Parallel preparation of hydrogen, carbon monoxide and a carbon-comprising product

Patent metadata

Field	Value
Publication number	US-9834440-B2
Application number	US-201314652346-A
Country	US
Kind code	B2
Filing date	Dec 17, 2013
Priority date	Dec 21, 2012
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

The invention relates to a process for the parallel preparation of hydrogen, carbon monoxide and a carbon-comprising product, wherein one or more hydrocarbons are thermally decomposed and at least part of the pyrolysis gas formed is taken off from the reaction zone of the decomposition reactor at a temperature of from 800 to 1400° C. and reacted with carbon dioxide to form a gas mixture comprising carbon monoxide and hydrogen (synthesis gas).

First claim

The invention claimed is:

1. A process for the parallel preparation of hydrogen, carbon monoxide, and a carbon-comprising product, the process comprising:
thermally decomposing one or more hydrocarbons in a reaction zone of a decomposition reactor in the presence of a support, to produce a hydrogen-comprising gas mixture and a carbon-comprising product, wherein the carbon-comprising product comprises at least 95% by weight of carbon and the carbon-comprising product formed by the decomposition reaction is deposited to an extent of at least 90% by weight, based on the total mass of the carbon formed, on the support;
taking off at least part of the hydrogen-comprising gas mixture formed from the reaction zone of the decomposition reactor at a temperature of from 800° C. to 1400° C.; and
reacting, by reverse water gas shift reaction, the hydrogen-comprising gas mixture taken off with carbon dioxide at a temperature of 800° C. to 1500° C. in a RWGS reactor, to form a synthesis gas mixture comprising carbon monoxide and hydrogen, wherein the process heat required for the reaction of hydrogen with carbon dioxide to form the synthesis gas mixture is introduced to an extent of at least 50% by the hydrogen-comprising gas mixture fed in, such that methanation makes up less than 10% based on the carbon dioxide used.

2. The process according to claim 1 , wherein from 10 to 40% of the hydrogen-comprising gas mixture, based on the total hydrogen-comprising gas mixture formed in the thermal decomposition reaction, is taken off from the reaction zone of the decomposition reactor.

3. The process according to claim 1 , wherein the process heat required for the reaction of hydrogen with carbon dioxide to form the synthesis gas mixture is introduced to an extent of at least 80% by the hydrogen-comprising gas mixture fed in.

4. The process according to claim 1 , wherein the hydrogen-comprising gas mixture comprises more than 80% by volume of hydrogen.

5. The process according to claim 1 , wherein the a ratio of the total heat of reaction taken up by the thermal decomposition and the RWGS reaction to the total quantity of heat supplied to the process, of the heat integration is greater than 84%.

6. The process according to claim 1 , further comprising:
adding an oxygen-comprising gas to the hydrogen-comprising gas mixture taken off before the reaction with carbon dioxide, to provide an oxygen-hydrogen-comprising gas mixture.

7. The process according to claim 6 , wherein the reaction of the hydrogen-comprising gas mixture with carbon dioxide takes place in a reactor which, above the catalyst bed, has a gas-free space into which the hydrogen-comprising gas mixture and the oxygen-comprising gas are introduced together or separately and mix to provide the oxygen-hydrogen-comprising gas mixture, which may pre-react.

8. The process according to claim 6 , wherein the oxygen-comprising gas is added to the hydrogen-comprising gas mixture in a side offtake line between the decomposition reactor and the RWGS reactor, to provide the oxygen-hydrogen-comprising gas mixture.

9. The process according to claim 6 , wherein the hydrogen-comprising mixture comprises methane, and
wherein a molar ratio of oxygen to methane in the oxygen-hydrogen-comprising gas mixture of the side offtake is from 0.1 to 5.

10. The process according to claim 6 , wherein oxygen of technical grade purity is used as oxygen-comprising gas.

11. The process according to claim 1 , wherein, for a target molar ratio in the synthesis gas of hydrogen to carbon monoxide of 2:1, the molar ratio of carbon dioxide to hydrogen in the hydrogen-comprising gas mixture is 1:2 to 1:2.5.

12. The process according to claim 1 , wherein, for a target molar ratio in the synthesis gas of hydrogen to carbon monoxide of 1:1, the molar ratio of carbon dioxide to hydrogen in the hydrogen-comprising gas mixture is 1:1 to 1:1.5.

Assignees

• Basf Se

Inventors

• Kern Matthias
• Glenk Friedrich
• Klingler Dirk
• Bode Andreas
• Kolios Grigorios
• Schunk Stephan
• Wasserschaff Guido
• Bernnat Jens
• Zoels Bernd
• Schmidt Sabine
• Koenig Rene

Classifications

• C01B2203/0272

  containing a non-catalytic decomposition step · CPC title

• C10K3/026

  Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS] · CPC title

• C01B3/24 Primary

  of hydrocarbons · CPC title

• C01B2203/0283

  containing a CO-shift step, i.e. a water gas shift step · CPC title

• C01B31/18

  Chemistry & Metallurgy · mapped topic