Immobilization of vanadia deposited on catalytic materials during carbo-metallic oil conversion

Claim 2

A process for converting a vanadium-containing hydrocarbon oil feed to lighter products comprising: contacting said oil feed under conversion conditions in a conversion zone with a cracking catalyst having a relative activity of at least about 20% to form lighter products and coke, whereby vanadium in an oxidation state less than +5 and coke are deposited on said catalyst; separating said lighter products from the spent catalyst carrying vanadium in an oxidation state less than +5 and coke; regenerating said spent catalyst by contacting it with an oxygen-containing gas under conditions whereby said coke on the spent catalyst is combusted, forming gaseous products comprising CO and CO 2 , said regeneration being carried out at least in part with the catalyst at a temperature greater than the melting point of vanadium in an oxidation state of +5, said regeneration further being carried out for a period of time and in the presence of sufficient oxygen so as to reduce the concentration of coke on said catalyst to a level less than about 0.15 percent by weight of the catalyst while promoting the retention of vanadium in an oxidation state less than +5; and recycling the regenerated catalyst to the conversion zone to contact fresh feed.

Claim 3

A process according to claim 1 wherein said feed contains 650° F. material characterized by a carbon residue on pyrolysis of at least about 1 and a Nickel Equivalent content of heavy metals of at least about 4.

Claim 4

A process according to claim 2 wherein said 650° F. + material represents at least about 70% by volume of said feed and includes at least about 10% by volume of material which will not boil below about 1000° F.

Claim 5

The process of claim 1 wherein the feed contains at least about 0.1 ppm vanadium.

Claim 6

The process of claim 1 wherein the feed contains at least about 1 ppm vanadium.

Claim 7

The process of claim 1 wherein the feed contains from about 1 to about 5 ppm vanadium.

Claim 8

The process of claim 3 wherein the feed contains more than about 5 ppm vanadium.

Claim 9

The process of claim 1 wherein the cracking catalyst comprises a zeolite molecular sieve catalyst containing from about 1 to about 60% by weight of sieve.

Claim 10

The process of claim 1 wherein the cracking catalyst comprises a zeolite molecular sieve catalyst containing about 15 to about 50% by weight of sieve.

Claim 11

The process of claim 1 wherein the cracking catalyst comprises a zeolite molecular sieve catalyst containing about 20 to about 45% by weight of sieve.

Claim 12

The process of claim 1 wherein the concentration of vanadium on said catalyst is greater than about 0.05% of the weight of the catalyst.

Claim 13

The process of claim 1 wherein the concentration of vanadium on said catalyst is greater than about 0.1% of the weight of the catalyst.

Claim 14

The process of claim 1 wherein the concentration of vanadium on said catalyst is greater than about 5% by weight of the catalyst.

Claim 15

The process of claim 1 wherein the concentration of vanadium on said catalyst is from 0.1 to about 5% by weight of the catalyst.

Claim 16

The process of claim 1 wherein coke in the amount of 0.3 to 3% by weight of the catalyst is deposited on said catalyst.

Claim 17

The process of claim 1 wherein the catalyst is regenerated at a temperature from about 1100° to about 1600° F.

Claim 18

The process of claim 1 wherein the catalyst is regenerated at a temperature from about 1200° to about 1500° F.

Claim 19

The process of claim 1 wherein said catalyst is regenerated at a temperature in the range of about 1275° to about 1425° F.

Claim 20

The process of claim 1 wherein sufficient coke is retained on the regenerated catalyst to provide vanadium deposited on the catalyst with a non-oxidizing environment.

Claim 21

The process of claim 1 wherein the concentration of coke on the regenerated catalyst is at least about 0.05%.

Claim 22

The process of claim 1 wherein the concentration of vanadium on said catalyst is greater than about 0.5% by weight of the catalyst.

Claim 23

The process of claim 1 wherein the regeneration is carried out in at least two stages and at least one stage contains CO and CO 2 in a molar ratio of at least about 0.25.

Claim 24

The process of claim 1 wherein said catalyst is regenerated in at least two stages, in the first stage of which said spent catalyst is contacted in a dense fluidized bed with a gas containing less than a stoichiometric amount of oxygen to convert the hydrogen in said coke to H 2 O and the carbon in said coke to CO and CO 2 , and in the final regeneration stage of which partially regenerated catalyst is contacted with a stoichiometric excess of oxygen for a period of time of less than about 2 seconds.

Claim 25

The process of claim 23 wherein the catalyst in said final stage comprises a dispersed phase having a density less than about 4 pounds per cubic foot.

Claim 26

The process of claim 23 wherein the residence time of the catalyst in said dense fluidized bed is at least about 5 minutes.

Claim 27

The process of claim 23 wherein said fluidized bed has a density from about 25 to about 50 pounds per cubic foot.

Claim 28

The process of claim 23 wherein the partially regenerated catalyst is contacted with at least a stoichiometric amount of oxygen in a riser regenerator, the residence time of the catalyst in the riser regenerator is less than about 2 seconds, and the regenerated catalyst is separated from the gaseous products.

Claim 29

The process of claim 27 wherein the residence time of the catalyst in the riser regenerator is less than about 1 second.

Claim 30

The process of claim 27 wherein the separated, regenerated catalyst is contacted with a reducing gas.

Claim 31

The process of claim 27 wherein the separated, regenerated catalyst is immediately contacted with a reducing gas and is then collected in a dense bed maintained under a reducing atmosphere.

Claim 32

The process of claim 27 wherein the density of the catalyst within the riser regenerator is less than about 4 pounds per cubic foot.

Claim 33

The process of claim 27 wherein the density of the catalyst within the riser is less than about 2 pounds per cubic foot.

Claim 34

The process of claim 27 wherein the regenerated catalyst is separated from the gaseous products by being projected in a direction established by the riser regenerator, or an extension thereof, while the gaseous products are caused to make an abrupt change of direction resulting in an abrupt, substantially instantaneous ballistic separation of gaseous products from regenerated catalyst.

Claim 35

The process of claim 3 wherein the feed contains more than about 25 ppm vanadium.

Claim 36

The process of claim 3 wherein the feed contains more than about 50 ppm vanadium.

Claim 37

The process of claim 3 wherein the feed contains more than about 100 ppm vanadium.

Claim 38

The process of claim 3 wherein the feed contains more than about 200 ppm vanadium.

Claim 39

The process of claim 1 wherein the concentration of vanadium on said catalyst is greater than about 1% by weight of the catalyst.

Claim 40

The process of claim 1 wherein the concentration of vanadium on said catalyst is greater than about 2% by weight of the catalyst.

Claim 41

A process for converting a hydrocarbon feed containing at least about 1 ppm vanadium to lighter products comprising: contacting said hydrocarbon feed with a cracking catalyst having a relative activity of at least about 20% and containing at least about 5000 ppm vanadium and less than about 0.15 percent carbon, said contact being made in a progressive flow reactor for a predetermined vapor riser residence time in the range of about 0.5 to about 10 seconds at a temperature of about 900 to about 1400° F. and under a pressure of about 10 to about 50 pounds per square inch absolute while causing a conversion per pass in the range of about 50 to about 90% while producing coke and laying down vanadium in an oxidation state less than +5 and coke on said catalyst; separating spent catalyst from the hydrocarbon products formed in said reactor; contacting said spent catalyst at a temperature of at least about 1275° F. with an oxygen-containing gas in at least two stages, in the first stage of which said spent catalyst comprises a fluidized bed having a density from about 25 to about 50 pounds per cubic foot, the average residence time of said catalyst in said bed is from about 5 to about 30 minutes, and said oxygen-containing gas is sufficiently deficient in oxygen to produce CO and CO 2 in the gases in heat exchange contact with the catalyst in a CO/CO 2 ratio of at least about 0.25; transferring the partially regenerated catalyst to a riser regenerator wherein the partially regenerated catalyst as a dilute phase of solids and at a temperature greater than about 1275° F. is contacted with a stoichiometric excess of oxygen for a period of time less than about 2 seconds so as to reduce the carbon concentration on said catalyst to less than about 0.15 percent by weight; separating the resulting regenerated catalyst from the oxygen containing gases; collecting the separated regenerated catalyst in the presence of a reducing gas; and recycling the regenerated catalyst containing at least about 5000 ppm vanadium by weight to the progressive flow reactor for contact with fresh feed.

Claim 42

A process for converting a hydrocarbon feed containing at least about 1 ppm vanadium to lighter products comprising: contacting said hydrocarbon feed with a cracking catalyst having a relative activity of at least about 20% and containing at least about 5000 ppm vanadium and less than about 0.15 percent carbon, said contact being made in a progressive flow reactor for a predetermined vapor riser residence time in the range of about 0.5 to about 10 seconds at a temperature of about 900 to about 1400° F. and under a pressure of about 10 to about 50 pounds per square inch absolute while causing a conversion per pass in the range of about 50 to about 90% while producing coke and laying down vanadium in an oxidation state less than +5 and coke on said catalyst; separating spent catalyst from the hydrocarbon products formed in said reactor; contacting said spent catalyst at a temperature of at least about 1275° F. with an oxygen-containing gas in at least two stages, in the first stage of which said spent catalyst comprises a fluidized bed having a density from about 25 to about 50 pounds per cubic foot, the average residence time of said catalyst in said bed is from about 5 to about 30 minutes, and said oxygen-containing gas is sufficiently deficient in oxygen to produce CO and CO 2 in the gases in heat exchange contact with the catalyst in a CO/CO 2 ratio of at least about 0.25; transferring the partially regenerated catalyst to a riser regenerator wherein the partially regenerated catalyst as a dilute phase of solids and at a temperature greater than about 1275° F. is contacted with a stoichiometric excess of oxygen for a period of time less than about 2 seconds so as to reduce the carbon concentration on said catalyst to less than about 0.15 percent by weight; separating the resulting regenerated catalyst from the oxygen containing gases; collecting the separated regenerated catalyst in the presence of a reducing gas; and recycling the regenerated catalyst containing at least about 5000 ppm vanadium by weight to the progressive flow reactor for contact with fresh feed.

Claim 43

A process for converting a vanadium-containing hydrocarbon oil feed to lighter products comprising: contacting said oil feed under conversion conditions in a conversion zone with a cracked catalyst to form lighter products and coke, whereby vanadium in an oxidation state less than +5 and coke are deposited on said catalyst; separating said lighter products from the spent catalyst carrying vanadium in an oxidation state less than +5 and coke; regenerating said spent catalyst in at least two stages, in the first stage of which said spent catalyst is contacted in a dense fluidized bed with a gas containing less than a stoichiometric amount of oxygen to convert hydrogen in said coke to H 2 O, and carbon in said coke to CO and CO 2 so as to retain vanadium on said catalyst in an oxidation state less than +5, and in the final regeneration stage of which partially regenerated catalyst is contacted with a stoichiometric excess of oxygen for a period of time of less than about 2 seconds.

Claim 44

A process for converting a vanadium-containing hydrocarbon oil feed to lighter products comprising: contacting said oil feed under conversion conditions in a conversion zone with a cracked catalyst to form lighter products and coke, whereby vanadium in an oxidation state less than +5 and coke are deposited on said catalyst; separating said lighter products from the spent catalyst carrying vanadium in an oxidation state less than +5 and coke; regenerating said spent catalyst in at least two stages, in the first stage of which said spent catalyst is contacted in a dense fluidized bed with a gas containing less than a stoichiometric amount of oxygen to convert hydrogen in said coke to H 2 O, and carbon in said coke to CO and CO 2 so as to retain vanadium on said catalyst in an oxidation state less than +5, and in the final regeneration stage of which partially regenerated catalyst is contacted with a stoichiometric excess of oxygen for a period of time of less than about 2 seconds.