Patent Application
20230384027
The present disclosure relates to a process and device for cryogenic separation of a stream containing methane, carbon dioxide, nitrogen and/or oxygen and more generally air gases, for producing a methane enriched stream.
The disclosed process has a particularly advantageous application in connection with biomethane production by purification of biogas from nonhazardous waste storage facilities (NHWSF).
Biogas is a gas produced by a biological process of breakdown of organic matter in an anaerobic environment, that is primarily composed of methane, carbon dioxide, water vapor and impurities in variable quantities depending on the organic material having produced the biogas. The impurities that are mainly found are hydrogen sulfide and when the organic material comes from household or industrial wastes, volatile organic compounds (VOCs).
The biogas can be produced in dedicated reactors (also called “digesters”) where the biological reaction operates in a perfectly anaerobic environment and with a controlled temperature. It can also be produced naturally in significant quantities in nonhazardous waste storage facilities (NHWSF), in which household wastes are stored in vaults and covered with a membrane when they are full. After the vault is closed, the process of methane production the organic material can began. The biogas thus produced is then collected by aspiration into a booster via collection tubes inserted in the vaults, thus creating a slightly reduced pressure in said vaults. Since these are not perfectly sealed, air is aspirated and found in the biogas in variable proportion. For this gas source, air gases therefore add to the previously mentioned impurities and must be removed to recover the biogas.
There are also other sources of gas containing methane, carbon dioxide, impurities and a variable concentration of air gases, like gas from mines, produced by degassing of coal seams in abandoned mines, and mixing with air present in the mining spaces. With the goal of recovering this gas for the applications mentioned above, the impurities that it contains must be eliminated.
More specifically, in order to produce a methane enriched stream, it is necessary to remove the carbon dioxide, nitrogen and oxygen impurities to a level such that the methane enriched stream thus produced can be used as natural gas, liquefied natural gas or vehicle fuel. Depending on the uses indicated, the required impurity level can vary. Just the same, a typical target for these impurities in the methane enriched stream is: under 2% by mole carbon dioxide, under 1% oxygen and under 1% nitrogen. When the methane enriched stream no longer contains carbon dioxide, required impurity level is: under 2.5% by mole nitrogen and under 1% oxygen.
The compositions in the remainder of the application are expressed in molar percentages.
In the case of biogas produced by NHWSF, a first treatment is necessary to remove most carbon dioxide and impurities. Many processes exist for that, like the use of gas permeation membranes combined with the treatment of impurities by adsorption (US-2004-0103782), the use of pressure modulated adsorption processes, the use of washing columns with water or amines and the use of cryotrapping processes. The biogas impurities and the majority of the carbon dioxide can be knocked down with these processes, but the air gases cannot be separated from the methane enriched gas stream. An additional treatment step is therefore required.
This additional treatment step can consist of pressure modulated adsorption with the use of specific adsorbents selective for nitrogen and oxygen (U.S. Pat. No. 8,221,524). However, a very low oxygen and nitrogen concentration is achieved at the detriment of the methane recovery rate from the process, which makes it economically uninteresting.
Another solution for removing air gases from methane is cryogenic distillation which can achieve a good separation power between methane on the one hand, recovered at the column bottom and oxygen and nitrogen on the other hand recovered at the column head, because of volatility differences between these components.
However, the presence of oxygen, whose volatility is included between that of methane and nitrogen, leads to this compound tending to concentrate in the distillation zone and to do so even for small oxygen concentrations in the column load. The increase of the gas phase oxygen concentration added to the decrease of the gas phase methane concentration can lead to a gas mixture which is, because of the composition thereof, explosive.
The principle of distillation of the methane and air gases mixture is at cryogenic temperatures known, as is the appearance within the column of potentially explosive gas mixtures. Thus, the document DE 981,875 proposes controlling the distillation in such a way that the gas leaving the column head is outside the upper explosiveness limit (UEL). However, no mention is made of the natural oxygen concentration in the distillation column and therefore the formation of an explosive gas mixture with this process cannot be avoided.
The document FR 1,410,494 identifies the risk of formation of this explosive mixture and proposes a means for avoiding the ignition of the mixture by placing a metal foam between the levels the distillation column with which to dissipate the methane oxidation reaction heat and therefore avoid an explosion. However, the means proposed do not avoid the methane oxidation reaction which will produce carbon dioxide and water, these are undesirable compounds because they could block the column at cryogenic temperatures.
The document U.S. Pat. No. 3,989,478 proposes to adjust the distillation such that the gas leaving the column head contains at least 20% methane, such that the composition of the gas phases in the distillation zone are not explosive. The disadvantage of such an adjustment is both that if the column head gas contains 20% methane, and the remainder air, it is extremely close to explosiveness. Also, the loss of methane in the head gas is significant. Finally, no mention is made of the natural oxygen concentration in the distillation column and therefore the formation of an explosive gas mixture with this process cannot be avoided.
Another solution would be to dilute the gas and/or liquid mixtures from the distillation column such that this concentration is returned to a value making the mixture nonexplosive in the areas having an enrichment of the oxygen concentration.
Thus the document FR 2,971,331 proposes a dilution by pumping liquid methane in the distillation column bottom and reinjection thereof in the column head. Although the means proposed avoids formation of an explosive mixture in the column, it leads to increasing the inventories of liquid methane in the column, and therefore the stored energy, which is not desirable from the process safety perspective. Also a liquid methane pump has to be installed which is a source of potentially dangerous leaks.
The document FR 2,971,332 proposes avoiding the formation of an explosive mixture within the column by dilution with nitrogen taken from an external source. It is therefore necessary to use a fluid, nitrogen, for the dilution. The fluid has a cost and therefore increases the operating costs for the process. It should be noted that in this document, the methane in the gas state injected in the column bottom is a combustible stream coming from the condenser-re-boiler. It is used exclusively as a rising gas phase in connection with the distillation of the feed stream. Without such a stream, distillation is not possible.
The document U.S. Pat. No. 2,519,955 describes a production process for a methane and oxygen mixture. The idea is not to separate the methane from the oxygen to reduce the explosion risk but instead to combine them. Essentially, the process consists of decompressing a biological gas stream rich in methane but depleted of oxygen and then to recover the heat produced within an exchanger placed in a distillation column. Within the exchanger, a portion of the feed stream composed of liquid methane is reinjected in the column bottom whereas the other part composed of nitrogen is reinjected in the column head at a level higher than that of the feed stream. The nitrogen stream is therefore not used as dilution stream but serves to limit the loss of methane by occupying the column head volume.
Further, in order to be able to perform the separation of O2 and N2 relative to CH4 by cryogenic distillation, it is necessary to have a stream whose CO2 concentration is particularly low. The commonly accepted value is 50 ppmv—parts per million by volume—of carbon dioxide maximum to avoid crystal formation which would plug the cryogenic exchangers. Similarly, water must be eliminated to avoid freezing.
To resolve that problem, the document FR 2,917,489 proposed regenerating the adsorbents used in the temperature or pressure modulated adsorbers by means of methane enriched gas, collected at the foot of the distillation column in the liquid state and next vaporized. The disadvantage of the use of this fluid for regeneration resides in the need to control the quantity of carbon dioxide to a constant value at the outlet of the adsorbent bed, by mixing the bed outlet stream with a methane enriched stream. This control is made necessary because the methane enriched stream containing a small quantity of carbon dioxide coming from the regeneration is intended to be used in biomethane form. However, in order to be injected in the natural gas network, it must strictly satisfy the quality requirements of the network operator.
The present disclosure addresses the problem of improving a process for cryogenic separation of the mixture for which the concentrations are always outside the explosiveness zone and that does not have the disadvantages raised above.
The present disclosure also addresses the problem of regenerating the adsorbents used in the temperature or pressure modulated adsorbers from a stream coming from the cryogenic separation without leading to the aforementioned drawbacks.
To resolve these problems and others, the Applicant developed a cryogenic separation process in which the O2 dilution stream consists essentially of nitrogen and comes from the feed stream and not an external source. An obvious cost reduction results.
More precisely, the object of the present disclosure is a cryogenic separation process for a feed stream containing methane and air gases wherein:
The process characterized in that the dilution stream is extracted from the feed stream.
In a preferred embodiment:
In practice, the feed stream contains 60 to 97% methane, between 3 and 50% nitrogen and oxygen and 3% or less carbon dioxide.
The Applicant showed that the prior decompression of the feed stream for the distillation column in a round-bottom separator, and then injection of the gas phase comprising essentially nitrogen, thus produced, in the low part of the packing of the distillation column, meaning upstream from the gas stream, would lead to a sufficient dilution of the gaseous oxygen, whose concentrations, because of this sweeping flow, are sufficiently low that the mixture with methane is not inflammable. The liquid fraction of the feed stream comprising essentially liquid methane is for its part next injected in the head of the column to be distilled.
Because of the separation of the gas phase from the liquid phase of the feed stream and the reinjection of all or part of this gas phase, it is not necessary to use gaseous nitrogen coming from an outside source as sweeping fluid, such that the nitrogen consumption decreases.
Just the same, the use of a gas coming from the feed stream to be treated itself as a dilution stream, whether it comes from decompressing the cooled stream or at the end of another treatment step thereof, does not exclude combining it with a dilution stream coming from an external source. The two dilution streams can be added to the distillation column in the form of one single mixture or separately.
In practice, it is necessary to cool the column head to condense the rising nitrogen rich gas in said column head and as necessary a portion of the gas coming from the feed stream from the separator.
In a first embodiment, the column head is cooled by cooling the feed stream coming from the decompression by mixing it with a refrigerant fluid. In other words, the refrigerant fluid stream is used as a cold source for condensation of the column head gas and participates in the effect of dilution of the oxygen in the distillation column by providing the condensation of only a portion of the gas coming from the decompression of the feed stream, the other part constituting the dilution stream.
The feed stream is cooled either before the separator by mixing said stream with the refrigerant fluid or in the separator by adding a refrigerant fluid directly into the separator.
In a second embodiment, the column head is cooled by means of a refrigerant fluid that is added directly to the column head.
In practice, the refrigerant fluid is liquid nitrogen.
In a specific embodiment, the column contains several distillation segments and the dilution feed is introduced between two segments.
In practice, the distillation segments are in the form of packing or distillation plateau. In all cases, the distillation segments are arranged so that the liquid phase releases the most volatile compounds thereof to the gas phase and the gas phase releases the least volatile compounds thereof to the liquid phase.
As already stated, the process has a particularly advantageous application in connection with biomethane production by purification of biogas from NHWS.
In order to be able to perform the separation of O2 and N2 relative to CH4 by cryogenic distillation, it is necessary to have a stream whose CO2 concentration is particularly low. The commonly accepted value is 50 ppmv—parts per million by volume—of carbon dioxide maximum to avoid crystal formation which would plug the cryogenic exchangers. Similarly, water must be eliminated for the same reason.
In other words, and, prior to the cryogenic separation, a feed stream is provided that is rich in methane, contains nitrogen and oxygen, and has a CO2 concentration that was previously reduced.
To do that, the CO2 concentration is reduced by adding the CO2 rich feed stream into at least one purification unit, preferably by adsorption, for example pressure (PSA) or temperature (PTSA) modulated, loaded with adsorbent able to reversibly adsorb the majority of the CO2.
This type of purifier is known to the person skilled in the art. In practice, for continuous operation at least two PSA or PTSA are used in parallel with one being in adsorption for eliminating the carbon dioxide while the other is in regeneration. Regeneration is done by lowering the pressure and by sweeping with the previously heated gas supplying the energy required for desorption.
In a first embodiment, the adsorbents used in the adsorbers are regenerated by means of the oxygen and nitrogen-rich gas stream drawn from the column head. In practice, the methane depleted stream drawn from the column head contains between 60 and 100% nitrogen and oxygen.
It was in fact found that the column head gas, methane depleted, and also containing nitrogen gas injected in the column, had a sufficient flow rate, because of the nitrogen injection, to perform the heating and cooling cycle of the adsorbent sieve, necessary for the carbon dioxide desorption, to be done during the regeneration time. In this case, it is no longer necessary to use the methane stream withdrawn from the column bottom to regenerate the adsorbents and therefore to maintain a constant carbon dioxide concentration in the bed outlet stream. It is thus possible to withdraw the methane enriched stream in liquid form and make use of it as liquefied natural gas.
In practice, the methane enriched stream at column bottom contains between 95 and 100% methane.
The CO2 loaded gas coming from regeneration can then be used in two different ways: either the loaded gases sent to a system for destruction by oxygen, or, if the methane concentration is sufficient, the loaded gases sent to a combustion system for electricity production (cogeneration micro-turbine or engine).
In a second embodiment, the adsorbents used in the adsorbers are regenerated by means of methane-rich gas drawn from the column bottom.
Another subject of the disclosure is a facility for producing biomethane by purifying biogas from non-hazardous waste storage facilities (NHWSF) implementing the process described above and comprises successively:
The facility further comprises:
The disclosed process and facility and resulting benefits will become clear from the following examples supported by the attached figures.
The explosiveness diagram for a methane, oxygen and nitrogen mixture is shown in
For each of
The stream thus produced (3) is then cooled in a heat exchanger (4) by exchanging heat with the methane enriched liquid stream (20) and the methane depleted stream (23). The cooled stream (5) is sent into a reboiler condenser (6) where it is cooled again by heat exchange with the bottom liquid, so that the bottom liquid can boil and generate methane-rich gas which will be used in the distillation, and also to condense the feed stream.
The condensed stream (7) is then decompressed in a decompression member (8) to the operating pressure of the column (18), included between 1 and 5 bar absolute.
According to
The embodiment differs from the one shown in
For all embodiments, the liquid nitrogen rich liquid phase (19) coming from the round-bottom separator (11) is next added into the upper part of the distillation column (18). The gas phase (17) is added into the lower part of the packing of the distillation column (18) to constitute the sweeping gas and participate in the distillation.
Distillation thus produces two streams: a methane enriched stream (20), bottom of the distillation column, and a methane depleted stream (23) that is rich in O2 and N2 at the head of the distillation column.
A fraction of the methane enriched liquid stream (20) is sent to the exchanger (4) to be vaporized and form a gaseous stream (22). This gaseous stream can be used in two ways.
As shown in
As shown in
In an embodiment not shown, the methane enriched stream (20) is drawn off in a liquid form and used as liquefied natural gas.
For all embodiments, the other fraction of the methane enriched liquid stream in column bottom is sent to the reboiler condenser (6) to be vaporized. The gas stream thus created (21) is sent to the distillation column to create the rising vapor participating in the distillation.
The gas stream (23) comprising oxygen, nitrogen and a methane fraction is then sent to the exchanger (4) to be reheated.
In the embodiment shown in
If the methane concentration is over 25%, the stream (25) can be used in a cogeneration engine or micro-turbine in order to produce electricity.
In the embodiment shown in
| Number | Date | Country | Kind |
|---|---|---|---|
| 1654798 | May 2016 | FR | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16303551 | Nov 2018 | US |
| Child | 18210413 | US |
