Synthesis of Cu/SAPO-34 with variable copper loadings

Patent metadata

Field	Value
Publication number	US-9475040-B2
Application number	US-201213709137-A
Country	US
Kind code	B2
Filing date	Dec 10, 2012
Priority date	Dec 10, 2012
Publication date	Oct 25, 2016
Grant date	Oct 25, 2016

Abstract

A Cu-amine complex of hydrated copper sulfate and ethylene diamine or an oligomer of ethylene diamine is employed in a direct (one-pot) synthesis of a copper-cation containing silicoaluminophosphate (SAPO) zeolite material having the Cu/SAPO-34 structure. The copper-amine complex is included in an aqueous gel of precursors of the SiO 2 , Al 2 O 3 , and P 2 O 5 constituents, which are mixed, aged, and thermally treated to form the desired Cu/SAPO-34 structure. The synthesized Cu/SAPO-34 material is demonstrated to be an effective catalyst material in conversion of nitric oxide to nitrogen (using ammonia as a reductant) in synthetic exhaust streams characteristic of diesel engine and other lean-burn vehicle engine exhaust streams.

First claim

The invention claimed is:

1. A method of forming Cu/SAPO-34 comprising:
forming an aqueous gel of Al 2 O 3 or a Al 2 O 3 precursor, P 2 O 5 or a P 2 O 5 precursor, and SiO 2 or a SiO 2 precursor;
adding to the aqueous gel, or forming in the aqueous gel, a water soluble amine complex of copper in its +2 oxidation state and an equal molar amount of ethylene diamine or an oligomer of ethylene diamine, the copper being provided by a water soluble copper salt;
stirring and aging the gel without heating;
heating the gel to form a solid product; and
calcining the solid product to form a crystalline product with SAPO-34 crystal structure containing copper +2 cations enclosed within the crystal structure.

2. A method of forming Cu/SAPO-34 as recited in claim 1 in which the copper salt is one or more of copper acetate, copper nitrate, and copper sulfate.

3. A method of forming Cu/SAPO-34 as recited in claim 1 in which one or more of ethylene diamine, diethylene triamine, triethylene tetraamine, and tetraethylene pentaamine are used in making the soluble amine complex with copper.

4. A method of forming Cu/SAPO-34 as recited in claim 1 in which the pH of the aqueous gel is adjusted, if necessary, to a value in the range of 7-9.

5. A method of forming Cu/SAPO-34 as recited in claim 4 in which propyl amine is added to the aqueous gel to adjust the pH of the gel to a value in the range of 7-9.

6. A method of forming Cu/SAPO-34 as recited in claim 1 in which the molar proportions of Al 2 O 3 to P 2 O 5 to SiO 2 in the aqueous gel are, respectively, about 1:1.14:0.57.

7. A method of forming Cu/SAPO-34 as recited in claim 1 in which the amount of copper cations in the Cu/SAPO-34 crystal structure is varied by varying the amount of the copper-amine complex stirred in the gel in proportion to the Al 2 O 3 .

8. A method of forming Cu/SAPO-34 as recited in claim 7 in which the amount of copper cations in the Cu/SAPO-34 crystal structure is varied by varying the amount of the copper-ethylene diamine complex within the range of from about 0.04 mole to about 0.571 mole of the complex per mole of alumina.

9. A method of forming Cu/SAPO-34 as recited in claim 1 in which the gel is stirred for a period of twelve hours or more.

10. A method of forming Cu/SAPO-34 as recited in claim 1 in which the gel is heated at a temperature of about 180° C. or higher for a period of twenty four hours or more.

11. A method of forming Cu/SAPO-34 comprising:
forming an aqueous gel of Al 2 O 3 or a Al 2 O 3 precursor, P 2 O 5 or a P 2 O 5 precursor, and SiO 2 or a SiO 2 precursor, the molar proportions of Al 2 O 3 /P 2 O 5 /SiO 2 in the aqueous gel being about 1:1.14:0.57;
adding to the aqueous gel, or forming within the aqueous gel, with stirring, a water soluble amine complex of copper in its +2 oxidation state and an equal molar amount of an oligomer of ethylene diamine, the copper being provided by a water soluble copper salt;
stirring and aging the gel without heating;
heating the gel to form a solid product; and
calcining the solid product to form a crystalline product with SAPO-34 crystal structure containing copper +2 cations enclosed within the crystal structure.

12. A method of forming Cu/SAPO-34 as recited in claim 11 in which the copper salt is one or more of copper acetate, copper nitrate, and copper sulfate.

13. A method of forming Cu/SAPO-34 as recited in claim 11 in which the oligomer of ethylene diamine is one or more of diethylene triamine, triethylene tetraamine, and tetraethylene pentaamine.

14. A method of forming Cu/SAPO-34 as recited in claim 11 in which the pH of the aqueous gel is adjusted, if necessary, to a value in the range of 7-9.

15. A method of forming Cu/SAPO-34 as recited in claim 14 in which propyl amine is added to the aqueous gel to adjust the pH of the gel to a value in the range of 7-9.

16. A method of forming Cu/SAPO-34 as recited in claim 11 in which the amount of copper cations in the Cu/SAPO-34 crystal structure is varied by varying the amount of the copper-amine complex stirred into the gel in proportion to the Al 2 O 3 moiety.

17. A method of forming Cu/SAPO-34 as recited in claim 16 in which the amount of copper cations in the Cu/SAPO-34 crystal structure is varied by varying the amount of the copper-ethylene diamine complex within the range of from about 0.040 mole to about 0.571 mole of the complex per mole of Al 2 O 3 .

18. A method of forming Cu/SAPO-34 as recited in claim 11 in which the gel is stirred for a period of twelve hours or more.

19. A method of forming Cu/SAPO-34 as recited in claim 11 in which the gel is heated at a temperature of about 180° C. or higher for a period of twenty four hours or more.

20. A method of forming Cu/SAPO-34 as recited in claim 11 in which the formed Cu/SAPO-34 is characterized by compositional molar proportions of 0.35-0.40 mole of silicon per mole of aluminum, 0.6-0.65 mole of phosphorus per mole of aluminum, and about 0.07-0.36 mole copper per mole of aluminum.

Assignees

• Gm Global Tech Operations Llc

Inventors

• Qi Gongshin
• Li Wei
• Meng Xiangju
• Xiao Fengshou

Classifications

• B01J2235/15

  X-ray diffraction · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/77

  Compounds characterised by their crystallite size · CPC title

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01D2258/012

  Diesel engines and lean burn gasoline engines · CPC title