Process for the production of synthesis gas from hard coal

Patent metadata

Field	Value
Publication number	US-9677018-B2
Application number	US-201414760117-A
Country	US
Kind code	B2
Filing date	Jan 8, 2014
Priority date	Jan 9, 2013
Publication date	Jun 13, 2017
Grant date	Jun 13, 2017

Abstract

A process for the production of synthesis gas from coke is described herein. The process comprises the steps of: (a) subjecting hard coal to dry pyrolysis, resulting in the production of a gas mixture containing hydrogen, methane, nitrogen and carbon monoxide as major constituents and carbon sulphides as minor constituents; (b) subjecting the gas mixture to hydrogenation at a temperature in the range of 200 to 280° C. over a sulphidic cobalt molybdenum catalyst provided on an aluminium oxide carrier material; and (c) separating the hydrogen sulphide obtained from hydrogenation from the gas mixture.

First claim

What is claimed is:

1. A process for the production of synthesis gas from coke, comprising the steps of:
(a) subjecting hard coal to dry pyrolysis, resulting in the production of a gas mixture containing hydrogen, methane, nitrogen and carbon monoxide as major constituents and carbon sulphides as minor constituents;
(b) subjecting the gas mixture to hydrogenation at a temperature in the range of 200 to 280° C. over a sulphidic cobalt molybdenum catalyst provided on an aluminium oxide carrier material; and
(c) separating the hydrogen sulphide obtained from hydrogenation from the gas Mixture;
wherein the sulphidic cobalt molybdenum catalyst comprises at least 50%-mole molybdenum sulphide.

2. The process of claim 1 , wherein the hydrogenation of step (b) is carried out in a temperature range between 240 and 260° C.

3. The process of claim 1 , wherein the hydrogenation of step (b) is carried out at a pressure of 1 to 15 bar.

4. The process of claim 3 , wherein the hydrogenation of step (b) is carried out at a pressure of 5 to 10 bar.

5. The process of claim 1 , wherein the hydrogenation of step (b) is carried out at a GHSV of 500 to 15001 l/h.

6. The process of claim 1 , wherein cobalt molybdenum catalysts are used which do not contain any other transition metals.

7. The process of claim 1 , wherein cobalt molybdenum catalysts are used which, with reference to the metal components, predominantly consist of molybdenum sulphide and contain cobalt sulphide as a promoter only.

8. The process of claim 1 , wherein aluminium oxides of a high specific surface area are used as carriers for cobalt molybdenum catalysts, the aluminium oxides have:
(i) a minimum V 37A of at least between 70 ml/100 g and 90 ml/100 g;
(ii) a maximum V 0.1 μm of between 10 ml/100 g and 35 ml/100 gM;
(iii) a maximum V 0.2 μm of between 5 ml/100 g and 25 ml/100 g; and
(iv) a ratio of V 0.1 μm to V 0.2 μm of at least 1.5.

9. The process of claim 8 , wherein the aluminium oxides have:
(i) a minimum V 37A of at least 75 ml/100 g;
(ii) a maximum V 0.1 μm of 31 ml/100 gM; and
(iii) a maximum V 0.2 μm of 20 ml/100 g.

10. The process of claim 8 , wherein the aluminium oxides have:
(i) a minimum V 37A of at least 80 ml/100 g;
(ii) a maximum V 0.1 μm of 25 ml/100 g;
(iii) a maximum V 0.2 μm of 15 ml/100 g.

11. The process of claim 8 , wherein the aluminium oxides have:
(i) a minimum V 37A of at least 85 ml/100 g;
(ii) a maximum V 0.1 μm of 15 ml/100 g;
(iii) a maximum V 0.2 μm of 10 ml/100 g.

12. The process of claim 8 , wherein the aluminium oxides have:
(i) a minimum V 37A of at least 75 ml/100 g;
(ii) a maximum V 0.1 μm of 31 ml/100 gM; and
(iii) a maximum V 0.2 μm of 20 ml/100 g.

13. The process of claim 8 , wherein the aluminium oxides have:
(i) a minimum V 37A of at least 80 ml/100 g;
(ii) a maximum V 0.1 μm of 25 ml/100 g;
(iii) a maximum V 0.2 μm of 15 ml/100 g.

14. The process of claim 8 , wherein the aluminium oxides have:
(i) a minimum V 37A of at least 85 ml/100 g;
(ii) a maximum V 0.1 μm of 15 ml/100 g;
(iii) a maximum V 0.2 μm of 10 ml/100 g.

15. The process according of claim 1 , wherein the hydrogenation of step (b) is carried out in a fixed-bed reactor.

16. The process of claim 15 , wherein the catalysts used in the fixed-bed reactor are provided as one of bulk layer and packing.

17. The process of claim 16 , wherein the hydrogenation product, after leaving the reactor, is passed through an absorption column, where the hydrogen sulphide is washed out with a basic liquid.

18. A method for preparing hydrogen sulphide, wherein carbon sulphides are subjected to hydrogenation in the presence of a working amount of sulphidic cobalt molybdenum catalysts provided on aluminium oxide carriers, wherein the sulphidic cobalt molybdenum catalysts comprises at least 50%-mole molybdenum sulphide.

19. The method of claim 18 , wherein carbon sulphides are subjected to hydrogenation in the presence of cobalt molybdenum catalysts which, with reference to the metal components, predominantly consist of molybdenum sulphide and contain cobalt sulphide as a promoter only.

20. The method of claim 18 , wherein said aluminium oxide carriers have:
(i) a minimum V 37A of at least between 70 ml/100 g and 90 ml/100 g; (specific volume-ratio of volume to mass-volume occupied by mass of substance)
(ii) a maximum V 0.1 μm of between 10 ml/100 g and 35 ml/100 gM;
(iii) a maximum V 0.2 μm of between 5 ml/100 g and 25 ml/100 g; and
(iv) a ratio of V 0.1 μm to V 0.2 μm of at least 1.5.

Assignees

• Thyssenkrupp Ind Solutions Ag

Inventors

• Rieger Michael
• Schöneberger Jan
• Thielert Holger

Classifications

• B01J23/882

  and cobalt · CPC title

• C10B53/00

  Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form (wet carbonising of peat C10F) · CPC title

• B01J35/1042

  Operations & Transport · mapped topic

• C10K1/004 Primary

  Sulfur containing contaminants, e.g. hydrogen sulfide · CPC title

• C10B53/04

  of powdered coal · CPC title