METHOD FOR PRODUCING A GASEOUS FLOW USING A STORAGE TANK

Abstract

A process for producing a purified gas stream having impurities, using a production unit for producing a gas stream and a storage reservoir. The process includes producing a first gas stream by means of the production unit. Storing at least a portion of the first gas stream in the storage reservoir. Extracting, from the storage reservoir, a second gas stream corresponding to at least one portion of the first stream polluted by the impurities. Purifying the second gas stream by transfer of at least one portion of the impurities contained in the second gas stream into the first gas stream. And recovery of the purified gas stream at the output of the purification.

Claims

1.-15. (canceled)

16. A process for producing a purified gas stream comprising impurities, using a production unit for producing a gas stream and a storage reservoir, the process comprising: a) producing a first gas stream by means of the production unit, b) storing at least a portion of the first gas stream in the storage reservoir, c) extracting, from the storage reservoir, a second gas stream corresponding to at least one portion of the first stream polluted by the impurities, d) purifying the second gas stream by transfer of at least one portion of the impurities contained in the second gas stream into the first gas stream, and e) recovery of the purified gas stream at the output of the purification.

17. The process according to claim 16, further comprising extracting a third gas stream.

18. The process as claimed in claim 16, wherein the storage reservoir is an above-ground storage reservoir or an underground storage reservoir, which is natural or artificial.

19. The process as claimed in claim 18, wherein the above-ground storage reservoir is a constant volume and variable pressure reservoir or a variable volume and constant pressure reservoir.

20. The process as claimed in claim 16, wherein the impurities contained in the storage reservoir are located on the walls of said reservoir and/or in the system for sealing said reservoir and/or in additional equipment associated with the reservoir.

21. The process as claimed in claim 16, wherein the purification of step d) is carried out by adsorption, absorption or permeation.

22. The process as claimed in claim 16, wherein the purification of step d) is carried out by adsorption by means of an adsorbent mass and comprises two sub-steps: a first sub-step i) comprising the co-current passage of the second gas stream through the adsorbent mass so as to remove at least one portion of the impurities contained in the second gas stream, and a second sub-step ii) comprising the passage in counter-current mode of the first gas stream through the adsorbent mass resulting from the first sub-step i) so as to desorb at least one portion of the impurities.

23. The process as claimed in claim 22, wherein the difference in inlet temperature of the first gas stream and the second gas stream in the absorbent mass is less than 50 C.

24. The process as claimed in claim 22, wherein a volume flow rate of the second gas stream represents less than 90% of a volume flow rate of the first gas stream.

25. The process as claimed in claim 22, wherein: a single adsorbent mass is used in step d) and alternately undergoes passage of the first gas stream and the second gas stream; and the second gas stream is batchwise so as to have no extraction of a second gas stream in the reservoir when the adsorbent mass undergoes passage of the first gas stream.

26. The process as claimed in claim 25, wherein the first gas stream is batchwise so as to have no storage of the first gas stream in the reservoir when the adsorbent mass undergoes passage of the second gas stream.

27. The process as claimed in claim 16, wherein the first gas stream comprises at least 50% hydrogen or helium and the reservoir is an above-ground constant volume storage reservoir or an underground storage reservoir;

28. The process as claimed in claim 17, wherein: the first gas stream comprises at least 50% of oxygen originating from at least one adsorber of a unit for separating gases from air by adsorption; the second gas stream makes it possible to regenerate at least one adsorber of said unit for separating gases from air; the third gas stream constitutes the oxygen-enriched production stream of said unit for separating gases from air and comprises the impurities from the storage reservoir.

29. The process as claimed in claim 28, wherein the purification of step d) is carried out by adsorption by means of an adsorbent mass and comprises two sub-steps: a first sub-step i) comprising the co-current passage of the second gas stream through the adsorbent mass so as to remove at least one portion of the impurities contained in the second gas stream, and a second sub-step ii) comprising the passage in counter-current mode of the first gas stream through the adsorbent mass resulting from the first sub-step i) so as to desorb at least one portion of the impurities, with the adsorbent mass comprising activated alumina and/or silica gel and/or a zeolite.

30. The production process as claimed in claim 18, wherein the impurities are essentially water and/or carbon dioxide.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0043] For a further understanding of the nature and objects for the present invention, reference should be made to the following detailed description, taken in conjunction with the accompanying drawings, in which like elements are given the same or analogous reference numbers and wherein:

[0044] FIG. 1A is a schematic representation of one situation that is known in the art.

[0045] FIG. 1B is a schematic representation of another situation that is known in the art.

[0046] FIG. 2A is a schematic representation of the use of permeation, in accordance with one embodiment of the present invention.

[0047] FIG. 2B is a schematic representation of the use of adsorption, in accordance with one embodiment of the present invention.

[0048] FIG. 2C is a schematic representation of the introduction into the system of the constituents used for washing, in accordance with one embodiment of the present invention.

[0049] FIG. 3A is a schematic representation of a hydrogen production, storage, transport and distribution unit, in accordance with one embodiment of the present invention.

[0050] FIG. 3B is a schematic representation wherein an adsorbent mass is integrated into the path of the fluid upstream of its entry into the reservoir, in accordance with one embodiment of the present invention.

[0051] FIG. 4 is a schematic representation of an oxygen production unit, in accordance with one embodiment of the present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0052] The present invention will be described in more detail with the aid of FIGS. 2 to 4.

[0053] In FIG. 2B, an adsorbent mass 20 which retains the impurities I of the stream B has been shown. Over time, the impurity front progresses towards the outlet. The stream A for its part regenerates the adsorbent mass 30 by pushing the impurities back to the reservoir. It is understood that by alternating the adsorbent masses between the streams B and A, it is possible to produce a purified stream B. Such a system no longer requires that the streams A and B be simultaneous and offers a few degrees of freedom. However, it must be possible for the stream A to be able to extract all of the impurities from the stream B stopped in the adsorbent mass. Those skilled in the art know how to determine the conditions necessary for such regeneration. At constant temperature, for example, the amount of actual m.sup.3 of the stream A which is passed through the adsorbent should be greater than the amount of actual m.sup.3 of the stream B passed in counter-current mode. At almost equal pressure for the two gas streams (for example reservoir pressure except for pressure drops), it would thus in theory be possible to purify a gas stream B representing approximately 90% by volume of the stream A, but in practice a lower percentage will lead to a more efficient unit.

It is also possible to use an absorption process 40, in other words a closed loop washing, the washing liquid I of the stream B being regenerated by the stream A. The latter process may have the disadvantage of introducing into the system the constituent(s) used for washing (cf. FIG. 2C).

[0054] It should be noted that the proposed process is different from a conventional purification by means of which an impurity is extracted for discharge out of the system. In this case, the impurities are transferred to the reservoir feed gas, taking advantage of the fact that it is itself free of said impurities or that it contains a small amount thereof. There is thus no loss of exploitable constituents. Another advantage may be the simplicity of implementation of the invention. Example 2 in particular illustrates this aspect of the invention.

It may seem paradoxical to reintroduce the impurities from the reservoir into the feed gas of this same reservoir, but in practice many applications are very well suited to this state of affairs. Here again, the examples will illustrate this point.

[0055] FIG. 3A schematically represents a hydrogen production, storage, transport and distribution unit. Hydrogen of 99.99 mo. % purity is produced in the unit 10. This unit 10 comprises, among other things, a steam reforming of natural gas which creates the H.sub.2 molecules and a PSA which purifies this hydrogen to the desired purity. These are very conventional units well known to those skilled in the art. Depending on the production capacity required, the geographical location and the economic conditions, it would be possible for there to be other units for producing hydrogen molecules (reforming of propane, of methanol, electrolysis, etc.). Most of this purified hydrogen 1 is injected into an underground reservoir 20 created in a salt deposit. The stored volume corresponds to several weeks of consumption. A fraction 3 of the hydrogen is extracted from the reservoir and feeds a pipe 4 which serves several consumers located tens or even hundreds of kilometers away (4.1, 4.2, 4.3, 4.4, etc.). Some of these customers require extremely high purity (99.9999 mol %) and a secondary purification is then implanted just upstream of the place of consumption. It is then, for example, hydrogen used for the manufacture of electronic components. The secondary purification is then generally carried out by cryogenic adsorption at the temperature of liquid nitrogen.

[0056] In normal operation, a small amount of pure hydrogen 2, of the order of 10%, is sent directly into a local network. The purity required is in accordance with that of the production.

[0057] The reservoir 20 essentially has 2 functions. The first is to be able to average production over a long consumption period. In fact, among the various users, the hydrogen requirements are far from constant: some processes using H.sub.2 are batchwise, some operate periodically at reduced load or at high load, etc. Despite all these variations, it is therefore possible to operate the unit 10 on a regular basis thus optimizing production. It is also possible to have it operate for a few weeks at nominal flow rate, that is to say under the best possible conditions, and to shut it down completely for a week. It is also possible to take advantage of preferential tariffs for energy and to temporarily stop or reduce production on demand, thereby making significant energy-cost savings.

[0058] The other function of the reservoir 20 is to have a large volume of gas in reserve to compensate for an unforeseen or programmed shutdown of the unit 10 while continuing to supply customers with hydrogen.

[0059] The reservoir 20 is essentially sealed due to the local geology, but some impurities pass from the wall to the gas. They will essentially be moisture, possibly traces of HCl, H.sub.2S, CO.sub.2. Depending on the geological nature of the reservoir, traces of various hydrocarbons may be found. These additional impurities in small amounts are generally acceptable for the majority of users, the purity of the product 1 generally being above the specifications required for direct use of hydrogen. In the opposite case, that is to say the need for very pure hydrogen, the additional purification 40, already provided for, is generally capable of removing the additional impurities.

[0060] On the other hand, these impurities can be troublesome for the local network 2 which is usually supplied directly with purified hydrogen and which would then periodically experience additional impurities. The conventional solution is then to use an additional purification unit 30 to treat the gas stream 5 extracted directly from the reservoir. This unit (30 in FIG. 3A) which is only used occasionally will not be of the cryogenic type because these units, while they are very safe in terms of operation, are very expensive, require special utilities. (liquid nitrogen) and do not lend themselves well to batchwise operation. The basic solution will be an adsorption purification unit, of the TSA (Temperature Swing Adsorption) type proportioned to retain the impurities and to produce a stream of hydrogen at the required specification 6. Regeneration of the adsorbent can be more or less complex depending on whether or not it is desired to limit the hydrogen losses in the purge flow 7. Such a unit will comprise 2 or 3 adsorbers, an electric or steam heater, and a valve skid to allow the cycle to proceed.

[0061] In the solution according to the invention (FIG. 3B), just an adsorbent mass 50 is integrated into the path of the fluid 1 upstream of its entry into the reservoir. This mass swept for a long time in normal operation by hydrogen stream exiting in this case the PSA will be saturated with the residual impurities present in the purified hydrogen (traces of CO, CH.sub.4, N.sub.2) but will be completely free of water, HCl, etc. . . . . When the production unit 10 is stopped, the network 4 will be normally supplied from the reservoir. The flow used locally will also be extracted from the reservoir 5 and will pass in the opposite direction to the stream 1 through the adsorbent mass 50. This mass will be proportioned according to the impurities present, the acceptable amounts and the expected duration of operation (duration of the downtime for maintenance for example, etc.). The amount of adsorbent will generally be greater than the amount required in the base solution described above, but the simplicity of operation, the absence of ancillary equipment and the fact that there is no loss of material mean that the latter solution has a much lower overall cost than the conventional solution. It is also safer since it does not require a succession of adsorption and desorption phases in order to operate.

[0062] Regeneration of the adsorbent mass occurs naturally when unit 10 is put back into production. The stream 1 then passes, in counter-current mode, through the various beds of adsorbents (zeolite, activated alumina, silica gel, etc.) and entrains the impurities introduced by the stream 5. As the temperature remains approximately constant and close to ambient temperature during adsorption and desorption, it is theoretically sufficient for the volume amount (actual m.sup.3) of the stream 1 sent to the reservoir to be greater than that of the stream 5 in order for it to be possible for the regeneration to be carried out. In practice, a much larger volume of gas is available and the adsorbent mass will be completely regenerated and ready for the next purification of the stream 5; it will be noted that a temperature of the stream 5 lower than that of the stream 1 will promote both the stopping of the impurities and the regeneration thereof. Conversely, a lower pressure of the stream 5 may require a greater adsorbent mass. These points are known to those skilled in the art who will have no difficulty in determining the parameters required for good operation (type of adsorbent, useful mass, etc.) and there is no need here to go into more detail about the precise proportioning of the purification 50.

[0063] The second example relates to a unit for producing oxygen from atmospheric air by adsorption. More specifically, it is a VSA type unit in which the oxygen is produced at a pressure close to atmospheric pressure (1.10 bar abs) referred to as high pressure of the cycle and the regeneration is carried out by producing a vacuum of a minimum pressure, referred to as low pressure, of the order of 0.35 bar abs. There are many cycles for VSA units of this type differing by the number of adsorbers, the number of storage tanks used and by the type and/or sequence of the substeps (balancing, decompression, elution, recompression, etc.). There is no need here to go into the details regarding the unit in question. Only a few characteristics are of interest with respect to the invention.

[0064] FIG. 4 schematically shows such an oxygen production unit. It comprises 2 adsorbers marked 10 and 20 which operate in phase shift. The air 1 is introduced into the system by means of the compressor 30, in practice here of the fan type. The vacuum is created by means of the vacuum pump 40 which extracts a nitrogen-rich residue 6.

[0065] The oxygen produced by an adsorber, for example 10, and which is not immediately used for the regeneration of the other adsorber 20stream 4 in the diagramis sent (gas stream A which here corresponds to gas stream 2) to the storage 50 after having passed through the purification unit 60. The gas stream C (gas stream 3 in the figure), which constitutes the production of the unit, is continuously extracted at constant flow rate from the storage 50. The production of oxygen leaving the adsorber is not continuous and instead takes place over only half the adsorption phase. In addition, as specified above, a portion of this oxygen is taken directly to participate in the regeneration of the other adsorber. A buffer tank 50 (storage reservoir) is therefore necessary for storing the oxygen from an adsorber in order to ensure constant production. Since the oxygen is produced at a pressure barely greater than atmospheric pressure in the example selected, a very advantageous solution for the storage reservoir 50 is to use a gasometer. The pressure of the gas will then remain constant, for example 1.050 bar abs and it is the volume of the reservoir that will naturally change during the course of the cycle. This type of gasometer is conventional and inexpensive. However, since the shell is made of polymer and since said polymer is slightly permeable to water, a little atmospheric moisture will pollute the very dry oxygen produced by adsorption. In almost all applications, these traces of moisture have no impact on the downstream process and are perfectly acceptable. However, in the cycle used here, it is necessary to finish recompressing the adsorber during regeneration with oxygen during a step where the other adsorber no longer produces this oxygen. A fraction of the oxygen (stream 5=gas stream B) stored in the storage reservoir 50 should therefore be used for this purpose. It has been seen that the oxygen in the storage contained traces of moisture, of the order of 1 ppm or a few ppm. These amounts are minute but nevertheless unacceptable for the VSA. This is because this water will get trapped at the top of the adsorber on the zeolite which separates the nitrogen from the oxygen at each cycle and then after accumulation will tend to migrate toward the inlet of the adsorber following the desorption of the nitrogen.

[0066] Moisture is a poison for zeolites, most particularly for the LiLSXs developed for this application, which are very efficient but also extremely sensitive to water. This risk is such that units for the production of oxygen by adsorption operating at atmospheric pressure (of the VSA type according to the current name) generally comprise more than two adsorbers in order to be able to make the production of oxygen at the outlet of the adsorbers continuous and thus to avoid low pressure storage.

[0067] It became apparent that by placing a simple adsorbent mass 60 upstream of the storage reservoir (in the direction of production), the problem of moisture is definitely solved. The gas stream A (stream 2) passes through the adsorbent mass in counter-current mode before being stored in the storage reservoir 50. The gas stream B (stream 5) polluted by the impurities from the storage reservoir then passes through the adsorbent mass in co-current mode. The gas entering the storage reservoir and the gas extracted for recompression are at almost the same pressure and at the same temperature. The amount of gas going to the storage reservoir is much greater than the amount of gas which is extracted for recompression. It corresponds in fact to the increased production of the volume of the recompression. The adsorbent mass is therefore regenerated at each phase without difficulty. As for the humidity, it is naturally discharged with the production 3 (gas stream C).

[0068] In other cycles, the oxygen extracted from the tank can also be used to perform all or part of the elution of the adsorbent at the end of vacuum pumping. The problem is identical.

[0069] It should be noted that an adsorbent mass placed just upstream of the reservoir according to the invention does not have the same effect at all as a mass placed at the head of each adsorber. This is because, in order for an adsorber to be able to continuously produce oxygen, the regeneration power should entrain the impurities, essentially nitrogen, toward the inlet of the adsorber. It is the role of the vacuum pump to create regenerative power from the outlet to the inlet. In other words, if the adsorbent mass were placed at the head of the adsorber, there would be no possibility of entraining all of the water in the production as is the case with the principle of the invention.

[0070] It will be understood that many additional changes in the details, materials, steps and arrangement of parts, which have been herein described in order to explain the nature of the invention, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims. Thus, the present invention is not intended to be limited to the specific embodiments in the examples given above.