Method for producing hydrogen by reforming hydrocarbons using steam, combined with carbon dioxide capture and steam production

Patent metadata

Field	Value
Publication number	US-9580314-B2
Application number	US-201314651122-A
Country	US
Kind code	B2
Filing date	Oct 31, 2013
Priority date	Dec 13, 2012
Publication date	Feb 28, 2017
Grant date	Feb 28, 2017

Abstract

A method for producing hydrogen by reforming hydrocarbons using steam, combined with carbon dioxide capture and steam production, which involves mixing the hydrocarbons to be reformed with steam in order to produce a feedstock for reforming, generating a syngas; the syngas produced is cooled, enriched with H2 and CO2, and then cooled; the condensates of the method are separated from the syngas in order to be used in the method, the saturated syngas being treated by adsorption with pressure modulation so as to produce hydrogen and a gaseous effluent containing CO 2 that is captured in a CPU unit. The condensates from the cooling of the syngas at the outlet of the shift reactor are used in the method for producing impure steam supplying the mixing point; the CPU unit also produces CPU condensates that are recycled to be treated jointly with the condensates of the method.

First claim

The invention claimed is:

1. A process for producing hydrogen by reforming hydrocarbons using steam, combined with carbon dioxide capture and steam production, the process comprising the steps of:
a) mixing the hydrocarbons to be reformed with steam so as to produce a feedstock for reforming;
b) reforming the feedstock under conditions effective to produce a synthesis gas comprising hydrogen, carbon monoxide and also excess steam, carbon dioxide, residual methane, water and impurities from feedstock;
c) cooling the synthesis gas;
d) generating a synthesis gas enriched with H 2 and CO 2 by steam conversion of the CO contained in the cooled synthesis gas resulting from step c);
e) cooling the synthesis gas enriched with H 2 and CO 2 resulting from step d) by indirect heat exchange to a temperature at least below or equal to 60° C., so as to produce a saturated synthesis gas and a first condensates;
f) separating the first condensates from the saturated synthesis gas resulting from e);
g) treating the synthesis gas resulting directly or indirectly from step f) in a unit for hydrogen purification by pressure swing adsorption, so as to produce a stream of hydrogen having a purity of at least 99% and a stream of offgas containing at least 40% of CO 2 ;
h) treating the stream of PSA offgas resulting from step g) in a cryogenic purification unit (CPU) unit producing at least one stream of purified CO 2 and at least one stream of non-condensables;
i) treating all or part of the first condensates resulting from the process, wherein step i) further comprises the steps of:
k1) reducing the pressure of the first condensates to a pressure of between 1 and 5 bar(a);
k2) passing the first condensates through a deaerator in order to eliminate a part of the gases dissolved in the first condensates;
k3) pumping the first condensates at a pressure between 15 and 90 bar(a);
k4) preheating the first condensates under pressure at a temperature between 150 and 290° C.;
k5) vaporizing the first condensates under pressure at a temperature of between 200 and 300° C., so as to produce a stream of impure steam; and
k6) recycling the impure steam to step a) so as to be mixed with the hydrocarbons to be reformed; and
j) producing highly pure steam intended for export, wherein step j) further comprises the steps of:
v1) feeding a steam circuit associated with the process with demineralized water alone or mixed with the first condensates;
v2) preheating the water;
v3) vaporizing the preheated water against the synthesis gas originating from the reforming in a waste heat boiler so as to produce a stream of steam; and
v4) recycling a part of the steam to step a) so as to be mixed with the hydrocarbons to be reformed,

wherein treatment step h) also produces at least one stream of second condensates, and the second condensates are recovered and recycled into the process upstream of step k5) of vaporizing the first condensates.

2. The process as claimed in claim 1 , wherein the second condensates are mixed with the first condensates before the deaeration of the first condensates.

3. The process as claimed in claim 1 , wherein the second condensates are preheated and then mixed with the first condensates before the deaeration of the first condensates.

4. The process as claimed in claim 1 , wherein the second condensates are mixed with the first condensates after the deaeration but before the pumping of the first condensates.

5. The process as claimed in claim 1 , wherein the second condensates are mixed with the first condensates after the deaeration and the pumping but before the preheating of the first condensates.

6. The process as claimed in claim 1 , wherein the second condensates are mixed with the first condensates after the preheating of the first condensates.

7. The process as claimed in claim 1 , wherein the second condensates are preheated and then mixed with the first condensates after the preheating of the first condensates.

8. The process as claimed in claim 1 , further comprising the steps of washing the PSA offgas stream with water, thereby producing an impurity-loaded stream; and recycling the impurity-loaded liquid stream into the process upstream of step k5) of vaporizing the first condensates.

9. The process as claimed in claim 1 , wherein only a part of the demineralized water of step v1) is mixed with the first condensates.

10. The process as claimed in claim 1 , wherein all the demineralized water of step v1) is mixed with the first condensates.

11. A facility for producing hydrogen by reforming hydrocarbons using steam, combined with carbon dioxide capture and steam production, the facility comprising:
(i) a mixing point configured to mix the hydrocarbons to be reformed with steam so as to produce the feedstock for the reforming;
(ii) a reformer configured to produce a synthesis gas comprising essentially hydrogen, carbon monoxide and also excess steam, carbon dioxide, residual methane, water and impurities from the mixture resulting from step a);
(iii) at least one heat exchanger configured to cool the synthesis gas;
(iv) at least one shift reactor for steam conversion of the CO contained in the cooled synthesis gas resulting from the exchanger (iii);
(v) at least one heat exchanger configured to cool the synthesis gas enriched with H 2 and CO 2 produced by the shift reactor (iv) by indirect heat exchange to a temperature at least below or equal to 60° C., so as to produce a saturated synthesis gas and the first condensates;
(vi) a separator configured to separate the first condensates from the saturated synthesis gas resulting from the exchanger (v);
(vii) a unit for hydrogen purification by pressure swing adsorption for treating the synthesis gas resulting directly or indirectly from step (vi) and producing a stream of hydrogen having a purity of at least 99% and a stream of offgas containing at least 40% of CO 2 ;
(viii) a cryogenic purification unit (CPU) unit configured to treat the PSA offgas stream produced by the PSA unit (vii) and producing at least one stream of purified CO 2 and at least one stream of non-condensables,

and also means for treating all or part of the first condensates from the separator (vi) and comprising at least
(ix) a valve configured to reduce the pressure of the first condensates to a pressure of between 1 and 5 bar(a);
(x) a deaerator configured to eliminate a part of the gases dissolved in the first condensates;
(xi) a pump configured to pump the first condensates at a pressure of between 15 and 90 bar(a);
(xii) a heat exchanger configured to preheat the first condensates under pressure at a temperature of between 150 and 290° C.;
(xiii) a heat exchanger configured to vaporize the first condensates under pressure at a temperature of between 200 and 300° C., so as to produce a stream of impure steam, wherein the heat exchanger is in fluid communication with the mixing point such that the mixing point is configured to receive the stream of impure steam from the heat exchanger;
(xiv) a steam production circuit configured to produce steam, and at least:
(xv) a conduit configured to feed a circuit of steam associated with the process with demineralized water alone or mixed with the first condensates;
(xvi) a heat exchanger configured to preheat the water;
(xvii) a heat exchanger configured to vaporize the preheated demineralized water against the synthesis gas originating from the reforming in a waste heat boiler so as to produce a stream of steam; and
(xviii) a recycling conduit configured to recycle a part of the steam to step a) so as to be mixed with the hydrocarbons to be reformed;

wherein since the C

Assignees

• Air Liquide
• L'Air Liquide Société Anonyme Pour L'Étude Et L'Exploitation Des Procedes Georges Claude

Inventors

• Darde Arthur
• Leclerc Mathieu
• Morel Thomas

Classifications

• C01B2203/043

  Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration · CPC title

• C01B2203/0883

  by indirect heat exchange · CPC title

• Y02P30/30

  Cross-Sectional Technologies · mapped topic

• B01J19/245

  placed in series · CPC title

• C01B3/48 Primary

  followed by reaction of water vapour with carbon monoxide · CPC title