JP2013533804A5

JP2013533804A5 -

Info

Publication number: JP2013533804A5
Application number: JP2013519191A
Authority: JP
Filing date: 2011-07-05
Publication date: 2014-08-21

Claims

The silica: alumina molar ratio is about 4 to about 50, the copper content as CuO is about 1 to about 10% by weight, based on the total weight of the calcined zeolitic material, and the alkali metal content as metal oxide is about 0. Copper-containing ZSM-34, OFF and / or ERI zeolitic material in the range of 7 to about 1.5% by weight, the copper-containing ZSM-34, OFF and / or ERI zeolite after curing at 750 ° C. The volume flow rate (space velocity) of gas per hour of the system material is 30000 h ⁻¹ , 500 ppm NO and 500 ppm NH ₃ , 10% O ₂ , 5% under the maximum NH ₃ slip condition in the steady state condition. of _H 2 O, remainder NO conversion in a mixed gas of _{N 2} is at least about 75% at 200 ° C., the copper-containing ZSM-34, OFF and at least about 90% at 450 ° C. / ERI zeolite-based materials.

The copper-containing ZSM-34, OFF and / or ERI zeolitic material according to claim 1, wherein the alkali metal content as the metal oxide is in the range of 0.9 to 5% by mass.

In a zeolitic material that is fresh or cured at 750 ° C., the copper content as CuO is in the range of 2 to 5% by mass with respect to the total mass of the calcined zeolitic material, and in the zeolitic material after curing at 800 ° C. The copper-containing ZSM-34, OFF and / or ERI zeolitic material according to claim 1 or 2, which is 2 to 4.2% by mass relative to the total mass of the calcined zeolitic material.

The copper-containing ZSM-34, OFF and / or ERI zeolitic material according to any one of claims 1 to 3, wherein the silica: alumina molar ratio is 8-15.

Whether the copper-containing ZSM-34, OFF and / or ERI zeolitic material has a silica: alumina molar ratio of 10-15, and is the copper-containing ZSM-34, OFF and / or ERI zeolitic material fresh 750 When after curing for 24 hours in 10% steam at ° C., the copper: aluminum atomic ratio is in the range of 0.04 to 0.5,
When the copper-containing ZSM-34, OFF and / or ERI zeolitic material is after curing for 12 hours in 800% 10% steam, the copper: aluminum atomic ratio is in the range of 0.04 to 0.3. And
Whether the copper-containing ZSM-34, OFF and / or ERI zeolitic material has a silica: alumina molar ratio of 4 to 10 and the copper-containing ZSM-34, OFF and / or ERI zeolitic material is fresh 750 When after curing for 24 hours in 10% steam at ° C., the copper: aluminum atomic ratio is in the range of 0.02-0.5,
When the copper-containing ZSM-34, OFF and / or ERI zeolitic material is after 12 hours of curing in 800% 10% steam, the copper: aluminum atomic ratio is in the range of 0.02-0.21. The copper-containing ZSM-34, OFF and / or ERI zeolitic material according to any one of claims 1 to 4.

Whether the copper-containing ZSM-34, OFF and / or ERI zeolitic material has a silica: alumina molar ratio of 10-15, and is the copper-containing ZSM-34, OFF and / or ERI zeolitic material fresh 750 When cured in 10% steam at 10 ° C. for 24 hours, the sum of Cu and alkali metal: aluminum atomic ratio (2Cu + M) / Al is in the range of 0.14 to 1;
When the containing ZSM-34, OFF and / or ERI zeolitic material is after curing in 800% 10% steam for 12 hours, the total Cu plus 2 times alkali metal: aluminum atomic ratio (2Cu + M) / Al is in the range of 0.14-0.86;
The silica-to-alumina molar ratio of the copper-containing ZSM-34, OFF and / or ERI zeolitic material is 4-10, and the copper-containing ZSM-34, OFF and / or ERI zeolitic material is 750 ° C. And after curing for 24 hours in 10% steam, the total of the Cu and twice the alkali metal: aluminum atomic ratio (2Cu + M) / Al is in the range of 0.07 to 1,
If the copper-containing ZSM-34, OFF and / or ERI zeolitic material is cured for 12 hours in 10% steam at 800 ° C., then 2 times Cu plus the total alkali metal: aluminum atomic ratio (2Cu + M) / Al is in the range of 0.07 to 0.6. The copper-containing ZSM-34, OFF and / or ERI zeolitic material according to any one of claims 1 to 5.

Whether the copper-containing ZSM-34, OFF and / or ERI zeolitic material has a silica: alumina molar ratio of 10-15, and is the copper-containing ZSM-34, OFF and / or ERI zeolitic material 750 fresh? When after curing for 24 hours in 10% steam at ° C., the copper: proton atomic ratio is in the range of 0.05-600,
When the copper-containing ZSM-34, OFF and / or ERI zeolitic material is after curing in 800% 10% steam for 12 hours, the copper: proton atomic ratio is in the range of 0.05-300. ,
The silica-to-alumina molar ratio of the copper-containing ZSM-34, OFF and / or ERI zeolitic material is 4-10,
When the copper-containing ZSM-34, OFF and / or ERI zeolitic material is fresh or after curing in 10% steam at 750 ° C. for 24 hours, the copper: proton atomic ratio is 0.02-100. Range of
When the copper-containing ZSM-34, OFF and / or ERI zeolitic material is after curing in 800% 10% steam for 12 hours, the copper: proton atomic ratio is preferably in the range of 0.02-20. The copper-containing ZSM-34, OFF and / or ERI zeolitic material according to any one of claims 1-6.

-When the volumetric flow rate (space velocity) of gas per hour is measured at 80000h- ^1, that is, the NO conversion rate at 200 ° C of the fresh copper-containing ZSM-34, OFF and / or ERI zeolitic materials. Is at least 60% and at least 75% at 450 ° C;
The NO conversion of the copper-containing ZSM-34, OFF and / or ERI zeolitic material after curing at 750 ° C. is at least 55% at 200 ° C. and at least 70% at 450 ° C.,
The NO conversion of the copper-containing ZSM-34, OFF and / or ERI zeolitic material after curing at 800 ° C is at least 45% at 200 ° C and at least 65% at 450 ° C. The copper-containing ZSM-34, OFF and / or ERI zeolitic material according to Item.

The copper-containing ZSM-34, OFF and / or ERI zeolitic material has a Langmuir surface area determined by DIN-ISO-9277 in the range of 400 to 900 m ² / g, the copper-containing ZSM-34, OFF and / or ERI 9. The surface area of the zeolitic material is maintained at least 60% of its fresh surface area after exposure for 1 to 48 hours at a temperature of 750 [deg.] C. in the presence of up to 10% by volume of steam. The copper-containing ZSM-34, OFF and / or ERI zeolitic material according to one item.

The copper-containing ZSM-34, OFF and / or ERI zeolitic material according to any one of claims 1 to 9, wherein ZSM-34 is used.

A catalyst comprising a copper-containing ZSM-34, OFF and / or ERI zeolitic material according to any one of claims 1 to 10 supported on a support.

A catalyst comprising the copper-containing ZSM-34, OFF and / or ERI zeolitic material according to any one of claims 1 to 10 or the catalyst of claim 11 is converted to NOx selective reduction (SCR), NH ₃ oxidation, N ₂ O decomposition, soot oxidation, or emission control in advanced emission systems, or as an additive in fluid catalytic cracking (FCC) processes, as catalysts for organic conversion reactions, or as catalysts for fixed emission processes Usage as.

An ammonia-containing exhaust gas stream and a catalyst comprising the copper-containing ZSM-34, OFF and / or ERI zeolitic material according to any one of claims 1 to 10 , or the catalyst of claim 11, a soot filter and a diesel oxidation catalyst. An exhaust gas treatment system consisting of

Selective of nitrogen oxide NOx, wherein a gas stream comprising nitric oxide NOx is contacted with the copper-containing ZSM-34, OFF and / or ERI zeolitic material according to any one of claims 1-10 or the catalyst of claim 11. Reduction method.