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    • 专利摘要:
    METHOD FOR RECOVERING CARBON DIOXIDE (CO 2 ) FROM A GAS CURRENT AND APPLIANCE FOR RECOVERING CARBON DIOXIDE (CO 2 ) FROM A GAS CURRENT This is a method for recovering carbon dioxide (CO2) from a gas stream . The method includes the step of reacting CO2 in the gas stream with fine droplets from a liquid absorbent, in order to form a solid material to which the CO2 is bound. The solid material is then transported to a desorption site, where it is heated, to release substantially pure CO2 gas. The CO2 gas can then be collected and used or transported in any way desired. A related apparatus for recovering carbon dioxide (CO2) from a gas stream is also disclosed in the present invention.
    公开号:BR112012009818B1
    申请号:R112012009818-7
    申请日:2010-06-08
    公开日:2021-05-04
    发明作者:Grigorrii Lev Soloveichik；Benjamin Rue Wood；Robert James Perry；Sarah Elizabeth Genovese
    申请人:Air Products And Chemicals, Inc.；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] This invention generally relates to processes for capturing carbon dioxide (CO2) from gas streams that contain a mixture of constituents. BACKGROUND OF THE INVENTION
    [002] The emission of carbon dioxide into the atmosphere from industrial sources such as power stations is considered, at present, to be a major cause of the “greenhouse effect”, which contributes to global warming. In response, tremendous efforts are made to reduce CO2 emissions. Many different processes have been developed in an attempt to accomplish this task. Examples include inorganic and polymeric membrane permeation; removal of CO2 by adsorbents such as molecular sieves; cryogenic separation; and scrubbing with a solvent that is chemically reactive with CO2, or that has a physical affinity for gas.
    [003] One technique has received a lot of attention to remove CO2 from flue gas streams, eg exhaust gas produced in power stations. In this technique, aqueous monoethanolamine (MEA) or hindered amines such as methyldiethanolamine (MDEA) and 2-amino-2-methyl-1-propanol (AMP) are used as the solvents in an absorption/removal type regeneration process. The technique has been used commercially to capture CO2 from coal-fired power stations and gas turbines.
    [004] There are certainly considerable advantages inherent in absorption processes based on MEA and amine. However, numerous shortcomings may be preventing broader adoption of this type of technology. For example, the process can sometimes result in considerable increases in the viscosity of the liquid absorbent, which can lead to clogging of pipelines. To avoid this problem, the concentration of MEA and other amines is sometimes kept at a relatively low level, for example below about 30% by weight in the case of MEA. However, lower concentrations can considerably reduce the absorptive capacity compared to the theoretical capacity of the pure sorbent.
    [005] Furthermore, the energy consumption in the MEA process can be very high, due considerably in part to the need for heating and evaporation of the solvent (eg water). For example, the process can consume around 10 to 30% of the steam generated in a boiler that is heated by combustion of a fossil fuel. Additionally, MEA-based absorption systems may not have long-term thermal stability in the presence of oxygen in environments where regeneration temperatures typically reach at least about 120°C.
    [006] Additional disadvantages may result from the fact that the liquid absorbent that is enriched with CO2 in the MEA or hindered amine process may still contain a substantial amount of free amine and solvent (usually water). Amine and water are moved in the vapor phase under thermal desorption, but can lead to corrosion and other degradation in the equipment in question. To address this issue, specialized equipment corrosion materials can be used for the equipment, but this can, in turn, increase the capital costs for the station. In some cases, corrosion inhibitors can be added, but the use of these specialized additives can also increase operating costs. In addition, oxidation of MEA or hindered amine absorbents can acidify some of the solvents present. In addition to the corrosion problems that can result, this can decrease the alkalinity available for CO2 capture, thereby reducing process efficiency.
    [007] Another example of a commercial post-combustion CO2 capture process uses aqueous solutions of potassium carbonate promoted by piperazine (K2CO3). However, this process is often very energy intensive and can be economically inferior to the MEA process. Yet another example involves the use of cooled ammonia. In this case, energy intensive cooling systems are usually required for such a system, and the risks associated with unintentional ammonia release may be unacceptable.
    [008] In view of these considerations, new methods to treat gas streams that contain CO2 would be welcome in the art. The new processes must effectively remove some portion of CO2 from the gas stream, under conditions that are economically viable in some industrial installations. Furthermore, the processes must be compatible with related systems, for example, power generation systems based on gasification, combustion and the like. DESCRIPTION OF THE INVENTION
    [009] One embodiment of this invention is directed to a method for recovering carbon dioxide (CO2) from a gas stream. The method comprises the following steps: a) reacting CO2 in the gas stream with fine droplets of a liquid absorbent, in order to form a solid material to which the CO2 is bound; b) transport the solid material to a desorption site; c) heating the solid material at the desorption site to release substantially pure CO2 gas; and d) collect CO2 gas.
    [010] Another embodiment of the invention is directed to an apparatus for recovering carbon dioxide (CO2) from a gas stream. The apparatus comprises: (i) a reaction chamber suitable for reacting CO2 gas with a reactant; in order to form a solid material to which CO2 is bound; (ii) a desorption site, to heat solid material to release CO2 gas and to regenerate the reactant; and (iii) a transport mechanism to transport solid material from the reaction chamber to the desorption site. BRIEF DESCRIPTION OF THE DRAWINGS
    [011] Figure 1 is a schematic view of an exemplary apparatus for recovering CO2 from a gas stream.
    [012] Figure 2 is a schematic view of another apparatus to recover CO2 from a gas stream.
    [013] Figure 3 is a schematic view of another exemplary apparatus for recovering CO2 from a gas stream.
    [014] Figure 4 is a schematic diagram of a test apparatus for reacting CO2 and a reagent. DESCRIPTION OF ACHIEVEMENTS OF THE INVENTION
    [015] The compositional ranges disclosed herein are inclusive and combinable (e.g., ranges of "up to about 25% by weight", or, more specifically, "about 5% by weight to about 20% by weight" , are inclusive of the end points and all intermediate values of the ranges). Weight levels are given based on the weight of the entire composition, unless otherwise specified; and the reasons are also given on a weight basis. Furthermore, the term “combination” is inclusive of blends, blends, alloys, reaction products and the like. Additionally, the terms "first," "second," and the like, in the present invention do not denote any order, quantity or importance, but rather are used to distinguish one element from another. The terms "a" and "an" in the present invention do not denote a quantity limitation, but rather denote the presence of at least one of the mentioned items. The “about” modifier used in conjunction with a quantity is inclusive of the stated value, and has meaning by context, (eg, includes the degree of error associated with measuring the particular quantity). The suffix "(s)" as used in the present invention is intended to include both the singular and plural of the term it modifies, thus including one or more of those terms (for example, "the compound" may include one or more compounds, unless otherwise specified). Reference throughout the descriptive report to "one (1) achievement", "another achievement", "an achievement", and others means that a particular element (e.g., resource, structure and/or characteristic) is described together with the embodiment is included in at least one embodiment described in the present invention, and may or may not be present in other embodiments. Furthermore, it is to be understood that the inventive features described may be combined in any suitable manner in the various embodiments.
    [016] As further described in the present invention, carbon dioxide is present in a wide variety of gas streams that can be treated according to the embodiments of this invention. Non-limiting examples include gas streams originating from a combustion process; a gasification process; to landfill; a furnace (eg, blast furnace or chemical reduction furnace); a steam generator; a boiler; and combinations thereof. In some embodiments, the CO2 gas stream is a stack stream originating from a coal-fired power station. In other embodiments, the CO2 gas stream originates at a coal gasification plant, exemplified by an integrated gasification combined cycle (IGCC) plant. In addition to CO2, the stack stream can include numerous other constituents such as oxygen, nitrogen, argon, carbon monoxide, nitrogen compounds and oxygen, sulfur compounds (eg, sulfur dioxide, carbonyl sulfide); rust particles and water vapor.
    [017] A variety of liquid absorbents can be reacted with carbon dioxide. In general, any liquid CO2 absorbent that can be converted to a solid through reaction with carbon dioxide can be used to carry out the process described in the present invention. Some of the liquid absorbents are described in the following references: "Reversible Gelation of Polyethyleneimide Solutions Using CO2", Kitchens et al, AIChE Annual Meeting, San Francisco, CA, USA, 2006 (p. 520f for background); and “Reversible, Room-Temperature Chiral Ionic Liquids. Amidinium Carbamates Derived From Amidines and Aliphatic Primary Amines with Carbon Dioxide”, Yamada et al, Chem. Mater., 19, (5), 967 to 969 (2007).
    [018] Usually, the liquid absorbent comprises at least one amine material. Various amine compounds (the term as used in the present invention also includes polymeric materials) are suitable. Many fall into the following classes: aliphatic primary, secondary and tertiary amines, and polyamines; polyimines (for example polyalkyleneimines); cyclic amines, amidine compounds; hindered amines; aminosiloxane compounds; amino acids; and combinations thereof. Non-limiting examples of these materials are noted below.
    [019] Exemplary aliphatic amines and polyamines are cyclohexyl amine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the like. In addition, materials such as substituted amines, eg alkanolamines, can also be used.
    [020] Exemplary polyimines are polyalkyleneimines. Many of these materials are made by the polymerization of one or more alkyleneimines, such as ethyleneimine, propyleneimine and 1,2-butyleneimine. In some embodiments, a preferred polyimine is polyethylenimine.
    [021] Preferred cyclic amines include piperidine, piperazine and pyridine based compounds such as 4-aminopyridine. Various bicyclic compounds can also be used, such as 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
    [022] Numerous amidine and guanidine compounds can also be used. Most amidines conform to the general structure
    .[023] where each R group individually can be hydrogen or a lower alkyl group. Many of the amidine compounds are considered to be oxoacid derivatives. (When the parent oxoacid is a carboxylic acid, the resulting amidine is a carboxamidine). Some of the amidine compounds are described in US4,162,280 (Kranz) and US4,129,739 (Tracy et al). Each such reference is incorporated herein by reference. Non-limiting examples of amidines include Formamidine .
    , em que cada grupo “R” pode, independentemente, ser hidrogênio ou um grupo alquila. Os exemplos não limitantes das guanidinas incluem 1,1,3,3- tetrametilguanidina ((Me2)N)2C=NH).[024] The guanidines are a group of organic compounds with the general structure , where each "R" group can independently be hydrogen or an alkyl group. Non-limiting examples of guanidines include 1,1,3,3-tetramethylguanidine ((Me2)N)2C=NH).
    [025] Hindered amine compounds that can be used as the liquid absorbent are also known in the art. Some of these compounds are described in patent US4,405,579 (Sartori et al) and US6,117,995 (Zedda et al), as well as EP application 0588175B1 (Yoshida et al). Each such reference is incorporated herein by reference. Non-limiting examples include polyalkyl substituted piperidine derivatives such as 2,2,6,6-tetramethyl piperidine. Other examples include 2,2,6,6-tetramethyl piperidine; tert-butylamine; cyclohexyldiamine; 2-(dimethylamino)-ethanol; 2-(diethylamino)-ethanol; 2-(ethylmethylamino)-ethanol; 1-(dimethylamino)-ethanol; 1-(diethylamino)-ethanol; 1-(ethylmethylamino)-ethanol; 2-(diisopropylamino)-ethanol; 1-(diethylamino)-2-propanol; 3-(diethylamino)-1-propanol; and combinations thereof.
    [026] Amino-siloxane compositions are also known in the art. Various types of such compounds are described in patents US5,939,574 (Schilling, Jr., et al) and US4,487,883 (Homan), which are incorporated herein by reference. Those skilled in the art will be able to determine which particular amino silixoxanes are capable of reacting with CO2 gas to form the solid material as described in the present invention. Some of the aminosiloxanes that are useful in this invention are described in a pending patent application by Perry et al; SN US12/512,105, filed July 30, 2009, which is incorporated herein by reference. A variety of aminosiloxanes are described in the aforementioned disclosure. Non-limiting examples of suitable aminosiloxanes include compositions comprising the chemical structure (I)
    [027] wherein R is a C1-C6 alkyl group, which may be linear or branched; and which can contain at least one hydroxy group; R1 is independently at each occurrence C1-C8 alkyl or aryl; R2 is R1 or RNR3R4, where R3 and R4 are independently a bond, hydrogen or C1-C8 alkyl (linear or branched).
    [028] A specific illustrative example of an amino-siloxane compound is provided below as compound (Ia), where "Me" is a methyl group:
    [029] The Perry et al application describes methods for preparing various aminosiloxane compounds as well.
    [030] The identity of the solid material that is formed by the reaction of the liquid absorbent with CO2 will largely depend on the specific liquid absorbent that is used. In the case of amine absorbers, the solid material will depend on the identity of the amine. In many cases, the solid material comprises a carbamate or bicarbonate compound, or a combination thereof.
    [031] The reaction of the liquid absorbent with the amine compound can be carried out in any chamber or large-scale confinement. The particular type of chamber is not critical to this invention as long as it allows sufficient contact between the CO2 and the liquid absorbent. Thus, the containment can be in the form of an absorption tower, a wet wall tower, a spray tower, or a venturi scrubber, optionally equipped with a drag separator. Furthermore, although a vertical camera is revealed in the figures discussed below, a horizontally oriented camera can alternatively be used.
    [032] As an example, Venturi scrubbers are known in the art and typically include at least three sections: a convergent section, a bottleneck section and a divergent section. An incoming gas stream can enter the converging section, and as the area decreases, the gas velocity increases. Liquids are usually introduced at the neck, or at the entrance to the converging section. In a typical scenario, the inlet gas is forced to move at very high speeds in the small neck section, shearing liquid matter from the vessel walls. This action can produce a large number of very tiny droplets, which can react with the incoming gas stream. As a non-limiting example, venturi systems are described in US5,279,646 (Schwab), which is incorporated herein by reference.
    [033] In some embodiments of this invention, the use of a spray tower is preferred. Sprinkler towers and absorption towers are well known in the art and described in many references. Several illustrations include patents US7,368,602 (Sakai et al); US5,206,002 (Skelley et al); and US 4,114,813 (Suga), all of which are incorporated herein by reference.
    [034] Figure 1 is a simplified non-limiting description of an apparatus 10 for performing the process according to the embodiments of this invention. The liquid absorbent 12 is directed from any suitable source (not shown) in the spray tower 14, through at least one conduit 16. The supply point for the absorbent is usually located in an upper region 15 of the spray tower 14 , to ensure fine absorbent droplet formation, as described below, and to provide sufficient contact time with CO2. The supply point for the absorbent can also be located above or in the narrow part (neck) of a venturi scrubber. The absorbent atomizing means 18 is employed to disperse the absorbent into droplets.
    [035] A variety of conventional atomization mechanisms can be used, such as spray atomization. For example, air or some other atomizing gas may be supplied from a nozzle tube 20 into the interior 22 of the tower 14. The atomizing mechanism will typically be located near the outlet of the conduit 16 within the tower, and more than one nozzle tube could also be used. In some embodiments, many nozzles can be placed along the tower at different heights to maximize the number of absorbent droplets. Furthermore, the atomizer 18 could, in fact, be incorporated in a portion of the conduit 16.
    [036] The size selected for the liquid absorbent droplets will depend on several factors, such as the composition of the absorbent; the reactivity of the absorbent material with CO2 gas; and the type and design of the absorption chamber. In general, the droplets must be small enough to collectively provide a maximum surface area for contact with CO2. In this way, a relatively high proportion of CO2 can be removed from the gas stream. In addition, the relatively small droplet size will help ensure that the droplet particles are less prone to “sticky” which could otherwise impede the movement and suspension of the droplets. However, the droplets must be large enough to provide sufficient mass for solid particle formation, as described below, and to prevent the solid particles formed from being carried out of the tower. As a non-limiting example for an amine-based absorbent used in a spray tower, the average droplet diameter is usually no greater than about 1000 microns and typically in the range of about 500 microns to about 1000 microns. In another embodiment, when a venturi scrubber is used, the average droplet diameter is typically in the range of about 10 microns to about 100 microns.
    [037] In continuation of reference to Figure 1, the flue gas 24 is directed to the spray tower 14 by any suitable conduit 26. In some embodiments (not all), the flue gas is directed to a lower region 28 of the spray tower, relative to the upper region 15. In this way, an induced counter-current flow exposes the exit gas (described below) which has the lowest concentration of CO2 to the coolest absorbent. At the same time, the input gas with the highest concentration of CO2 is exposed to most of the “converted” absorbent. This type of flow scheme can allow the resulting solid particles to agglomerate more readily, leading to faster solidification.
    [038] The flue gas flow rate entering chamber 14 is maintained to provide the residence time necessary for the complete reaction, as described below. Inlet pressure depends on the design of the absorption chamber. The pressure drop for flue gas entering the chamber may be relatively small in the case of a spray tower (eg, about 1 inch (2.54 cm) of water), but may be greater for other types of absorption towers.
    [039] The contact between the CO2 gas molecules and the liquid absorbent droplets results in the formation of solid particles 30, as mentioned above. CO2 is bound inside the particles. The size, shape and density of particles depend on several factors, such as the size of the initial droplets; the content of the liquid absorbent; the length of stay inside the spray tower or other type of chamber; and the gas flow rate. Particles 30 should be small enough to solidify to at least one non-tacky surface texture, but large enough to provide sufficient mass for effective transport out of spray tower 14. Particles 30 are usually spherical or substantially spherical. in format. Its average density can vary significantly, but is usually in the range of about 1.1 g/cc to about 1.5 g/cc. Particle size may vary, for example, depending on the initial spray technique used. In some cases, the average particle size is in the range of about 1000 microns to about 2000 microns.
    [040] The formation of solid particles 30 can remove a substantial amount of "free" CO2 from the gas stream, for example, at least about 50% by volume in some embodiments, and at least about 70% by volume in others achievements. The remaining tasteless CO2 flue gas can then be released as an off-gas through any suitable conduit 31. Alternatively, the tasteless flue gas can be routed to other locations for further treatment or use.
    [041] The particles are then transported to a desorption site. Any means of transport is possible. Non-limiting examples include mechanical means; gas flow; means facilitated by pressure; or gravity flow as described below. Referring to exemplary Figure 1, solid particles 30 can exit spray tower 14 through any practical opening 32. Particles can then fall or be directed onto a transport mechanism 34. Any suitable transport mechanism can be employed , for example, any type of belt, tube, conductor or other type of conveyor line, which can also be equipped with one or more pumps. In some embodiments, a screw driver, for example, an extruder screw, can be used effectively.
    [042] In other embodiments, particles can be directed to a desorption site by means of pressure, for example, with a carrier gas; or through a vacuum. Those skilled in the field of particle transport (eg resin powder or granules) are familiar with these types of systems. Additionally, as yet another alternative, desorption station 36 (described below) can be positioned below spray tower 14. In this way, solid particles 30 can simply fall into station 36 by gravity. In fact, the sprinkler tower and desorption unit could be sections of a structure as a whole.
    [043] The desorption station or chamber 36 may comprise any type of desorption unit used to separate volatile compounds from solid particles. In general, the desorption station 36 is a vessel or tube that can provide varying heat and pressure conditions to release CO2 from the solid particles 30. The station also includes a means to collect the released gas and separate the gas from any other constituents of desorption, for example, solid or liquid particles.
    [044] Desorption units are described in numerous references. A non-limiting example is the publication “Remediation Technology Health and Safety Hazards: Thermal desorption”, published by the Occupational Safety & Health Administration (OSHA); SHIB 02-03-03 (http://www.osha.gov/dts/shib/shib_02_03_03_tsds9.pdf), which is incorporated herein by reference. Many of the units are referred to as “thermal desorption units”, which are designed to operate at relatively low temperatures, for example, around 93°C to 316°C (200°F to 600°F); or relatively high temperatures, for example, around 316°C to 538°C (600°F to 1000°F).
    [045] In terms of applied temperature, thermal desorption units are often grouped into three types of process: directly heated units, indirectly heated units; and local units as described in the OSHA reference. Also, the configuration of the unit may vary, for example, depending on what type of solid material is being treated; and what temperature is needed. In some cases, the desorption unit can be operated under a vacuum or very low pressure conditions; and/or low oxygen conditions, to decrease the heat requirements needed for desorption. Adjusting the weather conditions can also provide flexibility in reducing the similarity of creating hazardous conditions, for example, the formation of hazardous products or flammable conditions.
    [046] In general, the desorption of solid particles 30 is typically performed by heating the particles. As mentioned above, the heat treatment regimen will depend on the composition and size of the solid particles; the amount of CO2 bound in the particles; pressure conditions within the desorption chamber 36; and the required reaction rate. The temperature must be high enough to release as much CO2 as possible from the solid particles, and is typically at least as high as the decomposition temperature of the particles. However, the temperature must not be excessively high, that is, requiring excessive energy use; or possibly resulting in decomposition to by-products that may be difficult to handle in the process as a whole. In most embodiments where the solid particles are carbamates, bicarbonates or related compositions, the desorption temperature is usually in the range of about 80°C to about 150°C. In some cases, the internal pressure conditions in chamber 36 can be lowered to speed up the desorption process.
    [047] In continuous reference to Figure 1, the substantially pure CO2 gas 38 is released or otherwise directed out of the desorption chamber 36 by any suitable conduit 40 (or multiple conduits). In some cases, CO2 gas is compressed and/or purified, for reuse, or for transport to a location for sequestration. Various uses for CO2 gas are described in numerous references, for example, patent application US2009/0202410 (Kawatra et al), which is incorporated in the present invention by way of reference.
    [048] The desorption step also functions to regenerate a substantial amount of the liquid absorbent 42. In some embodiments, the liquid absorbent can be directed to treatment, storage or disposal facilities. However, in preferred embodiments, the liquid absorbent 42 is directed back to the spray tower 14 through one or more conduits 44. One or more pumps 46 can be used to pump the absorbent back to the spray tower. However, other techniques for moving the absorbent through proper tubing may be anticipated by those skilled in the art.
    [049] Typically, the regenerated liquid absorbent 42 can be properly added to the spray tower, to react with additional CO2 from a gas stream, forming more solid material bound to CO2 in a closed-loop process. The regenerated liquid absorbent could be combined with "fresh" liquid absorbent 12 or it could be added to the spray tower 14 as a separate feed, along with the absorbent 12. In addition, the liquid absorbent could be combined with one or more solvents such as such as glycol ethers, eg glymes (oligoethylene glycol dimethyl ethers), triethylene glycol dimethyl ether, or with water to reduce the viscosity of material entering the spray chamber.
    [050] In some cases, the liquid absorbent used for reaction with CO2 has a relatively high vapor pressure, and is volatile under typical atmospheric conditions. In other cases, small droplets of regenerated absorbents may be carried away from the desorption site with the gas flow. Therefore, it may be desirable to include at least one condensation step in the process. In this way, the additional absorbent can be recovered from the tasteless CO2 flue gas resulting after the decomposition of solid material rich in CO2.
    [051] Figure 2 provides an illustration of these optional steps, and device features that are identical to those in Figure 1 need not be specifically described. Tasteless flue gas which may include some volatile absorbent is directed out of the spray tower 14, through at least one conduit 31, to a condenser 50. The condenser can be equipped with any type of conventional refrigerating system or device 52. for example, cooling tubes or jackets that use a variety of coolants, such as water.
    [052] The passage of tasteless flue gas through the condenser serves to liquefy the residual refrigerant, while also coalescing any small liquid droplets. The regenerated absorbent 54 can then be directed through any suitable conduit 56 to a storage vessel 58. The absorbent 54 can be mixed with the regenerated absorbent 42, which is also directed into the storage vessel 58, through the duct 44. The combined regenerated sorbent 60 can then be directed to the spray tower 14 for further reaction with CO2.
    [053] There are alternatives to the general process outlined in Figure 2. For example, storage vessel 58 may not be necessary or may not need to accommodate both regenerated absorbent 54 and regenerated absorbent 42. In other words, one or both of these sorbent streams could be sent directly to the spray tower 14.
    [054] Another alternative embodiment is disclosed in Figure 3, in which a separate desorption unit is not required. In that case, the screw conductor 34 can properly function as the desorption unit. For example, component 34 can be any type of an extruder, which would transport solid particles 30 through all or part of its length. As those skilled in the art know, solid particles can be directed through an extruder in many different ways. Non-limiting examples include mechanical means such as pile driving; or other means, such as hydraulic pressure or vacuum conditions. In some cases, a double or single screw auger is powered by an electric motor (or a ram). Mechanisms for heating solid particles in the extruder, i.e., to the desired desorption temperature, are also known in the art.
    [055] In continuation with reference to Figure 3, heating of the particles 30 releases carbon dioxide, which can be directed out of the extruder through any suitable outlets 45. The most appropriate shape, position and number of outlets can be determined without experimentation improper. As in the other realizations, the CO2 released can be directed to any desired location.
    [056] The liquid absorbent that is regenerated after desorption in the extruder (or any other suitable screw conductor type) can be collected and directed to a desired location. As an example, the absorbent could be directed through conduit 47 to supply conduit 16, for re-entry into the spray tower 14. Other alternatives to the regenerated material are possible, as noted above, eg premix with fresh absorbent or direct transport to the sprinkler tower. Furthermore, this embodiment, like the others, can be combined with various other features disclosed in the present invention. For example, such an embodiment could employ the condenser system described above in relation to Figure 2. EXAMPLES
    [057] The example presented below is intended to be illustrative only and should not be interpreted as being any kind of limitation on the scope of the claimed invention.
    [058] A chromatography column made of fritted glass was used as the reaction chamber 70, shown in Figure 4. A syringe 72 with a bent needle tip was loaded with a CO2 capture solvent (absorbent). In this case, the solvent was an amino-siloxane compound called “GAP-0”, which has the formula (NH2C3H6Si(Me)2OSiMe2C3H6NH2), where “Me” is a methyl group. The GAP-0 sorbent was introduced as a fine liquid spray into a stream 74 of CO2 gas flowing through the column. (Spray droplets 76 are illustrated for a general understanding of the process, but are not intended to be specific about their exact size and position in the figure).
    [059] As the liquid absorbent came in contact with the droplets in the gas stream, white solid particles 78 readily formed. Solid particles fell to the bottom of the column or were partially trapped in the column wall, where they were easily removed.
    [060] The material analysis of the solid particles 78 indicated a conversion of GAP-0 to about 70 to 80% of the corresponding carbamate. Subsequent heating of the solid carbamate to about 120°C for two to three minutes resulted in regeneration of the liquid sorbent material, with no apparent decomposition of the sorbent.
    [061] The present invention has been described in terms of some specific embodiments. They are for illustration only and are not to be construed as limiting in any way. Accordingly, it is to be understood that modifications can be made thereto which are within the scope of the invention and the appended claims. Additionally, all patents, patent applications, articles and texts that are mentioned above are incorporated in the present invention by way of reference.
    权利要求:
    Claims (27)
    [0001]
    1. METHOD TO RECOVER CARBON DIOXIDE (CO2) FROM A GAS CURRENT (24), characterized in that it comprises the following steps: a) reacting CO2 in the gas stream with fine droplets of a liquid absorbent (12), with the purpose of forming a solid material (30) to which CO2 is bound; b) transporting the solid material (30) to a desorption site (36); c) heating the solid material (30) at the desorption site (36) to release substantially pure CO2 gas (38); and d) collect CO2 gas.
    [0002]
    2. METHOD according to claim 1, characterized in that the reaction of CO2 with the fine droplets occurs in a spray tower (14) or a venturi scrubber.
    [0003]
    3. METHOD according to claim 1, characterized in that the fine droplets are formed by a spray atomization technique.
    [0004]
    4. METHOD according to claim 1, characterized in that the fine droplets have an average diameter not greater than about 1,000 microns.
    [0005]
    5. METHOD according to claim 4, characterized in that the fine droplets have an average diameter in the range of about 500 microns to about 1000 microns.
    [0006]
    6. METHOD according to claim 1, characterized in that the solid material comprises solid particles, with a density of at least about 1.1 g/cc.
    [0007]
    7. METHOD according to claim 6, characterized in that the solid particles have an average particle size in the range of about 1000 microns to about 2000 microns.
    [0008]
    8. METHOD according to claim 1, characterized in that the liquid absorbent (12) comprises at least one amine compound.
    [0009]
    9. METHOD according to claim 8, characterized in that the amine compound is selected from the group consisting of polyimines; polyamines; cyclic amines; guanidines; amidines; hindered amines; amino acids; aminosiloxane compounds and combinations thereof.
    [0010]
    10. METHOD according to claim 9, characterized in that the polyimine comprises polyethyleneimine.
    [0011]
    11. METHOD according to claim 9, characterized in that the cyclic amine is selected from the group consisting of 4-aminopyridine; 1,5-diazabicyclo[4.3.0]mpm-5-ene (DBN); and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
    [0012]
    12. METHOD, according to claim 9, characterized in that the amidine comprises formamidine (HC(=NH)NH2).
    [0013]
    13. METHOD according to claim 9, characterized in that the hindered amine is selected from the group consisting of 2,2,6,6-tetramethyl piperidine; tert-butylamine; cyclohexyldiamine; 2-(dimethylamino)-ethanol; 2-(diethylamino)-ethanol; 2-(ethylmethylamino)-ethanol; 1-(dimethylamino)-ethanol; 1-(diethylamino)-ethanol; 1-(ethylmethylamino)-ethanol; 2-(diisopropylamino)-ethanol; 1-(diethylamino)-2-propanol; 3-(diethylamino)-1-propanol; and combinations thereof.
    [0014]
    14. METHOD according to claim 9, characterized in that the amino-siloxane compound is (NH2C3H6Si(Me)2OSiMe2C3H6NH2), in which "Me" is a methyl group.
    [0015]
    15. METHOD according to claim 9, characterized in that reaction between the liquid absorbent (12) and the amine compound results in the formation of a carbamate, a bicarbonate or combinations thereof.
    [0016]
    16. METHOD according to claim 1, characterized in that the heating step (c) regenerates at least a portion of the liquid absorbent, which is separated from the collected CO2 gas.
    [0017]
    17. METHOD according to claim 16, characterized in that the heating step (c) is performed in a chamber adapted to apply heat to the solid material to which the CO2 is bound; or in an extruder.
    [0018]
    18. METHOD according to claim 16, characterized in that the regenerated liquid absorbent is directed back to a reaction site for reaction with additional CO2 from the gas stream to form additional solid material.
    [0019]
    19. METHOD according to claim 16, characterized in that the reaction site comprises a spray tower or a venturi debugging system.
    [0020]
    20. METHOD according to claim 18, characterized in that the regenerated liquid absorbent is directed back to the reaction site by means of pumping or pressure means.
    [0021]
    21. METHOD according to claim 1, characterized in that the heating step (c) is performed at a temperature sufficient to substantially decompose the solid material (30) formed by the reaction of CO2 and the liquid absorbent (12) .
    [0022]
    22. METHOD according to claim 1, characterized in that the reaction step (a) forms a CO2 tasteless stack gas.
    [0023]
    23. METHOD according to claim 22, characterized in that the CO2 tasteless flue gas contains volatile liquid absorbent, and the volatile liquid absorbent is condensed and directed back to a storage chamber, or to a storage site. reaction for reaction with additional CO2.
    [0024]
    24. METHOD, according to claim 1, characterized in that the gas source is selected from the group consisting of a combustion process; a gasification process; a landfill; a furnace; a steam generator; a boiler and combinations thereof.
    [0025]
    25. METHOD, according to claim 24, characterized in that the source of the gas stream is a power station powered by coal.
    [0026]
    26. METHOD according to claim 1, characterized in that the substantially pure CO2 gas released in step (c) is sequestered in a separate location.
    [0027]
    27. METHOD TO RECOVER CARBON DIOXIDE (CO2) FROM A GAS CURRENT, characterized by the fact that it originates in a coal-powered power station or a gasification station, which comprises the following steps: A) reacting the CO2 with fine droplets of a liquid absorbent in a spray tower or a venturi scrubber to form a solid material to which CO2 is bound; B) transporting the solid material to a desorption chamber; C) heating the solid material in the desorption chamber to release substantially pure CO2 gas; and to regenerate at least a portion of the liquid absorbent; D) collect CO2 gas; and E) directing the regenerated liquid absorbent back to the spray tower or venturi scrubber.
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    同族专利:
    公开号 | 公开日
    CN102665859A|2012-09-12|
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    AU2010313723B2|2016-05-19|
    JP2013509293A|2013-03-14|
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    BR112012009818A2|2020-09-24|
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    法律状态:
    2020-10-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-10-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-10| B25A| Requested transfer of rights approved|Owner name: AIR PRODUCTS AND CHEMICALS, INC. (US) |
    2021-03-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-04| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 04/05/2021, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/609,454|2009-10-30|
    US12/609,454|US8647413B2|2009-10-30|2009-10-30|Spray process for the recovery of CO2 from a gas stream and a related apparatus|
    PCT/US2010/037691|WO2011053390A1|2009-10-30|2010-06-08|A spray process for the recovery of co2 from a gas stream and a related apparatus|
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