EP0359787A1 - Verfahren und anlage zur entstickung der abgase von feuerungsanlagen - Google Patents
Verfahren und anlage zur entstickung der abgase von feuerungsanlagenInfo
- Publication number
- EP0359787A1 EP0359787A1 EP89901850A EP89901850A EP0359787A1 EP 0359787 A1 EP0359787 A1 EP 0359787A1 EP 89901850 A EP89901850 A EP 89901850A EP 89901850 A EP89901850 A EP 89901850A EP 0359787 A1 EP0359787 A1 EP 0359787A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gases
- heat
- gas
- catalytically active
- active compounds
- 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- Withdrawn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
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000008569 process Effects 0.000 title claims description 5
- 239000003546 flue gas Substances 0.000 title description 4
- 238000009434 installation Methods 0.000 title 1
- 239000007789 gas Substances 0.000 claims abstract description 106
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 230000009467 reduction Effects 0.000 claims abstract description 11
- 230000001172 regenerating effect Effects 0.000 claims abstract description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 45
- 239000003638 chemical reducing agent Substances 0.000 claims description 40
- 238000006722 reduction reaction Methods 0.000 claims description 15
- 238000011144 upstream manufacturing Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003303 reheating Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000002485 combustion reaction Methods 0.000 abstract description 7
- 239000000567 combustion gas Substances 0.000 abstract 3
- 230000005540 biological transmission Effects 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8631—Processes characterised by a specific device
-
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
Definitions
- the invention is based on a method for denitrification of the exhaust gases from combustion plants downstream of the dedusting or desulfurization with reheating of the exhaust gases and relates to the system intended for carrying out the method.
- Temperature level preheated and heated before they are fed to a catalyst Temperature level preheated and heated before they are fed to a catalyst.
- moving carriers of catalytically active surfaces have become known.
- the cooling of the flue gases in the combustion air preheater and the dedusting and desulfurization upstream high-dust catalysts use the high temperature level to carry out the reduction reaction and therefore do not require reheating.
- the so-called cold catalysts the smoke gas constituents leading to the deactivation are removed at the same time as the dedusting or desulphurization, for example arsenic in melt furnaces, so that these are the catalysts no longer burden and poison.
- the dedusted or desulfurized gases are given 3. If a preheating for drying is subsequently passed through a gas heat exchanger in order to transfer heat from the denitrified gases before they enter the chimney to the gases to be denitrified, before these gases are transferred to a steam heater or a combustion chamber for overcoming of the heat exchanger straightness are introduced in order to be heated to the optimum reaction temperature for denitrification before the gases enter the catalyst.
- the invention has for its object the reduction of nitrogen oxides in exhaust gases with high efficiency and low volume as well as simple measurement and control technology for the addition and distribution of reducing agents depending on the locally and temporally changing nitrogen oxide concentration and flow distribution before and after the main catalyst perform.
- the method according to the invention based on that according to the introduction of claim 1, is characterized in that, in a cyclical change, the exhaust gases to be denitrified upstream to their final heating to the temperature level of the reduction reaction and the denoxified exhaust gases downstream to reduce nitrogen oxides contained in a further catalyst serving as the main catalyst, are guided in countercurrent to one another via heat-exchanging storage masses, the surfaces of which are provided with catalytically active compounds.
- the method according to the invention can already be carried out with an apparatus constructed in the manner of a switchover heat exchanger, which includes heat-exchanging storage masses, the surfaces of which are provided with catalytically active compounds.
- a revolving regenerative heat exchanger be it that it has a revolving storage Mass carrier and stationary gas connections, or be it that it has a stationary storage mass carrier and circumferential gas connections.
- the gases to be denitrified upstream or the denitrified gases downstream, as they pass through the storage masses, the surfaces of which are provided with catalytically active compounds, are heated or cooled in cross-countercurrent within heat-exchanging storage masses become.
- this or this is introduced in a mixture with a carrier gas in upstream or downstream for final heating in the gas stream to be denitrified.
- An upstream connection of the reductant introduction is possible in particular in connection with the final heating in a steam heater, while in the case of final heating in a combustion chamber, the reducing agent is introduced downstream.
- the adsorption of the reducing agent residues on the surfaces of heat-exchanging masses provided with catalytically active compounds allows denitrified exhaust gases emerging from the main catalyst to not be contain set reducing agent. Furthermore, a precise setting of the required amount of reducing agent is advantageously to be carried out by introducing a further partial flow of the same in series connection to the main catalytic converter, after what has not subsequently been used up
- Reducing agents on the heat-exchanging storage masses, the surfaces of which are provided with catalytically active compounds, are bound in addition to the post-reaction that occurs at the same time by adsorption and transferred to the side of the gases to be denitrified.
- this addition of reducing agent only takes place to the extent that at the end of the heat-exchanging storage masses, the surface of which is provided with catalytically active compounds, the introduced reducing agent is completely reacted or adsorbed on these surfaces.
- the method is particularly advantageously carried out by a gas heat exchanger designed as a circulating regenerative heat exchanger with a layer of heat-exchanging storage masses arranged on the hot gas side, the surfaces of which are provided with catalytically active compounds, and the heater and main catalyst on the side of the gases to be denitrified follow and is connected to the main catalytic converter on the side of the denitrified gases on the hot gas side.
- the main catalytic converter can be designed as a static catalytic converter or in the manner of a Lungstr ⁇ air preheater with supports for filling quantities having catalytically active compounds that move relative to the gas connections.
- strands of reducing agent which emerge from the main catalyst are uniformized and subsequently deposited evenly distributed by adsorption on the heat-exchanging storage masses, the surfaces of which are provided with catalytically active compounds, and are deposited in this manner on the side of the denitrifying gases available.
- the desacti- Crossing the haptic catalyst which ultimately leads to an increasing slippage of reducing agent, can be extended by this adsorption of the reducing agent residues and the cyclical change of the action by the denitrified and the denitrified gases and their countercurrent flow, since the heat-exchanging storage masses, the surfaces of which act as catalysts Connections are provided, in this case only have to meet low reduction rates.
- the solution allows the main catalytic converter to be designed with a reduced catalytically active surface, ie with a smaller construction volume, or to further reduce the emission.
- complex measures in particular with regard to the flow rectification and the measurement and control technology for a precisely measured supply of the reducing agent quantities with their ongoing determination, can be dispensed with.
- the denitrification of exhaust gases using residues of unused reducing agents carried in the exhaust gases after the main catalyst is to be carried out in such a way that downstream system parts are not impaired by by-products of the selective, catalytic reduction and also at the end of longer travel times Main catalyst no impermissibly high slip of reducing agents leaves the plant.
- Sorbable coatings on the heat-exchanging storage mass of the gas heat exchanger can increase this effect of the absorption of the reducing agent slip and / or the nitrogen oxides as a result of the cyclical alternation between adsorption and desorption between the denitrified and the denitrified gas stream.
- the exhaust gases to be denitrified from a desulfurization 1 are first passed through an exhaust pipe 20 for predrying through a dryer 3. From the dryer 3, the exhaust gases are subsequently introduced via line 22 into a gas heat exchanger 5.
- the circulating carrier of this gas heat exchanger has heat-exchanging storage masses 5a on the so-called cold side, for example in the form of conventional heating plate packs.
- a layer of heat-exchanging storage masses, the surfaces of which are provided with catalytically active compounds 5b is arranged in this carrier. After leaving this position of the hot end of the gas heat exchanger, the gases are fed via a line 24 to a heater 7 in order to bring the temperature of the gases up
- the heater is heated by external heat.
- the gases to be denitrified are passed on the line path 26 via a branch line 28
- Reducing agent is supplied before the nitrogen oxides contained in the gases are largely removed in the downstream catalytic converter 9 as it passes through its catalytically active filling compound.
- the denitrified gases then enter via the line 30 into the position of heat exchanging the storage masses, the surfaces of which are provided with catalytically active compounds, on the hot side of the gas heat exchanger and through this position. After subsequent guidance through the cold-end heat-exchanging storage mass 5a, the exhaust gases are on the
- Gases to be denitrified emerge from a wet desulfurization plant 1 at approx. 45-50 ° C.
- the gases which are moist due to the wet desulfurization are heated to approximately 70-90 ° C. and fed via the connecting line 22 to the gas / gas heat exchanger 5 with a nitrogen oxide content of 100 ovpm.
- a first catalytic reduction of approximately 1% takes place.
- the . side to be cooled from the largely denitrified gases absorbed reducing agents, preferably ammonia. The gases occur at a temperature of approx.
- the ammonia slip is already converted in the area of the inlet side by the heat-exchanging storage masses 5b, the surfaces of which are provided with catalytically active compounds, so that the nitrogen oxides are further reduced to approx. 50vpm or ammonia is absorbed and transferred to the side of the gases to be denitrified. After further cooling within the heat storage mass 5a on the cold side of the regenerative heat exchanger, the denitrified exhaust gases are released from
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Chimneys And Flues (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3805791 | 1988-02-24 | ||
DE3805791A DE3805791A1 (de) | 1988-02-24 | 1988-02-24 | Verfahren und anlage zur entstickung der abgase von feuerungsanlagen |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0359787A1 true EP0359787A1 (de) | 1990-03-28 |
Family
ID=6348077
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89901850A Withdrawn EP0359787A1 (de) | 1988-02-24 | 1989-01-18 | Verfahren und anlage zur entstickung der abgase von feuerungsanlagen |
Country Status (8)
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4102075A1 (de) * | 1991-01-24 | 1992-07-30 | Veba Oel Ag | Verfahren zum entfernen von stickstoffoxiden aus einem abgas |
ES2074296T3 (es) * | 1991-03-04 | 1995-09-01 | Siemens Ag | Precalentador regenerativo y procedimiento para su funcionamiento. |
WO1992017267A1 (de) * | 1991-03-28 | 1992-10-15 | Apparatebau Rothemühle Brandt & Kritzler Gesellschaft Mit Beschränkter Haftung | Regenerativ-wärmetauscher |
US5213780A (en) * | 1991-06-04 | 1993-05-25 | Research-Cottrell, Inc. | Method for nitrogen oxide reduction and flue gas reheating |
US5233934A (en) * | 1992-08-20 | 1993-08-10 | Wahlco Environmental Systems, Inc. | Control of NOx reduction in flue gas flows |
US5237939A (en) * | 1992-08-20 | 1993-08-24 | Wahlco Environmental Systems, Inc. | Method and apparatus for reducing NOx emissions |
DE4301760A1 (de) * | 1993-01-23 | 1994-08-11 | Rothemuehle Brandt Kritzler | Verfahren und Vorrichtung für einen Regenerativ-Wärmetauscher zur Behandlung schadstoffhaltiger Abgase |
US5364259A (en) * | 1993-03-10 | 1994-11-15 | Monsanto Enviro-Chem Systems, Inc. | Process and apparatus for gas phase reaction in a regenerative incinerator |
DE4313861A1 (de) * | 1993-04-28 | 1994-11-03 | Rothemuehle Brandt Kritzler | Anlage zur Stickoxidminderung bei Feuerungsabgasen |
US5336471A (en) * | 1993-05-19 | 1994-08-09 | Abb Air Preheater, Inc. | Support of ceramic catalyst |
FR2720488B1 (fr) * | 1994-05-24 | 1996-07-12 | Inst Francais Du Petrole | Dispositif rotatif de transfert de chaleur et d'épuration thermique appliqué à des effluents gazeux. |
US5589142A (en) * | 1994-07-27 | 1996-12-31 | Salem Englehard | Integrated regenerative catalytic oxidation/selective catalytic reduction abatement system |
US5738024A (en) * | 1996-04-19 | 1998-04-14 | Winegar; Phillip | Catalytic reduction apparatus for NOX reduction |
US5823770A (en) * | 1997-02-26 | 1998-10-20 | Monsanto Company | Process and apparatus for oxidizing components of a feed gas mixture in a heat regenerative reactor |
US6264905B1 (en) * | 1999-10-12 | 2001-07-24 | Hera, Llc | Method and apparatus for reducing “ammonia slip” in SCR and/or SNCR NOX removal applications |
US6706246B2 (en) | 2001-02-26 | 2004-03-16 | Abb Lummus Global Inc. | System and method for the selective catalytic reduction of nitrogen oxide in a gas stream |
US20020159923A1 (en) * | 2001-02-26 | 2002-10-31 | Platvoet Erwin M.J. | Gas phase reactor and process for reducing nitrogen oxide in a gas stream |
US6663839B2 (en) | 2001-02-26 | 2003-12-16 | Abb Lummus Global Inc. | Radial flow gas phase reactor and method for reducing the nitrogen oxide content of a gas |
US6821490B2 (en) * | 2001-02-26 | 2004-11-23 | Abb Lummus Global Inc. | Parallel flow gas phase reactor and method for reducing the nitrogen oxide content of a gas |
US20030202927A1 (en) * | 2002-04-24 | 2003-10-30 | Minkara Rafic Y. | Reduction of ammonia in flue gas and fly ash |
JP2005265234A (ja) * | 2004-03-17 | 2005-09-29 | Babcock Hitachi Kk | アンモニア含有排ガス処理装置および方法 |
DE102010048065A1 (de) * | 2010-10-12 | 2012-04-12 | Martin GmbH für Umwelt- und Energietechnik | Vorrichtung mit einem Wärmetauscher und Verfahren zum Betreiben eines Wärmetauschers einer Dampferzeugungsanlage |
US9841242B2 (en) * | 2013-06-21 | 2017-12-12 | General Electric Technology Gmbh | Method of air preheating for combustion power plant and systems comprising the same |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3126945A (en) * | 1964-03-31 | kuhner | ||
JPS5332788B2 (enrdf_load_stackoverflow) * | 1973-10-12 | 1978-09-09 | ||
IT1070099B (it) * | 1975-09-23 | 1985-03-25 | Degussa | Catalizzatore supportato monolitico e disposizione di catalizzatori supportati monolitici per la depurazione dei gas di scarico di motori a combustione |
US4196170A (en) * | 1978-05-26 | 1980-04-01 | Caterpillar Tractor Co. | Multistage catalytic reactor having a pressure responsive gas flow control valve therein |
DE3406657A1 (de) * | 1984-02-24 | 1985-08-29 | Kraftanlagen Ag, 6900 Heidelberg | Verfahren und vorrichtung zur katalytischen reinigung der abgase von feuerungsanlagen |
DE3505354A1 (de) * | 1984-04-05 | 1985-10-17 | Linde Ag, 6200 Wiesbaden | Verfahren und vorrichtung zur entfernung unerwuenschter gasfoermiger bestandteile aus einem rauchgas |
DE8424417U1 (de) * | 1984-08-17 | 1986-07-10 | Lentjes BWE Energietechnik GmbH, 4000 Düsseldorf | Vorrichtung zur selektiven katalytischen Reduktion von Stickoxyden |
DE3533199A1 (de) * | 1985-09-18 | 1987-03-26 | Kraftanlagen Ag | Verfahren und anlage zur reinigung der abgase von feuerungsanlagen |
-
1988
- 1988-02-24 DE DE3805791A patent/DE3805791A1/de active Granted
-
1989
- 1989-01-13 GR GR890100019A patent/GR1000478B/el unknown
- 1989-01-18 AU AU29418/89A patent/AU2941889A/en not_active Abandoned
- 1989-01-18 WO PCT/EP1989/000048 patent/WO1989007975A1/de not_active Application Discontinuation
- 1989-01-18 EP EP89901850A patent/EP0359787A1/de not_active Withdrawn
- 1989-01-18 JP JP1501708A patent/JPH02503292A/ja active Pending
- 1989-01-25 ES ES8900241A patent/ES2009711A6/es not_active Expired
-
1991
- 1991-06-28 US US07/725,385 patent/US5145652A/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO8907975A1 * |
Also Published As
Publication number | Publication date |
---|---|
US5145652A (en) | 1992-09-08 |
GR1000478B (el) | 1992-07-30 |
AU2941889A (en) | 1989-09-22 |
ES2009711A6 (es) | 1989-10-01 |
JPH02503292A (ja) | 1990-10-11 |
DE3805791A1 (de) | 1989-08-31 |
WO1989007975A1 (en) | 1989-09-08 |
DE3805791C2 (enrdf_load_stackoverflow) | 1993-08-12 |
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Legal Events
Date | Code | Title | Description |
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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17P | Request for examination filed |
Effective date: 19890704 |
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AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT CH DE GB IT LI NL |
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17Q | First examination report despatched |
Effective date: 19911104 |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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18D | Application deemed to be withdrawn |
Effective date: 19930206 |