Germanosilicate compositions and methods of preparing the same
The present disclosure is directed to novel germanosilicate compositions and methods of producing the same. In particular, this disclosure describes an array of transformations originating from the extra-large-pore crystalline germanosilicate compositions, designated CIT-13, possessing 10- and 14-membered rings. Included among the new materials are the new phyllosilicate compositions, designated CIT-13P, new crystalline microporous germanosilicates including high silica versions of CIT-5 and CIT-13, with and without added metal oxides, and new germanosilicate compounds designated CIT-14 and CIT-15. The disclosure also describes methods of preparing these new germanosilicate compositions as well as the compositions themselves.
1. A crystalline microporous silicate composition comprising a three-dimensional framework having pore channels defined by 10-membered rings, the crystalline microporous silicate composition having a Si/Ge ratio of from 25 to infinity and having a an x-ray diffraction (XRD) pattern with characteristic peaks at 8.15±0.2, 10.13±0.2, 12.80±0.2, 16.35±0.2, 20.33±0.2, and 25.77±0.2 degrees 2-θ, wherein the peak at 10.13±0.2 degrees 2-θ is the most intense peak in the X-ray diffraction (XRD) pattern.
2. The crystalline microporous silicate composition of claim 1 , further comprising at least one oxide of a metal or metalloid, M, where M is aluminum, boron, gallium, hafnium, iron, tin, titanium, vanadium, zinc, or zirconium.
3. The crystalline microporous silicate composition of claim 1 that exhibits at least one of:
(a) a powder X-ray diffraction (XRD) pattern having at least eight of the characteristic peaks at 8.15±0.2, 10.13±0.2, 12.80±0.2, 16.35±0.2, 19.03±0.2, 19.97±0.2, 20.33±0.2, 23.79±0.2, 23.91±0.2, 24.10±0.2, 24.63±0.2, 25.77±0.2, 26.41±0.2, 27.75±0.2, 34.73±0.2, and 37.78±0.2, degrees 2-θ, including those set forth in claim 1 , wherein the park at 10.13±0.2 degrees 2-θ is the most intense peak in the X-ray diffraction (XRD) pattern;
(b) a powder X-ray diffraction (XRD) pattern substantially the same as shown in FIG. 27 or 29 ; or
(c) unit cell parameters substantially equal to the following:
Space group
Cmmm
a (Å)
17.4686(5)
b (Å)
13.8271(2)
c (Å)
5.1665(2)
α = β = γ
90°
Space Group
65 (Cmmm).
4. The crystalline microporous silicate composition of claim 1 that exhibits a powder X-ray diffraction (XRD) pattern having characteristic peaks at 8.15±0.2, 10.13±0.2, 12.80±0.2, 16.35±0.2, 19.03±0.2, 19.97±0.2, 20.33±0.2, 23.79±0.2, 23.91±0.2, 24.10±0.2, 24.63±0.2, 25.77±0.2, 26.41±0.2, 34.73±0.2, and 37.78±0.2 degrees 2-θ, including those peaks set forth in claim 1 , wherein the peak at 10.13±0.2 degrees 2-θ is the most intense peak in the X-ray diffraction (XRD) pattern.
5. The crystalline microporous silicate composition of claim 4 that exhibits a powder X-ray diffraction (XRD) pattern having at least ten of the characteristic peaks at 8.15±0.2, 10.13±0.2, 12.80±0.2, 16.35±0.2, 19.03±0.2, 19.97±0.2, 20.33±0.2, 23.79±0.2, 23.91±0.2, 24.10±0.2, 24.63±0.2, 25.77±0.2, 26.41±0.2, 27.75±0.2, 34.73±0.2, and 37.78±0.2 degrees 2-θ, including those peaks set forth in claim 1 , wherein the peak at 10.13±0.2 degrees 2-θ is the most intense peak in the X-ray diffraction (XRD) pattern.
6. The crystalline microporous silicate composition of claim 1 that exhibits a powder X-ray diffraction (XRD) pattern substantially the same as shown in FIG. 27 or 29 .
7. The crystalline microporous silicate composition of claim 1 having unit cell parameters substantially equal to the following:
Space group
Cmmm
a (Å)
17.4686(5)
b (Å)
13.8271(2)
c (Å)
5.1665(2)
a = β = γ
90°
Space Group
65 (Cmmm).
8. The crystalline microporous silicate composition of claim 1 , wherein the pore channels defined by 10-membered rings have channel dimensions of 5.6 Å×3.8 Å.
9. The crystalline microporous silicate composition of claim 1 , in its hydrogen form.
10. The crystalline microporous silicate composition of claim 1 , further comprising a metal cation salt, a transition metal, a transition metal oxide, or a transition metal salt in its micropores.
11. The crystalline microporous silicate composition of claim 1 that is a germanosilicate having a Si/Ge ratio of from 25 to 200.
12. The crystalline microporous germanosilicate composition of claim 11 having a Si/Ge ratio of from 50 to 100.
13. The crystalline microporous germanosilicate composition of claim 11 that exhibits at least one of:
(a) a powder X-ray diffraction (XRD) pattern having at least eight of the characteristic peaks at 8.15±0.2, 10.13±0.2, 12.80±0.2, 16.35±0.2, 19.03±0.2, 19.97±0.2, 20.33±0.2, 23.79±0.2, 23.91±0.2, 24.10±0.2, 24.63±0.2, 25.77±0.2, 26.41±0.2, 27.75±0.2, 34.73±0.2, and 37.78±0.2 degrees 2-θ, wherein the peak at 10.13±0.2 degrees 2-θ is the most intense peak in the X-ray diffraction (XRD) pattern;
(b) a powder X-ray diffraction (XRD) pattern substantially the same as shown in FIG. 27 or 29 ; or
(c) unit cell parameters substantially equal to the following:
Space group
Cmmm
a (Å)
17.4686(5)
b (Å)
13.8271(2)
c (Å)
5.1665(2)
a = β = γ
900
Space Group
65 (Cmmm).
14. The crystalline microporous germanosilicate composition of claim 11 that exhibits a powder X-ray diffraction (XRD) pattern having characteristic peaks at 8.15±0.2, 10.13±0.2, 12.80±0.2, 16.35±0.2, 19.03±0.2, 19.97±0.2, 20.33±0.2, 23.79±0.2, 23.91±0.2, 24.10±0.2, 24.63±0.2, 25.77±0.2, 26.41±0.2, 27.75±0.2, 34.73±0.2, and 37.78±0.2 degrees 2-θ, wherein the peak at 10.13±0.2 degrees 2-θ is the most intense peak in the X-ray diffraction (XRD) pattern.
15. The crystalline microporous germanosilicate composition of claim 14 that exhibits a powder X-ray diffraction (XRD) pattern having at least ten of the characteristic peaks at 8.15±0.2, 10.13±0.2, 12.80±0.2, 16.35±0.2, 19.03±0.2, 19.97±0.2, 20.33±0.2, 23.79±0.2, 23.91±0.2, 24.10±0.2, 24.63±0.2, 25.77±0.2, 26.41±0.2, 27.75±0.2, 34.73±0.2, and 37.78±0.2 degrees 2-θ, wherein the peak at 10.13±0.2 degrees 2-θ is the most intense peak in the X-ray diffraction (XRD) pattern.
16. The crystalline microporous silicate composition of claim 11 that exhibits a powder X-ray diffraction (XRD) pattern substantially the same as shown in FIG. 27 or 29 .
17. The crystalline microporous silicate composition of claim 11 having unit cell parameters substantially equal to the following:
Space group
Cmmm
a (Å)
17.4686(5)
b (Å)
13.8271(2)
c (Å)
5.1665(2)
a = β = γ
900
Space Group
65 (Cmmm).
18. The crystalline microporous germanosilicate composition of claim 11 , wherein the pore channels defined by 10-membered rings have channel dimensions of 5.6 Å×3.8 Å.
19. The crystalline microporous silicate composition of claim 11 , in its hydrogen form.
20. The crystalline microporous germanosilicate composition of claim 11 , further comprising a metal cation salt, a transition metal, a transition metal oxide, or a transition metal salt in its micropores.
21. A method of preparing the crystalline microporous germanosilicate composition of claim 11 , the method comprising calcining a phyllosilicate of CIT-13P topology under conditions sufficient to form the crystalline microporous germanosilicate composition of CIT-15 topology.
22. The method of claim 21 comprising calcining a phyllosilicate of CIT-13P topology at a temperature in a range of from 400° C. to 950° C., thereby producing the crystalline germanosilicate composition designated CIT-15, the calcining optionally done in the presence of a C 1-12 alkyl amine, the phyllosilicate comprising siloxylated silica-rich cfi-layers having a Si/Ge ratio in a range of from 25 to 250, wherein the phyllosilicate designated CIT-13P is characterized as exhibiting one or both of:
(i) two major peaks in the PXRD pattern a range of from 7.2 (±0.2) degrees 2-θ to 8.2 (±0.2) degrees 2-θ; or
(ii) a 29 Si MAS NMR spectrum showing characteristic peaks at chemical shifts of −105 ppm and −113 ppm or an 1 H- 29 Si CP MAS NMR spectrum showing peaks at −94 ppm, −105 ppm, and −113 ppm, relative to tetramethylsilane (TMS).
23. A catalyst comprising the crystalline microporous germanosilicate composition claim 11 , the catalyst further optionally comprising at least one metal cation salt, transition metal, transition metal oxide, or transition metal salt in its micropores.
24. A process for affecting an organic transformation, the process comprising:
(a) carbonylating DME with CO at low temperatures;
(b) reducing NOx with methane;
(c) cracking, hydrocracking, or dehydrogenating a hydrocarbon;
(d) dewaxing a hydrocarbon feedstock;
(e) converting paraffins to aromatic;
(f) isomerizing or disproportionating an aromatic feedstock;
(g) alkylating an aromatic hydrocarbon;
(h) oligomerizing an alkene;
(i) aminating a lower alcohol;
(j) separating and sorbing a lower alkane from a hydrocarbon feedstock;
(k) isomerizing an olefin;
(l) producing a higher molecular weight hydrocarbon from lower molecular weight hydrocarbon;
(m) reforming a hydrocarbon;
(n) converting a lower alcohol or other oxygenated hydrocarbon to produce an olefin product (including MTO);
(o) epoxidizing olefins with hydrogen peroxide;
(p) reducing the content of an oxide of nitrogen contained in a gas stream in the presence of oxygen;
(q) separating nitrogen from a nitrogen-containing gas mixture; or
(r) converting synthesis gas containing hydrogen and carbon monoxide to a hydrocarbon stream; or
(s) reducing the concentration of an organic halide in an initial hydrocarbon product;
by contacting the respective feedstock with the catalyst of claim 23 , under conditions sufficient to affect the named transformation.
25. A catalyst comprising the crystalline microporous germanosilicate composition claim 1 , the catalyst further optionally comprising at least one metal cation salt, transition metal, transition metal oxide, or transition metal salt in its micropores.
26. A process for affecting an organic transformation, the process comprising:
(a) carbonylating DME with CO at low temperatures;
(b) reducing NOx with methane:
(c) cracking, hydrocracking, or dehydrogenating a hydrocarbon;
(d) dewaxing a hydrocarbon feedstock;
(e) converting paraffins to aromatics:
(f) isomerizing or disproportionating an aromatic feedstock;
(g) alkylating an aromatic hydrocarbon;
(h) oligomerizing an alkene;
(i) aminating a lower alcohol;
(j) separating and sorbing a lower alkane from a hydrocarbon feedstock;
(k) isomerizing an olefin;
(l) producing a higher molecular weight hydrocarbon from lower molecular weight hydrocarbon;
(m) reforming a hydrocarbon
(n) converting a lower alcohol or other oxygenated hydrocarbon to produce an olefin product (including MTO);
(o) epoxidizing olefins with hydrogen peroxide;
(p) reducing the content of an oxide of nitrogen contained in a gas stream in the presence of oxygen;
(q) separating nitrogen from a nitrogen-containing gas mixture; or
(r) converting synthesis gas containing hydrogen and carbon monoxide to a hydrocarbon stream; or
(s) reducing the concentration of an organic halide in an initial hydrocarbon product; by contacting the respective feedstock with the catalyst of claim 25 , under conditions sufficient to affect the named transformation.