ALKYLATION CATALYST

• US 20190022631A1
• Filed: 06/26/2018
• Published: 01/24/2019
• Est. Priority Date: 07/19/2017
• Status: Active Grant

• Current Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Inventors: Nandi, Partha, Ide, Matthew S., Dakka, Jihad M., Nizami, Quddus A., Afeworki, Mobae
• Granted Patent: US 10,639,619 B2
• Time in Patent Office: Days
• CPC Class Codes: B01J 2229/18 to introduce other elements into or onto the molecular sieve itself
• CPC Class Codes: B01J 2229/183 in framework positions
• CPC Class Codes: B01J 2229/186 not in framework positions
• CPC Class Codes: B01J 2229/20 to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 29/7038 MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
• CPC Class Codes: B01J 29/7088 MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
• CPC Class Codes: B01J 37/0009 Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: B01J 37/0201 Impregnation
• CPC Class Codes: B01J 37/023 using molten compounds
• CPC Class Codes: B01J 37/08 Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/26 Fluorinating
• CPC Class Codes: C07C 15/085 Isopropylbenzene
• CPC Class Codes: C07C 2/12 with crystalline alumino-silicates or with catalysts comprising molecular sieves
• CPC Class Codes: C07C 2/66 Catalytic processes
• CPC Class Codes: C07C 2/68 with halides
• CPC Class Codes: C07C 2529/70 of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
• CPC Class Codes: C10G 29/12 Halides
• CPC Class Codes: C10G 29/205 by reaction with hydrocarbons added to the hydrocarbon oil
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

Catalyst compositions with improved alkylation activity and corresponding methods for making such catalyst compositions are provided. The catalyst(s) correspond to solid acid catalysts formed by exposing a catalyst precursor with a zeolitic framework structure to a molten metal salt that includes fluorine, such as a molten metal fluoride. The resulting fluorinated solid acid catalysts can have improved alkylation activity while having a reduced or minimized amount of structural change due to the exposure to the molten metal fluoride. This is in contrast to fluorinated solid acid catalysts that are exposed to higher severity forms of fluorination, such as exposure to ammonium fluoride or HF. SnF₂ is an example of a suitable molten metal fluoride.

Claims

1. A catalyst composition comprising an MWW framework structure, 0.1 wt % to 2.5 wt % fluorine relative to a weight of the catalyst composition, and a weight ratio of Sn to F in the catalyst composition of 0.1 to 2.0.

2. The catalyst composition of claim 1, wherein the catalyst composition comprises a weight ratio of Sn to F in the MWW framework structure of 0.1 to 2.0.

3. The catalyst composition of claim 1, wherein the catalyst composition comprises MCM-49, MCM-22, MCM-56, or a combination thereof.

4. The catalyst composition of claim 1, wherein the MWW framework structure comprises a silicon to aluminum ratio of 2 to 100.

5. The catalyst composition of claim 1, wherein at least one of the MWW framework structure and the catalyst composition comprises 2.5 wt % or less Sn.

6. The catalyst composition of claim 1, wherein the MWW framework structure comprises 0.1 wt % to 2.5 wt % fluorine.

7. The catalyst composition of claim 1, wherein the catalyst composition further comprises a binder.

8. A method for making an alkylation catalyst, comprising:

exposing a catalyst precursor comprising a zeolitic framework structure to a molten metal salt comprising fluoride anion at a temperature of 275°

C. or less; and

mixing the catalyst precursor and the molten metal salt during at least a portion of the exposing to form a catalyst comprising a fluorinated zeolitic framework structure.

9. The method of claim 8, wherein the catalyst precursor comprises a MWW framework structure, a FAU framework structure, a MOR framework structure, a MEI framework structure, a MFS framework structure, a *BEA framework structure, a EMT-FAU structural intermediate framework structure, or a combination thereof.

10. The method of claim 8, wherein the catalyst precursor comprises MCM-49, MCM-22, MCM-56, or a combination thereof.

11. The method of claim 8, wherein the fluorinated zeolitic framework structure comprises 0.1 wt % to 2.5 wt % fluorine.

12. The method of claim 8, wherein the molten metal salt comprises SnF₂.

13. The method of claim 12, wherein the fluorinated zeolitic framework structure comprises 2.5 wt % or less Sn.

14. The method of claim 12, wherein a weight ratio of Sn to F in the fluorinated zeolitic framework structure is 2.0 or less.

15. The method of claim 12, further comprising extruding at least a portion of the catalyst comprising a fluorinated zeolitic framework structure to form a catalyst composition, wherein a) the catalyst composition comprises 0.01 wt % to 2.5 wt % Sn;

b) the catalyst composition comprises a weight ratio of Sn to F in the fluorinated zeolitic framework structure of 2.0 or less;

c) the catalyst composition comprises 0.1 wt % to 2.5 wt % fluorine;

or d) a combination of two or more of a), b), and c).

16. The method of claim 15, wherein the catalyst composition further comprises a binder.

17. The method of claim 15, wherein a surface area of the catalyst composition is different from a surface area of a catalyst precursor composition formed under substantially similar extruding and calcining conditions by 25% or less relative to the surface area of the catalyst precursor composition.

18. The method of claim 8, wherein the molten metal salt comprises a molten metal fluoride, or wherein the molten metal salt comprises TaF₅.

19. A method for performing alkylation, comprising:

exposing a feedstock to a catalyst under effective alkylation conditions to form an alkylated effluent,

wherein the catalyst comprises an MWW framework structure, 0.1 wt % to 2.5 wt % fluorine relative to a weight of the catalyst composition, and a weight ratio of Sn to F in the catalyst composition of 0.1 to 1.5.

20. The method of claim 19, wherein the feedstock comprises olefinic hydrocarbons and 1-ring aromatic hydrocarbons.

21. The method of claim 20, wherein the 1-ring aromatic hydrocarbons comprises benzene.

22. The method of claim 19, wherein the effective alkylation conditions comprise effective transalkylation conditions, the feedstock comprising alkylated aromatics.