CN103547863A - Method for treating a carbon dioxide-containing waste gas - Google Patents

Method for treating a carbon dioxide-containing waste gas Download PDF

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Publication number
CN103547863A
CN103547863A CN201280005150.0A CN201280005150A CN103547863A CN 103547863 A CN103547863 A CN 103547863A CN 201280005150 A CN201280005150 A CN 201280005150A CN 103547863 A CN103547863 A CN 103547863A
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CN
China
Prior art keywords
gas
waste gas
carbon dioxide
hydrocarbon
converter
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Pending
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CN201280005150.0A
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Chinese (zh)
Inventor
曼弗雷德·巴利道夫
托马斯·马楚拉特
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Siemens AG
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Siemens AG
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Publication of CN103547863A publication Critical patent/CN103547863A/en
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J1/00—Production of fuel gases by carburetting air or other gases without pyrolysis
    • C10J1/20—Carburetting gases other than air
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
    • F23G5/027—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/061—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating
    • F23G7/065—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating using gaseous or liquid fuel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/08—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases using flares, e.g. in stacks
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/003—Arrangements of devices for treating smoke or fumes for supplying chemicals to fumes, e.g. using injection devices
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/06—Arrangements of devices for treating smoke or fumes of coolers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2201/00—Pretreatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2206/00—Waste heat recuperation
    • F23G2206/20—Waste heat recuperation using the heat in association with another installation
    • F23G2206/203—Waste heat recuperation using the heat in association with another installation with a power/heat generating installation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2207/00—Control
    • F23G2207/60—Additives supply
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2217/00—Intercepting solids
    • F23J2217/10—Intercepting solids by filters
    • F23J2217/102—Intercepting solids by filters electrostatic
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/12—Heat utilisation in combustion or incineration of waste
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/32—Direct CO2 mitigation

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Carbon Steel Or Casting Steel Manufacturing (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
  • Treating Waste Gases (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention relates to a method for treating a carbon dioxide-containing waste gas (2), in which a hydrocarbon-containing gas (5) is guided to the waste gas and the carbon dioxide of the waste gas is at least partially converted into carbon monoxide and hydrogen when reacted with hydrocarbon and said waste gas is used with the carbon monoxide hydrogen mixture (9) for an additional combustion process.

Description

Method for the treatment of carbonated waste gas
Technical field
The present invention relates to a kind of according to the method for the treatment of carbonated waste gas of claim 1.
Background technology
In industrial flow, particularly, in steel flow process processed, often can gather hot waste gas, this waste gas has a high proportion of CO 2.For example when moving, so-called converter (BOF=Blastoxygen Furnage) there will be this situation.At this, hot waste gas can overflow when about 1700 ° of C.Used heat is partly used in steam boiler.Remainder is cooling by devaporizer.And then by filtration, remove the dust particle in waste gas.In order to pass filter plant, the temperature of waste gas does not allow to surpass 180 ° of C.
The waste gas particularly gathering in converter comprises a high proportion of carbon dioxide (CO in many flow processs portion section 2).If carbon dioxide entered environment, carbon dioxide causes so-called greenhouse effects.
Summary of the invention
Accordingly, the object of the invention is to, a kind of method for the treatment of carbonated waste gas is provided, by the method, reduce the ratio of the carbon dioxide in freedom of entry atmosphere.
The solution of this object is present among the method with feature described in claim 1.
According to the method for the treatment of carbonated waste gas according to the present invention, to waste gas, carry the gas of hydrocarbon-containiproducts.The gas of this hydrocarbon-containiproducts in reaction with waste gas in carbon dioxide react, form at least in part product carbon monoxide (CO) and hydrogen (H 2).Comprise that the carbon monoxide of suitable concn and the waste gas of hydrogen mixture are for the flow process of further burning.At this, can store in advance this mixture if desired temporarily.This further burning flow process can be, but not need must be the part of the method, treated waste gas accumulates in this flow process.
In preferred design, the mixture of carbon monoxide and hydrogen (being designated hereinafter simply as fuel gas) has higher fuel value than the gas (hereinafter referred to as changing gas) of the hydrocarbon-containiproducts of input.This means again, and occurring in the reaction changing between gas and carbon dioxide is the endothermic reaction, namely absorbs the reaction of ambient heat.
By the present invention, the environmentally harmful carbon dioxide of remarkable ratio is siphoned away from waste gas thus, and its form that can using conversion flows to further burning flow process as fuel gas.Thus, the heat energy of waste gas changes into the chemical energy of the fuel gas of generation here.
Be proved to be to be applicable to, for the use methane for gas that changes of hydrocarbon-containiproducts, particularly with the form of natural gas.At this, in order to regain carbon dioxide, start the strong endothermic reaction, this causes forming carbon monoxide and hydrogen.
In steel processed, use the method according to this invention in an advantageous manner, because often produce the high-temp waste gas containing great amount of carbon dioxide in steel production process.Particularly the waste gas of converter in steel processed, is applicable to processing according to the method according to this invention.In steel process processed, converter is for reducing the content of molten iron carbon dioxide.
In a kind of design of the present invention, except changing gas, can also in waste gas, add water, preferably with the form of steam.By carrying additional water, change the proportionate relationship of carbon monoxide and hydrogen, this is suitable as fuel gas in different application scenarios.
Because the carbon content in waste gas is not constant at each time point of method flow, so what be applicable to is to control waste gas.Particularly, by introducing gas sensor, can monitor the carbon dioxide content in waste gas, and correspondingly control the importing that changes gas.
Same being applicable to, in converter, introduce adjustable ring, it exists in much traditional equipment, and can reduce gas leakage body, the namely suction of less desirable surrounding air, thereby can and not change at oxygen additional reaction occurs between gas.
Fuel gas can also be stored in the gas container that (preferably) existed temporarily.Fuel gas can also be applied in other different flow processs, particularly in steel industry.For example can be used in power plant and manufacture (may be combined with generating set) for generating or for flow process steam.In addition, fuel gas can be used in elevator furnace or pusher-type furnace or in burner as slab, bar-shaped base and compact preheating.For example be applicable to ladle and dry and heating process, be applicable to heating station or be applicable to the distributor in continuous casting equipment.
Accompanying drawing explanation
According to the following drawings, at large set forth other favourable design and feature of the present invention.
Accompanying drawing illustrates:
Fig. 1 is the schematic diagram of the single method step when the waste gas of processing from converter,
Fig. 2 is according to prior art original processing to waste gas in steel industry, and
Fig. 3 is according to the block diagram of the flow process shown in Fig. 2, has additional waste gas transformation.
The specific embodiment
Below to set forth according to converter example Fig. 1, that be used in iron and steel production the flow process of processing waste gas.Converter 4 is for removing the excessive carbon of molten iron.In iron, import oxygen, and the oxidation of coal being present in molten iron becomes carbon dioxide for this reason.For this reason, the waste gas 2 of converter 4 comprises the carbon dioxide of remarkable ratio.
Carbon dioxide content in converter waste gas is relevant with its operation parameters.According to oxygen infusion and running temperature, the ratio of carbon dioxide and carbon monoxide content fluctuation in waste gas 2.Waste gas 2 pours in exhaust steam passage, and by probe 3, checks its carbon dioxide content there.If carbon dioxide content is higher than default threshold value, by changing gas conveying member 6, to importing in exhaust steam passage 11, change gas 5 so.According to following reaction equation, change gas 6, for example can use for this reason and contain the natural gas of methane at high proportion, react at least in part with the carbon dioxide in waste gas, (dry type transformation 7, referring to Fig. 3).
CH 4+CO 2→2CO+2H 2 ΔH=+250kJ/mol
This reaction is the endothermic reaction, and every Mol absorbs the environment thermal energy of 25OkJ, namely from waste gas 2, draws heat energy.By following reaction, transform heat energy by this way, this heat energy is (CO+H in the fuel gas 7 forming 2, also referred to as forming gas) and be stored as chemical energy.Accordingly, also heat energy is converted into chemical energy, because the fuel gas 9 producing according to formula 1 has higher fuel value than the gas (methane) that changes of original use.
The single fuel value of analyte and product is:
CH 4:55.5MJ/kg=888MJ/kmol
CO:10.1MJ/kg=283MJ/kmol
H 2:143MJ/kg=286MJ/kmol
By 2Mol carbon monoxide and 2MolH 2the fuel value of the mixture forming is than the CH of 1Mol 4the fuel value of (methane) exceeds previous reaction entropy 250KJ/mol, and fuel gas 7 is from wherein producing.So the raising amount of fuel value is equivalent to the 28%(250KJ/mol:888KJ/mol of the fuel value of the methane that adds thus).
According to the service condition of fuel gas 7, can meaningfully, increase CO:H 2the ratio of middle hydrogen.In this case, may be simultaneously on gas conveying member 6, import the water form of steam (preferably with) changing simultaneously.Thereby can realize the CO transformationreation of heat release, accordingly
H 2O+CO→CO 2+H 2ΔH=H-42kJ/mol
H 2change with the ratio of CO.Although stored thus waste heat still less (because being exothermic reaction) here, can realize H in fuel gas 7 2content higher, this is favourable in some burning in flow process.Particularly when being while realizing heat transmission by radiation rather than by convection current in these burning flow processs, particularly favourable.Because combustion of hydrogen causes in waste gas water content higher, because its radiation zone is very wide, this is conducive to heat transmission.
In this example of converter, particularly when converter has adjustable ring 13, can be under two of reconstruction flow different flow states the CO to waste gas 2 advantageously 2carry out reforming processing.On the one hand, at so-called initial period and shutdown stage, be so, at initial period with in the shutdown stage, because the CO of waste gas 2too high levels, and CO content is too low, so not yet utilize so far waste gas.By the dry type of describing, transform, according to equation 1, obtain the sufficiently high available fuel gas of fuel value, this fuel gas is also described in the method flow about other, and can be stored in gas reservoir.
On the other hand, if this gas containing fuel rich will mix with the poor gas of miscellaneous part from steel mill, and the mixture for other burning flow process does not have enough fuel values, also can apply dry type transformation and further improve anyway the burning of gas value that assemble, that contain abundant CO according to prior art.
It is suitable using adjustable ring 13, to avoid being drawn into infiltration air, infiltrates air and causes methane or natural gas, namely changes the burning of gas 7, and cannot complete the described transformation according to equation 1.In addition, in air, high nitrogen content causes converter gas and fuel gas to thin out.
After reconstruction flow, waste gas is cooling in steam boiler 8, wherein, produces there steam, and steam again can be for generating.
Then waste gas 2 is carried out to rough dedusting 10, in this waste gas and then importing devaporizer 12.Devaporizer 12 is necessary, and this is because waste gas does not allow higher than 180 ° of C for ensuing dry type electro static filtering 14, removes remaining micronic dust in dry type electro static filtering from waste gas 2.After isolating micronic dust, by air blast 10, by waste gas 20 or by flare stack 18, burn, or in gas cooler 20 further in cooling rear importing gas container 22.
Whether constituent flammable in waste gas 2 burns by flare tower, or has CO and H 2the waste gas of high heat of mixture as fuel gas, whether be stored in gas container 22, these problems depend on the carbon dioxide content of waste gas 2.For example by sensor 3, is controlling aptly when transformation, as described in utilize and change gas methane and transform waste gas 2, cause CO and H in waste gas 2the content of mixture high like this after filtering, most waste gas or carbon monoxide and hydrogen can both leave in gas container 22, and can again utilize as fuel gas 9.Compared to existing technology, in flare tower 18, the waste gas of burning reduces to very little part by these measures.
In Fig. 2 and 3, again schematically by block diagram, show prior art and the difference between described method herein of the exhaust-gas treatment method of converter waste gas.
Far Left is to produce CO 2the process step of waste gas, here with the converter 4 that wherein produces waste gas 2 for exemplifying.Carbonated waste gas 2 is cooling in steam boiler 8, wherein, forms steam for other application.In addition, follow now devaporizer 12 below, in devaporizer, produce waste heat Q1, do not continue to utilize in this case waste heat.What follow is dry type electrostatic filter 14, wherein, and then, according to the carbon dioxide content of waste gas 2, by flare tower 18 burnt gas, or is stored in the application for other as fuel gas 9 in gas container 22.
Method described here according to Fig. 3 with according to the difference according to the method for Fig. 2 of prior art, be, between converter 4 and steam generator 8, with the form of dry type transformation, carry out reconstruction flow 7, wherein, by changing gas conveying member 6, to this flow process, carry and change gas 5, and as process waste gas 2 as described in equation 1.
Except transforming 7 by described such dry type of inserting, these two kinds of methods also have following difference,, the heat Q2 drawing on devaporizer 12 is less than according to the heat Q1 of the devaporizer 12 of Fig. 2, and the amount m2 of the gas 2 of burning is less than the amount m1 burning on flare tower 18' according to prior art on flare tower 18.
Because can recycle combustible gas mixture in the suitable equipment of steel mill, so the production phase of burning again in torch 18 according to prior art can be reduced or shorten.In storage, utilize in an advantageous manner the energy together with the flammable composition of the waste gas of the fuel gas forming waste heat in the situation that thus.By shortening torch running time, air accumulation time lengthening, and the CO2 emissions of converter installation or torch reduce.

Claims (11)

1. the method for the treatment of the waste gas that contains carbon dioxide (2), wherein, to described waste gas, carry the gas (5) that contains hydrocarbon, and the described carbon dioxide of described waste gas changes at least in part carbon monoxide and hydrogen in reaction, and the mixture of described carbon monoxide and described hydrogen (9) is for other burning flow process.
2. method according to claim 1, is characterized in that, the described carbon dioxide in described waste gas, with the gas (7) that contains hydrocarbon, the endothermic reaction occurs, and by the cooling described waste gas of the described endothermic reaction (2).
3. method according to claim 1 and 2, is characterized in that, the described gas (5) of hydrocarbon-containiproducts comprises methane.
4. according to method in any one of the preceding claims wherein, it is characterized in that, in the process of steel processed, gather described waste gas (2).
5. according to method in any one of the preceding claims wherein, it is characterized in that, described waste gas (2) accumulates in the converter (4) for reducing the carbon content of molten iron.
6. according to method in any one of the preceding claims wherein, it is characterized in that, except the described gas (5) that contains hydrocarbon, also to described waste gas (2), add water.
7. according to method in any one of the preceding claims wherein, it is characterized in that, utilize gas sensor to monitor the described carbon dioxide content of described waste gas, for regulating the conveying of the described gas (5) of hydrocarbon-containiproducts.
8. according to the method described in any one in claim 5 to 7, it is characterized in that, in described converter (4), be provided with for avoiding suction to infiltrate the adjustable ring of air.
9. according to method in any one of the preceding claims wherein, it is characterized in that, the described mixture (9) of described carbon monoxide and described hydrogen is stored in gas container temporarily.
10. according to method in any one of the preceding claims wherein, it is characterized in that, the described mixture (9) of described carbon monoxide and described hydrogen is as fuel gas.
11. according to method in any one of the preceding claims wherein, it is characterized in that, in the initial flow process of described converter and/or carry the described gas of hydrocarbon-containiproducts in shutting down flow process.
CN201280005150.0A 2011-01-13 2012-01-02 Method for treating a carbon dioxide-containing waste gas Pending CN103547863A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102011002612.6 2011-01-13
DE102011002612A DE102011002612A1 (en) 2011-01-13 2011-01-13 Process for treating a carbon dioxide-containing exhaust gas
PCT/EP2012/050015 WO2012095328A2 (en) 2011-01-13 2012-01-02 Method for treating a carbon dioxide-containing waste gas

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Publication Number Publication Date
CN103547863A true CN103547863A (en) 2014-01-29

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US (1) US20140013665A1 (en)
EP (1) EP2659185A2 (en)
KR (1) KR20140020846A (en)
CN (1) CN103547863A (en)
BR (1) BR112013017844A2 (en)
DE (1) DE102011002612A1 (en)
RU (1) RU2569105C2 (en)
WO (1) WO2012095328A2 (en)

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CN114196797A (en) * 2021-11-24 2022-03-18 中冶南方工程技术有限公司 Converter flue gas carbon dioxide recovery system and process

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DE102018219105A1 (en) * 2018-11-08 2020-05-14 Dürr Systems Ag Process for cleaning a raw gas stream and cleaning device

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WO2012095328A2 (en) 2012-07-19
RU2569105C2 (en) 2015-11-20
DE102011002612A1 (en) 2012-07-19
EP2659185A2 (en) 2013-11-06
US20140013665A1 (en) 2014-01-16
KR20140020846A (en) 2014-02-19
WO2012095328A3 (en) 2013-11-21
BR112013017844A2 (en) 2019-09-24
RU2013137756A (en) 2015-02-27

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