Oxygenate conversion for distillate fuel production

Patent metadata

Field	Value
Publication number	US-11130718-B2
Application number	US-202016909999-A
Country	US
Kind code	B2
Filing date	Jun 23, 2020
Priority date	Jun 24, 2019
Publication date	Sep 28, 2021
Grant date	Sep 28, 2021

Abstract

Systems and methods are provided for upgrading of methane and/or small alkanes to distillate boiling range hydrocarbons. The upgrading is performed using a reaction system where various types of integration are provided from downstream reaction stages to upstream reaction stages. Such integration can include recycle of various reaction products as well as thermal integration. Having a reaction system that begins with reforming of hydrocarbons and finishes with production of distillate can enable unexpected synergies between downstream reaction stages and upstream reaction stages.

First claim

The invention claimed is:

1. A method for producing distillate boiling range products, comprising:
exposing a feed comprising reformable hydrocarbons and at least one recycle input to a reforming catalyst under reforming conditions to produce a reformed effluent comprising H 2 and CO;
exposing at least a portion of the reformed product to a methanol synthesis catalyst under methanol synthesis conditions to produce a synthesis effluent comprising methanol;
exposing a conversion feed comprising at least a portion of the methanol from the synthesis effluent to a conversion catalyst under conversion conditions to form a conversion effluent comprising olefins and to form coke on the conversion catalyst;
passing at least a portion of the conversion effluent into a heat exchange stage to form a cooled conversion effluent and steam;
exposing at least a portion of the cooled conversion effluent and a recycled naphtha boiling range feed to an oligomerization catalyst under oligomerization conditions to form an oligomerized effluent;
separating a light ends product fraction, a naphtha boiling range product fraction, and a distillate boiling range product fraction from the oligomerized effluent, the recycled naphtha boiling range feed comprising at least a portion of the naphtha boiling range product fraction; and
combusting the coke on at least a portion of the conversion catalyst to regenerate the at least a portion of the conversion catalyst and to form a regeneration flue gas comprising CO 2 ,
wherein the at least one recycle input comprises at least a portion of the CO 2 from the regeneration flue gas, at least a portion of the steam, or a combination thereof.

2. The method of claim 1 , wherein exposing at least a portion of the reformed product to a methanol synthesis catalyst comprises exposing a combined methanol synthesis feed to the methanol synthesis catalyst, the combined methanol synthesis feed comprising the at least a portion of the reformed product and additional CO 2 .

3. The method of claim 2 , wherein the additional CO 2 comprises a second recycled portion of the CO 2 from the regeneration flue gas.

4. The method of claim 2 , wherein the at least one recycle input comprises the at least a portion of the CO 2 from the regeneration flue gas.

5. The method of claim 1 , wherein a module M of the reformed product is 1.7 to 3.0.

6. The method of claim 2 , wherein a Module M of the combined methanol synthesis feed is 1.7 to 2.3.

7. The method of claim 1 , wherein the conversion feed further comprises at least a portion of the light ends product fraction.

8. The method of claim 7 , wherein the at least a portion of the light ends product fraction is included in the conversion feed without compression of the light ends product fraction or the at least a portion of the light ends product fraction.

9. The method of claim 1 , wherein the conversion conditions comprise fluidized bed conversion conditions, and wherein combusting the coke on the at least a portion of the conversion catalyst comprises:
transferring the at least a portion of the conversion catalyst from a conversion reactor to a regenerator; and
combusting the coke on the at least a portion of the conversion catalyst in the regenerator.

10. The method of claim 1 , wherein the conversion catalyst comprises a zeotype framework structure selected from MFI, MEL, MTW, TON, MTT, FER, MRE, and combinations thereof.

11. The method of claim 1 , wherein the oligomerization catalyst comprises a zeotype framework structure selected from MFI, MEL, MTW, TON, MTT, FER, MRE, and combinations thereof.

12. The method of claim 1 , wherein at least one of the conversion catalyst and the oligomerization catalyst comprise ZSM-48, or wherein the conversion catalyst and the oligomerization catalyst are the same catalyst, or a combination thereof.

13. The method of claim 1 , wherein the reformable hydrocarbons comprise methane, natural gas, or a combination thereof.

14. The method of claim 1 , wherein the reforming conditions comprise steam reforming, dry reforming, or a combination thereof.

15. The method of claim 1 , wherein the light ends product fraction comprises C 3− hydrocarbons, or wherein the naphtha boiling range product fraction comprises C 4 -C 8 hydrocarbons, or a combination thereof.

16. The method of claim 1 , wherein the light ends product fraction comprises C 4− hydrocarbons, or wherein the naphtha boiling range product fraction comprises C 5 -C 9 hydrocarbons, or a combination thereof.

17. The method of claim 1 , wherein 1.0 wt % to 20 wt % of the distillate yield corresponds to distillate yield generated based on recycle of CO 2 as part of the at least one recycle input, recycle of CO 2 as part of the additional CO 2 , or a combination thereof.

18. A system for hydrocarbon upgrading comprising:
a reforming reactor;
a methanol synthesis stage in fluid communication with the reforming reactor;
a conversion reactor comprising one or more conversion inlets, a conversion outlet, and a conversion catalyst outlet, the conversion reactor being in fluid communication with the methanol synthesis stage via the one or more conversion inlets;
a regenerator comprising a regenerator catalyst inlet and a regenerator catalyst outlet, the regenerator catalyst outlet being in fluid communication with the one or more conversion inlets, the regenerator catalyst inlet being in fluid communication with the conversion catalyst outlet, the regenerator being further in fluid communication with at least one of the reforming reactor and the methanol synthesis stage via a regenerator recycle outlet;
an oligomerization reactor comprising an oligomerization inlet and an oligomerization outlet, the oligomerization reactor being in fluid communication with the conversion outlet via the oligomerization inlet; and
a separation stage comprising a separator inlet and one or more separator outlets, the separation stage being in fluid communication with the oligomerization outlet via the separator inlet, the separation stage being in fluid communication with the oligomerization inlet via the one or more separator outlets, the separation stage being further in fluid communication with the one or more conversion inlets via the one or more separator outlets.

19. The system of claim 18 , the system further comprising a waste heat boiler, the conversion reactor outlet being in indirect fluid communication with the oligomerization inlet via the waste heat boiler.

20. The system of claim 19 , wherein the waste heat boiler comprises a steam outlet, the steam outlet being in fluid communication with the reforming reactor.

Assignees

• Exxonmobil Res & Eng Co

Inventors

• Behkish Arsam
• Kovvali Anjaneya S

Classifications

• C01B2203/0238

  the reforming step being a carbon dioxide reforming step · CPC title

• C07C1/20

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

• C01B2203/061

  Methanol production · CPC title

• C01B2203/127

  Catalytic desulfurisation · CPC title

• C01B2203/1241

  Natural gas or methane · CPC title