Catalysts and methods of making the same

• US 10,195,600 B2
• Filed: 06/10/2016
• Issued: 02/05/2019
• Est. Priority Date: 06/10/2016
• Status: Active Grant

• Current Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Inventors: Podsiadlo, Paul, Li, Quanchang, Calabro, David C., Benitez, Kiara M., Mertens, Machteld M. W., Weigel, Scott J., Levin, Doron, Partridge, Randall D.
• Primary Examiner(s): Mayes, Melvin C.
• Assistant Examiner(s): Cohen, Stefanie J
• Application Number:
  US15/179,032
• Publication Number:
  US 20170354961A1
• Time in Patent Office: 970 Days
• CPC Class Codes: B01J 2229/32 Reaction with silicon compounds, e.g. TEOS, siliconfluoride
• CPC Class Codes: B01J 2229/36 Steaming
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 2231/641 Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
• CPC Class Codes: B01J 2231/646 of aromatic or heteroaromatic rings
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 29/44 Noble metals
• CPC Class Codes: B01J 29/70 of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
• CPC Class Codes: B01J 29/703 MRE-type, e.g. ZSM-48
• 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 29/7461 MRE-type, e.g. ZSM-48
• CPC Class Codes: B01J 29/7476 MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
• CPC Class Codes: B01J 31/125 Cyclic siloxanes
• CPC Class Codes: B01J 31/127 the siloxane units, e.g. silsesquioxane units, being grafted onto other polymers or inorganic supports, e.g. via an organic linker
• CPC Class Codes: B01J 31/26 containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
• CPC Class Codes: B01J 35/19 Catalysts containing parts with different compositions
• 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: C07C 5/10 of aromatic six-membered rings
• CPC Class Codes: C10G 45/54 containing crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C10G 45/64 containing crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C10G 47/16 : Crystalline alumino-silicate carriers

Abstract

Catalysts including at least one microporous material (e.g., zeolite), an organosilica material binder, and at least one catalyst metal are provided herein. Methods of making the catalysts, preferably without surfactants and processes of using the catalysts, e.g., for aromatic hydrogenation, are also provided herein.

Claims

1. A method of making a catalyst, the method comprising:

a) adding at least one compound into an aqueous mixture that contains essentially no structure directing agent and essentially no porogen to form a solution, wherein the at least one compound is selected from the group consisting of;

(i) a compound of Formula [Z¹Z²SiCH₂]₃ (Ia), wherein each Z¹ represents a C₁-C₄ alkoxy group and each Z² represents a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group; and

(ii) a cyclic compound of Formula

2. The method of claim 1, wherein the at least one compound includes a compound of Formula (Ia), and wherein each Z¹ represents a C₁-C₂ alkoxy group.

3. The method of claim 1, wherein the at least one compound includes a compound of Formula (Ia), and wherein each Z² represents a C₁-C₄ alkoxy group.

4. The method of claim 1, wherein the at least one compound includes a compound of Formula (Ia), and wherein each Z² represents a C₁-C₂ alkoxy group.

5. The method of claim 1, wherein the at least one compound includes a compound of Formula (Ia) and the compound of Formula (Ia) is 1,1,3,3,5,5-hexaethoxy-1,3,5-tri silacyclohexane.

6. The method of claim 1, wherein each X¹ represents a C₁-C₂ alkyl group;

X² and X³ each independently represent a C₁-C₂ alkyl group, or a C₁-C₂ alkoxy group; and

each X⁴ represents a C₁-C₄ alkylene group bonded to a nitrogen atom of the cyclic compound.

7. The method of claim 1, wherein the at least one compound includes a cyclic compound of Formula (IIa) and the cyclic compound of Formula (IIa) is tris(3-trimethoxysilylpropyl)isocyanurate.

8. The method of claim 1, wherein the independent units of the polymer include a monomer of Formula (I), and wherein each Z¹⁵ represents a hydroxyl group, a C₁-C₂ alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer and each Z¹⁶ represent a hydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer.

9. The method of claim 1, wherein the independent units of the polymer include a monomer of Formula (I), and wherein each Z¹⁵ represents a hydroxyl group, ethoxy, or an oxygen atom bonded to a silicon atom of another monomer and each Z¹⁶ represent a hydroxyl group, ethoxy, or an oxygen atom bonded to a silicon atom of another monomer.

10. The method of claim 1, wherein the independent units of the polymer include a cyclic polyurea monomer of Formula (II), and wherein each X⁵ represents a hydrogen atom, a C₁-C₂ alkyl group or a bond to a silicon atom of another monomer;

X⁶ and X⁷ each independently represent a hydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group or an oxygen atom bonded to a silicon atom of another monomer; and

X⁸ represents a C₁-C₄ alkylene group bonded to a nitrogen atom of the cyclic polyurea.

11. The method of claim 1, wherein the independent units of the polymer include a cyclic polyurea monomer of Formula (II), and wherein each X⁵ represents a hydrogen atom, methyl or a bond to a silicon atom of another monomer unit;

X⁶ and X⁷ each independently represent a hydroxyl group, methoxy or an oxygen atom bonded to a silicon atom of another monomer unit and X⁸ represents —

CH₂CH₂CH₂—

bonded to a nitrogen atom of the cyclic polyurea.

12. The method of claim 1, further comprising adding to the aqueous mixture at least one compound selected from the group consisting of:

(i) a further compound of Formula (Ia);

(ii) a further compound of Formula (IIa);

(iii) a compound of Formula Z¹⁷OZ¹⁸Z¹⁹Z²⁰Si (IIIa), wherein each Z¹⁷ represents a C₁-C₆ alkyl group, and Z¹⁸, Z¹⁹ and Z²⁰ are each independently selected from the group consisting of a C₁-C₆ alkyl group, a C₁-C₆ alkoxy group, a nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containing heteroaralkyl group, and a nitrogen-containing optionally substituted heterocycloalkyl group;

(iv) a compound of Formula Z²¹Z²²Z²³Si—

R¹—

Si Z²¹Z²³Z²⁴ (IVa), wherein each Z²¹ independently represents a C₁-C₄ alkoxy group;

Z²² and Z²³ each independently represent a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group; and

R¹ is selected from the group consisting a C₁-C₈ alkylene group, a C₂-C₈ alkenylene group, a C₂-C₈ alkynylene group, a nitrogen-containing C₁-C₁₀ alkylene group, an optionally substituted C₆-C₂₀ aralkyl and an optionally substituted C₄-C₂₀ heterocycloalkyl group;

(v) a source of a trivalent metal oxide; and

(vi) a combination thereof.

13. The method of claim 12, wherein the at least one compound is a further compound of Formula (Ia), wherein each Z¹ represents a C₁-C₂ alkoxy group and each Z² represent C₁-C₂ alkoxy group or a C₁-C₂ alkyl group.

14. The method of claim 13, wherein the further compound of Formula (Ia) is 1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane.

15. The method of claim 12, wherein the at least one compound is a compound of Formula (IIIa), wherein each Z¹⁷ represents a C₁-C₂ alkyl group and Z¹⁸, Z¹⁹ and Z²⁰ each independently selected from the group consisting of a C₁-C₂ alkyl group, C₁-C₂ alkoxy group, a nitrogen-containing C₃-C₁₀ alkyl group, a nitrogen-containing C₄-C₁₀ heteroaralkyl group, and a nitrogen-containing optionally substituted C₄-C₁₀ heterocycloalkyl group.

16. The method of claim 15, wherein the compound of Formula (IIIa) is selected from the group consisting of tetraethyl orthosilicate, methyltriethoxysilane, (N,N-dimethylaminopropyl)trimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 4-methyl-1-(3-triethoxysilylpropyl)-piperazine, 4-(2-(triethoxysily)ethyl)pyridine, 1-(3-(triethoxysilyl)propyl)-4,5-dihydro-1H-imidazole, and (3-aminopropyl)triethoxysilane.

17. The method of claim 12, wherein the at least one compound is a compound of Formula (IVa), wherein each Z²¹ represents a C₁-C₂ alkoxy group;

Z²² and Z²³ each independently represent a C₁-C₂ alkoxy group, or a C₁-C₂ alkyl group; and

R¹ is selected from the group consisting of a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group, a C₂-C₄ alkynylene group, and a nitrogen-containing C₄-C₁₀ alkylene group.

18. The method of claim 17, wherein the compound of Formula (IVa) is selected from the group consisting of 1,2-bis(methyldiethoxysilyl)ethane, bis(triethoxysilyl)methane, 1,2-bis(triethoxysilyl)ethylene, N,N′

-bis[(3-trimethoxysilyl)propyl]ethylenediamine, bis[(methyldiethoxysilyl)propyl]amine, and bis[(methyldimethoxysilyl)propyl]-N-methylamine.

19. The method of claim 12, wherein the at least one compound is a source of trivalent metal oxide, wherein the source of trivalent metal oxide is at least one of:

(i) a compound of Formula M³(OZ²⁴)₃ (Va), wherein M³ represents a Group 13 metal and each Z²⁴ independently represents a C₁-C₆ alkyl group;

or

(ii) a compound of Formula (Z²⁵O)₂M⁴-O—

Si(OZ²⁶)₃ (VIa), wherein M⁴ represents a Group 13 metal and Z²⁵ and Z²⁶ each independently represent a C₁-C₆ alkyl group.

20. The method of claim 19, wherein the source of trivalent metal oxide is a compound of Formula (Va), wherein M³ is Al or B and each Z²⁴ represents a C₁-C₄ alkyl group.

21. The method of claim 19, wherein the source of trivalent metal is a compound of Formula (VIa), wherein M⁴ is Al or B;

and Z²⁵ and Z²⁶ each independently represent a C₁-C₄ alkyl group.

22. The method of claim 12, wherein the at least one compound is a source of a trivalent metal oxide selected from the group consisting of aluminum trimethoxide, aluminum triethoxide, aluminum isopropoxide, and aluminum-tri-sec-butoxide.

23. The method of claim 1, wherein the aqueous mixture comprises a base and has a pH from about 8 to about 14.

24. The method of claim 23, wherein the base is ammonium hydroxide or a metal hydroxide.

25. The method of claim 1, wherein the aqueous mixture comprises an acid and has a pH from about 0.01 to about 6.0.

26. The method of claim 25, wherein the acid is an inorganic acid.

27. The method of claim 26, wherein the inorganic acid is hydrochloric acid.

28. The method of claim 1, wherein the at least one microporous material and the solution are mixed in step (b) for about 0.10 hour to about 10 hours.

29. The method of claim 1, wherein the catalyst particles are cured at a temperature of about 0°

C. to about 150°

C.

30. The method of claim 1, wherein the catalyst particles are dried at a temperature of about −

20°

C. to about 200°

C.

31. The method of claim 1, wherein the at least one catalyst metal is selected from the group consisting of a Group 8 metal, a Group 9 metal, a Group 10 metal and a combination thereof.

32. The method of claim 31, wherein the at least one catalyst metal is selected from the group consisting of Pt, Pd, Ir, Rh, Re, Ru, Os and a combination thereof.

33. The method of claim 32, wherein the at least one catalyst metal is selected from the group consisting of Pt, Pd, and a mixture thereof.

34. The method of claim 1, wherein the at least one catalyst metal is incorporated within the pores of the catalyst particles after drying of the catalyst particles or the at least one catalyst metal is incorporated within the pores of the at least one microporous material before it is mixed with the solution.

35. The method of claim 1, wherein the at least one microporous material is selected from the group consisting of a zeolite, a SAPO, an ALPO and a combination thereof.

36. The method of claim 1, wherein the at least one microporous material is selected from the group consisting of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, MCM-49, MCM-22, SAPO-11, SAPO-41, AlPO-11, AlPO—

H2, and AlPO-41.

37. The method of claim 1 further comprising adding a further organosilica material to the at least one microporous material and the solution to form the pre-product, wherein the further organosilica material is a polymer comprising independent units of at least one monomer selected from the group consisting of:

(i) a monomer of Formula (I); and

(ii) a cyclic polyurea monomer of Formula (II).

38. The method of claim 37, wherein the organosilica material further comprises at least one other monomer selected from the group consisting of

(i) at least one independent unit of Formula [Z³OZ⁴SiCH₂]₃ (III), wherein each Z³ represents a hydrogen atom, a C₁-C₄ alkyl group or a bond to a silicon atom of another monomer and Z⁴ represents a C₁-C₆ alkyl group;

(ii) at least one independent unit of Formula Z⁵OZ⁶Z⁷Z⁸Si (IV), wherein each Z⁵ represents a hydrogen atom or a C₁-C₄ alkyl group or a bond to a silicon atom of another monomer; and

Z⁶, Z⁷ and Z⁸ are each independently selected from the group consisting of a hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containing heteroalkyl group, a nitrogen-containing optionally substituted heterocycloalkyl group and an oxygen atom bonded to a silicon atom of another monomer;

(iii) at least one independent unit of Formula Z⁹Z¹⁰Z¹¹Si—

R—

SiZ⁹Z¹⁰Z¹¹ (V), wherein each Z⁹ independently represents a hydroxyl group, a C₁-C₄ alkoxy group or an oxygen bonded to a silicon atom of another monomer;

Z¹⁰ and Z¹¹ each independently represent a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group or an oxygen bonded to a silicon atom of another monomer; and

R is selected from the group consisting a C₁-C₈ alkylene group, a C₂-C₈ alkenylene group, a C₂-C₈ alkynylene group, a nitrogen-containing C₁-C₁₀ alkylene group, an optionally substituted C₆-C₂₀ aralkyl and an optionally substituted C₄-C₂₀ heterocycloalkyl group;

(iv) at least one independent unit of Formula M¹(OZ¹²)₃ (VI), wherein M¹ represents a Group 13 metal and each Z¹² independently represents a hydrogen atom, a C₁-C₆ alkyl or a bond to a silicon atom of another monomer;

(v) at least one independent unit of Formula (Z¹³O)₂M²-O—

Si(OZ¹⁴)₃ (VII), wherein M² represents a Group 13 metal and Z¹³ and Z¹⁴ each independently represent a hydrogen atom, a C₁-C₆ alkyl group or a bond to a silicon atom of another monomer; and

(vi) a combination thereof.

39. The method of claim 1, wherein shaping the pre-product comprises extruding, milling, spray-drying or a combination thereof.

40. A catalyst made according to the method of claim 1.