SYSTEM AND METHOD FOR CO-PRODUCING ULTRA-HIGH PURITY OXYGEN AND ULTRA-HIGH PURITY HYDROGEN

Abstract

A system and method for co-producing ultra-high purity oxygen and ultra-high purity hydrogen from a water electrolysis unit is provided. The presently disclosed system and method includes upgrading the crude oxygen stream coming from the water electrolysis unit by means of a small, stand-alone cryogenic distillation system wherein the refrigeration for such cryogenic distillation system is supplied by a nitrogen recycle refrigeration loop.

Claims

1. A system for co-producing an ultra-high purity oxygen product stream and an ultra-high purity hydrogen product stream from a stream of feed water comprising: a water pre-purification subsystem configured to receive the stream of feed water and produce a purified, de-ionized water stream; one or more electrolysis units configured to receive the purified, de-ionized water stream and produce one or more crude oxygen streams and one or more crude hydrogen streams; an oxygen purification subsystem comprising a distillation column arrangement configured to separate argon and other impurities from the one or more crude oxygen streams and produce the ultra-high purity oxygen product stream; and a hydrogen purification subsystem configured to receive the one or more crude hydrogen streams and produce the ultra-high purity hydrogen product, the hydrogen purification subsystem comprising a deoxo catalyst for removing oxygen impurities from the one or more crude hydrogen streams to produce a hydrogen-rich effluent stream substantially free of oxygen and a hydrogen dryer configured for drying the hydrogen-rich effluent stream to produce the ultra-high purity hydrogen product.

2. The system for co-producing the ultra-high purity oxygen product stream and the ultra-high purity hydrogen product stream of claim 1, wherein the oxygen purification subsystem further comprises an oxygen dryer configured to remove water vapor from the one or more crude oxygen streams.

3. The system for co-producing the ultra-high purity oxygen product stream and the ultra-high purity hydrogen product stream of claim 2, wherein the oxygen dryer further comprises a temperature swing adsorption system configured to remove water vapor from the oxygen-rich effluent stream.

4. The system for co-producing the ultra-high purity oxygen product stream and the ultra-high purity hydrogen product stream of claim 3, wherein the temperature swing adsorption system further comprises one or more adsorbents or catalysts configured to remove carbon dioxide and/or other impurities from the oxygen-rich effluent stream.

5. The system for co-producing the ultra-high purity oxygen product stream and the ultra-high purity hydrogen product stream of claim 1 wherein the oxygen purification subsystem further comprises a catalyst or adsorbent subsystem configured for removing hydrogen from the one or more crude oxygen streams to produce an oxygen-rich effluent stream; and an oxygen dryer configured for drying the oxygen-rich effluent stream to produce a dried oxygen-rich effluent stream.

6. The system for co-producing the ultra-high purity oxygen product stream and the ultra-high purity hydrogen product stream of claim 1 wherein the distillation column arrangement further comprises: a distillation column configured to separate argon and other impurities of the dried oxygen-rich effluent stream by rectifying an ascending vapor stream and a descending liquid reflux stream to produce an ultra-high purity oxygen bottoms and an argon containing overhead stream extracted from the distillation column proximate a top section of the distillation column; a condenser disposed proximate the top section of the distillation column and configured for condensing a portion of the argon containing overhead stream against a liquid nitrogen stream to produce a nitrogen boil-off stream and the liquid reflux stream; a reboiler disposed proximate the bottom section of the distillation column and configured for reboiling a first portion of ultra-high purity oxygen bottoms against a cooled, expanded nitrogen recycle stream to produce the ascending vapor stream and the liquid nitrogen stream; and a main heat exchanger configured to cool the dried oxygen-rich effluent stream and cool a nitrogen recycle stream via indirect heat exchange with a second portion of ultra-high purity oxygen bottoms and the nitrogen boil-off stream from the condenser.

7. The system for co-producing the ultra-high purity oxygen product stream and the ultra-high purity hydrogen product stream of claim 6 wherein the distillation column subsystem further comprises: a recycle compressor configured for compressing the warmed boil-off stream to produce the compressed nitrogen recycle stream; the main heat exchanger configured to cool the compressed nitrogen recycle stream; and an expansion valve configured for expanding the cooled, compressed nitrogen recycle stream to produce the cooled, expanded nitrogen recycle stream.

8. The system for co-producing the ultra-high purity oxygen product stream and the ultra-high purity hydrogen product stream of claim 7 further comprising one or more turbines operatively coupled to a booster, a generator, an oil brake, or an air brake, the one or more turbines configured to produce refrigeration for liquid oxygen production.

9. The system for co-producing the ultra-high purity oxygen product stream and the ultra-high purity hydrogen product stream of claim 1 wherein the one or more crude oxygen streams further comprises a crude oxygen stream from a storage tank or a truck in addition to the one or more crude oxygen streams from the one or more electrolysis units.

10. The system for co-producing the ultra-high purity oxygen product stream and the ultra-high purity hydrogen product stream of claim 1 wherein the catalyst or adsorbent subsystem configured for removing hydrogen from the one or more crude oxygen streams to produce an oxygen-rich effluent stream further comprises a heater configured for heating the one or more crude oxygen streams, a catalytic oxidizer bed configured for receiving the heated crude oxygen streams and removing hydrogen and other volatile organic compounds therefrom to produce the oxygen-rich effluent stream.

11. The system for co-producing the ultra-high purity oxygen product stream and the ultra-high purity hydrogen product stream of claim 1 wherein the oxygen purification subsystem further comprises a separator and dryer configured to remove water and water vapor from the oxygen-rich effluent stream.

12. The system for co-producing the ultra-high purity oxygen product stream and the ultra-high purity hydrogen product stream of claim 1 wherein the water purification subsystem further comprises an aeration unit configured to remove dissolved gases from the de-ionized water stream to produce the purified, de-ionized water stream.

13. A method for co-producing an ultra-high purity oxygen product stream and an ultra-high purity hydrogen product stream from a stream of feed water comprising: purifying the stream of feed water to produce a purified, de-ionized water stream; directing the purified, de-ionized water stream to one or more electrolysis units configured to produce one or more crude oxygen streams and one or more crude hydrogen streams; separating argon and other impurities from the one or more crude oxygen streams in a distillation column arrangement configured to produce the ultra-high purity oxygen stream; removing oxygen impurities from the one or more crude hydrogen streams using a catalyst to produce a hydrogen-rich effluent stream substantially free of oxygen; and drying the hydrogen-rich effluent stream to produce the ultra-high purity hydrogen product stream.

14. The method of claim 13, further comprising the steps of: removing hydrogen from the one or more crude oxygen streams to produce an oxygen-rich effluent stream; and drying the oxygen-rich effluent stream to remove water vapor and produce a dried oxygen-rich effluent stream; wherein the distillation column arrangement is configured to receive the dried, oxygen-rich effluent stream and produce the ultra-high purity oxygen stream.

15. The method of claim 13, wherein the step of separating argon and other impurities from the dried, oxygen-rich effluent stream in a distillation column subsystem further comprises: rectifying the dried, oxygen-rich effluent stream against a descending liquid stream of reflux to produce an ultra-high purity oxygen bottoms and an argon containing overhead stream extracted from the distillation column proximate a top section of the distillation column; condensing argon containing overhead stream against a stream of liquid nitrogen to produce a nitrogen boil-off stream and the argon containing waste stream in a condenser disposed proximate the top section of the distillation column; reboiling a first portion of ultra-high purity oxygen bottoms against a nitrogen recycle stream in a reboiler disposed proximate the bottom section of the distillation column; cooling the dried, oxygen-rich effluent stream in a main heat exchanger via indirect heat exchange with a second portion of ultra-high purity oxygen bottoms; and cooling the nitrogen recycle stream in the main heat exchanger via indirect heat exchange with the nitrogen boil-off stream from the condenser.

16. The method of claim 15, further comprising the step of compressing the warmed nitrogen boil-off stream exiting the main heat exchanger using a recycle compressor to form the compressed nitrogen recycle stream.

17. The method of claim 13, further comprising the step of heating the one or more crude oxygen streams before the step of removing hydrogen in a catalyst or adsorbent subsystem to produce an oxygen-rich effluent stream.

18. The method of claim 13, wherein the step of drying the oxygen-rich effluent stream to produce a dried, oxygen rich effluent stream further comprises separating the oxygen-rich effluent stream to remove a condensate and then drying the resulting vapor stream to remove water vapor the oxygen-rich effluent stream.

19. The method of claim 13, wherein the step of purifying the stream of feed water further comprises degassing the de-ionized water stream in an aeration unit configured to remove dissolved gases from the de-ionized water stream to produce the purified, de-ionized water stream.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0014] It is believed that the claimed invention will be better understood when taken in connection with the accompanying drawings in which:

[0015] FIG. 1 shows a schematic of the present system and method for co-producing an ultra-high purity oxygen product stream and an ultra-high purity hydrogen product stream from an electrolysis system; and

[0016] FIG. 2 shows a detailed schematic of the process flow diagram of an embodiment of the cryogenic distillation subsystem suitable for use with the present system and method of FIG. 1.

DETAILED DESCRIPTION

[0017] The present system and method 10 for co-producing ultra-high purity oxygen and ultra-high purity hydrogen from a water electrolysis unit is schematically depicted in FIG. 1 and FIG. 2. A differentiating aspect of the present system and method is the upgrading of the crude oxygen stream coming from the water electrolysis unit by means of a small, stand-alone cryogenic distillation system and process where the refrigeration for such cryogenic distillation system and process is driven with a nitrogen recycle loop.

[0018] As seen in FIG. 1, feed water 12 is preferably pumped via water pump 14 to a water purification subsystem 16 where it is purified and de-ionized. The purified and de-ionized water 17 is directed to a water tank 18 that is arranged to feed the electrolysis unit 20. The electrolysis unit 20 can be a polymer electrolyte membrane (PEM) electrolysis unit but is preferably an alkaline electrolysis unit, as the alkaline electrolysis unit typically has lower capital costs than PEM electrolysis units and is capable of producing the crude oxygen stream at a higher outlet pressure. The electrolysis unit 20 separates the purified water into a crude hydrogen stream 30 and a crude oxygen stream 40.

[0019] The ultra-high purity hydrogen stream 35 is produced by subjecting the crude hydrogen stream 30 exiting the electrolysis unit 20 to a deoxo catalyst 32 configured for removing oxygen impurities from the crude hydrogen stream 30 to produce a hydrogen-rich effluent stream 33 substantially free of oxygen and a dryer 34 configured for drying the hydrogen-rich effluent stream substantially free of oxygen 33 to produce the ultra-high purity hydrogen product stream 35. The resulting ultra-high purity hydrogen stream 35 preferably has less than about 3.5 ppm nitrogen and less than about 1 ppm of each of the other common impurities including water, carbon dioxide, carbon monoxide, oxygen, argon, and other hydrocarbon impurities.

[0020] The ultra-high purity oxygen stream 60 is produced by subjecting the crude oxygen stream 40 exiting the electrolysis unit 20 to an optional electric heater (not shown) and then to catalyst system 42 configured for removing hydrogen impurities from the crude oxygen stream 40 to produce an oxygen-rich effluent stream 43 substantially free of hydrogen is then cooled in aftercooler 44 via indirect heat exchange with a cooling water circuit. Water is then removed from the cooled, oxygen-rich effluent stream 45 in a separator 46. The oxygen-rich vapor effluent 47 from the separator 46 is directed to a dryer 48 configured for drying the oxygen-rich vapor effluent stream 47 preferably using a heated nitrogen regen stream 92 that is heated in a regen heater 94. In some embodiments, the dryer could be configured as an adsorption system, such as a temperature swing adsorption system, configured to remove water vapor and carbon dioxide from the oxygen-rich effluent stream.

[0021] The dried, oxygen-rich vapor effluent stream 49 that may include approximately 1 ppm of argon, 1 ppm of hydrogen, and 2 ppm of nitrogen is then directed to a cryogenic distillation system 50 and the refrigeration for such cryogenic distillation is driven with a nitrogen recycle loop that includes a nitrogen recycle compressor 52 and aftercooler 54. A source of pressurized gaseous nitrogen 55 is used for the refrigeration circuits in the cryogenic distillation system 50. The resulting ultra-high purity oxygen stream 60 contains less than about 10 ppb argon, and more preferably less than about 5 ppb of argon. In addition, the ultra-high purity oxygen stream 60 exiting the cryogenic distillation system 50 has less than 10 ppb, and more preferably less than about 1 ppb, of nitrogen as well as less than 10 ppb, and more preferably less than about 1 ppb, of hydrogen.

[0022] As indicated above, the cryogenic distillation process used in purifying the crude oxygen stream 40 may be implemented using a relatively small, stand-alone cryogenic distillation system 50 without the need to integrate the cryogenic distillation system and process within a cold-box of a large air separation unit. The small, stand-alone cryogenic distillation system 50 and process is self-contained and generates its own refrigeration by means of a nitrogen recycle loop and produces the ultra-high purity oxygen stream 60 without the need for oxygen compression. Although turboexpanders may be used to generate the refrigeration needed by the small, stand-alone system, a lower-cost alternative using Joule-Thomson expansion valves to generate the required refrigeration is preferred.

[0023] Turning now to FIG. 2, a schematic process flow diagram of the small, stand-alone cryogenic distillation system 50 is shown. The dried, oxygen-rich vapor effluent 49 is fed through a main heat exchanger 70 where it is fully condensed against boiling ultra-high purity product oxygen 89. The resulting liquid oxygen stream 56 exiting the cold end of the main heat exchanger 70 is introduced into an intermediate location of the distillation column 80, approximately 20% of the column height below from the top of the distillation column 80. The rising vapor in the distillation column 80 carries the more volatile impurities such as argon, nitrogen, and hydrogen to the top of the distillation column 80. A fraction of the vapor may be vented to release impurities while the remaining overhead vapor 82 is condensed in condenser 90 and sent back to the distillation column 80 as liquid reflux 84 where it forms the descending liquid. Non-condensable impurities may also be vented as a vent stream 85 from the condensed reflux stream 84. The descending liquid becomes higher in oxygen purity as it descends the distillation column 80, and a portion of ultra-high purity liquid oxygen stream 89 is withdrawn at the bottom of the distillation column 80. The remaining ultra-high purity liquid oxygen 88 is reboiled in reboiler 95 against a nitrogen stream and sent up the distillation column as the ascending vapor.

[0024] The distillation column 80 consists of between 40 and 130 stages of separation, and more preferably between 80 and 130 stages of separation, for example about 90 stages of separation. The number of stages of separation in the distillation column 80 depends on the level of argon in the dried, oxygen-rich vapor effluent 49. For example, if one degasses the feed water using an aeration unit as part of the water purification system to reduce the argon level in the water, a smaller distillation column could be used to achieve the purity levels required for the ultra-high purity oxygen product. The ultra-high purity liquid oxygen stream 89 withdrawn at the bottom of distillation column 80 is boiled and warmed in the main heat exchanger 70 and supplied to the customer as an ultra-high purity oxygen product 60. The ultra-high purity oxygen product 60 is preferably produced at pressures between about 9 bar(a) and 11 bar(a) and the distillation column 80 also operates at similar pressures.

[0025] The refrigeration and driving force for the reboiler 95 and condenser 90 comes from a nitrogen recycle loop. The nitrogen recycle loop eliminates the need for oxygen compression which can add significant capital and operational cost to the present system 10 and also introduce complexity into the present system required to address safety considerations regarding oxygen compression. The recycle aspect of the nitrogen recycle loop minimizes the amount of nitrogen that has to be introduced into the process from an external source. As seen in FIG. 2, a pressurized gaseous nitrogen stream 72 at about 35 bar(a) enters the main heat exchanger 70 where it is cooled via indirect heat exchange against a returning nitrogen stream 79, the ultra-high purity liquid oxygen stream 89, and the dried, oxygen-rich vapor effluent stream 49. The cooled nitrogen stream 75 exits the main heat exchange 70 at an intermediate location before the cold end of the main heat exchanger 70. Nitrogen is supplied to the oxygen purification subsystem from an external source and is used for the regen flow 92 to the dryer as well as for the refrigeration circuit in the distillation column system 50.

[0026] Refrigeration for the process is generated by expanding the gas in a valve to a lower pressure of about 27 bar(a) using a Joule-Thomson expansion valve 74. The cooled, expanded nitrogen gas stream 75 is then fed into the reboiler 95 at the bottom of the distillation column 80 where is condensed against the boiling oxygen 88. The liquid nitrogen stream 76 exiting the reboiler 95 is then throttled via valve 77 to lower pressure of about 22 bar(a) in order to decrease its boiling point. This throttle nitrogen stream 78 is then fed into condenser 90 disposed at the top of the distillation column 80 where the throttle nitrogen stream 78 is boiled against the condensing oxygen stream 82. The gaseous nitrogen stream 79 leaving the condenser 90 is then warmed in the main heat exchanger 70 to near ambient temperature. The warmed nitrogen stream 51 is then combined with a small make up stream of pressurized gaseous nitrogen 55. The combined recycle stream 53 is then compressed in the recycle compressor 52 and cooled in aftercooler 54 to produce a cooled, compressed nitrogen stream 71. A portion of the compressed, cooled recycle stream is them recycled to the main heat exchanger 70 as the pressurized gaseous nitrogen stream 72.

[0027] While the present system and method for co-producing an ultra-high purity oxygen product and an ultra-high purity hydrogen product have been described with reference to a preferred embodiment, it is understood that numerous additions, changes, and omissions can be made without departing from the spirit and scope of the present inventions as set forth in the appended claims.

[0028] For example, one can design and operate a system that employs one or more electrolysis units each producing a crude oxygen stream and a crude hydrogen stream and wherein the oxygen purification subsystem, including the cryogenic distillation column system, is configured to process the one or more crude oxygen streams collectively. Similarly, the hydrogen purification subsystem may be configured to process the one or more crude hydrogen streams collectively or separately.