Hydroprocessing for distillate production

Abstract

Methods are provided for hydrotreating a feed to generate a product with a reduced or minimized aromatics content and/or an increased distillate product yield. A distillate boiling range feed having an elevated content of sulfur and/or nitrogen can be hydrotreated using at least two hydrotreating stages with intermediate separation to produce a hydrotreated distillate boiling range product with a reduced or minimized aromatics content. Additionally or alternately, a mixed metal catalyst formed from a suitable precursor can be used during the hydrotreating. A mixed metal catalyst formed from a suitable precursor can provide an unexpectedly superior activity for aromatic saturation. A still further unexpected benefit can be achieved by combining a multi-stage hydrotreating process with intermediate separation with hydrotreating in the presence of a mixed metal catalyst formed from a suitable precursor.

What is claimed is: 
     
         1 . A hydrotreatment process comprising:
 reacting a feedstream, the feedstream having a sulfur content of about 500 wppm to about 50000 wppm and an aromatics content of at least about 60 wt %, in the presence of a hydrogen-containing treat gas and in the presence of a mixed metal catalyst under effective hydrotreating conditions for converting about 5 wt % or less of the feedstream relative to a conversion temperature of 350° F. (177° C.); and   separating the first liquid effluent to produce a vapor phase stream and a liquid product stream, the liquid product stream having a sulfur content of about 500 wppm or less,   wherein the mixed metal catalyst comprises a sulfided mixed metal catalyst formed by sulfiding a mixed metal catalyst precursor composition, the mixed metal catalyst precursor composition being produced by   a) heating a composition comprising at least one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, and a reaction product formed from (i) a first organic compound containing at least one amine group, and (ii) a second organic compound separate from said first organic compound and containing at least one carboxylic acid group to a temperature from about 195° C. to about 260° C. for a time sufficient for the first and second organic compounds to form a reaction product in situ that contains an amide moiety, unsaturated carbon atoms not present in the first or second organic compounds, oxygen atoms not present in the first or second organic compounds, or a combination thereof;   b) heating a composition comprising one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, and a reaction product formed from (iii) a first organic compound containing at least one amine group and at least 10 carbon atoms or (iv) a second organic compound containing at least one carboxylic acid group and at least 10 carbon atoms, but not both (iii) and (iv), wherein the reaction product contains additional unsaturated carbon atoms, relative to (iii) the first organic compound or (iv) the second organic compound, wherein the metals of the catalyst precursor composition are arranged in a crystal lattice, and wherein the reaction product is not located within the crystal lattice, to a temperature from about 195° C. to about 260° C. for a time sufficient for the first or second organic compounds to form a reaction product in situ that contains unsaturated carbon atoms not present in the first or second organic compounds, oxygen atoms not present in the first or second organic compounds, or a combination thereof; or   c) heating a composition comprising at least one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, and a pre-formed amide formed from (v) a first organic compound containing at least one amine group, and (vi) a second organic compound separate from said first organic compound and containing at least one carboxylic acid group, to form at least one of additional in situ unsaturated carbon atoms or in situ added oxygen atoms not present in the first organic compound, the second organic compound, or both, but not for so long that the pre-formed amide substantially decomposes, thereby forming a catalyst precursor containing at least one of in situ formed unsaturated carbon atoms or in situ added oxygen atoms.   
     
     
         2 . The process of  claim 1 , wherein reacting the feedstream in the presence of a mixed metal catalyst further comprises reacting the feedstream in the presence of one or more additional hydrotreating catalysts,
 the one or more additional hydrotreating catalysts and the mixed metal catalyst optionally comprising a catalyst mixture, or the one or more additional hydrotreating catalysts and the mixed metal catalyst optionally comprising a stacked bed of catalysts, or the one or more additional hydrotreating catalysts and the mixed metal catalyst optionally being located in separate catalyst beds, or a combination thereof.   
     
     
         3 . The process of  claim 1 , wherein the effective hydrotreating conditions comprise temperatures of about 200° C. to about 450° C.; pressures of about 250 psig (1.8 MPag) to about 5000 psig (34.6 MPag); liquid hourly space velocities (LHSV) of about 0.1 hr −1  to about 10 hr −1 ; and hydrogen treat rates of about 200 scf/B (35.6 m 3 /m 3 ) to about 10,000 sc/B (1781 m 3 /m 3 ). 
     
     
         4 . The process of  claim 1 , wherein the feedstream has a multi-ring aromatics content of at least about 40 wt %. 
     
     
         5 . The process of  claim 1 , wherein the catalyst precursor composition is treated first with said first organic compound and second with said second organic compound, or wherein the catalyst precursor composition is treated first with said second organic compound and second with said first organic compound, or wherein the catalyst precursor composition is treated simultaneously with said first organic compound and with said second organic compound. 
     
     
         6 . The process of  claim 1 , wherein said at least one metal from Group 6 is Mo, W, or a combination thereof, and wherein said at least one metal from Groups 8-10 is Co, Ni, or a combination thereof. 
     
     
         7 . The process of  claim 1 , wherein the mixed metal catalyst precursor composition is a bulk metal hydroprocessing catalyst precursor composition consisting essentially of the reaction product, an oxide form of the at least one metal from Group 6, an oxide form of the at least one metal from Groups 8-10, and optionally about 20 wt % or less of a binder. 
     
     
         8 . The process of  claim 1 , wherein a T10 boiling point of the feedstream is at least about 350° F. (177° C.), or wherein the T90 boiling point of the feedstream is about 850° F. (454° C.) or less, or a combination thereof. 
     
     
         9 . The process of  claim 1 , further comprising performing catalytic dewaxing, hydrofinishing, aromatic saturation, or a combination thereof on at least a portion of the liquid product stream or on at least a portion of the second liquid product stream. 
     
     
         10 . A multistage hydroprocessing process comprising:
 reacting a feedstream having a sulfur content of at least about 3000 wppm in a first hydroprocessing stage in the presence of a hydrogen-containing treat gas and in the presence of at least one first stage hydroprocessing catalyst, the first hydroprocessing stage being operated at first stage hydroprocessing conditions, thereby resulting in a first liquid effluent having a sulfur content of about 3000 wppm or less;   separating at least a portion of the first liquid effluent to produce a first vapor phase stream and a first liquid product stream;   reacting at least a portion of the first liquid product stream in a second hydroprocessing stage in the presence of a hydrogen-containing treat gas and a mixed metal catalyst, the second hydroprocessing stage being operated at second stage hydroprocessing conditions to produce a second liquid effluent; and   separating at least a portion of the second liquid effluent to produce a second vapor phase stream and a second liquid product stream having a sulfur content of about 500 wppm or less,   wherein the mixed metal catalyst comprises a sulfided mixed metal catalyst formed by sulfiding a mixed metal catalyst precursor composition, the mixed metal catalyst precursor composition being produced by   a) heating a composition comprising at least one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, and a reaction product formed from (i) a first organic compound containing at least one amine group, and (ii) a second organic compound separate from said first organic compound and containing at least one carboxylic acid group to a temperature from about 195° C. to about 260° C. for a time sufficient for the first and second organic compounds to form a reaction product in situ that contains an amide moiety, unsaturated carbon atoms not present in the first or second organic compounds, oxygen atoms not present in the first or second organic compounds, or a combination thereof;   b) heating a composition comprising one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, and a reaction product formed from (iii) a first organic compound containing at least one amine group and at least 10 carbon atoms or (iv) a second organic compound containing at least one carboxylic acid group and at least 10 carbon atoms, but not both (iii) and (iv), wherein the reaction product contains additional unsaturated carbon atoms, relative to (iii) the first organic compound or (iv) the second organic compound, wherein the metals of the catalyst precursor composition are arranged in a crystal lattice, and wherein the reaction product is not located within the crystal lattice, to a temperature from about 195° C. to about 260° C. for a time sufficient for the first or second organic compounds to form a reaction product in situ that contains unsaturated carbon atoms not present in the first or second organic compounds, oxygen atoms not present in the first or second organic compounds, or a combination thereof; or   c) heating a composition comprising at least one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, and a pre-formed amide formed from (v) a first organic compound containing at least one amine group, and (vi) a second organic compound separate from said first organic compound and containing at least one carboxylic acid group, to form at least one of additional in situ unsaturated carbon atoms or in situ added oxygen atoms not present in the first organic compound, the second organic compound, or both, but not for so long that the pre-formed amide substantially decomposes, thereby forming a catalyst precursor containing at least one of in situ formed unsaturated carbon atoms or in situ added oxygen atoms.   
     
     
         11 . The process of  claim 10 , wherein the first liquid effluent has a sulfur content of at least about 1000 wppm. 
     
     
         12 . The process of  claim 10 , further comprising hydroprocessing at least a portion of the first liquid product stream in an intermediate hydrotreating stage. 
     
     
         13 . The process of  claim 10 , wherein the feedstream has an aromatics content of at least about 60 wt %. 
     
     
         14 . The process of  claim 10 , wherein the feedstream has a multi-ring aromatics content of at least about 40 wt %. 
     
     
         15 . The process of  claim 10 , wherein the catalyst precursor composition is treated first with said first organic compound and second with said second organic compound, or wherein the catalyst precursor composition is treated first with said second organic compound and second with said first organic compound, or wherein the catalyst precursor composition is treated simultaneously with said first organic compound and with said second organic compound. 
     
     
         16 . The process of  claim 10 , wherein the first stage hydroprocessing conditions, the second stage hydroprocessing conditions, or both the first stage and the second stage hydroprocessing conditions comprise effective hydroprocessing conditions, the effective hydroprocessing conditions comprising temperatures of about 200° C. to about 450° C.; pressures of about 250 psig (1.8 MPag) to about 5000 psig (34.6 MPag); liquid hourly space velocities (LHSV) of about 0.1 hr −1  to about 10 hr −1 ; and hydrogen treat rates of about 200 scf/B (35.6 m 3 /m 3 ) to about 10,000 scf/B (1781 m 3 /m 3 ), the first stage and second stage hydroprocessing conditions optionally but preferably being selected independently. 
     
     
         17 . The process of  claim 10 ,
 wherein the first stage hydrotreating conditions are effective for conversion of about 10 wt % or less of the feedstream relative to a conversion temperature of about 350° F. (177° C.), or   wherein the second stage hydrotreating conditions are effective for conversion of about 10 wt % or less of the feedstream relative to a conversion temperature of about 350° F. (177° C.), or   wherein about 10 wt % or less of the feedstream is converted relative to a conversion temperature of 350° F. (177° C.) during the reacting in the first hydrotreating stage and the second hydrotreating stage, or   a combination thereof.   
     
     
         18 . The process of  claim 10 , wherein a T90 boiling point of the first liquid product stream is about 800° F. (427° C.) or less. 
     
     
         19 . The process of  claim 10 , wherein a T10 boiling point of the feedstream is at least about 350° F. (177° C.), or wherein the T90 boiling point of the feedstream is about 850° F. (454° C.) or less, or a combination thereof. 
     
     
         20 . A multistage hydroprocessing process comprising:
 reacting a feedstream in a first hydroprocessing stage in the presence of a hydrogen-containing treat gas, the first stage containing one or more reaction zones, each reaction zone operated at first stage hydroprocessing conditions and in the presence of a first hydroprocessing catalyst, thereby resulting in a first liquid effluent;   separating at least a portion of the first liquid effluent to produce a first vapor phase stream and a first liquid product stream, the first liquid product stream having a sulfur content of about 1000 wppm to about 5000 wppm;   reacting at least a portion of the first liquid product stream in a second hydroprocessing stage in the presence of a hydrogen-containing treat gas, the second hydroprocessing stage containing at least one reaction zone operated at second stage hydroprocessing conditions, the at least one reaction zone containing a mixed metal hydroprocessing catalyst, thereby resulting in a second liquid effluent; and   separating at least a portion of the second liquid effluent to produce a second vapor phase stream and a second liquid product stream, the second liquid product stream having a sulfur content of about 100 wppm or less;   wherein the mixed metal catalyst comprises a sulfided mixed metal catalyst formed by sulfiding a mixed metal catalyst precursor composition, the mixed metal catalyst precursor composition being produced by   a) heating a composition comprising at least one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, and a reaction product formed from (i) a first organic compound containing at least one amine group, and (ii) a second organic compound separate from said first organic compound and containing at least one carboxylic acid group to a temperature from about 195° C. to about 260° C. for a time sufficient for the first and second organic compounds to form a reaction product in situ that contains an amide moiety, unsaturated carbon atoms not present in the first or second organic compounds, oxygen atoms not present in the first or second organic compounds, or a combination thereof;   b) heating a composition comprising one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, and a reaction product formed from (iii) a first organic compound containing at least one amine group and at least 10 carbon atoms or (iv) a second organic compound containing at least one carboxylic acid group and at least 10 carbon atoms, but not both (iii) and (iv), wherein the reaction product contains additional unsaturated carbon atoms, relative to (iii) the first organic compound or (iv) the second organic compound, wherein the metals of the catalyst precursor composition are arranged in a crystal lattice, and wherein the reaction product is not located within the crystal lattice, to a temperature from about 195° C. to about 260° C. for a time sufficient for the first or second organic compounds to form a reaction product in situ that contains unsaturated carbon atoms not present in the first or second organic compounds, oxygen atoms not present in the first or second organic compounds, or a combination thereof; or   c) heating a composition comprising at least one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, and a pre-formed amide formed from (v) a first organic compound containing at least one amine group, and (vi) a second organic compound separate from said first organic compound and containing at least one carboxylic acid group, to form at least one of additional in situ unsaturated carbon atoms or in situ added oxygen atoms not present in the first organic compound, the second organic compound, or both, but not for so long that the pre-formed amide substantially decomposes, thereby forming a catalyst precursor containing at least one of in situ formed unsaturated carbon atoms or in situ added oxygen atoms.   
     
     
         21 . A hydrotreatment process comprising:
 reacting a naphtha boiling range feedstream comprising a cracked naphtha portion in the presence of a hydrogen-containing treat gas and in the presence of a mixed metal catalyst under effective hydrotreating conditions; and   separating the first liquid effluent to produce a vapor phase stream and a liquid product stream, the liquid product stream having a sulfur content of about 100 wppm or less,   wherein the mixed metal catalyst comprises a sulfided mixed metal catalyst formed by sulfiding a mixed metal catalyst precursor composition, the mixed metal catalyst precursor composition being produced by   a) heating a composition comprising at least one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, and a reaction product formed from (i) a first organic compound containing at least one amine group, and (ii) a second organic compound separate from said first organic compound and containing at least one carboxylic acid group to a temperature from about 195° C. to about 260° C. for a time sufficient for the first and second organic compounds to form a reaction product in situ that contains an amide moiety, unsaturated carbon atoms not present in the first or second organic compounds, oxygen atoms not present in the first or second organic compounds, or a combination thereof;   b) heating a composition comprising one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, and a reaction product formed from (iii) a first organic compound containing at least one amine group and at least 10 carbon atoms or (iv) a second organic compound containing at least one carboxylic acid group and at least 10 carbon atoms, but not both (iii) and (iv), wherein the reaction product contains additional unsaturated carbon atoms, relative to (iii) the first organic compound or (iv) the second organic compound, wherein the metals of the catalyst precursor composition are arranged in a crystal lattice, and wherein the reaction product is not located within the crystal lattice, to a temperature from about 195° C. to about 260° C. for a time sufficient for the first or second organic compounds to form a reaction product in situ that contains unsaturated carbon atoms not present in the first or second organic compounds, oxygen atoms not present in the first or second organic compounds, or a combination thereof; or   c) heating a composition comprising at least one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, and a pre-formed amide formed from (v) a first organic compound containing at least one amine group, and (vi) a second organic compound separate from said first organic compound and containing at least one carboxylic acid group, to form at least one of additional in situ unsaturated carbon atoms or in situ added oxygen atoms not present in the first organic compound, the second organic compound, or both, but not for so long that the pre-formed amide substantially decomposes, thereby forming a catalyst precursor containing at least one of in situ formed unsaturated carbon atoms or in situ added oxygen atoms.