Narrow pore size distribution monomodal and polymodal catalysts and catalyst carriers, and their manufacture

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 which can be varied in the mesopore range (2 to 50 mm) are known by hydrothermal synthesis. 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 polystyrene, 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 broad, 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 metallic molded parts and EP-A-444 475 the production of dense ceramic molded articles by 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 carrier materials with an essentially bimodal pore size distribution, the pore size distribution being relatively broad.

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 1-8 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<ul id="ul0001" list-style="none"><li>measured using the mercury pressure porosimetry method and</li><li>a) 10 to 95% of the pore volume at 0.2 to 100 times and / or</li><li>b) 10 to 80% of the pore volume at 0.8 to 100 times and / or</li><li>c) 50 to 95% of the pore volume at 0.2 to 1 times and / or</li><li>d) 50 to 80% of the pore volume is 0.8 to 1 times the average pore diameter and</li><li>e) the half width of the pore size distribution is less than 0.6 times the modal pore diameter, and</li></ul> a process for their preparation by molding a mixture<ul id="ul0002" list-style="none" compact="compact"><li>A) 15 to 70 vol .-% I) of 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<ul id="ul0003" list-style="none"><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, TiCCobalt, 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 polyethylene or polypropylene polymer or a copolymer of ethylene, propylene, butene-1 or isobutene or a polystyrene copolymer or a polymethyl methacrylate copolymer or a polyethylene oxide copolymer or an ethylene vinyl acetate copolymer or 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 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, Removal of the binder and subsequent pre-sintering and, if appropriate, application of active components III) to component A) or to the pre-sintered mass by, if appropriate, multiple impregnation, impregnation, spray impregnation, precipitation, hicoating, washcoating or spray drying, by means of component A) using a nanocrystalline powder with a average grain size from 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 pyrolysis at temperatures of 300 to 600 ° C and pre-sintered at temperatures of 600 to 1400 ° C and the catalyst supports or catalysts the pyrolytic removal of the binder has a BET specific surface area 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 oxy-dehydrogenation, for the production of aziridine 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.</li></ul>

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 0.2 to 100 times and / or</li><li>b) 10 to 80%, preferably 30 to 80%, particularly preferably 50 to 80% of the pore volume at 0.8 to 100 times and / or</li><li>c) 50 to 95%, preferably 70 to 95%, particularly preferably 80 to 95% of the pore volume at 0.2 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 0.8 to 1 times the average pore diameter and</li><li>e) the half width of the pore size distribution is less than 0.6 times, ie 0.001 to 0.59 times, preferably 0.005 to 0.4 times, particularly preferably 0.1 to 0.35 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 are met, particularly preferred are those in which the conditions a), b) and c) or a), b) and d) or a), c) and d) or a), c) and d) or b) , c) and d) are fulfilled simultaneously, 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 dispersant of component C) or first component C) and then component A) or components A) and C) are added together. The intimately (intensively) mixed masses can be, 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 up to 1600 bar. 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.

Carriage wheel profiles, honeycomb profiles and window frame profiles can be extruded into monoliths at temperatures of 120 to 280 ° C, particularly preferably at 180 to 200 ° C.

The green bodies obtained after the shaping process can be treated by pyrolysis at 300 to 600 ° C., preferably 350 to 600 ° C., particularly preferably 400 to 600 ° C. and by subsequent presintering, at temperatures of 600 to 1400 ° C., preferably 600 to 1100 ° C, particularly preferably at 600 to 800 ° C under oxidizing conditions (air), inert gas (N₂, Ar, He) or reducing conditions (N₂/H₂, Ar / H₂) to 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 in this way. 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 reactions.

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 and 150 m²/ g, particularly preferably 1 and 100 m²/ g, especially 2 to 8 m²/ g (800 ° C).

The average pore size is generally determined by the particle size of component A), the inorganic, metallic, organic powders and / or the active components, as a rule only by the spaces 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 preferably 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, Raney-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, F₂O₃, 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):

Polyethylene or polypropylene polymers or copolymers of ethylene, propylene, butene-1 or isobutene or polystyrene copolymers or polymethyl methacrylate copolymers or polyethylene oxide copolymers or ethylene-vinyl acetate copolymers or mixtures of<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 wt .-%, preferably 10 to 30 wt .-%, particularly preferably 12 to 25 wt .-% of one in B.₁) homogeneously dissolved or with an average particle size of less than 1 µm in B₁) dispersed polymer, preferably poly-1,3-dioxolane, poly-1,3-dioxane, poly-1,3-dioxepane, particularly preferably poly-1,3-dioxepane.</li></ul>

The organic binder can also consist of mixtures of one or more thermoplastic resins, such as polyacetal, polyethylene, polypropylene, polystyrene, polymethyl methacrylate and one or more plasticizers, such as polyethylene glycol, polypropylene glycol, polybutanediol formal, phthalic acid esters, ethylene-vinyl acetate copolymers and montan ester waxes.

A suitable polyacetal binder is, 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-dioxepane 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, polyvinyl pyrrolidine or polyvinyl alcohol. The amount of auxiliaries is generally between 0.1 and 12% by weight of the total mass.

Suitable as component C) are dispersing agents as are known from EPA-0 444 475, 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 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 uniformly large starting powder particles are thus 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 [P5-P-Tab 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 also 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 polyethylene or polypropylene polymer or a copolymer of ethylene, propylene, butene-1 or isobutene or a polystyrene copolymer or a polymethyl methacrylate copolymer or a polyethylene oxide copolymer or an ethylene vinyl acetate copolymer or 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 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 vol .-% of a dispersing aid, removal of the binder by pyrolysis at temperatures from 300 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 presintered mass by optionally multiple impregnation, impregnation, spray impregnation, conspicuity, hicoates, washcoats 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 300,000nm measured using the mercury pressure porosimetry method.</li></ul>

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 C.₂-, 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 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 or alkanes 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 furan, the oxidation of acrolein to acrylic acid, the oxidation of methacrolein to metharoylic 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 steam and optionally CO₂, the oxidation of propene to acrolein, elimination reaction such as N-formylalononitrile to N-vinylformamide, addition such as methanol and propyne to α-methoxypropene.</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 ∈-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 present invention also relates to the use of the monomodal or polymodal catalyst supports or 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 implementation of trimethylcyclohexenone Trimethylphenol, for reductions, hydrogenations, oxidations, dehydrogenations, 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

example 1

The ceramic powder 1 from Table I was treated 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% by weight (based on the powder used) of polyethylene glycol with a molecular weight of 800 as auxiliary, kneaded at 180 ° C. extruded into strands with a diameter of 4 mm at 180 ° C, which at 600 ° C for 1 h under N₂ pyrolyzed and then pre-sintered in air at various temperatures in a muffle furnace. The process parameters are Table II, the pore radius distributions and further properties of the strands are shown in Tables IIIa and IIIb.

Example 2

The ceramic powder 2 from Table I was compounded with the addition of polyethylene with a molecular weight of 150,000 and a density of 0.95 g / ml and polyethylene oxide with a molecular weight of 400 in a double sigma kneader at 220 ° C. The feedstock was granulated using a discharge screw. The granules were at a temperature of 600 ° C for 1h under N₂ pyrolyzed and then presintered in air in a muffle furnace at 800 ° C for 2 hours. The process parameters are Table II, the pore radius distributions and further properties of the strands are shown in Tables IIIa and IIIb.

Example 3

The ceramic powder 3 from Table I was compounded with the addition of polystyrene with a molecular weight of 100,000 and a density of 1.04 g / ml and polyethylene oxide with a molecular weight of 400 in a double sigma kneader at 200 ° C. The feedstock was granulated using a discharge screw. The granules were 0.5 h under N at a temperature of 500 ° C.₂ pyrolyzed and then pre-sintered at 800 ° C for 0.5 h with 50 l / h air in a rotary kiln. The process parameters are Table II, the pore radius distributions and further properties of the strands are shown in Tables IIIa and IIIb.

Example 4

The ceramic powder 4 from Table I with 90 wt .-% Si₃N₄ (HC STARCK, LC12) and 5 wt% Y₂O₃ (HC STARCK, grade fine) and 5% by weight Al₂O₃ (ALCOA, CT3000SG) was compounded with the addition of polymethyl methacrylate with a molecular weight of 150,000 and a density of 1.17 g / ml and polyethylene oxide with a molecular weight of 400 in a double sigma kneader at 200 ° C. The feedstock was granulated using a discharge screw. The granules were at a temperature of 600 ° C for 1 h under N₂ pyrolyzed and then pre-sintered at 600 ° C in air for 2 h in a muffle furnace. The process parameters are Table II, the pore radius distributions and further properties of the strands are shown in Tables IIIa and IIIb.

Example 5

The ceramic powder 5 from Table I was treated with a polyacetal-based binder consisting of a polyoxymethylene copolymer (POM / PBDF) made from trioxane and 2.5% by weight of butanediol formal with an average molecular weight of 150,000 and with 20% by weight of polybutanediol formal with a Molecular weight of 50,000 and 5 wt .-% (based on on the powder used) polyethylene glycol with a molecular weight of 800 as auxiliary, kneaded at 180 ° C., extruded into strands with a diameter of 4 mm at 180 ° C., which at 600 ° C. under N₂ pyrolyzed and then pre-sintered at 800 ° C for 2 h in a muffle furnace. The process parameters are Table II, the pore radius distributions and further properties of the strands are shown in Tables IIIa and IIIb.

Example 6

The ceramic powder 6 from Table I was treated 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 on the powder used) Polyethylene glycol with a molecular weight of 800 as an auxiliary, kneaded at 180 ° C, extruded into strands with a diameter of 4 mm at 180 ° C, which first pyrolyzed in a muffle furnace at 600 ° C for 1 hour under nitrogen and then at 1100 ° C were pre-sintered in air for 2 h. The process parameters are Table II, the pore radius distributions and further properties of the strands are shown in Tables IIIa and IIIb.

Example 7

The ceramic powder 7 from Table I with a bimodal grain size distribution with maxima at 1 µm was mixed 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 of polybutanediol formal with a molecular weight of 50,000 and 5% by weight (based on on the powder used) polyethylene glycol with a molecular weight of 800 as auxiliary, kneaded at 180 ° C, extruded into strands with a diameter of 4 mm at 180 ° C, which pyrolyzed in a muffle furnace at 600 ° C for 1 h under nitrogen and then at 800 ° C were pre-sintered in air for 2 h. The process parameters are shown in Table II, the pore radius distributions and further properties of the strands are shown in Tables IIIa and IIIb.

Example 8

The ceramic powder 8 from Table I with a bimodal grain size distribution with maxima at 1 μm was mixed 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 wt .-% polybutanediol formal with a molecular weight of 50,000 and 5 wt .-% (based on on the powder used) polyethylene glycol with a molecular weight of 800 as an auxiliary, kneaded at 180 ° C. The cooled product was granulated in a knife mill. The granules were pyrolyzed at 600 ° C. for 1 hour under nitrogen and then pre-sintered in air at 1100 ° C. for 2 hours. The process parameters are Table II, the pore radius distributions and further properties of the strands are shown in Tables IIIa and IIIb.<tables id="tabl0001" num="0001"><table frame="all"><title>Table I</title><tgroup cols="12" colsep="1" rowsep="1"><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"><b>Example No.</b></entry><entry namest="col2" nameend="col2" align="center"><b>powder</b></entry><entry namest="col3" nameend="col3" align="center"><b>designation</b></entry><entry namest="col4" nameend="col4" align="center"><b>Powder content [vol%]</b></entry><entry namest="col5" nameend="col5" align="center"><b>Amount of powder [g]</b></entry><entry namest="col6" nameend="col6" align="center"><b>Polyacetal [g]</b></entry><entry namest="col7" nameend="col7" align="center"><b>PBDF [g]</b></entry><entry namest="col8" nameend="col8" align="center"><b>PE [g]</b></entry><entry namest="col9" nameend="col9" align="center"><b>PMMA [g]</b></entry><entry namest="col10" nameend="col10" align="center"><b>PS [g]</b></entry><entry namest="col11" nameend="col11" align="center"><b>PEG [g]</b></entry><entry namest="col12" nameend="col12" align="center"><b>PEO [g]</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">1</entry><entry namest="col2" nameend="col2" align="center">Al₂O₃</entry><entry namest="col3" nameend="col3" align="center">ALCOA CT3000SG</entry><entry namest="col4" nameend="col4" align="center">56</entry><entry namest="col5" nameend="col5" align="center">1000</entry><entry namest="col6" nameend="col6" align="right">162</entry><entry namest="col7" nameend="col7" align="center">41</entry><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /><entry namest="col10" nameend="col10" /><entry namest="col11" nameend="col11" align="center">50</entry><entry namest="col12" nameend="col12" /></row><row><entry namest="col1" nameend="col1" align="right">2</entry><entry namest="col2" nameend="col2" align="center">Al₂O₃</entry><entry namest="col3" nameend="col3" align="center">ALCOA CT3000SG</entry><entry namest="col4" nameend="col4" align="center">56</entry><entry namest="col5" nameend="col5" align="center">1000</entry><entry namest="col6" nameend="col6" /><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" align="center">169</entry><entry namest="col9" nameend="col9" /><entry namest="col10" nameend="col10" /><entry namest="col11" nameend="col11" /><entry namest="col12" nameend="col12" align="right">20</entry></row><row><entry namest="col1" nameend="col1" align="right">3</entry><entry namest="col2" nameend="col2" align="center">Al₂O₃</entry><entry namest="col3" nameend="col3" align="center">ALCOA CT3000SG</entry><entry namest="col4" nameend="col4" align="center">56</entry><entry namest="col5" nameend="col5" align="center">1000</entry><entry namest="col6" nameend="col6" /><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /><entry namest="col10" nameend="col10" align="right">185</entry><entry namest="col11" nameend="col11" /><entry namest="col12" nameend="col12" align="right">20</entry></row><row><entry namest="col1" nameend="col1" align="right">4</entry><entry namest="col2" nameend="col2" align="center">90% Si₃N₄</entry><entry namest="col3" nameend="col3" align="center">HC STARCK LC12</entry><entry namest="col4" nameend="col4" align="center">50</entry><entry namest="col5" nameend="col5" align="center">900</entry><entry namest="col6" nameend="col6" /><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" align="right">334</entry><entry namest="col10" nameend="col10" /><entry namest="col11" nameend="col11" /><entry namest="col12" nameend="col12" align="right">20</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">5% Y₂O₃</entry><entry namest="col3" nameend="col3" align="center">HC STARCK grade fine</entry><entry namest="col4" nameend="col4" align="center">---</entry><entry namest="col5" nameend="col5" align="center">50</entry><entry namest="col6" nameend="col6" align="right">---</entry><entry namest="col7" nameend="col7" align="center">---</entry><entry namest="col8" nameend="col8" align="center">---</entry><entry namest="col9" nameend="col9" align="right">---</entry><entry namest="col10" nameend="col10" align="right">---</entry><entry namest="col11" nameend="col11" align="center">---</entry><entry namest="col12" nameend="col12" align="right">---</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">5% Al₂O₃</entry><entry namest="col3" nameend="col3" align="center">ALCOA CT3000SG</entry><entry namest="col4" nameend="col4" align="center">---</entry><entry namest="col5" nameend="col5" align="center">50</entry><entry namest="col6" nameend="col6" align="right">---</entry><entry namest="col7" nameend="col7" align="center">---</entry><entry namest="col8" nameend="col8" align="center">---</entry><entry namest="col9" nameend="col9" align="right">---</entry><entry namest="col10" nameend="col10" align="right">---</entry><entry namest="col11" nameend="col11" align="center">---</entry><entry namest="col12" nameend="col12" align="right">---</entry></row><row><entry namest="col1" nameend="col1" align="right">5</entry><entry namest="col2" nameend="col2" align="center">ZrO₂</entry><entry namest="col3" nameend="col3" align="center">TOSOH TZ-3YS</entry><entry namest="col4" nameend="col4" align="center">50</entry><entry namest="col5" nameend="col5" align="center">1000</entry><entry namest="col6" nameend="col6" align="right">127</entry><entry namest="col7" nameend="col7" align="center">32</entry><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /><entry namest="col10" nameend="col10" /><entry namest="col11" nameend="col11" align="center">50</entry><entry namest="col12" nameend="col12" /></row><row><entry namest="col1" nameend="col1" align="right">6</entry><entry namest="col2" nameend="col2" align="center">Al₂O₃</entry><entry namest="col3" nameend="col3" align="center">ALCOA CT3000SG</entry><entry namest="col4" nameend="col4" align="center">56</entry><entry namest="col5" nameend="col5" align="center">1000</entry><entry namest="col6" nameend="col6" align="right">162</entry><entry namest="col7" nameend="col7" align="center">41</entry><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /><entry namest="col10" nameend="col10" /><entry namest="col11" nameend="col11" align="center">50</entry><entry namest="col12" nameend="col12" /></row><row><entry namest="col1" nameend="col1" align="right">7</entry><entry namest="col2" nameend="col2" align="center">Al₂O₃</entry><entry namest="col3" nameend="col3" align="center">ALCOA tabular</entry><entry namest="col4" nameend="col4" align="center">50</entry><entry namest="col5" nameend="col5" align="center">1000</entry><entry namest="col6" nameend="col6" align="right">219</entry><entry namest="col7" nameend="col7" align="center">55</entry><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /><entry namest="col10" nameend="col10" /><entry namest="col11" nameend="col11" align="center">50</entry><entry namest="col12" nameend="col12" /></row><row rowsep="1"><entry namest="col1" nameend="col1" align="right">8</entry><entry namest="col2" nameend="col2" align="center">Al₂O₃</entry><entry namest="col3" nameend="col3" align="center">Norton FCP13NLC</entry><entry namest="col4" nameend="col4" align="center">49</entry><entry namest="col5" nameend="col5" align="center">1000</entry><entry namest="col6" nameend="col6" align="right">295</entry><entry namest="col7" nameend="col7" align="center">74</entry><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /><entry namest="col10" nameend="col10" /><entry namest="col11" nameend="col11" align="center">50</entry><entry namest="col12" nameend="col12" /></row><row rowsep="1"><entry namest="col1" nameend="col12" align="justify">Polyacetal = copolymer of trioxane and 2.5% butanediol formal, molecular weight 150,000 PBDF = polybutanediol formal, molecular weight 50,000 PE = polyethylene, molecular weight 150,000, d = 0.95g / ml PMMA = polymethyl methacrylate, molecular weight 150,000, d = 1.17g / ml, Lucryl G88 UV1 [BASF] PS = polystyrene, molecular weight 100,000, d = 1.04 g / ml, 168N [BASF] PEG = polyethylene glycol, molecular weight 800 PEO = polyethylene oxide, molecular weight 400</entry></row></tbody></tgroup></table></tables><tables id="tabl0002" num="0002"><img file="EP0764467B1_D0001.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0764467B1_D0002.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0764467B1_D0003.tif" /></tables>

Comparative Example A

586 g Si₃N₄ (HC STARCK, LC 12) were with 32 g Y₂O₃ (HC STARCK, grade fine) and 32 g α-Al₂O₃ (ALCOA, CT3000SG) were treated with 150 g H₂O and 48 g ENT₃ Kneaded for 35 minutes and extruded into 4 mm strands at 45 to 150 ° C.

The strands were calcined at 600, 800 and 1100 ° C in air for 2 hours. The strands disintegrated into powder (cutting hardness = 0 kg).

Comparative Example B

The commercially available α-Al₂O₃-Catalyst carrier SPH512 from Rhone Poulenc has a comparable BET of 5.4 m²/ g and a total pore volume (GPV) of 0.51 ml / g a significantly wider pore distribution (see Fig. 9) than the Al according to the invention₂O₃-Catalyst carrier CT3000SG from ALCOA in Tables IIIa and IIIb, Example No. 1b and Fig. 1b.

Comparative Example C

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

300 g ZrO₂Powder (starting product from Example 5) from TOSOH, TZ-3YS, and 9 g of extrusion aid were mixed with 31 ml of water, compressed 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 5).

The following properties were measured on the full strands: <tables id="tabl0005" num="0005"><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><entry namest="col1" nameend="col1" align="left"><b>example</b></entry><entry namest="col2" nameend="col2" align="center">C.</entry><entry namest="col3" nameend="col3" align="center">5</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left"><b>Cutting hardness [kg]</b></entry><entry namest="col2" nameend="col2" align="right">0,6</entry><entry namest="col3" nameend="col3" align="right">2,4</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>BET surface area [m</b>^<b>2</b><b>/G]</b></entry><entry namest="col2" nameend="col2" align="right">5,8</entry><entry namest="col3" nameend="col3" align="right">5,8</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>Water absorption [ml / g]</b></entry><entry namest="col2" nameend="col2" align="right">0,22</entry><entry namest="col3" nameend="col3" align="right">0,22</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left"><b>Ramming weight [g / ml]</b></entry><entry namest="col2" nameend="col2" align="right">1,455</entry><entry namest="col3" nameend="col3" align="right">1,543</entry></row></tbody></tgroup></table></tables>

Comparative Example D

Lower hardness of a conventional ZrO

2

Carrier even at high calcining temperatures.

100 g surface-rich Zr (OH)₄ (BET: 310 m²/ g) 3 g of extrusion aid and 45 ml of water were added and the mixture was 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 No. 9 (transient Deacon process)

Catalyst 1

Cu-K-Fe-Na on Si

3

N

4

-Carrier

Production of the Si

3

N

4

Carrier

900 g Si₃N₄ (HC STARCK; LC12) were treated with 50 g of Y₂O₃ (HC STARCK; grade fine) and 50 g Al₂O₃ (ALCOA; CT3000SG) with a polyacetal-based binder consisting of 276 g polyoxymethylene copolymer (POM / PBDF) made from trioxane and 2.5% by weight butanediol formal with an average molecular weight of 150,000, and with 69 g polybutanediol formal with a molecular weight of 50,000 and 50 g of polyethylene glycol with a molecular weight of 800 as an aid, kneaded at 180 ° C., granulated and in a muffle furnace under N₂ pyrolyzed at 600 ° C for 2 hours and presintered at 1000 ° C for 2 hours. An Si was obtained₃N₄Beams with a BET surface area of ​​22.3 m²/ g and a water absorption of 0.608 ml / g.

Impregnation of the Si

3

N

4

Carrier

111.5 g Si₃N₄Granules were twice with 67.8 ml of a solution of 7.06 g of CuCl₂* 2H₂O, 5.58 g KCI, 5.58 g NaCl and 9.29 g FeCl₃* 6H₂O dissolved in distilled water (total solution 135.6 ml), impregnated, dried for 16 h at 120 ° C (after each soaking step) and calcined for 3 h at 450 ° C. Brown grit was obtained with a BET surface area of ​​9.93 m²/G. The tamped weight was 0.978 g / ml (0.5 to 1 mm grit).

Subsequent impregnation with an FeCl

3

-NaCl solution

25th g of the previously impregnated Si₃N₄- Carrier were with a solution of 1.39 g NaCl and 2.21 g FeCl₃* 6H₂O impregnated once in 15.9 ml of water, dried for 16 hours at 120 ° C. and calcined for 3 hours at 450 ° C. The tamped weight of the catalyst was 0.995 g / ml (0.5 to 1 mm grit). The catalyst contained 1.8% by weight copper and 3% by weight iron.

Catalyst 2

Cu-K-Fe-Na on Si

3

N

4

-Carrier

Production of the Si

3

N

4

Carrier

1000 g SiC (HC STARCK; UF15) were made with a polyacetal-based binder consisting of 281 g polyoxymethylene copolymer (POM / PBDF) 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 Polyethylene glycol with a molecular weight of 800 as auxiliary, kneaded at 180 ° C, melted on a roller mill to a 0.5 mm thick skin, crushed into cookies and these in a rotary kiln at 600 ° C 2h below N₂ pyrolyzed and presintered. An SiC carrier with a BET surface area of ​​22.3 m was obtained²/ g and a water absorption of 0.35 ml / g.

Impregnation of the SiC carrier

150 g SiC biscuits were twice with 53 ml of a solution of 23.7 g CuCl₂* 2H₂O, 10.38 g KCI, 42, 78 g FeCl₃* 6H₂O and 9.26 g of NaCl dissolved in distilled water (total solution 106 ml) impregnated, dried for 16 h at 120 ° C (after each impregnation step) and calcined for 3 h at 450 ° C.

Subsequent impregnation with an FeCl

3

-NaCl solution

70 g of the previously impregnated SiC cookie were mixed with 22 ml of a solution of 3.92 g of NaCl and 18.22 g of FeCl₃* 6H₂O dissolved in distilled water (total solution 25ml impregnated once, dried for 16 hours at 120 ° C. and calcined for 3 hours at 450 ° C. Red-brown cookies of the composition 3.3% by weight copper and 7.8% by weight iron were 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 measured continuously 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 Tables 1 and 2.<tables id="tabl0006" num="0006"><img file="EP0764467B1_D0004.tif" /></tables><tables id="tabl0007" num="0007"><img file="EP0764467B1_D0005.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 KCI and 114 ml water soaked (water absorption: 0.46 ml / g), dried at 120 ° C for 16 h, calcined at 450 ° C for 3 h and then soaked with the remaining 85 ml of the solution, 16 h at 120 ° C dried and calcined at 450 ° C for 3h. 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.

Cu-Fe-K on Al

2

O

3

-Carrier

Analogous to the general instructions for the transient chlorine production of Examples 1 to 3, the comparative catalyst Cu-Fe-K on 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 of 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.