Patent Grant
8746009
This application is a 371 of International PCT Application PCT/FR2009/052210, filed Nov. 18, 2009, the entire contents of which are incorporated herein by reference.
The present invention relates to a hydrogen production process with capture of the CO2 produced simultaneously.
Most hydrogen is supplied from steam reforming of hydrocarbons, more particularly methane (SMR). The reformed gas is generally sent to a shift reactor (water-gas shift reactor) to produce more hydrogen. The water-gas shift reaction is a reaction between carbon monoxide and water in order to form carbon dioxide and water.
The gas produced generally has the following characteristics:
Such a gas is then generally sent directly to a hydrogen PSA (Pressure Swing Adsorption) in order to produce high-purity hydrogen (99% to 99.9999 mol %).
The waste from the PSA contains all the CO2, the great majority of the CH4 and CO, a large portion of the N2 and the hydrogen in an amount that depends on the yield of the PSA unit (from 75 to 90% depending on the desired efficiency).
This waste, with the CO2 contained therein, is burnt in the steam reforming furnace. The waste gas from this unit is vented to atmosphere after recovering some of the available heat.
However, climate change constitutes one of the greatest environmental challenges. The increase in carbon dioxide concentration in the atmosphere is for a very large part the reason for global heating. In the context for reducing CO2 emissions, capture of at least some of the CO2 emitted must be envisaged.
It is known to remove CO2 from such a fluid by scrubbing, for example scrubbing with amines, upstream of the PSA.
The drawback of such a solution is essentially its energy cost inappropriate to the capture problem.
Other solutions are based on adsorption.
Document EP 0 341 879 B1 treats the waste from an H2 PSA in order to extract the CO2 therefrom via a PSA and a refrigeration.
Document WO 2006/054008 also treats the waste from an H2 PSA via a PSA and a cryogenic unit.
Document U.S. Pat. No. 5,026,406 describes the production of two high-purity fractions using a PSA. Example 2 partly corresponds to the problem posed here. A CO2-rich (99.7 mol %) fraction and a fraction containing about 90 mol % 147 are obtained. In practice, this fraction has to be treated in a second unit, for example a PSA of the H2 PSA type, in order to obtain an H2 purity of 99%. It is necessary to use vacuum pumps and/or recycling in order to achieve the intended performance.
Document US 2007/0227353 also relates to the same technical problem. The recommended solution is again the use of a PVSA, i.e. an adsorption unit with vacuum steps. It is known that such steps, although they are efficient in terms of performance, are expensive in terms of capital investment (vacuum pumps) and in terms of energy.
Moreover, document FR 2 884 304 describes an adsorption unit operating at a maximum pressure of 10 bar absolute, producing a CO2-enriched gas which is sent to a cryogenic unit that enriches this gas up to a minimum of 80 mol %. The CO2-depeleted gas from the adsorption unit is expanded, after being cooled or not, in order to supply the refrigerating power of the cryogenic unit. At least one portion of the CO2-lean gas from the cryogenic unit is recycled to the PSA, after being expanded or not. At least one portion of the CO2-lean gas from the cryogenic unit is used as fuel. Said adsorption unit may be a VSA, a VPSA or a PSA.
The process and/or plant envisaged in document FR 2 884 304 comprises only a single adsorption unit.
That document essentially based on recovery of CO2 in a fluid at a pressure below 10 bar abs does not relate to the associated production of hydrogen. In particular, it does not relate to SMR output gases.
The use of a PSA as described in FR 2 884 304 is not effectively suitable a priori when it is desired to extract CO2 from a gas at a high pressure, such as syngas, whenever it is also desired to recover as a priority most of one of the least-adsorbable constituents. Specifically, since CO2 is an easily adsorbable constituent, a moderate partial pressure, of the order of one bar, is sufficient for obtaining quasi-saturation of the adsorbents conventionally used, such as zeolites or active carbons. The use of a high pressure therefore provides nothing to the arresting of CO2 but is unfavorable when it is desired to keep constituents, such as hydrogen, under pressure. Since the latter constituent is very weakly adsorbed, it is most particularly present in the adsorber in the gas phases, whether in the pore volume of the adsorbent, in the intergranular volume or in the in-out dead volumes. For a given volume, the loss of hydrogen is therefore proportional to the pressure. In such an application, it is normal to envisage instead to treat the waste from the H2 PSA in order to sequester the CO2 knowing that this is a low-pressure stream enriched in CO2 and depleted in hydrogen. WO 2006/054008 and EP 0 341 879 B1 are based on these considerations.
One solution envisaged for partially obviating these drawbacks is, as mentioned, the use of a complex PSA cycle employing a vacuum to extract the CO2. Under these conditions, the adsorbent may be used efficiently and the use of internal recycling then enables the loss of hydrogen to be limited. This pays for itself in terms of capital investment and energy consumption.
Starting from this situation, one problem that arises is how to provide a process capable of economically producing hydrogen with CO2 capture and with no appreciable loss of hydrogen.
The present invention provides a process for the production of hydrogen from a gas mixture utilizing a CO2 PSA, a cryogenic unit, and a H2 PSA.
One solution of the invention is a process for the production of hydrogen from a gas mixture 21 comprising hydrogen (H2), carbon dioxide (CO2), carbon monoxide (CO), methane (CH4) and water (H2O), employing a CO2 PSA unit 30, a cryogenic unit 40 and an H2 PSA unit 50, in which:
Depending on the case, the process according to the invention may have one or more of the following features:
The subject of the invention is also a plant for the production of hydrogen from a gas mixture 21, comprising hydrogen H2, carbon dioxide CO2, carbon monoxide CO, methane CH4 and water H2O, characterized in that said plant comprises a CO2 PSA 30 and an H2 PSA 50 in series, the CO2 PSA 30 being upstream of the H2 PSA 50 and combined with a cryogenic unit 40.
Depending on the case, the plant may have at least one of the following features:
The invention will now be described by means of
Natural gas (or more generally hydrocarbons) 1 and steam 2 are introduced into the reforming unit 10. The reformed gas, comprising hydrogen (H2), carbon dioxide (CO2), carbon monoxide (CO), methane (CH4), possibly argon (Ar) and nitrogen (N2), and water (H2O), is shifted in a shift reactor 20, in which at least some of the carbon monoxide reacts with at least some of the water to form hydrogen and carbon dioxide. The gas thus reformed and shifted corresponds to the gas mixture 21.
The gas mixture 21 feeds the CO2 PSA 30. The fluid 32 is the CO2-rich waste from the CO2 PSA 30. This fluid is at low pressure, i.e. at a pressure below 3 bar abs, generally around atmospheric pressure. Since this fluid is compressed in order to feed the cryogenic unit 40, it could be at a slight underpressure (for example 0.9 bar abs) without departing from the teaching of the invention.
The cryogenic unit 40 serves, on the one hand, to deliver CO2 (41) at the required purity for its use (sequestration, injection into gas or oil wells, chemistry, food processing, etc.) and, on the other hand, to recycle 43 most (more than 90%, preferably more than 95% and even more preferably more than 99%) of the hydrogen contained in the stream 32.
The cryogenic unit 40 may possibly produce a methane-enriched stream 42 that will be recycled into the unit 1 or used elsewhere.
The H2-enriched fraction 43 may be recycled to various points in the unit 1:
Depending on the hydrogen specification—or if there are also requirements in terms of impure hydrogen—all or some of the hydrogen-enriched stream 43 may be either used at 62 in another unit or mixed at 61 with the main hydrogen production 51. A complementary treatment 60, for example permeation or catalysis (methanation, etc.), may be envisaged in order to adapt the purity of this stream to the requirements.
The streams 46 and/or 48 may be mixed with the main feed streams, 21 and 31 respectively, or constitute a second feed.
The streams 47 and/or 49 may be used internally to the PSA, for example to completely or partly purge or repressurize it. If this stream were to be injected into the PSA other than as main or secondary feed, at a pressure below the adsorption pressure, there is the possibility of inserting a permeation unit in order to hydrogen-enrich a portion of the stream.
The fraction 31, produced by the CO2 PSA 30, is depleted in CO2 and feeds the H2 PSA 50. This produces an H2-rich fraction 51 which constitutes the main production of the unit and a waste 52 which comprises the non-produced fraction of hydrogen, the residual CO2 and most of the CH4, CO, N2 and Ar contained in the feed 31 to the H2 PSA 50.
The waste 52 from the H2 PSA may be completely recycled into the reformer 10, as fuel and/or as reactant 71 after being compressed in the compressor 70. A portion of this waste may also be recycled into the H2 PSA itself, or else all or some of this stream may be used in an external unit. These variants, which in no way modify the spirit of the invention, are not shown in
Indeed, in general, the process according to the invention uses a unit for capturing the CO2 by PSA-adsorption, that is to say not involving a vacuum regeneration, coupled to a cryogenic unit which makes it possible both to obtain the required CO2 purity and to recycle most of the hydrogen contained in the CO2 fraction 32 output by the CO2 PSA 30 into the reformed gas line. In other words, the hydrogen extracted from the CO2 PSA is reinjected into the high-pressure circuit going from the SMR feed to the hydrogen production, that is to say at a pressure ranging from around fifteen bar absolute to a maximum of 40 bar absolute. The coupling to a cryogenic unit thus makes it possible to compensate for the moderate performance of the PSA (compared with a unit employing vacuum regeneration) thanks to more thorough purification of the CO2 and improved recycling of the non-condensables. The term “non-condensable” is understood to mean H2, N2, CH4, CO, Ar. It turns out that the modifications made to the cryogenic unit—in relation to a conventional CO2 purification and production unit—such as the choice of a high operating pressure adapted to recycling, partial reboiling of the liquid CO2 to expel the dissolved hydrogen therefrom and partial expansion of the liquid CO2 to recover the vapor fraction rich in non-condensables, etc. entail a considerably lower cost than choosing a vacuum as driving force for regenerating the adsorption unit. It does not fall within the context of said invention to describe in detail the cryogenic units associated with the PSA for obtaining the required performance in respect of CO2 capture and in respect of recycling the non-condensables, more particularly the hydrogen. It should be noted that the cryogenic unit will be fed at a pressure above the pressure of the hydrogen production, in practice always above 15 bar abs, and will preferably include what is called a “stripping” device, for stripping the hydrogen contained in the CO2 and, more generally the nonncondensables: N2, CH4, CO and Ar, which device involves a lowering of the pressure and/or heating and/or injection of gas into a liquefied CO2 fraction.
The CO2-enriched fraction 32 feeding the cryogenic unit 40 will be compressed by the compressor 34 to a pressure above the pressure of the gas mixture 21 so as to be able to recycle the hydrogen-rich gas 43 without any other compression means. Since the CO2-rich gas 32 output by the CO2 PSA contains water vapor, this fluid will be at least partially dried before or after it is compressed and cooled (or on leaving an intermediate compression stage, after being cooled). The residual water content will be compatible with the proper operation of the cryogenic unit, the proper use of the materials adopted (corrosion) and the purity specification of the CO2. For the sake of clarity, in
The dryer may be of any type, but preferably of the TSA type as indicated above. The adsorbers may be of the cylindrical type with a vertical axis, of the cylindrical type with a horizontal axis or of the radial type for larger throughputs. The radial adsorber technology may be that used for overhead purification in front of cryogenic air separation units or that of O2 VSA units.
The waste 32 from the CO2 PSA may also feed a gasometer 33—or a buffer store—before being compressed at 34 and then dried at 35. This storage then has two effects, that of making the composition of the waste uniform and that of regulating its flow rate.
The shifted reformed gas 21 is mixed with the H2-enriched gas 46 output from the cryogenic unit, which includes all the hydrogen contained in the CO2-rich fraction (32), CO2—depending on the thermodynamic equilibria reached in the cryo unit—methane, carbon monoxide and possibly nitrogen and argon. These contents depend essentially on the required purity of the CO2.
The CO2-depleted fraction 31 output from the CO2 PSA unit 30 has a residual CO2 content generally lying within the range from 0.5 to 7.5 mol %, even more generally from 1.5 to 3.5%.
The H2 PSA 50 purifies said gas of CO2, CH4, CO, N2, etc. and produces the pure hydrogen 51, i.e. with a purity of greater than 98% and generally between 99 and 99.9999%.
The low-pressure waste 52 from the H2 PSA is generally used as fuel (in the SMR furnace) and/or as feedstock, after compression, for the SMR.
Since the feed gas for the H2 PSA has been CO2-deballasted, its hydrogen content may be equal to or exceed 85 mol %. It may therefore be economically advantageous to compress a portion of this waste so as to recycle it into the H2 PSA, thus increasing the hydrogen production.
This recycling principle is described for example in documents U.S. Pat. Nos. 5,254,154 and 6,315,818.
As described above, this recycle may be mixed with the main feed (31) or may constitute a second feed.
It should be noted that since the waste 52 from the H2 PSA is dry—the water having been removed in the CO2 PSA—and depleted in CO2—for the same reason—there is no particular problem in compressing this waste. Of course, this is not the case in the absence of the CO2 PSA or there is a stream containing simultaneously water and CO2 (corrosion problem).
Using the CO2 PSA as means of drying the reformed gas before it is fed to the H2 PSA is one of the advantages associated with this process. Since the waste 52 from the H2 PSA is dry, it is conceivable, at reduced cost, to improve the performance of said PSA not only by recycling, as described above, but also by lowering the pressure of this waste. Indeed, in the case of a conventional H2 PSA, the waste from the PSA is sent to the burners of the SMR furnace. The regulating means and the pressure drops in the pipes and accessories mean that the low pressure of the PSA cycle is around 1350 bar abs. Now, the performance of such a PSA is very sensitive to the low regeneration pressure. It has therefore been envisaged to counter-balance the various pressure drops in the circuit going to the burners by using a booster of the fan or roots type. The simultaneous presence of CO2 and moisture means that either the maintenance or the use of special corrosion-resistant materials counter-balances the gains due to an increase in the hydrogen extraction yield. The fact of being able to use ordinary carbon steel considerably reduces the capital investment of such machines and may justify their use. Thus, the regeneration pressure of the H2 PSA may be at atmospheric pressure, or even slightly below this pressure.
The cryogenic unit is a conventional unit, of the type with partial condensation as used for liquid CO2 production for industrial or food-processing purposes. A first example is given in document EP 0341 879 B 1. A more complicated example is shown in
The HP recycle 43 containing hydrogen is used to regenerate the dryer 35 after it has passed through the heater 44 in order to supply the energy to desorb the water. This fluid is then cooled at 45 for removal of the condensed water and for injection into the main stream 21. When combined with the cryogenic unit, the CO2 PSA 30 may operate in a cycle of the H2 PSA type.
Preferably, the CO2 PSA 30 includes at least two pressure-balancing phases, more preferably 3 or 4 pressure-balancing phases, and is capable of producing a pressurized hydrogen-rich gas containing 0.5 to 7.5% CO2, preferably 1.5 to 3.5 mol % CO2, 0.5 to 7% CO, 3 to 10% CH4 and 0 to 10% N2. This gas is essentially dry, i.e. it contains on average less than 1 ppm water.
The waste gas 32 produced at low pressure is rich in CO2 (80 to 95 mol %), the rest consisting of H2, CO, CH4, and possibly nitrogen. This gas also contains water vapor.
The overall degree of CO2 extraction is in the range from approximately 70 to 98%, preferably around 85 to 90%.
Depending on the throughput treated, there will be 5 to 14 or more adsorbers. The phase times will generally be between 20 and 120 seconds depending on the number of adsorbers used. It will be recalled that the cycle time corresponds to the time T required to bring an adsorber back to a given state and that, for a cycle comprising N adsorbers, the phase time is by definition equal to T/N.
To give an example, a 10-3-4 cycle will be described, this being, using the conventionally accepted terminology, a PSA adsorption cycle employing 10 identical adsorbers each following a cycle comprising 3 production phases and 4 pressure-balancing phases. Such a cycle may be represented as in the table below:
Such a table means that, on the one hand, a given adsorber will follow chronologically all the steps starting from the top-left box down to the bottom-right box and that, on the other hand, at a given moment, the 10 adsorbers are in a state corresponding to a column. A row corresponds to a phase as defined above. It may be seen that each phase comprises several steps that correspond to particular times in the control-and-command system (passing from one step to another generally implies at least one valve movement for the PSA). More particularly, the 10-3-4 cycle described here therefore comprises:
It will be noted that once the waste 32 is recompressed, it is potentially possible to add a high-pressure or medium-pressure purging step to purge the adsorbent. Such a step—often called a rinse—is for example described in “Pressure Swing Adsorption” by Ruthven et al., 1994, page 69, table 3.1.
Such a step enables the adsorber to be partially purged of the hydrogen that it contains, enabling a waste richer in CO2 to be obtained. Such a step is incorporated into the cycle during the depressurization and before the blow-down step. The improvement in performance thus obtained is to be compared with the greater complexity of the CO2 PSA.
In the CO2 PSA 30, it will be necessary to use adsorbents having a compromise between adsorption capacity and ease of desorption, since no vacuum is used for the end of desorption. More precisely, the use of type X or A zeolites, widely recommended for this application, will have to be proscribed or at the very least limited, preferably as final layer at the adsorber outlet, at the point where the CO2 content is reduced. Preferably, this zeolite A or X layer will represent less than 25% of the total volume of adsorbent. One of the best adsorbents tested for this application is silica gel, for example the product manufactured by BASF under the reference LE 32. It may be applied in particular in combination with activated alumina (5 to 25% of the total volume of adsorbent) preferably placed upstream, with active carbon (5 to 20%). Certain molecular sieves (NaY, etc.) having a limited affinity with CO2 may be used to optimize the performance in accordance with the CO2 extraction objective adopted. Recently synthesized adsorbents, such as MOF (Metal Organic Frame) adsorbents, also correspond to the selection criteria.
The geometry of the adsorbers for the CO2 PSA 30 may be of various types. Preferably cylindrical adsorbers having a vertical axis will be used for small throughputs, i.e. for feed flow rates up to a few thousand or tens of thousand Nm3/h, and then cylindrical adsorbers having a horizontal axis or radial adsorbers for the largest throughputs. The radial adsorber technology may be that used for overhead purification in front of cryogenic air separation units or that of O2 VSA units.
The H2 PSA 50 is a conventional H2 PSA with adsorbent distribution tailored to the feed composition. It may include a particular preprogrammed cycle in the event of a composition change, due for example to the CO2 PSA being taken out of service. The principle of such additional cycles is described in document U.S. Pat. No. 7,255,727. As regards a priori a large-capacity H2 PSA to be combined with CO2 capture, cycles comprising several adsorbers, generally 8 or more, will be used. The hydrogen extraction yield may be around 90%, around 92% with a booster on the waste going to the burners, and around 92 to 95% with a recycle.
A variant, shown in
Such a dryer 25 also prevents any water/CO2 interference in the CO2 PSA adsorbents and thus makes arresting the CO2 easier. However, the unit 25 must treat the entire syngas flow. The choice of the basic solution or of said variant will depend on the operating conditions, on the local economic conditions, etc. This choice forms part of the optimization work carried out by a person skilled in the art.
It will be noted that by placing the dryer in this position (25), it is obviously possible to retain the advantages of the drying carried out simultaneously with CO2 arrest, which advantages were described above.
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.
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| PCT/FR2009/052210 | 11/18/2009 | WO | 00 | 5/20/2011 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2010/066972 | 6/17/2010 | WO | A |
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