Patent US5082819A successfully refreshed from Google Patents.
US5082819A
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Catalyst for catalytic gas phase oxidation of olefins into unsaturated aldehydes and method for making the catalyst
Assignee: Evonik Operations GmbH
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Filing: 1990-09-13
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Granted: 1992-01-21
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Expires: 2010-09-13
Abstract
Abstract A catalyst is described for the production of unsaturated aldehydes by means of oxidation with a oxygen-containing gas where an active mass, containing at least the elements Mo, Bi, P and O, as well as Si-containing carrier material, is used in the form of a catalyst body with a certain ratio between the outer surface and the volume and with a defined extent in terms of space, porosity, density, specific surface, breaking strength, abrasion, and gas through-flow capability. Also described is a method of making the catalyst.
Inventors
- 👤 Wolfgang Boeck
- 👤 Dietrich Arntz
- 👤 Guenter Prescher
- 👤 Werner Burkhardt
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 23:47
CPC Classifications
B; B01; B01J; B01J27/00; B01J27/14; B01J27/186; B01J27/188; B01J27/19; B01J27/192; B01J35/00; B01J35/30; B01J35/34; B01J35/37; B01J35/38; B01J35/50; B01J35/60; B01J35/61; B01J35/613; C; C07; C07C; C07C45/00; C07C45/27; C07C45/32; C07C45/33; C07C45/34; C07C45/35
Claims Analysis
Total Claims: 22
Claim 1
Independent Claim
233 words
A catalyst for the production of unsaturated aldehydes from olefins, especially of acrolein from propene, through oxidation with a oxygen-containing gas, said catalyst comprising the following properties: (a) an active mass comprising at least the elements molybdenum, bismuth, phosphorus, and oxygen in atomic ratios of: Mo.sub.12 Bi.sub.0.2-10 P.sub.0.2-5 O.sub.x as well as silicon-containing carrier material wherein X denotes the number of oxygen atoms which satisfies the valences of the other elements; (b) a catalyst body having any desired geometrical shape whose ratio between the outside surface Op and the volume Vp is above 1.6 mm -1 and in which the spatial dimension, described by the diameter of a sphere which barely encloses it, is smaller than 7.5 mm; (c) a porosity of the catalyst amounting to at least 0.46, the absence of micropores (<2 nm), a mesopore volume (2-30 nm) of at least 0.03 cm 3 /g as well as a macropore volume (>30 nm) of at least 0.30 cm 3 /g; (d) a mercury density of the catalyst body amounting to at least 1.25 g/cm 3 ; (e) a specific BET surface area amounting to at least 10 m 2 /g; (f) a breaking strength of at least 6.0N; (g) an abrasion of less than 50 mg/g catalyst; and (h) a pressure loss of less than 1600 Pa/m of a catalyst charge inserted into a tube with a diameter of 2 cm.
Claim 2
Dependent Claim
233 words
A catalyst for the production of unsaturated aldehydes from olefins, especially of acrolein from propene, through oxidation with a oxygen-containing gas, said catalyst comprising the following properties: (a) an active mass comprising at least the elements molybdenum, bismuth, phosphorus, and oxygen in atomic ratios of: Mo.sub.12 Bi.sub.0.2-10 P.sub.0.2-5 O.sub.x as well as silicon-containing carrier material wherein X denotes the number of oxygen atoms which satisfies the valences of the other elements; (b) a catalyst body having any desired geometrical shape whose ratio between the outside surface Op and the volume Vp is above 1.6 mm -1 and in which the spatial dimension, described by the diameter of a sphere which barely encloses it, is smaller than 7.5 mm; (c) a porosity of the catalyst amounting to at least 0.46, the absence of micropores (<2 nm), a mesopore volume (2-30 nm) of at least 0.03 cm 3 /g as well as a macropore volume (>30 nm) of at least 0.30 cm 3 /g; (d) a mercury density of the catalyst body amounting to at least 1.25 g/cm 3 ; (e) a specific BET surface area amounting to at least 10 m 2 /g; (f) a breaking strength of at least 6.0N; (g) an abrasion of less than 50 mg/g catalyst; and (h) a pressure loss of less than 1600 Pa/m of a catalyst charge inserted into a tube with a diameter of 2 cm.
Claim 3
Dependent Claim
15 words
A catalyst according to claim 1, wherein said mesopore volume is 0.03-0.10 cm 3 /g.
Claim 4
Dependent Claim
15 words
A catalyst according to claim 1, wherein said macropore volume is 0.30-0.50 cm 3 /g.
Claim 5
Dependent Claim
15 words
A catalyst according to claim 1, wherein said mercury density is 1.25-1.85 g/cm 3 .
Claim 6
Dependent Claim
17 words
A catalyst according to claim 1, wherein said specific BET surface area is 10-25 m 2 /g.
Claim 7
Dependent Claim
61 words
A catalyst according to claim 1, wherein said active mass has the following composition: Mo.sub.12 Fe.sub.0.4-4.0 Co.sub.0.4-4.0 Ni.sub.1.0-9.0 Bi.sub.0.2-2.0 P(As).sub.0.2-2.0 K(Rb,Cs).sub.0-0.1 Sm.sub.0.01-0.2 Si.sub.5-40 O.sub.x, wherein the element silicon is present as pyrogenic or highly-dispersed precipitated silicic acid, silicic acid brine or fine-particle aluminum silicate and wherein X denotes the number of oxygen atoms which satisfies the valences of the other elements.
Claim 8
Dependent Claim
14 words
A catalyst according to claim 6, wherein said element silicon is present as montmorillonite.
Claim 9
Dependent Claim
64 words
A catalyst according to claim 6, wherein said active mass has the following composition: Mo.sub.12 Fe.sub.0.6-2.0 Co.sub.0.6-2.0 Ni.sub.2.0-6.0 Bi.sub.0.5-1.5 P(As).sub.0.5-1.5 K(Rb,Cs).sub.0.001-0.05 Sm.sub.0.02-0.1 Si.sub.10-30 O.sub.x, wherein the element silicon is present in the form of pyrogenic SiO 2 and montmorillonite in a weight ratio of 1:0.5 to 1:4 and wherein X denotes the number of oxygen atoms which satisfies the valences of the other elements.
Claim 10
Dependent Claim
26 words
A catalyst according to claims 6, 7, or 8 wherein said montmorillonite has a reduced specific BET surface area of less than 2.0 m 2 /g.
Claim 11
Dependent Claim
208 words
A method for making the catalyst according to claim 1, comprising the following steps: (a) mixing a suspension, obtained by combining salt solutions of said elements with the insoluble, silicon-containing carrier material, spray-drying the suspension thus obtained at an initial temperature of 300° C.-600° C., separating the resulting dry powder and heating at 120° C.-220° C. to thereby obtain a spray dried powder with an average particle diameter of less than 30 μm, wherein the time of heating the spray dried powder is between 2 and 25 seconds to thereby obtain a dry spray dried powder; (b) calcining the dry spray dried powder in a kiln for 5 to 60 minutes whereby the temperature of the spray dried powder is raised to between 320° C. and 480° C.; (c) extruding the calcined spray dried powder with 5 to 40 weight %, related to the weight of spray dried powder, of a pore forming agent which is completely decomposable at a temperature of less than 400° C., at a temperature of less than 80° C., in the desired geometrical shape, at a pressure of less than 50 bar, and subdividing the extruded strand by cutting it to the length of the desired body; (d) drying the extruded individual bodies.
Claim 12
Dependent Claim
23 words
The process according to claim 10, wherein in step (c) there is also added a quantity of wetting agent, lubricant, and binding agent.
Claim 13
Dependent Claim
20 words
A method according to claim 11 wherein said lubricant is petroleum, water or a 1-10 weight % aqueous methylcellulose solution
Claim 14
Dependent Claim
21 words
A method according to claim 11 wherein said wetting agent and binding agent is a 1-10 weight % aqueous methylcellulose solution.
Claim 15
Independent Claim
21 words
A method according to claims 12 or 13 in which said methylcellulose solution is in the form of an oil-in-water emulsion.
Claim 16
Dependent Claim
55 words
The process according to claim 10, further comprising after step (d) burning out the decomposable substance in said extruded individual bodies in a kiln and then tempering for 5 to 60 minutes at a temperature, measured in the pouring of the individual bodies, amounting to between 450° C. and 650° C. in an air current.
Claim 17
Dependent Claim
27 words
A method according to claim 10 wherein said pore forming agent is selected from the group consisting of pentaerythritol, cellulose powder, urea, oxalic acid, and polyvinyl alcohol.
Claim 18
Dependent Claim
24 words
A method according to claim 10 wherein said pore forming agent is solid pentaerythritol with an average particle diameter of less than 40 μm.
Claim 19
Dependent Claim
14 words
A method according to claim 10 wherein said binding agent is dry methycellulose powder.
Claim 20
Dependent Claim
21 words
A method according to claim 10 in which said burn-out and tempering of the extruded individual bodies occurs in separate steps.
Claim 21
Dependent Claim
24 words
A method according to claim 10, wherein said extruded individual bodies and air current during the burn-out process are conducted in a direct current.
Claim 22
Dependent Claim
17 words
A method according to claim 10, wherein said burn-out is performed at a maximum of 400° C.
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