Multistage upgrading hydrocarbon pyrolysis tar

Patent metadata

Field	Value
Publication number	US-10894925-B2
Application number	US-201816025736-A
Country	US
Kind code	B2
Filing date	Jul 2, 2018
Priority date	Jul 14, 2017
Publication date	Jan 19, 2021
Grant date	Jan 19, 2021

Abstract

A multi-stage process for upgrading tars is provided. A predominantly hydrotreating stage can be applied before a cracking stage, which can be a hydrocracking or a thermal cracking stage. Alternatively, a predominantly cracking stage, which can be a hydrocracking or a thermal cracking stage, can be applied before a hydrotreating stage. Apparatus suitable for performing the method is also provided.

First claim

What is claimed is:

1. A hydrocarbon conversion process, comprising:
(a) providing a feedstock comprising:
≥10.0 wt. % of pyrolysis tar hydrocarbon based on the weight of the feedstock, the pyrolysis tar hydrocarbon having a I N ≥100 and viscosity measured at 50° C. of ≥10,000 cSt, and
a utility fluid comprising aromatic hydrocarbons and having an ASTM D86 10% distillation point >60° C. and a 90% distillation point <425° C.;

(b) hydroprocessing the feedstock in a first hydroprocessing zone in the presence of a first treat gas comprising molecular hydrogen under first catalytic hydroprocessing conditions to produce a first hydroprocessed product having a vapor phase and a liquid phase;
(c) separating a vapor phase product and a liquid phase product from the first hydroprocessed product, wherein the vapor phase product comprises hydrogen sulfide and molecular hydrogen;
(d) hydroprocessing the liquid phase product in a second hydroprocessing zone in the presence of a second treat gas comprising molecular hydrogen under second catalytic hydroprocessing conditions to produce a second hydroprocessed product, wherein:
the first catalytic hydroprocessing conditions are such that in the first hydroprocessing zone a catalyst is used that promotes a hydrotreating reaction over a hydrocracking reaction at the same reaction conditions, and
the second catalytic hydroprocessing conditions are such that in the second hydroprocessing zone a catalyst is used that promotes a hydrocracking reaction over a hydrotreating reaction at the same reaction conditions; and

(e) contacting the vapor phase product with an amine solution to remove at least a portion of the hydrogen sulfide to produce a spent amine stream and a gas effluent comprising the molecular hydrogen.

2. The process of claim 1 , in which the catalyst in the first hydroprocessing zone comprises Mo, Co, or Ni supported on alumina; Pt—Pd/Al 2 O 3 —SiO 2 ; Ni—W/Al 2 O 3 ; Ni—Mo/Al 2 O 3 ; Fe or Fe—Mo supported on a non-acidic support; or Mo supported on a non-acidic support; and the catalyst in the second hydroprocessing zone comprises a zeolite or Co, Mo, P, Ni or Pd supported on amorphous Al 2 O 3 and/or amorphous SiO 2 and/or a zeolite.

3. The process of claim 1 , in which the catalyst in the first hydroprocessing zone comprises Ni—Co—Mo/Al 2 O 3 and the catalyst in the second hydroprocessing zone comprises Co—Mo/Al 2 O 3 .

4. The process of claim 1 , in which the temperature in the first hydroprocessing zone ranges from 200-425° C. and the temperature in the second hydroprocessing zone ranges from 350-425° C.

5. The process of claim 1 , in which the pyrolysis tar hydrocarbon has an I N ≥105, a viscosity ≥15,000 cSt measured at 50° C., ≥10.0 wt. % of molecules having an atmospheric boiling point ≥565° C. that are not asphaltenes, and ≤1.0×10 3 ppmw metals.

6. The process of claim 1 , in which the hydroprocessing conditions within the first hydroprocessing zone and the second hydroprocessing zone comprise a pressure of 800-1800 psig.

7. The process of claim 1 , in which the weight hourly space velocity (WHSV) of the feedstock through the first hydroprocessing zone and the second hydroprocessing zone is from 0.5 hr −1 to 4.0 hr −1 .

8. The process of claim 1 , in which the utility fluid comprises ≥25% by weight of ring aromatics and the utility fluid has a SBN of ≥100.

9. The process of claim 1 , wherein (i) the hydroprocessing is conducted continuously in the first and second hydroprocessing zones from a first time t 1 to a second time t 2 , t 2 being ≥(t 1 +80 days) and (ii) the pressure drop in either hydroprocessing zone at the second time is increased ≤10.0% over the pressure drop at the first time.

10. The process of claim 1 , wherein the catalyst in the first hydroprocessing zone promotes the hydrotreating reaction at a reaction rate that is ≥1.1 times a reaction rate of a hydrocracking reaction at the same reaction conditions, and wherein the catalyst in the second hydroprocessing zone promotes the hydrocracking reaction at a reaction rate that is ≥1.1 times a reaction rate of a hydrotreating reaction at the same reaction conditions.

11. The process of claim 1 , wherein the catalyst in the first hydroprocessing zone promotes the hydrotreating reaction at a reaction rate that is ≥2 times a reaction rate of a hydrocracking reaction at the same reaction conditions, and wherein the catalyst in the second hydroprocessing zone promotes the hydrocracking reaction at a reaction rate that is ≥2 times a reaction rate of a hydrotreating reaction at the same reaction conditions.

12. The process of claim 1 , wherein the catalyst in the first hydroprocessing zone promotes the hydrotreating reaction at a reaction rate that is ≥5 times a reaction rate of a hydrocracking reaction at the same reaction conditions, and wherein the catalyst in the second hydroprocessing zone promotes the hydrocracking reaction at a reaction rate that is ≥5 times a reaction rate of a hydrotreating reaction at the same reaction conditions.

13. The process of claim 1 , further comprising contacting the vapor phase product with water to remove a first portion of the hydrogen sulfide to produce a sour water and a first hydrogen sulfide lean vapor phase product, wherein the first hydrogen sulfide lean vapor phase product is contacted with the amine solution to remove a second portion of the hydrogen sulfide.

14. The process of claim 1 , further comprising contacting the liquid phase product with a stripping gas to form a stripped product, wherein the stripped product is hydroprocessed in the second hydroprocessing zone.

15. A hydrocarbon conversion process, comprising:
(a) providing a feedstock comprising:
≥10.0 wt. % of pyrolysis tar hydrocarbon based on the weight of the feedstock, the pyrolysis tar hydrocarbon having a I N <105 and viscosity measured at 50° C. of <15,000 cSt, and
a utility fluid comprising aromatic hydrocarbons and having an ASTM D86 10% distillation point >60° C. and a 90% distillation point <425° C.;

(b) hydroprocessing the feedstock in a first hydroprocessing zone in the presence of a first treat gas comprising molecular hydrogen under first catalytic hydroprocessing conditions to produce a first hydroprocessed product having a vapor phase and a liquid phase; and
(c) hydroprocessing at least a portion of the first hydroprocessed product in a second hydroprocessing zone in the presence of a second treat gas comprising molecular hydrogen under second catalytic hydroprocessing conditions to produce a second hydroprocessed product, wherein:
the first catalytic hydroprocessing conditions are such that in the first hydroprocessing zone a catalyst is used that promotes a hydrocracking reaction over a hydrotreating reaction at the same reaction conditions, and
the second catalytic hydroprocessing conditions are such that in the second hydroprocessing zone a catalyst is used that promotes a hydrotreating reaction over a hydrocracking reaction at the same reaction conditions.

16. The process of claim 15 , in which the catalyst in the first hydroprocessing zone comprises a zeolite or Co, Mo, P, Ni, or Pd supported on amorphous alumina and/or amorphous SiO 2 and/or a zeolite; and the catalyst in the second hydroprocessing zone comprises Mo, Co, or Ni supported on alumina; Pt—Pd/Al 2 O 3 —SiO 2 ; Ni—W/Al 2 O 3 ; Ni—Mo/Al 2 O 3 ; Fe or Fe—Mo supported on a non-acidic support; or Mo supported on a non-acidic support.

17. The process of claim 15 , in which the catalyst in the first hydroprocessing zone comprises Co—Mo/Al 2 O 3 and the catalyst in the s

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Kandel Kapil
• Patel Bryan A
• Raman Sumathy
• Coleman John S
• KOC-KARABOCEK Reyyan
• Xu Teng
• Rachal Cyrus J
• Nayak Subramanya V

Classifications

• C10G2300/4006

  Temperature · CPC title

• C10G2300/302

  Viscosity · CPC title

• C10G2300/301

  Boiling range · CPC title

• C10G2300/206

  Asphaltenes · CPC title

• C10G65/02

  plural serial stages only · CPC title