LOW TEMPERATURE ADSORBENT FOR REMOVING SULFUR FROM FUEL

• US 20130109895A1
• Filed: 09/18/2012
• Published: 05/02/2013
• Est. Priority Date: 09/23/2011
• Status: Abandoned Application

• Current Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Inventors: Novak, William J., Gatt, Joseph E.
• Application Number:
  US13/622,043
• Publication Number:
  US 20130109895A1
• Time in Patent Office: Days
• US Class Current: 585/240
• CPC Class Codes: B01J 20/186 Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
• CPC Class Codes: C07C 7/12 by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/301 Boiling range
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 2400/04 Diesel oil
• CPC Class Codes: C10G 25/05 Removal of non-hydrocarbon compounds, e.g. sulfur compounds
• CPC Class Codes: C10G 35/085 containing platinum group metals or compounds thereof
• CPC Class Codes: C10G 61/06 the refining step being a sorption process
• CPC Class Codes: C10G 67/06 including a sorption process as the refining step in the absence of hydrogen

Abstract

The present invention relates to methods for removing sulfur from a hydrocarbon fuel or fuel precursor feedstream, such as methods comprising contacting a hydrocarbon fuel or fuel precursor feedstream having a relatively low sulfur content with a sulfur sorbent material comprising an active copper component disposed on a zeolitic and/or mesoporous support under conditions sufficient to reduce the sulfur content by at least 20 wt % and/or to about 15 wppm or below, thus forming a hydrocarbon fuel product. In some advantageous embodiments, the contacting conditions can include a temperature of about 392° F. (about 200° C.) or less.

Claims

1. A method for removing sulfur from a hydrocarbon fuel or fuel precursor feedstream comprising:

contacting a hydrocarbon fuel or fuel precursor feedstream having a sulfur content from about 2 wppm to about 100 wppm with a sulfur sorbent material comprising an active copper component disposed on a porous support under conditions sufficient to reduce the sulfur content by at least about 20 wt %, thus forming a hydrocarbon fuel product,

wherein the conditions include at least a temperature of about 392°

F. (about 200°

C.) or less, optionally a pressure at which the hydrocarbon fuel or fuel precursor feedstream remains substantially liquid, and optionally an average contact/residence time of less than about 4 hours; and

wherein the porous support is comprised of a zeolite, a mesoporous material, or a combination thereof.

2. The method of claim 1, wherein the hydrocarbon fuel or fuel precursor feedstream comprises a naphtha stream, a gasoline precursor stream, a gasoline fuel stream, a diesel precursor stream, a hydrotreated diesel stream, a diesel fuel stream, a jet fuel precursor stream, a jet fuel stream, a kero precursor stream, a kero fuel stream, or a combination thereof;

and wherein the hydrocarbon fuel product comprises a gasoline fuel, a jet fuel, a kerosene fuel, a diesel fuel, or a combination thereof.

3. The method of claim 1, wherein the hydrocarbon fuel or fuel precursor feedstream exhibits one or more of the following:

an IBP of at least about 90°

F. (about 32°

C.);

IBP of about 450°

F. (about 232°

C.) or less;

a T5 boiling point of at least about 100°

F. (about 38°

C.);

a T5 boiling point of about 450°

F. (about 232°

C.) or less;

a T95 boiling point of at least about 350°

F. (about 177°

C.);

a T95 boiling point of about 725°

F. (about 385°

C.) or less;

an FBP of at least about 350°

F. (about 177°

C.); and

an FBP of about 750°

F. (about 399°

C.) or less.

4. The method of claim 1, wherein the hydrocarbon fuel or fuel precursor feedstream comprises a naphtha stream, a gasoline precursor stream, a gasoline fuel stream, or a combination thereof, and also exhibits one or more of the following:

an IBP of at least about 90°

F. (about 32°

C.);

an IBP of about 150°

F. (about 66°

C.) or less;

a T5 boiling point of at least about 100°

F. (about 38°

C.);

a T5 boiling point of about 200°

F. (about 93°

C.) or less;

a T95 boiling point of at least about 325°

F. (about 163°

C.);

a T95 boiling point of about 425°

F. (about 218°

C.) or less;

an FBP of at least about 350°

F. (about 177°

C.); and

an FBP of about 425°

F. (about 218°

C.) or less.

5. The method of claim 1, wherein the hydrocarbon fuel or fuel precursor feedstream comprises a jet fuel precursor stream, a jet fuel stream, a kero precursor stream, a kero fuel stream, or a combination thereof, and also exhibits one or more of the following:

an IBP of at least about 150°

F. (about 66°

C.);

an IBP of about 375°

F. (about 191°

C.) or less;

a T5 boiling point of at least about 200°

F. (about 93°

C.);

a T5 boiling point of about 400°

F. (about 204°

C.) or less;

a T95 boiling point of at least about 500°

F. (about 260°

C.);

a T95 boiling point of about 575°

F. (about 302°

C.) or less;

an FBP of at least about 500°

F. (about 260°

C.); and

an FBP of about 625°

F. (about 329°

C.) or less.

6. The method of claim 1, wherein the hydrocarbon fuel or fuel precursor feedstream comprises a diesel precursor stream, a hydrotreated diesel stream, a diesel fuel stream, or a combination thereof, and also exhibits one or more of the following:

an IBP of at least about 350°

F. (about 177°

C.);

an IBP of about 450°

F. (about 232°

C.) or less;

a T5 boiling point of at least about 375°

F. (about 191°

C.);

a T5 boiling point of about 450°

F. (about 232°

C.) or less;

a T95 boiling point of at least about 650°

F. (about 343°

C.);

a T95 boiling point of about 725°

F. (about 385°

C.) or less;

an FBP of at least about 675°

F. (about 357°

C.); and

an FBP of about 750°

F. (about 399°

C.) or less.

7. The method of claim 1, wherein the porous support comprises a zeolite having framework type AFS, ATS, BEA, BOG, CON, DFO, EMT, EON, ETR, EZT, FAU, a structural EMT-FAIT intermediate, GME, LTL, MAZ, MEI, MOR, MOZ, MSE, OFF, SAO, SFO, and/or UFI, or a combination or structural intermediate thereof.

8. The method of claim 1, wherein the porous support comprises a MAPO-46, a MAPO-36, an SSZ-55, a zeolite beta, a boggsite, a CIT-1, a SSZ-26, a SSZ-33, a DAF-1, an EMC-2, an ECR-1, a TNU-7, an ECR-34, an EMM-3, a zeolite Y, a zeolite X, a SAPO-37, a CSZ-1, an ECR-30, a ZSM-20, a ZSM-3, a gmelinite, a zeolite L, a perlialite, an LZ-212, a mazzite, an LZ-202, an omega, a ZSM-4, a ZSM-18, an ECR-40, a mordenite, a ZSM-10, a MCM-68, an offretite, an LZ-217, an STA-1, an SSZ-51, a UZM-5, an MCM-41, an SBA-15, or a combination or structural intermediate thereof.

9. The method of claim 1, wherein the active copper component comprises an active copper (I) component exchanged onto the porous support.

10. The method of claim 4, wherein one or more of the following is satisfied:

the hydrocarbon fuel or fuel precursor feedstream exhibits a sulfur content from about 10 wppm to about 50 wppm;

the sulfur sorbent material comprises an active copper (I) component disposed on zeolite Y;

the contacting conditions are sufficient to reduce the sulfur content of the feedstream by at least about 20 to 80 wt %; and

the contacting conditions include a temperature of about 302°

F. (about 150°

C.) or less.

11. The method of claim 6, wherein one or more of the following is satisfied:

the hydrocarbon fuel or fuel precursor feedstream exhibits a sulfur content from about 15 wppm to about 100 wppm;

the sulfur sorbent material comprises an active copper (I) component disposed on zeolite Y;

the contacting conditions are sufficient to reduce the sulfur content of the feedstream by at least about 30 to 90 wt %; and

the contacting conditions include a temperature of about 149°

F. (about 65°

C.) or less.

12. The method of claim 1, wherein the hydrocarbon fuel or fuel precursor feedstream comprises at least 5 wt % of a biocomponent feed.

13. The method of claim 6, wherein the hydrocarbon fuel or fuel precursor feedstream comprises at least 5 wt % of a biocomponent feed.

14. The method of claim 1, wherein the hydrocarbon fuel or fuel precursor feedstream remains as a liquid during the contacting with the sulfur sorbent material.

15. The method of claim 1, wherein at least a portion of the hydrocarbon fuel product is contacted with a reforming catalyst comprising at least one metal from Group VIII of the Periodic Table of Elements.

16. The method of claim 15, wherein the Group VIII metal is selected from platinum and palladium.

17. The method of claim 16, wherein the reforming catalyst further comprises at least one promoter metal from Group IIA, Group IVA, Group IB, Group VIB, and Group VIIB of the Periodic Table of Elements.

18. The method of claim 1, wherein the hydrocarbon fuel or fuel precursor feedstream is a product of a hydrocracking process;

wherein the hydrocracking process comprises a hydrocracking catalyst which is a supported catalyst containing nickel, nickel-cobalt-molybdenum, cobalt-molybdenum, nickel-tungsten, or nickel-molybdenum components deposited thereon; and

the hydrocracking process is operated at hydrocracking conditions which include a temperature from about 200°

C. to about 450°

C., a total pressure from about 5 barg (about 0.5 MPag) to about 300 barg (about 30 MPag), a hydrogen-containing treat gas ratio from about 100 scf/bbl (about 17 Nm³/m³) to about 5000 scf/bbl (about 840 Nm³/m³), and an LHSV from about 0.05 hr<sup>−

1</sup> to about 10 hr<sup>−

1</sup>.