Monomodal and polymodal catalyst supports and catalysts with a narrow pore size distribution and method for producing the same

The present invention relates to catalyst supports and catalysts with a narrow pore size distribution, processes for their preparation and their uses.

From US Pat. No. 5,191,144, zeolites with a very uniform pore size between 2 and 10 mm nm that can be varied in the mesopore range from 2 to 10 mm nm by hydrothermal synthesis are known. Due to the small pore size, the size of the molecules that can be converted is limited. Since an zeolite contains an SiO₂-Binder is used, these zeolites are stable only up to 700 ° C and not resistant to chemicals above 400 ° C, and their mechanical resistance is poor. The zeolites also have very acidic surfaces, which limits their use to acid-catalyzed reactions.

Chem. Ind., 10 (1993) 48 to 49 describes a process for the preparation of catalyst supports in the mesopore range (2 to 50 nm) from pyrogenic oxides (SiO₂, Al₂O₃, TiO₂, ZrO₂) by reaction of the halides in the oxyhydrogen flame, the pore sizes of which are between 10 and 70 nm, with no pores in the range of less than 8 nm. However, the pore distributions are widely spread.

From Chem. Ing. Tech., 56 (1984) 455 to 463, melamine is known as a macroporous former. However, pyrolysis leads to cracking.

From US-A-3,755,204 porous ceramic bodies by molding a mixture of ceramic powder, a polyolefin (polyethylene copolymer) and a plasticizer (mineral oil, diethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone) are known, which are produced by pyrolysis and sintering. The cracks in the ceramic body that occur during pyrolysis can be avoided by extracting the plasticizer with aqueous surfactant solutions (DE-A-24 59 475). These are ceramic honeycomb bodies, in which the open pores are introduced as channel structures through the thermoplastic shape.

DE-A-24 59 475 discloses a process for the production of shaped porous metal structures, in which a mixture of metal powder, polyolefin and a plasticizer is compounded and the plasticizer is dissolved out of the mixture with a solvent prior to pyrolysis.

DE-A-41 20 687 discloses porous sintered parts made of metal or ceramic, with a polyolefin, a plasticizer and an additive which is not miscible with the binder system. The additive is a vinyl aromatic copolymer based on polysryrol, which is inserted with a particle size of 20 to 250 µm as a placeholder between the metal or ceramic particles. By varying the additive particle size, different but unspecified pore sizes can be produced. The pore size distribution is bimodal and widely dispersed, since the pores are formed on the one hand by the particle size distribution of the additive and on the other hand by the spaces between the metal or ceramic particles.

EP-A-446 708 discloses the production of dense metal moldings and EP-A-444 475 the production of dense ceramic moldings by means of the deformation of thermoplastic materials.

EP-A-413 231 discloses a method for producing dense inorganic sintered molded parts, green bodies being formed from sinterable powders and polyoxymethylene or a copolymer with a predominant proportion of oxymethyl units as binders by extrusion, injection molding or extrusion. The binder is removed from these green parts quickly, free of cracks and without distortion by treatment with a gaseous acid or boron trifluoride. The debindered porous parts have a low mechanical stability and are sintered to full density. In this way, complex shaped, dense, ceramic or metallic structural materials or functional materials are produced that are not suitable as catalyst supports or catalysts.

Sinterable organic polymers such as Teflon (EP-A-513 500), polyamide or non-plasticizable polymers (EP-A-517 025) can also be processed into dense components using this manufacturing process.

From DE-A-41 20 687 it is known that it is very difficult to reproducibly produce mechanically stable parts with a constant pore distribution from very fine metal or ceramic powders (particle size approx. 1 µm) using the known methods.

DE-A-41 28 629 relates to silver-containing alumina support catalysts for the selective decomposition of pure or nitrous oxide contained in gas mixtures. The carrier materials are commercially available or customary aluminum oxide with a BET surface area of ​​26 to 350 m²/G. FIGS. 1 and 2 show the pore size distributions of commercially available aluminum oxide supports. These are support materials with an essentially bimodal pore size distribution, the pore size distribution being relatively wide.

The object of the present invention was therefore to remedy the disadvantages mentioned above.

Accordingly, new and improved monomodal or polymodal catalyst supports or catalysts have been found, which are characterized in that the catalyst supports or catalysts have a BET specific surface area of ​​0.01 to 250 m²/ g a pore volume of 0.05 to 5 ml / g, a cutting hardness of 1 to 8 kg for samples presintered at 800 ° C and a monomodal or a polymodal pore size distribution with an average pore diameter of 50 to 300,000 nm measured with Hg pressure porosimetry Method and<ul id="ul0001" list-style="none"><li>a) 10 to 95% of the pore volume at 0.1 to 3 times and / or</li><li>b) 10 to 80% of the pore volume at 0.4 to 3 times and / or</li><li>c) 50 to 95% of the pore volume at 0.1 to 1 times and / or</li><li>d) 50 to 80% of the pore volume is 0.4 to 1 times the average pore diameter and</li><li>e) the half-width of the pore size distribution is less than 0.5 times the modal pore diameter,</li></ul> such as a process for their preparation by molding a mixture<ul id="ul0002" list-style="none" compact="compact"><li>A) 15 to 70% by volume<ul id="ul0003" list-style="none"><li>I) an inorganic powder selected from the group of oxides, nitrides, carbides, silicates, aluminosilicates of the elements beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, antimony , Selenium, tellurium, polonium, astatine, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, zinc, cadmium, mercury, scandium, yttrium, lanthanum, actinium, titanium, zircon , Hafnium, vanadium, niobium, Tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, cerium, praseodymium or their mixtures and / or</li><li>II) a metallic powder selected from metals and alloys of the elements boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, antimony, selenium, tellurium, polonium, neodymium, samarium, dysprosium, astatine, iron, cobalt, Raney cobalt, nickel, Raney nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, zinc, cadmium, mercury, scandium, yttrium, lanthanum, actinium, titanium, zirconium, hafnium, vanadium, Niobium, tantalum, chrome, molybdenum, tungsten, Manganese, technetium, rhenium, cerium, praseodymium, WC, TiC, TaC, VC or their mixtures, WC-Cobalt, TiC-Cobalt, TaC-Cobalt, VC-Cobalt or their mixtures as well as carbon and / or</li><li>III) an active component selected from the group of inorganic acids, the metals selected from lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, silicon, Germanium, tin, lead, arsenic, antimony, bismuth, selenium, tellurium, polonium, astatine, iron, cobalt, Raney cobalt, Nikkel, Raney nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, Gold, zinc, cadmium, mercury, Scandium, yttrium, lanthanum, actinium, titanium, zircon, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, cerium, praseodymium, their mixtures, or their borates, carbonates, silicates, nitrates, phosphates , Arsenates, antimonates, bismuthates, sulfates, selenates, tellurates, vanadates, molybdate, niobates, chromates, oxides, hydroxides, halides, sulfides, selenides, tellurides, nitrides, phosphides, arsenides, acetates, acetylacetonates, palladates, platinates, Cyanides, rhodanides, manganates, rhenates, osmates, carbides, silicides, borides, their ammonium compounds or their mixtures and / or</li><li>IV) an organic powder selected from the group Teflon or polyimide</li></ul></li><li>B) 30 to 85 vol .-% of a mixture of<ul id="ul0004" list-style="none"><li>B₁) 50 to 100 wt .-% of a polyoxymethylene homo- or copolymer and</li><li>B₂) 0 to 50% by weight of a polymer homogeneously dissolved in B1) or dispersed in B1) with an average particle size of less than 1 μm and</li></ul></li><li>C) 0 to 15% by volume of a dispersing aid,</li></ul>

Removal of the binder and subsequent presintering and, if appropriate, application of active components III to component A) or to the presintered mass by, if appropriate, repeated impregnation, impregnation, spray impregnation, precipitation, hicoating, washcoating or spray drying, characterized in that component A) is a nanocrystalline powder with an average grain size of 5 nm to 500,000 nm, the deviations of the grain size in 80% of the grains being 0 to 30% of the mean grain size and the binder being removed by treatment with a gaseous acid at temperatures from 100 to 160 ° C, residual pyrolysis at temperatures from 400 to 600 ° C and then at Temperatures of 600 to 1400 ° C is pre-sintered and the catalyst support or catalysts after the pyrolytic removal of the binder has a specific surface area according to BET of 0.01 to 250 m²/ g and a pore size distribution of 50 to 300,000 nm measured by the mercury pressure porosimetry method, and their use for the production of chlorine from hydrogen chloride in a transient Deacon process, for the conversion of ethylbenzene to styrene in a transient oxydehydrogenation, for aziridine production Ethanolamine, for the conversion of trimethylcyclohexenone to trimethylphenol, for reductions, hydrogenations, oxidations, dehydrations, acidic or basic catalyzed reactions or reactions in the fluidized bed, for the removal of combustion residues from diesel exhaust gases and for the removal of NO_x from exhaust gases, in bioreactors together with bacteria and as a biocatalyst support with immobilized enzymes or microbes.

The catalyst supports or catalysts according to the invention are preferably not zeolitic and have a BET specific surface area of ​​0.01 to 250 m²/ g, preferably 0.1 to 200 m²/ g, particularly preferably 0.5 to 120 m²/ g and a monomodal or a polymodal, i.e. a bimodal, trimodal, tetramodal or higher modal, preferably a bimodal, trimodal or tetramodal, particularly preferably a bimodal or trimodal pore size distribution with an average pore diameter of 50 to 300,000 nm, preferably 100 to 50,000 nm, particularly preferably have 150 to 25,000 nm measured using the mercury pressure porosimetry method and<ul id="ul0005" list-style="none"><li>a) 10 to 95%, preferably 30 to 95%, particularly preferably 50 to 95% of the pore volume at 0.1 to 3 times and / or</li><li>b) 10 to 80%, preferably 30 to 80%, particularly preferably 50 to 80% of the pore volume at 0.4 to 3 times and / or</li><li>c) 50 to 95%, preferably 70 to 95%, particularly preferably 80 to 95% of the pore volume at 0.1 to 1 times and / or</li><li>d) 50 to 80%, preferably 60 to 80%, particularly preferably 65 to 80% of the pore volume is 0.4 to 1 times the average pore diameter and</li><li>e) the full width at half maximum of the pore size distribution is less than 0.5 times, ie 0.001 to 0.49 times, preferably 0.005 to 0.4 times, particularly preferably 0.1 to 0.3 times of the modal pore diameter is.</li></ul>

Preferred catalyst supports or catalysts according to the invention are those in which the conditions a) and b) or a) and c) or a) and d) or b) and c) or b) and d) or c) and d) at the same time those in which the conditions a), b) and c) or a), b) and d) or a), c) and d) or b), c) and d) are simultaneously fulfilled are particularly preferred , in particular those catalyst supports or catalysts in which all four conditions a), b), c) and d) are fulfilled at the same time.

The catalyst supports or catalysts according to the invention can be prepared as follows:

In a mixing device, preferably with a heating device, for example a kneader, an extruder or a shear roller extruder, the polymer of component B) can be melted at temperatures from 80 to 250 ° C., preferably 100 to 220 ° C., particularly preferably 120 to 200 ° C. component A), the inorganic, metallic, organic powder and / or the active components and then the dispersing aid of component C) or first component C) and then component A) or components A) and C) are added together. The intimately (intensely) mixed masses can, for example by granulating, pressing, rolling, extrusion, extrusion or injection molding, in particular by injection molding at temperatures from 120 to 250 ° C., preferably 140 to 220 ° C., particularly preferably 150 to 200 ° C. and pressures from 500 to 2000 bar, preferably 600 to 1800 bar, particularly preferably 700 to 1600 bar are deformed. In this way, in a molding step at injection mold temperatures of 40 to 160 ° C, preferably 60 to 150 ° C, particularly preferably 80 to 140 ° C, any shaped catalyst support or catalyst as a bed of individual parts or as monoliths such as Raschig rings, saddle bodies, star rings , perforated and / or ribbed geometric bodies such as rings, spheres, cuboids, cubes, cones, pyramids, prisms, octahedra, cylinders, truncated pyramids and truncated cones, are usually produced without post-processing.

Weigh wheel profiles, honeycomb profiles, window frame profiles can be extruded at temperatures of 120 to 250 ° C, particularly preferably at 150 to 200 ° C to monoliths.

The green bodies obtained after the shaping process can be subjected to catalytic debinding in a gaseous, acidic atmosphere at temperatures from 100 to 160 ° C., preferably 100 to 150 ° C., particularly preferably below the softening temperature of the polyacetal (component B).

The demolded green compacts are treated in accordance with the invention in a (gaseous) acidic atmosphere in order to remove the binder. (Gaseous) acidic atmospheres can be understood to mean both pure acid which is gaseous at the treatment temperatures, but it can also be understood to mean mixtures of acids with a carrier gas. Suitable carrier gases are, for example, air or nitrogen or noble gases. Suitable acids are the inorganic acids which are gaseous at room temperature, for example the hydrogen halide, hydrogen sulfide or those acids which can be evaporated to a considerable extent at the treatment temperatures, for example nitric acid.

Suitable organic acids are in principle those acids or acid mixtures which have a boiling point or sublimation point at normal pressure of below 130 ° C., for example oxalic acid, formic acid, acetic acid or trifluoroacetic acid.

Instead of the gaseous, acidic atmosphere, the demolded green compacts can also be treated in a gaseous atmosphere containing boron trifluoride to remove the binder. Gaseous atmospheres containing boron trifluoride can be understood to mean both pure boron trifluoride, but it can also be understood to mean mixtures of boron trifluoride with a carrier gas. Suitable carrier gases are, for example, air or nitrogen or noble gases.

Instead of boron trifluoride, it is of course also possible to use adducts of boron trifluoride which can be reversibly split back into the starting components at the treatment temperatures and without decomposition of the components. The addition compounds of boron trifluoride with ether, for example dimethyl ether, diethyl ether, dibutyl ether and tert-butyl methyl ether, are particularly suitable.

Nitric acid, anhydrous oxalic acid or oxalic acid dihydrate are particularly preferred. Glyoxalic acid is also suitable. Benzenesulfonic acid, the naphthalenesulfonic acids and maleic acid or mixtures of these acids are also suitable. These can be used alone or together with a carrier gas such as air, nitrogen or a noble gas for debinding.

To facilitate metering, it may be expedient to use the abovementioned acids as a solution in polar solvents, preferably with boiling points below 200 ° C. Water, isopropanol, acetone, dioxane, ethanol, acetic acid and formic acid are particularly suitable as such.

The acid-catalyzed debinding can be 1 × 10 at normal pressure or at reduced pressure² to 1 · 10⁵ Pa (0.001 to 1 bar).

Subsequent presintering, at temperatures from 600 to 1400 ° C., preferably 600 to 1100 ° C., particularly preferably at 600 to 800 ° C. under oxidizing conditions (air), inert gas (N.₂, Ar, He) or reducing conditions (N₂/H₂, Ar / H₂) the molded body can be converted to the catalyst supports or catalysts with their final strength and pore distribution. The pre-sintering process generally increases the stability and hardness of the porous molded articles considerably. The cutting hardness of the samples presintered at 800 ° C. is 1 to 8 kg (800 ° C.), preferably 1.5 to 7 kg (800 ° C.), particularly preferably 2 to 6 kg (800 ° C.). Cutting hardnesses of up to 20 kg were achieved with samples pre-sintered at 1100 ° C. The water absorption is in the range from 0.05 to 5 ml / g, preferably 0.1 to 3 ml / g, particularly preferably 0.1 to 1 ml / g, so that more active component can be applied to a catalyst support according to the invention without usually to achieve significant losses in hardness. Due to the excellent absorption of active components, the catalysts can be easily recycled after use by soaking the active components.

In addition to strictly monomodal pore size distributions, polymodal (bimodal, trimodal, tetramodal and higher modal) pore size distributions can also be produced. This process can be used to produce catalyst supports and catalysts with high strength and high thermal or chemical stability. All shapes are conceivable as geometries of the shaped bodies, which can be produced by granulation, rolling, pressing, extrusion, extrusion or injection molding. The moldings can be used in bulk or in the form of monoliths in catalytic reactors.

The BET specific surface areas of the catalyst supports and catalysts according to the invention are from 0.01 to 250 m²/ g, preferably 0.1 to 150 m²/ g, particularly preferably 1 to 100 m²/ g, especially 2 to 8 m²/ g (800 ° C).

The average pore size is generally determined by the grain size of component A), the inorganic, metallic, organic powders and / or the active components, as a rule only by the gaps between the powder particles used. The average pore size and the pore size distribution are therefore dependent on the average grain size and the particle size distribution of the powder used. With commercially available metal or ceramic powders, mechanically stable, crack-free, monomodal or polymodal porous materials, such as the catalyst supports or catalysts according to the invention, can be produced in this way. The narrow pore size distribution can thus be adjusted as required in the mesopore and macropores range and generally leads to a highly monodisperse pore distribution.

If polymodal catalyst supports or catalysts are to be obtained, powders with a polymodal particle size distribution or with internal porosity are used.

The average grain size of the powders of component A) used according to the invention is a nanocrystalline powder from 5 nm to 500,000 nm, preferably 300 nm to 100,000 nm, particularly preferably 500 nm to 50,000 nm, the deviations in the grain size being 80%, preferably 90%, 95% of the grains is particularly preferably 0 to 30%, preferably 0 to 20%, particularly preferably 0 to 10% of the average grain size.

The following are suitable as component A):<ul id="ul0006" list-style="none"><li>I) an inorganic powder selected from the group of oxides, nitrides, carbides, silicates, aluminosilicates of the elements beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, antimony , Selenium, tellurium, polonium, astatine, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, zinc, cadmium, mercury, scandium, yttrium, lanthanum, actinium, titanium, zircon , Hafnium, vanadium, niobium, tantalum, Chromium, molybdenum, tungsten, manganese, technetium, rhenium, cerium, praseodymium or mixtures thereof, preferably oxides, nitrides, carbides, silicates of the elements magnesium, calcium, strontium, barium, boron, aluminum, silicon, tin, lead, antimony, iron , Cobalt, nickel, ruthenium, rhodium, palladium, platinum, copper, silver, gold, zinc, yttrium, lanthanum, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, cerium or mixtures thereof, particularly preferred Oxides, nitrides, carbides, of the elements magnesium, calcium, strontium, barium, boron, aluminum, silicon, tin, antimony, iron, cobalt, nickel, copper, yttrium, titanium, zircon, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese or mixtures thereof ,</li><li>II) a metallic powder selected from metals and alloys of the elements boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, antimony, selenium, tellurium, polonium, neodymium, samarium, dysprosium, astatine, iron, cobalt, Raney cobalt, nickel, Raney nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, zinc, cadmium, mercury, scandium, yttrium, lanthanum, actinium, titanium, zirconium, hafnium, vanadium, Niobium, tantalum, chrome, molybdenum, tungsten, Manganese, technetium, rhenium, cerium, praseodymium, WC, TiC, TaC, VC or their mixtures, WC-Cobalt, TiC-Cobalt, TaC-Cobalt, VC-Cobalt or their mixtures and carbon, preferably metals and alloys of the elements boron, Aluminum, silicon, tin, lead, antimony, selenium, neodymium, samarium, dysprosium, iron, cobalt, Raney cobalt, nickel, Raney nickel, palladium, platinum, copper, silver, gold, zinc, yttrium, lanthanum, titanium, Zircon, vanadium, niobium, tantalum, chrome, molybdenum, tungsten, manganese, cerium, WC, TiC, TaC, VC or their mixtures, WC-Cobalt, TiC-Cobalt, TaC-Cobalt, VC-Cobalt or their mixtures and carbon, particularly preferably metals and alloys of the elements boron, aluminum, silicon, tin, neodymium, samarium, dysprosium, iron , Cobalt, Raney cobalt, nickel, Raney nickel, copper, zinc, yttrium, titanium, zircon, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, WC, TiC, TaC, VC or mixtures thereof, WC- Cobalt, TiC-cobalt, TaC-cobalt, VC-cobalt or mixtures thereof,</li><li>III) an active component selected from the group of inorganic acids, in particular H₂SO₄, H₃PO₄, ENT₃ and heteropolyacids, the metals selected from lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, arsenic, antimony , Bismuth, selenium, tellurium, polonium, astatine, iron, cobalt, Raney cobalt, nickel, Raney nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, zinc, cadmium, mercury, scandium , Yttrium, lanthanum, actinium, titanium, zircon, Hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, cerium, praseodymium, their mixtures, or their borates, carbonates, silicates, nitrates, phosphates, arsenates, antimonates, bismuthates, sulfates, selenates, tellurates , Vanadate, Molybdate, Niobate, Chromate, Oxide, Hydroxide, Halide, Sulfide, Selenide, Telluride, Nitride, Phosphide, Arsenide, Acetate, Acetylacetonate, Palladate, Platinate, Cyanide, Rhodanide, Manganate, Rhenate, Osmate, Carbide, Silicide, Boride , their ammonium compounds or their mixtures, preferably metals selected from lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, boron, aluminum, silicon, tin, lead, arsenic, antimony, bismuth, selenium, tellurium, polonium, iron, Cobalt, Rancy-Cobalt, Nickel, Raney-Nickel, Ruthenium, Rhodium, Palladium, Osmium, Iridium, Platinum, Copper, Silver, Gold, Zinc, Yttrium, Lanthanum, Titanium, Zircon, Vanadium, Niobium, Tantalum, Chromium, Molybdenum, Tungsten, manganese, rhenium, cerium, their mixtures, or their borates, carbonates, silicates, nitrates, phosphates, arsenates, antimonates, bismuthates, sulfates, selenates, vanadates, molybdates, niobates, chromates, oxides, hydroxides, halides, sulfides, selenides, tellurides, nitrides, phosphides, arsenides, acetates, Acetylacetonates, palladates, platinates, manganates, carbides, silicides, borides, their ammonium compounds or their mixtures, particularly preferably metals selected from lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, Aluminum, silicon, tin, lead, arsenic, antimony, bismuth, iron, cobalt, nickel, ruthenium, rhodium, palladium, platinum, copper, silver, zinc, titanium, zircon, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, Manganese, cerium, their mixtures, or their carbonates, silicates, nitrates, phosphates, arsenates, antimonates, bismuthates, sulfates, vanadates, molybdates, niobates, chromates, oxides, hydroxides, halides, sulfides, nitrides, carbides, their ammonium compounds or their mixtures .</li></ul>

Aluminum, iron, cobalt, nickel, palladium, platinum, copper, silver, molybdenum, zinc, titanium, zirconium, tungsten, niobium, chromium or carbon or as an inorganic powder Al are preferably used as metals₂O₃, MgO, SiO₂, TiO₂, Y₂O₃, ZrO₂, ZnO, Fe₃O₄, Fe₂O₃, CoO, Co₂O₃, Cr₂O₃, NiO, B₂O₃, Ce₂O₃, CeO₂, Pr₂O₃, B₄C, SiC, WC, TiC, TaC, Si₃N₄, AlN, BN, TiN, ZrN, or mixtures thereof, more preferably as metal iron, cobalt, nickel, chromium, molybdenum, titanium or as an inorganic powder SiC, Si₃N₄, BN, B₄C, WC, TiC, TiN, ZrN and AlN, or their mixtures and in particular as an inorganic powder SiC, Si₃N₄ or mixtures thereof.

If full catalysts are to be produced, component A) only contains active components III) and, if appropriate, IV), an organic powder selected from the group consisting of Teflon or polyimide.

The following are suitable as component B):<ul id="ul0007" list-style="none"><li>B₁) 50 to 100 wt .-%, preferably 70 to 90 wt .-%, particularly preferably 80 to 88 wt .-% of a polyoxymethylene homo- or copolymer as are known from EP-A-444 475 and</li><li>B₂) 0 to 50% by weight, preferably 10 to 30% by weight, particularly preferably 12 to 25% by weight, of a polymer which is homogeneously dissolved in B1) or dispersed in B1) with an average particle size of less than 1 μm, preferably Poly-1,3-dioxolane, poly-1,3-dioxane, poly-1,3-dioxepane, particularly preferably poly-1,3-dioxepane.</li></ul>

Suitable organic binders are polyacetal binders, for example polyoxymethylene, which advantageously has a molecular weight of 10,000 to 500,000. In addition to homopolymers of formaldehyde or trioxane, copolymers of trioxane also come with, for example cyclic ethers such as ethylene oxide and 1,3-dioxolane or formals such as 1,3-dioxepane, 1,3-dioxane, or their mixtures or homopolymeric poly-1,3-dioxolane, poly-1,3-dioxane, or poly-1 , 3-dioxepan into consideration, the amounts of the copolymers generally being from 10 to 30% by weight of the polymers.

They can also contain auxiliaries, such as thermoplastic binders, such as polyethylene, polymethyl methacrylate or polyethylene oxide, and dispersants or lubricants, such as polyethylene glycol, stearic acid, fatty alcohols, polyvinylpyrrolidone or polyvinyl alcohol. The amount of auxiliaries is generally between 0.1 and 12% by weight of the total mass.

As component C) are suitable dispersing agents as are known from EP-A-444 475, for example organic carboxylic acids, amines, amides or maleimides, stearic acid, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyethylene oxide and montan waxes, preferably organic carboxylic acids, amines, amides or maleimides, polyethylene glycol and polyethylene oxide, particularly preferably organic carboxylic acids, amines, maleimides, polyethylene glycol and polyethylene oxide.

The mixtures used to prepare (mixing) the catalyst supports or catalysts according to the invention generally contain or consist of 15 to 70% by weight, preferably 30 to 70% by weight, particularly preferably 50 to 65% by weight of component A), from 30 to 85% by weight, preferably 30 to 70% by weight, particularly preferably 35 to 50% by weight of component B) and from 0 to 15% by weight, preferably 1 to 12% by weight, particularly preferably 2 to 8% by weight of component C).

Ceramic, metallic or organic powders made of AI, II and IV are suitable as carrier materials.

In the case of the unsupported catalyst, the active components can be used directly as powder or, in the case of supported catalysts, applied to the inorganic powder I), the metallic powder II), the organic powder IV) or mixtures thereof, or subsequently applied to the support material, or together with the support material be compounded.

Furthermore, inorganic or organic fibers or whiskers made of, for example, Al₂O₃, SiO₂, SiC, Si₃N₄, C or mixtures thereof are added.

In the production process according to the invention, components A) are generally deagglomerated with the aid of a disperser C) and the starting powder, which is thus uniformly large, is incorporated into an organic binder [component B)] with a comparatively high degree of filling. The organic binder fills the usually uniformly large and regularly arranged spaces between the powder particles. The macropores present in the starting powder of component A) due to the formation of agglomerates in the region around 100 μm are generally eliminated by the deagglomeration. After removal of the organic binder and the organic dispersant, when using powders with a narrow monomodal particle size distribution, there are strictly uniformly large pores between the powder particles. As a rule, the average pore diameter is 25% of the average grain diameter of the powder used (see Table IIIa [dm / kg]). When using powders with a polymodal particle size distribution or when using porous powders, polymodal (bimodal, trimodal, tetramodal or higher-modal) pore distributions can also be produced, the pore size being determined by the spaces between the powder particles and by the internal porosity of the powder particles.

The catalysts according to the invention can be heterogeneous supported catalysts or unsupported catalysts. Fully catalytic converters consist of catalytically active material. Supported catalysts can be produced by coating inert porous ceramic or metallic catalyst supports with catalytically active components or precursors of catalytically active components by impregnation, impregnation, spray impregnation, spray drying, precipitation, hicoates, washcoats.

The invention further relates to monomodal or polymodal catalyst supports or catalysts which can be prepared by shaping a mixture<ul id="ul0008" list-style="none" compact="compact"><li>A) 15 to 70% by volume<ul id="ul0009" list-style="none"><li>I) an inorganic powder selected from the group of oxides, nitrides, carbides, silicates, aluminosilicates of the elements beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, antimony , Selenium, tellurium, polonium, astatine, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, zinc, cadmium, mercury, scandium, yttrium, lanthanum, actinium, titanium, zircon , Hafnium, vanadium, niobium, Tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, cerium, praseodymium or their mixtures and / or</li><li>II) a metallic powder selected from metals and alloys of the elements boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, antimony, selenium, tellurium, polonium, neodymium, samarium, dysprosium, astatine, iron, cobalt, Raney cobalt, nickel, Raney nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, zinc, cadmium, mercury, scandium, yttrium, lanthanum, actinium, titanium, zirconium, hafnium, vanadium, Niobium, tantalum, chrome, molybdenum, tungsten, Manganese, technetium, rhenium, cerium, praseodymium, WC, TiC, TaC, VC or their mixtures, WC-Cobalt, TiC-Cobalt, TaC-Cobalt, VC-Cobalt or their mixtures as well as carbon and / or</li><li>III) an active component selected from the group of inorganic acids, the metals selected from lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, silicon, Germanium, tin, lead, arsenic, antimony, bismuth, selenium, tellurium, polonium, astatine, iron, cobalt, Raney cobalt, Nikkel, Raney nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, Gold, zinc, cadmium, mercury, Scandium, yttrium, lanthanum, actinium, titanium, zircon, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, cerium, praseodymium, their mixtures, or their borates, carbonates, silicates, nitrates, phosphates , Arsenates, antimonates, bismuthates, sulfates, selenates, tellurates, vanadates, molybdate, niobates, chromates, oxides, hydroxides, halides, sulfides, selenides, tellurides, nitrides, phosphides, arsenides, acetates, acetylacetonates, palladates, platinates, Cyanides, rhodanides, manganates, rhenates, osmates, carbides, silicides, borides, their ammonium compounds or their mixtures and / or</li><li>IV) an organic powder selected from the group Teflon or polyimide</li></ul></li><li>B) 30 to 85 vol .-% of a mixture of<ul id="ul0010" list-style="none" compact="compact"><li>B₁) 50 to 100 wt .-% of a polyoxymethylene homo- or copolymer and</li><li>B₂) 0 to 50% by weight of one in B₁) homogeneously dissolved or with an average particle size of less than 1 µm in B₁) dispersed polymer and</li></ul></li><li>C) 0 to 15% by volume of a dispersing aid,</li></ul>

Removal of the binder by treatment with a gaseous acid at temperatures from 100 to 160 ° C, residual pyrolysis at temperatures from 400 to 600 ° C and subsequent presintering at temperatures from 600 to 1400 ° C and optionally applying active components III on component A) or on the pre-sintered mass by, if necessary, multiple impregnation, impregnation, spray impregnation, striking, hicoating, washcoating or spray drying, characterized in that that the catalyst supports or catalysts after the pyrolytic removal of the binder have a BET specific surface area of ​​0.01 to 250 m²/ g and a pore size distribution of 50 to 300,000 nm measured using the mercury pressure porosimetry method.

The catalyst supports or catalysts according to the invention are generally suitable for use in:<ul id="ul0011" list-style="dash"><li>Reductions (hydrogenations), for example: Hydrogenation of alkynes such as the selective hydrogenation of acetylene in C₂-, C₃-, C₄Mixtures, the selective hydrogenation of vinyl acetylene in C₄-Cuts and the hydrogenation of butynediol to butenediol or butanediol, the hydrogenation of alkenes such as the hydrogenation of unsaturated compounds in oxo synthesis, the aminating hydrogenation, the aromatic hydrogenation, the diolefin hydrogenation such as the hydrogenation of diolefins in pyrolysis gasoline, the fat hydrogenation, the hydrogenation Desulphurization such as the hydrogenation of inorganic sulfur compounds, e.g. COS, CS₂, SO₂ and S_x to hydrogen sulfide, the hydrogenating refining of aromatics or paraffins, the hydrogenation of organic chlorine compounds, the hydrogenation of aldehydes, carboxylic acids, carboxylic acid esters, ketones, nitriles, nitro compounds, oximes and oxo products such as the reduction of nitrobenzene to aniline, the hydrogenation of carbonyl groups and aromatics e.g. for white oil production, the hydrogenation of trimethylquinone to trimethylhydroquinone, the hydrogenation of adiponitrile to hexamethylenediamine, acrylonitrile, NH₃ and the hydrogenation of adipic acid to hexanediol, the hydrogenation of cyclohexyl hydroperoxide to cyclohexanol, the hydrogenation of citral to citronellal, the production of lilial from dehydrolilial, the removal of NO_x from exhaust gases by reduction with ammonia and the production of alkanes, olefins, alcohols, aldehydes and / or carboxylic acids from synthesis gas, the hydrogenation of adiponitrile to aminocapronitrile, the aminating hydrogenation of adipic acid to aminocapronitrile;</li><li>Oxidations (dehydrations), for example: Oxidations of alkanes such as the dehydrogenation of ethylbenzene to styrene or dimethylcyclohexylamine to 2,6-dimethylaniline, of alkenes, of alcohols such as the dehydrogenation of cyclohexanol to cyclohexanone and the production of ethylhexanoic acid and ethylhexanal from ethylhexenol, the ammoxidation such as the production of hydrogen cyanide from methane or from o-xylene to phthalonitrile, from aromatics, epoxidation, oxidative halogenation, oxidative coupling, Oxidation of hydrogen sulfide gases to sulfur by the Claus process, the production of vinyl chloride by the oxychlorination process (Stauffer process), the oxidation of hydrogen sulfide and / or organic sulfur compounds to sulfur dioxide, the production of sulfuric acid by the "contact process" from SO₂-containing gases, the production of phthalic anhydride from o-xylene and air, the catalytic combustion of hydrocarbons, solvents or CO-contaminated exhaust gas, the production of ethylene dichloride by oxychlorination of ethylene, the oxidation of propene to acrylic acid, the production of methacrylic acid from methacrolein, the production of methacrylic acid from isobutyric acid, the dehydrogenation of DMCHA to xylidine and the dehydrogenation of trimethylcyclohexenone to trimethylphenol, the Oxidation of ethylene to ethylene oxide, oxidation of butadiene to furan, oxidation of propene to acrolein, the oxidation of methacrolein to methacrylic acid;</li><li>acidic or basic catalyzed reactions, for example: Alkoxylations, for example of ethylene oxide or propylene oxide, dealkoxylations, for example of N-vinylformamide from α-methoxyethylformamide, alkylations, acylations, hydrations, dehydrations, for example of aziridine from ethanolamine or of hydrocyanic acid from formamide, aminations, aldol reactions, oligomerizations, polymerizations, polymer-analog reactions, cyclizations, isomerizations, esterifications, cracking of gaseous hydrocarbons (cracking), for example natural gas with water vapor and optionally CO₂, the oxidation of propene to acrolein, elimination reactions such as N-formylalanine nitrile to N-vinylformamide, additives such as methanol or propyne on α-methoxy groups.</li></ul>

In addition, macroporous supports with a pore size between 100 and 10,000 nm are suitable for removing combustion residues (soot) from diesel exhaust gases and for bioreactors in connection with the use of bacteria (1 to 2 µm).

The catalyst supports or catalysts produced by the process according to the invention have comparatively high mechanical strengths and are therefore particularly suitable for fluidized bed reactions.

Fluid bed reactions include, for example, the rearrangement of cyclohexanone oxime to ε-caprolactam, the ammoxidations, for example toluene to benzonitrile or propene to acrylonitrile, the production of maleic anhydride from butene or the production of aniline from nitrobenzene.

Accordingly, the invention also relates to the use of the catalyst supports and catalysts according to the invention for the production of chlorine from hydrogen chloride in a transient Deacon process, for the conversion of ethylbenzene to styrene in a transient oxy-dehydrogenation, for the production of aziridine from ethanolamine, for the conversion of trimethylcyclohexenone to trimethylphenol in the case of reductions, Hydrogenations, oxidations, dehydrations, acidic or basic catalyzed reactions or reactions in the fluidized bed, for the removal of combustion residues from diesel exhaust gases and for the removal of NO_x from exhaust gases, in bioreactors together with bacteria and as a biocatalyst support with immobilized enzymes or microbes.

Examples

Examples 1 to 9

The ceramic powders from Table I were made with a polyacetal-based binder consisting of a polyoxymethylene copolymer (POM / PBDF) made from trioxane and 2.5% by weight butanediol formal with an average molecular weight of 150,000 and with 20% by weight polybutanediol formal with a molecular weight of 50,000 and 5 wt .-% (based on the powder used) polyethylene glycol with a molecular weight of 800 as an auxiliary, kneaded at 180 ° C. The modeling clay of powder no. 1, 2, 7, 8 from Table I was processed into granules using a knife mill. The modeling clay of powders No. 3, 4, 5, 6, 9 from Table I was extruded at 180 ° C. into strands with a diameter of 4 mm. The granules and the strands were in a HERAEUS debinding oven (60 l) with 70 ml / h of a 5% by weight solution of oxalic acid in acetic acid (99%) or 30 ml / h of 100% nitric acid at 140 ° C. under an N₂- Stream of 300 l / h debinded for 10 hours, the polyoxymethylene depolymerizing to formaldehyde. The strands and the granules were then presintered in air in the muffle furnace or rotary tube furnace at the temperatures given in Table II. The pore radius distributions and further properties of the strands and the granules can be found in Tables IIIa and IIIb.<tables id="tabl0001" num="0001"><img file="EP0761307B1_D0001.tif" /></tables><tables id="tabl0002" num="0002"><img file="EP0761307B1_D0002.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0761307B1_D0003.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0761307B1_D0004.tif" /></tables><tables id="tabl0005" num="0005"><img file="EP0761307B1_D0005.tif" /></tables>

Examples 10 and 11

The metal powders No.10 (BASF, CEP) and No.11 (HC STARCK, 316L, Fe-Cr-Ni-Mo) from Table IV were mixed with a polyacetal-based binder consisting of a polyoxymethylene copolymer (POM / PBDF) made from trioxane and 1.5% by weight of butanediol formal with an average molecular weight of 150,000, and with about 10% by weight of polyethylene or polymethyl methacrylate, both with a molecular weight of 150,000 and 2% by weight (based on on the powder used) polyethylene oxide with a molecular weight of 400 as an auxiliary, kneaded at 180 ° C., granulated via a kneader discharge screw and in a HERAEUS debinding oven (60 l) with 70 ml / h of a 5% by weight solution of oxalic acid and Acetic acid (99%) or 30 ml / h 100% nitric acid at 140 ° C under a N.₂Stream of 300 l / h debinded for 10 hours, the polyoxymethylene depolymerizing to formaldehyde. The pellets were then presintered in air at the temperatures given in Table V. The pore radius distributions and other properties of the granules can be found in Tables VIa and VIb.

Example 12

The bimodal ZrO₂Powder (MEL, E101, 60% of particles d = 1.3 µm, 40% of particles d &lt;1.0 µm) from Table IV, No. 10 was extruded at 180 ° C. together with a polyacetal-based binder, granulated and in a HERAEUS debinding oven (60 l) with 55 ml / h of a 5% by weight solution of oxalic acid and acetic acid (99%) or 30 ml / h of 100% nitric acid at 140 ° C under an N₂- Stream of 300 l / h debinded for 10 hours, the polyoxymethylene depolymerizing to formaldehyde. The pellets were then presintered in air at the temperatures given in Table V. The pore radius distributions and other properties of the granules can be found in Tables VIa and VIb.<tables id="tabl0006" num="0006"><table frame="all"><title>Table IV</title><tgroup cols="11" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="14.31mm" /><colspec colnum="2" colname="col2" colwidth="14.31mm" /><colspec colnum="3" colname="col3" colwidth="14.31mm" /><colspec colnum="4" colname="col4" colwidth="14.31mm" /><colspec colnum="5" colname="col5" colwidth="14.31mm" /><colspec colnum="6" colname="col6" colwidth="14.31mm" /><colspec colnum="7" colname="col7" colwidth="14.31mm" /><colspec colnum="8" colname="col8" colwidth="14.31mm" /><colspec colnum="9" colname="col9" colwidth="14.31mm" /><colspec colnum="10" colname="col10" colwidth="14.31mm" /><colspec colnum="11" colname="col11" colwidth="14.31mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">Example No.</entry><entry namest="col2" nameend="col2" align="center">powder</entry><entry namest="col3" nameend="col3" align="center">Name [vol .-%]</entry><entry namest="col4" nameend="col4" align="center">Powder content [g]</entry><entry namest="col5" nameend="col5" align="center">Amount of powder [g]</entry><entry namest="col6" nameend="col6" align="center">Polyacetal [g]</entry><entry namest="col7" nameend="col7" align="center">PBDF [g]</entry><entry namest="col8" nameend="col8" align="center">PE [g]</entry><entry namest="col9" nameend="col9" align="center">PMMA [g]</entry><entry namest="col10" nameend="col10" align="center">PEG [g]</entry><entry namest="col11" nameend="col11" align="center">PEO [g]</entry></row></thead><tbody valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">10</entry><entry namest="col2" nameend="col2" align="center">Fe</entry><entry namest="col3" nameend="col3" align="left">BASF CEP</entry><entry namest="col4" nameend="col4" align="center">57</entry><entry namest="col5" nameend="col5" align="center">1000</entry><entry namest="col6" nameend="col6" align="center">92</entry><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" align="center">10</entry><entry namest="col9" nameend="col9" /><entry namest="col10" nameend="col10" /><entry namest="col11" nameend="col11" align="center">20</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">11</entry><entry namest="col2" nameend="col2" align="center">316L</entry><entry namest="col3" nameend="col3" align="left">HC STARCK 316L</entry><entry namest="col4" nameend="col4" align="center">64</entry><entry namest="col5" nameend="col5" align="center">1000</entry><entry namest="col6" nameend="col6" align="center">64</entry><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" align="center">7</entry><entry namest="col10" nameend="col10" /><entry namest="col11" nameend="col11" align="center">20</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">12</entry><entry namest="col2" nameend="col2" align="center">ZrO₂</entry><entry namest="col3" nameend="col3" align="left">MEL E101</entry><entry namest="col4" nameend="col4" align="center">35</entry><entry namest="col5" nameend="col5" align="center">1000</entry><entry namest="col6" nameend="col6" align="center">276</entry><entry namest="col7" nameend="col7" align="center">69</entry><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /><entry namest="col10" nameend="col10" align="center">50</entry><entry namest="col11" nameend="col11" /></row><row><entry namest="col1" nameend="col11" align="justify">Polyacetal: copolymer of trioxane and 2.5% butanediol formal, molecular weight 150,000</entry></row><row><entry namest="col1" nameend="col11" align="justify">PBDF = polybutanediol formal, molecular weight 50,000</entry></row><row><entry namest="col1" nameend="col11" align="justify">PE = polyethylene, molecular weight 150,000, D = 0.95g / ml</entry></row><row><entry namest="col1" nameend="col11" align="justify">PMMA = polymethyl methacrylate, molecular weight 150,000, D = 1.17g / ml, Lucryl G88 UV1 [BASF]</entry></row><row><entry namest="col1" nameend="col11" align="justify">PEG = polyethylene glycol, molecular weight 800</entry></row><row rowsep="1"><entry namest="col1" nameend="col11" align="justify">PEO = polyethylene oxide, molecular weight 400</entry></row></tbody></tgroup></table></tables><tables id="tabl0007" num="0007"><table frame="all"><title>Table V</title><tgroup cols="7" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="22.50mm" /><colspec colnum="2" colname="col2" colwidth="22.50mm" /><colspec colnum="3" colname="col3" colwidth="22.50mm" /><colspec colnum="4" colname="col4" colwidth="22.50mm" /><colspec colnum="5" colname="col5" colwidth="22.50mm" /><colspec colnum="6" colname="col6" colwidth="22.50mm" /><colspec colnum="7" colname="col7" colwidth="22.50mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">Example No.</entry><entry namest="col2" nameend="col2" align="center">powder</entry><entry namest="col3" nameend="col3" align="center">designation</entry><entry namest="col4" nameend="col4" align="center">average grain size [µm]</entry><entry namest="col5" nameend="col5" align="center">Sintering temperature [° C]</entry><entry namest="col6" nameend="col6" align="center">Sintered tent [h]</entry><entry namest="col7" nameend="col7" align="center">Pore ​​size distribution Fig. No.</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="center">10</entry><entry namest="col2" nameend="col2" align="left">Fe</entry><entry namest="col3" nameend="col3" align="left">BASF CEP</entry><entry namest="col4" nameend="col4" align="left">4</entry><entry namest="col5" nameend="col5" align="left">600</entry><entry namest="col6" nameend="col6" align="left">2</entry><entry namest="col7" nameend="col7" align="left">10</entry></row><row><entry namest="col1" nameend="col1" align="center">11</entry><entry namest="col2" nameend="col2" align="left">316L</entry><entry namest="col3" nameend="col3" align="left">HC STARCK 316L</entry><entry namest="col4" nameend="col4" align="left">10</entry><entry namest="col5" nameend="col5" align="left">1000</entry><entry namest="col6" nameend="col6" align="left">1</entry><entry namest="col7" nameend="col7" align="left">11</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">12</entry><entry namest="col2" nameend="col2" align="left">ZrO₂</entry><entry namest="col3" nameend="col3" align="left">MEL E101</entry><entry namest="col4" nameend="col4" align="left">0,9</entry><entry namest="col5" nameend="col5" align="left">800</entry><entry namest="col6" nameend="col6" align="left">2</entry><entry namest="col7" nameend="col7" align="left">12</entry></row></tbody></tgroup></table></tables><tables id="tabl0008" num="0008"><table frame="all"><title>Table VIa</title><tgroup cols="12" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="13.12mm" /><colspec colnum="2" colname="col2" colwidth="13.12mm" /><colspec colnum="3" colname="col3" colwidth="13.12mm" /><colspec colnum="4" colname="col4" colwidth="13.12mm" /><colspec colnum="5" colname="col5" colwidth="13.12mm" /><colspec colnum="6" colname="col6" colwidth="13.12mm" /><colspec colnum="7" colname="col7" colwidth="13.12mm" /><colspec colnum="8" colname="col8" colwidth="13.12mm" /><colspec colnum="9" colname="col9" colwidth="13.12mm" /><colspec colnum="10" colname="col10" colwidth="13.12mm" /><colspec colnum="11" colname="col11" colwidth="13.12mm" /><colspec colnum="12" colname="col12" colwidth="13.12mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">Example No.</entry><entry namest="col2" nameend="col2" align="center">dm nm</entry><entry namest="col3" nameend="col3" align="center">dm / KG</entry><entry namest="col4" nameend="col4" align="center">d10 nm</entry><entry namest="col5" nameend="col5" align="center">d10 / dm</entry><entry namest="col6" nameend="col6" align="center">d50</entry><entry namest="col7" nameend="col7" align="center">d50 / dm</entry><entry namest="col8" nameend="col8" align="center">d80</entry><entry namest="col9" nameend="col9" align="center">d80 / dm</entry><entry namest="col10" nameend="col10" align="center">d90</entry><entry namest="col11" nameend="col11" align="center">d95</entry><entry namest="col12" nameend="col12" align="center">d95 / dm</entry></row></thead><tbody valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">10</entry><entry namest="col2" nameend="col2" align="center">1850</entry><entry namest="col3" nameend="col3" align="char" char=",">0,46</entry><entry namest="col4" nameend="col4" align="center">1940</entry><entry namest="col5" nameend="col5" align="char" char=",">1,0</entry><entry namest="col6" nameend="col6" align="center">1870</entry><entry namest="col7" nameend="col7" align="char" char=",">1,0</entry><entry namest="col8" nameend="col8" align="center">1650</entry><entry namest="col9" nameend="col9" align="char" char=",">0,9</entry><entry namest="col10" nameend="col10" align="center">1422</entry><entry namest="col11" nameend="col11" align="center">1073</entry><entry namest="col12" nameend="col12" align="char" char=",">0,6</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">11</entry><entry namest="col2" nameend="col2" align="center">4422</entry><entry namest="col3" nameend="col3" align="char" char=",">0,44</entry><entry namest="col4" nameend="col4" align="center">5200</entry><entry namest="col5" nameend="col5" align="char" char=",">1,2</entry><entry namest="col6" nameend="col6" align="center">4300</entry><entry namest="col7" nameend="col7" align="char" char=",">1,0</entry><entry namest="col8" nameend="col8" align="center">3600</entry><entry namest="col9" nameend="col9" align="char" char=",">0,8</entry><entry namest="col10" nameend="col10" align="center">2830</entry><entry namest="col11" nameend="col11" align="center">1955</entry><entry namest="col12" nameend="col12" align="char" char=",">0,4</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">12</entry><entry namest="col2" nameend="col2" align="center">350/40</entry><entry namest="col3" nameend="col3" align="char" char=",">0,39</entry><entry namest="col4" nameend="col12" align="center">bimodal pore distribution</entry></row><row><entry namest="col1" nameend="col12" align="justify">Hg pressure porosimetry with Autopore II 9220 V3.03 according to DIN 66133</entry></row><row><entry namest="col1" nameend="col12" align="justify">KG = medium grain size</entry></row><row><entry namest="col1" nameend="col12" align="justify">dm = average pore diameter</entry></row><row><entry namest="col1" nameend="col12" align="justify">d10 = pore diameter at 10% of the total pore volume</entry></row><row><entry namest="col1" nameend="col12" align="justify">d50 = pore diameter at 50% of the total pore volume</entry></row><row><entry namest="col1" nameend="col12" align="justify">d80 = pore diameter at 80% of the total pore volume</entry></row><row><entry namest="col1" nameend="col12" align="justify">d90 = pore diameter at 90% of the total pore volume</entry></row><row rowsep="1"><entry namest="col1" nameend="col12" align="justify">d95 = pore diameter at 95% of the total pore volume</entry></row></tbody></tgroup></table></tables><tables id="tabl0009" num="0009"><table frame="all"><title>Table VIb</title><tgroup cols="6" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">Example No.</entry><entry namest="col2" nameend="col2" align="center">HWB [nm]</entry><entry namest="col3" nameend="col3" align="center">HWB / dm</entry><entry namest="col4" nameend="col4" align="center">GPV [ml / g]</entry><entry namest="col5" nameend="col5" align="center">GPF [m²/G]</entry><entry namest="col6" nameend="col6" align="center">BET surface area [m²/G]</entry></row></thead><tbody valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">10</entry><entry namest="col2" nameend="col2" align="center">100</entry><entry namest="col3" nameend="col3" align="char" char=",">0,05</entry><entry namest="col4" nameend="col4" align="char" char=",">0,09</entry><entry namest="col5" nameend="col5" align="char" char=",">1,1</entry><entry namest="col6" nameend="col6" align="char" char=",">0,4</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">11</entry><entry namest="col2" nameend="col2" align="center">600</entry><entry namest="col3" nameend="col3" align="char" char=",">0,14</entry><entry namest="col4" nameend="col4" align="char" char=",">0,09</entry><entry namest="col5" nameend="col5" align="char" char=",">0,8</entry><entry namest="col6" nameend="col6" align="char" char=",">0,1</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">12</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" align="char" char=",">0,33</entry><entry namest="col5" nameend="col5" align="char" char=",">12,5</entry><entry namest="col6" nameend="col6" /></row><row><entry namest="col1" nameend="col6" align="justify">Hg pressure porosimetry with Autopore II 9220 V3.03 according to DIN 66133</entry></row><row><entry namest="col1" nameend="col6" align="justify">HWB = half-width of the pore size distribution</entry></row><row><entry namest="col1" nameend="col6" align="justify">dm = average pore diameter</entry></row><row><entry namest="col1" nameend="col6" align="justify">GPV = total pore volume (300 to 0.005 µm)</entry></row><row rowsep="1"><entry namest="col1" nameend="col6" align="justify">GPF = total pore area (300 to 0.005 µm)</entry></row></tbody></tgroup></table></tables>

Comparative Example A

650g SiC (HC STARCK, UF15) were mixed with 150g H₂O and 48g ENT₃ Kneaded for 35 minutes and extruded into 4mm strands at 45 to 150 ° C.

The strands were calcined in air at 800 and 1100 ° C. The strands fell into powder (cutting hardness = 0 kg)

Comparative Example B

The commercially available α-Al₂O₃-Catalyst carrier SPHS12 from Rhone Poulenc has a comparable BET surface area of ​​5.4 m²/ g and a total pore volume of (GPV) of 0.51 ml / g a much wider pore distribution (see FIG. 13) than the Al according to the invention₂O₃-Catalyst carrier CT3000SG from ALCOA in Tables IIIa and IIIb, Examples No. 1b and 1b.

Comparative Example C

ZrO₂-The carrier has a lower hardness after conventional kneading and extrusion.

300g ZrO₂Powder (starting product from Example 3) from TOSOH, TZ-3YS, and 9 g of extrusion aids were mixed with 31 ml of water, compacted in a kneader for 2.5 h and then shaped into 3 mm full strands in an extruder. The strands were dried at 120 ° C. for 2 hours and then calcined in air at 800 ° C. for 2 hours (same calcining temperature as in Example 3).

The following properties were measured on the full strands: <tables id="tabl0010" num="0010"><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="left"><b>example</b></entry><entry namest="col2" nameend="col2" align="center"><b>C.</b></entry><entry namest="col3" nameend="col3" align="center"><b>3</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Cutting hardness [kg]</entry><entry namest="col2" nameend="col2" align="char" char=",">0,6</entry><entry namest="col3" nameend="col3" align="char" char=",">2,6</entry></row><row><entry namest="col1" nameend="col1" align="left">BET surface area [m²/G]</entry><entry namest="col2" nameend="col2" align="char" char=",">5,8</entry><entry namest="col3" nameend="col3" align="char" char=",">5,8</entry></row><row><entry namest="col1" nameend="col1" align="left">Water absorption [ml / g]</entry><entry namest="col2" nameend="col2" align="char" char=",">0,22</entry><entry namest="col3" nameend="col3" align="char" char=",">0,19</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Ramming weight [g / ml]</entry><entry namest="col2" nameend="col2" align="char" char=",">1,455</entry><entry namest="col3" nameend="col3" align="char" char=",">1,543</entry></row></tbody></tgroup></table></tables>

Comparative Example D

Much lower hardness than a conventional ZrO₂Carrier even at high calcining temperatures.

100g surface-rich Zr (OH)₄ (BET: 310 m²/ g) was added with 3 g of extrusion aid and 45 ml of water and compacted in a kneader for 1.5 hours. Extrusion attempts to shape this ZrO₂- Carriers do not get there, since the strands disintegrated into powder again when drying (cutting hardness = 0 kg). Therefore, the undrawn plasticine was calcined at 500 ° C for 2 hours. The BET surface area of ​​the powder after calcination at 500 ° C. was 69.8 m²/G. After the calcination (2 hours at 800 ° C.), the BET surface area was 11.2 m²/G.

Example 13 [Transient Deacon Process]

Catalyst: Cu-K-Fe-Na on SiC support

Production of the SiC carrier

:

1000 g SiC (NORTON, FCP-13-NLC) were mixed with a polyacetal-based binder consisting of 281 g polyoxymethylene copolymer (POM / PDF) made from trioxane and 2.5% by weight butanediol formal with an average molecular weight of 150,000 and with 70 g Polybutanediol formal with a molecular weight of 50,000 and 50 g of polyethylene glycol with a molecular weight of 800 as auxiliary, kneaded at 180 ° C., extruded, granulated and in a HERAEUS debindering oven (60 l) with 70 ml / h of a 5% by weight solution of oxalic acid in acetic acid (99%) or 30 ml / h of 100% nitric acid at 140 ° C under an N₂-Binded flow of 300 l / h for 10 h. The granules were then at 600 ° C for 2 h under N₂ presintered. An SiC support with a BET surface area of ​​17.1 m was obtained²/ g and a water absorption of 0.342 ml / g.

Impregnation of the SiC carrier

:

300 g of the SiC carrier were washed twice with 102.6 ml of a solution of 95.99 g of CuCl₂* 2H₂O, 41.97g KCl dissolved in distilled water (total solution 205.2 ml), impregnated, dried for 16 h at 120 ° C (after each impregnation step) and calcined at 450 ° C for 3 h.

307 g of the previously impregnated SiC carrier were three times with 105 ml of a solution of 37.39 g NaCl and 172.99 g FeCl₃* 6H₂O dissolved in distilled water (total solution 315 ml), impregnated for 16 h at 120 ° C (after each impregnation step) and calcined for 3 h at 450 ° C. A red-brown granulate with the chemical composition 8.1% by weight of iron and 6.4% by weight of copper was obtained.

General regulation for transient chlorine production

:

A split fraction of 0.5 to 1 mm was introduced into a heated tubular reactor with a 20 ml fixed bed of catalyst. After the loading phase with a dry HCl stream and subsequent purging phase with inert gas (N.₂ or CO₂) was regenerated (dechlorinated) with air or pure oxygen. This cycle was repeated.

The HCl concentration was measured by on-line IR analysis and the chlorine concentration was continuously measured with high time resolution by on-line UV analysis. The integral amount of chlorine which was released during the dechlorination could also be determined by wet chemical (iodometric) control.

The results are summarized in Table VII.<tables id="tabl0011" num="0011"><img file="EP0761307B1_D0006.tif" /></tables><tables id="tabl0012" num="0012"><img file="EP0761307B1_D0007.tif" /></tables>

Comparative Example E [Transient Deacon Process]:

Comparative catalyst: (Cu-Fe-K on Al

2

O

3

-Carrier)

200 g Al₂O₃ (Pural SCF rings) were mixed with 92 ml of a solution of 32.16 g of CuCl₂* 2H₂0.58 g FeCl₃* 6H₂O, 30 g KCl and 114 ml water soaked (water absorption: 0.46 ml / g), dried for 16 h at 120 ° C, calcined for 3 h at 450 ° C and then soaked with the remaining 85 ml of the solution, 16 h at 120 ° C dried and calcined at 450 ° C for 3 h. The comparative catalyst C contained 3.8% by weight of Cu and 4.5% by weight of Fe; Tamped weight: 0.974 g / ml (9.5 to 1 mm grit); BET surface area: 68.6 m²/G.

When trying to soak the contact a third time, it fell apart.

Comparative Example F

Cu-Fe-K on Al

2

O

3

-Carrier

Analogous to the general rule for transient chlorine production, the comparative catalyst Cu-Fe-K was changed to Al₂O₃ at 365 ° C and HCl gas flows between 4 to 5 Nl / h with 25% HCl (higher concentrations of HCl the carrier could not withstand) with an HCl breakthrough time of 10 to 14 minutes. The dechlorination was carried out with 20 Nl / h air at a regeneration temperature of 365 ° C with dechlorination times of 60 minutes and an integral amount of chlorine of 0.9 g, which resulted in a space-time yield of 34 kg chlorine / t cat. * H .

If the dechlorination was carried out with 20 Nl / h air at a regeneration temperature of 380 ° C, dechlorination times of 35 minutes and an integral amount of chlorine of 0.7 g were found, resulting in a space-time yield of 38 kg chlorine / t cat. * h resulted.

At a reactor temperature of 400 ° C during loading and during dechlorination, a maximum chlorine concentration of 8 vol.% Cl was obtained₂ and an average chlorine concentration of 4 vol.% Cl₂ with dechlorination times (up to &lt;2 vol.% chlorine) of 25 minutes. The total amount of chlorine released was 1 g. The maximum measured space-time yield was 40 kg chlorine / t cat. * H.