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-9522854-B2
Application number	US-201213426347-A
Country	US
Kind code	B2
Filing date	Mar 21, 2012
Priority date	Jul 29, 2009
Publication date	Dec 20, 2016
Grant date	Dec 20, 2016

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 system for converting oligomers into dimer products, comprising:
at least one oligomer-based composition or feedstock selected from the group consisting of terpene(s), alpha-olefin oligomer(s), and other mono- and di-olefins having from about 5 to about 30 carbon atoms;
at least one solid acid catalyst for isomerization and dimerization of said at least one oligomer based composition feedstock housed in a minimum temperature zone to extend a lifetime of said at least one solid acid catalyst, and wherein a concentration of said at least one oligomer-based composition or feedstock is maximized during isomerization through protonation;
a transfer device for recovering and utilizing the initial heat of said isomerization;
at least one distillation/evaporation device that utilizes said heat of isomerization to actively recycle unreacted or isomerized said at least one oligomer-based composition or feedstock into said minimum temperature zone to produce dimer products with decreased trimers and heavier oligomers formation, and wherein said at least one distillation/evaporation device includes a first fractionation device that reduces pressure for the evaporation of unreacted said at least one oligomer-based composition or feedstock to further produce purer dimer products having less than 2 wt % total of trimers and heavier oligomers, combined;
a hydrogenation system/device receiving said purer dimer products to produce fully saturated hydrocarbon dimer products that can be directly placed in use as diesel and jet/turbine fuels with a flashpoint greater than 61 ° C.; and
a hydrocracking reactor system/device to reduce the molecular weight of said fully saturated hydrocarbon dimer products and/or to produce a lower boiling fuel product from said fully saturated hydrocarbon dimer products, said hydrocracking reactor system/device further comprising at least one hydrocracking catalyst selected from the group consisting of palladium, platinum, nickel, and combinations thereof being supported on a high surface substrate selected from the group consisting of silicate, aluminate, zeolite, and other mesoporous inorganic supports.

2. The system according to claim 1 , further comprising diluents to initially dilute said at least one oligomer-based composition or feedstock.

3. The system according to claim 1 , wherein said terpene(s) is selected from the group consisting of monoterpenes, sesquiterpenes, diterpenes, terpenes being linear or having more than one ring, terpenes having at least one side being unsaturated, terpenes having at least one double bond that can be hydrogenated, and terpenes having from about C 5 to about C 30 carbons.

4. The system according to claim 1 , wherein said terpene(s) is acyclic including farnesene and/or cyclic including limonene.

5. The system according to claim 1 , wherein said alpha-olefin oligomer(s) have about C 6 to about C 28 carbon atoms.

6. The system according to claim 1 , wherein said alpha-olefin oligomer(s), comprises bio-2-ethyl-1-hexene.

7. The system according to claim 1 , wherein the actively recycled unreacted or isomerized said at least one oligomer-based composition or feedstock dilutes said at least one oligomer-based composition or feedstock.

8. The system according to claim 1 , wherein said first fractionation device comprises at least one evaporator selected from the group consisting of at least one wiped film evaporator, thin film evaporator, and other flash distillation systems.

9. The system according to claim 1 , wherein said first fractionation device includes more than one column.

10. The system according to claim 1 , wherein said unreacted said at least one oligomer-based composition or feedstock obtained from said first fractionation device is recycled for complete conversion to dimer products.

11. The system according to claim 1 , wherein a monitor system/device is utilized prior to said first fractionation device to detect for presence of oligomers.

12. The system according to claim 1 , wherein said first fractionation device reduces pressure to such a level that the boiling temperature of isomerized yet non-dimerized said at least one oligomer based composition or feedstock matches the target temperature of said dimerizing of said at least one oligomer-based composition or feedstock.

13. The system according to claim 1 , wherein said hydrogenation system/device is selected from the group consisting of at least one trickle bed reactor and fixed volume reaction vessel with mechanical stirring.

14. The system according to claim 1 , wherein said hydrogenation system/device comprises at least one hydrogenation catalyst.

15. The system according to claim 14 , wherein said at least one hydrogenation catalyst comprises transition metals selected from the group consisting of palladium, platinum, nickel, and any combination thereof.

16. The system according to claim 1 , further comprising at least one reagent which is introduced into said hydrogenation system/device and said hydrocracking system/device.

17. The system according to claim 16 , wherein said at least one reagent includes H 2 .

18. The system according to claim 1 , further comprising a second fractionation device to produce a fully saturated hydrocarbon biofuel with sufficient flashpoint and cold flow properties from said lower boiling fuel product.

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

• C07C5/03

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

• B01J8/04

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

• B01J2219/0004

  Processes in series · CPC title