Method for preparing hexadecahydropyrene

Patent metadata

Field	Value
Publication number	US-11111191-B2
Application number	US-201716464405-A
Country	US
Kind code	B2
Filing date	Nov 30, 2017
Priority date	Nov 30, 2016
Publication date	Sep 7, 2021
Grant date	Sep 7, 2021

Abstract

A method for preparing hexadecahydropyrene includes the step of carrying out the hydrogenation reaction to hydrocarbon oil containing pyrene compounds in the presence of a hydrogenation catalyst. The pyrene compounds are selected from at least one of pyrene and unsaturated hydrogenation products thereof. The hydrogenation catalyst contains a carrier and an active metal component loaded on the carrier. The active metal component is Pt and/or Pd and the carrier contains a small crystal size Y zeolite, alumina and amorphous silica-alumina. The small crystal size Y zeolite has an average grain diameter of 200-700 nm, a molar ratio of SiO2 to Al2O3 of 40-120, a relative crystallinity of ≥95%, and a specific surface area of 900-1,200 m2/g. The pore volume of secondary pores in 1.7-10 nm diameter is more than 50% of the total pore volume.

First claim

The invention claimed is:

1. A method for preparing hexadecahydropyrene, comprising:
hydrogenating a hydrocarbon oil raw material that contains pyrene compounds in the presence of a first hydrogenation catalyst in a first reactor;
hydrogenating an effluent from the first reactor in the presence of a second hydrogenation catalyst in a second reactor;
separating an effluent from the second reactor to obtain a product stream comprising hexadecahydropyrene;
cooling the product stream; and
separating hexadecahydropyrene from the cooled product stream,

wherein the pyrene compounds are selected from at least one of pyrene and unsaturated hydrogenation products thereof,
wherein each of the first hydrogenation catalyst and the second hydrogenation catalyst comprises a carrier and an active metal component loaded on the carrier,
wherein the active metal component is Pt, Pd, or Pt and Pd, the carrier comprises a small crystal size Y zeolite, alumina, and amorphous silica-alumina, wherein the small crystal size Y zeolite has an average grain diameter of 200-700 nm, a molar ratio of SiO 2 /Al 2 O 3 of 40-120, a relative crystallinity of ≥95%, a specific surface area of 900-1,200 m 2 /g, and a pore volume of secondary pores having 1.7-10 nm in diameter that accounts for 50% or more of a total pore volume, and
wherein a weight percentage of the active metal component in the first hydrogenation catalyst (x 1 ) is lower than a weight percentage of the active metal component in the second hydrogenation catalyst (x 2 ), and a weight percentage of the small crystal size Y zeolite in the first hydrogenation catalyst (y 1 ) is higher than a weight percentage of the small crystal size Y zeolite in the second hydrogenation catalyst (y 2 ), wherein x 1 and y 1 are based on a total weight of the first hydrogenation catalyst, and x 2 and y 2 are based on a total weight of the second hydrogenation catalyst.

2. The method according to claim 1 , wherein the average grain diameter of the small crystal size Y zeolite is 300-500 nm, the relative crystallinity is 95-120%, and the pore volume of secondary pores having 1.7-10 nm in diameter accounts for 50-80% of the total pore volume.

3. The method according to claim 1 , wherein the small crystal size Y zeolite has a lattice constant of 2.425-2.435 nm and a pore volume of 0.5-0.8 mL/g.

4. The method according to claim 1 , wherein both x 1 and x 2 are in a range of 0.1-2 wt %.

5. The method according to claim 1 , wherein (x 2 −x 1 ) is in a range of 0.1-1.5%, and (y 1 −y 2 ) is in a range of 5-35%.

6. The method according to claim 5 , wherein (x 2 −x 1 ) is in a range of 0.3-1.5%, and (y 1 −y 2 ) is in a range of 10-35%.

7. The method according to claim 1 , wherein conditions of the first reactor and the second reactor include: a partial pressure of hydrogen of 4-20 MPa; a liquid hourly space velocity of 0.05-6 h −1 ; a volume ratio of hydrogen to oil of 50-3,000; and an average reaction temperature of 150-380° C.

8. The method according to claim 1 , wherein the average reaction temperature in the second reactor is lower than the average reaction temperature in the first reactor by 10-150° C.

9. The method according to claim 8 , wherein the average reaction temperature in the first reactor is 180-380° C., and the average reaction temperature in the second reactor is 150-350° C.

10. The method according to claim 1 , wherein a content of the pyrene compounds in the hydrocarbon oil raw material is 0.5 wt % or more.

11. The method according to claim 1 , wherein the hydrocarbon oil raw material is a heavy distillate oil having an initial boiling point of 130-220° C. and a final boiling point of 300-400° C.

12. The method according to claim 11 , wherein the hydrocarbon oil raw material is a diesel distillate having an initial boiling point of 160-200° C. and a final boiling point of 300-350° C.

13. The method according to claim 1 , further comprising preparing the hydrocarbon oil raw material through a plurality of steps that comprise:
(1) pretreating a coal tar raw material;
(2) hydrofining the pretreated coal tar raw material;
(3) hydrocracking an effluent from the hydrofining reaction;
(4) separating an effluent from the hydrocracking reaction to obtain a liquid phase and a gas phase, then fractionating the liquid phase to obtain a fractionated heavy distillate, and using the fractionated heavy distillate as the hydrocarbon oil raw material.

14. The method according to claim 13 , wherein the coal tar raw material has an aromatic content of 20-100 wt %, a density of 1.023-1.235 g/cm 3 at 20° C., and a distillation range of 200-700° C.

15. The method according to claim 13 , wherein the coal tar raw material is a high-temperature coal tar or a remaining fraction obtained by extracting at least one of anthracene, phenanthrene, carbazole and fluoranthene from the high-temperature coal tar.

16. The method according to claim 13 , wherein step (1) includes pretreating the coal tar raw material by mechanical impurity removal, dehydration, and electrostatic desalting.

17. The method according to claim 13 , wherein conditions of the hydrofining reaction include: a hydrogen partial pressure of 3-19 MPa, an average reaction temperature of 260-440° C., a liquid hourly space velocity of 0.1-4 h −1 , and a volume ratio of hydrogen to oil of 300:1-3,000:1.

18. The method according to claim 13 , wherein conditions of the hydrocracking reaction include: a hydrogen partial pressure of 3-19 MPa, an average reaction temperature of 260-440° C., a liquid hourly space velocity of 0.3-4 h −1 , and a volume ratio of hydrogen to oil of 300:1-5,000:1.

19. The method according to claim 1 , wherein separating hexadecahydropyrene from the cooled product stream comprises filtration and extraction.

20. The method according to claim 1 , wherein, in the first hydrogenation catalyst and the second hydrogenation catalysts, based on a total weight of the carrier, a content of the small crystal size Y zeolite is 5-40 wt %, a content of the alumina is 10-40 wt %, and a content of the amorphous silica-alumina is 20-65 wt %.

21. The method according to claim 1 , wherein a yield of hexadecahydropyrene is 0.3% to 1.4%.

22. The method according to claim 1 , wherein a purity of hexadecahydropyrene is 98% or higher.

Assignees

• China Petroleum & Chem Corp
• Fushun Res Institute Of Petroleum And Petrochemicals Sinopec Corp

Inventors

• Sun Guoquan
• Fang Xiangchen
• Fan Hongfei
• Yao Chunlei
• Quan Hui

Classifications

• B01J2235/15

  X-ray diffraction · CPC title

• B01J35/80

  characterised by their amorphous structures · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J35/40

  characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) · CPC title