The present invention concerns a method for removal of carbon dioxide (CO2) from a gas stream using chemical solvents such as monoethanolamine (MEA). In particular, a method is provided to capture CO2 from flue gas, to avoid CO2 release to the atmosphere, which method uses chemical absorption and recovery of CO2 with low energy consumption.
A typical method of removing acid gases such as CO2 (and potentially other gases such as hydrogen sulfide or H2S) from a gas stream involves using an absorber unit and a regenerator unit, supplemented with suitable accessory equipment. In the absorber unit, a down flowing amine solvent absorbs the acid gas such as CO2 from an up flowing CO2-containing gas stream to produce a gas stream that is essentially devoid of CO2 and optionally other acid gases such as H2S, and an amine solvent enriched with the absorbed acid gases. The resultant enriched amine solvent is then routed into the regenerator unit, for instance embodied as a stripper provided with a reboiler, to produce regenerated or “lean” amine that is recycled for reuse in the absorber. The stripped overhead gas from the regenerator typically comprises a concentrated acid gas stream that is rich in CO2. In this way, pure CO2 may be recovered. The recovered pure CO2 may then be transported and stored in a suitable storage, for instance underground.
The above-described known method involving absorption and recovery through stripping of CO2 suffers from a relatively high energy consumption. As an example, the energy required is typically in the range of 3-4 GJ per ton of recovered CO2. This may increase the amount of flue gas from which the CO2 must be captured. The high energy input, needed to operate an integrated chemical absorber/stripper unit producing pure and pressurized CO2, may be reduced by proper selection of the chemical solvent, its concentration, operating conditions, heat integration, and other. However, a significant part of the energy requirement cannot be reduced: recovery of CO2 in pure form at increased pressure requires high stripper temperatures to release the chemically bound CO2 from the solvent. This takes sensible heat, to heat up the solvent to stripper temperature, and power for pumping and compression.
It is an aim of the present invention therefore to provide a method for recovery and reusing CO2 from a sorbent, with a low energy consumption at low temperature levels.
These and other aims are provided by a method in accordance with claim 1. The invention provides a method for removing carbon dioxide (CO2) from a gas, for instance a flue gas, the method comprising:
One element of the present invention is to use the loaded sorbent liquid as means for transport and storage of the absorbed CO2.
A further element of the invention is that transportable containers are used for transport and storage of enriched and lean sorbent liquid. There is no direct, permanent pipe connection between the first facility, where the absorbing step is performed, and the second facility, where the stripping step is performed.
A further element of the invention is that the CO2 is stripped from the sorbent liquid at the location of an end-user of the CO2, under conditions which preferably are adapted to the specific requirements of the end-user.
The invented method enables re-use of captured CO2 with efficient transport, optional intermediate storage, low energy input at low temperature levels, low operating costs, without the need for permanent pipeline connections and/or stationary storage tanks. The invented method enables complete uncoupling of time, rate and location of CO2 capture and CO2 recovery and re-use.
The method provides a sorbent liquid for the CO2, such as an amine solvent. Suitable amine solvents comprise diethanolamine (DEA), monoethanolamine (MEA), methyldiethanolamine (MDEA), diisopropanolamine (DIPA), and also aminoethoxyethanol (diglycolamine) (DGA). Other solvents and mixtures of solvents may also be used, optionally with or without additives.
Another embodiment of the invention relates to a method wherein the sorbent liquid enriched with the absorbed CO2 is stored at the first facility before transporting it to the second facility.
Yet another embodiment of the invention relates to a method wherein the sorbent liquid enriched with the absorbed CO2 is stored at an intermediate location in between the first and second facilities.
Yet another embodiment of the invention relates to a method wherein the sorbent liquid enriched with the absorbed CO2 is stored at the second facility.
According to yet another embodiment, a method is provided wherein the total time of transporting and storing the sorbent liquid enriched with the absorbed CO2 is at least 24 hours.
According to yet another embodiment, a method is provided wherein any number of absorbing facilities can be combined with any number intermediate storage facilities and with any number of stripping facilities.
According to yet another embodiment, a method is provided wherein the rate of absorption in the first facility, or facilities, and the rate of stripping in the second facility (or facilities) are independent from each other.
The transport of the absorbed CO2 may be performed by any method known in the art. According to a preferred embodiment, a method is provided wherein the sorbent liquid enriched with the absorbed CO2 is transported at ambient pressure and/or ambient temperature, for instance by a road transport vehicle. Indeed, according to the invention, there is no need to compress and/or liquefy the recovered CO2 for transport, as is typically done in prior art methods. This eliminates costs of compression equipment and energy consumption thereof. A further advantage is that there also is no need for dedicated CO2 transportation (or storage) facilities such as pipelines and/or dedicated containment facilities. The CO2 absorbed in the sorbent liquid may be handled by conventional facilities including lorries, barges, tank containers, warehousing, and the like.
A preferred embodiment in this context provides a method wherein direct pipe connections between the first facility and the second facility are lacking.
Another embodiment provides a method wherein a shortest distance between the first and the second facilities is at least 4 km, more preferably at least 5 km, and most preferably at least 10 km. With a shortest distance between a first location A and a second location B is meant in the context of the present disclosure the distance covered by a linear line connecting the two locations A and B.
The first and second facility may be stationary or non-stationary. An embodiment of choice relates to a method wherein the first facility comprises a sailing or harboured vessel and the second facility comprises a, preferably stationary, onshore facility. The shortest distance between the first location A of the vessel and the second location B of the on-shore facility is then defined as the distance covered by a linear line connecting the location A in which the vessel is harboured, and location B.
One advantage of the invention relates to the possibility of adapting the recovery-or stripping-rate of the CO2 from the sorbent according to the needs, conditions, and specific requirements of an end-user, for instance situated at the second facility.
Another advantage of the invention relates to the possibility to perform the recovery or stripping of the CO2 from the sorbent at any time according to the needs of an end-user, for instance situated at the second facility. The time difference between absorption and recovery is not limited to a maximum of one day as is typical in prior art methods. The time difference is at least 24 hours, but this can be extended to multiple days, weeks or months.
According to an embodiment of the invention, a method is provided wherein the stripping step b) is performed at a temperature below 100° C., more preferably below 70° C., even more preferably below 40° C., and most preferably at ambient temperature. Desorption of the CO2 from the absorbent liquid or solvent is in this embodiment performed at low or mildly elevated (relative to ambient) temperature. This offers the possibility of saving sensible heat. In a conventional integrated system according to the state of the art, stripping is performed at temperatures in the range of 110-140° C., which means that sensible heat must be supplied at temperatures accordingly. In conventional stripping according to the state of the art, the required stripping heat supply may account for half of the total energy consumption of the process or more. In the invented method, the heat required can be obtained from the stripping medium itself, such as air extracted from a greenhouse in one embodiment, at substantially lower temperatures in comparison to prior art.
According to yet another embodiment, a method is provided wherein the stripping step b) is performed at ambient pressure. Desorption of the CO2 from the sorbent liquid may be performed against a relatively or even extremely low CO2 partial pressure in the gas phase. Ambient air contains about 420 ppm CO2 and, when used as stripping gas, this results in a CO2 partial pressure of only about 0.042 kPa in the inlet of a stripper operated at ambient pressure. It is obvious to a person skilled in the art that this is very beneficial for a shift of the solvent-CO2 chemical equilibrium to release CO2 to the gas phase. This enables a high degree of recovery of CO2 from the solvent. In conventional, integrated stripping according to the state of the art the CO2 partial pressure is within the range of 100-300 kPa.
A particularly useful embodiment provides a method wherein the second facility comprises a greenhouse and the stripping step b) uses greenhouse air and/or ambient air as stripping gas and/or as transport medium of the CO2-containing gas back to the greenhouse. A greenhouse user does not require CO2 in pure and/or pressurized form, and the invented method offers an adequate CO2 source for a greenhouse user. The greenhouse air is enriched by CO2 stripped from the absorbent liquid to enhance crop growth. Stripping is preferably done by warm air that originates from the greenhouse itself.
In a preferred embodiment of the method therefore, the CO2-containing gas as obtained after the stripping step b) is carried back to the greenhouse to enhance crop growth. The greenhouse air in this embodiment acts as heat source, as stripping fluid for the CO2 recovery process, and as transport medium to the greenhouse.
The dissociation energy for CO2, chemically absorbed in aqueous amine solutions, is typically in the range of −50 to −100 kJ/mole CO2. As known in the art, maximum enhancement of crop growth in a greenhouse is typically closely achieved (pending crop) by adding approx. 600 ppm CO2 to the CO2 already present in ambient air. It will be obvious to a person skilled in the art that the temperature drop of air, from which the dissociation heat is extracted to achieve 600 ppm CO2 enrichment, will be in the range of 1-2° C.
Another preferred embodiment relates to a method as claimed in any one of the preceding claims, wherein the stripping step b) is carried out with a stripper unit, preferably without a reboiler and/or condenser unit.
The method according to several embodiments offers several advantages. The stripper may operate at ambient pressure and at moderately elevated temperature. The hardware used may thus be simple, safe and cost-effective. Equipment, solvent piping and air ducting may be constructed from cheap materials such as (recycled) plastic. A small pump and a greenhouse fan in other embodiments provide solvent-and air-circulation. This represents a significant simplification compared to a conventional stripper according to the state of the art, which is typically a steel pressure vessel, fitted with a reboiler and a top condenser, and operated at temperatures above 100° C.
The heat required is at a low temperature level in some embodiments. Therefore, it is easy to obtain and at low cost, compared to conventional stripper heat input, which is typically provided as steam. Also, there may be no or less need for cooling water (or another coolant) required for the condenser in a conventional absorber/stripper. In addition, Also, a steam source and/or a boiler feed water preparation system and/or a condensate processing system may not be needed either.
The desorption capacity of the stripper is small compared to a conventional integrated stripper. The CO2 stripping capacity is in preferred embodiments matched with the CO2 uptake capacity of the crop in the greenhouse, and there is no need to adapt to the capacity of the absorber in a conventional CO2 capture system. The time-and rate-of CO2-absorption and-stripping are independent from each other. This is of particular practical importance in a greenhouse, without assimilation lighting during night-time, when the crop is not consuming CO2, as CO2 supply can be stopped. Capacities of external power supply for heating, pumping and ventilation may be selected small and may further be provided locally by CO2 neutral options such as solar cells and solar heaters.
Further, the absorbent liquid (chemical solvent) may in certain embodiments be heated to low or moderate temperatures only. Such temperatures are significantly lower than the approximate 110-140° C. temperature level required for conventional integrated strippers. The reduced temperature also slows down or even prevents thermal degradation of the solvent.
The low stripping temperature may also reduce evaporation losses of the chemical solvent. An option according to an embodiment is to add a guard bed and/or a washing section to the outlet of the stripper to capture traces of solvent vapor.
By using air (in a preferred embodiment extracted from the greenhouse) for the stripping, the chemical solvent is exposed to oxygen. As will be known to persons skilled in the art, this may contribute to degeneration of the chemical solvent. However, in a preferred embodiment the stripping is performed at ambient temperature and at ambient pressure and the frequency of absorption/stripping cycles of the solvent is very low compared to prior art. This reduces and slows down degeneration of the chemical solvent to a low level, compared to prior art where stripping is performed without presence of oxygen but at high pressures and temperatures and at a high frequency of absorption/stripping cycles.
The method according to certain embodiments also provides safe operation. Release of CO2 from the solvent at the relatively low operating temperatures according to embodiments is slow, and CO2 partial pressure may be very low. This eliminates suffocation risk of personnel involved, compared to conventional stripping where pure CO2 at pressure must be handled.
According to another embodiment, a method is provided wherein the CO2-containing gas obtained from the stripping step b) contains from 100 to 10000 ppm (1 vol. %), more preferably from 200 to 5000 ppm, and most preferably from 400 ppm to 1500 ppm CO2.
In yet another embodiment of the invented method, at least 10 wt. % of the CO2 that is present in the gas stream comprising the CO2 is absorbed in the sorbent liquid during the absorbing step a), more preferably at least 30 wt. % CO2, and most preferably at least 50 wt. % CO2.
In another embodiment a method is provided wherein at most 90 wt. % of the CO2 that is present in the gas stream comprising the CO2 is absorbed in the sorbent liquid during the absorbing step a), more preferably at most 70 wt. % CO2, and most preferably at most 50 wt. % CO2.
According to an embodiment of the invention, the stripper in the second facility can be used in reverse mode as an absorber. In this method flue gas from a fired heater, used during night time to provide heat to a greenhouse in case no assimilation light is used, is carried through the absorber. The sorbent liquid is enriched with CO2 absorbed from the flue gas. This method is useful in a greenhouse during night time, when no assimilation light is used. At such conditions there is no CO2 consumption by the crop. The CO2 in the flue gas is not wasted but is captured by the solvent.
During daytime, the stripper is used in the normal operating mode as a stripper, CO2 released from the sorbent is utilized to enhance crop growth.
It is explicitly mentioned that the embodiments disclosed in the present application may be combined in any possible combination of these embodiments, and that each separate embodiment may be the subject of a divisional application.
The above brief description, as well as other objects, features and advantages of the present invention will be more fully appreciated by reference to the following detailed description of a presently preferred, but nonetheless illustrative embodiment, when taken in conjunction with the accompanying drawing wherein:
A scheme of the absorption system at a first offshore facility, a vessel, is shown in
As known in the art, the scrubber 2 may be fitted with a liquid distributor and packing material for improvement of flue gas-sorbent liquid contact and CO2 transfer, at the same time keeping pressure drop as low as possible. The scrubber 2 is preferably operated with counter-current flow of flue gas and sorbent liquid. The optional sorbent liquid cooler 5 removes absorption heat from the sorbent liquid and keeps sorbent liquid temperature low to maximize the CO2 absorption capacity of the sorbent.
Operation of the absorption system is straightforward: the sorbent liquid is circulated through the scrubber 2 until saturation of the sorbent at operating conditions is achieved. Maximum CO2 absorption capacity depends on type and concentration of the sorbent liquid chemical, and temperature and CO2 content of the flue gas stream (S1), as well as temperatures of the flue gas and the sorbent liquid.
As shown in
Referring to
With reference to
The stripper 10 may be fitted with a liquid distributor and packing material for improvement of flue gas-sorbent liquid contact and CO2 transfer, at the same time keeping pressure drop as low as possible. The stripper 10 is preferably operated with counter-current flow of air and sorbent liquid. The optional sorbent liquid heater 13 increases the temperature of the sorbent liquid, to improve stripping of CO2 from the sorbent liquid.
Operation of the stripper system is straightforward: the sorbent liquid (S3) is supplied to the stripper 10, air (S5) is passed through the stripper. CO2 analysers (14, 15) provide information on the CO2 content of the air in the greenhouse. Control is by switching on or off, or throttling sorbent liquid flow and/or air flow through the stripper. Analysers (14, 15) also indicate when the sorbent liquid is stripped from CO2.
As is known to a person skilled in the art of conventional sorbent stripping, recovery of pure CO2 at 1-3 bar pressure from a CO2-containing MEA solvent requires high temperatures. Stripping at about 120° C. to release pure CO2 at about 3 bar is indicated by point P2. At this condition, about 0.4-0.45 kmole CO2 /kmole MEA remains in the sorbent liquid. Only about 30% of the CO2 contained in the sorbent liquid is recovered. Stripping with ambient air, which has low CO2 partial pressure (currently about 420 ppm CO2, about 0.00042 bar), results in far higher recovery of CO2 from the sorbent liquid. The stripper can be operated at low temperature, ambient or mildly elevated. Energy consumption is minimized. The achievable condition of the sorbent liquid is indicated by point P3. At about 40° C. only about 0.2 kmole CO2 /kmole MEA remains in the sorbent liquid, more than 60% of the CO2 contained in the sorbent liquid can be recovered.
An option is to increase the temperature of the sorbent liquid supplied to the stripper to 80-100° C., if cheap heat at this temperature level is available. The sorbent liquid can then be stripped to the condition indicated by point P4, increasing CO2 recovery to about 90%.
CO2 in the flue gas enriches the sorbent, and can be stripped and utilized for crop growth during daytime. Pump (11) circulates sorbent liquid (stream S3) from the sorbent liquid tank container (3) through the absorber (10). The absorption is performed at near ambient pressure and-temperature. Sorbent liquid leaving the absorber (S4) is returned the sorbent container (3). Flue gas discharged by the absorber (10) is discharged to ambient (stream S6). The heat produced by the fired heater (16) is transferred to the greenhouse. Optional, cooler (17) removes absorption heat from the sorbent, which can be used to supply additional heat to the greenhouse by a heat transfer fluid circulated by pump (19) through a greenhouse heater (21). Pump (18) circulates heat transfer fluid through the fired heater (16) and through a heater (20) in the greenhouse. The CO2 analysers in the flue gas stream S5 entering the absorber (15) and in the flue gas stream S6 leaving the absorber (14) enable monitoring of the absorption process.
The absorber (10) may be fitted with a liquid distributor and packing material for improvement of flue gas-sorbent liquid contact and CO2 transfer, at the same time keeping pressure drop as low as possible. Further, the absorber (10) is preferably operated with counter-current flow of air and sorbent liquid, and the optional sorbent liquid cooler (17) may reduce the temperature of the sorbent liquid, to improve the absorption of CO2 by the sorbent liquid.
The absorption system operates such that the sorbent liquid (stream S3) is supplied to the absorber (10) by pump (11). The enriched sorbent liquid (stream S4) returns to the sorbent storage container after (optional) cool down by cooler (17).
Number | Date | Country | Kind |
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2028603 | Jul 2021 | NL | national |
Filing Document | Filing Date | Country | Kind |
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PCT/NL2022/050351 | 6/21/2022 | WO |