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US-20260124608-A1 - MOLECULAR SIEVE BORON SSZ-113

US20260124608A1US 20260124608 A1US20260124608 A1US 20260124608A1US-20260124608-A1

Abstract

Provided is a novel synthetic crystalline borongermanosilicate molecular sieve material, designated boron SSZ-113. The boron SSZ-113 can be synthesized using 1,3 bis(2,3-dimethyl-1H-imidazolium) propane dications as a structure directing agent. The boron SSZ-113 may be used in organic compound conversion reactions and/or sorptive processes, and in particular, in reforming reactions.

Inventors

  • Stacey I. Zones
  • Cong-Yan Chen

Assignees

  • CHEVRON U.S.A. INC.

Dates

Publication Date
20260507
Application Date
20251210

Claims (15)

  1. 1 . A molecular sieve having in its as-synthesized form, a powder X-ray diffraction pattern including the following peaks: 2-Theta (a) d-Spacing, nm Relative Intensity (b) 7.87 1.123 W 8.84 1.000 S 9.63 0.918 M 15.81 0.560 VS 16.85 0.526 VS 18.20 0.487 M 20.92 0.424 S 23.40 0.380 VS 23.78 0.374 VS 24.71 0.360 W 26.12 0.341 S 27.47 0.324 W and with the molecular sieve comprising boron and germanium.
  2. 2 . The molecular sieve of claim 1 , having a composition comprising the molar relationship: wherein n is ≥10; and T is a tetravalent element comprising silicon and germanium.
  3. 3 . The molecular sieve of claim 1 , having a composition comprising the molar relationship: wherein n is ≥15; and T is a tetravalent element comprising silicon and germanium.
  4. 4 . The molecular sieve of claim 1 , having a chemical composition comprising the following molar relationships: TO 2 /B 2 O 3 ≥10 Q/TO 2 >0 to 0.1 F/TO 2 >0 to 0.1 wherein T is a tetravalent element comprising silicon and germanium; and Q comprises 1,3 bis(2,3-dimethyl-1H-imidazolium) propane dications.
  5. 5 . The molecular sieve of claim 4 , which is sulfided and comprises a Group VIII metal.
  6. 6 . The molecular sieve of claim 5 , wherein the Group VIII metal is platinum or palladium.
  7. 7 . The molecular sieve of claim 1 , prepared by a method comprising: (a) providing a reaction mixture comprising: (1) a source of silicon oxide; (2) a source of germanium; (3) a source of boron that comprises boric acid; (4) 1,3 bis(2,3-dimethyl-1H-imidazolium) propane dications (Q); (5) a source of fluoride ions; and (6) water; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve.
  8. 8 . The molecular sieve of claim 7 , wherein the reaction mixture used in the synthesis has a composition, in terms of molar ratios, as follows: TO 2 /B 2 O 3 ≥10 Q/TO 2 0.05 to 0.50 F/TO 2 0.10 to 1.00 H 2 O/TO 2 + B 2 O 3 3 to 8 wherein T is a tetravalent element comprising silicon and germanium.
  9. 9 . The molecular sieve of claim 7 , wherein the reaction mixture used in the synthesis has a composition, in terms of molar ratios, as follows: TO 2 /B 2 O 3 15 to 20 Q/TO 2 0.05 to 0.50 F/TO 2 0.15 to 0.50 H 2 O/TO 2 + B 2 O 3 4 to 6 wherein T is a tetravalent element comprising silicon and germanium.
  10. 10 . The molecular sieve of claim 7 , wherein the source of silicon oxide used in the synthesis comprises a zeolite Y having a SiO 2 /Al 2 O 3 ratio of at least 250.
  11. 11 . A process for converting a feedstock comprising an organic compound to a conversion product, the process comprising contacting the feedstock at organic compound conversion conditions with a catalyst comprising the molecular sieve of claim 5 .
  12. 12 . A process for converting a feedstock comprising an organic compound to a conversion product, the process comprising contacting the feedstock at organic compound conversion conditions with a catalyst comprising the molecular sieve of claim 6 .
  13. 13 . The process of claim 11 , wherein the conversion reaction is reforming.
  14. 14 . The process of claim 12 , wherein the conversion reaction is reforming.
  15. 15 . A process of ion exchanging metals, the process comprising contacting a stream comprising heavy metals with the molecular sieve of claim 4 .

Description

CROSS REFERENCE TO RELATED APPLICATIONS The present application is a continuation of U.S. application Ser. No. 18/325,475, filed May 30, 2023, which claims priority to U.S. Provisional Application No. 63/365,538, filed May 31, 2022, the complete disclosures of which are incorporated herein by reference in their entireties. FIELD This disclosure relates to a novel synthetic crystalline molecular sieve designated SSZ-113 comprising boron in its framework. The disclosure also relates to its synthesis. BACKGROUND Molecular sieves are a commercially important class of materials that have distinct crystal structures with defined pore structures that are shown by distinct X-ray diffraction (XRD) patterns. The molecular sieves also have specific chemical compositions. The crystal structure defines cavities and pores that are characteristic of the specific type of molecular sieve. Providing new molecular sieves that offer differences in the crystal structure as well as the composition can lead to unique catalysts or adsorption/separation materials. Changing a crystal structure is always fraught with difficulties, but success can provide rewards in a new catalyst for organic compound conversion reactions. U.S. patent publication 2019/0256364 discloses the preparation of SSZ-113. It does not, however, disclose a boron SSZ-113. SUMMARY According to the present disclosure, a crystalline molecular sieve, designated boron SSZ-113, is synthesized using 1,3 bis(2,3-dimethyl-1H-imidazolium) propane dications as a structure directing agent (SDA). The synthesis has been found to be successful in providing a boron containing molecular sieve having the SSZ-113 crystal structure. In one aspect, there is prepared a boron SSZ-113 molecular sieve having, in its as-synthesized form, a powder X-ray diffraction pattern including at least the peaks in Table 3 below. In its as-synthesized and anhydrous form, the boron molecular sieve can have a chemical composition comprising the following molar relationships: TABLE 1TypicalPreferredTO2/B2O3≥10≥15Q+/TO2>0 to 0.1>0 to 0.1F/TO2>0 to 0.1>0 to 0.1 wherein T is a tetravalent element comprising silicon and germanium; and Q+ comprises 1,3 bis(2,3-dimethyl-1H-imidazolium) propane dications. In one embodiment, the ratio of TO2/B2O3 is in the range of from 15-20. In its calcined form, the boron SSZ-113 molecular sieve can have a chemical composition comprising the following molar relationship: wherein n is ≥10; and T is a tetravalent element comprising silicon and germanium. In a further aspect, there is provided a method of synthesizing the boron molecular sieve. The method comprises (a) providing a reaction mixture comprising: (1) a source of silicon oxide; (2) a source of germanium; (3) a source of boron; (4) 1,3 bis(2,3-dimethyl-1H-imidazolium) propane dihydroxide (Q); (5) a source of fluoride ions; and (6) water. The reaction mixture is then subjected to crystallization conditions sufficient to form crystals of a SSZ-113 boron molecular sieve. T is as described above. The boron containing molecular sieve is then treated to remove the structure directing agent (SDA), noted as Q above. The SDA can be removed by calcination, or by ozone treatment, e.g., at 150° C. It has also been found that treatment of the molecular sieve with dimethylformamide can also remove the SDA. In yet a further aspect, there is provided a process of converting a feedstock comprising an organic compound to a conversion product which comprises contacting the feedstock at organic compound conversion conditions with a catalyst comprising the boron SSZ-113 molecular sieve. Among other factors, the present process allows one to obtain a boron SSZ-113 molecular sieve, which is a borongermanosilicate. This new molecular sieve prepared by the present process offers unique abilities as a catalyst in organic compound conversion reactions, particularly reforming. The molecular sieve also finds important value as an adsorption/separation material. DETAILED DESCRIPTION Definitions The term “framework type” has the meaning described in the “Atlas of Zeolite Framework Types,” by Ch. Baerlocher and L. B. McCusker and D. H. Olsen (Elsevier, Sixth Revised Edition, 2007). The term “borongermanosilicate” refers to a crystalline microporous solid including boron, germanium and silicon oxides within its framework structure. The borongermanosilicate may be a “pure-borongermanosilicate” (i.e., absent other detectable metal oxides with its framework structure) or optionally substituted. When described as “optionally substituted,” the respective framework may contain other atoms (e.g., Al, Ga, In, Fe, Ti, Zr) substituted for one or more of the atoms not already present in the parent framework. The term “as-synthesized” is employed herein to refer to a molecular sieve in its form after crystallization, prior to removal of the structure directing agent. The term “anhydrous” is employed herein to refer to a molecular sieve substantially devoid of b