Pyrolysis tar conversion

Patent metadata

Field	Value
Publication number	US-11162037-B2
Application number	US-201716467790-A
Country	US
Kind code	B2
Filing date	Dec 1, 2017
Priority date	Dec 16, 2016
Publication date	Nov 2, 2021
Grant date	Nov 2, 2021

Abstract

This invention relates to a process for determining the suitability of pyrolysis tar, such as steam cracker tar, for upgrading using hydroprocessing without excessive fouling of the hydroprocessing reactor. The invention includes establishing a reference activity for the thermally treating the pyrolysis tar to produce a treated tar having a lesser reactivity.

First claim

The invention claimed is:

1. A pyrolysis tar conversion process, comprising:
(a) providing a pyrolysis tar, wherein, at least 70 wt. % of the pyrolysis tar's components have a normal boiling point of at least 290° C., based upon the total weight of the pyrolysis tar;
(b) maintaining the pyrolysis tar within a temperature range of from T 1 to T 2 for time t HS to produce a pyrolysis tar composition having an Insolubles Content (IC) ≤6 wt. %, wherein T 1 is ≥150° C., T 2 is ≤320° C., and t HS is ≥1 minute;
(c) combining the pyrolysis tar composition with a sufficient amount of a utility fluid to produce a tar-fluid mixture having a 50° C. kinematic viscosity that is ≤500 cSt;
(d) determining a reactivity R M of the tar-fluid mixture and comparing R M to a predetermined reference activity R Ref of a hydroprocessing stage; and
(e) when:
(i) R M is ≤R Ref , producing a hydroprocessed tar by hydroprocessing at least a portion of the tar-fluid mixture in the hydroprocessing stage under Standard Hydroprocessing Conditions; and
(ii) R M is both >R Ref and ≤18 Bromine Number (“BN”), producing the hydroprocessed tar by hydroprocessing at least a portion of the tar-fluid mixture in the hydroprocessing stage under Mild Hydroprocessing Conditions.

2. The process of claim 1 , wherein the pyrolysis tar has an R T is in the range of from 29 BN to 45 BN, and the R M of the tar-fluid mixture is ≤17 BN.

3. The process of claim 1 , wherein ≥90 wt. % of the pyrolysis tar components have a normal boiling point ≥290° C., and the pyrolysis tar has a 50° C. kinematic viscosity ≥1×10 4 cSt and/or a density ≥1.1 g/cm 3 .

4. The process of claim 1 , wherein in the pyrolysis tar is a steam cracker tar having an insolubility number (I N ) >80.

5. The process of claim 1 , wherein R Ref is ≤11 BN.

6. The process of claim 1 , wherein the IC of the pyrolysis tar composition is ≤5 wt. %.

7. The process of claim 1 , wherein (i) hydroprocessed tar has a 15° C. density that is at least 0.10 g/cm 3 less than that of the pyrolysis tar, and (ii) the hydroprocessed tar has a 50° C. kinematic viscosity <200 cSt.

8. The process of claim 1 , further comprising blending the hydroprocessed tar to produce a fuel oil composition comprising <0.5 wt. % sulfur.

9. The process of claim 1 , wherein T 1 is ≥160° C. and T 2 is ≤310° C., and t HS is in the range of from 1 minute to 400 minutes.

10. The process of claim 1 , wherein T 1 is ≥180° C. and T 2 is ≤300° C., and t HS is in the range of from 5 minutes to 100 minutes.

11. The process of claim 1 , wherein T 1 is ≥200° C. and T 2 is ≤290° C., and t HS is in the range of from 5 minutes to 30 minutes.

12. The process of claim 1 , wherein R Ref is ≤12 BN, and wherein the temperature at which the pyrolysis tar is maintained is (i) constant at a temperature T HS during t Hs and (ii) T HS is at least 10° C. greater than T 1 .

13. The process of claim 1 , wherein step (e) further comprises:
(iii) when R M is >18, increasing T HS and/or t HS and repeating steps (c)-(e).

14. The process of claim 1 , wherein the utility fluid comprises ≥15 wt. % of combined two-ring and three-ring aromatic hydrocarbon compounds, and wherein the utility fluid has an A.S.T.M. D86 10% distillation point ≥60° C. and a 90% distillation point ≤425° C.

15. The process of claim 1 , wherein the hydroprocessing of step (e)(i) exhibits a 566° C.+ conversion of at least 20 wt. % continuously for at least ten days.

16. The process of claim 1 , wherein the hydroprocessed pyrolysis tar of step (e)(i) has a density measured at 15° C. that is at least 0.10 g/cm 3 less than that of the pyrolysis tar.

17. The process of claim 1 , wherein (i) the hydroprocessing of step (e)(i) and/or the hydroprocessing of step (e)(ii) is carried out in the presence of a catalytically effective amount of at least one catalyst, (ii) the catalyst comprises at least one metal from any of Groups 5 to 10 of the Periodic Table, and (iii) the catalyst comprises the metal in an amount in the range of from 0.005 grams to 0.3 grams per gram of catalyst.

18. The process of claim 1 , wherein the Standard Hydroprocessing Conditions include a temperature T S ≥200° C., a pressure P S ≥8 MPa, a weight hourly space velocity (“WHSV S ”, pyrolysis tar basis) ≥0.3 hr −1 , and a molecular hydrogen consumption rate C S in the range of 270 S m 3 /m 3 of molecular hydrogen per cubic meter of the pyrolysis tar (S m 3 /m 3 ) to 534 S m 3 /m 3 .

19. The process of claim 1 , wherein the Mild Hydroprocessing Conditions include a temperature T M that is ≥200° C. but less than T S , a pressure P M that is ≥8 MPa but less than P S , a WHSV M of the pyrolysis tar that is ≥0.3 hr −1 and greater than WHSV S , and a molecular hydrogen consumption rate (C M ) that is in the range of from 150 standard cubic meters of molecular hydrogen per cubic meter of the pyrolysis tar (S m 3 /m 3 ) to about 400 S m 3 /m 3 (845 SCF/B to 2250 SCF/B), but less than C S .

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Emanuele Krystle J
• Kandel Kapil
• Heeter Glenn A
• Yeh Jeffrey C
• Xu Teng

Classifications

• C10G1/02

  by distillation · CPC title

• C10G1/002

  in combination with oil conversion- or refining processes · CPC title

• C10G2300/302

  Viscosity · CPC title

• C10G69/06 Primary

  including at least one step of thermal cracking in the absence of hydrogen · CPC title

• C10G45/00

  Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds · CPC title