Molecular sieve SCM-14, a preparation process and use thereof

Patent metadata

Field	Value
Publication number	US-11097256-B2
Application number	US-201716622806-A
Country	US
Kind code	B2
Filing date	Oct 31, 2017
Priority date	Jun 13, 2017
Publication date	Aug 24, 2021
Grant date	Aug 24, 2021

Abstract

The invention relates to a molecular sieve SCM-14, a preparation process and use thereof. The molecular sieve has a schematic chemical composition of a formula of “SiO2.1/nGeO2” or a formula of “kF.mQ.SiO2.1/nGeO2.pH2O”, wherein the molar ratio of silicon to germanium, n, satisfies n≤30, and other values and symbols are defined in the specification. The molecular sieve has unique XRD diffraction data and can be used as an adsorbent or a catalyst.

First claim

The invention claimed is:

1. A molecular sieve SCM-14 having an X-ray diffraction pattern substantially as shown in Table A-1 or Table A-2 below,

TABLE A-1

Relative intensity

2θ (°) (a)
d-distance (Å) (b)
(I/I 0 × 100)

6.632
13.317
s-vs

8.384
10.537
s-vs

15.587
5.680
w-m

20.661
4.295
W

21.692
4.094
w-vs

25.693
3.464
w-m

(a) = ±0.3°,

(b) is a function of 2 θ,

TABLE A-2

Relative intensity

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

6.632
13.344 ± 0.603 
s-vs

8.384
10.551 ± 0.377 
s-vs

15.587
5.682 ± 0.109
w-m

20.661
4.296 ± 0.062
W

21.692
4.094 ± 0.056
w-vs

25.693
3.465 ± 0.040
w-m

(a) = ±0.3°.

wherein the as-synthesized molecular sieve, before being subject to calcination, has a schematic chemical composition of the formula “kF.mQ.SiO 2 .1/nGeO 2 .pH 2 O”,
wherein, the molar ratio of silicon to germanium is n, n≤30, 0.01≤k≤0.6, Q is an organic template, and 0.01≤m≤0.6,
wherein the organic template is 4-pyrrolidinyl pyridine, a quaternary ammonium form of formula (A-1), a quaternary ammonium form of formula (A-2), or a quaternary ammonium form of formula (A-3),

wherein R 1 and R 2 are each independently H or C 1-8 alkyl, and X − is a halogen ion or a hydroxide ion (OH − ), and 0.005≤p≤0.5.

2. The molecular sieve SCM-14 according to claim 1 , wherein the as-synthesized molecular sieve, before being subject to calcination, has a schematic chemical composition of the formula “kF.mQ.SiO 2 .1/nGeO 2 .pH 2 O”, wherein 1≤n≤5, 0.02≤k≤0.2, 0.04≤m≤0.1, and 0.02≤p≤0.2.

3. A process of preparing molecular sieve SCM-14, comprising:
crystallizing a mixture containing a silicon source, a germanium source, a fluorine source, an organic template, and water to obtain the molecular sieve; and
optionally calcining the obtained molecular sieve, wherein the organic template is 4-pyrrolidinyl pyridine, a quaternary ammonium form of formula (A-1), a quaternary ammonium form of formula (A-2), or a quaternary ammonium form of formula (A-3),

wherein R 1 and R 2 are each independently H or C 1-8 alkyl, and X − is a halogen ion or a hydroxide ion (OH − ).

4. The process of preparing molecular sieve SCM-14 according to claim 3 , wherein the silicon source is at least one selected from the group consisting of silicic acid, silica gel, silica sol, tetraalkyl orthosilicate and water glass;
the germanium source is at least one selected from the group consisting of germanium oxide, germanium nitrate and tetraalkoxygermanium; and
a molar ratio of the silicon source (calculated as SiO 2 ), the germanium source (calculated as GeO 2 ), the fluorine source (calculated as F), the organic template agent and water is 1:(0.05-2): (0.1-0.8): (0.1-0.8): (10-40).

5. The process according to claim 4 , wherein the molar ratio of the silicon source (calculated as SiO 2 ), the germanium source (calculated as GeO 2 ), the fluorine source (calculated as F), the organic template agent and water is 1:(0.2-1): (0.3-0.5): (0.3-0.5): (15-20).

6. The process of preparing molecular sieve SCM-14 according to claim 3 , wherein the crystallization step further comprises: firstly, crystallizing at 91-130° C. for 8 hours to 3 days, and then crystallizing at 140-210° C. for 1-15 days.

7. The process according to claim 6 , wherein the crystallization step comprises firstly crystallizing at 100-120° C. for 12 to 36 hours and then crystallizing at 160-180° C. for 2 to 7 days.

8. The process of preparing molecular sieve SCM-14 according to claim 3 , further comprising: prior to crystallization, ageing the mixture at an ageing temperature of 50-90° C. for an ageing duration of 30 minutes to 2 days.

9. The process of preparing molecular sieve SCM-14 according to claim 3 , wherein the mixture further comprises a source of an element other than silicon and germanium, wherein the source of element other than silicon and germanium is at least one selected from the group consisting of boron, aluminum, tin, zirconium and titanium, and the molar ratio of the oxide source (calcul

Assignees

• China Petroleum & Chem Corp
• Shanghai Res Inst Petrochemical Tech Sinopec

Inventors

• Yang Weimin
• Wang Zhendong
• Luo Yi
• Sun Hongmin
• Zhang Bin

Classifications

• B01J37/0018

  Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat) · CPC title

• C01B39/08

  the aluminium atoms being wholly replaced · CPC title

• C01B39/06 Primary

  Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements {, i.e. by direct or secondary synthesis} · CPC title

• C07C4/18

  Catalytic processes · CPC title

• C01B39/48 Primary

  using at least one organic template directing agent · CPC title