EP2164613A1 - Method for separating carbon dioxide from flue gases and associated device - Google Patents
Method for separating carbon dioxide from flue gases and associated deviceInfo
- Publication number
- EP2164613A1 EP2164613A1 EP08774407A EP08774407A EP2164613A1 EP 2164613 A1 EP2164613 A1 EP 2164613A1 EP 08774407 A EP08774407 A EP 08774407A EP 08774407 A EP08774407 A EP 08774407A EP 2164613 A1 EP2164613 A1 EP 2164613A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- reactor
- gas
- catalytic
- adsorption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20723—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
-
- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Definitions
- the invention relates to a process for the separation of carbon dioxide (CO 2 ) from flue gases using an adsorption process in which the CO 2 is attached to an adsorber.
- the invention relates to an associated apparatus for carrying out the method.
- Reducing the emission of the greenhouse gas carbon dioxide (CO 2 ) from power plants and industrial plants can be achieved by using low-carbon fuels.
- the removal of CO 2 from exhaust gas can be done by physical or / or chemical binding in the volume (“absorption”) or by attachment to active surfaces (“adsorption").
- the physical or chemical absorption is in both cases multi-step processes, in which the CO 2 -containing exhaust gas is brought into contact with a physical or chemical absorber until it is completely loaded with CO 2 . Thereafter, the absorber must be discharged, the CO 2 is released in the presence of a Spulgases and finally separated from this.
- Potential problems here are the slippage necessary for the Bin ⁇ dung substance, ie, the absorber, the doors ⁇ voltage of the CO 2 from the Spulgas in a form which allows further use of the CO 2, and possibly the high energy consumption for regeneration especially in the case of chemical bonding.
- DE 1 911 670 A describes a process for the purification of gases which contain acidic components such as CO 2 , in which case as in the following three documents the further use of the purified gas is the primary objective and not the further use of the adsorbent bound gas.
- JP 04-022415 discloses the separation of CO 2 from process gases for the semiconductor industry by means of adsorption on ammonia-laden zeolites, the CO 2 being chemically chemically oxidized by reaction with the ammonia at ambient temperature remains bound.
- the separation of CO2 from exhaust gases, z. B. of thermal power plants, by carbonate formation at Tempe ⁇ temperatures between 600 0 C to 800 0 C, is disclosed in JP 10-272336 A.
- membrane processes for the separation of CO 2 are possible, but hitherto, for cost and efficiency reasons, ie, low selectivity of the separation process between CO 2 and, for example, N 2 , are unsuitable for applications in large plants.
- CO 2 carbon dioxide
- the equilibrium of reaction (2) is at low temperatures and high surface concentrations of NH 3 on the right side of the reaction equation, but at high temperatures or low surface concentrations of NH 3 on the left side.
- the catalyst is regenerated, excluding the Abga ⁇ ses at a higher temperature in a gas mixture of ⁇ serdampf and CO 2 , wherein CO 2 is selectively released and thus fed to a final separation, but the absorbent is returned to its original state and thereby remains bound to the surface:
- Reaction (3) represents the inverse of Reaction (1), which is forced by providing excess water vapor and raising the temperature above the window indicated in (Ia). This shifts the equilibrium of the reaction (2) to the left side because isocyanuric acid (HNCO) is constantly eliminated by the hydrolysis reaction (3).
- the subsequent separation of water vapor and CO 2 can be achieved by condensation by means of suitable pressure and temperature control.
- Ammonium carbamate (NH 2 CO 2 ⁇ NH 4 + ) can be converted to ammonium carbonate by hydrolysis in aqueous solution or on a suitable catalytic surface even at low temperatures:
- ammonium carbonate decomposes thermally with an increase in temperature, with elimination of water in NH 3 and CO 2 :
- Suitable catalysts can be used to ensure that NH 3 remains bound to the surface.
- the subsequent separation of water vapor and CO 2 can be achieved again by condensation by means of suitable pressure and temperature control.
- At least two reactors are present.
- two parallel reactors are alternately charged to adsorb the CO 2 with exhaust gas and the respective Häreak ⁇ tor when the adsorber is largely implemented, taken from the exhaust stream and fed with the brought to the required temperature regeneration gas.
- the catalyst for example, as a rotatable disc stack, which is arranged so that the catalytic surfaces alternately pass through the adsorption and the regeneration reactor.
- a substantial part of the CO 2 is separated from exhaust gases in such a form, which allows the subsequent use of CO 2 with little energy consumption in order to come to a sustainable CC ⁇ -Emissionsminderung.
- catalytic materials preferably oxides and Mi ⁇ mixtures of oxides come into consideration such.
- B. T1O 2 and V 2 Os, with titanium dioxide z. B. is a suitable hydrolysis catalyst, while V 2 O 5 is favorable for the binding of ammonia to the O- berflache.
- ion-exchanged zeolites can be used as catalysts, which can also bind ammonia very selectively.
- the application of the inventive method is msbeson- particular interest in the CO 2 separation ammonia solutions at process temperatures> 10 0 C, since in this case is still present a abhangiger on the temperature ratio of NH 3 in the range of several percent by volume in the separated CO 2, which can not be economically eliminated by conventional methods.
- FIGS. 4 and 5 show the senso ⁇ k in the case of an alternating function of the reactors according to FIGS. 1 to 3 as adsorption reactor on the one hand or as desorption reactor on the other hand.
- FIG. 1 while one of the two reactors 10, 10 'serves to adsorb the CO 2 in the CO 2 -containing exhaust gas, the other of the two reactors 10, 10' is discharged, which will be explained in detail below.
- fluid lines with a number of Venti ⁇ len are necessary as well as a Vorratsbehalter for an absorbent for CO 2 and a unit for separating the CO 2 from Regenerat.
- the two reactors 10 and 10 'of Figure 1 each have a catalyst bed 11 and 11' on.
- C ⁇ 2 -containing exhaust gas is supplied via an exhaust pipe 1 and guided via the branch 2 either into the first reactor 10 or via a parallel line 1a with a branch line 2a into the second reactor 10 'connected in parallel.
- valves V1, V2, V7 and V8 are connected in the lines 1, Ia.
- the associated control unit is not shown.
- Each one of the reactors 10, 10 ' is thus in the adsorption onsbet ⁇ eb, while the other reactor is in regeneration mode.
- a reaction gas mixture which is also referred to as regenerate
- the line 6 is fed via the line 6 with the parallel line 6a and the branch lines 7 and 7a the two reactors in the alternating operation.
- the lines 6, 6a valves V3, V4, V5 and V6 connected, the function of which results from the representation of the alternating operation.
- Via the line 8 C ⁇ 2 -reduced exhaust gas is led away and guided via the line 3 C ⁇ 2 -containing regenerate to the unit 5.
- the CO 2 separation is carried out by the regenerate, so that here Rei ⁇ nes CO 2 dislocation is carried away.
- the container for the absorbent is denoted by 4 and via a valve V9 with the fluid circuit in operative connection.
- the two reactors 10, 10 'in Figure 1 have - as already mentioned - catalyst beds 11 and 11' containing a solid catalyst, the z. B. is formed as a plate catalyst. Alternatively, such a catalyst bed can also be designed as a so-called packed bed.
- FIG. 2 shows a simplified representation of an alternative arrangement to Figure 1 with reactors 20 and 20 '.
- the individual valves are not shown here except valve V9.
- the two reactors 20, 20 ' are connected to each other via a gas-tight lock.
- plate catalysts 15 arranged rotatably about a vertical axis are present here. Both reactors are connected via a gas-tight lock 30, wherein a fully loaded catalyst half can be brought into the second reactor by rotation for generation by rotation of the catalyst plate assembly and the discharged catalyst plate half is available for reloading.
- inventions include plate reactors coated with catalysts, in particular those with moving plates or other structures having a large specific surface, in which the plates are circulated in a discharge manner from the loading area (flue gas, CO 2 gas stream) via a lock system into the discharge area CÜ 2 separation and back to the loading area.
- the invention defined by the protective claim also includes arrangements in which the gas stream to be purified is passed through a fluidised bed reactor, whereby in particular small particles and those with a high specific surface, The loaded particles are continuously removed from the loading area, fed to a desorption area and then recirculated back into the adsorption reactor.
- the gas stream to be purified is passed through a "shower” of catalyst-coated particles with a high specific surface in a countercurrent process ("trickle reactor”), the loaded particles likewise being taken off continuously, regenerated and discharged Rieselreaktor be fed back.
- reactors 30 and 30 ' are shown, which operate in countercurrent flow. Both reactors 30, 30 'have catalyst plates 31 and 31', which are each designed as a bed of catalytic particles. Both reactors 30 and 30 'are connected at their ends by a gas-tight lock 32 and 32', respectively.
- the device operates according to Figure 3 according to Figure 2. It is essential here, however, that the CO 2 -containing exhaust gas is introduced via line 1 into the reactor 30 and flows there in countercurrent to the catalyst particles. Correspondingly, conversely, the regenerate is introduced into the reactor 30 ', in which case the catalyst particles in turn flow in countercurrent according to the arrow. In practice, a flow pump is used for this purpose, which is not shown in detail in FIG.
- the Senso ⁇ k one hand, and the signal processing are not included in the examples of Figures 1 to 3. In the way It is similar for all three examples according to FIGS. 1 to 3 and is explained in detail with reference to FIGS. 4 and 5.
- an adsorption reactor is referred to as 40.
- a valve VlO For the flue gas supply via a line 41 is a valve VlO and for the gas discharge at the outlet of the reactor via the line 49, a valve VIl is present.
- a temperature sensor 42 and a gas sensor 43 for the CO 2 concentration are located on the input side.
- Another gas sensor 44 for the CO 2 concentration is present on the downstream side. It is therefore essential that the concentrations c (CO 2 ) at the input on the one hand and on the output on the other hand can be measured and correlated with the temperature T according to a thermally activated process. From the decrease of the CO 2 concentration at a certain temperature T, the adsorption capacity of the adsorber can be determined. When the adsorption capacity falls below a certain limit, regeneration is initiated.
- a desorption reactor 50 is shown, the input lines 51, 51a and an output line 59 has ⁇ . Again, there are valves V12 and V13 in the inlet and outlet, and further in the supply line 51a, there is a valve V14 for the supply of an absorbent.
- a sensor 52 for the temperature T and at the output a sensor 53 for the concentration c (Abs) of the absorbent is present at the entrance.
- the signals for the concentrations on the one hand and the temperatures on the other hand are processed in a control device not described in detail, for example a known microprocessor control unit.
- Control is that the adsorption capacity of the catalytic material for CO 2 , which is determined from current CO 2 measurements on the adsorption reactor, by storing Absorbent on the catalytic surface in rea ⁇ chender manner is maintained.
- valve V12 is closed to stop the supply of Desorbergasgemisch.
- valve V14 is opened to supply absorbent (eg, ammonia).
- absorbent eg, ammonia
- valve V13 is closed to a slip of the Absorptionsmitteis to vermei ⁇ .
- valve V14 is closed.
- the devices with two reactors described with reference to the figures can advantageously be used for the separation of CO 2 from CO 2 -containing exhaust gases.
- the following process steps take place:
- the CO 2 is converted by means of chemical reactions with the NH 3 into a stable compound likewise bound to the catalyst surface.
- This temperature is designated T x .
- the so loaded with CO2 catalyst is at a second process temperature, which is higher than the first process temperature, a Coulomb, consisting of CO 2 and water vapor (H 2 O) exposed. This temperature is measured with T 2 draws (T 2 > T x ). At this temperature, the compound decomposes from CO 2 and NH 3 , the CO 2 is released into the Spulgasstrom, while the NH 3 remains attached to the surface of the catalyst.
- the enriched with CO 2 Spulgasstrom is überbowt in the other reactor and there to a temperature which is niedri ⁇ ger than the first process temperature, cooled. This temperature is T 3 denotes (T 3 ⁇ Ti). At this temperature, the water is condensed and discharged.
- an oxidic catalyst is advantageously used as adsorber.
- the catalyst consists for example of titanium oxide (TiO 2 ) or a mixture of
- Titanium oxide TiO 2
- another metal oxide in particular doped with vanadium oxide (V 2 O 5 ).
- He can also be one ion-exchanged zeolites exist.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007030069A DE102007030069A1 (en) | 2007-06-29 | 2007-06-29 | Process for the separation of carbon dioxide from flue gases and associated apparatus |
PCT/EP2008/058240 WO2009003929A1 (en) | 2007-06-29 | 2008-06-27 | Method for separating carbon dioxide from flue gases and associated device |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2164613A1 true EP2164613A1 (en) | 2010-03-24 |
Family
ID=39800565
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08774407A Withdrawn EP2164613A1 (en) | 2007-06-29 | 2008-06-27 | Method for separating carbon dioxide from flue gases and associated device |
Country Status (6)
Country | Link |
---|---|
US (1) | US20100196234A1 (en) |
EP (1) | EP2164613A1 (en) |
CN (1) | CN101790409A (en) |
DE (1) | DE102007030069A1 (en) |
RU (1) | RU2473379C2 (en) |
WO (1) | WO2009003929A1 (en) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102917773A (en) * | 2010-03-30 | 2013-02-06 | 里贾纳大学 | Catalytic method and apparatus for separating a gaseous component from an incoming gas stream |
CN101905111A (en) * | 2010-08-09 | 2010-12-08 | 郑州树仁科技发展有限公司 | Absorption and desorption training device |
CN102008930A (en) * | 2010-11-12 | 2011-04-13 | 同济大学 | Photo-biological reaction device for removing carbon dioxide from flue gas |
DE102011013318A1 (en) | 2011-03-07 | 2012-09-13 | Hochschule Heilbronn | Process for the regeneration of CO2-loaded amine-containing washing solutions in acid gas scrubbing |
CN102303503A (en) * | 2011-06-20 | 2012-01-04 | 邯郸派瑞电器有限公司 | Method and device for removing CO2 in vehicle |
US20130129612A1 (en) * | 2011-11-18 | 2013-05-23 | Basf Se | Process for Ion Exchange on Zeolites |
DE102014100750B4 (en) | 2013-04-30 | 2023-08-17 | Schott Ag | Process for the manufacture of glass components |
WO2018037461A1 (en) * | 2016-08-22 | 2018-03-01 | フタバ産業株式会社 | Carbon dioxide supply device |
US11041420B2 (en) | 2016-09-21 | 2021-06-22 | M-Trigen, Inc. | Carbon capture system, apparatus, and method |
CN106582206A (en) * | 2016-12-19 | 2017-04-26 | 孟庆东 | Method for decreasing haze by reducing content of carbon dioxide |
CN107890756A (en) * | 2017-12-27 | 2018-04-10 | 滦南富瑞慈新能源科技有限公司 | A kind of method and special equipment for removing carbon dioxide in methane |
US10315986B1 (en) * | 2018-04-06 | 2019-06-11 | Solenis Technologies, L.P. | Systems and methods for forming a solution of ammonium carbamate |
CN110465185A (en) * | 2018-05-10 | 2019-11-19 | 襄阳先天下环保设备有限公司 | A kind of catalytic desulfurizing Sulphuric acid equipment |
CN109665976B (en) * | 2018-11-15 | 2021-10-19 | 锦西天然气化工有限责任公司 | Ammonia process for recovering CO in flue gas2Process for combined production with urea |
RU2733774C1 (en) * | 2020-02-13 | 2020-10-06 | Общество с ограниченной ответственностью "Дельта-пром" | Method of extracting carbon dioxide from flue gases and device for realizing said method |
CN112007510B (en) * | 2020-09-07 | 2022-11-11 | 中建材环保研究院(江苏)有限公司 | Rotary SCR denitration system for high-temperature and high-dust of cement kiln |
CN112221327A (en) * | 2020-09-25 | 2021-01-15 | 河南理工大学 | Carbon dioxide ammonia capture and low-temperature liquefaction system and method for coal-fired power plant |
EP4301491A1 (en) * | 2021-03-04 | 2024-01-10 | Echeneidae Inc. | System and method for mobile carbon capture |
CN114452768A (en) * | 2022-03-03 | 2022-05-10 | 霖和气候科技(北京)有限公司 | CO based on wet-process regenerated adsorption material2Direct air capture system and method |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL22102C (en) * | 1926-06-15 | |||
US3517484A (en) * | 1968-03-13 | 1970-06-30 | Union Carbide Corp | Selective adsorption process |
DE3229646A1 (en) * | 1982-08-09 | 1984-02-09 | Bosch-Siemens Hausgeräte GmbH, 7000 Stuttgart | CONTINUOUSLY WORKING ADSORPTION REFRIGERATION SYSTEM, ESPECIALLY FOR OPERATION THROUGH HEAT FROM COMBUSTION ENGINES OR THE LIKE |
SU1279658A1 (en) * | 1985-01-03 | 1986-12-30 | Предприятие П/Я Р-6603 | Method of cleaning gas from carbon dioxide |
SU1745314A1 (en) * | 1990-04-16 | 1992-07-07 | Украинский научно-исследовательский институт природных газов | Method of recovering carbon dioxide from gases |
JPH0422415A (en) * | 1990-05-15 | 1992-01-27 | Kobe Steel Ltd | Method for adsorbing and removing carbon dioxide |
US5846295A (en) * | 1997-03-07 | 1998-12-08 | Air Products And Chemicals, Inc. | Temperature swing adsorption |
JPH10272336A (en) * | 1997-03-31 | 1998-10-13 | Nissan Motor Co Ltd | Carbon dioxide-absorbing material, and method for separating and recovering carbon dioxide in exhaust gas |
US6755892B2 (en) * | 2000-08-17 | 2004-06-29 | Hamilton Sundstrand | Carbon dioxide scrubber for fuel and gas emissions |
US7410524B2 (en) * | 2003-06-19 | 2008-08-12 | Tower Paul M | Regenerable purification system for removal of siloxanes and volatile organic carbons |
US20070141430A1 (en) * | 2005-12-21 | 2007-06-21 | Qunjian Huang | Gas scrubber and method related thereto |
-
2007
- 2007-06-29 DE DE102007030069A patent/DE102007030069A1/en not_active Withdrawn
-
2008
- 2008-06-27 CN CN200880104824A patent/CN101790409A/en active Pending
- 2008-06-27 US US12/665,120 patent/US20100196234A1/en not_active Abandoned
- 2008-06-27 RU RU2010102885/05A patent/RU2473379C2/en not_active IP Right Cessation
- 2008-06-27 EP EP08774407A patent/EP2164613A1/en not_active Withdrawn
- 2008-06-27 WO PCT/EP2008/058240 patent/WO2009003929A1/en active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO2009003929A1 * |
Also Published As
Publication number | Publication date |
---|---|
RU2473379C2 (en) | 2013-01-27 |
DE102007030069A1 (en) | 2009-01-02 |
US20100196234A1 (en) | 2010-08-05 |
CN101790409A (en) | 2010-07-28 |
RU2010102885A (en) | 2011-08-10 |
WO2009003929A1 (en) | 2009-01-08 |
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