EP2701838A1 - Basische katalysatorträgerkörper mit niedriger oberfläche - Google Patents

Basische katalysatorträgerkörper mit niedriger oberfläche

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Publication number
EP2701838A1
EP2701838A1 EP12723835.0A EP12723835A EP2701838A1 EP 2701838 A1 EP2701838 A1 EP 2701838A1 EP 12723835 A EP12723835 A EP 12723835A EP 2701838 A1 EP2701838 A1 EP 2701838A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
carrier body
catalyst carrier
metal
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12723835.0A
Other languages
German (de)
English (en)
French (fr)
Inventor
Alfred Hagemeyer
Gerhard Mestl
Andreas Pritzl
Peter Scheck
Peter Bauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant Produkte Deutschland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant Produkte Deutschland GmbH filed Critical Clariant Produkte Deutschland GmbH
Publication of EP2701838A1 publication Critical patent/EP2701838A1/de
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
    • C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds

Definitions

  • the present invention relates to a catalyst carrier body containing a SiC> 2-containing material and a metal selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals and mixtures thereof, wherein the total content of metal in the range of 0.5 to 10 wt. %, based on the total weight of the
  • Catalyst support In addition, the present invention relates to a catalyst comprising a novel
  • Catalyst support body and a catalytically active metal in particular palladium and / or gold.
  • the present invention also relates to a process for producing a catalyst support according to the invention, wherein a SiO 2 -containing material is treated with a metal-containing compound, dried and then calcined.
  • a further embodiment of the present invention is a process for preparing a catalyst according to the invention, wherein a catalyst support body according to the invention
  • Solution is applied with a precursor compound of a catalytically active metal.
  • treated carrier bodies are present and so in plants
  • Catalyst can be done. However, a reduction in the activity or selectivity of a catalyst bed can also be done by damage to the catalysts, which in the filling or when heated to high
  • Catalyst is blown off, the catalyst no longer has the desired surface finish, which is important to the desired functions of the catalyst
  • a known approach to increasing mechanical strength is based on improving the adhesion of the catalyst coating to the catalyst
  • properties of the catalyst coating are usually associated with high labor or material costs and may be accompanied by a deterioration of the catalytic properties of the catalyst coating. For one thing there is
  • Catalysts in which an additional coating is carried out on a catalyst support in which the catalytically active substances are.
  • the catalytically active Materials are not present in an additional coating on the catalyst carrier body, but are present directly in the form of a shell in a certain area of the surface of the catalyst carrier material itself.
  • Catalyst carrier itself a high mechanical
  • a catalyst carrier body which comprises both a SiO 2 -containing material and a metal, wherein the total content of metal in the range of 0.5 to 10 wt .-%, preferably in the range of 0.5 to 5 Wt%, more preferably in the range of 1 to 4 wt%, even more preferably in the range of 2 to 3.5 wt%, and most preferably in the range of 2.1 to 3.1 wt%. %, based on the total weight of the catalyst carrier body.
  • the metal is here preferably selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals and mixtures thereof.
  • catalyst carrier body is understood to mean a carrier body designed as a shaped body.
  • the catalyst carrier body can basically take the form of any geometric body on which a catalytically active substance can be applied. However, it is preferred if the catalyst carrier body as a ball, cylinder (also with rounded faces), hole cylinder (also with
  • Tetraiobus ring, donut, star, cartwheel, "inverse” cartwheel, or as a strand, preferably as Rippstrang or star train, is formed. Particularly preferred is the
  • Catalyst support body formed as a sphere or in spherical form or as a ring.
  • the diameter or the length and thickness of the catalyst support body according to the invention is preferably 2 to 9 mm, depending on the reactor geometry in which the catalyst is to be used. If the catalyst support body is in spherical form, it preferably has a diameter in the range of 3 to 8 mm, in particular 4 to 6 mm. Is that
  • Catalyst carrier body in the form of a ring it preferably has the following dimensions: (4-6) mm x (4-6) mm (1-4) mm (diameter x height x hole diameter).
  • rings with the following dimensions: 5.56 mm x 5.56 mm x 2.4 mm (diameter x height hole diameter).
  • the catalyst support body according to the invention has
  • the catalyst carrier body is in spherical form, it preferably has one
  • the catalyst support body is in the form of a ring, it preferably has an average
  • the pore diameters are determined by means of mercury porosimetry according to DIN 66133 at a maximum pressure of 2000 bar.
  • the catalyst support body according to the invention preferably has a total pore volume in the range from 280 to 550 mm 3 / g. If the catalyst carrier body is in spherical form, it preferably has a total pore volume in the
  • the catalyst carrier body is in the form of a ring, it preferably has a total pore volume in the range from 280 to 500 mm 3 / g, particularly preferably from 300 to 450 mm 3 / g.
  • the porosity of the catalyst support bodies is preferably in the range of 40 to 65%, more preferably in the range of 24 to 60%, and most preferably in the range of 45 to 58%.
  • Catalyst carrier body is preferably in the range of 0.8 to 1.2 g / cm 3 , more preferably in the range of 0.9 to 1.15 g / cm 3 and most preferably in the range of 1 to 1.1 g / cm 3 .
  • mercury density which is determined by mercury porosimetry.
  • Hg porosimetry provides a very reliable, precise and reproducible measure of
  • Catalyst support body is preferably in the range of 50 to 150 m 2 / g, more preferably in the range of 50 to 140 m 2 / g, and most preferably in the range of 60 to 130 m 2 / g.
  • the catalyst carrier body is in spherical form, it preferably has a BET surface area in the range from 50 to 120 m 2 / g, particularly preferably in the range from 60 to 115 m 2 / g.
  • the catalyst carrier body is in the form of a ring, it preferably has a BET surface area in the range from 80 to 135 m 2 / g, particularly preferably in the range from 90 to 130 m 2 / g.
  • the BET surface area is determined by the BET method according to DIN 66131; a publication of the BET method can also be found in J. Am. Chem. Soc. 60, 309 (1938).
  • the sample for example, with a fully automatic
  • Nitrogen porosimeter Micromeritics, type ASAP 2010 are measured by means of which an absorption and
  • the basicity of the catalyst carrier body can advantageously influence the activity of the inventive catalyst prepared therefrom.
  • the catalyst support according to the invention has a high basicity. Therefore, the basicity of the catalyst carrier body of the present invention or later described is
  • catalyst according to the invention in the range of 100 to 800 pval / g, more preferably in the range of 110 to 750 ⁇ val / g and most preferably in the range of 130 to 700 ⁇ val / g.
  • alkali metal is understood in the present invention to mean a metal of main group 1 of the Periodic Table of the Elements. Li, Na or K, more preferably Na or K, and most preferably K are preferably used here.
  • a metal of the 2nd main group of the Periodic Table of the Elements Preference is given to using Ca, Mg, Sr and Ba, particularly preferably Ca, Sr and Ba.
  • a rare earth metal in the present invention means a metal from the following list (ordinal numbers in parentheses): scandium (21), yttrium (39), lanthanum (57), cerium
  • Y praseodymium
  • neodymium 60
  • promethium 61
  • samarium 62
  • europium 63
  • gadolinium 64
  • terbium 65
  • dysprosium 66
  • holmium 67
  • erbium 68
  • thulium 69
  • ytterbium 70
  • lutetium 71
  • the following are particularly preferred according to the invention: Y, La, Ce and Nd.
  • Catalyst carrier body an alkali metal, in particular Li, Na or K, wherein Na and K, or K, is particularly preferred.
  • Total content of metal in the range of 0.5 to 5 wt .-%, more preferably in the range of 1 to 4 wt .-%, even more preferably in the range of 1.5 to 3.5 wt .-%, and most preferably in the range of 1.6 to 3.1 wt .-%, based on the total weight of the catalyst carrier body.
  • Catalyst carrier body potassium In this case it is
  • the content of potassium in the range of 1 to 4 wt .-%, even more preferably in the range of 1.5 to 3.5 wt .-%, and most preferably in the range of 1.6 to 3.1 Wt .-%, based on the total weight of
  • Catalyst support body
  • the metal is preferably bound in the form of a metal-containing
  • the metal is potassium and is in the form of potassium silicates, such as potassium silicates.
  • K 2 S1O 3 potassium metasilicate
  • K 4 Si0 4 potassium orthosilicate
  • Catalyst support body in the form of K 2 SiC> 3 are present.
  • the potassium may also be uniformly distributed in the matrix of the SiC> 2-containing material in the form of potassium-containing mica or potassium-containing feldspars.
  • the catalyst carrier body also comprises a SiC> 2-containing material.
  • the catalyst carrier body consists of the metal-containing compound and the SiC> 2-containing material.
  • SiC 2 -containing material any synthetic or naturally occurring material that
  • the S1O2-containing material is precipitated or fumed silica, such as the synthetically prepared silicate Aerosil or a natural phyllosilicate.
  • silica such as the synthetically prepared silicate Aerosil or a natural phyllosilicate.
  • natural layer silicate for the term “phyllosilicate” is used in the literature, derived untreated or treated silicate mineral is understood from natural sources, in which S1O 4 - tetrahedra, which form the basic structural unit of all silicates, in Layers of the general formula [Si 2 O 5 ] 2 ⁇
  • alternating deposits with so-called octahedral layers in which a cation, especially Al and Mg (in the form of its cations), octahedrally surrounded by OH or 0 is.
  • Preferred layered silicates are clay minerals
  • Nontronite, mica, vermiculite and smectites, with smectites and in particular montmorillonite are particularly preferred.
  • layer silicates can also be found, for example, in "Lehrbuch der anorganischen Chemie", Hollemann Wiberg, de Gruyter Verlag, 102nd edition, 2007 (ISBN 978-3-11-017770-1) or in "Rompp Lexikon Chemie", 10.
  • the natural sheet silicate is a bentonite
  • the natural sheet silicate is present in the catalyst carrier body in the form or as part of a bentonite.
  • the natural layered silicate may also be a zeolite.
  • the silicate-containing material is a zeolite
  • the zeolite may be a fiber zeolite, folic zeolite, cube zeolite, zeolite of the MFI structure, beta-type zeolite, zeolite A, zeolite X, zeolite Y, and the like
  • Fiber zeolites and the like Natrolite, laumontite, mordenite, thomsomite, to leaf zeolites and the like, heulandite, stilbite, as well as to
  • the catalyst carrier body contains Zr and / or Nb.
  • the SiC> 2-containing material is preferably doped with Zr and / or Nb, ie it is present in the catalyst support body in the form of Zr oxide (ZrC> 2) or Nb oxide (Nb20 5 ).
  • the Zr oxide or Nb oxide is preferably present in a proportion in the range of 5 to 25 wt .-%, preferably in a range of 10 to 20 wt .-% based on the weight of the catalyst carrier body without the metal.
  • the metal-containing material is a potassium-containing material
  • the content of potassium is preferably in the range from 1.8 to 3.5% by weight, and most preferably in the range from 2.1 to 3, 1% by weight, based on the total weight of the catalyst carrier body.
  • the content of potassium is preferably in the range of 1.4 to 2.6% by weight, and most preferably in the range of 1.6 to 2.4% by weight, based on the total weight the catalyst carrier body.
  • the catalyst carrier body is spherical shape, it preferably has an average pore radius in the range of 15 to 20 nm.
  • the catalyst carrier body contains Zr and is in the form of a ring, it preferably has one
  • the present invention also relates to a catalyst comprising a catalyst support body according to the invention and a catalytically active metal.
  • a catalytically active metal is any metal that has a
  • the catalytically active metal is preferably present in a shell of the catalyst carrier body. Consequently, the catalyst support of the invention is
  • shell catalyst is understood to mean one
  • Catalyst comprising a catalyst carrier body and a shell with catalytically active material, wherein the shell are formed in two different ways: on the one hand, a catalytically active material in the outer region of the Carrier so that the material of the carrier serves as a matrix for the catalytically active material and the region of the carrier, which is impregnated with the catalytically active material forms a shell around the non-impregnated core of the carrier.
  • a catalytically active material in the outer region of the Carrier so that the material of the carrier serves as a matrix for the catalytically active material and the region of the carrier, which is impregnated with the catalytically active material forms a shell around the non-impregnated core of the carrier.
  • Catalyst carrier body to be applied a layer in which a catalytically active material is present.
  • This layer forms the shell of the shell catalyst.
  • the catalyst support material is not part of the shell, but the shell is formed by the catalytically active material itself or another matrix material comprising a catalytically active material.
  • Invention may be both terms of a
  • Shell catalyst act but it is
  • the following metals can be used for the catalyst: Pd, Pt, Rh, Ir, Ru, Ag, Au, Cu, Ni and Co. Particular preference is given here to the metal combinations palladium or platinum in
  • the catalyst according to the invention preferably has one
  • side pressure resistance means the so-called
  • Hardness, breaking strength or dimensional stability of a catalyst, or its support body under pressure load It is determined by placing the carrier body between two jaws is subjected to pressure. It is determined the load pressure that just leads to the bursting of the body. This is preferably done with a tablet hardness tester 8M (with printer) of the company Dr. med. Schleuniger Pharmatron AG. For this purpose, the catalyst is first in the halogen dryer to the
  • the test is carried out, for example, with a
  • the device parameters are set as follows:
  • the present invention relates to a process for the preparation of an inventive
  • Catalyst support body wherein a SiC> 2-containing material treated with a metal-containing compound, then dried and then calcined at a temperature in the range of 400 to 1000 ° C, wherein the metal of the
  • Metal-containing compound is selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals and mixtures thereof.
  • the treatment of the SiC> 2-containing material with the metal-containing compound ⁇ includes both the treatment of the
  • the metal-containing compound is preferably an organic or inorganic metal salt.
  • the nitrates, nitrites, carbonates, bicarbonates and silicates of the metals come into consideration according to the invention in particular.
  • the metal-containing material may also be potassium mica or potassium feldspar, preferably when admixed with the Si0 2 -containing material in powder form prior to molding to the catalyst support body.
  • Organic potassium salts are the following: potassium acetate,
  • inorganic potassium salts KNO 3 , KNO 2 , K 2 CO 3 , KHCO 3 , K 2 SiO 3 ,
  • KNO 3 Potassium waterglass and KOH, with KNO 3 , KNO 2 and KHCO 3 being more preferred and KNO 3 being most preferred.
  • the metal-containing compound is preferably dissolved in a solvent.
  • a solvent In addition to the following solvents acetic acid, acetone and
  • Acetonitrile is especially here as a solvent
  • Compound, in particular potassium-containing compound is located preferably in the solvent in a range of 0.5 to 10 wt%, more preferably 1 to 8 wt%, most preferably 2 to 5 wt%.
  • Treating the SiC> 2 -containing material with a metal ⁇ containing compound can be accomplished by numerous known to those skilled procedures. From a procedural point of view can advantageously immersion of the catalyst carrier body in the solution according to the invention or a spraying of the catalyst carrier body with the
  • Solution is introduced, in particular immersed and while for example 2 minutes to 24 hours, in particular 10 to 20 minutes by means of passage of gas, for example air or nitrogen, is circulated.
  • gas for example air or nitrogen
  • the calcination is preferably carried out at an atmosphere of air, nitrogen or argon. If the treatment of the SiC> 2-containing material with the metal-containing compound ⁇ before shaping to
  • the SiC> 2-containing material preferably silicate
  • the SiC> 2-containing material in powder form with preferably powdered metal-containing material (preferably
  • Reactor is slowly released the metal (preferably potassium), which converts at the surface in the presence of acetic acid in potassium acetate.
  • metal preferably potassium
  • a further embodiment of the present invention relates to a process for the preparation of a catalyst according to the invention, wherein an inventive
  • the metals mentioned in connection with the catalyst according to the invention are also the metals which are used in the precursor compound of a catalytically active metal. Examples of Pd-containing
  • Precursor compounds are the following: Pd (NH 3 ) 4 (OH) 2 ,
  • Ethylene amine or ethanolamine can also be used here as a ligand.
  • Pd (OAc) 2 it is also possible to use other carboxylates of palladium, preferably the salts of the aliphatic monocarboxylic acids having 3 to 5 carbon atoms, for example the propionate or the butyrate salt.
  • the Au precursor compound is selected from the group consisting of KAuO 2 , HAuCl 4 , KAu (NO 2 ) 4 , NaAu (NO 2 ) 4 , AuCl 3 , NaAuCl 4 , KAuCl 4 , KAu ( OAc) 3 (OH), HAu (N0 3) 4, NaAu0 2, NMe 4 Au0 2, RbAu0 2, CsAu0 2,
  • the Pt precursor compound is selected from the group consisting of Pt (NH 3 ) 4 (OH) 2 , K 2 PtCl 4 , K 2 PtCl 6 , Na 2 PtCl 6 , Pt (NH 3 ) 4 Cl 2 ,
  • Pt (OAc) 2 other carboxylates of platinum can be used, preferably the salts of aliphatic
  • Monocarboxylic acids having 3 to 5 carbon atoms for example the propionate or the butyrate salt.
  • An embodiment of the process according to the invention is the Ag precursor compound selected from the group consisting of Ag (NH 3 ) 2 (OH), Ag (NO 3 ), Ag citrate, Ag tartrate, ammonium Ag oxalate, K 2 Ag (OAc ) (OH) 2 , Ag (NH 3 ) 2 (NO 2 ), Ag (NO 2 ), Ag-lactate, trifluoroacetate, Ag-oxalate, Ag 2 C0 3 , K 2 Ag (NO 2 ) 3 , Na 2 Ag (NO 2 ) 3 , Ag (OAc), AgCl ammoniacal solution or ammoniacal Ag 2 C0 3 solution or ammoniacal AgO solution.
  • the Ag precursor compound selected from the group consisting of Ag (NH 3 ) 2 (OH), Ag (NO 3 ), Ag citrate, Ag tartrate, ammonium Ag oxalate, K 2 Ag (OAc ) (OH) 2 , Ag (NH 3 ) 2 (NO 2 ), Ag (NO 2 ), Ag-lactate, triflu
  • Precursor compounds are soluble and after application to the catalyst support body of the same can be easily removed by drying again.
  • Solvent examples are the following: water, dilute nitric acid, carboxylic acids, especially acetic acid,
  • Method preferably prepared a shell catalyst, wherein the metal precursor compounds are applied to the catalyst in the region of an outer shell of the catalyst carrier body according to known methods.
  • the application of solutions of precursor compounds can be carried out by impregnation by immersing the support in the solution or by soaking in the incipient wetness process.
  • the solutions can also on the
  • Catalyst carrier be sprayed.
  • a solution of the precursor compound is applied by the solutions to a fluidized bed or a fluidized bed of
  • Catalyst carrier body are sprayed, preferably by means of an aerosol of the solutions. This allows the
  • Shell thickness continuously adjusted and optimized, for example, up to a thickness of 2 mm. But also very thin shells with a thickness of less than 100 pm are possible.
  • Catalyst support body with the / the precursor compound (s) of the catalytically active metals may optionally drying and calcination and / or a reduction of the metal of the
  • the reduction of the metal component of the precursor compound to the elemental metal may be in the liquid phase or gas phase.
  • the following reducing agents can be used in the following reducing agents.
  • Liquid phase reduction can be used: hydrazine,
  • Citric acid, tartaric acid, malic acid, alcohols, NaBH 4 and oxalic acid The gas phase reduction can be carried out prior to incorporation into the reactor for the synthesis use of the catalyst (ex-situ), but it can also be carried out in the reactor for the synthesis use of the catalyst (in situ).
  • ex-situ reduction is preferably with hydrogen, forming gas or Ethylene reduced.
  • in-situ reduction is carried out, in particular in the synthesis of VAM, preferably with
  • the present invention also includes a method for the production of VAM, in which a first
  • Precursor compound is introduced into a reactor for the synthesis of VAM, then by passing ethylene reduces the metal component of the precursor compound of the catalytically active metal to elemental metal and then reacted in the reactor acetic acid and ethylene by reaction with oxygen to vinyl acetate monomer.
  • the present invention also relates to the use of a
  • the catalyst may be, but is not limited to, a catalyst of the invention.
  • Fig. 1 In Fig. 1, the activity or selectivity
  • inventive and non-inventive catalysts (5 mm balls) with respect to the synthesis of VAM shown.
  • Fig. 2 In Fig. 2 is the activity or selectivity
  • inventive and non-inventive catalysts with respect to the synthesis of VAM shown.
  • the carrier 7 is a spherical KA-Zrl4 carrier body (14% ZrO 2) of
  • 100 g of the support 1 are mixed with an aqueous mixed solution of Pd (NH 3 ) 4 (OH) 2 and KAuO 2 (prepared by mixing 34, 49 g of a 3.415% Pd solution and 10.30 g of a 5.210% Au).
  • the LOI-free metal contents of the finished catalyst A determined by chemical elemental analysis are 1.12% Pd and 0.47% Au.
  • Catalyst B was prepared in the same manner as
  • Carrier 2 started and the following weights were used: 1. 34.78 g of Pd solution
  • the LOI-free metal contents of the finished catalyst B determined by chemical elemental analysis are 1.12% Pd and 0.47% Au.
  • Catalyst D was prepared in the same manner as
  • Catalyst A prepared, with the difference that it started from the carrier 4 and the following weights were used:
  • Catalyst E was prepared in the same way as
  • Catalyst A prepared, with the difference that it started from the carrier 5 and the following weights were used:
  • Catalyst F was prepared in the same way as
  • Catalyst A prepared, with the difference that it started from the carrier 6 and the following weights were used:
  • Concentrations of the components used were: 39% ethylene, 6% O 2 , 0.6% CO 2 , 9% methane, 12.5% acetic acid, balance N 2 .
  • Figure 1 shows the VAM selectivity of the catalysts A to G as a function of the O 2 conversion. The values are also listed in tables in Tables 2, 3 and 4:
  • Example 9 There were first four catalyst carrier body (carrier 8 to 11) with the following potassium levels (based on the
  • Carrier 11 no impregnation with potassium nitrate
  • the support 11 is a ring-shaped KA-Zrl4 support (14% ZrO 2) from Südchemie AG, to which no potassium-containing compound
  • Catalyst I was prepared by mixing 100 g of the support 8 with a mixed solution of 27.44 g of a 4.76% strength
  • Pore filling method (incipient wetness) were impregnated.
  • the catalyst K was the same as the catalyst I.
  • the LOI-free metal loading determined by chemical analysis was 1% Pd + 0.45% Au.
  • the catalyst L was the same as the catalyst I.
  • FIG. 2 shows the VAM selectivity of the catalysts I to L as a function of the O 2 conversion. The values are also listed in tables in Tables 6 and 7.
  • the carrier 18 was an unimpregnated KA-160 carrier.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
EP12723835.0A 2011-04-26 2012-04-25 Basische katalysatorträgerkörper mit niedriger oberfläche Withdrawn EP2701838A1 (de)

Applications Claiming Priority (2)

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DE102011018532A DE102011018532A1 (de) 2011-04-26 2011-04-26 Basische Katalysatorträgerkörper mit niedriger Oberfläche
PCT/EP2012/057523 WO2012146600A1 (de) 2011-04-26 2012-04-25 Basische katalysatorträgerkörper mit niedriger oberfläche

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US (1) US20140113806A1 (ko)
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Publication number Priority date Publication date Assignee Title
TW330160B (en) * 1992-04-08 1998-04-21 Hoechst Ag Supported catalyst, process for its preparation and its use for the preparation of vinyl acetate
DE4323980C1 (de) * 1993-07-16 1995-03-30 Hoechst Ag Palladium und Kalium sowie Cadmium, Barium oder Gold enthaltender Schalenkatalysator, Verfahren zu dessen Herstellung sowie dessen Verwendung zur Herstellung von Vinylacetat
GB9622911D0 (en) * 1996-11-04 1997-01-08 Bp Chem Int Ltd Process
DE102006058800A1 (de) * 2006-12-13 2008-06-19 Wacker Chemie Ag Verfahren zur Herstellung von Katalysatoren und deren Verwendung für die Gasphasenoxidation von Olefinen
DE102007025356A1 (de) * 2007-05-31 2009-01-08 Süd-Chemie AG Verfahren zur Herstellung eines Schalenkatalysators und Schalenkatalysator
DE102007025443A1 (de) 2007-05-31 2008-12-04 Süd-Chemie AG Pd/Au-Schalenkatalysator enthaltend HfO2, Verfahren zu dessen Herstellung sowie dessen Verwendung
DE102008059342A1 (de) * 2008-11-30 2010-06-10 Süd-Chemie AG Schalenkatalysator, Verfahren zu seiner Herstellung sowie Verwendung

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Title
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