Monomodal and polymodal catalyst supports and catalysts having narrow pore size distributions and their production

• US 5,935,898 A
• Filed: 09/10/1996
• Issued: 08/10/1999
• Est. Priority Date: 09/12/1995
• Status: Expired due to Term

• Current Assignee: BASF AG (BASF SE)
• Original Assignee: BASF AG (BASF SE)
• Inventors: Dingerdissen, Uwe, Hagemeyer, Alfred, Brocker, Franz Josef, Trubenbach, Peter, Flick, Klemens, Lauth, Gunter
• Primary Examiner(s): Manoharan, Virginia
• Assistant Examiner(s): Preisch, Nadine
• Application Number:
  US08/711,989
• Time in Patent Office: 1,064 Days
• Field of Search: 502/300, 502/150, 502/174, 502/173, 502/232, 502/63, 502/177, 502/200, 502/159, 502/162, 502/167, 502/168, 502/201, 502/208, 502/217, 502/344, 502/352, 502/325, 502/326 , 502/339, 502/345, 502/349, 502/355, 502/303, 502/319, 502/350, 502/527.14
• US Class Current: 502/300
• CPC Class Codes: B01J 35/60 characterised by their surface properties or porosity
• CPC Class Codes: B01J 35/612 less than 10 m2/g
• CPC Class Codes: B01J 35/613 10-100 m2/g
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/66 Pore distribution
• CPC Class Codes: B01J 35/67 monomodal
• CPC Class Codes: B01J 37/0018 Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)

Abstract

Monomodal or polymodal catalyst supports or catalysts having a BET specific surface area of from 0.01 to 250 m² /g and a monomodal or polymodal pore size distribution having a mean pore diameter of from 50 to 300,000 nm measured by the mercury pressure porosimetry method, wherein

a) from 10 to 95% of the pore volume is at from 0.1 to 3 times the mean pore diameter and/or

b) from 10 to 80% of the pore volume is at from 0.4 to 3 times the mean pore diameter and/or

c) from 50 to 95% of the pore volume is at from 0.1 to 1 times the mean pore diameter and/or

d) from 50 to 80% of the pore volume is at from 0.4 to 1 times the mean pore diameter and

e) the width at half height of the pore size distribution is less than 0.5 times the mean pore diameter,

which are useful for preparing chlorine from hydrogen chloride in a non-steady-state Deacon process, for the reaction of ethylbenzene to give styrene in a non-steady-state oxydehydrogenation, for preparing aziridine from ethanolamine, in reductions, hydrogenations, oxidations, dehydrogenations, acid- or base-catalyzed reactions or reactions in a fluidized bed, for removing combustion residues from diesel exhaust gases and for removing NO_x from waste gases, in bioreactors together with bacteria and as biocatalyst supports with immobilized enzymes or microbes, and a process for producing said monomodal or polymodal catalyst supports or catalysts.

Claims

1. A monomodal or polymodal catalyst support or catalyst having a BET specific surface area of from 0.01 to 250 m² /g and a monomodal or polymodal pore size distribution having a mean pore diameter of from 50 to 300,000 nm measured by the mercury pressure porosimetry method, wherein the pore size distribution fulfills at least one of the following conditions (a) to (d)

a) from 10 to 95% of the pore volume is from about 0.1 to 3 times the mean pore diameter,

b) from 10 to 80% of the pore volume is from about 0.4 to 3 times the mean pore diameter,

c) from 50 to 95% of the pore volume is from about 0.1 to 1 times the mean pore diameter, and

d) from 50 to 80% of the pore volume is from about 0.4 to 1 times the mean pore diameter,

and the condition

e) the width at half height of the pore size distribution is less than 0.5 times the mean pore diameter.

2. A process for producing a monomodal or polymodal catalyst support or catalyst as defined in claim 1, comprising the steps of shaping a mixture of

A) from 15 to 70% by volume of at least one of

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, zirconium, haffium, vanadinium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, cerium, praseodymium and mixtures thereof,

II) a metallic powder selected from compounds, 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, hafijum, vanadinium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, cerium, praseodymium, WC, TiC, TaC, VC and mixtures thereof, WC-cobalt, TiC-cobalt, TaC-cobalt, VC-cobalt and mixtures thereof and also carbon,

III) an active component selected from the group of the inorganic acids, the metals 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, zirconium, haffium, vanadinium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, cerium, praseodymium, mixtures thereof, and their borates, carbonates, silicates, nitrates, phosphates, arsenates, antimonates, bismutates, sulfates, selenates, tellurates, vanadates, molybdates, niobates, chromates, oxides, hydroxides, halides, sulfides, selenides, tellurides, nitrides, phosphides, arsenides, acetates, acetylacetonates, palladates, platinates, cyanides, thiocyanates, manganates, rhenates, osmates, carbides, silicides, borides, and ammonium compounds and all mixtures component thereof, and

IV) an organic powder selected from the group of teflon and polyimide

B) as a binder from 30 to 85% by volume of a mixture of

B₁) from 50 to 100% by weight of a polyoxymethylene homopolymer or copolymer and

B₂) from 0 to 50% by weight of a polymer homogeneously dissolved in B₁) or dispersed in B₁) at a mean particle size of less than 1 μ

m and

C) from 0 to 15% by volume of a dispersant,

removing the binder by treatment with a gaseous acid at from 100 to 160°

C. in order to form a residue,

pyrolysing the residue at from 400 to 600°

C. and

subsequent presintering at from 600 to 1400°

C. and,

optionally, applying active components III to the component A) or to the presintered composition by single or multiple steeping, impregnating, spray impregnating, precipitating on, hicoating, washcoating or spray drying,

wherein the catalyst support or catalyst after the pyrolytic removal of the binder has a BET specific surface area of from 0.01 to 250 m² /g and a pore size distribution of from 50 to 300,000 nm measured by the mercury pressure porosimetry method.

3. A process for producing a polymodal catalyst support or catalyst as claimed in claim 2, wherein said organic powder has a polymodal particle size distribution or internal porosity.

4. A process for producing a monomodal or polymodal catalyst support or catalyst as claimed in claim 2, containing at least one or more members selected from the group of aluminium, iron, cobalt, nickel, palladium, platinum, copper, silver, molybdenum, zinc, titanium, zirconium, tungsten, niobium, chromium carbon, an inorganic powder selected from the group of Al₂ O₃, MgO, SiO₂, TiO₂, Y₂ O₃, ZrO₂, ZnO, Fe₃ O₄, Fe₂ O₃, CoO, Co₂ O₃, Cr₂ O₃, NiO, B₂ O₃, Ce₂ O₃, CeO₂, Pr₂ O₃, B₄ C, SiC, WC, TiC, TaC, Si₃ N₄, AlN, BN, TiN and ZrN, and a mixture of two or more thereof.

5. A process for producing a monomodal or polymodal catalyst support or catalyst as claimed in claim 2, containing at least one or more members selected from the group of iron, cobalt, nickel, chromium, molybdenum and titanium, an inorganic powder selected from the group of SiC, Si₃ N₄, BN, B₄ C, WC, TiC, TiN, ZrN and AlN, and a mixture of two or more thereof.

6. A process for producing a monomodal or polymodal catalyst support or catalyst as claimed in claim 2, containing an inorganic powder selected from the group consisting of SiC, Si₃ N₄ and a mixture thereof.

7. A process for producing a monomodal or polymodal catalyst support or catalyst as claimed in claim 2, comprising the step of shaping the mixture of A), B) and C) by a method selected from the group of granulation, pressing, rolling, extrusion, injection molding and continuous casting at from 80 to 250°

C.

8. A process for producing a monomodal or polymodal catalyst support or catalyst as claimed in claim 2, wherein an acid selected from the group of nitric acid, oxalic acid dihydrate, anhydrous oxalic acid, acetic acid, formic acid, a mixture thereof and boron triffuoride is appllied for removing the binder.

9. A monomodal or polymodal catalyst support or catalyst obtained by the process according to claim 2.

10. A process for producing a monomodal or polymodal catalyst support or catalyst as claimed in claim 2, wherein said catalyst or catalyst support is a monolith or a bed of individual parts with a shape comprising Raschig rings, saddles, star rings, perforated and ribbed geometric bodies, wherein the said ribbed geometric bodies are rings, spheres, cuboids, cubes, cones, pyramids, prisms, octahedra, cylinders, truncatede pyramids, truncated cones, wagon wheel profiles, window frames profiles and mixtures thereof.