Process and apparatus for the selective dimerization of terpenes and poly-alpha-olefins with a single-stage reactor and a single-stage fractionation system

Patent metadata

Field	Value
Publication number	US-9932279-B2
Application number	US-201213426294-A
Country	US
Kind code	B2
Filing date	Mar 21, 2012
Priority date	Jul 29, 2009
Publication date	Apr 3, 2018
Grant date	Apr 3, 2018

Abstract

An improved process and apparatus for the selective reaction of terpenes (including mono-, sesqui-, di-terpenes, and others in the terpene family), alpha-olefin oligomers (OOA's), and related olefins to their respective dimeric product in high purity using heterogeneous acid catalyst concurrent with full utilization of energy created in the process. Embodiments of the invention carry out a unique and highly efficient dimerization of terpenes, alpha-olefin oligomers (OOA's), and olefins using cost effective catalysts and low cost equipment that are ideally suited for commercialization of jet/turbine and diesel biofuel processes producing fuels with high flashpoints and superb cold flow properties.

First claim

What is claimed is:

1. A dimerization process comprising:
concurrently isomerizing and dimerizing a feedstock comprising mixtures of non-isomerized terpene(s) and non-isomerized alpha-olefin oligomer(s) (AOO) with at least one solid acid catalyst to produce dimerized products and isomerized feedstock;
conducting a first fractionation that utilizes the heat produced from said isomerization and said dimerization at a reduced pressure to separate a recycle stream comprising isomerized feedstock and a dimerized product stream having less than 2 wt-% total of trimers and oligomers combined;
recycling the recycle stream comprising isomerized feedstock as an active recycle protocol to dilute the feedstock with isomerized feedstock and to decrease the formation of trimers and oligomers; and
extending said at least one solid acid catalyst lifetime by conducting said isomerization and said dimerization at a minimum temperature.

2. The process according to claim 1 , wherein said non-isomerized terpene is selected from the group consisting of monoterpenes, sesquiterpenes, diterpenes, and terpenes having from 5 to 30 carbons.

3. The process according to claim 1 , wherein said non isomerized terpene is farnesene and/or limonene.

4. The process according to claim 1 , wherein said non isomerized AOO has from 6 to 28 carbons.

5. The process according to claim 1 , wherein said non-isomerized AOO comprises bio-2-ethyl-1-hexene.

6. The process according to claim 1 , wherein said first fractionation comprises at least one evaporator selected from a wiped film evaporator and a thin film evaporator.

7. The process according to claim 1 , wherein said first fractionation includes more than one fractionation column.

8. The process according to claim 1 , wherein the isomerized feedstock comprised in the recycle stream is dimerized to make dimer products.

9. The process according to claim 1 , wherein prior to said first fractionation a monitoring system is utilized to detect the presence of oligomers.

10. The process according to claim 1 , wherein said reduced pressure in said first fractionation is reduced to a value such that the boiling temperature of the isomerized feedstock matches the temperature of said isomerization and said dimerization.

11. The process according to claim 1 , further comprising processing said dimerized products through hydrogenation to produce fully saturated hydrocarbon dimer products having a flashpoint greater than 61° C.

12. The process according to claim 11 , wherein said hydrogenation is conducted in a reactor selected from the group consisting of a trickle bed reactor and a fixed volume reaction vessel with mechanical stirring.

13. The process according to claim 11 , further comprising introducing at least one hydrogenation catalyst into said hydrogenation.

14. The process according to claim 13 , wherein said at least one hydrogenation catalyst comprises palladium, platinum, nickel, or any combination thereof.

15. The process according to claim 11 , further comprising processing said fully saturated hydrocarbon dimer products through hydrocracking to reduce the molecular weight of said fully saturated hydrocarbon dimer products and/or to produce a lower boiling fuel product.

16. The process according to claim 15 , further comprising introducing at least one catalyst into said hydrocracking.

17. The process according to claim 16 , wherein said at least one catalyst comprises i) palladium, platinum, nickel, or a combination thereof; and ii) a support selected from the group consisting of silicate, aluminate, and zeolite.

18. The process according to claim 15 , wherein said hydrogenation and said hydrocracking utilize at least one reagent.

19. The process according to claim 18 , wherein said at least one reagent comprises H 2 .

20. The process according to claim 15 , further comprising processing said lower boiling fuel product through a second fractionation to produce a fully saturated hydrocarbon biofuel with a flashpoint of greater than 61° C.

21. A dimer product having no more than 2 wt-% combined total mass of trimer, tetramer, and oligomers produced by the process of claim 1 .

22. A fully saturated diesel biofuel, jet engine biofuel, and/or turbine biofuel produced by the process of claim 20 .

Assignees

• Wright Michael E
• Harvey Benjamin G
• Us Navy

Inventors

• Wright Michael E
• Harvey Benjamin G

Classifications

• C07C2531/08

  Ion-exchange resins · CPC title

• C07C2/08

  Catalytic processes · CPC title

• B01J8/04

  the fluid passing successively through two or more beds · CPC title

• C07C2/28 Primary

  with ion-exchange resins · CPC title

• C07C5/03

  of non-aromatic carbon-to-carbon double bonds · CPC title