Systems and methods for synthesis of phenolics and ketones

• US 10,239,812 B2
• Filed: 04/26/2018
• Issued: 03/26/2019
• Est. Priority Date: 04/27/2017
• Status: Active Grant

• Current Assignee: Sartec
• Original Assignee: Sartec
• Inventors: Fedie, Ronald Leigh, Yan, Bingwen, McNeff, Larry C., Greuel, Peter G., McNeff, Clayton V.
• Primary Examiner(s): Witherspoon, Sikarl A
• Application Number:
  US15/963,583
• Publication Number:
  US 20180312457A1
• Time in Patent Office: 334 Days
• CPC Class Codes: B01J 19/0013 Controlling the temperature of the process
• CPC Class Codes: B01J 19/2415 Tubular reactors
• CPC Class Codes: B01J 19/32 Packing elements in the form of grids or built-up elements for forming a unit or module inside the apparatus for mass or heat transfer
• CPC Class Codes: B01J 21/06 Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 21/066 Zirconium or hafnium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 2219/00051 Controlling the temperature
• CPC Class Codes: B01J 2219/00162 controlling the pressure
• CPC Class Codes: B01J 23/002 Mixed oxides other than spinels, e.g. perovskite
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/657 larger than 1000 nm
• CPC Class Codes: C07C 2601/08 the ring being saturated
• CPC Class Codes: C07C 2601/10 the ring being unsaturated
• CPC Class Codes: C07C 27/26 Purification; Separation; Stabilisation
• CPC Class Codes: C07C 37/004 by obtaining phenols from plant material or from animal material
• CPC Class Codes: C07C 39/04 Phenol
• CPC Class Codes: C07C 39/07 containing only methyl groups, e.g. cresols, xylenols
• CPC Class Codes: C07C 45/60 in six-membered rings
• CPC Class Codes: C07C 49/04 Saturated compounds containing keto groups bound to acyclic carbon atoms
• CPC Class Codes: C07C 49/11 monocyclic
• CPC Class Codes: C07C 49/395 of a five-membered ring
• CPC Class Codes: C07C 49/597 : of a five-membered ring
• CPC Class Codes: C08B 15/02 : Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
• CPC Class Codes: C08H 8/00 : Macromolecular compounds derived from lignocellulosic materials pretreatment thereof B27N
• CPC Class Codes: C08J 2301/02 : Cellulose; Modified cellulose
• CPC Class Codes: C08J 7/12 : Chemical modification
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

Embodiments herein relate to apparatus and systems for phenolic and ketone synthesis and methods regarding the same. In an embodiment, a method of producing phenolics and ketones is included. The method can specifically include forming a reaction mixture comprising nanocrystalline cellulose (NCC) and water. The method can also include contacting the reaction mixture with a metal oxide catalyst at a temperature of 350 degrees Celsius or higher and a pressure of at least about 3200 psi to form a reaction product mixture. The reaction product mixture can include at least about 20 wt. % phenolics and at least about 10 wt. % ketones as a percentage of the total mass of nanocrystalline cellulose (NCC). Other embodiments are also included herein.

Claims

1. A method of producing phenolics and ketones comprising:

forming a reaction mixture comprising

nanocrystalline cellulose (NCC); and

water; and

contacting the reaction mixture with a metal oxide catalyst at a temperature of 350 degrees Celsius or higher and a pressure of at least about 3200 psi to form a reaction product mixture, the reaction product mixture comprising at least about 20 wt. % phenolics and at least about 10 wt. % ketones as a percentage of the total mass of nanocrystalline cellulose (NCC).

2. The method of claim 1, the reaction mixture further comprising a material selected from the group consisting of lipids, proteins, and carbohydrates other than NCC.

3. The method of claim 1, wherein the temperature and pressure conditions are supercritical for water.

4. The method of claim 1, the nanocrystalline cellulose comprising rod-shaped cellulose crystals with widths from 5 to 70 nm and lengths from 100 to 1,000 nm.

5. The method of claim 1, wherein the temperature is greater than 374 degrees Celsius.

6. The method of claim 1, wherein the temperature is between about 374 and 600 degrees Celsius.

7. The method of claim 1, wherein the temperature is between about 500 and 600 degrees Celsius.

8. The method of claim 1, wherein the proportion of phenolics amongst the total amount of phenolics and ketones in the reaction product mixture is at least about 55 wt. %.

9. The method of claim 1, wherein the proportion of phenolics amongst the total amount of phenolics and ketones in the reaction product mixture is at least about 75 wt. %.

10. The method of claim 1, wherein the temperature is between about 374 and 525 degrees Celsius.

11. The method of claim 1, wherein the proportion of ketones amongst the total amount of phenolics and ketones in the reaction product mixture is at least about 60 wt. %.

12. The method of claim 1, wherein the proportion of ketones amongst the total amount of phenolics and ketones in the reaction product mixture is at least about 65 wt. %.

13. The method of claim 1, the reaction product mixture comprising at least about 10 wt. % cyclopentanone of the total phenolic and ketone content of the reaction product mixture.

14. The method of claim 1, the reaction product mixture comprising at least about 8 wt. % phenol of the total phenolic and ketone content of the reaction product mixture.

15. The method of claim 1, wherein 4-methyl phenol and phenol account for at least 40 wt. % combined of the total phenolic content of the reaction product mixture.

16. The method of claim 1, wherein 4-methyl phenol and phenol account for at least 50 wt. % combined of the total phenolic content of the reaction product mixture.

17. The method of claim 1, wherein the product mixture includes a liquid portion and at least about 80 wt. % of the liquid portion is phenolics and ketones.

18. The method of claim 1, wherein the product mixture includes a liquid portion and at least about 95 wt. % of the liquid portion is phenolics and ketones.

19. The method of claim 1, wherein the reaction product mixture includes an organic portion having less than about 20 ppm sulfur.

20. The method of claim 1, wherein the reaction product mixture includes an organic portion having less than about 15 ppm sulfur.

21. The method of claim 1, wherein the contact time is less than about five minutes.

22. The method of claim 1, wherein the contact time is about two minutes.

23. The method of claim 1, further comprising contacting the NCC with water at a temperature of greater than 100 degrees Celsius in a solubilization chamber to form the reaction mixture prior to contacting the reaction mixture with the metal oxide catalyst.

24. The method of claim 1, the metal oxide catalyst selected from the group consisting of zirconia, titania, and hafnia.

25. The method of claim 1, the metal oxide catalyst comprising spherical porous zirconia having an average diameter of 25 microns.

26. The method of claim 1, wherein the method is performed as a continuous flow process.

27. A system for producing a reaction product mixture including phenolics and ketones comprising:

a feedstock tank comprising a nanocrystalline cellulose (NCC) feedstock;

a water supply line;

a reactor vessel in direct or indirect fluid communication with the feedstock tank and the water supply line;

a plurality of metal oxide catalyst particles disposed within the reactor vessel;

a heating element; and

a back pressure regulator in fluid communication with the reactor vessel.

28. The system of claim 27, the heating element configured to maintain the temperature within the reactor vessel between about 374 and 600 degrees Celsius.

29. The system of claim 27, further comprising a high pressure pump in fluid communication with the feedstock tank.

30. The system of claim 27, further comprising a solubilization chamber in fluid communication between the feedstock tank and the reactor vessel.