METHOD FOR COMPOSITIONAL SORTING OF CATALYST OR ADSORBENT IN MIXTURES OF CATALYSTS AND/OR ADSORBENTS

Abstract

A method for separation of at least one catalyst or adsorbent from a homogeneous mixture of catalysts or adsorbents, used in a method for treatment of gas or hydrocarbon feedstock, in which the grains of catalysts or adsorbents are separated according to a sorting threshold corresponding to a content of the constituent element that is sought and defined by the user.

Claims

1. Method for separation of at least one catalyst or adsorbent from a homogeneous mixture of catalysts and/or adsorbents, with said catalysts or adsorbents having been used in a method for treatment of gas or hydrocarbon feedstock, method in which the catalyst grains or adsorbents are separated according to a sorting threshold corresponding to a content of the constituent element that is sought and defined by the user, method in which: The catalyst to be separated contains as a constituent element a non-metal element, preferably selected from the group that is formed by P, B, Si, Li, Na, K, Ca, Cl and/or that contains as a constituent element Cr, Cu, Al, Ti, Zn, The catalyst grains of said mixture run past an LIES detection system that detects the wavelength that is characteristic of said constituent element, The analyzing device associated with LIES processes the signal sent by the detection system by comparing it to a set-point value that indicates the sorting threshold, The analyzing device sends a signal to order the evacuation of grains according to the content thereof in said element, and at least 2 batches are obtained: at least one batch of catalysts heavily loaded with said element in relation to the sorting threshold and at least one batch of catalysts lightly loaded with said element in relation to the sorting threshold, And at least one of the batches of catalysts that are lightly loaded with said element is recycled into the gas or hydrocarbon batch treatment method after possible regeneration.

2. Method according to claim 1, in which the sorting threshold is 0%.

3. Method according to claim 1, in which the hydrocarbon feedstock treatment method is selected from the group that is formed by hydrotreatment, hydrocracking, dehydrogenation, hydroconversion of distillates, hydrogenation, isomerization, reforming, and the gas treatment is selected from the group that is formed by the Claus method and tail gas treatments.

4. Method according to claim 1, in which the catalysts are spent hydrotreatment and/or hydrocracking catalysts, whose substrate consists of alumina or silica-alumina with the optional presence of zeolite.

5. Method according , in which the catalysts come in a homogeneous form, preferably in the form of cylindrical extrudates, balls, trilobes, or multilobes.

6. Method according to claim 1, in which the number of grains detected/analyzed at least 100 per second for a detection time of less than 10 ms.

7. Method according to claim 1, in which the spacing between the grains is less than or equal to the mean length of the grains.

8. Method according to claim 1, in which the sorting threshold for P is between 1 and 2% by weight of P.

9. Method according to claim 1 , in which the sorting threshold for B is between 0.5 and 2% by weight of B.

10. Method according to claim 1, in which the sorting threshold for Cr is between 3 and 6% by weight of Cr.

11. Method according to claim 1, in which the sorting threshold for Si is between 1 and 3% by weight.

12. Method according to claim 1, in which the sorting threshold for Na is between 0.5 to 2% by weight.

Description

EXAMPLES

Example 1

Sorting of a Batch of a Mixture of NiMoPB and NiMoP Catalysts

[0164] Two catalysts of the NiMoPB and NiMoP types were mixed. 40 grains of a mixture were analyzed by LIBS to determine the presence or the absence of boron in these catalyst grains. An LIBS laboratory device (MobiLIBS III, IVEA) was used for this test and consists of a laser (Brio, Quantel, Nd-YAG at 532 nm) and a spectrometer (Mechelle Andor, 200-900 nm). A single laser shot was required, and each catalyst grain was analyzed under the following conditions: 12 mJ/spot of 140 m/3-5 ns of pulse time. The doublet of the lines of B with a wavelength of 249.772 and 249.677 nm was used. A signal close to 2,000 hits on the line at 249.772 nm and a bit lower on the second line is observed in 43% of the grains being analyzed.

[0165] In the small quantity of material harvested during this sorting, 100 mg of each of the two categories formed by the sorting was mineralized under cold conditions for metering by ICP/OES (ICP Spectro Arcos). The mean boron content on the grains generating a signal of 2,000 hits on the line at 249.772 nm is 1,500 mg/kg whereas boron is not detected in the mineralizate formed by the grains having provided no boron signal. The sorting carried out on the basis of the detection of B on the doublet 249.772 and 249.677 nm is therefore effective for distinguishing the catalyst grains that may or may not contain boron.

Example 2

Mixture of NiMoP and Zeolitic Catalysts, Selection by Si

[0166] In the same way as the preceding example, 40 grains of two families of catalysts have been subjected to LIBS analysis. It is a matter of a catalyst with an NiMoP-type alumina substrate. The second catalyst is a zeolitic catalyst that essentially contains a ZSMS zeolite and an aluminum binder, and it contains between 30 and 40% Si.

[0167] The LIBS system that is used is equipped with a laser (Centurion, 1064 nm, 100 Hz) and a spectrometer with high acquisition frequency (HR2000+, grating at 1,200 lines/mm, resolution of 0.18 nm for the 180-350 nm zone). The sorting was carried out on the basis of the presence or absence of the Si line at 280.308 nm, a signal of more than 20,000 hits being visible when the catalyst grain is a catalyst that contains zeolite.

[0168] The LIBS technique readily makes it possible to differentiate a batch of catalysts containing an NiMoP/alumina and zeolitic catalyst mixture.