US4549958A — Immobilization of vanadia deposited on sorbent ma…

Claim 1

Independent Claim 215 words

In a process for demetallizing and decarbonizing a residual hydrocarbon oil feed having a significant content of vanadium and Conradson carbon contributing material with fluidizable sorbent particle material in a progressive flow reaction zone to provide an oil product substantially lower in vanadium and Conradson carbon components and regenerating said sorbent under oxidizing conditions of temperatures causing formed vanadium pentoxide to melt and effect coalescence of fluid sorbent particles, the improvement which comprises: A. contacting said oil feed with fluidizable sorbent particle material containing one or more additive metal components in an amount sufficient to complex with and immobilize the flow characteristics of vanadium pentoxide formed during sorbent regeneration, said additive metal component selected from one or more Mg, Ca, Ba, Sc, Y, La, Ti, Zr, Hf, Nb, Ta, Mn, In, Te, an element in the lanthanide or actinide series or an organo-metallic compound of said additive metal component; B. removing deposited carbonaceous material from said sorbent comprising said additive metal component with an oxygen containing gas at an elevated combustion temperature; C. complexing deposited vanadium with said additive metal components to form a complex having a melt temperature above the regeneration temperature, and D. recycling said regenerated fluid sorbent particle material for contact with said hydrocarbon oil feed in a progressive flow reaction zone.

Claim 2

Dependent Claim 215 words

In a process for demetallizing and decarbonizing a residual hydrocarbon oil feed having a significant content of vanadium and Conradson carbon contributing material with fluidizable sorbent particle material in a progressive flow reaction zone to provide an oil product substantially lower in vanadium and Conradson carbon components and regenerating said sorbent under oxidizing conditions of temperatures causing formed vanadium pentoxide to melt and effect coalescence of fluid sorbent particles, the improvement which comprises: A. contacting said oil feed with fluidizable sorbent particle material containing one or more additive metal components in an amount sufficient to complex with and immobilize the flow characteristics of vanadium pentoxide formed during sorbent regeneration, said additive metal component selected from one or more Mg, Ca, Ba, Sc, Y, La, Ti, Zr, Hf, Nb, Ta, Mn, In, Te, an element in the lanthanide or actinide series or an organo-metallic compound of said additive metal component; B. removing deposited carbonaceous material from said sorbent comprising said additive metal component with an oxygen containing gas at an elevated combustion temperature; C. complexing deposited vanadium with said additive metal components to form a complex having a melt temperature above the regeneration temperature, and D. recycling said regenerated fluid sorbent particle material for contact with said hydrocarbon oil feed in a progressive flow reaction zone.

Claim 3

Dependent Claim 41 words

The process of claim 1 wherein the oil feed is a reduced crude or crude oil containing 100 ppm or more of metals consisting of nickel, vanadium, iron and copper and having a Conradson carbon value of at least 2 wt%.

Claim 4

Dependent Claim 34 words

The process of claim 1 wherein the oil feed is a reduced crude or crude oil containing 200 ppm or more of metals and having a Conradson carbon value of at least 2 wt%.

Claim 5

Dependent Claim 30 words

The process of claim 1 wherein said sorbent comprises a hydrated clay providing a surface area below 50 m 2 /g and a pore volume of at least 0.2 cc/g.

Claim 6

Dependent Claim 24 words

The process of claim 1 wherein said sorbent is prepared in spherical form and of a particle size in the range of 10-200 microns.

Claim 7

Dependent Claim 29 words

The process in claim 1 wherein said sorbent is prepared from a clay, selected from the group consisting of bentonite, kaolin, mullite, pumice, silica, laterite, or pillared interlayered clays.

Claim 8

Dependent Claim 27 words

The process of claim 1 wherein said metal additive is added to the process as a water soluble inorganic metal salt or a hydrocarbon soluble organo-metallic compound.

Claim 9

Dependent Claim 36 words

The process of claim 1 wherein said metal, additive reacts with vanadium compounds to form one or more of the following: binary metal vanadates, mixtures of said vanadates, ternary or quaternary compounds, complexes, and alloys therewith.

Claim 10

Dependent Claim 23 words

The process of claim 1 wherein said metal additive is present in the sorbent in the range of about 1 to 20 wt%.

Claim 11

Dependent Claim 21 words

The process of claim 1 wherein said vanadium compounds deposited on the sorbent include vanadium oxides, sulfides, sulfites, sulfates or oxysulfides.

Claim 12

Dependent Claim 31 words

The process of claim 1 wherein said metal additive is added to an aqueous slurry of the ingredients comprising said sorbent and said aqueous slurry containing said additive is spray dried.

Claim 13

Dependent Claim 42 words

The process of claim 1 wherein said metal additive is introduced into said sorbent by adding an aqueous solution of a metal salt or a hydrocarbon solution of an organo-metallic compound at any point in the sorbent cycle of said treatment process.

Claim 14

Dependent Claim 24 words

The process of claim 1 wherein the concentration of vanadium deposited on said sorbent ranges from about 0.05 to 5 wt% of sorbent weight.

Claim 15

Dependent Claim 30 words

The process of claim 1 wherein said oil feed contains nickel and the ratio of said vanadium to said nickel is in the range of from about 1:3 to 5:1.

Claim 16

Dependent Claim 30 words

The process of claim 1 wherein said oil feed has a significant content of heavy metals and the vanadium portion of said total metals content is greater than fifty percent.

Claim 17

Dependent Claim 27 words

The process of claim 12 wherein the atomic ratio of metal in said metal additive to the vanadium present in said oil feed is at least 0.5.

Claim 18

Dependent Claim 35 words

The process of claim 1 wherein said metal additive is a water soluble inorganic metal salt comprised of a halide, nitrate, sulfate, sulfite, or carbonate or a combination of two or more of said salts.

Claim 19

Dependent Claim 37 words

The process of claim 1 wherein said metal additive is a hydrocarbon soluble metal compound comprised of an alcoholate, ester, phenolate, naphthenate, carboxylate, or dienyl sandwich compound or a combination of two or more of said compounds.

Claim 20

Dependent Claim 16 words

The process of claim 1 wherein said metal additive to immobilize vanadium compounds is tetraisopropyl titanate.

Claim 21

Dependent Claim 16 words

The process of claim 1 wherein said metal additive to immobilize vanadium compounds is titanium tetrachloride.

Claim 22

Dependent Claim 17 words

The process of claim 1 wherein said metal additive to immobilize vanadium compounds is methylcyclopentadienyl manganese tricarbonyl.

Claim 23

Dependent Claim 17 words

The process of claim 1 wherein said metal additive to immobilize vanadium compounds is a titanium compound.

Claim 24

Dependent Claim 12 words

The process of claim 1 wherein said metal additive is zirconium acetate.

Claim 25

Dependent Claim 33 words

The process of claim 1 wherein said sorbent includes 0.1 to 20 wt% of said metal additive incorporated in said sorbent as a gelatinous precipitate in the pores of a spray dried gel.

Claim 26

Dependent Claim 36 words

The process of claim 1 wherein the composition of said sorbent comprises a mixture of kaolin clay and titania gel in an amount in the range of about 1 to 8 weight percent of said sorbent.

Claim 27

Dependent Claim 36 words

The process of claim 1 wherein the composition of said sorbent comprises a mixture of kaolin clay and zirconia gel in an amount in the range of about 1 to 8 weight percent of said sorbent.

Claim 28

Dependent Claim 36 words

The process of claim 1 wherein the composition of said sorbent comprises a mixture of kaolin clay and alumina gel in an amount in the range of about 1 to 5 weight percent of said sorbent.

Claim 29

Dependent Claim 44 words

The process of claim 1 wherein conversion of the oil feed to gasoline and lighter products is below 20 volume percent, the Conradson carbon value is reduced by at least 20 percent, and the heavy metals content is reduced by at least 50 percent.

Claim 30

Dependent Claim 58 words

The process of claim 1 wherein the oil feed comprises 70 percent or more of 650° F. plus material having a fraction greater than 20% boiling about 1025° F. at atmospheric pressure, a metals content of greater than 5.5 ppm nickel equivalents of which at least 5 ppm is vanadium and a Conradson carbon residue greater than 4.0.

Claim 31

Dependent Claim 19 words

The process of claim 1 wherein the sorbent material replacement rate is about 3 or 4 percent of inventory.

Claim 32

Dependent Claim 17 words

The process of claim 1 wherein the oil feed is one having more than 1.0 ppm vanadium.

Claim 33

Dependent Claim 17 words

The process of claim 1 wherein the oil feed is one having more than 5 ppm vanadium.

Claim 34

Dependent Claim 27 words

The process of claim 1 wherein the concentration of additive metal on the sorbent is in the range of 1 to 8 wt% as the metal element.

Claim 35

Dependent Claim 55 words

The process of claim 1 wherein the metal additive is mixed with the oil feed prior to contact with the sorbent in an amount sufficient to give an atomic ratio between the metal additive and vanadium in the feed in a range of 0.25 to 3.0 and preferably within the range of 0.75 to 1.5.

Claim 36

Dependent Claim 32 words

The process of claim 1 wherein the sorbent material has a surface area below 25 m 2 /g, a pore volume of about 0.2 or greater and a micro-activity value below 20.

Claim 37

Dependent Claim 251 words

In a process for upgrading residual oil feeds comprising substantial metal contaminants and Conradson carbon producing components by contact with solid fluidizable sorbent particle material whereby said metal contaminants and hydrocarbonaceous material are laid down on said sorbent particle material during thermal conversion of said residual oil feed and deposited hydrocarbonaceous material is removed from said metal contaminated sorbent by combustion with an oxygen containing gas, thereby oxidizing said deposited metal contaminants comprising Ni, V, Cu and Fe, the improvement for immobilizing the low melting flow characteristics of vanadium pentoxide during oxidation regeneration at temperatures above 1150° F. which comprises, (a) adding a metal component to the sorbent particles used to contact said residual oil feed which will complex with or form compounds with deposited vanadium having a melting point above the temperature encountered during oxidation regeneration of the sorbent material, (b) said metal component added to said sorbent material prior to use, during use, or a combination of prior to use and during use by contact of said residual oil feed with said sorbent material to maintain a concentration of the metal element in the range of 0.5 to 25 percent by weight of the virgin sorbent, and (c) said added metal component selected as the metal, it's oxide or salt or as an organo-metallic compound and selected from the group consisting of Mg, Ca, Ba, Sc. Y, La, Ti, Zr, Hf, Nb, Ta, Mn, Ni, In, Te, the rare earths, or the actinide or the lanthanide series of elements.

Claim 38

Dependent Claim 251 words

In a process for upgrading residual oil feeds comprising substantial metal contaminants and Conradson carbon producing components by contact with solid fluidizable sorbent particle material whereby said metal contaminants and hydrocarbonaceous material are laid down on said sorbent particle material during thermal conversion of said residual oil feed and deposited hydrocarbonaceous material is removed from said metal contaminated sorbent by combustion with an oxygen containing gas, thereby oxidizing said deposited metal contaminants comprising Ni, V, Cu and Fe, the improvement for immobilizing the low melting flow characteristics of vanadium pentoxide during oxidation regeneration at temperatures above 1150° F. which comprises, (a) adding a metal component to the sorbent particles used to contact said residual oil feed which will complex with or form compounds with deposited vanadium having a melting point above the temperature encountered during oxidation regeneration of the sorbent material, (b) said metal component added to said sorbent material prior to use, during use, or a combination of prior to use and during use by contact of said residual oil feed with said sorbent material to maintain a concentration of the metal element in the range of 0.5 to 25 percent by weight of the virgin sorbent, and (c) said added metal component selected as the metal, it's oxide or salt or as an organo-metallic compound and selected from the group consisting of Mg, Ca, Ba, Sc. Y, La, Ti, Zr, Hf, Nb, Ta, Mn, Ni, In, Te, the rare earths, or the actinide or the lanthanide series of elements.

Claim 39

Dependent Claim 36 words

The process of claim 36 in which the added metal component is one which forms a binary mixture with vanadium pentoxide to yield a solid material having a melting point of at least about 1600° F.

Claim 40

Dependent Claim 42 words

The process of claim 36 in which the added metal component is an organo-metallic compound selected from tetraisopropyl-titanate; methylcyclopentodienyl manganese tricarbonyl; zirconium isopropoxide; barium acetate, calcium oxalate; magnesium stearate; indium 2,4 pentanedionate; tantalum ethoxide; zirconium 2,4 pentanedionate; titanium tetrachloride and manganese acetate.

Claim 41

Dependent Claim 54 words

The process of claim 36 in which the added metal component is added with a residual oil feed charged to the progressive flow contact zone and in an amount to provide an atomic ratio between the added metal component and the vanadium in the residual oil feed in the range of 0.5 to 3.0.

Claim 42

Dependent Claim 35 words

The process of claim 36 in which the residual oil feed comprises at least 5 ppm Ni equivalent, a vanadium content of at least 2 ppm and a Conradson residue of at least about 2.0.

Claim 43

Dependent Claim 46 words

The process of claim 36 in which water as a liquid or as steam is added to said sorbent regeneration operation to assist with controlling the regeneration temperature and influence maintaining a carbon dioxide to carbon monoxide ratio in the effluent gases thereof less than 4.0.

Claim 44

Dependent Claim 50 words

The process of claim 36 wherein the metal component is added to the sorbent following an accumulation of vanadium sufficient to cause undesired sorbent particle coalescence interfering with the fluid sorbent particle operation during thermal conversion of the oil feed and regeneration of sorbent particles to remove deposited carbonaceous material.

Claim 45

Dependent Claim 25 words

The process of claim 36 wherein the metal component is added to the sorbent after the sorbent reaches a vanadium level of about 1000 ppm.

Claim 46

Dependent Claim 30 words

The process of claim 36 wherein the sorbent material is replaced at a rate to maintain an equilibrated vanadium level selected from within the range of 5000 to 30,000 ppm.

Claim 47

Dependent Claim 32 words

The process of claim 36 wherein the circulated sorbent material equilibrated vanadium level is maintained in the range of 20,000 to 30,000 ppm when using titanium tetrachloride as the added metal component.

Claim 48

Dependent Claim 52 words

A process for the conversion of a hydrocarbon oil feed having a significant concentration of vanadium to lighter oil products which comprises contacting said feed under conversion conditions with fluid solid particle material containing an additive of calcium or barium in combination with an element selected from titanium, zirconium or mixtures thereof.

Claim 49

Dependent Claim 52 words

A process for the conversion of a hydrocarbon oil feed having a significant concentration of vanadium to lighter oil products which comprises contacting said feed under conversion conditions with fluid solid particle material containing an additive of calcium or barium in combination with an element selected from titanium, zirconium or mixtures thereof.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1988-10-28	1989-04-29	1989-10-29	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1992-10-28	1993-04-29	1993-10-29	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1996-10-28	1997-04-29	1997-10-29	$7700.00	Window Closed / Lapsed

Immobilization of vanadia deposited on sorbent materials during treatment of carbo-metallic oils

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