IP Library Granted Patent US 10,227,533
Granted Patent B2
US 10,227,533 · App. 15/756,202 · Granted Mar 12, 2019

Process to prepare paraffins and waxes

Inventors: Gerrit Leendert Bezemer (Amsterdam, NL); Harold Boerrigter (Amsterdam, NL); Hai Ming Tan (Amsterdam, NL)
Assignee: SHELL OIL COMPANY
C10G2/33B01D3/143C10G2/331C10G2/341C10G45/00C10G45/02C10G65/04C10G73/44B01D2256/24B01D2257/7022C10G2300/1022C10G2300/1085
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Quick Facts
Patent No.
US 10,227,533
App. No.
15/756,202
Granted
Mar 12, 2019
Kind
B2
Abstract

Paraffins and waxes are produced from a gaseous feed stream comprising hydrogen and carbon monoxide in a Fischer-Tropsch reactor using a fixed bed of reduced Fischer-Tropsch catalyst having cobalt as catalytically active metal. A nitrogen-containing compound is added to the gaseous feed stream in a concentration of up to 10 ppmV and the mixture if fed to the reactor to obtain paraffins having from 5 to 300 carbon atoms. The product is subjected to a hydrogenation step, to obtain a hydrogenated fraction comprising 5 to 300 carbon atoms. The hydrogenated product is separated into C5-C9, C10-C17, and C18-300 fractions. The C18-C300 fraction is separated to obtain one or more first light waxes having a congealing point in the range of 30 to 75° C. and a second heavy wax having a congealing point in the range of 75 to 120° C.

Claims (31)

1. A process for the preparation of paraffins and waxes from a gaseous feed stream comprising hydrogen and carbon monoxide in a Fischer-Tropsch reactor comprising a fixed bed of reduced Fischer-Tropsch catalyst that comprises cobalt as catalytically active metal, said process at least comprises the following steps:

(a) adding to the gaseous feed stream a nitrogen-containing compound such that the nitrogen-containing compound is present in the gaseous feed stream in a concentration of up to 10 ppmV to obtain a mixture, wherein the nitrogen-containing compound is a compound selected from the group consisting of ammonia, HCN, NO, amines, nitriles, and a heterocyclic compound containing at least one nitrogen atom as ring member of a heterocyclic ring;

(b) feeding the mixture of step (a) to the Fischer-Tropsch reactor to obtain a Fischer-Tropsch product comprising paraffins having from 5 to 300 carbon atoms;

(c) subjecting the Fischer-Tropsch product of step (b) to a hydrogenation step, thereby obtaining hydrogenated fraction comprising 5 to 300 carbon atoms;

(d) separating the hydrogenated Fischer-Tropsch product stream of step (c), thereby obtaining at least a fraction comprising 5 to 9 carbon atoms, a fraction comprising 10 to 17 carbon atoms and a fraction comprising 18 to 300 carbon atoms, wherein the fraction comprising 10 to 17 carbon atoms is separated into a fraction comprising 10 to 13 carbon atoms and a fraction comprising 14 to 17 carbon atoms;

(e) separating the hydrogenated fraction comprising 18 to 300 carbon atoms of step (d), thereby obtaining one or more first light waxes having a congealing point in the range of 30 to 75° C. and a second heavy wax having a congealing point in the range of 75 to 120° C.

2. The process according to claim 1 , wherein a nitrogen-containing compound other than molecular nitrogen is added to the gaseous feed stream in step (a) such that the nitrogen-containing compound is present in the gaseous feed stream in a concentration in the range of 0.05 to 10 ppmV.

3. The process according to claim 1 , wherein the nitrogen-containing compound is a compound selected from the group consisting of ammonia, HCN, NO, an amine and combinations of two or more thereof.

4. The process according to claim 3 , wherein the nitrogen-containing compound is ammonia.

5. The process according to claim 1 , wherein the amount of the fraction comprising 5 to 9 carbon atoms of step (e) is in the range of from 3-16 wt. % based on the full Fischer-Tropsch hydrocarbonaceous product comprising a C1 to C300 fraction.

6. The process according to claim 1 , wherein the amount of the fraction comprising 10 to 13 carbon atoms is in the range of from 3-12 wt. % and the amount of the fraction comprising 14 to 17 carbon atoms is in the range of from 3-11 wt. % based on the full Fischer-Tropsch hydrocarbonaceous product comprising a C1 to C300 fraction.

7. The process according to claim 1 , wherein one or more wax fractions having a congealing point in the range of 30 to 75° C. of step (e) are hydrofinished to obtain one or more hydrofinished wax fractions having a congealing point in the range of 30 to 75° C.

8. The process according to claim 7 , wherein the amount of hydrofinished wax fraction having a congealing point of 30° C. is in the range of from 2-8 wt % based on the full Fischer-Tropsch hydrocarbonaceous product comprising a C1 to C300 fraction.

9. The process according to claim 7 , wherein the amount of hydrofinished wax fraction having a congealing point of 50° C. is in the range of from 4-15 wt % based on the full Fischer-Tropsch hydrocarbonaceous product comprising a C1 to C300 fraction.

10. The process according to claim 7 , wherein the amount of hydrofinished wax fraction having a congealing point of 70° C. is in the range of from 6-20 wt % based on the full Fischer-Tropsch hydrocarbonaceous product comprising a C1 to C300 fraction.

11. A process for the preparation of process to prepare paraffins and waxes from a gaseous feed stream comprising hydrogen and carbon monoxide in a Fischer-Tropsch reactor comprising a fixed bed of reduced Fischer-Tropsch catalyst that comprises cobalt as catalytically active metal, said process at least comprises the following steps:

(a) adding to the gaseous feed stream a nitrogen-containing compound such that the nitrogen-containing compound is present in the gaseous feed stream in a concentration of up to 10 ppmV to obtain a mixture, wherein the nitrogen-containing compound is a compound selected from the group consisting of ammonia, HCN, NO, amines, nitriles, and a heterocyclic compound containing at least one nitrogen atom as ring member of a heterocyclic ring;

(b) feeding the mixture of step (a) to the Fischer-Tropsch reactor to obtain a Fischer-Tropsch product comprising paraffins having from 5 to 300 carbon atoms;

(c) subjecting the Fischer-Tropsch product of step (b) to a hydrogenation step, thereby obtaining hydrogenated fraction comprising 5 to 300 carbon atoms;

(d) separating the hydrogenated Fischer-Tropsch product stream of step (c), thereby obtaining at least a fraction comprising 5 to 9 carbon atoms, a fraction comprising 10 to 17 carbon atoms and a fraction comprising 18 to 300 carbon atoms;

(e) separating the hydrogenated fraction comprising 18 to 300 carbon atoms of step (d), thereby obtaining one or more first light waxes having a congealing point in the range of 30 to 75° C. and a second heavy wax having a congealing point in the range of 75 to 120° C., wherein the second heavy wax of step (e) is separated, thereby obtaining at least one distillate wax fraction having a congealing point in the range of between 75 to 85° C. and at least one residual wax fraction having a congealing point in the range of from 95 to 120° C.

12. The process according to claim 11 , the heavy distillate wax fraction having a congealing point in the range of between 75 to 85° C. is hydrofinished to obtain a hydrofinished heavy distillate wax fraction having a congealing point in the range of between 75 and 85° C.

13. The process according to claim 11 , wherein the heavy residual wax fraction having a congealing point in the range of 95 to 120° C. is hydrofinished to obtain a hydrofinished heavy residual wax fraction having a congealing point in the range of 95 to 120° C.

14. The process according to claim 11 , wherein a nitrogen-containing compound other than molecular nitrogen is added to the gaseous feed stream in step (a) such that the nitrogen-containing compound is present in the gaseous feed stream in a concentration in the range of 0.05 to 10 ppmV.

15. The process according to claim 11 , wherein the nitrogen-containing compound is a compound selected from the group consisting of ammonia, HCN, NO, an amine

and combinations of two or more thereof.

16. The process according to claim 11 , wherein the amount of the fraction comprising 5 to 9 carbon atoms of step (e) is in the range of from 3-16 wt. % based on the full Fischer-Tropsch hydrocarbonaceous product comprising a C1 to C300 fraction.

17. The process according to claim 11 , wherein the fraction comprising 10 to 17 carbon atoms is separated into a fraction comprising 10 to 13 carbon atoms and a fraction comprising 14 to 17 carbon atoms.

18. The process according to claim 17 , wherein the amount of the fraction comprising 10 to 13 carbon atoms is in the range of from 3-12 wt. % and the amount of the fraction comprising 14 to 17 carbon atoms is in the range of from 3-11 wt. % based on the full Fischer-Tropsch hydrocarbonaceous product comprising a C1 to C300 fraction.

19. The process according to claim 11 , wherein one or more wax fractions having a congealing point in the range of 30 to 75° C. of step (e) are hydrofinished to obtain one or more hydrofinished wax fractions having a congealing point in the range of 30 to 75° C.

20. The process according to claim 19 , wherein the amount of hydrofinished wax fraction having a congealing point of 30° C. is in the range of from 2-8 wt % based on the full Fischer-Tropsch hydrocarbonaceous product comprising a C1 to C300 fraction.

Assignments (2)
CHANGE OF NAME Recorded Mar 7, 2022
From: SHELL OIL COMPANY
To: SHELL USA, INC.
Reel/Frame 059694/0819 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 21, 2018
From: BEZEMER, GERRIT LEENDERT; BOERRIGTER, HAROLD; TAN, HAI MING
To: SHELL OIL COMPANY
Reel/Frame 045304/0474 →
Priority Claims (1)
EP 15183837 · Sep 4, 2015 · regional
Continuity (1)
Related Publication 20180251683A1 · Sep 6, 2018