Patent Application
20110146489
The present application relates to a process for removal of CO2 from a gas stream and to a multi-stage absorber system for removal of CO2 from a gas stream. After removal of CO2, ammonia is removed from the gas stream by absorption in an absorption liquid.
In processes used for industrial separation of acidic components such as H2S, CO2, COS and/or mercaptans from a gas stream such as flue gas, natural gas, syngas or other gas streams mainly containing nitrogen, oxygen, hydrogen, carbon monoxide and/or methane, liquid solutions comprising amine compounds or aqueous ammonia solutions are commonly used as a solvent. The acidic components are absorbed in the solvent in an absorption process. This process may be generally referred to as the main scrubbing process.
After “scrubbing” of said acidic components by said solutions, contaminants, such as traces of ammonia, amine compounds or degradation products of amine compounds, remain in the gas stream. These contaminants have to be removed from the gas stream.
Currently known systems and methods provide for the removal of these contaminants from a gas stream in a water wash step. In the water wash step, the gas stream is scrubbed with water in a suitable contacting device. Typically, the water used to scrub the gas stream is either fresh water or water obtained from a stripping process related to the treatment of the gas stream. After the gas stream is scrubbed with water, the water is 1) sent back to the stripping unit from which it was obtained or 2) simply mixed with the solution used in the main scrubbing process.
WO 2006/022885 (U.S. patent application Ser. No. 11/632,537, filed Jan. 16, 2007, and which is incorporated by reference herein in its entirety) discloses one such method of removing carbon dioxide from a flue gas, which method includes capturing carbon dioxide from the flue gas in a CO2 absorber by means of an ammoniated solution or slurry. The CO2 is absorbed by the ammoniated solution in the absorber at a reduced temperature of between about 0° C. and 20° C., after which the ammoniated solution is regenerated in a regenerator under elevated pressure and temperature to allow the CO2 to escape the ammoniated solution as gaseous carbon dioxide of high purity.
U.S. Pat. No. 5,378,442 discloses a method for recovering carbon dioxide by absorbing carbon dioxide present in a combustion exhaust gas using an aqueous alkanolamine solution, comprising the step of bringing a combustion exhaust gas from which carbon dioxide has been absorbed and removed into contact with water containing carbon dioxide. It is taught that contact of the treated exhaust gas with water containing CO2 permits the effective removal of ammonia from the treated exhaust gas (exhaust gas after the absorption of CO2) and that part of recovered CO2 can be used to easily increase the concentration of dissolved CO2. The CO2-containing water is brought into contact with the treated exhaust gas at the top of an absorbing column using an ordinary gas-liquid contact method which uses a tray, so as to absorb ammonia present therein, and the water containing ammonia is then led to effluent treating facilities or the like installed outside the CO2 absorbing and recovering system.
Regeneration of used wash liquids, for example in a stripping unit, is generally an energy intensive, and thus expensive, process. Leading used absorption liquid to an external effluent treating facility is on the contrary to the general environmental desire to close industrial processes, and results in high water consumption. Thus, there is a need for improvements as regards the handling of wash and/or absorption liquids.
It is an object to provide an improved manner for handling of a wash and/or absorption liquid in a process or a system for removal of CO2 from a gas stream.
Another object, related to the above mentioned object, is to reduce the costs of a process or a system for removal of CO2 from a gas stream by an improved manner of recycling a wash and/or absorption liquid in such a process or system.
Other objects may be to obtain environmental, health and/or economical benefits of reduced emission of chemicals used in a gas purification process or system.
According to aspects illustrated herein, there is provided a process for removal of CO2 from a gas stream, comprising the steps of:
In this process, the CO2 supplied to the second absorption liquid is CO2 released by regeneration of a first absorption liquid obtained from removal of CO2 from a gas stream, said removal comprising the step of contacting said gas stream with a first absorption liquid comprising ammonia or an amine compound.
Thus, it is allowed for elimination of a water wash and stripper process conventionally following a CO2 absorption stage. Consequently, it is allowed for savings in respect of equipment as well as in operational costs, mainly energy costs, associated with the operation of a water wash unit and its stripper. By recycling of the used absorption liquid leaving the contaminant absorption step the amount of liquid used may be lowered, possibly resulting in lowered costs and lowered environmental impact.
The term “contaminant”, as used herein, refers generally to an undesired component present in a gas stream. The contaminant will generally be present in a minor amount by volume in the gas stream. The contaminant may be undesired e.g. because it lowers the usefulness of the gas stream in a subsequent application or further treatment process or because it imparts undesirable properties to the gas stream, such as toxicity, environmental disadvantages, odors, etc. An example of a contaminant is ammonia. Thus, a “contaminant absorption stage” or a “contaminant absorber” refers to a process or a device for absorption of such a contaminant.
Alkaline compounds are often used in absorption processes for removal of acidic gases, such as CO2, H2S and COS from gas streams, such as in step (a). Step (e) provides for the removal of alkaline contaminants from gas streams. At least one of the contaminants to be removed is ammonia. The supply of CO2 to the second absorption liquid prior to use in an contaminant absorption stage results in a substantial improvement of the efficiency of the absorption stage for the removal of alkaline contaminants such as e.g. ammonia. Although the present invention is not bound by any particular scientific explanation, a contributing factor in this substantial improvement may be a shift of the pH value in the absorption liquid to the acidic side caused by the dissolution of CO2 in the absorption liquid as carbonic acid. Generally, the contaminants introduced in the gas stream through the first absorption liquid being used in the main scrubbing process have a caustic or slightly caustic character. As such, the vapor/liquid equilibrium of the respective contaminant can be improved if the pH value of the water is shifted to the acidic side. However, the substantial improvement goes far beyond what could be attributed solely to such shift of the pH value.
The passing, in step (f), of a liquid portion of used absorption liquid to regeneration may occur when step (f) is performed without substantially releasing ammonia from the used absorption liquid resulting from step (e). In this context it is clear to a skilled person that the phrase “without substantially releasing” allows for, e.g., minor leakages or discharges of ammonia, whereas, e.g., gas/liquid fractionation of the used absorption liquid resulting from step (e), in order to send a gaseous stream of ammonia to regeneration, is not within the scope of step (f). As an example, no stripping of the used absorption liquid resulting from step (e), or of the portion of used absorption liquid resulting from step (e), takes place. The portion of used absorption liquid from step (e) passed to regeneration in step (c) is combined with used absorption liquid from the CO2 absorption stage (a), possibly in a regenerator feed tank, in order to recover the captured ammonia in the regenerating step (c). The passing of a portion of used absorption liquid from step (e) passed to regeneration in step (c) will also maintain the desired CO2 flow from regeneration step (c). The portion of used absorption liquid resulting from step (e) being withdrawn in step (f) may be a minor portion of used absorption liquid resulting from step (e). The minor portion may represent 25% or less, 10% or less, 5% or less or 1% or less of the used absorption liquid resulting from step (e).
The CO2 introduced into the second absorption liquid may be in various physical forms. The CO2 may for example be introduced in solid, liquid, supercritical fluid, or gas form, or a mixture thereof. It has been found that the CO2 may conveniently be introduced into the second absorption liquid in liquid form. Thus, CO2 released from step (c) may be transferred to liquid state before being supplied, in step (d), to the second absorption liquid. Said transfer may be performed or assisted by cooling of gaseous CO2 released in step (c).
In order to account for reaction heat evolved by chemical reactions occurring during step (e), e.g., heat of the NH3—CO2—H2O reaction, and to decrease CO2 vapor release from the second absorption liquid during step (e), the second absorption liquid may be cooled before being contacted, in step (e), with the gas stream leaving step (a).
The contacting of the gas stream containing contaminants to be removed with the second absorption liquid to allow absorption of the contaminants into the second absorption liquid may be brought about in various arrangements, which will be readily recognizable to a person skilled in the art. It has been found that especially efficient absorption is achieved when in step (e) the gas stream is contacted with the second absorption liquid in a counter current flow. To accommodate precipitated solids, the contaminant absorption stage of step (e) may comprise a mass transfer device of a suitable liquid/gas contacting design, preferably of a tray design.
The recited process is applicable when the CO2 absorption stage (a) is operated according to the so-called chilled ammonia process wherein the he flue gas is cooled below ambient (room) temperature before entering the CO2 absorption tower. For example, the flue gas may be cooled below 25° C., preferably below 20° C., and optionally below 10° C. in step (a). An ammoniated solution or slurry may be used as the CO2 absorption liquid, which may be cooled, for example, below 25 C, preferably below 20 C, and optionally below 100.
It is contemplated that the recited process is applicable also when the CO2 absorption stage (a) is operated according to an amine based process. In other words, the recited process may be operated in a manner wherein in step (a) the first absorption liquid comprises an amine compound and wherein in step (e) ammonia, an amine compound or a decomposition product of an amine compound is removed. Examples of amine compounds include, but are not limited to, monoethanolamine (MEA), diethanolamine (DEA), methyldiethanolamine (MDEA), diisopropylamine (DIPA) and aminoethoxyethanol (diglycolamine) (DGA). The most commonly used amines compounds in industrial plants are the alkanolamines MEA, DEA, and MDEA. It is further contemplated that the absorption liquid may also include a promoter to enhance the chemical reaction kinetics involved in the capture of CO2 by the ammoniated solution. For example, the promoter may include an amine (e.g. piperazine) or an enzyme (e.g., carbonic anhydrase or its analogs), which may be in the form of a solution or immobilized on a solid or semi-solid surface.
Step (e) and step (a) may be performed in a common vessel. Step (e) may be performed above the performance of step (a) in a common absorption column. Such arrangements allow for material and cost savings.
Features mentioned in respect of the above aspect may also be applicable to the aspect of the invention described below.
According to other aspects illustrated herein, there is provided a multi-stage absorber system for removal of CO2 from a gas stream having a flow direction, comprising
a CO2 absorber for contacting a gas stream comprising CO2 with a first absorption liquid,
a regenerator for regenerating the first absorption liquid by releasing CO2 from used absorption liquid,
a first conduit connecting the CO2 absorber and the regenerator for passing used absorption liquid to the regenerator, and
a second conduit connecting the regenerator and the CO2 absorber for returning the first absorption liquid to the CO2 absorber; and downstream of the CO2 absorber in respect of the flow direction of the gas stream
a contaminant absorber for contacting the gas stream with a second absorption liquid, and
a recycling circuit connecting a liquid outlet and a liquid inlet of the contaminant absorber for recycling of used absorption liquid as second absorption liquid to the contaminant absorber; the multi-stage absorber system further comprising
a CO2 conduit connecting the regenerator and the recycling circuit for supplying CO2 released from the regenerator to the second absorption liquid, and
a liquid conduit connecting the recycling conduit and the regenerator for passing a portion of the used absorption liquid from the contaminant absorber to the regenerator.
The term “liquid conduit” refers to a conduit adapted and intended for passing of a liquid from the contaminant absorber to the regenerator. A liquid is passed through the liquid line, e.g., when the recycling circuit and the liquid conduit are void of equipment, such as a stripper, for transferring the used absorption liquid or the portion of the used absorption liquid to gaseous state.
Means for supplying CO2 into the second absorption liquid may be adapted for introducing CO2 in solid, liquid supercritical fluid, or gaseous form into the second absorption liquid. CO2 in liquid form may for example be introduced into the second absorption liquid via an injection nozzle. Thus, the CO2 conduit may comprise means, such as a cooler, for liquefying CO2.
As considered above, reaction heat may evolve in the contaminant absorber. To account for that, and for decreasing CO2 vapor release in the contaminant absorber, the recycling circuit may comprise a cooler.
The design of the mass transfer device of the contaminant absorber has been discussed above. Thus, the contaminant absorber may be a counter current absorber. In order to accommodate precipitated solids, the contaminant absorber may comprise a mass transfer device of a suitable liquid/gas contacting design, preferably of a tray design.
It is applicable to operate the recited multi-stage absorber system according to the so-called chilled ammonia process. Thus, the CO2 absorber may be adapted for operation below ambient temperature. For example, at a temperature below 25° C., preferably below 20° C., and optionally below 10° C.
It is contemplated that it is applicable to operate the recited multi-stage absorber system also according to a amine based process. Thus, the CO2 absorber may be adapted for contacting a gas stream comprising CO2 with a first absorption liquid comprising an amine compound, and the contaminant absorber may be adapted for contacting the gas stream with a second absorption liquid for absorption of ammonia, an amine compound or a decomposition product of an amine compound.
The contaminant absorber and the CO2 absorber may be arranged in a common vessel. The contaminant absorber may be arranged above the CO2 absorber in a common absorption column. Such arrangements allow for material and cost savings.
The above described and other features are exemplified by the following figure and detailed description.
Referring now to the figure, which is an exemplary embodiment:
The system represented by
The used absorption liquid leaving the contaminant absorber 306 via the line 308 is recycled via a feed tank 315 and the line 307 to the contaminant absorber 306. A cooler in line 307 accommodates for the heat of the NH3—CO2—H2O reaction and cools the second absorption liquid to decrease CO2 vapor in the contaminant absorber 306. In the feed tank 315, CO2 released from the regenerator 311 is supplied via a line 313 to the second absorption liquid. With assistance of a cooler in line 313, CO2 supplied to the feed tank 315 is liquid. From the feed tank 315, a bleed stream of the second absorption liquid is sent via a line 316 to a regenerator feed tank 317 and further to the regenerator 311 in order to recover the captured ammonia in the regenerator.
While the invention has been described with reference to various exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
This application claims the benefit of U.S. Provisional Patent Application No. 61/287,222, filed Dec. 17, 2009 and entitled “Ammonia Removal, Following Removal Of CO2 From A Gas Stream”, which is incorporated by reference herein in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 61287222 | Dec 2009 | US |
