JPH06142514A - Catalyst for decomposing nitrous oxide - Google Patents

Abstract

PURPOSE:To enhance decomposition efficiency and durability in the catalyst for exhaust gas of an automobile by making at least one kind of ruthenium and rhodium and at least one kind selected from among La2O3, CeO2, Pr2O3, Nd2O3, Sm2O3, Tb2O3 and Y2O3 carried on a hydrophobic carrier. CONSTITUTION:At least one kind of noble metal selected from ruthenium and rhodium and at least one kind selected from among La2O3, CeO2, Pr2O3, Nd2O3, Sm2O3, Tb2O3 and Y2O3 are carried on a hydrophobic carrier such as silica gel and activated alumina. The catalyst is produced as followes. The hydrophobic carrier is immersed in the aqueous solution of ruthenium and rhodium chlorides and impregnated with noble metal. The hydrophobic carrier is dried and immersed in the aqueous solution of nitrates selected from among La, Ce, Pr, Nd, Sm, Tb and Y nitrates and impregnated with the precursor of oxide thereof and dried and thereafter burned. Then reducing treatment is performed in H2 flow.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for decomposing and removing nitrogen oxides in exhaust gas, particularly nitrous oxide (N ₂ O), and more specifically, factories, automobiles, refuse incinerators, sewage sludge incinerators, etc. The present invention relates to a suitable catalyst for decomposing nitrogen oxides, which is used when decomposing and removing nitrous oxide contained in exhaust gas discharged from the waste treatment facility.

2. Description of the Related Art Nitrogen oxides (hereinafter referred to as NOx) in various kinds of exhaust gas are harmful to health and may cause photochemical smog and acid rain, so their emission Is severely limited, and the development of effective removal means is desired. By the way, the nitrogen oxides conventionally required to be emission regulated are mainly nitric oxide (NO) and nitrogen dioxide (NO ₂ ). As methods for removing these NOx, some methods for reducing NOx in exhaust gas using a catalyst have already been put into practical use. For example, (a) a three-way catalyst method in a gasoline automobile, and (b) a selective catalytic reduction method using ammonia for exhaust gas from a large facility emission source such as a boiler. Recently, as a method for removing NOx in exhaust gas using (c) hydrocarbons, zeolite containing a metal such as copper, or a gas containing NO in the presence of hydrocarbons using a metal oxide such as alumina as a catalyst is used. Methods such as contacting have been proposed. However, none of these methods is not sufficient, but not sufficient, to treat N ₂ O in the exhaust gas, and conventionally, these have been discharged untreated in the downstream of the above-mentioned denitration equipment. This is related to the fact that there is no legal regulation value for N ₂ O and no official measurement method such as JIS has been established so far. However, the reality is that they have been ignored as targets for denitration. However, in the above-described denitration method, N ₂ O may be added depending on the operating conditions.
It has been confirmed that methane is generated, and recently, a relatively high concentration of N ₂ O has been obtained from garbage incinerators and sewage sludge incinerators.
Are also reported to be generated. In addition, in recent years, N ₂ O
Has attracted particular attention as a global pollutant that causes destruction of the Ozo layer in the stratosphere, or temperature rise due to the greenhouse effect, together with CO ₂ , chlorofluorocarbon, CH _{4, and the} like. Under such circumstances, there has been increasing interest in N ₂ O treatment methods, particularly decomposition catalysts thereof, and several methods have been proposed. They are, for example, a zeolite-based carrier on which various transition metals are supported, or a basic carrier such as magnesium oxide or zinc oxide on which various transition metals are supported. However, all of them have a high temperature at which they are active, and they do not provide sufficient performance at low temperatures, and have a weak point that they are strongly affected by the presence of water in the process gas and are deactivated. In order to solve such problems, the present inventors have already applied for a method of supporting various noble metals such as ruthenium or rhodium on a hydrophobic carrier (May 2, 1992).
6th). However, even by such a method, it was revealed that among the noble metals, Ru and Rh have extremely weak activities in the initial stage, but change over time during the reaction, resulting in a decrease in activity. It was The present invention has been made in view of these circumstances, and an object of the present invention is to provide a catalyst for decomposing N ₂ O that can decompose N ₂ O in exhaust gas efficiently and has excellent simultaneous durability. To do.

[Means for Solving the Problems] A catalyst for decomposing nitrous oxide according to the present invention for achieving the above object is silica gel,
(A) at least one or more noble metals selected from ruthenium (Ru) and rhodium (Rh), and (b) L on a hydrophobic carrier such as activated alumina or silica-alumina.
_{a 2 O 3, CeO 2,} Pr 2 O 3, Nd 2 O 3, Sm 2
At least 1 selected from O ₃ , Tb ₂ O ₃ , and Y ₂ O _3.
It is formed by supporting at least one kind of oxide. The catalyst for decomposing nitrous oxide according to the present invention is prepared, for example, as follows.
That is, the hydrophobic carrier in the present invention does not exhibit a water adsorption capacity in the temperature range used, or has a very small adsorption amount. This water adsorption capacity is TG-DT of a sample in which water is saturated and adsorbed at room temperature.
It can be found by analyzing the A curve. As such a hydrophobic carrier, SYLOID97, a fine powder synthetic silica manufactured by Fuji Devison Chemical Co., Ltd.
8, the same 308, the same 255, the spherical silica gel CARIACT10, the same 15, the same 3 made by Fuji Davison Kagaku
0, 50 and Sumitomo Chemical spherical activated alumina KHD-
24 (-46), the same NKHD-24 (-46) and the like. Alternatively, a precipitate is formed by a method of neutralizing or hydrolyzing a solution in which a water-soluble salt such as a soda salt or an alcohol solution of an alkoxide is homogeneously mixed, and then filtration, washing with water, and repulsion are repeated, followed by drying and baking. Thus, it is also possible to prepare fine powders of silica gel, alumina, or silica-alumina, respectively. The catalyst according to the present invention is
For example, it can be prepared by the following method. The above-mentioned hydrophobic carrier is immersed in an aqueous solution of a chloride such as Ru or Rh for a certain period of time, impregnated with these noble metals, dried, and then further lanthanum nitrate, cerous nitrate, praseodymium nitrate, neodymium nitrate, samarium nitrate. , Terbium nitrate, yttrium nitrate, etc., soaked in an aqueous solution for a certain period of time to impregnate these oxide precursors, and after drying,
Baking is performed at 300 ° C to 500 ° C for 3 to 5 hours, and further reduction treatment is performed at 400 ° C to 500 for 3 to 5 hours in an H ₂ gas stream. As described above, the catalyst according to the present invention can be obtained, and the preferable loading amount of these precious metals is 0.3 to 2 wt.
%. When the amount is 0.3 wt% or less, these effects are not sufficiently exhibited, and even when the amount exceeds 2 wt%, the activity improvement corresponding to the effect cannot be obtained. Also, La ₂ O ₃ , C
eO ₂ , Pr ₂ O ₃ , Nd ₂ O ₃ , Sm ₂ O ₃ , Tb ₂
A preferable loading amount of oxides such as O ₃ and Y ₂ O ₃ is 5 to 20 wt% as oxides. If it is 5 wt% or less, these effects are not sufficiently exhibited, and if it exceeds 20 wt%, the hydrophobicity of the carrier is lowered, which is not preferable. The catalyst for decomposing nitrous oxide according to the present invention can be molded into various shapes such as a spherical shape by a conventionally known molding method. Furthermore, only the above-mentioned hydrophobic carrier may be molded and a noble metal or the like may be impregnated after molding. Furthermore, the above-mentioned catalyst powder may be wash-coated on a separately formed ceramic carrier, ceramic fiber base material, cordierite honeycomb, or the like. Further, at the time of molding, a molding aid, an inorganic fiber, an organic binder and the like may be appropriately mixed. The catalyst for decomposing nitrous oxide according to the present invention is N
_The optimum temperature at which it exhibits activity with respect to ₂ O varies depending on the catalyst species, but is usually 200 ° C to 600 ° C, and in this temperature range, exhaust gas can be passed at a space velocity (SV) of about 500 to 500,000. preferable. A more suitable operating temperature range is 300 ° C to 500 ° C.

EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to the following examples, and various modifications may be made without departing from the scope of the invention. Is possible. (I) Preparation of catalyst Example 1 Spherical activated alumina NKHD- manufactured by Sumitomo Chemical Co., Ltd. having a particle size of 2 mm to 4 mm, a pore volume of 0.65 ml / g and a water absorption rate of 78%.
24 was immersed in an aqueous solution of RhCl ₃ to obtain Rh of 1.5.
It was impregnated so that it would be wt%. After blowing off excess water, it was dried at 100 ° C. for 2 hours. Next, this was immersed in an aqueous solution of lanthanum nitrate (La (NO ₃ ) ₃ .6H ₂ O) and impregnated with La ₂ O _{3 in an amount} of 5 wt%.
After blowing off excess water, it was dried at 100 ° C. for 2 hours and then baked at 400 ° C. for 2 hours. Then these are H
_A reduction treatment was performed at 400 ° C. for 2 hours in _two air streams to obtain a catalyst in which 1.5 wt% of Rh and 5 wt% of La ₂ O ₃ were supported on a spherical alumina carrier. Medium Example 2 In Example 1, instead of RhCl ₃ aqueous solution, RuC
A spherical alumina carrier containing 1.5 wt% of Ru and 5 wt% of La ₂ O ₃ was prepared in the same manner as in Example 1 except that the aqueous solution was 1 ₃ aqueous solution.
% Supported catalyst was obtained. Example 3 In Example 1, instead of the RhCl ₃ aqueous solution, RuC was used.
and l ₃ aqueous lanthanum nitrate solution (La _(NO 3)
₃ . 6H ₂ O) instead of a ceric nitrate aqueous solution (C
e (NO ₃ ) ₃ · nH ₂ O), except that the spherical alumina carrier contains 1.5 wt% Ru and C in the same manner as in Example 1.
A catalyst supporting 5 wt% of eO ₂ was obtained. Example 4 In Example 1, instead of the RhCl ₃ aqueous solution, RuC was used.
and l ₃ aqueous lanthanum nitrate solution (La _(NO 3)
₃ · _6H 2 O) in place, the embodiment except that the praseodymium nitrate aqueous solution _{(Pr (NO 3) 3 ·} 6H 2 O) 1
In the same manner as above, 1.5 wt% of Ru was added to the spherical alumina carrier.
%, Pr ₂ O ₃ of 5 wt% was obtained. Example 5 In Example 1, instead of the RhCl ₃ aqueous solution, RuC was used.
and l ₃ aqueous lanthanum nitrate solution (La _(NO 3)
₃ · _6H 2 O) in place, neodymium nitrate aqueous solution (Nd
_{(NO 3) 3 · 6H 2} O) except that as in the same manner as in Example 1, 1.5 wt% of Ru in spherical alumina carrier, Nd
A catalyst supporting 5% by weight of ₂ O ₃ was obtained. Example 6 In Example 1, instead of the RhCl ₃ aqueous solution, RuC was used.
and l ₃ aqueous lanthanum nitrate solution (La _(NO 3)
₃ · _6H 2 O) in place, samarium nitrate solution (Sm
_{(NO 3) 3 · 6H 2} O) except that as in the same manner as in Example 1, 1.5 wt% of Ru in spherical alumina carrier, Sm
A catalyst supporting 5% by weight of ₂ O ₃ was obtained. Example 7 In Example 1, instead of the RhCl ₃ aqueous solution, RuC was used.
and l ₃ aqueous lanthanum nitrate solution (La _(NO 3)
₃ · _6H 2 O) in place, terbium nitrate aqueous solution (Tb
_{(NO 3) 3 · 6H 2} O) except that as in the same manner as in Example 1, 1.5 wt% of Ru in spherical alumina support, Tb
A catalyst supporting 5% by weight of ₂ O ₃ was obtained. Example 8 In Example 1, instead of the RhCl ₃ aqueous solution, RuC was used.
and l ₃ aqueous lanthanum nitrate solution (La _(NO 3)
₃ · _6H 2 O) in place, yttrium nitrate solution (Y
_{(NO 3) 3 · 6H 2} O) except that as in the same manner as in Example 1, 1.5 wt% of Ru in spherical alumina support, _{Y 2}
A catalyst supporting 5 wt% of O ₃ was obtained. Example 9 In Example 3, a cerium nitrate aqueous solution (Ce (N
O ₃ ) ₃ · nH ₂ O) was added to the spherical alumina support in an amount of 1.5 w in the same manner as in Example 3 except that the concentration was doubled.
A catalyst supporting t% and 10 wt% CeO ₂ was obtained. Example 10 In Example 3, a ceric nitrate aqueous solution (Ce (N
O ₃ ) ₃ · nH ₂ O) was added to the spherical alumina carrier in an amount of 1.5 w in the same manner as in Example 3 except that the concentration was tripled.
A catalyst supporting t% and CeO ₂ at 15 wt% was obtained. Example 11 In Example 3, the spherical activated alumina NKHD-24 was replaced with a particle size of 2 mm to 4 mm and a pore volume of 1.05 ml.
/ G, average pore size 500Å, water absorption rate 111% spherical silica CARIACT-50 manufactured by Fuji Davisson Chemical Co., Ltd.
A catalyst supporting 1.5 wt% and 5 wt% CeO ₂ was obtained. Example 12 SYLOID, a fine powdery synthetic silica manufactured by Fuji Devison Chemical Co., Ltd., having an average particle diameter of 2.5 μm and a pore volume of 1.25 ml / g.
978 was repulsed in water. CeO ₂ is added to this slurry in an amount of 5 wt% with respect to SYLOID 978, and cerium nitrate (Ce (NO ₃ ) ₃ · nH ₂ O) is added.
Aqueous solution was added and stirred for 30 minutes. Then (1 + 1)
Neutralized with NH ₄ OH until pH = 8. The slurry was filtered, washed with water, dried, and then calcined at 500 ° C. for 4 hours to obtain a CeO ₂ -supported synthetic silica powder. Next, a part of this powder was passed through a granulator using silica sol as a binder and passed through a sieve to give a granular material of about 1 mm. Using this as a core, the remaining powder was also subjected to a tumbling granulator using silica sol as a binder and passed through a sieve to obtain a spherical granule having a particle diameter of 2 mm to 4 mm. 1 of these granules
After drying at 00 ° C. for 5 hours, it was further baked at 500 ° C. for 4 hours. Then, this is immersed in an aqueous RuCl ₃ solution to remove Ru
As 1.5 wt%. After blowing off excess water, it was baked at 100 ° C. for 2 hours. Then. These were subjected to reduction treatment in a H ₂ stream at 400 ° C. for 2 hours, and a spherical silica carrier with 1.5 wt% Ru and CeO ₂ 2
To obtain a catalyst supporting 5 wt%. Comparative Example 1 In Example 1, without supporting La ₂ O ₃ by impregnation, H 2
_A reduction treatment was performed at 400 ° C. for 2 hours in _two air streams to obtain a catalyst in which only 1.5 wt% of Rh was supported on the spherical alumina carrier. Comparative Example 2 In Example 2, without impregnating and supporting La ₂ O ₃ , H 2
_A reduction treatment was carried out at 400 ° C. for 2 hours in _two air streams to obtain a catalyst in which 1.5 wt% of only Ru was supported on the spherical alumina carrier. (II), Measurement of water adsorption amount The catalysts obtained in Examples 1 to 12 and Comparative Examples 1 to 2 were lightly crushed and put in a desiccator filled with water placed in a warm water tank at 50 ° C for one day. The catalyst was left to stand and water was adsorbed on the catalyst. Seiko Denshi Kogyo Co., Ltd. SSC-5200 model thermal analysis system was used in N ₂ gas flow from room temperature to 500 ° C.
The temperature is raised at ℃ / min, TG-DTA analysis is performed, and 3
The water adsorption amount at 00 ° C was measured. (III), Evaluation Test For the catalysts obtained in Examples 1 to 12 and Comparative Examples 1 to 2, the nitrous oxide-containing gas was catalytically decomposed by using a normal pressure flow reactor under the following test conditions. 1 hour after the start
The nitrous oxide decomposition rate after 10 hours and 100 hours was measured. Incidentally, nitrite nitrogen decomposition rate was calculated by quantifying the N ₂ by gas chromatography a conversion to N ₂ of nitrous oxide. Test conditions , gas composition N ₂ O 50 ppm O ₂ 5% H ₂ O 2% He balance, space velocity 5000 Hr ¹ , reaction temperature 350 ° C. The results are shown in Table 1.

As described in detail above, the catalyst for decomposing nitrous oxide according to the present invention is capable of efficiently catalytically decomposing nitrous oxide in exhaust gas and, at the same time, is unlikely to change with time. It has an excellent unique effect.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenji Nakahira 5-1, Ebishimacho, Sakai City, Osaka Prefecture Sakai Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1. A hydrophobic carrier comprising (a) ruthenium (R)
u), at least one selected from rhodium (Rh),
And _{(b) La 2 O 3,} CeO 2, Pr 2 O 3, Nd 2
A catalyst for decomposing nitrous oxide, which carries at least one selected from O ₃ , Sm ₂ O ₃ , Tb ₂ O ₃ , and Y ₂ O ₃ .