Process to prepare paraffins and waxes

Patent metadata

Field	Value
Publication number	US-10227533-B2
Application number	US-201615756202-A
Country	US
Kind code	B2
Filing date	Sep 1, 2016
Priority date	Sep 4, 2015
Publication date	Mar 12, 2019
Grant date	Mar 12, 2019

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.

First claim

That which is claimed is:

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 comp

Assignees

• Shell Oil Co

Inventors

• Bezemer Gerrit Leendert
• Boerrigter Harold
• Tan Hai Ming

Classifications

• C10G2/331

  containing group VIII-metals · CPC title

• C10G2300/1022

  Fischer-Tropsch products · CPC title

• C10G65/04

  including only refining steps · CPC title

• C10G45/02

  to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing · CPC title

• C10G45/00

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