Chemistry of inorganic compounds – Modifying or removing component of normally gaseous mixture – Nitrogen or nitrogenous component
Reexamination Certificate
2001-04-11
2004-04-20
Hendrickson, Stuart L. (Department: 1754)
Chemistry of inorganic compounds
Modifying or removing component of normally gaseous mixture
Nitrogen or nitrogenous component
C502S340000, C502S341000
Reexamination Certificate
active
06723295
ABSTRACT:
The present invention relates to a catalyst for the decomposition of N
2
O, a process for its preparation and a process for the decomposition of N
2
O using this catalyst.
N
2
O forms as a byproduct in many processes in which HNO
3
is used in the liquid phase as an oxidizing agent. Particularly in the conversion of alcohols, aldehydes and ketones, e.g. cyclohexanol and cyclohexanone, to adipic acid, acetaldehyde to glyoxal or glyoxal to glyoxylic acid, considerable amounts of N
2
O are liberated. Furthermore, N
2
O is emitted in the preparation of nicotinic acid and hydroxylamine. N
2
O also forms the byproduct in the preparation of nitric acid by combustion of NH
3
.
In an article published in 1991 in Science, 251 (1991), 932, Thiemens and Trogler show that N
2
O potentially harms the earth's atmosphere to a certain degree. In the stratosphere, N
2
O is considered to be an important source of NO, which in turn is said to have a substantial effect on the degradation of ozone in the stratosphere. In addition, N
2
O is considered a greenhouse gas, and the potential of N
2
O for heating up the earth is 290 times greater than that of CO
2
.
Recent years have seen a large number of publications which are concerned with reducing the N
2
O emissions caused by anthropogenic activities.
The use of catalysts in the reduction or decomposition of N
2
O makes it possible to carry out the reaction at a temperature level substantially lower in comparison with the purely thermal decomposition.
EP-A 0 687 499 describes a catalyst for catalytic reduction of NO
x
and/or for oxidation of hydrocarbons in off-gases, which consists of a copper oxide-zinc oxide-aluminum oxide spinel of the chemical formula Cu
A
Zn
c
Al
D
O4, where A+C +D=3, A>0, C>0 and D>0. In this publication, the ratio of Cu and Zn to Al can be freely chosen within wide limits. In an example, NO is reacted with propene of the disclosed catalysts to give N
2
and H
2
O. The decomposition of N
2
O at high temperatures is not discussed.
WO 94/16798 describes a process for the catalytic decomposition of pure N
2
O or N
2
O contained in gas mixtures. The catalyst used is an M
x
Al
2
O
4
catalyst. This is prepared by mixing CuAl
2
O
4
with Sn, Pb or an element of the 2nd main group or subgroup of the Periodic Table of the Elements as an oxide or salt or in elemental form and then calcining at from 300° C. to 1300° C. and from 0.1 to 200 bar. According to Comparative Examples 1 and 2, as presented further below in the present description at the beginning of “Examples”, the x value in the formula M
x
Al
2
O
4
is 0.61 (Comparative Example 1) and 0.76 (Comparative Example 2).
The catalyst systems known from the prior art are suitable for the decomposition of N
2
O. Their thermal stability at above 500° C. is, however, not optimum. One problem which still exists in many cases is the deactivation of the catalysts, necessitating frequent replacement of the catalyst bed Particularly at above 500° C., as is advantageous for virtually complete degradation of the N
2
O with an acceptable amount of catalyst, pronounced, irreversible deactivation occurs.
It is an object of the present invention to provide a catalyst for the decomposition of N
2
O, which catalyst is thermally stable at high temperatures.
We have found this object is achieved by a copper-containing catalyst for the decomposition of N
2
O, containing a compound of the formula M
x
Al
2
O
4
, where M is Cu or a mixture of Cu with Zn and/or Mg. According to the invention, x is typically from 0.8 to 1.5 in the catalyst.
The novel catalysts are preferably essentially spinels which may still contain small amounts of free oxides in crystalline form, such as MO (where M is, for example, Cu, Zn or Mg) and M
2
O
3
(where M is, for example, Al). The presence of a spinet phase can be detected by recording XRD spectra. The amount of the oxides in the catalyst is in general from 0 to 5, preferably from 0 to 3.5, % by weight.
The amount of Cu and any Zn and/or Mg should be chosen such that a filled or virtually filled spinet is obtained. This means x in the formula M
x
Al
2
O
4
is from 0.8 to 1.5, preferably from 0.9 to 1.2, particularly preferably from 0.95 to 1.1. We have found that, for x values below 0.8, the thermal stability is substantially lost. x values above 1.5 likewise lead to a deterioration in the catalyst activity and catalyst stability. The novel catalyst having an x value of from 0.8 to 1.5, preferably from 0.9 to 1.2, particularly preferably from 0.95 to 1.1, in the formula M
x
Al
2
O
4
is thus a high temperature-stable catalyst for decomposition of N
2
O. The catalyst has advantageous aging behavior, i.e. the catalyst remains active for a long time without being thermally deactivated.
The novel catalysts contain copper in oxide form, calculated as a copper oxide, CuO, in an amount of in general from 1 to 54, preferably from 5 to 40, particularly preferably from 10 to 30, % by weight, based on the total catalyst.
The novel catalyst may additionally contain further dopants, in particular Zr and/or La, in oxide form. Doping with Zr and/or La further increases thermal stability of the catalysts, but the initial activity is slightly reduced. It is particularly advantageous to introduce Zr and/or La dopants via corresponding element-doped aluminum oxides. The content of the dopant compounds in the novel catalyst is in general from 0.01 to 5.0, preferably from 0.05 to 2, % by weight.
In addition, the novel catalyst may contain further metallic active components. Such metallic active components are preferably metals of the 8th subgroup of the Periodic Table of the Elements, particularly preferably Pd, Pt, Ru or Rh. As a result, it is possible to obtain catalysts which not only are very active at high temperatures but have a very high activity at temperatures as low as below 400° C. The novel catalysts can therefore be used in a wide temperature range, which is a major advantage in the case of adiabatically operated N
2
O decomposition processes. The amount of the metals of the 8th subgroup in the novel catalyst is in general from 0.01 to 5, preferably from 0.1 to 2, % by weight.
The novel supported catalysts may be present in the form of pellets, honeycombs, rings, chips or solid or hollow extrudates or in other geometric shapes. For specific applications, it is important that the shape and size are chosen such that a very small pressure loss results.
The novel catalysts generally have a BET surface area of from 30 to 150, preferably from 50 to 100, m
2
/g.
The novel catalysts preferably have a bimodal or trimodal pore structure. They contain mesopores of from 10 to 100 nm, preferably from 10 to 30 nm, and macropores of from 100 to 5000 nm, preferably from 100 to 2000 nm. Such catalysts are substantially more active than catalysts having a monomodal pore structure.
The porosity of the carrier should advantageously be such that the pore volume is from 0.10 to 0.70 ml/g.
The novel catalysts can be prepared from oxide starting materials or from starting materials which are converted into the oxide form during the final calcination. They can be prepared by a process in which the starting materials, containing Al, Cu and, if required, Zn and/or Mg, and, if required, further additives, are mixed, converted into moldings and, if required, treated at above 500° C. in one step.
In a preferred embodiment of the process a mixture of the starting materials is processed, for example by drying and pelleting, to give corresponding moldings. These are then heated at from 500 to 1000° C. for from 0.1 to 10 hours (calcination). Alternatively, a molding material can be prepared with the addition of water in a kneader or mix-muller and extruded to give corresponding moldings. The moist moldings are dried and then calcined as described.
Particularly preferably, the novel catalysts are prepared by a process which comprises the following steps:
a) preparation of a Cu—Al oxide molding,
b) impregnation of the molding with soluble Cu compounds and, if required, Mg compounds a
Baier Michael
Bürger Gert
Fetzer Thomas
Harth Klaus
Hesse Michael
BASF - Aktiengesellschaft
Hendrickson Stuart L.
Keil & Weinkauf
Lish Peter J
LandOfFree
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