Renewable hydrocarbons, method for producing the same and use thereof

Patent metadata

Field	Value
Publication number	US-10968397-B2
Application number	US-201615392886-A
Country	US
Kind code	B2
Filing date	Dec 28, 2016
Priority date	Dec 29, 2015
Publication date	Apr 6, 2021
Grant date	Apr 6, 2021

Abstract

A method for conversion of levulinic acid and to a hydrocarbon composition obtainable by the method. The method includes a step of providing a feedstock, a conversion step of subjecting the feedstock to a C—C coupling reaction and a hydrotreatment, and a hydrodeoxygenation step. The content of levulinic acid dimer derivatives having 4 oxygen atoms subjected to the hydrodeoxygenation step is 20 wt.-% or more.

First claim

The invention claimed is:

1. A method for conversion of levulinic acid comprising:
providing a feedstock containing levulinic acid;
a conversion step of subjecting the feedstock to a C—C coupling reaction, wherein the C—C coupling reaction is carried out using an acidic ion exchange resin carrying a hydrogenating metal, as a catalyst, and to a hydrotreatment so as to produce a product containing levulinic acid dimer derivatives having 4 oxygen atoms, wherein the hydrotreatment is carried out in a separate mild hydrodeoxygenation (HDO) step after the C—C coupling reaction at a temperature of from 235° C. to 270° C. so as to produce the product containing levulinic acid dimer derivatives having 4 oxygen atoms;
adjustment of levulinic acid dimer derivatives having 4 oxygen atoms by performing a mild hydrogenation step after completion of the C—C coupling reaction and the mild HDO step; and
a hydrodeoxygenation step of subjecting at least the levulinic acid dimer derivatives to a hydrodeoxygenation (HDO) reaction to produce a HDO product, wherein a content of levulinic acid dimer derivatives having 4 oxygen atoms relative to all levulinic acid dimer derivatives is 20 wt.-% or more, wherein the HDO product contains at least 5% by weight of hydrocarbons derived from levulinic acid trimers.

2. The method according to claim 1 , wherein the content of levulinic acid dimer derivatives having 4 oxygen atoms and no carbon-carbon double bonds is 30 wt.-% or more based on the total amount of levulinic acid dimer derivatives having 4 oxygen atoms and/or the total content of levulinic acid dimer derivatives having 4 oxygen atoms and no carbon-carbon double bonds and levulinic acid dimer derivatives having 4 oxygen atoms and at least one carbon-carbon double bonds is 30 wt.-% or more based on the total amount of levulinic acid dimer derivatives having 4 oxygen atoms.

3. The method according to claim 2 , wherein the hydrodeoxygenation (HDO) reaction is carried out at a temperature of at least 290° C.

4. The method according to claim 2 , wherein the C—C coupling reaction is carried out in the presence of hydrogen (H 2 ) under a hydrogen pressure of from 20 to 45 bar (absolute).

5. The method according to claim 1 , wherein the hydrodeoxygenation (HDO) reaction is carried out at a temperature of at least 280° C.

6. The method according to claim 5 , which further comprises:
a separation step of removing at least unreacted levulinic acid before the HDO reaction.

7. The method according to claim 1 , which comprises:
a separation step of removing at least unreacted levulinic acid before the HDO reaction.

8. The method according to claim 1 , wherein the C—C coupling reaction is carried out in a presence of hydrogen (H 2 ) under a hydrogen pressure of 20 bar (absolute) or more.

9. The method according to claim 1 , wherein the C—C coupling reaction in the conversion step is carried out in the presence of hydrogen under a hydrogen pressure of less than 25 bar (absolute).

10. The method according to claim 9 , wherein the mild HDO step employs a hydrogenation catalyst and wherein the hydrogenation catalyst is a NiMo catalyst or a metal catalyst.

11. The method according to claim 1 , wherein the C—C coupling reaction in the conversion step is carried out in the presence of hydrogen under a hydrogen pressure in the range of 1-20 bar (absolute).

12. The method according to claim 1 , wherein the mild HDO step employs a hydrogenation catalyst and wherein the hydrogenation catalyst is a NiMo catalyst or a metal catalyst.

13. The method according to claim 12 , wherein the hydrogenating metal carried by the acidic ion exchange resin is selected from metals of Group VIII of the Periodic Table of Elements.

14. The method according to claim 1 , wherein the hydrogenating metal carried by the acidic ion exchange resin is selected from metals of Group VIII of the Periodic Table of Elements.

15. The method according to claim 1 , wherein the C—C-coupling reaction is conducted at a temperature in the range of 100-200° C.

16. The method according to claim 15 , wherein the C—C-coupling reaction is conducted at a temperature in the range of 120-140° C.

17. A method for conversion of levulinic acid comprising:
providing a feedstock containing at least levulinic acid; and
a conversion step of subjecting the feedstock to a C—C coupling reaction, wherein the C—C coupling reaction is carried out using an acidic ion exchange resin carrying a hydrogenating metal as a catalyst and under a hydrogen pressure of 3 bar (absolute) or less, and to a hydrotreatment so as to produce a product containing levulinic acid dimer derivatives having 4 oxygen atoms, wherein the hydrotreatment is carried out in a separate mild hydrodeoxygenation (HDO) step after the C—C coupling reaction at a temperature of from 235° C. to 270° C. so as to produce the product containing levulinic acid dimer derivatives having 4 oxygen atoms;
adjustment of levulinic acid dimer derivatives having 4 oxygen atoms by performing a mild hydrogenation step after completion of the C—C coupling reaction and the mild HDO step; and
wherein the method includes a hydrodeoxygenation step of subjecting at least the levulinic acid dimer derivatives to a hydrodeoxygenation (HDO) reaction to produce a HDO product, wherein a content of levulinic acid dimer derivatives having 4 oxygen atoms relative to all levulinic acid dimer derivatives subjected to the HDO reaction is 20 wt.-% or more, and wherein the HDO product contains at least 5% by weight of hydrocarbons derived from levulinic acid trimers.

18. A method for conversion of levulinic acid comprising:
providing a feedstock containing at least levulinic acid; and
a conversion step of subjecting the feedstock to a C—C coupling reaction, wherein the C—C coupling reaction is carried out using an acidic ion exchange resin carrying a hydrogenating metal as a catalyst and under a hydrogen pressure of 40 bar (absolute) or more, and to a hydrotreatment so as to produce a product containing levulinic acid dimer derivatives having 4 oxygen atoms, wherein the hydrotreatment is carried out in a separate mild hydrodeoxygenation (HDO) step after the C—C coupling reaction at a temperature of from 235° C. to 270° C. so as to produce the product containing levulinic acid dimer derivatives having 4 oxygen atoms;
adjustment of levulinic acid dimer derivatives having 4 oxygen atoms by performing a mild hydrogenation step after completion of the C—C coupling reaction and the mild HDO step; and
wherein the method includes a hydrodeoxygenation step of subjecting at least the levulinic acid dimer derivatives to a hydrodeoxygenation (HDO) reaction to produce a HDO product, wherein a content of levulinic acid dimer derivatives having 4 oxygen atoms relative to all levulinic acid dimer derivatives subjected to the HDO reaction is 20 wt.-% or more, and wherein the HDO product contains at least 5% by weight of hydrocarbons derived from levulinic acid trimers.

19. The method according to claim 1 , wherein the content of levulinic acid dimer derivatives having 4 oxygen atoms and no carbon-carbon double bonds is 30 wt.-% or more based on the total amount of levulinic acid dimer derivatives having 4 oxygen atoms and/or the total content of levulinic acid dimer derivatives having 4 oxygen atoms and no carbon-carbon double bonds and levulinic acid dimer derivatives having 4 oxygen atoms and at least one carbon-carbon double bonds is 40 wt.-% or more based on the total amount of levulinic acid dimer derivatives having 4 oxygen

Assignees

• Neste Oyj

Inventors

• Myllyoja Jukka
• Lindblad Marina
• Käldström Mats
• Piilola Rami
• Ikonen Elias

Classifications

• C07C51/377

  by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups {(C07C51/36 - C07C51/373 take precedence)} · CPC title

• C10G3/47

  containing platinum group metals or compounds thereof · CPC title

• Y02P30/20

  using bio-feedstock · CPC title

• C10G2400/02

  Gasoline · CPC title

• C10G45/10

  containing platinum group metals or compounds thereof · CPC title