Hydrorefining with a regenerated catalyst

Claim 2

A process for hydrorefining hydrocarbons boiling primarily above 300° F. which comprises contacting said hydrocarbons with hydrogen under hydrorefining conditions comprising a super atmospheric hydrogen partial pressure and an elevated temperature in the presence of a catalytic composition regenerated by a method comprising: (1) contacting a deactivated hydrorefining catalyst, said deactivated catalyst containing a refractory oxide and having, from previous use in refining, nickel and vanadium contaminants and sulfur-containing coke deposits on the surface thereof, with a phosphorus component selected from the group consisting of elemental phosphorus and a non-metallic phosphorus compound, said phosphorus component being incorporated in said catalyst in an amount such that the catalyst from step (2) comprises at least one weight percent of phosphorus, calculated as P; and (2) combusting said coke deposits from said catalyst obtained from step (1) under conditions such that no significant sulfation of said refractory oxide occurs and wherein the regenerated catalyst comprises at least a portion of said nickel and vanadium contaminants.

Claim 3

The process defined in claim 1 wherein said method further comprises said catalyst prior to step (1), mixing said catalyst obtained from step (2) with a binding agent, forming particulates of said mixture and then calcining.

Claim 4

The process defined in claim 1 wherein said method further comprises combusting part of said coke deposits from said catalyst prior to step (1).

Claim 5

The process defined in claim 1 wherein said method further comprises extracting said vanadium and nickel contaminants from said catalyst prior to step (1).

Claim 6

The process defined in claim 1 wherein said method further comprises crushing said catalyst obtained from step (2), mixing said crushed catalyst with a binding agent, forming particulates and calcining said particulates.

Claim 7

The process defined in claim 1 wherein a reactor guard chamber is used and said regenerated catalyst is further disposed in said guard chamber to demetallize said hydrocarbons.

Claim 8

A process for hydrorefining hydrocarbons boiling primarily above 300° F. which comprises contacting said hydrocarbons with hydrogen under hydrorefining conditions comprising a super atmospheric hydrogen partial pressure and an elevated temperature in the presence of a catalytic composition regenerated by a method comprising: (1) contacting a deactivated hydrorefining catalyst, said deactivated catalyst containing a refractory oxide and having, from previous use in refining, nickel and vanadium contaminants and sulfur-containing coke deposits on the surface thereof, with a phosphorus component selected from the group consisting of elemental phosphorus and non-metallic phosphorus compound, said phosphorus component being incorporated in said catalyst in an amount such that the catalyst from step (2) comprises at least one weight percent of phosphorus, calculated as P; and (2) combusting said coke deposits from said catalyst obtained from step (1) under conditions such that no substantial loss of surface area occurs as compared to said deactivated catalyst and wherein the regenerated catalyst comprises at least a portion of said nickel and vanadium contaminants.

Claim 9

A process for hydrorefining hydrocarbons boiling primarily above 300° F. which comprises contacting said hydrocarbons with hydrogen under hydrorefining conditions comprising a super atmospheric hydrogen partial pressure and an elevated temperature in the presence of a catalytic composition regenerated by a method comprising: (1) contacting a deactivated hydrorefining catalyst, said deactivated catalyst containing a refractory oxide and having, from previous use in refining, nickel and vanadium contaminants and sulfur-containing coke deposits on the surface thereof, with a phosphorus component selected from the group consisting of elemental phosphorus and non-metallic phosphorus compound, said phosphorus component being incorporated in said catalyst in an amount such that the catalyst from step (2) comprises at least one weight percent of phosphorus, calculated as P; and (2) combusting said coke deposits from said catalyst obtained from step (1) under conditions such that no substantial loss of surface area occurs as compared to said deactivated catalyst and wherein the regenerated catalyst comprises at least a portion of said nickel and vanadium contaminants.

Claim 10

A process for hydrorefining hydrocarbons boiling primarily above 300° F. which comprises contacting said hydrocarbons with hydrogen under hydrorefining conditions comprising a super atmospheric hydrogen partial pressure and an elevated temperature in the presence of a catalytic composition regenerated by a method comprising: (1) contacting a deactivated hydrorefining catalyst, said deactivated catalyst containing a refractory oxide and having, from previous use in refining, nickel and vanadium contaminants and sulfur-containing coke deposits on the surface thereof, with a phosphorus component selected from the group consisting of elemental phosphorus and a non-metallic phosphorus compound, said phosphorus component being incorporated in said catalyst in an amount such that the catalyst from step (2) comprises at least one weight percent of phosphorus, calculated as P; and (2) combusting said coke deposits from said catalyst obtained from step (1) under conditions such that no substantial loss of average crushing strength occurs as compared to said deactivated catalyst and wherein the regenerated catalyst comprises at least a portion of said nickel and vanadium contaminants.

Claim 11

A process for hydrorefining hydrocarbons boiling primarily above 300° F. which comprises contacting said hydrocarbons with hydrogen under hydrorefining conditions comprising a super atmospheric hydrogen partial pressure and an elevated temperature in the presence of a catalytic composition regenerated by a method comprising: (1) contacting a deactivated hydrorefining catalyst, said deactivated catalyst containing a refractory oxide and having, from previous use in refining, nickel and vanadium contaminants and sulfur-containing coke deposits on the surface thereof, with a phosphorus component selected from the group consisting of elemental phosphorus and a non-metallic phosphorus compound, said phosphorus component being incorporated in said catalyst in an amount such that the catalyst from step (2) comprises at least one weight percent of phosphorus, calculated as P; and (2) combusting said coke deposits from said catalyst obtained from step (1) under conditions such that no substantial loss of average crushing strength occurs as compared to said deactivated catalyst and wherein the regenerated catalyst comprises at least a portion of said nickel and vanadium contaminants.

Claim 12

The process defined in claim 7 further comprising combusting part of said coke deposits from said deactivated catalyst prior to step (1).

Claim 13

The process defined in claim 8 further comprising combusting part of said coke deposits from said deactivated catalyst prior to step (1).

Claim 14

The process defined in claim 3 wherein said combustion, prior to step (1) of said method, results at a temperature of about 250° F. to about 600° F.

Claim 15

The process defined in claim 3 wherein said combustion in step (2) of said method results at a temperature of about 600° F. to about 1500° F.

Claim 16

The process defined in claim 1 wherein said deactivated catalyst comprises cobalt and molybdenum components.

Claim 17

The process defined in claim 3 wherein said method further comprises the step of extracting said vanadium and nickel contaminants from said catalyst obtained from combusting part of said coke deposits from said catalyst prior to step (1).

Claim 18

The process defined in claim 4 wherein said vanadium and nickel metals are extracted in said method by contact with an extraction solution containing oxalic acid and aluminum nitrate.

Claim 19

The process defined in claim 4 further comprises incorporating Group VIB and Group VIII metal components with said contaminant metals-extracted catalyst.

Claim 20

The process defined in claim 1 wherein said catalyst obtained from step (2) of said method contains substantially less sulfur than said deactivated catalyst.

Claim 21

The process defined in claim 1 further comprising step (3) wherein the catalyst obtained from step (2) is crushed and mixed with a binding agent, followed by particulate formulation and calcination.

Claim 22

The process defined in claim 1 wherein the catalyst obtained from step (2) of said method contains less than about 0.5 weight percent coke.

Claim 23

A process for hydrodesulfurizing hydrocarbons which comprises contacting said hydrocarbons with hydrogen under hydrogenative conversion conditions comprising a hydrogen partial pressure greater than 500 p.s.i.g. and temperature greater than 500° F. in the presence of a catalytic composition regenerated by a method comprising: (1) contacting a deactivated hydrodesulfurization catalyst, said deactivated hydrodesulfurization catalyst containing a refractory oxide and having, from previous use in refining, nickel and vanadium contaminants and sulfur-containing coke deposits on the surface thereof, with a phosphorus component selected from the group consisting of elemental phosphorus and a non-metallic phosphorus compound, said phosphorus component being incorporated in said catalyst in an amount such that the catalyst from step (2) comprises at least one weight percent of phosphorus, calculated as P; and (2) combusting said coke deposits from said catalyst obtained from step (1) under conditions such that no significant sulfation of said refractory oxide occurs and wherein the regenerated catalyst comprises at least a portion of said nickel and vanadium contaminants.

Claim 24

A process for hydrodesulfurizing hydrocarbons which comprises contacting said hydrocarbons with hydrogen under hydrogenative conversion conditions comprising a hydrogen partial pressure greater than 500 p.s.i.g. and temperature greater than 500° F. in the presence of a catalytic composition regenerated by a method comprising: (1) contacting a deactivated hydrodesulfurization catalyst, said deactivated hydrodesulfurization catalyst containing a refractory oxide and having, from previous use in refining, nickel and vanadium contaminants and sulfur-containing coke deposits on the surface thereof, with a phosphorus component selected from the group consisting of elemental phosphorus and a non-metallic phosphorus compound, said phosphorus component being incorporated in said catalyst in an amount such that the catalyst from step (2) comprises at least one weight percent of phosphorus, calculated as P; and (2) combusting said coke deposits from said catalyst obtained from step (1) under conditions such that no significant sulfation of said refractory oxide occurs and wherein the regenerated catalyst comprises at least a portion of said nickel and vanadium contaminants.

Claim 25

The process defined in claim 20 further comprising crushing said catalyst prior to step (1), mixing said catalyst obtained from step (2) with a binding agent, forming particulates of said mixture and then calcining.

Claim 26

The process defined in claim 20 further comprising combusting part of said coke deposits from said catalyst prior to step (1).

Claim 27

The process defined in claim 20 further comprising extracting said vanadium and nickel contaminants from said catalyst prior to step (1).

Claim 28

The process defined in claim 20 further comprising crushing said catalyst obtained from step (2), mixing said crushed catalyst with a binding agent, forming particulates and calcining said particulates.

Claim 29

The process defined in claim 20 wherein a reactor guard chamber is used and said regenerated catalyst is further disposed in said guard chamber to demetallize said hydrocarbons.

Claim 30

A process for hydrodesulfurizing hydrocarbons which comprises contacting said hydrocarbons with hydrogen under hydrogenative conversion conditions comprising a hydrogen partial pressure greater than 500 p.s.i.g. and temperature greater than 500° F. in the presence of a catalytic composition regenerated by a method comprising: (1) contacting a deactivated hydrodesulfurization catalyst, said deactivated hydrodesulfurization catalyst containing a refractory oxide and having, from previous use in refining, nickel and vanadium contaminants and sulfur-containing coke deposits on the surface thereof, with a phosphorus component selected from the group consisting of elemental phosphorus and a non-metallic phosphorus compound, said phosphorus component being incorporated in said catalyst in an amount such that the catalyst from step (2) comprises at least one weight percent of phosphorus, calculated as P; and (2) combusting said coke deposits from said catalyst obtained from step (1) under conditions such that no substantial loss of surface area occurs as compared to said deactivated catalyst and wherein the regenerated catalyst comprises at least a portion of said nickel and vanadium contaminants.

Claim 31

A process for hydrodesulfurizing hydrocarbons which comprises contacting said hydrocarbons with hydrogen under hydrogenative conversion conditions comprising a hydrogen partial pressure greater than 500 p.s.i.g. and temperature greater than 500° F. in the presence of a catalytic composition regenerated by a method comprising: (1) contacting a deactivated hydrodesulfurization catalyst, said deactivated hydrodesulfurization catalyst containing a refractory oxide and having, from previous use in refining, nickel and vanadium contaminants and sulfur-containing coke deposits on the surface thereof, with a phosphorus component selected from the group consisting of elemental phosphorus and a non-metallic phosphorus compound, said phosphorus component being incorporated in said catalyst in an amount such that the catalyst from step (2) comprises at least one weight percent of phosphorus, calculated as P; and (2) combusting said coke deposits from said catalyst obtained from step (1) under conditions such that no substantial loss of surface area occurs as compared to said deactivated catalyst and wherein the regenerated catalyst comprises at least a portion of said nickel and vanadium contaminants.

Claim 32

A process for hydrodesulfurizing hydrocarbons which comprises contacting said hydrocarbons with hydrogen under hydrogenative conversion conditions comprising a hydrogen partial pressure greater than 500 p.s.i.g. and temperature greater than 500° F. in the presence of a catalytic composition regenerated by a method comprising: (1) contacting a deactivated hydrodesulfurization catalyst, said deactivated hydrodesulfurization catalyst containing a refractory oxide and having, from previous use in refining, nickel and vanadium contaminants and sulfur-containing coke deposits on the surface thereof, with a phosphorus component selected from the group consisting of elemental phosphorus and a non-metallic phosphorus compound, said phosphorus component being incorporated in said catalyst in an amount such that the catalyst from step (2) comprises at least one weight percent of phosphorus, calculated as P; and (2) combusting said coke deposits from said catalyst obtained from step (1) under conditions such that no substantial loss of average crushing strength occurs as compared to said deactivated catalyst and wherein the regenerated catalyst comprises at least a portion of said nickel and vanadium contaminants.

Claim 33

A process for hydrodesulfurizing hydrocarbons which comprises contacting said hydrocarbons with hydrogen under hydrogenative conversion conditions comprising a hydrogen partial pressure greater than 500 p.s.i.g. and temperature greater than 500° F. in the presence of a catalytic composition regenerated by a method comprising: (1) contacting a deactivated hydrodesulfurization catalyst, said deactivated hydrodesulfurization catalyst containing a refractory oxide and having, from previous use in refining, nickel and vanadium contaminants and sulfur-containing coke deposits on the surface thereof, with a phosphorus component selected from the group consisting of elemental phosphorus and a non-metallic phosphorus compound, said phosphorus component being incorporated in said catalyst in an amount such that the catalyst from step (2) comprises at least one weight percent of phosphorus, calculated as P; and (2) combusting said coke deposits from said catalyst obtained from step (1) under conditions such that no substantial loss of average crushing strength occurs as compared to said deactivated catalyst and wherein the regenerated catalyst comprises at least a portion of said nickel and vanadium contaminants.

Claim 34

The process defined in claim 22 wherein said combustion prior to step (1) of said method results at a temperature of about 250° F. to about 600° l F.

Claim 35

The process defined in claim 22 wherein said combustion in step (2) of said method results at a temperature of about 600° F. to about 1500° F.

Claim 36

The process defined in claim 20 wherein said deactivated catalyst comprises cobalt and molybdenum components.

Claim 37

The process defined in claim 22 wherein said method further comprises the step of extracting said vanadium and nickel contaminants from said catalyst obtained from combusting part of said coke deposits from said catalyst prior to step (1).

Claim 38

The process defined in claim 23 wherein said vanadium and nickel metals are extracted in said method by contact with an extraction solution containing oxalic acid and aluminum nitrate.

Claim 39

The process defined in claim 23 further comprises incorporating Group VIB and Group VIII metal components with said contaminant metals-extracted catalyst.

Claim 40

The process defined in claim 20 wherein said catalyst obtained from step (2) of said method contains substantially less sulfur than said deactivated catalyst.

Claim 41

The process defined in claim 20 further comprising step (3) wherein said catalyst obtained from step (2) is crushed and mixed with a binding agent, followed by particulate formulation and calcination.

Claim 42

The process defined in claim 20 wherein the catalyst obtained from step (2) of said method contains less than about 0.5 weight percent coke.

Claim 43

A process for hydrodesulfurizing hydrocarbons which comprises contacting said hydrocarbons with hydrogen under hydrogenative conversion conditions comprising a hydrogen partial pressure greater than 500 p.s.i.g. and temperature greater than 500° F. in the presence of a catalytic composition regenerated by a method comprising: (1) extracting vanadium and nickel components from a deactivated hydrodesulfurization catalyst comprising cobalt and molybdenum components on a refractory oxide containing alumina, said deactivated catalyst further containing nickel and vanadium metal contaminants and sulfur-containing coke deposits on the surface thereof, by contacting said deactivated catalyst with an extraction solution containing components selected from the group consisting of oxalic acid, aluminum nitrate, glycolic acid, and ammonium nitrate; (2) combusting part of said coke deposits from the catalyst obtained from step (1) by heating said catalyst to a temperature in the range from about 350° F. to about 550° F.; (3) incorporating cobalt, molybdenum, and phosphorus components with said catalyst obtained from step (2), said phosphorus component being incorporated in said catalyst in an amount sufficient to yield essentially no loss of surface area of said catalyst in step (4); (4) calcining said catalyst obtained from step (3) at a temperature in the range from about 700° F. to about 1300° F. such that a substantial proportion of said coke deposits are combusted from said catalyst without substantial loss in surface area thereof; (5) crushing said catalyst obtained from step (4) and mixing said crushed catalyst with alumina; and (6) forming said mixture obtained from step (5) into particulates and calcining.

Claim 44

A process for hydrodesulfurizing hydrocarbons which comprises contacting said hydrocarbons with hydrogen under hydrogenative conversion conditions comprising a hydrogen partial pressure greater than 500 p.s.i.g. and temperature greater than 500° F. in the presence of a catalytic composition regenerated by a method comprising: (1) extracting vanadium and nickel components from a deactivated hydrodesulfurization catalyst comprising cobalt and molybdenum components on a refractory oxide containing alumina, said deactivated catalyst further containing nickel and vanadium metal contaminants and sulfur-containing coke deposits on the surface thereof, by contacting said deactivated catalyst with an extraction solution containing components selected from the group consisting of oxalic acid, aluminum nitrate, glycolic acid, and ammonium nitrate; (2) combusting part of said coke deposits from the catalyst obtained from step (1) by heating said catalyst to a temperature in the range from about 350° F. to about 550° F.; (3) incorporating cobalt, molybdenum, and phosphorus components with said catalyst obtained from step (2), said phosphorus component being incorporated in said catalyst in an amount sufficient to yield essentially no loss of surface area of said catalyst in step (4); (4) calcining said catalyst obtained from step (3) at a temperature in the range from about 700° F. to about 1300° F. such that a substantial proportion of said coke deposits are combusted from said catalyst without substantial loss in surface area thereof; (5) crushing said catalyst obtained from step (4) and mixing said crushed catalyst with alumina; and (6) forming said mixture obtained from step (5) into particulates and calcining.

Claim 45

The method defined in claim 37 wherein said phosphorus components are selected from the group consisting of orthophosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous pyrophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium phosphate.

Claim 46

The process defined in claim 26 further comprising combusting part of said coke deposits from said deactivated catalyst prior to step (1).

Claim 47

The process defined in claim 27 further comprising combusting part of said coke deposits from said deactivated catalyst prior to step (1).