IPC분류정보
국가/구분 |
United States(US) Patent
등록
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국제특허분류(IPC7판) |
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출원번호 |
UP-0340387
(2008-12-19)
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등록번호 |
US-7837960
(2011-01-22)
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발명자
/ 주소 |
- Bhaduri, Rahul S.
- Stiksma, John
- Berezowsky, Roman
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출원인 / 주소 |
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대리인 / 주소 |
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인용정보 |
피인용 횟수 :
23 인용 특허 :
33 |
초록
▼
A method is disclosed for separating and recovering base metals from a used hydroprocessing catalyst originating from Group VIB and Group VIII metals and containing at least a Group VB metal. In one embodiment, the method comprises the steps of: contacting the used catalyst with an ammonia leaching
A method is disclosed for separating and recovering base metals from a used hydroprocessing catalyst originating from Group VIB and Group VIII metals and containing at least a Group VB metal. In one embodiment, the method comprises the steps of: contacting the used catalyst with an ammonia leaching solution under conditions sufficient to dissolve the group VIB metal and the Group VIII metal into the leaching solution; forming a leached slurry containing at least a group VIB metal complex and at least a group VIII metal complex, ammonium sulfate and a solid residue containing at least a Group VB metal complex and coke; separating and removing from the leached slurry the solid residue and coke; precipitating from the remaining solution at least a portion of the Group VIB metal complex and at least a portion of the Group VIII metal complex by controlling the pH to form a liquid material substantially free of Group VB, Group VIB and Group VIII metals and another solid material comprising substantially Group VIB and Group VIII metal complexes. Said solid material is further processed by dissolution, means of separation, further means of precipitation and oxidative dissolution to produce, separately, a Group VIB metal product solution, a Group VIII metal product solution and a purified ammonium sulfate product solution.
대표청구항
▼
The invention claimed is: 1. A method of recovering metals from a used catalyst comprising the steps of: (a) leaching a Group VB metal, a Group VIB metal and a Group VIII metal from the used catalyst with an ammonia containing leach solution at a temperature and a pressure sufficient to form a pres
The invention claimed is: 1. A method of recovering metals from a used catalyst comprising the steps of: (a) leaching a Group VB metal, a Group VIB metal and a Group VIII metal from the used catalyst with an ammonia containing leach solution at a temperature and a pressure sufficient to form a pressure leach slurry comprising at least a Group VIB soluble metal complex and at least a Group VIII soluble metal complex and a first solid residue; (b) separating and removing the first solid residue from the pressure leach slurry to form a first pressure leach solution comprising the Group VIB soluble metal complex and the Group VIII soluble metal complex; (c) precipitating from the first pressure leach solution, at a first pre-selected pH, a second solid residue comprising at least a portion of the Group VIB soluble metal complex to form a first slurry comprising the second solid residue and at least a portion of the Group VIII soluble metal complex; (d) separating from the first slurry the second solid residue and a primary filtrate substantially free of Group VB, Group VIB and the Group VIII metals; (e) dissolving the second solid residue at a second pre-selected pH to form a group VIB metal precipitate and a group VIII metal containing solution; (f) separating the group VIB metal precipitate from the Group VIII metal containing solution of step (e); (g) dissolving said Group VIB metal precipitate in a dilute base at a sufficient temperature to form a Group VIB soluble metal product. 2. The method of claim 1 wherein the step (f) further comprises: (i) recovering a secondary filtrate comprising substantially the Group VIII soluble metal complex and a trace amount of Group VB and Group VIB metals; (ii) combining the secondary filtrate with the primary filtrate from step (d) to form a combined filtrate comprising substantially the Group VIII soluble metal complex and a trace quantity of Group VB and Group VIB metals; (iii) precipitating from the combined filtrate the Group VB, Group VIB and Group VIII metals in a sulfidation process to form a third solid residue and a tertiary filtrate; (iv) separating the third solid residue from the tertiary filtrate and dissolving the third solid residue to form a group VIII metal product solution. 3. The method of claim 2 further comprising, subjecting the tertiary filtrate to hydrolysis to form a purified solution. 4. The method of claim 3 wherein the purified solution is ammonium sulfate. 5. The method of claim 1 wherein the precipitation step (c) is carried out at a pH in a range between 2.5 to 3.5, at a temperature between about 75° C. and 85° C. for at least two hours. 6. The method of claim 1 wherein the first solid residue comprises at least a Group VB metal, a Group VB metal complex and Coke. 7. The method of claim 6, wherein the Group VB metal is vanadium, and wherein the Group VB metal complex comprises ammonium metavanadate. 8. The method of claim 1 wherein the separation steps (b), (d) and (f) each comprise at least a separation means selected from settling, filtration, decantation, centrifugation and combinations thereof. 9. The method of claim 1, wherein the primary filtrate comprises 0.1 to 3% of the Group VIB metal in the used catalyst, 1 to 20% of the Group VB metal in the used catalyst, and 1 to 35% of the Group VIII metal in the used catalyst. 10. The method of claim 2, wherein the combined filtrate comprises at least a portion of the Group VB metal, Group VIB metal and at least a portion of the Group VIII metal, wherein the sulfidation process is carried out at a third pre-selected pH to precipitate as metal sulfides and oxy-hydroxides at least 95% of the Group VB metal, at least 95% of the Group VIB metal and at least 95% of the Group VIII metal present in the combined filtrate. 11. The method of claim 2, wherein the separation step (iv) comprises at least a separation means selected from settling, filtration, decantation, centrifugation and combinations thereof. 12. The method of claim 11 wherein the tertiary filtrate comprises less than 100 ppm of the group VIB metal, less than 20 ppm of the Group VIII metal, and less than 100 ppm of the Group VB metal. 13. The method of claim 1, wherein at least 90% of the Group VIB metal precipitates from the pressure leach solution as a metal complex. 14. The method of claim 1, wherein the Group VIB metal is molybdenum and wherein the first pre-selected pH is in the range of 2.5 to 3.3 to precipitate greater than 90% of the molybdenum as a molybdate complex. 15. The method of claim 14, wherein the pressure leach solution (PLS) is adjusted to the first pre-selected pH by adding to the PLS at least one of a mineral acid or a sulfur compound having a sulfhydryl group or an ionized sulfhydryl group, or mixtures thereof. 16. The method of claim 15, wherein the pH of the PLS is adjusted to a pH of 3.5 or less with an acid selected from the group of sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid. 17. The method of claim 16, wherein the PLS is adjusted to a pH of 3 or less with the addition of a sulfuric acid for at least 95% of the molybdenum to precipitate out as an octamolybdate complex. 18. The method of claim 15, wherein the pH of the pressure leach solution is adjusted to a pH of 3 or less with at least one of a water soluble sulfide, a water soluble polysulfide, or mixtures thereof. 19. The method of claim 1, wherein the Group VIB metal in the used catalyst is molybdenum, the Group VIII metal in the used catalyst is nickel, the Group VB metal in the used catalyst is vanadium. 20. The method of claim 2, wherein at least one of a water soluble sulfide, a water soluble polysulfide, or mixtures thereof is added to the combined filtrate for a pH level of between 6 and 9 to obtain a precipitate of Mo, Ni, and V sulfides and oxy hydroxides or combinations thereof. 21. The method of claim 20, wherein H2S is added to the combined filtrate at a pressure from atmospheric to 100 psig, a temperature ranging from 50 to 110° C. for at least 30 minutes. 22. The method of claim 2, wherein the Group VIB metal in the used catalyst is molybdenum, the Group VIII metal in the used catalyst is nickel, the Group VB metal in the used catalyst is vanadium, the pressure leach solution is adjusted to a pH of 3 or less with the addition of sulfuric acid to precipitate and form the second solid residue comprising at least 95% of the molybdenum as an octamolybdate complex and at least 75% of the nickel as a nickel ammonium sulfate compound, at least partially dissolving the second solid residue in acidic water having a pH of 2.5 or less at a temperature of 80° C. to form an octamolybdate precipitate and a solution of the double salt of nickel and dissolving the octamolybdate precipitate in a dilute ammonia at a temperature ranging from 50° C. to 75° C. to form an ammonium molybdate product. 23. The method of claim 22 further comprising: separating the octamolybdate precipitate from the double salt of nickel solution to form the secondary filtrate; combining the primary filtrate and the secondary filtrate to form the combined filtrate comprising at least 80% of the nickel present in the used catalyst, from 0.1 to 3% of the molybdenum present in the used catalyst and from 1 to 20% of the vanadium present in the used catalyst; adding H2S to the combined filtrate at a pressure from atmospheric to 100 psig and at a temperature ranging from 50-110° C. to obtain the third solid residue, which comprises a precipitate of Mo and Ni sulfides and V oxy-hydroxides; separating the Mo, Ni, and V sulfides and oxy-hydroxides by filtration to obtain the tertiary filtrate, which comprises 100 to 1000 gpL ammonium sulfate, less than 100 ppm molybdenum, less than 20 ppm nickel, and less than 100 ppm vanadium. 24. The method of claim 23 further comprising: dissolving the third solid residue at a pH of five or less in the presence of oxygen at a temperature between 150° C. and 170° C., a total pressure ranging from 150 psig to 170 psig for a time between 30 minutes and 1.5 hours to obtain a nickel sulfate product solution. 25. A method of recovering metals from a used catalyst originating from a hydroprocessing catalyst having a general formula (X)a(M)b[(CH3CH2)cN(CH3)3]dOz and containing at least a group VB metal, wherein X is a Group VIII non-noble metal, M is a group VIB metal selected from Mo and W and combinations thereof, c is an integer from 10 to 40, the molar ratio of a:b is from 0.5/1 to 3/1, the method comprising the steps of: (a) leaching a Group VB metal, a Group VIB metal and a Group VIII metal from the used catalyst with an ammonia containing leach solution at a temperature and a pressure sufficient to form a pressure leach slurry comprising at least a Group VIB soluble metal complex and at least a Group VIII soluble metal complex and a first solid residue; (b) separating and removing the first solid residue from the pressure leach slurry to form a first pressure leach solution comprising the Group VIB soluble metal complex and the Group VIII soluble metal complex; (c) precipitating from the first pressure leach solution, at a first pre-selected pH, a second solid residue comprising at least a portion of the Group VIB soluble metal complex to form a first slurry comprising at least a portion of the Group VIII soluble metal complex; (d) separating from the first slurry the second solid residue and a primary filtrate substantially free of Group VB, Group VIB and the Group VIII metals; (e) dissolving the second solid residue at a second pre-selected pH to form a group VIB metal precipitate and a group VIII metal containing solution; (f) separating the group VIB metal precipitate from the Group VIII metal containing solution of step (e) and dissolving said Group VIB metal precipitate in a dilute base at a sufficient temperature to form a Group VIB metal product. 26. The method of claim 25, further comprising the steps of: (i) recovering a secondary filtrate comprising substantially the Group VIII soluble metal complex and a trace amount of Group VB and Group VIB metals; (ii) combining the secondary filtrate with the primary filtrate of step (d) to form a combined filtrate comprising substantially the Group VIII soluble metal complex and a trace quantity of Group VB and Group VIB metals; (ii) precipitating from the combined filtrate the Group VB, Group VIB and Group VIII metals in a sulfidation process to form a third solid residue and a tertiary filtrate; (iv) separating the third solid residue from the tertiary filtrate and dissolving the third solid residue to form a group VIII metal product solution. 27. The method of claim 26, wherein the Group VIB metal is molybdenum and wherein the pre-selected pH is in the range of 2.5 to 3.3 to precipitate greater than 90% of the molybdenum. 28. The method of claim 25, wherein the used catalyst originates from a hydroprocessing catalyst having a median particle size of 0.01 to 200 microns. 29. The method of claim 25, wherein the used catalyst has a pore volume of 0.05-5 ml/g as determined by nitrogen adsorption. 30. A method of recovering metals, including vanadium, from a used catalyst having a general formula (Mt)a(Xu)b(Sv)d(Cw)e(Hx)f(Oy)g(Nz)h containing at least a Group VB metal, wherein M is at least one group VIB metal, X is at least one of a non-noble Group VIII metal, a Group VIIIB metal, a Group VIB metal, a Group IVB metal, and a Group IIB metal, 0=<b/a=<5, (a+0.5b)<=d<=(5a+2b), 0<=e<=11(a+b), 0<=f<=7(a+b), 0<=g<=5(a+b), 0<=h<=0.5(a+b); t, u, v, w, x, y, z, each representing total charge for each of: M, X, S, C, H, O and N, respectively; ta+ub+vd+we+xf+yg+zh=0 the method comprising the steps of: (a) leaching a Group VB metal, a Group VIB metal and a Group VIII metal from the used catalyst with an ammonia containing leach solution at a temperature and a pressure sufficient to form a pressure leach slurry comprising at least a Group VIB soluble metal complex and at least a Group VIII soluble metal complex and a first solid residue; (b) separating and removing the first solid residue from the pressure leach slurry to form a first pressure leach solution comprising the Group VIB soluble metal complex and the Group VIII soluble metal complex; (c) precipitating from the first pressure leach solution, at a first pre-selected pH, a second solid residue comprising at least a portion of the Group VIB soluble metal complex to form a first slurry comprising the second solid residue and at least a portion of the Group VIII soluble metal complex; (d) separating from the first slurry the second solid residue and a primary filtrate substantially free of Group VB, Group VIB and the Group VIII metals; (e) dissolving the second solid residue at a second pre-selected pH to form a Group VIB metal precipitate and a Group VIII metal containing solution; (f) separating the Group VIB metal precipitate from the Group VIII metal containing solution of step (e) and dissolving said Group VIB metal precipitate in a dilute base at a sufficient temperature to form a Group VIB metal product; (g) recovering a secondary filtrate comprising substantially the Group VIII soluble metal complex and a trace amount of Group VB and Group VIB metals; (h) combining the secondary filtrate with the primary filtrate of step (d) to form a combined filtrate comprising substantially the Group VIII soluble metal complex and a trace quantity of Group VB and Group VIB metals; (i) precipitating from the combined filtrate the Group VB, Group VIB and Group VIII metals in a sulfidation process to form a third solid residue and a tertiary filtrate; (j) separating the third of solid residue from the tertiary filtrate and dissolving the third solid residue to form a Group VIII metal product solution.
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