SOLIDS REACTOR, SYSTEM, AND METHOD FOR SEPARATING OUT CARBON DIOXIDE, IN PARTICULAR FROM WASTE GASES
20220193607 · 2022-06-23
Inventors
Cpc classification
B01J20/28004
PERFORMING OPERATIONS; TRANSPORTING
B01J20/3293
PERFORMING OPERATIONS; TRANSPORTING
B01J2220/66
PERFORMING OPERATIONS; TRANSPORTING
F28D20/0056
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Y02C20/40
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01J20/043
PERFORMING OPERATIONS; TRANSPORTING
B01J19/0013
PERFORMING OPERATIONS; TRANSPORTING
B01D2259/655
PERFORMING OPERATIONS; TRANSPORTING
Y02P20/129
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01D53/96
PERFORMING OPERATIONS; TRANSPORTING
B01J20/3078
PERFORMING OPERATIONS; TRANSPORTING
Y02E60/14
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01J20/3204
PERFORMING OPERATIONS; TRANSPORTING
B01D2259/657
PERFORMING OPERATIONS; TRANSPORTING
B01J2208/00389
PERFORMING OPERATIONS; TRANSPORTING
C09K5/16
CHEMISTRY; METALLURGY
B01J2220/42
PERFORMING OPERATIONS; TRANSPORTING
B01J20/3236
PERFORMING OPERATIONS; TRANSPORTING
B01J2219/00117
PERFORMING OPERATIONS; TRANSPORTING
F28D20/003
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
International classification
B01D53/34
PERFORMING OPERATIONS; TRANSPORTING
B01D53/96
PERFORMING OPERATIONS; TRANSPORTING
B01J19/00
PERFORMING OPERATIONS; TRANSPORTING
B01J20/04
PERFORMING OPERATIONS; TRANSPORTING
B01J20/28
PERFORMING OPERATIONS; TRANSPORTING
B01J8/02
PERFORMING OPERATIONS; TRANSPORTING
C09K5/16
CHEMISTRY; METALLURGY
Abstract
Described herein is a system (100) for storage and releasing of carbon dioxide comprising at least one solids reactor (1), at least one compressor (7, 8) for compressing the carbon dioxide-containing gas or fluid, respectively, which is introduced through the inlet (3) of the solids reactor, wherein the compressor (7, 8) is constructed in such a way that it adiabatically expands the gas or fluid, respectively, depleted of carbon dioxide that is discharged from the reactor by means of the outlet (2) of the solids reactor, and at least one countercurrent recuperator (6), which is constructed for the heat exchange of the compressed exhaust gas or fluid, respectively, that contains carbon dioxide and the gas or fluid, respectively, depleted of carbon dioxide.
Described is furthermore a solids reactor for storage and releasing carbon dioxide, comprising a gas-tight or fluid-tight, respectively, housing, which has an interior, at least one inlet for feeding in fluids and at least one outlet for discharging of gases or fluids, respectively, wherein the interior of the housing is filled with at least two different solids, wherein one solid is provided for storing thermal energy and the other solid is provided for regenerative storage and releasing of carbon dioxide.
Furthermore described is a method for storage and releasing of carbon dioxide.
Claims
1. Solid reactor for storage and releasing carbon dioxide, comprising a fluid-tight housing, which has an interior, at least one inlet for feeding in fluids and at least one outlet for discharging of fluids, wherein the interior of the housing is filled with at least two different solids, wherein one solid is provided for storing thermal energy and the other solid is provided for reversible storage and release of carbon dioxide.
2. The solids reactor according to claim 1, wherein the housing further comprises components which are constructed for introducing or discharging the solids.
3. The solids reactor according to claim 1, characterized in that the area of the inlet and in the area of the outlet of fluids shut-off devices are arranged, which are constructed to change the pressure in the interior of the solids reactor, and/or to introduce fluids into the solids reactor and/or to discharge fluids that escape from the solids reactor.
4. The solids reactor according to claim 1, characterized in that the solids for the storage and releasing of carbon dioxide are selected from calcium oxide and calcium oxide-containing substances selected from limestones and dolomites.
5. The solids reactor according to claim 1, characterized in that the solids for storing thermal energy are selected from inert mineral materials such as quartz, granite, silicon dioxide, igneous rocks, silicon carbides, zirconium oxides, metallic phase change materials, cast iron, grey cast iron or mixtures of the solids mentioned.
6. The solids reactor according to claim 1, characterized in that the at least different solids are in the form of coated solids, consisting of an outer coating and an inner core, wherein the inner core is intended to store the thermal energy and the outer coating is provided for the reversible storage and release of carbon dioxide.
7. The solids reactor according to claim 1, characterized in that the at least two different solids are in form of double salts, wherein one of the salts of the double salt is suitable for storing thermal energy and the other salt of the double salt is suitable for reversible storage and release of carbon dioxide.
8. The solids reactor according to claim 6, characterized in that the double salts are selected from dolomite, dolomite stone, dolomitic rocks, rocks containing dolomite or dolomite stone, or mixtures the thereof.
9. The solids reactor according to claim 1, characterized in that the at least two different solids have a particle size which is in the cm range.
10. The solids reactor according to claim 1, characterized in that the solids introduced into the solids reactor form a fixed bed that allows through-flow.
11. System for storing and releasing carbon dioxide, comprising at least one solids reactor according to claim 1, at least one compressor for compressing the carbon dioxide-containing fluid, which is introduced through the inlet of the solids reactor, wherein the compressor is constructed in such a way that it adiabatically expands the fluid depleted of carbon dioxide that is discharged from the reactor by means of the outlet of the solids reactor, and at least one countercurrent recuperator, which is constructed for the heat exchange of the compressed fluid that contains carbon dioxide and of the fluid depleted of carbon dioxide.
12. The system according to claim 11, characterized in that in the area of the inlet at least one supply for heated fluids is arranged, to further heat the carbon dioxide-containing fluid after heating in the counter-current recuperator and before entering the inlet of the solids reactor.
13. The system according to claim 12, characterized in that, one or more compressors is/are provided which compress or compresses and burn air and/or natural gas and/or heating oil and inject the combustion gas via the supply device.
14. The system according to claim 12, characterized in that the supply device is electrically heatable, and in that the introduced fluid is hydrogen gas.
15. The system according to claim 11, characterized in that furthermore pipelines and shut-off devices are provided, which allow the solids reactor to be constructed to be decoupled from the system, and which connect the solids reactor fluidically via the outlet to the recuperator for discharging fluids.
16. The system according to claim 11, characterized in that system has at least two solids reactors, wherein the solids reactors are fluidically connected with components of systems in that the respective solids reactors are provided independently of one another for storage and for releasing of carbon dioxide.
17. Method for storage and releasing of carbon dioxide, wherein one a) provides at least one solids reactor according to claim 1, for storage and releasing of carbon dioxide, b) introduces a carbon dioxide-containing fluid in the solids reactor, wherein one compresses the fluid in a way that the partial pressure of the carbon dioxide is 1 to 2 bar, c) stops the introducing of the carbon dioxide-containing fluid, when the temperature in the interior of the solids reactor is 910 to 960° C., d) releases the tension of the solids reactor to a pressure of 0.1 bis 0.5 after reaching the internal temperature of 910° C. to 960° C.; e) discharges the carbon dioxide released again by the expansion from the solids reactor until the temperature inside the solids reactor is 810 to 850° C., f) compresses the discharged carbon dioxide to normal pressure and stores it.
18. The method according to claim 17, characterized in that the partial pressure of the carbon dioxide in step b) is above 1 bar.
19. The method according to claim 17, characterized in that the pressure in the interior of the solids reactor in step d) is less than 0.4 bar, especially preferred less than 0.2 bar.
20. The method according to claim 17, characterized in that the temperature in the interior of the solids reactor in step c) is more than 910° C.
21. The method according to claim 17, characterized in that the temperature in the interior of the solids reactor in step e) is below 850° C.
22. The method according to claim 17, characterized in that storage of the carbon dioxide and the subsequent release take place in the same temperature range and in the same reactor.
23. The method according to claim 17, characterized in that the enthalpy released during carbon dioxide absorption or during storage, causes the increase in temperature and thereby is stored in the material which remains inert.
24. The method according to claim 17, characterized in that the stored heat is reused after the pressure reduction for the releasing of the carbon dioxide.
Description
[0038] The present invention is explained in more detail with the accompanying drawings. It shows:
[0039]
[0040]
[0041]
[0042]
[0043]
[0044]
[0045]
[0046]
[0047]
[0048] The carbon dioxide reacts according to the chemical equation CaO+CO.sub.2—>CaCO.sub.3 to limestone (CaCO.sub.3). In
[0049] The CO.sub.2 must be expelled again from the limestone formed in accordance with CaCO.sub.3—>CaO+CO.sub.2. For this so-called calcination, the equilibrium pressure must be higher than the partial pressure. In the case that it is intended to generate pure CO.sub.2 of one bar (ambient pressure), the temperature of the particles must therefore be above 910° C., as this is the temperature for the equilibrium pressure of 1 bar. The calcination is endothermic, so heat is required namely at a temperature level above 910° C.
[0050] With the process according to the invention and the solids reactor, carbon dioxide can be separated from combustion gases with considerably less energy than with the existing processes of the art. The separation of carbon dioxide from the exhaust gases during energy generation with fossil fuels and subsequent underground storage or use in other processes is seen worldwide as an indispensable component in minimizing global warming. Due to the very low energy requirements of the CO.sub.2 separation, the reactor is suitable for the worldwide implementation of CO.sub.2 sequestration. In principle, the reactor can be installed behind all power plants and industrial plants such as cement and lime plants (responsible for 5% of the CO.sub.2 emissions worldwide).
[0051] The aim of the method according to the invention is to reuse the reaction enthalpy released during carbonization directly in a reactor for the endothermic calcination. Therefore, there are appropriate materials in the reactor that store the heat. The exothermic and endothermic reaction enthalpies are of the same size. This eliminates both the annoying use of waste heat from carbonization and the laborious energy generation of calcination. Since, according to the second law of thermodynamics, heat can only flow from a higher to a lower temperature, the carbonization (CaO+CO.sub.2.fwdarw.CaCO.sub.3) must take place at a higher temperature level than the endothermic calcination (CaCO.sub.3.fwdarw.CaO+CO.sub.2)
[0052] The objects of the present invention have the following features and advantages: [0053] A reconstruction of existing plants such as for example with Oxyfuel is not necessary. The solids reactor contains dolomite and/or limestone or lime particles, respectively, and inert inorganic material, for example gravel particles which can store heat. Phase change materials of the known type are also suitable. Dolomite has the advantage that the internal magnesite fraction already serves as a storage medium. [0054] For absorption of the carbon dioxide according to CaO+CO.sub.2—>CaCO.sub.3 (carbonization), the exhaust gas is passed through the fixed bed under excess pressure. Thereby the temperature level of this carbonization reaction is increased. [0055] The subsequent calcination (CaCO.sub.3—>CaO+CO.sub.2) is carried out under low pressure. Thereby the temperature level of this calcination reaction is lowered. [0056] The CO.sub.2 partial pressure of the exhaust gas must be higher during the carbonization than that of the pure gas of the CO.sub.2 during the calcination, as shown in
[0059] In a particularly preferred embodiment of the present invention, lumpy limestones or dolomitic stones in the cm range are in the reactor. The area close to the surface absorbs the carbon dioxide (marked in
[0060] Dolomitic stones are preferred as stones. On the one hand, the inert MgO fraction serves as a storage mass; on the other hand, the MgO fraction prevents the CaO fraction from sintering, so that many cycles can be carried out without the so-called dead burning of the lime occurring. In preliminary tests, over 500 cycles were carried out without a decrease in the absorption capacity taking place. In previous processes with particles in the μm range, the original absorption capacity had dropped to about 10% after 10 cycles.
[0061] After the pressure reduction for the calcination, the endothermic reaction enthalpy is then covered by the stored, latent enthalpy and the stones cool down again, as shown in
[0062] According to the invention it is particularly advantageous that the stones used according to the invention in the reactor have a size in the cm range. This ensures that at the loading of the stones with carbon dioxide, which increases the volume of the stones, the passage of gases or fluids, respectively, is not disturbed. The size of the stones also effects that the number of cycles can be increased, since sintering is avoided. Stone sizes from 0.5 cm to 10 cm are preferred, very particularly preferably 2 cm to 5 cm.
[0063] The following embodiments explain the invention in more detail without restricting the scope of the invention.
[0064] The inventive basic idea of the method according to the invention is that the exhaust gas is compressed for the carbonization and that the subsequent calcination is carried out under low pressure. The pressure ratio must be set so that the CO.sub.2 partial pressure during carbonization is above the CO.sub.2 pressure during calcination. This principle is explained with
[0065] A solids reactor is used for the transfer of the heat from carbonization to calcination. According to
[0066] If the reactor is charged to 910° C., the exhaust gas flow is passed into another, discharged reactor (see
[0067] In
[0068] If the reactor is charged to 910° C., the exhaust gas flow is passed into another, discharged reactor, as shown in
[0069] In
[0070] The system according to the invention shown in
[0071] If the solids reactor 1 is now in state 1b of the unloading of the CO.sub.2, the CO.sub.2, which is bound in the calcium carbonate, is discharged from the outlet 2 during the cooling of the solids reactor. The CO.sub.2 is cooled in the low-pressure heat exchanger 15, then brought to ambient pressure in the compressor 16 and cooled again in the normal pressure heat exchanger 17. The heat dissipated into the heat exchangers 15 and 17 is converted into electricity in the ORC system 18, which could also be a steam turbine. This electricity is used in the system for the compressors. Pure CO.sub.2 now exhausts through outlet 19 under normal conditions. By the energetic coupling of the fluid flows a high level of energy efficiency is achieved, so that only a small amount of energy has to be introduced into the system from the outside in order to be able to carry out the respective reaction processes of carbonization and calcination.
[0072] In
[0073] The system according to the invention shown in
[0074] If the solids reactor 1 is now in state 1b of the unloading of the CO.sub.2, the CO.sub.2, which is bound in the calcium carbonate, is discharged during the cooling of the solids reactor therefrom via outlet 2. The CO.sub.2 is cooled in the low-pressure heat exchanger 15, then brought to ambient pressure in the compressor 16 and cooled again in the normal-pressure heat exchanger 17. Pure CO.sub.2 now exhausts through the outlet 19 under normal conditions. The energetic coupling of the gas streams achieves a high level of energy efficiency, so that only a small amount of energy has to be introduced from outside into the system in order to be able to carry out the corresponding reaction processes of carbonization and calcination.
[0075] In
LIST OF REFERENCE NUMERALS
[0076] 1 Solid reactor [0077] 1a Solid reactor in the state of loading with CO.sub.2 [0078] 1b Solid reactor in the state of discharging the CO.sub.2 [0079] 2 Outlet [0080] 3 Inlet [0081] 4 Inlet line [0082] 5 Outlet line [0083] 6 Countercurrent recuperator [0084] 7 Compressor for exhaust gas [0085] 8 Expansion device for clean gas [0086] 9 Fuel gas supply [0087] 10 Compressor [0088] 11 Air supply [0089] 12 Combustion gas supply [0090] 13 Exhaust gas inlet or outlet [0091] 14 Exhaust gas outlet (low CO.sub.2) [0092] 15 Low pressure heat exchanger [0093] 16 Compressor for CO.sub.2 [0094] 17 Normal pressure heat exchanger [0095] 18 ORC system for power generation [0096] 19 CO.sub.2 outlet [0097] 20 Shut-off devices [0098] 21 Hydrogen injection [0099] 22 Electric heating [0100] 100 System for storing and releasing carbon dioxide