Method for sorting spent catalyst as a function of the metals of the catalyst

• US 9,855,588 B2
• Filed: 12/01/2014
• Issued: 01/02/2018
• Est. Priority Date: 12/06/2013
• Status: Active Grant

• Current Assignee: IFP Energies Nouvelles
• Original Assignee: IFP Energies Nouvelles
• Inventors: Gauthier, Thierry, Lienemann, Charles Philippe
• Primary Examiner(s): MATTHEWS, TERRELL HOWARD
• Application Number:
  US15/101,470
• Publication Number:
  US 20160318073A1
• Time in Patent Office: 1,128 Days
• Field of Search: 209576, 209577, 209579, 209580
• CPC Class Codes: B01J 2235/00 Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
• CPC Class Codes: B01J 23/28 Molybdenum
• CPC Class Codes: B01J 23/30 Tungsten
• CPC Class Codes: B01J 23/75 Cobalt
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 23/882 and cobalt
• CPC Class Codes: B01J 23/883 and nickel
• CPC Class Codes: B01J 23/888 Tungsten
• CPC Class Codes: B01J 23/8885 containing also molybdenum
• CPC Class Codes: B01J 23/94 of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
• CPC Class Codes: B01J 23/96 of catalysts comprising metals, oxides or hydroxides of the noble metals
• CPC Class Codes: B01J 29/072 Iron group metals or copper
• CPC Class Codes: B01J 29/076 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• CPC Class Codes: B01J 29/90 Regeneration or reactivation
• CPC Class Codes: B01J 35/19 Catalysts containing parts with different compositions
• CPC Class Codes: B01J 35/50 characterised by their shape or configuration
• CPC Class Codes: B01J 35/55 Cylinders or rings
• CPC Class Codes: B01J 38/68 including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
• CPC Class Codes: B01J 38/72 including segregation of diverse particles
• CPC Class Codes: B07C 2501/0018 Sorting the articles during free fall
• CPC Class Codes: B07C 5/342 : according to optical properties, e.g. colour according to radiation transmittivity B07C5/3416
• CPC Class Codes: B07C 5/3427 : by changing or intensifying the optical properties prior to scanning, e.g. by inducing fluorescence under UV or x-radiation, subjecting the material to a chemical reaction
• CPC Class Codes: C10G 45/00 : Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
• CPC Class Codes: C10G 45/08 : in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• CPC Class Codes: C10G 45/12 : containing crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C10G 47/00 : Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions C10G15/00 takes precedence; destructive hydrogenation of non-melting solid carbonaceous or similar materials C10G1/06
• CPC Class Codes: C10G 47/20 : the catalyst containing other metals or compounds thereof
• CPC Class Codes: G01N 21/718 : Laser microanalysis, i.e. with formation of sample plasma
• CPC Class Codes: G01N 21/85 : Investigating moving fluids or granular solids

Abstract

A method and device for separating at least one catalyst from a mixture of homogeneously shaped catalysts, the catalysts comprising at least one metal selected from the group formed by Ni, Co, Mo, W, the catalyst to be separated comprising a characteristic metal selected from the group formed by Ni, Co, Mo, W and the other catalysts of the mixture not containing said characteristic metal, in which method:

• • the grains of the catalyst of said mixture pass in front of the LIBS detection system,
  • the presence of said characteristic metal in the catalysts is detected by the LIBS technique, the wavelength being selected so as to detect said characteristic metal,
  • the LIBS detection system sends a signal to a means for evacuating grains of catalyst to be separated in a manner such as to separate said grains from the other catalysts of said mixture.

Claims

1. A method for separating at least one catalyst from a mixture of homogeneously shaped catalysts, the catalysts being in the form of grains and comprising at least one metal selected from Ni, Co, Mo, and W, the catalyst to be separated comprising W as a characteristic metal and the other catalysts of the mixture containing at least one metal selected from Ni, Co and Mo but not containing said characteristic metal W, said method comprising:

passing the grains of the catalyst of said mixture in front of a Laser Induced Breakdown Spectroscopy (LIBS) detection system,

detecting the presence of said characteristic metal in the catalysts by the LIBS, the wavelength of the LIBS being selected so as to detect said characteristic metal, and

sending a signal from the LIBS detection system to a means for evacuating the grains of catalyst comprising said characteristic metal W in a manner such as to separate said grains comprising said characteristic metal W from the grains of the other catalysts of said mixture containing at least one metal selected from Ni, Co and Mo, but not containing W.

2. The method according to claim 1, in which the other catalysts of the mixture not containing said characteristic metal W include at least one catalyst containing molybdenum.

3. The method according to claim 1, in which the catalyst to be separated comprising W as the characteristic metal also contains Ni, and the other catalysts of the mixture not containing said characteristic metal W include at least one catalyst containing NiMo or CoMo or NiCoMo.

4. The method according to claim 1, in which the catalysts of the mixture are hydrotreatment and/or hydrocracking catalysts.

5. The method according to claim 1, in which the catalysts are spent hydrotreatment and/or hydrocracking catalysts the support of which is constituted by alumina or silica-alumina, with zeolite optionally being present.

6. The method according to claim 1, in which the catalysts are homogeneously shaped.

7. The method according to claim 1, in which the catalysts of the mixture are in the form of cylindrical extrudates.

8. The method according to claim 1, in which the catalysts of the mixture are spent catalysts.

9. The method according to claim 1, in which the time period for one grain to pass in front of the LIBS detection system is less than 50 ms.

10. The method according to claim 1, in which the maximum spacing between the grains, when passing in front of the LIBS, is equal to their largest characteristic dimension.

11. The method according to claim 1, in which the grains, when passing in front of the LIBS, flow in a manner such that they are spaced apart by a distance in the range from zero to their largest characteristic dimension, the measurement frequency being in the range 1/t to 1/2t, t being the period of time for a grain to pass in front of the LIBS detection system.

12. The method according to claim 1, in which the grains are passed in front of the LIBS via a transport means and the LIBS is positioned in a manner such that the depth of the analysis field above the surface of the transport means is in the range 1/3 to 3 times the smallest characteristic dimension of the grain.

16. The method according to claim 6, in which the catalysts are in the form of cylindrical extrudates, beads, trilobes or multilobes.

17. The method according to claim 1, in which the time period for one grain to pass in front of the LIBS detection system is less than 10 ms.

13. A device for separating at least one catalyst from a mixture of homogeneously shaped catalysts, the catalysts being in the form of grains, the catalyst to be separated comprising W as a characteristic metal and the other catalysts of the mixture containing at least one metal selected from Ni, Co and Mo but not containing said characteristic metal W, said device comprising:

a Laser Induced Breakdown Spectroscopy (LIBS) detection system comprising at least one laser in front of which the catalyst grains pass, the detection time for the LIBS being less than 50 ms, and the detecting wavelength of the LIBS being that of the characteristic metal W, at least one analyser (8) and at least one control means (10),

a line for transporting the grains of the mixture of catalysts in front of the LIBS, the line being provided with a transport means, means for controlling the rate of flow of the grains onto said transport means and means for controlling the speed of said transport means, said transport means being regulated in a manner such that the maximum distance between the grains of catalyst when being transported in front of the LIBS is equal to the largest characteristic dimension of a grain and in that the period of time for a grain to pass in front of the LIBS detection means is less than 50 ms, and

at least one means for evacuating grains of the catalyst to be separated comprising said characteristic metal W and at least one means for evacuating grains of the other catalysts containing at least one metal selected from Ni, Co and Mo but not containing said characteristic metal W, said means for evacuating grains of catalyst to be separated being actuated from said control means when the characteristic metal is detected by the LIBS.

14. The device according to claim 13, in which the transport means is a ribbed belt, the depth of the ribs being in the range 0.7 to 1.3 times the largest characteristic dimension of the grains.

15. The device according to claim 13, in which the transport means is provided so that the grains flow in a manner such that their spacing is in the range from zero to their largest characteristic dimension, the measurement frequency being in the range 1/t to 1/2t, t being the period of time for a grain to pass in front of the LIBS detection system.

18. The device according to claim 13, wherein the detection time for the LIBS is less than 10 ms, and the period of time for a catalyst grain to pass in front of the LIBS detection means is less than 10 ms.

19. The device according to claim 13, wherein the device allows for separating at least one catalyst from a mixture of homogeneously shaped catalysts wherein the catalyst are in the form of cylindrical extrudates.