Catalytic hydrotreating of feedstocks

Patent metadata

Field	Value
Publication number	US-12275896-B2
Application number	US-202017787834-A
Country	US
Kind code	B2
Filing date	Dec 18, 2020
Priority date	Dec 23, 2019
Publication date	Apr 15, 2025
Grant date	Apr 15, 2025

Abstract

A process for hydrotreating recycled or renewable feedstocks with a catalytic microparticle slurry, and a process for manufacturing the catalytic microparticle slurry, are disclosed.

First claim

The invention claimed is:

1. A hydrotreatment process comprising:
a. providing in a reactor a liquid feedstock; and
b. hydrotreating the liquid feedstock in liquid phase and at a temperature selected from a range 280-380° C. in a presence of catalytic MoS 2 microparticle slurry, to provide a liquid reaction product with decreased heteroatom content; wherein:
at least 90 wt % of catalytic MoS 2 microparticles in the MoS 2 microparticle slurry have a size below 7 μm, wherein the size of a microparticle is expressed as an average of the longest dimension and the shortest dimension of the microparticle,
at least 90 wt % of the microparticles have an aspect ratio of 0.40-1.0, and
the MoS 2 microparticle slurry is used in an amount of 10 ppm-500 ppm, based on a total weight amount of a reaction mixture in the reactor.

2. The hydrotreatment process of claim 1 , wherein the feedstock contains about 1-40 wt % oxygen.

3. The hydrotreatment process of claim 1 , wherein the feedstock contains at least one or more of:
crude tall oil, tall oil pitch, crude fatty acid, tall oil fatty acid, distilled tall oil, liquefied lignocellulosic biomass, bio-oil, biocrude, liquefied waste polymer, and/or a combination thereof.

4. The hydrotreatment process of claim 1 , wherein the temperature is selected from a range of 320-370° C.

5. The hydrotreatment process of claim 1 , wherein the feedstock contains:
liquefied polymer waste, and the temperature is selected from a range of 280-320° C.

6. The hydrotreatment process of claim 1 , wherein the hydrotreating step is carried out at a pressure selected from a range of 70-200 bar such that the feedstock is in liquid phase.

7. The hydrotreatment process of claim 6 , comprising:
controlling the pressure by feeding hydrogen gas into the reactor.

8. The hydrotreatment process of claim 1 , wherein the feedstock contains:
liquefied polymer waste, and the pressure is selected from a range of 70-90 bar.

9. The hydrotreatment process of claim 1 , wherein the hydrotreatment removes at least 50 wt % of sulphur, at least 40 wt % of nitrogen, and optionally at least 50 wt % of oxygen from the feedstock.

10. The hydrotreatment process of claim 1 , wherein the catalytic MoS 2 microparticles are provided in at least partially crystalline form in the reactor.

11. The hydrotreatment process of claim 1 , wherein the liquid reaction product predominantly contains hydrocarbons having a maximum boiling point of 565° C. at atmospheric pressure.

12. The hydrotreatment process of claim 1 , wherein the process is carried out in a stirred tank reactor.

13. The hydrotreatment process of claim 1 , wherein the catalytic MoS 2 microparticle slurry has below 5 wt % molybdenum based on a total weight of the catalytic MoS 2 microparticle slurry.

14. A process for manufacturing catalytic molybdenum sulphide microparticles comprising:
a. providing in a hydrocarbon solvent a Mo precursor and a H 2 S source to provide a reaction mixture; and
b. hydrogenating, under stirring, the reaction mixture at a temperature of at least 180° C. to form a hydrogenated reaction mixture, such that a combination of temperature and pressure is sufficient for evaporating water in the reaction mixture,
wherein at least 90 wt % of the catalytic molybdenum sulphide microparticles manufactured from the process have a size below 7 μm, wherein the size of a microparticle is expressed as an average of the longest dimension and the shortest dimension of the microparticle, and
wherein the hydrogenated reaction mixture contains the Mo precursor in an amount ranging from 2.4-6.2 wt % based on a total amount of the hydrogenated reaction mixture.

15. The process of claim 14 , wherein the Mo precursor is selected from at least one or more of:
molybdenum 2-ethyl hexanoate, carboxylate anion of 3-cyclopentylpropionic acid, cyclohexanebutyric acid, biphenyl-2-carboxylic acid, 4-heptylbenzoic acid, 5-phenylvaleric acid, and/or geranic acid (3,7-dimethyl-2,6-octadienoic acid).

16. The process of claim 14 , wherein the H 2 S source is a polysulphide.

17. The process of claim 14 , wherein an amount of H 2 S source and an amount of Mo precursor provides a molar excess of sulphur to molybdenum, which is 4-7 mol S/mol Mo.

18. The process of claim 14 , wherein the H 2 S source is selected from at least one or more of:
a disulphide, di-tert-dodecyl polysulphide, a mercaptan, H 2 S gas, and/or any combination thereof.

Assignees

• Neste Oyj

Inventors

• Lamminpää Kaisa
• Lindblad Marina
• Seläntaus Maaria
• Isokoski Kaija
• Tiitta Marja
• Sairanen Emma
• Paasikallio Ville

Classifications

• B01J2235/10

  Infrared [IR] · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• C10G2300/70

  Catalyst aspects · CPC title