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WO2012146462A1 - Procédé pour réduire l'émission d'oxydes d'azote dans l'effluent gazeux d'un four lors du traitement thermique de matières et four fonctionnant selon ledit procédé - Google Patents

Procédé pour réduire l'émission d'oxydes d'azote dans l'effluent gazeux d'un four lors du traitement thermique de matières et four fonctionnant selon ledit procédé Download PDF

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Publication number
WO2012146462A1
WO2012146462A1 PCT/EP2012/056022 EP2012056022W WO2012146462A1 WO 2012146462 A1 WO2012146462 A1 WO 2012146462A1 EP 2012056022 W EP2012056022 W EP 2012056022W WO 2012146462 A1 WO2012146462 A1 WO 2012146462A1
Authority
WO
WIPO (PCT)
Prior art keywords
furnace
exhaust gas
agent
content
nitrogen oxides
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.)
Ceased
Application number
PCT/EP2012/056022
Other languages
German (de)
English (en)
Inventor
Victor Yuardi RISONARTA
Markus Abel
Michel HEIN
Alexander Müller
Mehmet Fatih GÖKCE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Siemens AG, Siemens Corp filed Critical Siemens AG
Priority to RU2013152604/05A priority Critical patent/RU2013152604A/ru
Priority to CN201280019785.6A priority patent/CN103702743A/zh
Publication of WO2012146462A1 publication Critical patent/WO2012146462A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • 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
    • B01D53/30—Controlling by gas-analysis apparatus
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B01D53/565—Nitrogen oxides by treating the gases with solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/202—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/204—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/208—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0233—Other waste gases from cement factories
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/025—Other waste gases from metallurgy plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

Definitions

  • the invention relates to a method for reducing the emission of nitrogen oxides in the exhaust gas of a furnace during the thermal treatment of materials in at least indirect presence of oxygen and nitrogen, in particular when melting iron-containing starting materials in an electric arc furnace.
  • the invention also relates to a furnace operated by this method.
  • thermal treatment is at least indirectly, ie at least in the exhaust oxygen and nitrogen at high temperatures anwe ⁇ send, so that thermal nitrogen oxides NO x can arise and get into the environment.
  • These nitrogen oxides NO x is environmentally harmful and toxic gases that both un ⁇ indirectly endanger the health and contribute, among other things as greenhouse gases to global warming, so the TERMS ⁇ on nitrogen oxides that arise in industrial processes, for reasons of Environmental protection should be avoided as much as possible.
  • the invention is therefore based on the object, a method for reducing the emission of nitrogen oxides in a Ab- to provide gas to be thermally treated at the factory ⁇ materials in at least indirect presence of oxygen and nitrogen in a furnace at high temperature is produced during a process.
  • the invention is based on the object of specifying a furnace operated by this method.
  • the stated object is achieved by a method having the features of claim 1.
  • the exhaust gas is at least one reducing agent and / or at least one supplied with oxygen in a competing reaction agent.
  • the metering of such agent which may be a substance or a mixture of different substances, can thus the emission of nitrogen oxides significantly reduced the ⁇ .
  • the method is particularly suitable for the treatment of exhaust gases that arise during the melting of metal scrap in an electric arc furnace.
  • the method is also applicable to the exhaust gas treatment in other processes in which metallic or non-metallic materials are subjected to a heat treatment at temperatures above 500 ° C.
  • These are for example stoves, which come in Stahlerzeu ⁇ supply is used, for example, LD converters, ladle furnaces, dies, reheating furnaces or blast furnaces.
  • Equally applicable is the method for the treatment of exhaust gases that arise in sintering furnaces, rolling mills in the reheating of slabs or in so-called bonnet furnaces in which, for example, ceramic materials are produced arise.
  • the process is equally applicable in the cement industry, in coal-fired power plants, chemical plants and in the oil and gas industry.
  • the agent can additionally be introduced directly into a furnace vessel of the furnace.
  • At least one of C, Na, Mg, Al, Si, Ca, Ti, Cr, Mn, Ni, Cu, Zn and Pb is preferably added either in pure form or in the form of a compound having another element of this group ,
  • hydrogen H 2 , carbon monoxide CO, methane CH 4 or urea CO (NH) 2 or a mixture of these gases can also be supplied.
  • These elements and gases act as a reducing agent for nitrogen monoxide NO and nitrous oxide N 2 O, since the free Gibbs Ener gy ⁇ the reduction reaction of nitrogen monoxide NO and
  • Nitrous oxide N 2 O with one of these elements or gases in the particularly relevant temperature range between 1000 and 2000 ° C is negative, this reduction reaction takes place even in the absence of catalysts.
  • the free Gibbs energies g (Gibbs energy or free enthalpy) in kJ / mol N o or kJ / mol N 2 o for selected reduction reactions against the temperature T are shown by way of example in FIGS. 1 and 2.
  • Oxygen oxidizes and in this way displaces the chemical balance to the disadvantage of the formation of nitrogen oxides NO x . Also for the competition reactions with oxygen, the free Gibbs energies g are negative in the interesting temperature range between 1000 and 2000 ° C., as can be seen from FIG. 3.
  • the reactions are also accelerated catalytically, if the exhaust gas in a preferred embodiment additionally a catalytically active solid, especially dust, sand,
  • Potassium K, sodium Na, iron Fe, calcium Ca or calcium monoxide CaO be supplied.
  • the content of nitrogen oxides in the exhaust gas is measured and the agent is added as a function of this content of the exhaust gas in the flow direction of the exhaust gas, in particular after the sampling point.
  • carbon monoxide CO, methane CH 4 or urea CO (NH) 2 can be measured and the agent is seen as a function of this content to the exhaust gas in the flow direction of the exhaust gas in particular according to the sampling point insbeson ⁇ dere metered then, if their content in the exhaust gas below predetermined values or the content of nitrogen oxides is greater than a predetermined value for each nitric oxide.
  • the supply of the agent dosage occurs in particular only if also the temperature exceeds a predetermined value, preferably 500 ° C to 1000 ° C ⁇ particular because then the reaction kinetics are accelerated and the reactions with a particularly high Ge ⁇ speed take place.
  • a predetermined value preferably 500 ° C to 1000 ° C ⁇ particular because then the reaction kinetics are accelerated and the reactions with a particularly high Ge ⁇ speed take place.
  • the object is achieved according to the invention with a furnace having the features of claim 10.
  • Advantageous embodiments of the furnace are given in the subordinate claims subordinate to this claim.
  • the advantages of the related to the oven claims entspre ⁇ chen thereby mutatis mutandis the advantages indicated for the respective corresponding method claims.
  • FIG. 1 and 2 in each case a diagram in which the free Gibbss che energy g is plotted for reactions according to the invention used agents with nitrogen oxides against the temperature T
  • FIG. 3 is a diagram in which the free Gibbs energy is applied Ener ⁇ g for reactions of the agents used in this invention with oxygen against the temperature T,
  • Fig. 4 is a schematic representation of a furnace ge ⁇ according to the invention.
  • a furnace comprises the thermal treatment of materials, which in the example is an electric arc furnace, a furnace vessel 2, in which ferrous output ⁇ material, for example steel scrap, DRI or HBI by ei ⁇ NEN between electrodes 4 and the Scrap steel burning arc is melted, with a slag layer 8 forms above the melt 6.
  • ferrous output ⁇ material for example steel scrap, DRI or HBI by ei ⁇ NEN between electrodes 4 and the Scrap steel burning arc is melted, with a slag layer 8 forms above the melt 6.
  • Additives for the melting process for example oxygen or carbon 0 C zugege ⁇ ben.
  • the resulting during melting exhaust gas OG is discharged via a connected to the furnace vessel 2 exhaust pipe 12 and performed for dedusting to a cyclone not shown in the figure.
  • the exhaust pipe 12 includes a nozzle 14, which opens into a main line 16 leaving an annular gap 15. Through the annular gap 15 ambient air A is sucked in, which leads to an afterburning of the
  • a sampling system 18 is connected to the at least one sampling point from the exhaust gas OG a gas sample SG removed and an Analy ⁇ se noticed 20 is supplied in the gas sample SG on the content of nitrogen oxides NO x and / or hydrogen H 2 , carbon monoxide CO, methane CH 4 or urea CO (NH) 2 is analyzed.
  • the temperature T of the exhaust gas OG at the location of the sampling is measured with a temperature measuring device 22.
  • the measured values M determined by the analysis device 20 and the temperature T determined by the temperature measuring device 22 are forwarded to a control device 24 in which, depending on this measured value M and this temperature T, a control signal S1 for a metering device 26 is generated which is supplied via a supply line 28 is connected to the exhaust gas line 12. With the feed line 28 opening into the exhaust gas line 12, the agent O reducing or reacting in a competing reaction is fed to the exhaust gas OG.
  • the exhaust gas OG amount depends on the concentration existing at the sampling point in the From ⁇ gas OG abovementioned substances.
  • a the metered addition of the reduzie- rend acting or reacting in a competing reaction agent R is effecting control signal Sl only then ⁇ evidence when this temperature T exceeds a predetermined value, in particular 500 ° C, and in addition the NOx content prescribed in the exhaust gas OG Values exceeds or the content of methane CH 4 or carbon monoxide CO or hydrogen H 2 or urea CO (NH) 2 in the exhaust gas OG predetermined values undershoot ⁇ or not exceeded.
  • a Zudo ⁇ tion of the agent R does not take place in this procedure, if the temperature T falls below this predetermined value.
  • the sampling location is in Strö ⁇ direction of flow of the exhaust gas OG seen the point in the supply line opens into the exhaust pipe 12 28th Prin- Piell, a reverse arrangement is conceivable in which the supply of the agents R is controlled so then that in ⁇ play, the content of nitrogen oxides NO x in the area of the sampling site is minimal.
  • an agent R can also be supplied via a further supply line 30 opening into the furnace vessel 2 be introduced directly into the furnace vessel 2.
  • a control signal S2 is generated by the controller 24 connected with the one on the other supply line 30 to the furnace vessel 2 further metering device 32 is ⁇ is controlled.
  • reduzie ⁇ rend acting or reacting in a competing reaction agent R is preferably only supplied to the furnace vessel, in this case, when the temperature T exceeds a predetermined value in the exhaust gas OG, and additionally exceed the NO x content in the exhaust gas OG specified differently bene values or the content of methane CH 4 or carbon monoxide CO or hydrogen H2 or urea CO (NH) 2 in the exhaust gas OG falls below predetermined values.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
  • Catalysts (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé pour réduire l'émission d'oxydes d'azote dans l'effluent gazeux d'un four lors du traitement thermique de matières et un four fonctionnant selon ledit procédé. La présente invention concerne un procédé pour réduire l'émission d'oxydes d'azote dans l'effluent gazeux (OG) d'un four lors du traitement thermique de matières en présence au moins indirecte d'oxygène et d'azote, en particulier lors de la fusion de matières premières contenant du fer dans un four à arc électrique, et un four fonctionnant selon ce procédé, dans lesquels un agent (A) à action réductrice et/ou un agent (A) réagissant avec l'oxygène dans une réaction concurrente sont amenés à l'effluent gazeux (OG).
PCT/EP2012/056022 2011-04-27 2012-04-03 Procédé pour réduire l'émission d'oxydes d'azote dans l'effluent gazeux d'un four lors du traitement thermique de matières et four fonctionnant selon ledit procédé Ceased WO2012146462A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
RU2013152604/05A RU2013152604A (ru) 2011-04-27 2012-04-03 Способ уменьшения выбросов оксидов азота в отработанный газ печи при термической обработке материалов и работающая по данному способу печь
CN201280019785.6A CN103702743A (zh) 2011-04-27 2012-04-03 用于在材料的热处理中降低炉子的废气中的氧化氮的排放量的方法和根据此方法运行的炉子

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011017600.4 2011-04-27
DE201110017600 DE102011017600A1 (de) 2011-04-27 2011-04-27 Verfahren zum Vermindern der Emission von Stickoxiden im Abgas eines Ofens bei der thermischen Behandlung von Werkstoffen und nach diesem Verfahren betriebener Ofen

Publications (1)

Publication Number Publication Date
WO2012146462A1 true WO2012146462A1 (fr) 2012-11-01

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PCT/EP2012/056022 Ceased WO2012146462A1 (fr) 2011-04-27 2012-04-03 Procédé pour réduire l'émission d'oxydes d'azote dans l'effluent gazeux d'un four lors du traitement thermique de matières et four fonctionnant selon ledit procédé

Country Status (4)

Country Link
CN (1) CN103702743A (fr)
DE (1) DE102011017600A1 (fr)
RU (1) RU2013152604A (fr)
WO (1) WO2012146462A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016224116A1 (de) 2016-12-05 2018-06-07 Sms Group Gmbh Verfahren und Vorrichtung zur NOx-Minderung in Abgasströmen metallurgischer Gefäße und Öfen
US11104975B2 (en) * 2017-07-13 2021-08-31 Andritz Technology And Asset Management Gmbh Method for reducing nitrogen oxides in strip treatment furnaces
RU2816467C1 (ru) * 2023-09-08 2024-03-29 федеральное государственное бюджетное образовательное учреждение высшего образования "Белгородский государственный технологический университет им. В.Г. Шухова" Способ сжигания твердого топлива во вращающихся печах цементного производства

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102017103701A1 (de) * 2017-02-23 2018-08-23 Markus Kunkel Verfahren zur Nachverbrennung von Rauchgasen
DE102022201570A1 (de) * 2022-02-16 2023-08-17 Sms Group Gmbh Verfahren und Vorrichtung zur Behandlung von Primärgas aus einem metallurgischen Gefäß

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US5750084A (en) * 1994-12-28 1998-05-12 Kawasaki Jukogyo Kabushiki Kaisha Fluidized-bed denitrating method
DE19738056A1 (de) * 1997-09-01 1999-03-04 Anneliese Zementwerke Ag Entstickung von Feuerungsanlagen
DE10045429A1 (de) * 2000-09-14 2002-03-28 Nachtmann F X Bleikristall Verfahren zur Reduzierung des NOx-Gehaltes

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DE3927096A1 (de) * 1988-09-30 1990-04-05 Still Otto Gmbh Verfahren zur reduzierung des stickoxidgehaltes im rauchgas von verkokungsofenbatterien
US5750084A (en) * 1994-12-28 1998-05-12 Kawasaki Jukogyo Kabushiki Kaisha Fluidized-bed denitrating method
DE19738056A1 (de) * 1997-09-01 1999-03-04 Anneliese Zementwerke Ag Entstickung von Feuerungsanlagen
DE10045429A1 (de) * 2000-09-14 2002-03-28 Nachtmann F X Bleikristall Verfahren zur Reduzierung des NOx-Gehaltes

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016224116A1 (de) 2016-12-05 2018-06-07 Sms Group Gmbh Verfahren und Vorrichtung zur NOx-Minderung in Abgasströmen metallurgischer Gefäße und Öfen
WO2018104169A1 (fr) 2016-12-05 2018-06-14 Sms Group Gmbh Procédé et dispositif de réduction de nox dans des flux de gaz brûlés de récipients et de fours métallurgiques
US11104975B2 (en) * 2017-07-13 2021-08-31 Andritz Technology And Asset Management Gmbh Method for reducing nitrogen oxides in strip treatment furnaces
RU2816467C1 (ru) * 2023-09-08 2024-03-29 федеральное государственное бюджетное образовательное учреждение высшего образования "Белгородский государственный технологический университет им. В.Г. Шухова" Способ сжигания твердого топлива во вращающихся печах цементного производства

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RU2013152604A (ru) 2015-06-10
DE102011017600A1 (de) 2012-10-31
CN103702743A (zh) 2014-04-02

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