Dewaxing of renewable diesel fuel
Feeds containing a hydrotreated biocomponent portion, and optionally a mineral portion, can be processed under catalytic conditions for isomerization and/or dewaxing. The sulfur content of the feed for dewaxing can be selected based on the hydrogenation metal used for the catalyst. Diesel fuel products with improved cold flow properties can be produced.
1. A method for isomerizing and/or dewaxing a diesel fuel, comprising:
mixing a biocomponent feed portion with a mineral feed portion to form a combined feedstock, the combined feedstock having a sulfur content of less than about 500 wppm, the biocomponent feed portion being at least about 25 wt % of the combined feedstock; and
contacting the combined feedstock with an isomerization/dewaxing catalyst under effective isomerization and/or dewaxing conditions including a temperature of at least about 350° C., the isomerization/dewaxing catalyst comprising ZSM-48 and at least 0.5 wt % of Pt, Pd, or a combination thereof, the ZSM-48 having a silica to alumina ratio of about 75:1 or less, the isomerization and/or dewaxing conditions being sufficient to produce an isomerized and/or dewaxed product having a cloud point of about −20° C. or less,
wherein the biocomponent feed portion is hydrotreated prior to contacting the combined feedstock with the isomerization/dewaxing catalyst.
2. The method of claim 1 , wherein the biocomponent feed portion includes a fat and/or oil whose source is at least one of vegetable, animal, fish, and algae.
3. The method of claim 1 , wherein the effective catalytic isomerization/dewaxing conditions include a total pressure of about 400 psig (about 2.8 MPag) to about 1500 psig (about 10.3 MPag), an LHSV of about 0.5 hr −1 to about 5.0 hr −1 , and a treat gas rate of about 500 scf/bbl (about 84 Nm 3 /m 3 ) to about 2000 scf/bbl (about 340 Nm 3 /m 3 ).
4. The method of claim 1 , wherein the mineral feed portion is hydrotreated by contacting with a hydrotreating catalyst including at least one hydrogenation metal under effective hydrotreating conditions prior to mixing with the biocomponent feed portion.
5. The method of claim 4 , wherein the effective hydrotreating conditions include a temperature of about 315° C. to about 425° C., a total pressure of about 300 psig (about 2.1 MPag) to about 3000 psig (about 21 MPag), an LHSV of about 0.2 hr −1 to about 10 hr −1 , and a hydrogen treat gas rate of about 500 scf/bbl (about 84 Nm 3 /m 3 ) to about 10000 scf/bbl (about 1700 Nm 3 /m 3 ).
6. The method of claim 4 , wherein the hydrotreated feedstream is cascaded to the isomerization/dewaxing step without intermediate separation.
7. The method of claim 1 , wherein the combined feedstock has a sulfur content of about 50 wppm or less and a nitrogen content of about 20 wppm or less.
8. The method of claim 1 , wherein the mineral feed portion is mixed with the biocomponent feed portion prior to hydrotreatment of the biocomponent feed portion.
9. The method of claim 1 , wherein the isomerized and/or dewaxed product is hydrofinished under effective hydrofinishing conditions.
10. A method for isomerizing and/or dewaxing a diesel fuel, comprising:
hydrotreating a feedstock, including a biocomponent portion of at least about 25 wt % of the feedstock, under effective hydrotreating conditions, the biocomponent portion having an oxygen content of at least about 8 wt % prior to hydrotreatment; and
contacting the hydrotreated feedstock with an isomerization/dewaxing catalyst under effective isomerization and/or dewaxing conditions including a temperature of at least about 370° C., the isomerization/dewaxing catalyst comprising a molecular sieve selected from Beta, USY, ZSM-5, ZSM-35, ZSM-23, ZSM-48, or a combination thereof, and including at least about 2 wt % of a hydrogenation metal being a combination of Ni and at least one of W and Mo, the isomerization/dewaxing conditions being effective to produce an isomerized and/or dewaxed product having a cloud point of about −20° C. or less.
11. The method of claim 10 , wherein the hydrotreated feedstock has a sulfur content from about 100 wppm sulfur to about 500 wppm sulfur.
12. The method of claim 10 , wherein hydrotreating the feedstock produces a hydrotreated feedstock and a gas phase effluent containing H 2 S, and wherein contacting the hydrotreated feedstock with the isomerization/dewaxing catalyst further comprises contacting at least a portion of the gas phase effluent with the isomerization/dewaxing catalyst.
13. The method of claim 10 , further comprising combining the hydrotreated feedstock with a second feedstock prior to said contacting with the isomerization/dewaxing catalyst, the combined feedstock having a sulfur content from about 100 wppm sulfur to about 500 wppm sulfur.
14. The method of claim 13 , wherein the second feedstock comprises a mineral feedstock portion that is hydrotreated under effective hydrotreating conditions prior to mixing with the biocomponent feed.
15. The method of claim 14 , wherein effective hydrotreating conditions include exposing the feed to a catalyst including at least one hydrogenation metal at a temperature of about 315° C. to about 425° C., a total pressure of about 300 psig (about 2.1 MPag) to about 3000 psig (about 21 MPag), an LHSV of about 0.2 hr −1 to about 10 hr −1 , and a hydrogen treat gas rate of about 500 scf/bbl (about 84 Nm 3 /m 3 ) to about 10000 scf/bbl (about 1700 Nm 3 /m 3 ).
16. The method of claim 10 , wherein the biocomponent portion includes a fat and/or oil whose source is at least one of vegetable, animal, fish, and algae.
17. The method of claim 10 , wherein the effective isomerization and/or dewaxing conditions include a total pressure of about 400 psig (about 2.8 MPag) to about 1500 psig (about 10.3 MPag), an LHSV of about 0.5 hr −1 to about 5.0 hr −1 , and a treat gas rate of about 500 scf/bbl (about 84 Nm 3 /m 3 ) to about 2000 scf/bbl (about 340 Nm 3 /m 3 ).
18. The method of claim 10 , wherein the isomerized and/or dewaxed product is hydrofinished under effective hydrofinishing conditions.
19. The method of claim 10 , wherein the molecular sieve is ZSM-23 or ZSM-48 with a silica to alumina ratio of about 90:1 or less.
20. The method of claim 10 , wherein the dewaxing catalyst comprises at least about 2 wt % of Ni and at least about 10 wt % of W, Mo, or a combination thereof.