Mn+-exchanged beta zeolite, gas adsorbent comprising same, method for producing same, and method for removing nitrogen monoxide

Patent metadata

Field	Value
Publication number	US-9968909-B2
Application number	US-201414897946-A
Country	US
Kind code	B2
Filing date	Jun 13, 2014
Priority date	Jun 14, 2013
Publication date	May 15, 2018
Grant date	May 15, 2018

Abstract

Provided are: a M n+ -exchanged beta zeolite which is useful for the catalytic removal of nitrogen monoxide contained in a gas to be purified even when oxygen is contained in the gas at a high concentration or when the gas has a low temperature; and a method for producing the M n+ -exchanged beta zeolite. The M n+ -exchanged beta zeolite according to the present invention has a SiO 2 /Al 2 O 3 ratio of 7 to 18, and is ion-exchanged by a M n+ ion (wherein M n+ represents a n-valent metal cation; n represents a numeral value of 1 to 3; and M represents an element selected from the group consisting of Ni, Co, Cu, Mn, Zn, Sn, Ag, Li, K, Cs, Au, Ca, Mg, Pt, Pd, Rh and Ir). The amount of the M n+ ion carried on the M n+ -exchanged beta zeolite is preferably from 0.01 to 2.5 mmol/g relative to the amount of the M n+ -exchanged beta zeolite.

First claim

The invention claimed is:

1. An M n+ -exchanged beta zeolite which has been ion-exchanged with an M n+ ion (wherein M n+ represents an n-valent metal cation; n represents a numerical value of 1 to 3; and M represents an element selected from the group consisting of Ni, Co, Cu Mn, Zn, Sn, Ag, Li, K, Cs, Au, Ca, Mg, Pt, Pd, Rh and Ir), in which:
SiO 2 /Al 2 O 3 ratio ranges from 7 to 18; a BET specific surface area ranges from 400 to 700 m 2 /g; a micropore specific surface area ranges from 290 to 500 m 2 /g; a micropore volume ranges from 0.15 to 0.25 cm 3 /g, and the intensity of the Kubelka-Munk function f (R∞) obtained by Ultraviolet-visible spectroscopy shows the maximal intensity in the wavelength range from 300 to 600 nm which is larger than the maximal intensity in the wavelength range from 200 to 250 nm.

2. The M n+ -exchanged beta zeolite according to claim 1 , wherein the amount of the M n+ ion relative to the amount of the M n+ -exchanged beta zeolite ranges from 0.01 to 2.5 mmol/g.

3. The M n+ -exchanged beta zeolite according to claim 1 , wherein a beta zeolite, in which an SiO 2 /Al 2 O 3 ratio ranges from 7 to 18, a BET specific surface area that is measured in the form of a sodium-type beta zeolite ranges from 400 to 700 m 2 /g, a micropore specific surface area that is measured in the form of a sodium-type beta zeolite ranges from 250 to 500 m 2 /g, and a micropore volume that is measured in the form of a sodium-type beta zeolite ranges from 0.15 to 0.25 cm 3 /g, is used as a beta zeolite before having been ion-exchanged with the M n+ ion.

4. The M n+ -exchanged beta zeolite according to claim 2 , wherein a beta zeolite, in which an SiO 2 /Al 2 O 3 ratio ranges from 7 to 18, a BET specific surface area that is measured in the form of a sodium-type beta zeolite ranges from 400 to 700 m 2 /g, a micropore specific surface area that is measured in the form of a sodium-type beta zeolite ranges from 250 to 500 m 2 /g, and a micropore volume that is measured in the form of a sodium-type beta zeolite ranges from 0.15 to 0.25 cm 3 /g, is used as a beta zeolite before having been ion-exchanged with the M n+ ion.

5. The M n+ -exchanged beta zeolite according to claim 1 , wherein a hydrogen consumption amount when the temperature of the M n+ -exchanged beta zeolite increases at the rate of 10° C./min under the mixed gas atmosphere consisting of 5 vol % of hydrogen and 95 vol % of helium has a peak at a temperature of 400° C. or less.

6. The M n+ -exchanged beta zeolite according to claim 2 , wherein a hydrogen consumption amount when the temperature of the M n+ -exchanged beta zeolite increases at the rate of 10° C./min under the mixed gas atmosphere consisting of 5 vol % of hydrogen and 95 vol % of helium has a peak at a temperature of 400° C. or less.

7. The M n+ -exchanged beta zeolite according to claim 3 , wherein a hydrogen consumption amount when the temperature of the M n+ -exchanged beta zeolite increases at the rate of 10° C./min under the mixed gas atmosphere consisting of 5 vol % of hydrogen and 95 vol % of helium has a peak at a temperature of 400° C. or less.

8. The M n+ -exchanged beta zeolite according to claim 4 , wherein a hydrogen consumption amount when the temperature of the M n+ -exchanged beta zeolite increases at the rate of 10° C./min under the mixed gas atmosphere consisting of 5 vol % of hydrogen and 95 vol % of helium has a peak at a temperature of 400° C. or less.

9. A gas adsorbent comprising the M n+ -exchanged beta zeolite according to claim 1 .

10. A gas adsorbent comprising the M n+ -exchanged beta zeolite according to claim 2 .

11. A gas adsorbent comprising the M n+ -exchanged beta zeolite according to claim 3 .

12. A gas adsorbent comprising the M n+ -exchanged beta zeolite according to claim 4 .

13. The gas adsorbent according to claim 9 , which is used in the adsorption of nitrogen monoxide.

14. A method for producing an M n+ -exchanged beta zeolite, which comprises the steps of dispersing a beta zeolite, in which an SiO 2 /Al 2 O 3 ratio ranges from 7 to 18, a BET specific surface area that is measured in the form of a sodium-type beta zeolite ranges from 400 to 700 m 2 /g, a micropore specific surface area that is measured in the form of a sodium-type beta zeolite ranges from 250 to 500 m 2 /g and a micropore volume that is measured in the form of a sodium-type beta zeolite ranges from 0.15 to 0.25 cm 3 /g, in an aqueous solution of an n-valent metal wherein the concentration of a water-soluble compound of the n-valent metal is 0.3 to 1.0 mol/L, so that the proportion of the beta zeolite is 0.5 to 7 parts by mass based on 100 parts by mass of the aqueous solution; and then mixing the dispersion under stirring to cause said beta zeolite to carry an M n+ ion (wherein M n+ represents an n-valent metal cation; n represents a numerical value of 1 to 3; and M represents an element selected from the group consisting of Ni, Co, Cu, Mn, Zn, Sn, Ag, Li, K, Cs, Au, Ca, Mg, Pt, Pd, Rh and Ir),
wherein the intensity of the Kubelka-Munk function f (R∞) obtained by Ultraviolet-visible spectroscopy shows the maximal intensity in the wavelength range from 300 to 600 nm which is larger than the maximal intensity in the wavelength range from 200 to 250 nm.

15. A method for removing nitrogen monoxide, which comprises of:
bringing an M n+ -exchanged beta zeolite into contact with nitrogen monoxide or a nitrogen monoxide-containing gas to cause nitrogen monoxide to be adsorbed on said M n+ -exchanged beta zeolite,
wherein, said M n+ -exchanged beta zeolite has been ion-exchanged with an M n+ ion (wherein M n+ represents an n-valent metal cation; n represents a numerical value of 1 to 3; and M represents an element selected from the group consisting of Ni, Co, Cu, Mn, Zn, Sn, Ag, Li, K, Cs, Au, Ca, Mg, Pt, Pd, Rh and Ir),
and wherein, SiO 2 /Al 2 O 3 ratio ranges from 7 to 18, a BET specific surface area ranges from 400 to 700 m 2 /g, a micropore specific surface area ranges from 290 to 500 m 2 /g, and a micropore volume ranges from 0.15 to 0.25 cm 3 /g, in said M n+ -exchanged beta zeolite.

Assignees

• Unizeo Co Ltd
• Mitsui Mining & Smelting Co

Inventors

• Elangovan Shanmugam Palani
• Yamamoto Masahiro
• Hieda Toyohiko

Classifications

• B01J20/28071

  being less than 0.5 ml/g · CPC title

• B01J20/186 Primary

  Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity · CPC title

• B01D53/9454

  characterised by a specific device · CPC title

• Y02T10/22

  Cross-Sectional Technologies · mapped topic

• B01D53/9481

  Catalyst preceded by an adsorption device without catalytic function for temporary storage of contaminants, e.g. during cold start · CPC title