Silicoaluminophosphate, method for producing the same, and solid acid catalyst comprising the same

Patent metadata

Field	Value
Publication number	US-9637392-B2
Application number	US-201314403013-A
Country	US
Kind code	B2
Filing date	May 23, 2013
Priority date	May 24, 2012
Publication date	May 2, 2017
Grant date	May 2, 2017

Abstract

The present invention relates to a silicoaluminophosphate represented by the following formula (1) and having a powder X-ray diffraction pattern shown in Table 1 below:

(Si x Al y P z )O 2   (1)

wherein x is the molar fraction of Si and 0.05<x≦0.15; y is the molar fraction of Al and 0.47≦y≦0.52; z is the molar fraction of P and 0.40≦z≦0.46; and x+y+z=1;

TABLE 1

Interplanar Spacing
Relative Intensity

Å
I/I 0

9.30 ± 0.15
1000

6.85 ± 0.10
from 100 to 300 

6.60 ± 0.10
from 10 to 100
B

5.50 ± 0.10
from 50 to 300

5.24 ± 0.10
from 10 to 100
B

4.64 ± 0.10
from 10 to 100

4.29 ± 0.05
from 100 to 500 

4.17 ± 0.05
from 10 to 150
B

3.82 ± 0.05
from 10 to 100

3.42 ± 0.05
from 20 to 150

2.87 ± 0.02
from 20 to 200

I/I 0 is the relative intensity when the peak of 9.30 ± 0.15 Å is taken as 1,000; and B indicates a broad peak.

First claim

The invention claimed is:

1. A silicoaluminophosphate represented by the following formula (1) having a powder X-ray diffraction pattern shown in Table 1 below, and a crystal in which an intergrowth ratio of CHA structure and AEI structure is from 50/50 to 30/70 in terms of CHA/AEI ratio:
(Si x Al y P z )O 2   (1)

wherein x is a molar fraction of Si and 0.05≦x≦0.15;
y is a molar fraction of Al and 0.47≦y≦0.52;
z is a molar fraction of P and 0.40≦z≦0.46; and
x+y+z=1;

TABLE 1

Interplanar Spacing
Relative Intensity

Å
I/I 0

9.30 ± 0.15
1000

6.85 ± 0.10
from 100 to 300 

6.60 ± 0.10
from 10 to 100
B

5.50 ± 0.10
from 50 to 300

5.24 ± 0.10
from 10 to 100
B

4.64 ± 0.10
from 10 to 100

4.29 ± 0.05
from 100 to 500 

4.17 ± 0.05
from 10 to 150
B

3.82 ± 0.05
from 10 to 100

3.42 ± 0.05
from 20 to 150

2.87 ± 0.02
from 20 to 200

I/I 0 is a relative intensity when the peak of 9.30 ± 0.15 Å is taken as 1,000; and B indicates a broad peak.

2. The silicoaluminophosphate according to claim 1 ,
wherein an average crystal size is from 0.5 to 10 μm.

3. The silicoaluminophosphate according to claim 1 , wherein a solid acidity of a crystal is 0.5 mmol/g or more.

4. The silicoaluminophosphate according to claim 1 ,
wherein a solid acidity of at least 50% is retained after a crystal in a hydrogen-type state resulting from removal of a structure directing agent is stored in saturated water vapor at 80° C. for 8 days.

5. A method for producing the silicoaluminophosphate according to claim 1 , comprising:
mixing a silicon source, a phosphorus source, an aluminum source, water and a structure directing agent to prepare a reaction mixture having, when expressed by molar ratios of oxides, the following molar compositional ratio:

P 2 O 5 /Al 2 O3
from 0.7 to 1.5,

SiO 2 /Al 2 O 3
from 0.1 to 1.2,

H 2 O/Al 2 O 3
from 5 to 100, and

R/Al 2 O 3
from 0.5 to 5

in which R represents a structure directing agent; and
holding the reaction mixture at a temperature of from more than 160° C. to 220° C. for 5 to 100 hours, wherein the structure directing agent is triethylamine or a mixture of triethylamine and other alkylamine or an ammonium salt thereof.

6. The method for producing the silicoaluminophosphate, wherein the silicoaluminophosphate according to claim 1 is added as a seed crystal to the reaction mixture in a ratio of 0.05 to 10 wt % relative to a total weight of the silicon source, the phosphorus source and the aluminum source in the reaction mixture when the amounts are converted in terms of oxides (SiO 2 , P 2 O 5 , Al 2 O 3 ),
wherein the reaction mixture having, when expressed by molar ratios of oxides, the following molar compositional ratio:
P 2 O 51 Al 2 O 3 from 0.7 to 1.5,
SiO 2 /Al 2 O 3 from 0.1 to 1.2,
H 2 O/Al 2 O 3 from 5 to 100, and
R/Al 2 O 3 from 0.5 to 5

in which R represents a structure directing agent,
wherein the structure directing agent is triethylamine or a mixture of triethylamine
and other alkylamine or an ammonium salt thereof.

7. A solid acid catalyst, comprising:
the silicoaluminophosphate according to claim 1 .

Assignees

• Tosoh Corp

Inventors

• Okaniwa Hiroshi
• Aoyama Hidekazu

Classifications

• C01B39/54 Primary

  Phosphates, e.g. APO or SAPO compounds · CPC title

• C01B37/08 Primary

  Silicoaluminophosphates [SAPO compounds] {, e.g. CoSAPO} · CPC title

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title

• C01P2004/03

  obtained by SEM · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title