Mercaptan removal using microreactors

Patent metadata

Field	Value
Publication number	US-9267083-B2
Application number	US-201314095137-A
Country	US
Kind code	B2
Filing date	Dec 3, 2013
Priority date	Dec 21, 2012
Publication date	Feb 23, 2016
Grant date	Feb 23, 2016

Abstract

Processes are provided herein for producing naphtha boiling range products with a desired sulfur content by reducing the mercaptan content of the naphtha boiling range products after the products exit a hydroprocessing stage. Due to mercaptan reversion, naphtha boiling range products that contain even small amounts of olefins can have a higher than expected sulfur content after hydroprocessing. In order to reduce or mitigate the effects of mercaptan reversion, microchannel reactors (or microreactors) can be placed in a processing system downstream of a reactor that produces a low sulfur naphtha product. The microreactors can include a coating of metals that have activity for hydrodesulfurization. By passing at least a portion of the naphtha product through the downstream microreactors, the mercaptans formed by reversion reactions can be reduced or eliminated, resulting in a naphtha product with possessing a very low sulfur content.

First claim

What is claimed is:

1. A method for treating a naphtha boiling range fraction, comprising:
receiving a hydroprocessed effluent comprising a naphtha boiling range fraction, the naphtha boiling range fraction comprising a sulfur content of about 200 wppm or less and comprising at least about 50 wppm of olefins, mercaptans, or a combination thereof; and
exposing at least a portion of the naphtha boiling range fraction to a hydrotreating catalyst at a temperature of from about 400° F. (204° C.) to about 600° F. (316° C.) and H 2 at a partial pressure of about 5 psig to about 25 psig to form a treated effluent portion having a sulfur content of about 50 wppm or less, the treated effluent portion having a lower sulfur content than the sulfur content of the naphtha boiling range fraction,
wherein the hydrotreating catalyst is located on surfaces of walls for a plurality of microchannels, the plurality of microchannels having a length dimension of about 10 μm to about 2 mm and a depth dimension of about 10 μm to about 2 mm, the plurality of microchannels being located in a different vessel from a hydroprocessing reaction stage that generated the naphtha boiling range fraction.

2. The method of claim 1 , further comprising:
performing a hydrodesulfurization process on a naphtha boiling range feed to form a desulfurized effluent;
passing the desulfurized effluent into a separation stage; and
separating the desulfurized effluent to form at least a gas phase effluent and a naphtha boiling range effluent, the naphtha boiling range fraction comprising at least a portion of the naphtha boiling range effluent.

3. The method of claim 2 , wherein a mercaptan content of the desulfurized effluent prior to passing the desulfurized effluent into the separation stage is less than a mercaptan content of the naphtha boiling range fraction.

4. The method of claim 2 , wherein separating the desulfurized effluent is performed in one or more separators, the plurality of microchannels being located in at least one of the one or more separators.

5. The method of claim 2 , further comprising fractionating the desulfurized effluent, the plurality of microchannels being associated with a fractionator for performing the fractionating.

6. The method of claim 4 , wherein the plurality of microchannels are located in one or more output conduits of the fractionator.

7. The method of claim 2 , wherein the hydrodesulfurization process comprises a selective hydrodesulfurization process and wherein the naphtha boiling range fraction comprises at least about 20 wt % of olefins.

8. The method of claim 1 , further comprising:
hydroprocessing a feedstock under effective conditions to convert at least 10 wt % of the feedstock relative to a conversion temperature to form a hydroprocessed effluent, at least 30 wt % of the feedstock having a boiling point greater than the conversion temperature, the hydroprocessed effluent including a naphtha boiling range portion;
passing the hydroprocessed effluent into a separation stage;
separating the hydroprocessed effluent to form at least a gas phase effluent and a liquid phase effluent; and
fractionating at least a portion of the liquid phase effluent to form the naphtha boiling range fraction, the naphtha boiling range fraction comprising at least a portion of the naphtha boiling range portion.

9. The method of claim 8 , wherein a mercaptan content of the naphtha boiling range portion prior to passing the hydroprocessed effluent into the separation stage is less than a mercaptan content of the naphtha boiling range fraction.

10. The method of claim 8 , wherein the plurality of microchannels are located in one or more output conduits from the fractionator that correspond to the at least one naphtha boiling range fraction.

11. The method of claim 8 , wherein the feedstock comprises a distillate boiling range feedstock.

12. The method of claim 11 , wherein the conversion temperature is at least about 400° F. (204° C.).

13. The method of claim 8 , wherein the conversion temperature is about 700° F. (371° C.) or less.

14. The method of claim 8 , wherein the hydroprocessing comprises at least one of hydrotreating the feedstock under effective hydrotreating conditions and hydrocracking the feedstock under effective hydrocracking conditions.

15. The method of claim 1 , wherein the naphtha boiling range fraction has a sulfur content of about 25 wppm or less and the treated effluent portion has a sulfur content of about 15 wppm or less.

16. The method of claim 1 , wherein the naphtha boiling range fraction is exposed to the hydrotreating catalyst at a temperature of about 450° F. (232° C.) to about 550° F. (288° C.).

17. The method of claim 1 , wherein the temperature for exposing the naphtha boiling range fraction to the hydrotreating catalyst is at least about 25° C. greater than a temperature of the vessel the microchannels are located in.

18. The method of claim 1 , the naphtha boiling range fraction is exposed to the hydrotreating catalyst in the presence of about 5 psig to about 25 psig of hydrogen.

19. The method of claim 1 , wherein the naphtha boiling range fraction comprises at least about 5 wt % of olefins.

Assignees

• Umansky Benjamin S
• Bolz Charles R
• Kovvali Anjaneya S
• Lopez Carlos N
• Davuluri Rathna P
• Exxonmobil Res & Eng Co

Inventors

• Umansky Benjamin S
• Bolz Charles R
• Kovvali Anjaneya S
• Lopez Carlos N
• Davuluri Rathna P

Classifications

• C10G2300/1044

  Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C · CPC title

• B01J2219/00873

  Heat exchange · CPC title

• B01J2219/00835

  Comprising catalytically active material · CPC title

• C10G45/02

  to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing · CPC title

• C10G2300/70

  Catalyst aspects · CPC title