Hydroconversion multi-metallic catalyst and method for making thereof
First Claim
1. A process for forming a hydroprocessing catalyst composition with minimal amount of metals to waste treatment, the method comprises:
- co-precipitating at reaction conditions at least a Group VIB metal precursor feed and at least a Promoter metal precursor feed selected from Group VIII, Group IIB, Group IIA, Group IVA and combinations thereof, to form a mixture comprising a catalyst precursor, wherein the reaction conditions comprise a temperature between 25-350°
C. and at a pressure between 0 to 3000 psig and a pH of 0-12;
isolating the catalyst precursor from the mixture, forming a supernatant containing at least a Promoter metal residual and at least a Group VIB metal residual in a total amount of at least 10 mole % of the metal precursor feeds;
mixing the supernatant with at least a base or an acid for a sufficient amount of time to precipitate at least 50 mole % of metal ions in at least one of the metal residuals, wherein the precipitation is carried out at a pre-selected pH;
isolating the precipitate to recover a first effluent containing less than 50 mole % of metal ions in at least one of the metal residuals in the supernatant;
contacting the first effluent with a chelated ion exchange resin for a sufficient amount of time for at least 50 mole % of metal ions in at least one of the metal residuals in the first effluent to be bound onto the resin, forming a second effluent containing less than 1000 ppm of metal ions of at least one of the metal residuals;
eluting the resin to produce an eluate containing the metal ions previously bound onto the resin;
treating the second effluent stream or the eluate to recover at least 80 mol % of the metal ions in the second effluent stream to form at least a metal precursor feed;
recycling the at least a metal precursor feed formed by treating the second effluent stream or the eluate to the co-precipitating step; and
sulfiding the catalyst precursor forming the bulk catalyst;
wherein an effluent stream from the process to waste treatment contains less than 50 ppm metal ions.
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Abstract
In a process for forming a bulk hydroprocessing catalyst by sulfiding a catalyst precursor made in a co-precipitation reaction, up to 60% of the metal precursor feeds end up in the supernatant. The metals can be recovered via any of chemical precipitation, ion exchange, electro-coagulation, and combinations thereof to generate an effluent stream containing less than 50 mole % of metal ions in at least one of the metal residuals, and for at least one of the metal residuals recovered as a metal precursor feed for use in the co-precipitation reaction. In one embodiment, the resin functions as an anion exchange resin with an acidic supernatant to recover Group VIB metal residuals, and a cation exchange resin with a basic supernatant to recover Promoter metal residuals. An effluent stream from the process to waste treatment contains less than 50 ppm metals.
123 Citations
35 Claims
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1. A process for forming a hydroprocessing catalyst composition with minimal amount of metals to waste treatment, the method comprises:
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co-precipitating at reaction conditions at least a Group VIB metal precursor feed and at least a Promoter metal precursor feed selected from Group VIII, Group IIB, Group IIA, Group IVA and combinations thereof, to form a mixture comprising a catalyst precursor, wherein the reaction conditions comprise a temperature between 25-350°
C. and at a pressure between 0 to 3000 psig and a pH of 0-12;isolating the catalyst precursor from the mixture, forming a supernatant containing at least a Promoter metal residual and at least a Group VIB metal residual in a total amount of at least 10 mole % of the metal precursor feeds; mixing the supernatant with at least a base or an acid for a sufficient amount of time to precipitate at least 50 mole % of metal ions in at least one of the metal residuals, wherein the precipitation is carried out at a pre-selected pH; isolating the precipitate to recover a first effluent containing less than 50 mole % of metal ions in at least one of the metal residuals in the supernatant; contacting the first effluent with a chelated ion exchange resin for a sufficient amount of time for at least 50 mole % of metal ions in at least one of the metal residuals in the first effluent to be bound onto the resin, forming a second effluent containing less than 1000 ppm of metal ions of at least one of the metal residuals; eluting the resin to produce an eluate containing the metal ions previously bound onto the resin; treating the second effluent stream or the eluate to recover at least 80 mol % of the metal ions in the second effluent stream to form at least a metal precursor feed; recycling the at least a metal precursor feed formed by treating the second effluent stream or the eluate to the co-precipitating step; and sulfiding the catalyst precursor forming the bulk catalyst; wherein an effluent stream from the process to waste treatment contains less than 50 ppm metal ions. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14)
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15. A process for forming a hydroprocessing catalyst composition, the method comprises:
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co-precipitating at reaction conditions at least a Group VIB metal precursor feed and at least a Promoter metal precursor feed selected from Group VIII, Group IIB, Group IIA, Group IVA and combinations thereof, to form a mixture comprising a catalyst precursor, wherein the reaction conditions comprise a temperature between 25-350°
C. and at a pressure between 0 to 3000 psig and a pH of 0-12;isolating the catalyst precursor from the mixture, forming a supernatant containing at least a Promoter metal residual and at least a Group VIB metal residual in an amount of at least 10 mole % of the metal precursor feeds; mixing the supernatant with at least one of a base, an acid, a sulfide-containing compound, and combinations thereof; contacting the supernatant with a chelated ion exchange resin for a sufficient amount of time for at least 50 mole % of metal ions in at least one of the metal residuals in the supernatant to be bound onto the resin, forming a first effluent containing less than 1000 ppm of at least one of the metal residuals; eluting the resin to produce an eluate stream containing the metal ions previously bound onto the resin; treating the first effluent stream or the eluate stream to recover at least 80 mol % of the metal ions in the stream to form at least a metal precursor feed; recycling the at least a metal precursor feed formed by treating the first effluent stream or the eluate to the co-precipitating step; and sulfiding the catalyst precursor forming the bulk catalyst. - View Dependent Claims (16, 17, 18, 19, 20, 21)
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22. A process for forming a hydroprocessing catalyst composition, the method comprises:
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co-precipitating at reaction conditions at least a Group VIB metal precursor feed and at least a Promoter metal precursor feed selected from Group VIII, Group IIB, Group IIA, Group IVA and combinations thereof, to form a mixture comprising a catalyst precursor, wherein the reaction conditions comprise a temperature between 25-350°
C. and at a pressure between 0 to 3000 psig and a pH of 0-12;isolating the catalyst precursor from the mixture, forming a supernatant containing at least a Promoter metal residual and at least a Group VIB metal residual in an amount of at least 10 mole % of the metal precursor feeds; mixing the supernatant with at least one of an acid, a sulfide-containing compound, and combinations thereof for a sufficient amount of time to precipitate at least a portion of metal ions in at least one of the metal residuals, wherein the precipitation is carried out at a first pre-selected pH; isolating the precipitate to recover a first effluent stream containing less than 50 mole % of metal ions in at least one of the metal residuals in the supernatant; contacting the first effluent stream with a first chelated ion exchange resin at a second pre-selected pH for a sufficient amount of time for at least 50 mole % of metal ions in at least one of the metal residuals in the first effluent stream to be bound onto the resin, forming a second effluent stream containing less than 1000 ppm of metal ions in at least one of the metal residuals; contacting the second effluent stream with a second chelated ion exchange resin at a third pre-selected pH for a sufficient amount of time for at least 50 mole % of metal ions in at least one of the metal residuals in the first effluent stream to be bound onto the resin, forming a third effluent stream containing less than 100 ppm of metal ions in at least one of the metal residuals. - View Dependent Claims (23, 24, 25, 26, 27, 28, 29)
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30. A process for forming a hydroprocessing catalyst composition, the method comprises:
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co-precipitating at reaction conditions at least a Group VIB metal precursor feed and at least a Promoter metal precursor feed selected from Group VIII, Group IIB, Group IIA, Group IVA and combinations thereof, to form a mixture comprising a catalyst precursor, wherein the reaction conditions comprise a temperature between 25-350°
C. and at a pressure between 0 to 3000 psig and a pH of 0-12;isolating the catalyst precursor from the mixture, forming a supernatant containing at least a Promoter metal residual and at least a Group VIB metal residual in an amount of at least 10 mole % of the metal precursor feeds; contacting the supernatant with a chelated ion exchange resin at a pre-selected pH for a sufficient amount of time for at least 50 mole % of metal ions in at least one of the metal residuals in the supernatant to be bound onto the resin, forming a first effluent containing less than 1000 ppm of metal ions in at least one of the metal residuals; eluting the resin to produce an eluate stream containing the metal ions previously bound onto the resin; treating the first effluent stream or the eluate stream to recover at least 80 mol % of the metal ions in the stream to form at least a metal precursor feed; recycling the at least a metal precursor feed formed by treating the effluent stream or the eluate stream to the co-precipitating step; and sulfiding the catalyst precursor forming the bulk catalyst. - View Dependent Claims (31, 32, 33, 34, 35)
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Specification