Copper containing ZSM-34, OFF and/or ERI zeolitic material for selective reduction of NOx
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C01B-039/30
B01J-029/68
B01J-029/76
B01J-037/30
B01D-053/86
B01D-053/94
출원번호
US-0183634
(2011-07-15)
등록번호
US-9289756
(2016-03-22)
발명자
/ 주소
Bull, Ivor
Mueller, Ulrich
출원인 / 주소
BASF SE
인용정보
피인용 횟수 :
0인용 특허 :
5
초록▼
Described is a copper containing ZSM-34, OFF and/or ERI zeolitic material having a silica to alumina mole ratio ranging from about 4 to about 50 and a copper content, reported as CuO, ranging from about 1 to about 10 wt.-%, based on the total weight of the calcined zeolitic material, and having an a
Described is a copper containing ZSM-34, OFF and/or ERI zeolitic material having a silica to alumina mole ratio ranging from about 4 to about 50 and a copper content, reported as CuO, ranging from about 1 to about 10 wt.-%, based on the total weight of the calcined zeolitic material, and having an alkali metal content, reported as the metal oxide, of less than about 0.7 wt.-%.
대표청구항▼
1. A copper containing ZSM-34, OFF and/or ERI zeolitic material for selective reduction of NOx having a silica to alumina mole ratio ranging from about 4 to about 50 and a copper content, reported as CuO, ranging from about 1 to about 10 wt.-%, based on the total weight of the calcined zeolitic mate
1. A copper containing ZSM-34, OFF and/or ERI zeolitic material for selective reduction of NOx having a silica to alumina mole ratio ranging from about 4 to about 50 and a copper content, reported as CuO, ranging from about 1 to about 10 wt.-%, based on the total weight of the calcined zeolitic material, and having an alkali metal content, reported as the metal oxide, of less than or equal to 0.1 wt.-%. 2. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1 having a copper content, reported as CuO, ranging from 2 to 10 wt.-%, based on the total weight of the calcined zeolitic material for fresh or a 750° C. aged zeolitic material or ranging from 2 to 5 wt.-%, based on the total weight of the calcined zeolitic material for 800° C. aged zeolitic material. 3. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1 having a silica to alumina mole ratio ranging from 8 to 15. 4. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, wherein the copper containing ZSM-34, OFF and/or ERI zeolitic material has a mole ratio of silica to alumina from 10 to 15 and the copper containing ZSM-34, OFF and/or ERI zeolitic material being fresh or aged at 750° C. in 10% steam for 24 hours, the atomic ratio of copper to aluminum ranges from 0.04 to 0.5. 5. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, wherein the copper containing ZSM-34, OFF and/or ERI zeolitic material has a mole ratio of silica to alumina from 10 to 15 and the copper containing ZSM-34, OFF and/or ERI zeolitic material being aged at 800° C. in 10% steam for 12 hours, the atomic ratio of copper to aluminum ranges from 0.04 to 0.35. 6. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, wherein the copper containing ZSM-34, OFF and/or ERI zeolitic material has a mole ratio of silica to alumina from 4 to 10 and the copper containing ZSM-34, OFF and/or ERI zeolitic material being fresh or aged at 750° C. in 10% steam for 24 hours, the atomic ratio of copper to aluminum ranges from 0.02 to 0.5. 7. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, wherein the copper containing ZSM-34, OFF and/or ERI zeolitic material has a mole ratio of silica to alumina from 4 to 10 and the copper containing ZSM-34, OFF and/or ERI zeolitic material being aged at 800° C. in 10% steam for 12 hours, the atomic ratio of copper to aluminum ranges from 0.02 to 0.15. 8. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, wherein if the copper containing ZSM-34, OFF and/or ERI zeolitic material has a mole ratio of silica to alumina from 10 to 15 and the copper containing ZSM-34, OFF and/or ERI zeolitic material being fresh or aged at 750° C. in 10% steam for 24 hours, the atomic ratio of the sum of two times Cu and alkali metal to aluminum (2Cu+M)/Al ranges from 0.08 to 1; or the copper containing ZSM-34, OFF and/or ERI zeolitic material being aged at 800° C. in 10% steam for 12 hours, the atomic ratio of the sum of two times Cu and alkali metal to aluminum (2Cu+M)/Al ranges from 0.08 to 0.8. 9. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, wherein if the copper containing ZSM-34, OFF and/or ERI zeolitic material has a mole ratio of silica to alumina from 4 to 10 and the copper containing ZSM-34, OFF and/or ERI zeolitic material being fresh or aged at 750° C. in 10% steam for 24 hours, the atomic ratio of the sum of two times Cu and alkali metal to aluminum (2Cu+M)/Al ranges from 0.04 to 1. 10. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, wherein if the copper containing ZSM-34, OFF and/or ERI zeolitic material has a mole ratio of silica to alumina from 4 to 10 and the copper containing ZSM-34, OFF and/or ERI zeolitic material being aged at 800° C. in 10% steam for 12 hours, the atomic ratio of the sum of two times Cu and alkali metal to aluminum (2Cu+M)/Al ranges from 0.04 to 0.6. 11. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, wherein the copper containing ZSM-34, OFF and/or ERI zeolitic material has a mole ratio of silica to alumina from 10 to 15 and the copper containing ZSM-34, OFF and/or ERI zeolitic material being fresh or aged at 750° C. in 10% steam for 24 hours, the atomic ratio of copper to proton ranges from 0.04 to 30. 12. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, wherein the copper containing ZSM-34, OFF and/or ERI zeolitic material has a mole ratio of silica to alumina from 10 to 15 and the copper containing ZSM-34, OFF and/or ERI zeolitic material being aged at 800° C. in 10% steam for 12 hours, the atomic ratio of copper to proton ranges from 0.04 to 1.6. 13. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, wherein the copper containing ZSM-34, OFF and/or ERI zeolitic material has a mole ratio of silica to alumina from 4 to 10 and the copper containing ZSM-34, OFF and/or ERI zeolitic material being fresh or aged at 750° C. in 10% steam for 24 hours, the atomic ratio of copper to proton ranges from 0.02 to 30. 14. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, wherein the copper containing ZSM-34, OFF and/or ERI zeolitic material has a mole ratio of silica to alumina from 4 to 10 and the copper containing ZSM-34, OFF and/or ERI zeolitic material being aged at 800° C. in 10% steam for 12 hours, the atomic ratio of copper to proton ranging from 0.02 to 0.16. 15. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, wherein, measured at a gas hourly volume based space velocity of 80000 h−1, the fresh copper containing ZSM-34, OFF and/or ERI zeolitic material exhibits an aged NO conversion at 200° C. of at least 50% and at 450° C. of at least 75%;the 750° C.-aged copper containing ZSM-34, OFF and/or ERI zeolitic material exhibits NO conversion at 200° C. is at least 50% and at 450° C. at least 75%;the 800° C.-aged copper containing ZSM-34, OFF and/or ERI zeolitic material exhibits NO conversion at 200° C. is at least 50% and at 450° C. at least 70%. 16. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, wherein the Langmuir surface area, determined according to DIN ISO 9277, of the copper containing ZSM-34, OFF and/or ERI zeolitic material is in the range from 400 to 900 m2/g and the surface area of the copper containing ZSM-34, OFF and/or ERI zeolitic material retains after exposure to a temperature of 750° C. in the presence of up to 10 volume percent water vapor for a time ranging from 1 to 48 hours at least 60% of its fresh surface area. 17. The copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, wherein ZSM-34 is used. 18. A catalyst containing the copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1 disposed on a substrate. 19. A process for the preparation of a zeolitic material, the process comprising synthesizing the copper containing ZSM-34 zeolitic material of claim 1, wherein, during the synthesis, (i) at least one ammonium exchange is conducted, (ii) the ammonium containing zeolitic material is calcined at least for one time and (iii) at least one copper exchange is conducted. 20. A method for promoting a reaction, the method comprising contacting an exhaust gas stream with a catalyst comprising the copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, wherein the reaction is selected from one or more of selective reduction (SCR) of nitrogen oxides NOx; oxidation of NH3; decomposition of N2O; soot oxidation; emission control in Advanced Emission Systems; fluid catalytic cracking (FCC); organic conversion; or stationary source processes. 21. An exhaust gas treatment system comprising an exhaust gas stream containing ammonia, a catalyst containing comprising the copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1, a soot filter, and a diesel oxidation catalyst. 22. A method of selectively reducing nitrogen oxides NOx, the method comprising contacting a gaseous stream containing nitrogen oxides NOx with the copper containing ZSM-34, OFF and/or ERI zeolitic material of claim 1.
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이 특허에 인용된 특허 (5)
Rubin ; Mae K. ; Rosinski ; Edward J. ; Plank ; Charles J., Crystalline zeolite ZSM-34 and method of preparing the same.
Pence Dallas T. (Idaho Falls ID) Thomas Thomas R. (Idaho Falls ID), Reduction of nitrogen oxides with catalytic acid resistant aluminosilicate molecular sieves and ammonia.
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