Process and apparatus for the cryogenic separation of a mixture of carbon monoxide, hydrogen and methane for the production of CH4

Patent metadata

Field	Value
Publication number	US-11965694-B2
Application number	US-201916520878-A
Country	US
Kind code	B2
Filing date	Jul 24, 2019
Priority date	Jul 25, 2018
Publication date	Apr 23, 2024
Grant date	Apr 23, 2024

Abstract

In a process of the separation of a mixture of carbon monoxide, hydrogen and methane, the mixture is sent to a scrubbing column, a bottom liquid withdrawn at the bottom of the scrubbing column is depleted in hydrogen with respect to the mixture and is sent to a stripping column, a bottom liquid from the stripping column is sent to a separation column and a liquid enriched in methane withdrawn from the bottom of the separation column is vaporized in order to form a final product.

First claim

The invention claimed is:

1. A process for separation of a mixture comprising carbon monoxide, hydrogen and methane, the process comprising the steps of:
i) sending the mixture or a fluid derived from the mixture, after cooling to a cryogenic temperature in a heat exchanger, to a scrubbing column fed at a top portion with a liquid containing at least 80 mol % carbon monoxide or to at least one phase separator;
ii) withdrawing a bottom liquid at a bottom portion of the scrubbing column or of the phase separator or of one of the phase separators that is depleted in hydrogen with respect to the mixture and then sending the bottom liquid to a stripping column;
iii) withdrawing a gas at a top portion of the stripping column;
iv) sending a bottom liquid from the stripping column to a separation column that is configured to separate the bottom liquid into a top gas enriched in carbon monoxide and a liquid enriched in methane; and
v) withdrawing the liquid enriched in methane from a bottom portion of the separation column and then vaporizing the liquid enriched in methane in the heat exchanger in order to form gaseous methane,
wherein the gaseous methane is compressed in a compressor and a first part of the gaseous methane following compression is returned at the bottom of the separation column for separation therein, and a second part of the gaseous methane following compression is collected as a compressed methane product stream,
wherein the separation column has a top condenser cooled by a closed nitrogen cycle comprising a gaseous nitrogen compressor or by a closed carbon monoxide cycle comprising a gaseous carbon monoxide compressor,
wherein the first part of the gaseous methane following compression that is returned to the bottom of the separation column has the same methane concentration as the liquid enriched in methane withdrawn the bottom portion of the separation column.

2. The process according to claim 1 , in which the first part of the gaseous methane following compression is at a lower pressure than that of the compressed methane product stream.

3. The process according to claim 1 , wherein the liquid fed to the top portion of the scrubbing column comprises condensate formed from at least a part of a gas from the top portion of the scrubbing column.

4. The process according to claim 1 , in which the mixture contains nitrogen and in which the separation column produces, at the bottom portion, the liquid enriched in methane and depleted in carbon monoxide and, at the top portion, the top gas enriched in carbon monoxide.

5. The process according to claim 1 , in which the nitrogen cycle is used to reboil the stripping column.

6. The process according to claim 1 , in which a maximum pressure of the nitrogen or carbon monoxide cycle is less than the critical pressure of the nitrogen or the critical pressure of the carbon monoxide.

7. The process according to claim 1 , in which a maximum pressure of the nitrogen or carbon monoxide cycle is chosen so that a condensation temperature of nitrogen or carbon monoxide in the heat exchanger at the maximum pressure is within 10° C. warmer than a vaporization temperature of the liquid methane in the heat exchanger.

8. The process according to claim 1 , in which the mixture or the fluid derived from the mixture is used to reboil the stripping column.

9. The process according to claim 1 , in which the separation column operates at between 1.5 and 15 bars abs.

10. An apparatus for separation of a mixture comprising carbon monoxide, hydrogen and methane, the apparatus comprising:
a scrubbing column having a top portion and/or at least one phase separator;
a stripping column having a top portion and a bottom portion;
a separation column having a top portion and a bottom portion;
a heat exchanger;
means for sending the mixture to be cooled to a cryogenic temperature to the heat exchanger;
means for sending the cooled mixture or a fluid derived from said cooled mixture to the scrubbing column fed at the top portion with a liquid containing at least 80 mol % carbon monoxide and/or to at least one phase separator;
means for withdrawing a bottom liquid from the scrubbing column and/or the at least one phase separator, wherein the bottom liquid is depleted in hydrogen with respect to the mixture;
means for sending the withdrawn bottom liquid to the stripping column;
means for withdrawing a gas at the top portion of the stripping column;
means for sending a bottom liquid from the stripping column to the separation column, wherein the separation column is configured to separate the bottom liquid into a top gas enriched in carbon monoxide and a liquid enriched in methane;
means for withdrawing the liquid enriched in methane from the bottom of the separation column, wherein the means for withdrawing the liquid enriched in methane are in fluid communication with the heat exchanger in order to form gaseous methane;
a compressor;
means for sending the gaseous methane to the compressor; and
means for returning a part of the gaseous methane following compression in the compressor to the bottom portion of the separation column for separation therein,
wherein the separation column comprises a top condenser that is cooled by a closed refrigeration cycle, wherein the closed refrigeration cycle is selected from the group consisting of a closed nitrogen refrigeration cycle and a closed carbon monoxide refrigeration cycle,
wherein the part of the gaseous methane following compression that is returned to the bottom of the separation column has the same methane concentration as the liquid enriched in methane withdrawn the bottom portion of the separation column.

11. The apparatus according to claim 10 , wherein the closed refrigeration cycle comprises the closed nitrogen cycle comprising a gaseous nitrogen compressor.

12. The apparatus according to claim 10 , wherein the closed refrigeration cycle comprises the closed carbon monoxide cycle comprising a gaseous carbon monoxide compressor.

13. The apparatus according to claim 10 , in which the means for returning the part of the gas compressed in the compressor at the bottom portion of the separation column are connected to the heat exchanger.

14. The apparatus according to claim 10 , wherein the separation column comprises an absence of a reboiler.

15. The process according to claim 1 , wherein the separation column comprises an absence of a reboiler.

Assignees

• Air Liquide

Inventors

• Cortale Manon
• Demolliens Bertrand
• Hernandez Antoine
• Teixeira Guillaume

Classifications

• F25J3/0223 Primary

  H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas (production of carbon monoxide containing gas in general C01B32/40, C10J, C10K; production of hydrogen containing gas C01B3/00) · CPC title

• F25J3/0252

  separation of hydrogen (production of hydrogen containing gas in general C01B3/00, e.g. separation of hydrogen or hydrogen containing gases form gaseous mixtures at low temperatures C01B3/506) · CPC title

• F25J3/0257

  separation of nitrogen (from air F25J3/04, production of nitrogen in general C01B21/00) · CPC title

• F25J3/0261

  separation of carbon monoxide (production of carbon monoxide containing gas in general C01B32/40, C10J, C10K) · CPC title

• F25J3/0271

  separation of H2/CO mixtures, i.e. of synthesis gas (production of carbon monoxide containing gas in general C01B32/40, C10J, C10K, production of hydrogen containing gas C01B3/00) · CPC title