Production of aromatics from methanol and co-feeds

Patent metadata

Field	Value
Publication number	US-9809505-B1
Application number	US-201715646889-A
Country	US
Kind code	B1
Filing date	Jul 11, 2017
Priority date	Sep 30, 2014
Publication date	Nov 7, 2017
Grant date	Nov 7, 2017

Abstract

Methods are provided for improving the yield of aromatics during conversion of oxygenate feeds. An oxygenate feed can contain a mixture of oxygenate compounds, including one or more compounds with a hydrogen index of less than 2, so that an effective hydrogen index of the mixture of oxygenates is between about 1.4 and 1.9. Methods are also provided for converting a mixture of oxygenates with an effective hydrogen index greater than about 1 with a pyrolysis oil co-feed. The difficulties in co-processing a pyrolysis oil can be reduced or minimized by staging the introduction of pyrolysis oil into a reaction system. This can allow varying mixtures of pyrolysis oil and methanol, or another oxygenate feed, to be introduced into a reaction system at various feed entry points.

First claim

What is claimed is:

1. A method for converting oxygenates to aromatics, comprising:
exposing a first feed comprising a first oxygenate feed comprising methanol and having an effective hydrogen index of at least about 1 and a first portion of a pyrolysis oil feed to an aromatization catalyst at a first location under effective conversion conditions to react methanol in the first oxygenate feed with pyrolysis oil in the first portion of the pyrolysis oil feed to form a first conversion effluent comprising one or more aromatic compounds, the volume percentage of the first portion of the pyrolysis oil feed being about 5 vol % to about 25 vol % of the volume of the first feed;
exposing at least a portion of the first conversion effluent and a second feed comprising a second oxygenate feed comprising methanol and having an effective hydrogen index of at least about 1 and a second portion of the pyrolysis oil feed to the aromatization catalyst under effective conversion conditions to react methanol in the second oxygenate feed with pyrolysis oil in the second portion of the pyrolysis oil feed to form a second conversion effluent comprising one or more aromatic compounds, the volume of the second feed being less than the volume of the first feed;
wherein the volume percentage of the first and second portions of the pyrolysis oil feed based on the total volume of the first and second feeds is greater than the volume percentage of the first portion of the pyrolysis oil feed in the first feed, and
wherein said aromatization catalyst comprises ZSM-5 and at least one metal from Groups 8-14 of the Periodic Table.

2. The method of claim 1 , further comprising exposing at least a portion of the second conversion effluent and a third feed comprising a third oxygenate feed having an effective hydrogen index of at least about 1 and a third portion of the pyrolysis oil feed to the aromatization catalyst under effective conversion conditions to form a third conversion effluent comprising one or more aromatic compounds, the volume of the third feed being less than the volume of the second feed.

3. The method of claim 1 , wherein the volume percentage of the second portion of the pyrolysis oil feed is about 25 vol % to about 70 vol % of the volume of the second feed.

4. The method of claim 1 , wherein the total volume percentage of pyrolysis oil feed exposed to the aromatization catalyst is about 15 vol % to about 70 vol % based on the total volume of the oxygenate feeds and pyrolysis oil feed.

5. The method of claim 1 , wherein the total volume percentage of pyrolysis oil feed exposed to a conversion catalyst is at least about 50 vol % based on the total volume of the oxygenate feeds and pyrolysis oil feed.

6. The method of claim 1 , wherein the at least one element from Groups 8-14 is selected from the group consisting of Zn, Ga, Ag and combinations thereof.

7. A method for converting oxygenates to aromatics, comprising:
introducing an oxygenate feed comprising methanol and having an effective hydrogen index of at least about 1 and a pyrolysis oil feed into a conversion reaction system at a plurality of feed entry points, the reaction system having a direction of flow, each of the plurality of feed entry points being located at a different location of the reaction system relative to the direction of flow, the plurality of feed entry points comprising at least a first upstream entry point and a final downstream entry point;
exposing the portions of the oxygenate feed and the pyrolysis oil feed introduced at each of the plurality of feed entry points to an aromatization catalyst to react methanol with pyrolysis oil to form a plurality of converted effluents comprising one or more aromatic compounds, at least a portion of the converted effluents from upstream feed entry points being combined with the portions of the oxygenate feed and the pyrolysis oil feed introduced at a downstream feed entry point;
wherein the volume percentage of the pyrolysis oil feed based on the total volume of the oxygenate feed and the pyrolysis oil is greater than the volume percentage of the portion of the pyrolysis oil feed introduced at the first upstream entry point based on the total volume of the portion of the pyrolysis oil feed and the portion of the oxygenate feed introduced at the first upstream entry point, and
wherein said aromatization catalyst comprises ZSM-5 and at least one metal from Groups 8-14 of the Periodic Table.

8. The method of claim 7 , wherein the volume percentage of the portion of the pyrolysis oil feed introduced at each feed entry point is greater than the volume percentage of the portion of the pyrolysis oil feed introduced at upstream feed entry points, the volume percentage of the portion of the pyrolysis oil feed being based on the total volume of the portions of the oxygenate feed and the pyrolysis oil feed introduced at the same entry point.

9. The method of claim 7 , wherein the volume percentage of the portion of the pyrolysis oil feed introduced at least two feed entry points is substantially similar, the volume percentage of the portion of the pyrolysis oil feed being based on the total volume of the portions of the oxygenate feed and the pyrolysis oil feed introduced at the same entry point.

10. The method of claim 7 , wherein the volume percentage of the portion of the pyrolysis oil feed introduced to at least one feed entry point is about 25 vol % to about 70 vol % based on the total volume of the portions of the oxygenate feed and the pyrolysis oil feed introduced at the same entry point.

11. The method of claim 7 , wherein the total volume percentage of the pyrolysis oil feed exposed to the aromatization catalyst is about 15 vol % to about 70 vol % based on the total volume of the oxygenate feed and the pyrolysis oil feed.

12. The method of claim 7 , wherein the total volume percentage of pyrolysis oil feed exposed to the aromatization catalyst is at least about 50 vol % based on the total volume of the oxygenate feed and the pyrolysis oil feed.

13. The method of claim 7 , wherein the at least one element from Groups 8-14 is selected from the group consisting of Zn, Ga, Ag and combinations thereof.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Buchanan John S
• Brown Stephen H
• Decaul Lorenzo C
• Loveless Brett T
• Vijay Rohit
• Mccarthy Stephen J
• Daage Michel
• Shekhar Mayank

Classifications

• C07C1/20 Primary

  starting from organic compounds containing only oxygen atoms as heteroatoms · CPC title

• C10G2400/30

  Aromatics · CPC title

• C07C2529/44

  Noble metals · CPC title

• C07C1/2076

  by a transformation in which at least one -C(=O)- moiety is eliminated · CPC title

• C10G3/49

  containing crystalline aluminosilicates, e.g. molecular sieves · CPC title