Molecular sieve, its preparation and application thereof

Patent metadata

Field	Value
Publication number	US-11091372-B2
Application number	US-202016946927-A
Country	US
Kind code	B2
Filing date	Jul 11, 2020
Priority date	Apr 27, 2016
Publication date	Aug 17, 2021
Grant date	Aug 17, 2021

Abstract

The present invention relates to a molecular sieve, particularly to an ultra-macroporous molecular sieve. The present invention also relates to a process for the preparation of the molecular sieve and to its application as an adsorbent, a catalyst, or the like. The molecular sieve has a unique X-ray diffraction pattern and a unique crystal particle morphology. The molecular sieve can be produced by using a compound represented by the following formula (I),

wherein the definition of each group and value is the same as that provided in the specification, as an organic template. The molecular sieve is capable of adsorbing more/larger molecules, thereby exhibiting excellent adsorptive/catalytic properties.

First claim

We claim:

1. A method for the preparation of a molecular sieve, comprising:
contacting a first oxide source, a second oxide source, an organic template, and water under crystallization conditions to produce a molecular sieve,
wherein the first oxide is at least one selected from silica, germanium dioxide, tin dioxide, titania, and zirconium dioxide,
the second oxide is at least one selected from alumina, a boron oxide, an iron oxide, a gallium oxide, a rare earth oxide, an indium oxide, and a vanadium oxide, and
wherein the organic template comprises a compound represented by the following formula (I),

wherein the groups R 1 and R 2 are different from each other, each independently selected from C 3-12 linear alkylene groups, C 3-12 branched alkylene groups, C 3-12 linear oxaalkylene groups, and C 3-12 branched oxaalkylene groups;
the plural groups R are identical or different from each other, each independently selected from C 1-4 linear alkyl groups and C 1-4 branched alkyl groups; and
X is OH.

2. The method according to claim 1 , wherein the first oxide is silica or a combination of silica and germanium dioxide.

3. The method according to claim 1 , wherein the second oxide is alumina.

4. The method according to claim 1 , wherein the groups R 1 and R 2 are different from each other, with one of them being selected from C 3-12 linear alkylene groups, and the other being selected from C 3-12 linear alkylene groups and C 3-12 linear oxaalkylene groups.

5. The method according to claim 1 , wherein the groups R 1 and R 2 are different from each other, with one of them being selected from C 3-12 linear alkylene groups and the other being selected from C 4-6 linear alkylene groups and C 4-6 linear oxaalkylene groups.

6. The method according to claim 5 , wherein one of the groups R 1 and R 2 is selected from C 3-12 linear alkylene groups and the other of the groups R 1 and R 2 is selected from C 4-6 linear oxaalkylene groups, wherein the C 4-6 linear oxaalkylene group is represented by the formula —(CH 2 ) m —O—(CH 2 ) m —, wherein each value m, being identical or different from each other, independently represents 2 or 3.

7. The method according to claim 1 , wherein the plural groups R are identical or different from each other, each independently selected from methyl and ethyl.

8. The method according to claim 1 , wherein:
a molar ratio of the first oxide source, calculated on the basis of the first oxide, to the second oxide source, calculated on the basis of the second oxide, is in a range from 5 to ∞;
a molar ratio of water to the first oxide source, calculated on the basis of the first oxide, is in a range from 5 to 50; and
a molar ratio of the organic template to the first oxide source, calculated on the basis of the first oxide, is in a range from 0.02 to 0.5.

9. The method according to claim 1 , wherein:
a molar ratio of the first oxide source, calculated on the basis of the first oxide, to the second oxide source, calculated on the basis of the second oxide, is in a range from 25 to 95;
a molar ratio of water to the first oxide source, calculated on the basis of the first oxide, is in a range from 5 to 15; and
a molar ratio of the organic template to the first oxide source, calculated on the basis of the first oxide, is in a range from 0.15 to 0.5.

10. The method according to claim 1 , wherein the contacting step is carried out in the presence of an alkali source that is an inorganic base comprising an alkali metal or alkaline earth metal as the cation.

11. The method according to claim 10 , wherein the molar ratio of the alkali source, calculated on the basis of OH − , to the first oxide source, calculated on the basis of the first oxide, is in a range from 0.04 to 1.

12. The method according to claim 1 , wherein the crystallization conditions include: a crystallization temperature ranging from 80° C. to 120° C., and a crystallization period of at least 1 day.

13. The method according to claim 1 , wherein the method further comprises calcining the molecular sieve under the following conditions: a calcination temperature ranging from 300° C. to 750° C., and a calcination period ranging from 1 hour to 10 hours.

14. A molecular sieve obtained by the method according to claim 1 , having an X-ray diffraction pattern substantially as shown in the following table,

2θ (°)
d-distance (Å)
Relative intensity (I/I 0 × 100)

 5.2048 ± 0.05
16.96501 ± 0.05 
>70

 8.4762 ± 0.27
10.42335 ± 0.34 
<20

 9.0095 ± 0.06
9.80755 ± 0.07
20-40

10.3943 ± 0.05
8.50381 ± 0.05
<20

16.1228 ± 0.50
5.49296 ± 0.50
<20

23.7405 ± 0.22
3.74484 ± 0.03
<20.

15. The molecular sieve according to claim 14 , wherein the X-ray diffraction pattern further comprises X-ray diffraction peaks substantially as shown in the following table,

2θ (°)
d-distance (Å)
Relative intensity (I/I 0 × 100)

14.3448 ± 0.66
6.16955 ± 0.27
<20

15.2971 ± 0.50
5.78752 ± 0.50
<20

16.1979 ± 0.50
5.46765 ± 0.50
<20

20.8653 ± 0.11
4.25393 ± 0.02
<20

23.9532 ± 0.14
3.71207 ± 0.02
<20.

Assignees

• China Petroleum & Chem Corp
• Sinopec Res Inst Petroleum

Inventors

• Wang Yongrui
• Zhu Jincheng
• Sun Mingyi
• Mu Xuhong
• Shu Xingtian

Classifications

• C01P2002/82

  by IR- or Raman-data · CPC title

• C01P2002/72

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

• C10G45/60

  characterised by the catalyst used · CPC title

• C01B39/04

  using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound · CPC title

• C01P2004/54

  Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension · CPC title