Oxidic material comprising a zeolite having framework type AEI

Patent metadata

Field	Value
Publication number	US-12448296-B2
Application number	US-202017423590-A
Country	US
Kind code	B2
Filing date	Jan 21, 2020
Priority date	Jan 23, 2019
Publication date	Oct 21, 2025
Grant date	Oct 21, 2025

Abstract

A process for preparing an oxidic material comprising a zeolitic material having framework type AEI and a framework structure comprising a tetravalent element Y, a trivalent element X, and O, the process comprising preparing a synthesis mixture comprising water, a source of Y, a source of X comprising sodium, an AEI framework structure directing agent, and a source of sodium other than the source of X; and heating the synthesis mixture obtained from (i) to a temperature in the range of from 100 to 180° C. and keeping the synthesis mixture under autogenous pres-sure at a temperature in this range for a time in the range of at least 6 h, obtaining the oxidic material comprising a zeolitic material having framework type AEI and a framework structure comprising a tetravalent element Y, a trivalent element X, and O, comprised in its mother liquor; wherein the AEI framework structure directing agent according to (i) comprises a N, N-diethyl-2,6-dimethylpiperidinium cation.

First claim

What is claimed is:

1. A process for preparing an oxidic material comprising a zeolitic material having framework AEI and a framework structure comprising a tetravalent element Y, a trivalent element X, and O, the process comprising:
(i) preparing a synthesis mixture comprising water, a source of Y, a source of X comprising sodium, an AEI framework structure directing agent, and a source of sodium other than the source of X;
(ii) heating the synthesis mixture obtained from (i) to a temperature in the range of from 100 to 180° C. and keeping the synthesis mixture under autogenous pressure at a temperature in this range for a time in the range of at least 6 hrs, obtaining the oxidic material comprising a zeolitic material having framework AEI and a framework structure comprising a tetravalent element Y, a trivalent element X, and O, comprised in its mother liquor;
(iii) cooling the mixture obtained from (ii) to a temperature in the range of 10 to 50° C.; and
(iv) separating the oxidic material comprising a zeolitic material from the mixture obtained from (ii), said separating comprising:
(iv.1) subjecting the mixture obtained from (ii) to a solid-liquid separation method comprising a filtration method or a spraying method,

wherein the process for preparing the oxidic material does not comprise an addition of a source of X comprising sodium other than the step of (i) preparing the synthesis mixture comprising water, a source of Y, a source of X comprising sodium, and AEI framework structure directing agent, and a source of sodium other than the source of X,
wherein the AEI framework structure directing agent according to (i) comprises an N,N—(C 1 -C 3 )dialkyl-(C 1 -C 3 )dialkylpiperidinium cation;
wherein in the synthesis mixture prepared in (i) which is subjected to (ii), the molar ratio of the source of Y calculated as YO 2 , relative to the source of X calculated as X 2 O 3 , defined as YO 2 :X 2 O 3 , is in the range from 40:1 to 500:1;
wherein in the synthesis mixture prepared in (i) which is subjected to (ii), the molar ratio of sodium calculated as Na 2 O, relative to the source of Y calculated as YO 2 , defined as Na 2 O:YO 2 , is in the range of from 0.25:1 to 0.50:1; and
wherein the synthesis mixture prepared in (i) is heated to the temperature in (ii) with a heating rate in the range of from 0.5 to 4 K/min;
wherein Y comprises a colloidal silica;
wherein X is Al;
wherein the source of X comprises NaAlO 2 , and
wherein the source of sodium other than the source of X comprises NaOH.

2. The process of claim 1 , wherein the N,N-dialkyl-dialkylpiperidinium cation comprises an N,N—(C 1 -C 2 )dialkyl-(C 1 -C 2 )dialkylpiperidinium cations, or
wherein the N,N-dialkyl-dialkylpiperidinium cation is selected from the group consisting of an N,N—(C 1 -C 2 )dialkyl-2,6-(C 1 -C 2 )dialkylpiperidinium cation, an N,N—(C 1 -C 2 )dialkyl-3,5-(C 1 -C 2 )dialkylpiperidinium cation and a mixture of two or more thereof, or
wherein the N,N-dialkyl-dialkylpiperidinium cation is selected from the group consisting of an N,N-dimethyl-2,6-(C 1 -C 2 )dialkylpiperidinium cation, an N,N-dimethyl-3,5-(C 1 -C 2 )dialkyl-piperidinium cation and a mixture of two or more thereof, or
wherein the N,N-dialkyl-dialkylpiperidinium cation is selected from the group consisting of N,N-diethyl-2,6-dimethylpiperidinium cation, N,N-diethyl-3,5-dimethylpiperidinium cation and a mixture thereof, or
wherein the N,N-dialkyl-dialkylpiperidinium cation comprises N,N-diethyl-cis-2,6-dimethylpiperidinium cation;
wherein the AEI framework structure directing agent according to (i) is one or more of a salt, a hydroxide or a halide, wherein the halide is one or more of an iodide, a chloride, a fluoride or a bromide, or wherein the AEI framework structure directing agent according to (i) comprises a hydroxide;
wherein the AEI framework structure directing agent according to (i) comprises N,N-diethyl-2,6-dimethylpiperidinium hydroxide or N,N-diethyl-cis-2,6-dimethylpiperidinium hydroxide.

3. The process of claim 1 , wherein in the synthesis mixture prepared in (i) which is subjected to (ii),
the molar ratio of the source of Y calculated as YO 2 , relative to the water, defined as YO 2 : water, is in the range of from 0.01:1 to 1:1;
wherein the synthesis mixture prepared in (i) which is subjected to (ii) further comprises a crystalline seed material comprising a zeolitic material having framework AEI and a framework structure comprising the tetravalent element Y, the trivalent element X, and O.

4. The process of claim 1 , wherein the temperature according to (ii) is in the range of from 120 to 160° C., wherein according to (ii), the synthesis mixture is kept at the temperature for a time in the range of from 6 to 12 hrs.

5. The process of claim 1 , further comprising
(vi) subjecting the oxidic material comprising a zeolitic material obtained from (iv) to ion exchange conditions, obtaining an oxidic material comprising a zeolitic material having framework AEI in its ammonium form.

6. The process of claim 5 , wherein the ion exchange conditions are ammonium exchange conditions, and the process further comprises bringing a solution comprising ammonium ions in contact with the oxidic material comprising the zeolitic material obtained from (iv).

7. The process of claim 6 , wherein bringing the solution in contact with the oxidic material comprises impregnating the zeolitic material with the solution, or spraying the solution onto the oxidic material.

8. The process of claim 7 , further comprising (vii) calcining the oxidic material in a gas atmosphere at a temperature of 300 to 700° C., and obtaining an oxidic material comprising the zeolitic material in its H form.

9. The process of claim 1 , further comprising
(viii) supporting a metal M on the zeolitic material comprised in the oxidic material.

10. The process of claim 1 , wherein the source of X is free of NaOH.

11. The process of claim 1 , wherein (ii) is carried out in an autoclave.

12. The process of claim 1 , wherein the temperature according to (ii) is in the range of 120 to 160° C., or 130 to 150° C.

13. The process of claim 1 , wherein (iv) further comprises:
(iv.2) washing the oxidic material comprising the zeolitic material obtained from (iv.1); and
(iv.3) drying the oxidic material comprising the zeolitic material obtained from (iv.1) or (iv.2) in a gas atmosphere having a temperature in the range of from 80 to 170° C.

14. The process of claim 13 , wherein the gas atmosphere in (iv.3) comprises oxygen, optionally, wherein the gas atmosphere comprises air, lean air, or synthetic air.

15. The process of claim 1 , further comprising (v) calcining the oxidic material comprising a zeolitic material obtained from (iv) in a gas atmosphere having a temperature in the range of 400 to 600° C., wherein at least a portion of the mother liquor obtained according to (iv.1) from separating the oxidic material from the mixture obtained from (ii) is recycled to (i) as part of the synthesis mixture prepared in (i).

16. The process of claim 15 , wherein the gas atmosphere in (v) comprises oxygen, optionally, wherein the gas atmosphere comprises air, lean air, or synthetic air.

17. The process of claim 1 , wherein the oxidic material exhibits a temperature programmed desorption of ammonia (NH 3 -TPD) curve exhibiting a peak having its maximum at (460±15) ° C., and a further peak having its maximum at (175±15) ° C.

18. The process of claim 1 , wherein the oxidic material exhibits a BET specific surface area in the range of 550 to 700 m 2 /g

Assignees

• Basf Se

Inventors

• Parvulescu Andrei-Nicolae
• Xiao Feng-Shou
• Meng Xiangju
• Wu Qinming
• Dai Yu
• Maurer Stefan
• Mueller Ulrich
• Xu Hao

Classifications

• C01P2006/12

  Surface area · CPC title

• C01B39/265

  using at least one organic template directing agent · CPC title

• C01B39/023

  Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48 · CPC title

• C01B39/48 Primary

  using at least one organic template directing agent · CPC title

• B01J29/76

  Iron group metals or copper · CPC title