CATALYST AND CATALYST CARRIER

• US 20140100379A1
• Filed: 10/10/2012
• Published: 04/10/2014
• Est. Priority Date: 10/14/2011
• Status: Active Grant

• Current Assignee: Saint-Gobain Ceramics & Plastics Incorporated (Compagnie De Saint-Gobain)
• Original Assignee: Saint-Gobain Ceramics & Plastics Incorporated (Compagnie De Saint-Gobain)
• Inventors: Lockemeyer, John R., Richard, Michael A.
• Granted Patent: US 9,073,035 B2
• Time in Patent Office: Days
• US Class Current: 549/523
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 23/50 Silver
• CPC Class Codes: B01J 23/66 Silver or gold
• CPC Class Codes: B01J 27/02 Sulfur, selenium or tellurium; Compounds thereof
• CPC Class Codes: B01J 27/047 with chromium, molybdenum, tungsten or polonium
• CPC Class Codes: B01J 27/055 with alkali metals, copper, gold or silver
• CPC Class Codes: B01J 35/1085 monomodal
• CPC Class Codes: B01J 35/109 bimodal
• CPC Class Codes: B01J 35/1095 polymodal
• CPC Class Codes: B01J 35/67 monomodal
• CPC Class Codes: B01J 35/69 bimodal
• CPC Class Codes: B01J 35/695 polymodal
• CPC Class Codes: C07D 301/04 with air or molecular oxygen
• CPC Class Codes: C07D 301/10 with catalysts containing silver or gold
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

The carrier of the present invention includes at least 85 wt percent alpha alumina, at least 0.06 wt percent SiO₂ and no more than 0.04 wt percent Na₂O. The carrier has a water absorption no greater than 0.35 g/g and a ratio of water absorption (g/g) to surface area (m²/g) no greater than 0.50 g/m². Another aspect of the invention is a catalyst for the epoxidation of olefins which comprises the above described carrier and silver dispersed thereon, where the carrier has a monomodal, bimodal or multimodal pore distribution and where the quantity of silver is between 5 and 50 wt %, relative to the weight of the catalyst. A reactor to system for the epoxidation of olefins is also disclosed.

Claims

1. A carrier comprising at least 85 wt percent alpha alumina, at least 0.06 wt percent SiO₂ and no more than 0.04 wt percent Na₂O, said carrier comprising a water absorption no greater than 0.35 gram of water/gram of carrier and a ratio of water absorption (gram of water/gram of carrier) to surface area (m² of carrier/gram of carrier) no greater than 0.50 gram of water/m² of carrier.

2. The carrier of claim 1 wherein said SiO₂ does not exceed 0.40 wt percent.

3. The carrier of claim 1 wherein said SiO₂ does not exceed 0.30 wt percent.

4. The carrier of claim 1 wherein said Na₂O does not exceed 0.03 wt percent.

5. The carrier of claim 1 wherein said carrier comprises at least 0.15 wt percent SiO₂.

6. The carrier of claim 1 wherein said ratio does not exceed 0.45 g/m².

7. The carrier of claim 1 wherein said ratio does not exceed 0.40 g/m².

8. The carrier of claim 1 wherein said water absorption does not exceed 0.30 g/g.

9. The carrier of claim 8 wherein said surface area exceeds 0.70 m²/g.

10. The carrier of claim 1 wherein said surface area exceeds 0.75 m²/g.

11. The carrier of claim 1, wherein said carrier further comprises a total pore volume and at least 60% of the total pore volume is contributed by pores having diameters within a range no greater than 3.8 microns.

12. The carrier of claim 1 wherein at least 80% of the total pore volume is contributed by pores having diameters within a range no greater than 3.8 microns.

13. The carrier of claim 1, wherein at least 90% of the total pore volume is contributed by pores having diameters within a range no greater than 3.8 microns.

14. The carrier of claim 1 wherein said carrier has a total pore volume and no more than 20% of said total pore volume is contributed by pores greater than 10 microns.

15. The carrier of claim 1 wherein no more than 15% of said total pore volume is contributed by pores greater than 10 microns.

16. The carrier of claim 1 wherein no more than 10% of said total pore volume is contributed by pores greater than 10 microns

17. The carrier of claim 1 wherein said carrier comprises a bond material.

18. The carrier of claim 1 wherein said carrier comprises non-platelet morphology.

19. A catalyst for the epoxidation of olefins comprising the carrier of claim 1 and silver dispersed thereon.

20. The catalyst of claim 19 wherein the carrier has a monomodal, bimodal or multimodal pore distribution.

21. The catalyst of claim 19 wherein the quantity of said silver is between 5 and 50 wt %, relative to the weight of the catalyst.

22. The catalyst of claim 19 wherein the quantity of said silver relative to the volume of a packed bed of catalyst is between 50 and 500 kg/m³.

23. The catalyst of claim 21 wherein said catalyst further comprises a rhenium promoter, a first co-promoter and a second co-promoter, wherein the first co-promoter is selected from sulfur, phosphorus, boron, and mixtures thereof;

and the second co-promoter is selected from tungsten, molybdenum, chromium, and mixtures thereof.

24. The catalyst of claim 23 wherein the rhenium promoter is present in a quantity in the range of from 0.1 to 50 mmole/kg, relative to the weight of the catalyst.

25. The catalyst of claim 24 wherein the first co-promoter is sulfur and the second co-promoter is tungsten, and wherein the first co-promoter is present in a quantity in the range of from 0.2 to 50 mmole/kg, relative to the weight of the catalyst and the second co-promoter is present in a quantity in the range of from 0.1 to 40 mmole/kg, relative to the weight of the catalyst.

26. The catalyst of claim 25 wherein the molar ratio of the first co-promoter to the second co-promoter is greater than 1.

27. The catalyst of claim 26 wherein the catalyst further comprises a further element selected from the group consisting of nitrogen, fluorine, alkali metals, alkaline earth metals, titanium, hafnium, zirconium, vanadium, thallium, thorium, tantalum, niobium, gallium, germanium, and mixtures thereof.

28. The catalyst of claim 27 wherein said catalyst further comprises cesium, lithium and potassium.

29. The catalyst of claim 28 wherein said cesium is present in a quantity in the range of from 0.2 to 50 mmole/kg, relative to the weight of the catalyst;

said lithium is present in a quantity in the range of from 0.2 to 50 mmole/kg, relative to the weight of the catalyst; and

said potassium is present in a quantity in the range of from 0.2 to 50 mmole/kg, relative to the weight of the catalyst.

30. A reactor system for the epoxidation of ethylene, which reactor system comprises at least one elongated tube having an internal tube diameter of between 20 and 50 mm, wherein contained is a catalyst bed of catalyst particles comprising silver in a quantity between 5 and 50 wt %, relative to the weight of the catalyst, said catalyst comprising the catalyst of claim 20.

31. The reactor system of claim 30 wherein the length of the elongated tube is in the range of from 3 to 25 m, and the wall thickness of the elongated tube is in the range of from 0.5 to 10 mm.

32. The reactor system of claim 31 wherein the catalyst particles have a generally hollow cylinder geometric configuration having a length of from 4 to 20 mm, an outside diameter of from 4 to 20 mm, an inside diameter of from 0.1 to 6 mm and a ratio of the length to the outside diameter in the range of from 0.5 to 2.

33. A process for the epoxidation of ethylene comprising reacting ethylene with oxygen in the presence of the catalyst bed contained in a reactor system as claimed in claim 30.

34. The process as claimed in claim 33, wherein ethylene is reacted with oxygen in the additional presence of one or more organic halides.

35. The process as claimed in claim 34, wherein carbon dioxide is present in the reactor feed in a quantity of at most 6 mole percent based on the total epoxidation reactor feed.

36. A method of preparing ethylene glycol, an ethylene glycol ether, an ethylene carbonate, or an ethanol amine comprising obtaining ethylene oxide by a process for the epoxidation of ethylene as claimed in claim 33, and converting the ethylene oxide into ethylene glycol, the ethylene glycol ether, an ethylene carbonate or the ethanol amine.