DE3607269A1 - Process for the simultaneous desulphurisation and denitration of flue gases - Google Patents
Process for the simultaneous desulphurisation and denitration of flue gasesInfo
- Publication number
- DE3607269A1 DE3607269A1 DE19863607269 DE3607269A DE3607269A1 DE 3607269 A1 DE3607269 A1 DE 3607269A1 DE 19863607269 DE19863607269 DE 19863607269 DE 3607269 A DE3607269 A DE 3607269A DE 3607269 A1 DE3607269 A1 DE 3607269A1
- Authority
- DE
- Germany
- Prior art keywords
- catalyst
- flue gases
- flue gas
- denitration
- simultaneous
- 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- Withdrawn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 23
- 239000003546 flue gas Substances 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 27
- 239000000126 substance Substances 0.000 description 6
- 229910052815 sulfur oxide Inorganic materials 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000005108 dry cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037074 physically active Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000005406 washing Methods 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
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur gleichzeitigen Entschwefelung und Entstickung von SO2 und NO/NOx ent haltenden Rauchgasen.The invention relates to a process for the simultaneous desulphurization and denitrification of SO 2 and NO / NO x containing flue gases.
Industrie- und Kraftwerksabgase enthalten je nach Art des eingesetzten Brennstoffes unterschiedliche Mengen an Schwefeloxiden und Stickoxiden neben anderen Schad stoffen, wie z.B. Schwermetallen. Es ist bekannt, daß diese Schadstoffe zu einem erheblichen Teil für das Phänomen des Waldsterbens verantwortlich sind, weshalb es aufgrund gesetzlicher Vorschriften erforderlich ist, ihre Emissionen im Rauchgas auf zulässige Werte zu be grenzen.Industrial and power plant emissions contain depending on the type of different amounts of fuel used Sulfur oxides and nitrogen oxides among other harmful substances such as Heavy metals. It is known that these pollutants to a significant extent for that Phenomenon of forest extinction are responsible for why it is required by law, to reduce their emissions in the flue gas to permissible values limit.
Es gibt demgemäß eine Reihe von bekannten Verfahren, die es gestatten, einerseits Schwefeloxide, andererseits Stickoxide aus Gasen zu entfernen.Accordingly, there are a number of known methods that allow, on the one hand, sulfur oxides, on the other hand Remove nitrogen oxides from gases.
Die bekannten Verfahren arbeiten dabei teils als Naß-, teils als Trockenreinigungsverfahren und bedürfen ent weder eines chemisch oder physikalisch wirkenden Wasch mittels, das die Schadstoffbestandteile aus dem Gas löst oder einer Trockenreinigungsmasse oder eines Adsorptions mittels, das die Schadstoffbestandteile aus dem Gas adsorp tiv entfernt. In beiden Fällen sind relativ große Mengen an Chemikalien oder Adsorptionsmitteln bereitzustellen, um den gewünschten Effekt zu erzielen. Da diese Mittel in der Regel relativ teuer sind, ist eine Regenerierung zum Zwecke der Wiederverwendung ein wirtschaftliches Gebot.The known methods work partly as wet, partly as a dry cleaning process and require ent neither a chemical or physical washing means that releases the pollutant components from the gas or a dry cleaning composition or an adsorption means that adsorbs the pollutant components from the gas tiv removed. In both cases there are relatively large amounts of To provide chemicals or adsorbents to the to achieve the desired effect. Since these funds in the Usually relatively expensive is regeneration for the purpose reuse an economic imperative.
Bei einem neueren bekannten Verfahren (DE-OS 34 12 870) werden Schwefeloxide und Stickoxide in einem Verfahrens zug aus Rauchgas entfernt. Hierzu wird das Rauchgas zu nächst mit einem physikalisch wirkenden Lösungsmittel von SO2 befreit, wonach es zur Entfernung von Stickoxiden mit NH3 versetzt und zur Umwandlung der Stickoxide über einen geeigneten Katalysator geleitet wird.In a newer known method (DE-OS 34 12 870) sulfur oxides and nitrogen oxides are removed from flue gas in one process. For this purpose, the flue gas is first freed of SO 2 with a physically active solvent, after which it is mixed with NH 3 to remove nitrogen oxides and passed over a suitable catalyst to convert the nitrogen oxides.
Auch dieses bekannte Verfahren bedarf zur SO2-Entfernung eines Waschmittels und zur NOx-Entfernung eines sich dabei verbrauchenden Reduktionsmittels, nämlich NH3, so daß auch bei diesem Verfahren der Chemikalienverbrauch nachteilig in Erscheinung tritt.This known process also requires a detergent for SO 2 removal and a reducing agent, namely NH 3 , for NO x removal, so that the chemical consumption also occurs disadvantageously in this process.
Es ist die Aufgabe der vorliegenden Erfindung, ein Ver fahren zu schaffen, das es ermöglicht, Rauchgase gleich zeitig von Schwefel- und Stickoxiden zu befreien, ohne daß hierzu dem Rauchgas Chemikalien zugegeben werden müssen.It is the object of the present invention to provide a ver driving that creates smoke gases right away rid of sulfur and nitrogen oxides early without that chemicals are added to the flue gas have to.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß das Rauchgas bei einer Temperatur zwischen 120 und 350°C über einen Katalysator geleitet wird, der eine Umsetzung zwischen SO2 und NO/NOx unter Bildung von SO3 und N2 bzw. N2O beschleunigt. This object is achieved in that the flue gas is passed at a temperature between 120 and 350 ° C over a catalyst that accelerates a reaction between SO 2 and NO / NO x to form SO 3 and N 2 or N 2 O. .
Als geeignete Katalysatoren haben sich Mischkatalysatoren aus Eisen- und Kupferoxiden, z.B. aus etwa 95 Gew-% Eisen- und 5 Gew-% Kupferoxid, erwiesen. Desgleichen können auch Edelmetallkatalysatoren, z.B. Platinkatalysatoren, auf einem inerten Träger, z.B. in einer Konzentration von 0,02 bis 0,1 Gew-% auf Tonerdegel angewendet werden.Mixed catalysts have been found to be suitable catalysts from iron and copper oxides, e.g. from about 95% by weight of iron and 5% by weight of copper oxide. The same can also Noble metal catalysts, e.g. Platinum catalysts an inert carrier, e.g. in a concentration of 0.02 to 0.1% by weight can be applied to alumina gel.
Beim erfindungsgemäßen Verfahren laufen folgende Reaktionen ab:The following reactions take place in the method according to the invention from:
2 NO + 2 SO₂ → N₂ + 2 SO₃
2 NO + SO₂ → N₂O + SO₃2 NO + 2 SO₂ → N₂ + 2 SO₃
2 NO + SO₂ → N₂O + SO₃
Das erfindungsgemäße Verfahren ist demzufolge überall dort mit Erfolg einsetzbar, wo Rauchgase gleichzeitig Schwefel oxide und Stickoxide enthalten. Und zwar ist die Wirksam keit des erfindungsgemäßen Verfahrens in weiten Grenzen unabhängig vom Verhältnis der Mengen an NO und SO2 im Rauchgas, da bei einem NO-Überschuß vorzugsweise die zweite Reaktion, bei etwa gleichen Mengen NO und SO2 vorzugsweise die erste Reaktion abläuft.The method according to the invention can consequently be used successfully wherever flue gases contain sulfur oxides and nitrogen oxides at the same time. In fact, the effectiveness of the process according to the invention is largely independent of the ratio of the amounts of NO and SO 2 in the flue gas, since if there is an excess of NO the second reaction preferably takes place, with approximately equal amounts of NO and SO 2 the first reaction preferably takes place.
Eine Abkühlung der Rauchgase vor Anwendung des erfindungs gemäßen Verfahrens ist nicht notwendig, da dieses im Bereich von 120 bis 350°C arbeitet.A cooling of the flue gases before application of the Invention According to the procedure is not necessary, as this is in the area works from 120 to 350 ° C.
Zum Schutz der Katalysatoren ist es lediglich notwendig, das Rauchgas zuvor einer Vorreinigung zu unterziehen und dabei Staub und Ruß sowie gegebenenfalls HF oder HCl abzu trennen.To protect the catalysts, it is only necessary to subject the flue gas to preliminary cleaning and thereby removing dust and soot as well as HF or HCl separate.
Das erfindungsgemäße Verfahren hat gegenüber den bekann ten Verfahren den außerordentlichen Vorteil, daß dem Rauch gas keine Fremdchemikalien zugesetzt werden müssen, um irgendwelche Schadstoffe daraus abzutrennen. Es gelingt vielmehr auf eine überraschend einfache Weise, die beiden Hauptschadstoffe, nämlich Stickoxide und Schwefeloxide, gleichzeitig aus Rauchgasen zu entfernen, indem sie durch die Wirkung der erfindungsgemäßen Katalysatoren mitein ander zur Reaktion gebracht und in unschädliche Bestand teile umgewandelt werden.The method according to the invention has been known ten process the extraordinary advantage that the smoke No foreign chemicals need to be added to gas to separate any pollutants from it. It succeeds rather, in a surprisingly simple way, the two Main pollutants, namely nitrogen oxides and sulfur oxides, remove from flue gases at the same time by going through the effect of the catalysts of the invention other reacted and in harmless stock parts are converted.
Das bei der erfindungsgemäßen Umsetzung durch Oxidation aus dem SO2 entstehende SO3 läßt sich aus dem behandelten Rauchgas in einfacher Weise mit Hilfe einer Wasserwäsche entsprechendThe SO 3 formed in the reaction according to the invention by oxidation from the SO 2 can be appropriately removed from the treated flue gas with the aid of a water wash
SO₃ + H₂O ⇄ H₂SO₄SO₃ + H₂O ⇄ H₂SO₄
entfernen. Desgleichen wird mit dieser Wasserwäsche naturgemäß auch im Rauchgas von Haus aus gegebenenfalls enthaltenes SO3 mit ausgewaschen. Das dabei entstehende Produkt, nämlich Schwefelsäure, läßt sich, nach Erreichen einer bestimmten Konzentration, sogar gewinnbringend verkaufen.remove. Likewise, with this water scrubbing, SO 3 which may be present in the flue gas is naturally also washed out. The resulting product, namely sulfuric acid, can even be sold at a profit after reaching a certain concentration.
Der Erfolg des erfindungsgemäßen Verfahrens kann durch die Wahl geeigneter Feuerungsmaterialien beeinflußt werden. Wird z.B. ein schwefelarmes Öl verfeuert, das bei seiner Verbrennung zu wenig SO2 im Sinne der obigen Gleichungen liefern würde, kann dieser Nachteil durch Zumischen eines an Schwefelverbindungen reichen Öles ausgeglichen werden. Umgekehrt ist es natürlich auch möglich, eine im Vergleich zu den Stickoxiden zu große Menge an SO2 durch Einsatz schwefelärmerer Ölsorten auszugleichen.The success of the method according to the invention can be influenced by the choice of suitable firing materials. If, for example, a low-sulfur oil is burned, which would not supply enough SO 2 in the sense of the above equations, this disadvantage can be compensated for by adding an oil rich in sulfur compounds. Conversely, it is of course also possible to compensate for an excessive amount of SO 2 compared to the nitrogen oxides by using low-sulfur oil types.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863607269 DE3607269A1 (en) | 1986-03-05 | 1986-03-05 | Process for the simultaneous desulphurisation and denitration of flue gases |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863607269 DE3607269A1 (en) | 1986-03-05 | 1986-03-05 | Process for the simultaneous desulphurisation and denitration of flue gases |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE3607269A1 true DE3607269A1 (en) | 1987-09-10 |
Family
ID=6295586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19863607269 Withdrawn DE3607269A1 (en) | 1986-03-05 | 1986-03-05 | Process for the simultaneous desulphurisation and denitration of flue gases |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE3607269A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115646084A (en) * | 2022-09-28 | 2023-01-31 | 江苏宝辰环保科技有限公司 | Coal fired boiler tail gas low temperature SOx/NOx control purifier |
-
1986
- 1986-03-05 DE DE19863607269 patent/DE3607269A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115646084A (en) * | 2022-09-28 | 2023-01-31 | 江苏宝辰环保科技有限公司 | Coal fired boiler tail gas low temperature SOx/NOx control purifier |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8139 | Disposal/non-payment of the annual fee |