Catalytic hydrotreating of feedstocks

Patent metadata

Field	Value
Publication number	US-2023069301-A1
Application number	US-202017787834-A
Country	US
Kind code	A1
Filing date	Dec 18, 2020
Priority date	Dec 23, 2019
Publication date	Mar 2, 2023
Grant date	—

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

1 . A hydrotreatment process comprising:
a. providing in a reactor a liquid feedstock; 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; and wherein at least 90% 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.

2 . The hydrotreatment process of claim 1 , wherein the feedstock contains about 1-40 wt-% oxygen, and/or 5-40 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 320-370° C., and/or from a range 330-360° C.

5 . The hydrotreatment process of claim 1 , wherein the feedstock contains:
liquefied polymer waste, and the temperature is selected from a range 280-320° C., and/or from a range 290-310° C.

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

7 . The hydrotreatment process of claim 1 , wherein the feedstock contains:
liquefied polymer waste, and the pressure is selected from a range 70-90 bar, and/or from the range 75-85 bar.

8 . The hydrotreatment process of claim 6 , comprising:
Controlling wherein the pressure is controlled by feeding hydrogen gas into the reactor.

9 . The hydrotreatment process of claim 1 , wherein the hydrotreatment removes at least 50% of sulphur, at least 40% of nitrogen, and optionally at least 50% 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 MoS 2 microparticle slurry is used in an amount of 10 ppm-2 wt-%, based on an amount of Mo in the total amount of the reaction mixture in the reactor.

12 . The hydrotreatment process of claim 1 , wherein the feedstock contains liquefied polymer waste, and the MoS 2 microparticle slurry is used in an amount of 10 ppm-500 ppm, based on an amount of Mo in a total amount of a reaction mixture in the reactor.

13 . (canceled)

14 . The hydrotreatment process of claim 1 , wherein at least 90% of the micro particles have an aspect ratio of 0.40-1.0.

15 . 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.

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

17 . 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 vigorous stirring, the reaction mixture at a temperature of at least 180° C., such that a combination of temperature and pressure is sufficient for evaporating water in the reaction mixture.

18 . The process of claim 17 , 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).

19 . The process of claim 17 , wherein the H 2 S source is selected from at least one or more of:
dimethyl disulphide, dimethyl sulphide, disulphide, alkyl disulphide, polysulphide, di-tert-dodecyl polysulphide, mercaptan, n-butyl mercaptan, H 2 S gas, and/or any combination thereof.

20 . The process of claim 17 wherein an amount of H 2 S source and an amount of Mo precursor provides a molar excess of sulphur to molybdenum, which is at least one or more of: at least 4 mol S/mol Mo, at least 5 mol S/mol Mo, at least 6 mol S/mol Mo, at least 7 mol S/mol Mo, and/or 4-7 mol S/mol Mo, and/or 5-6 mol S/mol Mo.

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

• C10G2300/1003

  Waste materials · CPC title