Patent Application
20240307814
The present disclosure relates to a method and a system for carbon dioxide absorption, in particular to a method and system for treating a steam condensate generated by a high-pressure generator for the regeneration of a carbon dioxide absorption solution.
Carbon dioxide has many uses. For example, carbon dioxide is used to produce urea, to carbonate beverages, to chill, freeze and package seafood, meat, poultry, baked goods, fruits, and vegetables, and to extend the shelf-life of dairy products. It is an important environmental component in industrial waste and process water treatment as a replacement for sulfuric acid to control pH levels. Other uses include drinking water treatment, an environmentally friendly pesticide, and an atmosphere additive in greenhouses to improve the growth of vegetables.
In general, carbon dioxide is produced by purifying a waste stream which is a by-product of an organic or inorganic chemical process. The waste stream, which comprises a high concentration of carbon dioxide, is condensed and purified in multiple stages and then distilled to produce the product grade carbon dioxide.
Upgrading of the carbon dioxide concentration in a feed can be carried out in a number of ways. One particularly preferred method is the chemical absorption of carbon dioxide from the crude carbon dioxide feed into an alkanolamine based absorbent. The resulting carbon dioxide loaded absorbent then undergoes separation into a carbon dioxide product for recovery and into alkanolamine containing absorbent which may be recycled for reuse within the recovery system.
The recovery of carbon dioxide is particularly important in the ammonia process in order to separate hydrogen from carbon dioxide, in the mixture of hydrogen and carbon dioxide produced by the shift conversion unit; hydrogen cannot be used in an ammonia converter, for the production of ammonia, unless it is essentially free of carbon dioxide.
In GB996543A, it is described how a carbon dioxide containing gas is scrubbed with an aqueous solution of an alkanolamine in a tower (18), wherein the solution having absorbed carbon dioxide is withdrawn from the tower (18), and is regenerated in a tower (32), being heated indirectly by the steam from the waste-heat boiler (2) and stripped by steam from the waste-heat boiler (9).
In DE102018210921A1, a unit and a related process for the production of hydrogen-containing synthesis gas it is described, at least comprising (a) a reformer (1); (b) a carbon monoxide (CO) converter (2); (c) a synthesis gas condenser (4); (d) a carbon dioxide (CO2) scrubber unit with regeneration (3); characterized in that the synthesis gas condenser (4) is connected to a deaerator (5) and the deaerator (5) is connected to a reformer burner (6) and/or a fired auxiliary steam boiler (7).
In CN107866134A, it is disclosed providing heat to a regenerator operating under reflux conditions of the solution to be regenerated, and also heating the solution to be treated in the regenerator with a rich and lean solution and also with heat from the CO2/steam mixture produced inside the regenerator. Further, the steam condensate achieved after heat has been supplied to the regenerator is heated with steam.
Hence, the prior art describes the regeneration of a carbon dioxide absorbing solution by heating with steam and the condensation of a synthesis gas and its subsequent processing in a de-aerator. The prior art does not provide teaching as to how the condensate from the steam used to regenerate a solution having absorbed carbon dioxide is to be treated.
Regenerating the steam used to regenerate a solution having absorbed carbon dioxide is important from an energy recovery perspective and should be performed in an energy-efficient manner. At the same time, the process condensate generated from the use of steam should be treated and used for regenerating steam in such a manner that the equipment in the unit is not subjected to corrosion.
The present disclosure provides a method and a system for utilizing the complete heat content of a steam condensate generated by a high-pressure regenerator, at the same time as ensuring that the equipment in the unit is not subjected to corrosion.
In one aspect of the disclosure, a method is disclosed for treating a steam condensate generated by a high-pressure regenerator operating at a pressure ranging from 1.0 to 1.2 kg/cm2 for regenerating a carbon dioxide absorption solution. The method comprises the steps of:
Surprisingly, the inventors have found that the method of the disclosure allows for utilizing the complete heat content of the steam condensate generated by the high-pressure regenerator, at the same time as ensuring that the equipment in the unit is not subjected to corrosion since it is energy-efficiently processed in the de-aerator. Further, the use of the low-pressure steam used for supplying the high-pressure regenerator results in the maximum heat content of the steam being used, such that energy recovery is maximised in the system.
In one embodiment according to the method of the disclosure, the aqueous solution suitable for producing steam has an oxygen content ranging from 7 ppb to less than 20 ppb.
In one embodiment according to the method of the disclosure, the method further comprises the step of
In one embodiment according to the method of the disclosure, the carbon dioxide absorption solution comprises about 30% potassium carbonate, optionally partly or completely converted to potassium bicarbonate.
In one embodiment according to the method of the disclosure, the carbon dioxide absorption solution comprises about 30% potassium carbonate, about 5% potassium bicarbonate, about 0.5% diethanolamine and about 0.5% glycine.
In one embodiment according to the method of the disclosure, the method further comprises the step of:
f) producing steam from the aqueous solution produced by step d).
In one embodiment according to the method of the disclosure, the method further comprises the steps of:
In one embodiment according to the method of the disclosure, the method further comprises the step of:
m) feeding the mixture of hydrogen and methane obtained from step l) to an ammonia converter for producing ammonia.
In another aspect of the disclosure, a system is disclosed for recovering the heat content of a steam condensate generated by a high-pressure regenerator operable at a pressure ranging from 1.0 to 1.2 kg/cm2 for regenerating a carbon dioxide absorption solution. The system comprises:
In one embodiment according to the system of the disclosure, the system further comprises means for recycling the regenerated carbon dioxide absorption solution regenerated in the high-pressure regenerator.
In one embodiment according to the system of the disclosure, the system further comprises means for producing steam with an oxygen content ranging from 7 ppb to less than 20 ppb from the aqueous solution produced in the de-aerator, wherein the means for producing steam are in direct fluid communication with the de-aerator.
In one embodiment according to the system of the disclosure, the system is the front end of an ammonia production unit and further comprises:
wherein:
In one embodiment according to the system of the disclosure, the front end is fluidly connected to an ammonia converter for producing ammonia.
In another aspect of the disclosure, the use of the system for recovering heat of the disclosure for performing the method for recovering heat of the disclosure is disclosed.
In another aspect of the disclosure, a method for revamping a system for recovering heat comprising:
into a system according to the present disclosure, comprising the steps of:
Before the present system and method of the disclosure are described, it is to be understood that this disclosure is not limited to particular systems and methods or combinations described, since such systems and methods and combinations may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims.
As used herein, the singular forms “a”, “an”, and “the” include both singular and plural referents unless the context clearly dictates otherwise.
The terms “comprising”, “comprises” and “comprised of” as used herein are synonymous with “including”, “includes” or “containing”, “contains”, and are inclusive or open-ended and do not exclude additional, non-recited members, elements or method steps. It will be appreciated that the terms “comprising”, “comprises” and “comprised of” as used herein comprise the terms “consisting of”, “consists” and “consists of”.
The enumeration of numeric values by means of ranges of figures comprises all values and fractions in these ranges, as well as the cited end points. The term “from . . . to . . . ” as used when referring to a range for a measurable value, such as a parameter, an amount, a time period, and the like, is intended to include the limits associated to the range that is disclosed.
The term “about” or “approximately” as used herein when referring to a measurable value such as a parameter, an amount, a temporal duration, and the like, is meant to encompass variations of +/−10% or less, preferably +/−5% or less, more preferably +/−1% or less, and still more preferably +/−0.1% or less of and from the specified value, insofar such variations are appropriate to perform in the disclosed disclosure. It is to be understood that the value to which the modifier “about” or “approximately” refers is itself also specifically, and preferably, disclosed.
Whereas the terms “one or more” or “at least one”, such as one or more or at least one member(s) of a group of members, is clear per se, by means of further exemplification, the term encompasses inter alia a reference to any one of said members, or to any two or more of said members, such as, e.g., any ≥3, ≥4, ≥5, ≥6 or ≥7 etc. of said members, and up to all said members.
Reference is made to
As defined herein, a carbon dioxide absorption unit is any unit in which gaseous carbon dioxide from a mixture of gases is absorbed in a liquid, the so-called carbon dioxide absorption solution. As a result of this absorption, a carbon dioxide absorption solution comprising absorbed carbon dioxide is generated and the mixture of gases from which carbon dioxide has been separated is, therefore, purified from carbon dioxide. As it is economically interesting to re-use the carbon dioxide solution, a technical solution is required in order to regenerate the solution after it has absorbed carbon dioxide. Said otherwise, there is a need for desorbing the carbon dioxide after it has been absorbed such that the carbon dioxide absorption solution is regenerated and has the capacity to absorb additional carbon dioxide. The desorbed carbon dioxide can, for example, be utilised in processes consuming carbon dioxide, such as urea production.
Typically, the carbon dioxide is regenerated by heating the solution comprising absorbed carbon dioxide in a heat exchange system. A heat exchange system comprising a high-pressure regenerator (57) comprising the solution to be regenerated, and a steam-fired reboiler (58) exchanging steam to the solution, is a known such heat-exchange system. As a result of the heat exchange process, the carbon dioxide absorbed in the solution to be regenerated is evaporated and the solution is, therefore, suitable for being re-used in the carbon dioxide absorption unit (56). On the side of the reboiler (58), after the heat exchange of steam, a process condensate is produced. In particular, in the context of the present application, in such heat-exchange system, in the reboiler (58), the carbon dioxide containing solution to be regenerated is heated and the low pressure steam is condensed to liquid. The condensation of the low-pressure steam thus contributes to the heat required for regeneration of the carbon dioxide absorption solution and the evaporation of the carbon dioxide in the high-pressure regenerator (57). In certain embodiments, the regenerated carbon dioxide absorption solution exiting the high-pressure regenerator may be further treated in a low-pressure regenerator (not shown), typically operating at a pressure below 0.2 kg/cm2, such as at a pressure of about 0.1 kg/cm2, to further evaporate and remove carbon dioxide from the carbon dioxide absorption solution before the latter is reused in the CO2 absorption tower.
Typically, in prior art systems, the process condensate is processed in a process condensate stripper (63) for stripping any gas. In the stripper, the condensate to be stripped comes in contact with steam and the gases dissolved in the condensate are stripped, such that water of a suitable gas content is recovered and can be used for producing additional steam. Typically, the stripped condensate is subsequently treated in a water demineralisation unit (64) to further purify the water before it is used for producing steam. In addition, the demineralised water then needs to be treated in a de-aerator in order to reduce the oxygen content to levels below 20 ppb: this reduction of the level of oxygen is necessary in order to prevent the corrosion of the equipment in which steam is generated from water and subsequently used for exchanging heat.
The presence and the use associated to the presence of a process condensate stripper (63) and of a water demineralisation unit (64) imply high energy consumption. The inventors of the present disclosure have established that the presence of such process condensate stripper and demineralisation unit (64) is not necessary for processing the condensate generated in the steam-fired reboiler (58). Instead of processing the process condensate from the steam-fired reboiler (58) through a process condensate stripper (63) and a water demineralisation unit (64), the process condensate can be sent directly to the de-aerator. In this manner, energy is not only saved by avoiding the actual chemical treatment of the process condensate in the process condensate stripper (63) and in the water demineralisation unit (64), but also by avoiding the pumping of an equivalent amount of demineralised water to the de-aerator (59). All that is necessary is to supply the process condensate directly to the de-aerator (59), in particular via a direct connection between the reboiler (58) and de-aerator (59), by connecting the process condensate outlet (61) of the reboiler (58) to the inlet (69) of the de-aerator (59). As a result, the equipment in the process is greatly simplified, the footprint of the system is greatly reduced, thereby reducing the costs associated to the system and to its operation. Further, the use of the low-pressure steam and its condensation to liquid results in the maximum heat content of the steam being used for supplying heat to the high pressure regenerator (57), such that energy recovery is maximised in the system.
In one embodiment according to the method of the disclosure, the aqueous solution suitable for producing steam obtained in step d) has an oxygen content ranging from 7 ppb to less than 20 ppb.
In one embodiment according to the method of the disclosure, the method further comprises the step e) of re-using the regenerated carbon dioxide absorption solution produced in step c) for absorbing additional carbon dioxide in the carbon dioxide absorption unit (56). As described above, this allows for the reduction of the amount of absorption solution to be used for absorbing a defined quantity of carbon dioxide.
In one embodiment according to the method of the disclosure, the carbon dioxide absorption solution comprises about 30% potassium carbonate, optionally partly or completely converted to potassium bicarbonate.
In one embodiment according to the method of the disclosure, the carbon dioxide absorption solution comprises about 30% potassium carbonate, about 5% potassium bicarbonate, about 0.5% diethanolamine and about 0.5% glycine.
In one embodiment according to the method of the disclosure, the method further comprises the step of f) producing steam from the aqueous solution produced by step d). By using water with a content in oxygen lower than 20 ppb, particularly ranging from 7 ppb to 20 ppb, steam can be produced and can be being supplied, for example, to the steam-fired reboiler (58) for regenerating an additional quantity of a carbon dioxide absorption solution comprising absorbed carbon dioxide, in the high-pressure regenerator (57).
Reference is made to
Hence, the disclosure provides for the possibility to apply the method of the disclosure to the carbon dioxide removal unit (28) in the “front end”, that is the hydrogen production section, of an ammonia production system (71).
In one embodiment according to the method of the disclosure, the method further comprises the steps of m) feeding the mixture of hydrogen and methane obtained from step l) to an ammonia converter (36).
Hence, the disclosure not only provides for the possibility to apply the method of the disclosure to the carbon dioxide removal unit (28) in the “front end”, that is the hydrogen production section, of an ammonia production system, it further allows for the reaction of the produced hydrogen with nitrogen in an ammonia converter. Ammonia can, therefore, be produced while energy is saved from the carbon dioxide removal unit (28).
Reference is made to
As described above in conjunction with the method developed, the inventors of the present disclosure have established that the presence of a process condensate stripper (63) and demineralisation unit (64) is not necessary for processing the condensate generated in the steam-fired reboiler. Since, instead of processing the process condensate from the steam-fired reboiler (58) through a process condensate stripper (63) and a water demineralisation unit (64), the process condensate can be sent directly to the de-aerator, the equipment in the process is greatly simplified, the footprint of the system is greatly reduced, thereby reducing the costs associated to the system. Further, the use of the low-pressure steam and its condensation to liquid results in the maximum heat content of the steam being used for supplying heat to the high-pressure regenerator (57), such that energy recovery is maximised in the system.
In certain embodiments, the system further comprises a low-pressure regenerator (not shown) positioned downstream of the high-pressure regenerator (57), for further removal of CO2 from the regenerated carbon dioxide absorption solution.
In one embodiment according to the system of the disclosure, the system further comprises means for recycling the regenerated carbon dioxide absorption solution regenerated in the high-pressure regenerator (57) or the low-pressure regenerator. Such a system allows for, as described above, subsequently re-using the regenerated carbon dioxide absorption solution produced in step a) for absorbing additional carbon dioxide in the carbon dioxide absorption unit (56). Therefore, this system allows for the reduction of the amount of absorption solution to be used for absorbing a defined quantity of carbon dioxide.
In one embodiment according to the system of the disclosure, the system further comprises means for producing steam (62) with an oxygen content ranging from 7 ppb to less than 20 ppb from the aqueous solution produced in the de-aerator (59), wherein the means for producing steam (62) are in direct fluid communication with the de-aerator (59).
Reference is made to
Hence, the disclosure not only provides for a carbon dioxide removal unit (28), it provides a “front end”, that is a hydrogen production section, of an ammonia production system.
In one embodiment according to the system of the disclosure, the system further comprises an ammonia converter (36) in direct fluid communication with the methanation unit (32).
Hence, the disclosure not only provides for a carbon dioxide removal unit (28) and a “front end”, that is the hydrogen production section, of an ammonia production system, it further provides an ammonia converter for reacting of the produced hydrogen with nitrogen in an ammonia converter. Ammonia can, therefore, be produced while energy is saved from the carbon dioxide removal unit (28).
In another aspect of the disclosure, the use of the system for recovering heat of the disclosure for performing the method for recovering heat of the disclosure is disclosed.
Reference is made to
The method for revamping comprises the steps of (I) fluidly deconnecting the outlet (61) of the steam-fired reboiler (58) from the inlet (65) of the process condensate stripper (63); (II) fluidly deconnecting the inlet (67) water demineralisation unit (64) from the outlet (66) of the process condensate stripper (63); and (III) fluidly connecting the outlet (61) of steam-fired reboiler (58) to the inlet (69) of the de-aerator (59).
By performing such revamping method, this is possible to convert the system according to the state of the art into the system of the disclosure, thereby, as described in conjunction with the system of the disclosure, removing the process condensate stripper (63) and the water demineralisation unit (64). As a result, the equipment in the process is greatly simplified, the footprint of the system is greatly reduced, thereby reducing the costs associated to the system.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202111008669 | Mar 2021 | IN | national |
| 21172485.1 | May 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/055204 | 3/2/2022 | WO |
