AFI-CHA hybrid crystal zeolite and NH3-SCR catalyst using same as carrier, and preparation methods thereof

Patent metadata

Field	Value
Publication number	US-11241675-B2
Application number	US-202017283969-A
Country	US
Kind code	B2
Filing date	May 10, 2020
Priority date	May 10, 2019
Publication date	Feb 8, 2022
Grant date	Feb 8, 2022

Abstract

An AFI-CHA hybrid crystal molecular sieve and an NH 3 -SCR catalyst using the AFI-CHA hybrid crystal molecular sieve as a carrier, and preparation methods thereof are disclosed. The AFI-CHA hybrid crystal molecular sieve includes an AFI-type SAPO-5 molecular sieve and a CHA-type SAPO-34 molecular sieve, with hybrid crystal grains of AFI and CHA. The hybrid crystal molecular sieve is synthesized by a hydrothermal synthesis method and can be obtained by changing the structure directing agent, the heating rate and the calcinating temperature in the preparation process. Further, copper is loaded on the basis of the hybrid crystal molecular sieve to prepare copper-based NH 3 -SCR catalyst and corresponding monolithic catalyst. The catalytic activity and hydrothermal stability of the catalyst are significantly improved by the hybrid crystal molecular sieve.

First claim

What is claimed is:

1. A Cu/AFI-CHA supported zeolite catalyst based on an AFI-CHA hybrid crystal zeolite, wherein Cu is supported on the AFI-CHA hybrid crystal zeolite; the AFI-CHA hybrid crystal zeolite comprises an AFI-type SAPO-5 zeolite and a CHA-type SAPO-34 zeolite, grains of the AFI-CHA hybrid crystal zeolite are hybrid crystal grains of AFI and CHA; and the AFI-CHA hybrid crystal zeolite is prepared by the following method:
(1) performing a feeding according to a molar ratio of aluminum:phosphorus:silicon:a structure directing agent:water in the AFI-CHA hybrid crystal zeolite of (0.06-0.10):(0.06-0.10):(0.040-0.050):(0.12-0.35):(0.5-6), mixing pseudoboehmite, phosphoric acid, and water uniformly to obtain a first mixture, stirring and aging the first mixture at the room temperature to prepare a P/Al oxide gel, and then adding a Si source, the structure directing agent and water into the P/Al oxide gel to obtain a second mixture, aging the second mixture at room temperature to obtain a first mixed solution; and
(2) then keeping the first mixed solution at 120° C.-160° C. for 2-20 h, then heating to 190° C.-210° C. and holding for 5-30 h, cooling to the room temperature and separating a solid from the first mixed solution, then calcinating the solid at 500° C.-600° C. for 5-8 h to remove the structure directing agent to obtain an AFI-CHA hybrid crystal zeolite powder; wherein a heating rate of step (2) is 3-6° C.·min −1 ;
in step (1) and step (2), zeolites with different AFI/CHA hybrid crystal proportions are obtained by selecting different values for at least one of the molar ratio of the structure directing agent, a keeping temperature of the first mixed solution, a calcinating temperature of the solid, and the heating rate.

2. The Cu/AFI-CHA supported zeolite catalyst according to claim 1 , wherein the pseudoboehmite is 8-15 parts by weight, the phosphoric acid is 13-23 parts by weight, the Si source is 5-8 parts by weight, and the structure directing agent is 1-41 parts by weight.

3. The Cu/AFI-CHA supported zeolite catalyst according to claim 1 , wherein the structure directing agent is triethylamine or tetraethyl ammonium hydroxide.

4. A monolithic catalyst, comprising a substrate and a powder of the Cu/AFI-CHA supported zeolite catalyst according to claim 1 , wherein the powder of the Cu/AFI-CHA supported zeolite catalyst is washcoated on a cordierite monolith substrate.

5. A method for preparing the Cu/AFI-CHA supported zeolite catalyst according to claim 1 , comprising using a copper salt compound as a precursor to prepare a copper salt solution, mixing and stirring the AFI-CHA hybrid crystal zeolite with the copper salt solution to obtain a third mixture until the third mixture is viscous, to make the Cu evenly disperse into the AFI-CHA hybrid crystal zeolite; after drying the third mixture in a water bath, performing a calcination on the third mixture in a muffle furnace at 300° C.-600° C. for 3-6 h to obtain a powder of the Cu/AFI-CHA supported zeolite catalyst.

6. A method for preparing the monolithic catalyst according to claim 4 , comprising preparing the powder of the Cu/AFI-CHA supported zeolite catalyst into a slurry and washcoating the slurry on the cordierite monolith substrate to obtain a washcoated substrate, wherein an amount of the Cu/AFI-CHA supported zeolite catalyst has a loading amount on the cordierite monolith substrate is 120-130 g·L −1 ; drying the coated substrate at 70° C.-150° C., and then calcinating the coated substrate at 300° C.-600° C. for 3-6 h.

7. The Cu/AFI-CHA supported zeolite catalyst according to claim 2 , wherein the structure directing agent is triethylamine or tetraethyl ammonium hydroxide.

Assignees

• Univ Sichuan

Inventors

• Xu Haidi
• Lin Qingjin
• Chen Yaoqiang
• Wang Yun
• Feng Xi
• Wang Jianli
• Zhao Ming
• Jiao Yi

Classifications

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/30

  characterised by their physical properties · CPC title

• B01J35/56

  Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional [3D] monoliths · CPC title