Oligomerization of olefins derived from oxygenates

Patent metadata

Field	Value
Publication number	US-11352571-B2
Application number	US-201916524565-A
Country	US
Kind code	B2
Filing date	Jul 29, 2019
Priority date	Aug 14, 2018
Publication date	Jun 7, 2022
Grant date	Jun 7, 2022

Abstract

Systems and methods are provided for conversion of oxygenate feeds to lubricant and/or distillate boiling range compounds with desirable properties by first selectively converting oxygenates to light olefins and then converting the light olefins to distillate and lubricant boiling range compounds with beneficial properties. The distillate boiling range products can have an unexpectedly high cetane, while the lubricant boiling range products can have an unexpectedly high viscosity index. The ability to form the distillate boiling range products and lubricant boiling range products is facilitated by using a Ni-enhanced oligomerization catalyst.

First claim

The invention claimed is:

1. A method for conversion of oxygenates, comprising:
exposing a feed comprising one or more oxygenates to an oxygenate conversion catalyst under conditions for producing an olefin-containing effluent, the olefin-containing effluent comprising 60 wt % or more of C 3 -C 6 olefins and 10 wt % or less aromatics relative to a weight of hydrocarbons in the olefin-containing effluent, a ratio of C 5 C 6 olefins versus C 4 olefins in the olefin-containing effluent being 1.0 or more, the oxygenate conversion catalyst comprising a zeotype framework structure having a largest pore channel corresponding to a 10-member ring pore channel;
separating a light olefin effluent from the olefin-containing effluent, the light olefin effluent comprising 70 wt % or more total olefins relative to a weight of hydrocarbons in the light olefin effluent; and
exposing at least a portion of the light olefin effluent to an oligomerization catalyst comprising Ni supported on a support comprising a zeotype framework structure having 1-D 10-member ring pore channels under oligomerization conditions to form an oligomerized effluent comprising distillate fuel boiling range hydrocarbons, lubricant boiling range hydrocarbons, or a combination thereof, the at least a portion of the light olefin effluent comprising 5.0 wt % or more ethylene relative to a weight of olefins in the at least a portion of the light olefin effluent,
wherein the oligomerization conditions comprise conversion of 50 wt % or more of the ethylene in the at least a portion of the light olefin effluent.

2. The method of claim 1 , wherein the olefin-containing effluent comprises 40 wt % or more of C 4 -C 6 olefins.

3. The method of claim 1 , wherein the one or more oxygenates comprise 50 wt % or more of methanol, dimethyl ether, or a combination thereof.

4. The method of claim 1 , wherein the light olefin effluent comprises 80 wt % or more C 3 -C 6 olefins relative to a weight of olefins in the light olefin effluent.

5. The method of claim 1 , wherein the oxygenate conversion catalyst comprises a zeotype framework structure including a 10-member, 1-D pore channel as the largest pore channel in the framework structure.

6. The method of claim 5 , wherein the oxygenate conversion catalyst comprises ZSM-48.

7. The method of claim 1 , wherein the oligomerization conditions comprise conversion of 70 wt % or more of the ethylene in the at least a portion of the light olefin effluent.

8. The method of claim 1 , wherein the oligomerized effluent comprises a yield of 55 wt % or more of distillate fuel boiling range hydrocarbons relative to a total weight of hydrocarbons in the at least a portion of the light olefin fraction, or wherein the oligomerized effluent comprises a yield of 10 wt % or more of lubricant boiling range hydrocarbons, or a combination thereof.

9. The method of claim 8 , wherein the distillate fuel boiling range compounds have a cetane index of 40 or more.

10. The method of claim 8 , wherein a 360° C. to 455° C. portion of the lubricant boiling range hydrocarbons has a viscosity index of 85 or more.

11. The method of claim 1 , wherein the oligomerized effluent comprises a yield of 35 wt % or less of naphtha boiling range compounds relative to a total weight of hydrocarbons in the at least a portion of the light olefin fraction.

12. The method of claim 1 , wherein the oligomerization catalyst comprises 0.1 wt % to 10 wt % Ni supported on a support comprising an MRE framework structure, a zeotype framework structure including a 10 -member ring, 1-D pore channel as the largest pore channel in the framework structure, or a combination thereof.

13. The method of claim 1 , wherein the oligomerization catalyst comprises 0.1 wt % to 10 wt % Ni supported on a support comprising ZSM-48.

14. A method for conversion of oxygenates, comprising:
exposing a feed comprising one or more oxygenates to an oxygenate conversion catalyst under conditions for producing an olefin-containing effluent, the olefin-containing effluent comprising 60 wt % or more of C 3 -C 6 olefins and 10 wt % or less aromatics relative to a weight of hydrocarbons in the olefin-containing effluent, a ratio of C 5 -C 6 olefins versus C 4 olefins in the olefin-containing effluent being 1.0 or more, the oxygenate conversion catalyst comprising a zeotype framework structure having a largest pore channel corresponding to a 10-member ring pore channel;
separating a light olefin effluent from the olefin-containing effluent, the light olefin effluent comprising 70 wt % or more total olefins relative to a weight of hydrocarbons in the light olefin effluent;
exposing at least a portion of the light olefin effluent to a first oligomerization catalyst comprising a solid acid catalyst having zeotype framework structure under first oligomerization conditions to form a first oligomerized effluent, the at least a portion of the light olefin effluent comprising 10 wt % or more ethylene relative to a weight of olefins in the at least a portion of the light olefin effluent, a weight of C 2 olefins in the first oligomerized effluent being 50 wt % or more of a weight of C 2 olefins in the light olefin effluent; and
exposing at least a portion of the first oligomerized effluent to a second oligomerization catalyst comprising Ni supported on a support comprising a zeotype framework structure having 1-D 10-member ring pore channels under second oligomerization conditions to form a second oligomerized effluent comprising distillate fuel boiling range hydrocarbons, lubricant boiling range hydrocarbons, or a combination thereof,
wherein the second oligomerization conditions comprise conversion of 50 wt % or more of the ethylene in the at least a portion of the first oligomerization effluent.

15. The method of claim 14 , wherein the second oligomerization catalyst comprises 0.1 wt % to 10 wt % Ni supported on a support comprising ZSM-48.

16. The method of claim 1 , wherein the one or more oxygenates comprise 75 wt % or more of methanol, dimethyl ether, or a combination thereof.

17. The method of claim 1 , wherein the second oligomerization conditions comprise conversion of 70 wt % or more of the ethylene in the at least a portion of the light olefin effluent.

Assignees

• Exxonmobil Technology & Engineering Company

Inventors

• Deimund Mark A
• O'Neill Brandon J
• Dandekar Ajit B

Classifications

• B01J29/7261

  MRE-type, e.g. ZSM-48 · CPC title

• C10G2300/302

  Viscosity · CPC title

• B01J37/084

  Decomposition of carbon-containing compounds into carbon · CPC title

• C10G2300/1088

  Olefins · CPC title

• B01J29/703

  MRE-type, e.g. ZSM-48 · CPC title