcination, the shaped bodies were treated with 20% hydrochloric acid for 3 hours, washed with a large amount of water and calcined at 6 ° C for 5 hours. The shaped body has the characteristics listed in Table 丨 (Example i) or Table 2 (Example 2): 32 201026387 ❹ Table geometry diameter Moisture content Compressive strength Bulk density Water absorption specific surface area (BET) Si02 content Zr 〇 2 content Zr02 yield ratio of tetragonal Zr〇2 (determined according to XRD diffraction pattern) ai2o3 content, 7Π 〇〇✓ ^ ^ - 1000 ° C loss on ignition, acidity overall pore volume ', Zr release, average pore diameter (according to BJH) (4V/A) Microporosity as a percentage of the total pore volume, diameter The pores of 2.0 nm to 6 nm account for the proportion of the total pore volume. The diameter of the pores larger than 6.0 nm to 50 nm accounts for the total pore volume. You 丨—————————______ The pores with a diameter of 2.0 nm to 5 〇nm occupy the whole pore. The ratio of the volume is 84.5% The average particle size of Zr〇2 "(determined according to the EDX diagram) 20 μ m 33 201026387 Table 2: Geometric shape ~~~~- Broken diameter - ^ mm Moisture content 6 XXU.11 〇4* weight % Compressive strength ~~~~~·_ 33 N Bulk density 580 ε/1 Water absorption 67 1% Specific surface area (BET) ' 132 m2/g Si02 content~- 69.5% by weight Zr02 Content ~~~~~~- 24 5 #-§·% Zr〇2 yield 99% ratio of tetragonal Zr〇2 - > 90% by weight (determined according to XRD diffraction pattern) Al2〇3 content ------- 1 8 wt% 1000 Loss of ignition at °C - 16% by weight Acidity ~~- // val Overall pore volume ' 〇A τπ1/ρ Zr Release ~~-- I1XX/ ^ 0 001% by weight Average pore diameter (according to BJHU4V/A, ~ - 110 nm microporosity as a whole pore volume ratio 丨~~ < 1% diameter 2.0 nm to 6 nm pores account for the total pore volume plus 13.6% from 6.0 nm to 50 nm Examples of pores occupying the entire pore volume 71.7% The pores directly controlled by 2.0 nm to 50 nm account for the fk of the whole pore volume 丨 LgEgg^·The average particle size d50 (determined according to the EDX diagram) _____-----

34 201026387 Example 3: In the "Innojet® Aircoater 25" fluidized bed reactor of Innojet Technologies, Steinen, Germany, 7 〇g of Example 1 was controlled by means of air controlled at 90 ° C. The catalyst carrier is converted to a fluidized bed state in which the catalyst carrier is in a toroidal cycle. Once the temperature of the catalyst carrier has been controlled at 9 (TC), it is sprayed with a solution prepared from 150 ml of water and 11.35 g of 8.82% Pd(NH3)4(OH)2 solution (relative to pd 4.5%). The catalyst carrier of the toroidal cycle 〇·5 hours. Once the solution has been sprayed onto the carrier, the loaded catalyst carrier is calcined in air at a temperature of 350 ° C for 2 hours. Once the catalyst carrier has been calcined, it is again In the device, the air is controlled to a fluidized bed state by means of air controlled at 90 C. In this state, the catalyst carrier is in a circular loop. Once the temperature of the catalyst carrier has been controlled at 9 (c) The solution prepared by 150 ml of water and 4·4 g of 8.44% KAu02 solution (relative to Au 6.2%) was sprayed in a circular circulation for 5 hours. To reduce the precious metal component, the catalyst carrier was at 20 (The mixture was exposed to 5 vol.% of hydrogen in nitrogen at a temperature of rc for 5 hours. After reduction, the catalyst carrier was impregnated with an aqueous solution of potassium acetate by means of "incipient wetness", followed by a nitrogen atmosphere. Drying at 12 〇 1 / m·degree for 1 hour. The ratio of the resulting shell catalyst is 2.6 wt% (calculated from the amount of potassium acetate used). The theoretical loading of Pd of the carrier is 〇·73% by weight, and the experimental loading of Au is 39 weight of 〇66% by weight, and Au is 〇36% by weight (by induction Coupling plasma (ICP); Au/Pd atomic ratio: 〇29). 35 201026387 Layer thickness is 124^111 (average value). In a fixed-bed tubular reactor at 153 °C at 10 bar, Exposing 38 catalyst spheres to 55 〇mL/mirl by 15 v〇1 % H〇Ae, 6 v〇l.% Or 39 vol.% under the action of an inlet stream consisting of Na' The output of the reactor was analyzed by means of gas chromatography. The calculation was carried out according to the equation S(C2H4)=moles of acetate (/the number of moles of vinyl acetate + the number of moles of C〇2/2) Sex (the selectivity of ethylene to vinyl acetate). Space-time yield is expressed in grams of acetate per liter of catalyst per hour. Calculate oxygen conversion according to the following formula: (input ❹ 〇 2 The molar number - the number of moles of the output 〇 2) / the number of moles of the input 〇 2. The catalyst of the present invention shows a selectivity S (C2H4) of 91 · 〇 %, and conversion of oxygen at 64.0% Next, the space time yield (determined by gas chromatography) is 922 g of acetate per liter of catalyst per hour. 'Example 4: "jnn〇jet@ Aircoater 25" type flow at Innojet Technologies, Stanley, Germany In the chemical bed reactor, 70 g of the catalyst carrier of Example 2 was converted into a fluidized bed state by means of temperature control at a temperature of 9 (in the air), and in this state, the catalyst carrier was in a circular circulation. Once the temperature of the catalyst carrier has been controlled at 90, it is sprayed with a solution prepared from 15 〇ml water and 3.5 8g 8.823⁄4 Pd(NH3)4(〇H)2 solution (relative to pd 4.5%). The catalytic carrier of the cycle was 〇. 5 hours. Once the solution has been sprayed onto the support, the loaded catalyst carrier is calcined in air at a temperature of 35 (rc) for 2 hours. Once the catalyst carrier has been calcined, it is again in the device by means of temperature control 36 201026387 The air at 90 ° C converts it into a fluidized bed state in which the catalyst carrier circulates in a loop. Once the temperature of the catalyst carrier has been controlled at 9 〇 <>c, it is used by 150 mi. The solution prepared by water and 3 84g of 8 44〇/〇kau02 solution (6.2% relative to Au) was sprayed in a ring-shaped catalyst carrier for 5 hours. To reduce the precious metal component, the catalyst carrier was at 2 〇 (rc) At room temperature, the mixture was exposed to 5 vol.% of hydrogen in nitrogen for 5 hours. After reduction, the catalyst carrier was impregnated with an aqueous solution of potassium acetate by means of "incipient wetness" followed by a nitrogen atmosphere at 12 °c. When drying at 1 °, the ratio of potassium in the obtained shell catalyst is 2.6 wt% (calculated from the amount of potassium acetate used). The theoretical loading of Pd of the carrier is 0.23 wt%, and Au is 〇34 wt. /〇' Pd experimental loading is 〇· 21% by weight, and Au is 〇. 3 1 weight /〇- (by means of (ICP); Au/Pd atomic ratio: 0.8). Shell thickness is 130 "m (average). In fixed bed tubular reactor at 14_7,6_. (: at temperature Under iqba, 暴露 Exposure of 38 catalyst spheres to 550 mL/min by 15 vol.% H〇Ac, 6 v〇l·% 〇2, 39 vol·% CsH4 in N2 Underneath and analyze the output of the reactor by means of gas chromatography. The catalyst of the invention shows a selectivity of SCCzH4) of 95.7%, and at an oxygen conversion of 28 5 Å, the space-time yield (by gas) Phase tomographic determination) 408 g of acetate per liter of catalyst per hour. [Schematic description of the drawings] Figure 1A: longitudinal section of a preferred apparatus for carrying out the method of the invention; 37 201026387 Figure 1B: numbering in Figure 1A Figure 2A is a perspective sectional view of a preferred apparatus, schematically showing the movement trajectory of two catalyst carriers in a sugar circular cycle; Figure 2B: Preferred device and movement trajectory according to Figure 2A Figure 3A is a perspective sectional view of a preferred apparatus, schematically showing the movement trajectory of the catalytic carrier in the form of a loop; Figure 3B: Figure 3A is a plan view of the preferred apparatus and movement trajectory. [Main component symbol description] 10 Apparatus 15 Processing chamber 16 Bottom 18 Vertical cylindrical side wall 20 Container 25 Outermost annular plate 26 Overlap annular plate 27 Overlap annular plate 28 Ring Slot 29 central highest inner annular plate 30 blowing chamber 40 processing air 50 annular gap nozzle 52 orifice gap 53 orifice gap

38 201026387 54 orifice gap 55 spout 56 rod body 57 conical head 58 frustoconical wall 59 small hole 60 slit 70 spray cloud

72 Support air flow 210 Elliptical movement track 220 Elliptical movement trace 310 Circular movement track

39

Claims (1)

201026387 VII. Patent application scope: 1. A shell catalyst comprising a catalyst carrier containing Zr〇2 and a shell layer containing Pd and Au, wherein the Au/pd atomic ratio of the shell catalyst is 〇2 To 1.2, characterized in that the ratio of pd in the shell catalyst is less than/equal to the weight % of ruthenium. 〇2. The shell catalyst of the third aspect of the patent application is characterized by the proportion of Pd in the shell catalyst. It is from 7.55% by weight to 〇15% by weight. 3. The shell layer catalyst according to any one of the preceding claims, wherein the shell layer catalyst has an Au/Pd atomic ratio of from 0.3 to 4. The shell layer according to any one of the preceding claims. The catalyst is characterized in that at least 50% by weight of Zr〇2 contained in the catalyst carrier is present in a tetragonal modification. A shell catalyst according to any one of the preceding claims, characterized in that the Zr〇2 system is present in the form of particles. 6. A shell catalyst according to any one of the claims, characterized in that the Zr〇2 is contained in the catalyst carrier in a uniformly distributed manner. 7. The shell catalyst according to any one of the preceding claims, wherein the ratio of Zr 〇 2 in the catalyst carrier is from 1% by weight to 30% by weight. A shell catalyst according to any one of the preceding claims, characterized in that the catalyst carrier comprises a natural layered niobate. 9. A shell catalyst according to any one of the claims, characterized in that the natural layered niobate is an acid activated layered niobate. 10. The shell catalyst according to Item 8 or Item 9 of the patent application, characterized in that the proportion of the natural layered tantalate in the catalyst carrier is at least 50% by weight 〇201026387 11 · as claimed The shell catalyst according to any one of the items 8 to 1, wherein the natural layered niobate contained in the catalyst carrier has a Si〇2 content of at least 65% by weight. 12. The shell catalyst of any one of clauses 8 to 5, wherein the natural layered niobate contained in the carrier contains less than 5% by weight of Al2〇3. 13. The shell catalyst of any of the preceding claims, wherein the catalyst carrier has an acidity of 115 Å #val/g. The shell catalyst according to any one of the preceding claims, wherein the catalyst carrier has an average pore diameter of from 8 μm to 30 nm. The shell catalyst according to any one of the preceding claims, wherein the catalyst carrier has a specific surface area of less than or equal to 18 〇 m 2 /g. The shell catalyst according to any one of the preceding claims, wherein the catalyst carrier has a specific surface area of from 18 〇 m 2 /g to 6 〇 m 2 /g. 17. The shell catalyst of any of the preceding claims, wherein the catalyst carrier has a hardness greater than/equal to 55N. The shell catalyst according to any one of the preceding claims, wherein the catalyst carrier has an overall pore volume of from 〇25 ml/g to 〇.7 ml/g. A shell catalyst according to any one of the preceding claims, characterized in that the overall pore volume of the catalyst support is at least 80% formed by mesopores and large pores (rnacr〇p〇res). A shell catalyst according to any one of the preceding claims, wherein the catalyst carrier has a bulk density greater than 〇 3 g/ml. A shell catalyst according to any one of the preceding claims, characterized in that the catalyst carrier is formed into a shaped body. A shell catalyst according to any one of the preceding claims, characterized in that the catalyst carrier has a size of at most 1 mm to 25 mm. 23. The shell catalyst according to claim 21 or 22, wherein the catalyst carrier is a sphere. 24. The shell catalyst of claim 23, wherein the sphere has a diameter of from 2 mm to 1 mm. 25. The shell catalyst according to any one of the preceding claims, characterized in that the catalyst carrier is doped with at least one metal oxide selected from the group consisting of free Hf, Ti, Nb, Ta, W, Mg. , a group of Re, Y, and Fe. 26. The shell catalyst according to claim 25, wherein the ratio of the mixed oxide in the catalyst is from 1% by weight to 2% by weight 〇/0. 27. The shell catalyst of any of the preceding claims, wherein the shell layer has a thickness of from 30/^111 to 5 〇〇//111. A method of preparing a shell catalyst according to any one of claims 1 to 27, which comprises a fluidized bed of a catalyst carrier by means of a gas, wherein the catalysts are loaded Moving in an elliptical or circular trajectory in the fluidized bed; spraying the catalyst carrier moving in an elliptical or circular trajectory in the fluidized bed with a first solution in which the Pd precursor is dissolved; The catalyst carrier that moves the liquid in the fluidized bed in an elliptical or circular trajectory. 29. The method of claim 28, wherein the catalyst carriers move in a circular trajectory in the fluidized bed. The method of claim 28, wherein the method further comprises 'drying the catalyst loaded by the first solution and/or the second solution. 31. The method of claim 28 to 3, wherein the method further comprises converting the metal component of the metal precursor sprayed onto the catalyst carrier to an oxide form The catalyst carrier sprayed by the first solution and/or the second solution is calcined at a temperature. The method of any one of claims 28 to 31, wherein the method further comprises converting the Pd component of the Pd precursor and the Au component of the Au precursor to a 0 oxidation state. . The method of any one of claims 28 to 32, wherein the first solution and the second solution are the same solution. The method of any one of claims 28 to 33, wherein the Pd precursor is Pd(NH3)4(〇H)2. The method of any one of claims 28 to 34, wherein the Au precursor is KAu02. 36. The method of any one of claims 28 to 35, wherein the first solution and the second solution are aqueous solutions. 37. The method of any one of claims 28 to 36, wherein the method is carried out using a set (10) of a fluidized bed set up to produce particulate matter by means of a gas (cut), Wherein the substance 43 201026387 particles move in an elliptical or circular trajectory in the fluidized bed. 38. The method of claim 37, wherein the device (ίο) comprises a processing chamber (15) having a bottom portion (16) and a sidewall (18), wherein the gas (40) is radially outward Aligning the horizontal movement component through the processing chamber to the bottom (16) of the (15) feed into the processing chamber (15) to produce the catalyst carrier fluidized bed, wherein the bottom portion (16) is preferably comprised of a plurality of The overlapping annular guide plates (25, 26, 27, 29) which are stacked one on top of the other and which form an annular slit (28) are constructed. 39. The method of claim 38, wherein the gas (40) fed into the processing chamber (15) is subjected to a circumferential flow component. 40. The method of claim 39, characterized in that the feeding into the processing chamber (15) by means of a guiding element disposed between the annular guiding plates (25, 26, 27, 29) The gas (4 〇) is subjected to this circumferential flow component. - 41. The method of claim 39 or 40, wherein the additional gas (61) is moved through the bottom of the processing chamber (15) by moving the additional gas (61) in a diagonally upward direction (16) Feed into the processing chamber (15) q such that the gas (4〇) fed into the processing chamber (15) is subjected to the circumferential flow component. 42. The method of claim 38, wherein the method of moving in an elliptical or circular trajectory in the fluidized bed is carried out by means of an atomized spray cloud. The annular gap nozzle (50) of (70) is sprayed with the solution, wherein the spray cloud (7 〇) flows substantially parallel to the plane of the bottom (16). 44. The method of claim 42, wherein the annular gap nozzle (50) is disposed intermediate the bottom portion (16) and the orifice (55) of the annular gap nozzle (55) is wrapped Buried in the fluidized bed. 44. The method of claim 42 or claim 43, wherein the gas support pad (72) is produced on a bottom surface of the spray cloud (70). The method of any one of claims 28 to 44, wherein the gas (40) is selected from the group consisting of air, oxygen, nitrogen, and a rare gas and a mixture of the above gases. The method of any one of claims 28 to 45, wherein the catalyst carrier passes the first solution and/or the second solution at a temperature greater than/equal to 60 ° C. spray. The method of any one of claims 38 to 46, wherein the gas (40) passes through the first solution, the second solution before being fed into the processing chamber (15). Or the solvent of the first solution and the second solution is enriched. The shell catalyst according to any one of claims 1 to 27, which can be obtained by the method of any one of claims 28 to 47. A use of a shell catalyst as claimed in any one of claims 1 to 27, or as claimed in claim 48, for the preparation of an acetate. Eight, the pattern: (such as the next page) 45