WO2003011756A1 - Methode de production d'un charbon actif presentant une grande resistance et un grand pouvoir de denitration, et charbon actif produit par cette methode - Google Patents

Methode de production d'un charbon actif presentant une grande resistance et un grand pouvoir de denitration, et charbon actif produit par cette methode Download PDF

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Publication number
WO2003011756A1
WO2003011756A1 PCT/JP2001/011682 JP0111682W WO03011756A1 WO 2003011756 A1 WO2003011756 A1 WO 2003011756A1 JP 0111682 W JP0111682 W JP 0111682W WO 03011756 A1 WO03011756 A1 WO 03011756A1
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WO
WIPO (PCT)
Prior art keywords
activated carbon
denitration
exhaust gas
sintering
ammonia
Prior art date
Application number
PCT/JP2001/011682
Other languages
English (en)
Japanese (ja)
Inventor
Hisao Kamiyama
Takashi Yoshimura
Original Assignee
Nippon Steel Corporation
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 Nippon Steel Corporation filed Critical Nippon Steel Corporation
Publication of WO2003011756A1 publication Critical patent/WO2003011756A1/fr

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Classifications

    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents

Definitions

  • the present invention relates to a method for producing activated carbon having excellent strength, denitration performance, and desulfurization performance used in a sintering exhaust gas treatment device of a steel mill or the like, and an activated carbon produced by this method.
  • raw materials such as iron ore and coke are pulverized and mixed, and then sintered into blast furnaces into particles of a suitable size before being put into a blast furnace.
  • Sintered exhaust gas containing N0 X and S0 X is generated.
  • the sintering waste gas at a temperature of about 90 to 120 ° C, is intended to include N0 X and 120 PP m approximately S0 X of about 150 ppm. Therefore, conventionally, in order to purify the sintering exhaust gas, an exhaust gas treatment apparatus provided with an adsorption tower filled with activated carbon has been used.
  • Fig. 4 shows a conventional sintering flue gas treatment device.
  • the sintering flue gas is sent to an adsorption tower 1 filled with activated carbon having a diameter of about 10 mm and a length of about 15 mm.
  • S0 X sintering in the exhaust gas is adsorbed on the surface of the connexion activated carbon, such as the form of H 2 S0 4.
  • N0 X in the sintered exhaust gas is reduced decomposed to I Ri New 2 gas to the catalytic action of the active carbon.
  • Sintering exhaust gas ⁇ 0 ⁇ and S0 X has been removed in this good jar is released into the atmosphere.
  • the activated carbon filled in the adsorption tower 1 is gradually moved downward and extracted to the outside from the lower end of the tower, and the fine powder crushed during the movement is removed by the classifier 2.
  • the fine powder is removed in the classifier 2.
  • the reason for this is that activated carbon destroyed by one band or less may increase the ventilation resistance of the sintering flue gas in the adsorption tower 1 and render the adsorption tower 1 inoperable.
  • the activated carbon from which fine powder has been removed by the classifier 2 is sent to the desorption tower 3 and heated to about 400 ° C. to desorb and regenerate the adsorbed H 2 SO 4 .
  • the regenerated activated carbon is then sent to the adsorption tower 1 again, and this cycle is repeated until it is finally removed by the classifier 2.
  • the present invention solves the above-mentioned conventional problems, and can drastically increase the denitration rate of sintering exhaust gas from about 40% to 90% or more of the conventional sintering exhaust gas.
  • An object of the present invention is to provide a method for producing an activated carbon having high strength and high denitration performance, which hardly powders even when circulated between the tower and the activated carbon produced by the method.
  • a method for producing activated carbon having high strength and high denitrification performance comprising the step of producing activated carbon using coal as a raw material, wherein the activation is performed by adding ammonia to a sintering exhaust gas from a steel mill or the like. It is characterized by activating the gas by contacting the activated carbon with the gas.
  • ammonia concentration added to the sintering exhaust gas S0 2 concentration of 1.1 times to 1.5 times the child and is favored arbitrary sintering exhaust gas.
  • the activated carbon having high strength and high denitration performance according to the third invention is manufactured by the first or second invention using coal as a raw material, and contains 8.5% or more of volatile components. It is characterized by the following. BRIEF DESCRIPTION OF THE FIGURES
  • FIG. 1 is a block diagram showing an embodiment of the present invention.
  • FIG. 2 is a graph showing the relationship between the number of cycles and the denitration rate.
  • Figure 3 is a graph showing the relationship between the volatile components in activated carbon and the denitration rate.
  • FIG. 4 is a block diagram showing a conventional sintering exhaust gas treatment apparatus. BEST MODE FOR CARRYING OUT THE INVENTION
  • the present invention has a remarkable feature in that the gas obtained by adding ammonia to sintering exhaust gas from a steel mill or the like is used as an activation gas to improve the denitration performance of activated carbon. This is completely different from the conventional technology in which activated carbon is directly packed in an adsorption tower in the activated carbon production method as described above.
  • activated carbon formed into pellets using coal as a raw material is filled into the adsorption tower 1 shown in FIG. 1 and discharged from the sintering machine at 90 to 120 ° C.
  • the activation treatment is carried out by contact with the sintering flue gas, but a suitable amount of ammonia is added to the sintering flue gas in advance.
  • Ammonia concentration added to the sintering waste gas S0 2 concentration of 1.1 times to 1.5 times the child and is favored arbitrary sintering exhaust gas.
  • the denitration rate of activated carbon at the time of introduction is about 25 to 30%, but as the number of cycles increases, the denitration rate gradually increases. In 48 cycles, the denitration rate is 95%, which is unprecedented. This is because the functional groups gradually grow during the cycle.
  • the amount of the functional groups can be measured as the amount of volatile components in the activated carbon. As shown in the graph of Fig. 3, the denitration rate is about 25 to 30% in the initial state where the volatile component amount is about 3%, but when the volatile component amount reaches a level of 8.5% or more, the denitration rate becomes 80 %. Therefore, Claim 3 specifies the amount of volatile components to be 8.5% or more. Note ⁇ Nmonia concentration to be added to the sintering exhaust gas without functional groups: 1. less than 1 times the S0 2 concentration in the sintering exhaust gas is fully grown, thus also an increase in volatile component amount improves the denitrification rate not It is not preferable because it becomes sufficient.
  • the addition of ammonia may decrease the strength of the activated carbon and increase the powdering rate, but as a result of investigating the cause, it has been found that it is related to the amount of ammonia added. That the active carbon Ri by the addition of en Moyua is destroyed, the added ammonia ⁇ reacts with S0 X in the sintered waste gas (NH 3) 2 S0 4 is produced, which is the crystal on the surface of the activated carbon When activated, it expands the pores and destroys the activated carbon.
  • the raw material of the activated carbon is coal.However, general activated carbon made from coconut shell has a low strength, and may be crushed by several tens of cycles. The present invention is not suitable for the purpose of increasing the denitration rate as the number of cycles is increased.
  • the denitration rate of the activated carbon can be much higher than the conventional level. increase can and this, moreover, the amount of ammonia Ri fOR a FULL set in an appropriate range in consideration of the S0 2 concentration in the sintering exhaust gas, suppress the powdering ratio and ensure high strength be able to.
  • the present invention can be used to increase the denitrification rate of activated carbon newly produced from coal, and can also be used to reprocess activated carbon that has been used elsewhere and has reduced activity. it can. In this case, too, by circulating between the adsorption tower 1 and the desorption tower 3, the denitration rate is reduced. Can be increased to about 90%.
  • the present invention is aimed at producing activated carbon having excellent strength, denitration performance, and desulfurization performance used in a sintering flue gas treatment device at a steel mill or the like.
  • the treatment of the sintering exhaust gas can be continued with almost no external replenishment of activated carbon.
  • the circulation cycle is repeated until the gas is discharged from the classifier 2.
  • the purpose is to reprocess the activated carbon as described above, it may be extracted outside during the cycle. It goes without saying that reprocessed activated carbon can be used for various purposes other than treating sintering exhaust gas from steelworks.
  • Coal powder ground to a particle size of 0.1 mm or less was formed into a cylindrical pellet with a diameter of 10 mm and a length of 15 mm, and was prefired to obtain activated carbon with pores.
  • This activated carbon was filled in the contact tower shown in Fig. 1, and was brought into contact with the sintering exhaust gas from a steel mill. Temperature of the sintering exhaust gas is 100, comprised the S0 X of N0 X and 120ppm of 150p pm. This sintered waste gas was added ammonia 150p P m corresponding to 1.3 times the S0 X concentration.
  • the initial activated carbon had a desulfurization rate of 99%, but the denitrification rate was only 35%.
  • Activated carbon extracted from the lower part of the contact tower was sent to the desorption tower via a classifier, and the cycle of heating to 400 ° C to desorb the adsorbed sulfuric acid and returning to the contact tower again was repeated 50 times.
  • the desulfurization rate remained the same at 99%, the denitrification rate increased significantly to 95%.
  • the powdering rate conventionally separated by a classifier was 1.6 to 4%, but the powdering rate of the activated carbon produced by the present invention was only 0.8%, and the new activated carbon was The amount of replenishment was greatly reduced.
  • the denitration rate of the sintering exhaust gas is reduced by 40% compared to the conventional method.
  • Activated carbon can be dramatically increased from about 90% to more than 90%, and the powdering rate is much lower than that of conventional products.
  • the present invention can be applied not only to the activation treatment of new activated carbon, but also to the recycling of used activated carbon. Further, the present invention is directed to the production of activated carbon for a sintering exhaust gas treatment device of a steel mill, but the produced activated carbon can be used for other general purposes.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treating Waste Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne une méthode de production d'un charbon actif présentant une grande résistance et un grand pouvoir de dénitration. La méthode se caractérise en ce que, dans un processus de production d'un charbon actif dont la matière première et le charbon, un charbon actif est soumis à un traitement d'activation qui consiste à placer le charbon actif au contact d'un gaz activant obtenu par adjonction d'ammonium à un gaz d'échappement de frittage provenant d'une aciérie. Elle concerne également un charbon actif produit par cette méthode. L'ammonium présente, de préférence, une concentration de 1,1 à 1,5 fois supérieure à celle du SO2 dans le gaz d'échappement de frittage. Des groupes fonctionnels sont formés à la surface du charbon actif au moyen dudit traitement et, pendant que le charbon actif est recyclé plusieurs fois entre une colonne d'absorption et une colonne de libération, le pourcentage de dénitration est augmenté progressivement jusqu'à 90 % et le pourcentage de poudrage réduit de moitié au plus par rapport au pourcentage obtenu par une méthode classique. La méthode de l'invention améliore sensiblement le pourcentage de dénitration qui passe d'environ 40 % avec la méthode classique à 90 % ou plus avec un faible poudrage.
PCT/JP2001/011682 2001-07-27 2001-12-28 Methode de production d'un charbon actif presentant une grande resistance et un grand pouvoir de denitration, et charbon actif produit par cette methode WO2003011756A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-227379 2001-07-27
JP2001227379A JP4015829B2 (ja) 2001-07-27 2001-07-27 高強度・高脱硝性能を有する活性炭の製造方法

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WO2003011756A1 true WO2003011756A1 (fr) 2003-02-13

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101254394B (zh) * 2008-04-25 2010-10-06 武汉凯迪电力环保有限公司 烧结机烟气多污染物脱除工艺及其***
CN104741113A (zh) * 2015-04-02 2015-07-01 易能（马鞍山）大气治理科技有限公司 一种低成本的脱硝催化剂及其制备方法
CN109876784A (zh) * 2019-03-07 2019-06-14 大同新成新材料股份有限公司 一种活性炭脱硫脱硝实验装置
CN110585854A (zh) * 2019-09-23 2019-12-20 中国科学院过程工程研究所 一种烟气净化吸收装置及活性炭脱硫脱硝***

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102380308A (zh) * 2010-09-03 2012-03-21 鞍钢集团工程技术有限公司 一种烧结烟气脱硫净化方法及设备
CN104129777B (zh) * 2014-08-26 2016-03-30 武汉科技大学 一种多功能化生物炭及其制备方法

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JPH0780245A (ja) * 1993-09-10 1995-03-28 Sumitomo Heavy Ind Ltd 排ガスの処理方法
JPH0966222A (ja) * 1995-08-31 1997-03-11 Sumitomo Heavy Ind Ltd 排ガスの処理方法
JPH11165034A (ja) * 1997-12-02 1999-06-22 Sumitomo Heavy Ind Ltd 排ガス処理方法

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* Cited by examiner, † Cited by third party
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US3926590A (en) * 1972-10-24 1975-12-16 Takeda Chemical Industries Ltd Process for treatment of waste gases
JPS60220129A (ja) * 1984-04-16 1985-11-02 Sumitomo Heavy Ind Ltd 排ガスの処理方法
JPS61287423A (ja) * 1985-06-12 1986-12-17 Sumitomo Heavy Ind Ltd 排ガスの処理方法
JPH0780245A (ja) * 1993-09-10 1995-03-28 Sumitomo Heavy Ind Ltd 排ガスの処理方法
JPH0966222A (ja) * 1995-08-31 1997-03-11 Sumitomo Heavy Ind Ltd 排ガスの処理方法
JPH11165034A (ja) * 1997-12-02 1999-06-22 Sumitomo Heavy Ind Ltd 排ガス処理方法

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101254394B (zh) * 2008-04-25 2010-10-06 武汉凯迪电力环保有限公司 烧结机烟气多污染物脱除工艺及其***
CN104741113A (zh) * 2015-04-02 2015-07-01 易能（马鞍山）大气治理科技有限公司 一种低成本的脱硝催化剂及其制备方法
CN104741113B (zh) * 2015-04-02 2017-07-14 易能环境技术有限公司 一种低成本的脱硝催化剂及其制备方法
CN109876784A (zh) * 2019-03-07 2019-06-14 大同新成新材料股份有限公司 一种活性炭脱硫脱硝实验装置
CN109876784B (zh) * 2019-03-07 2021-10-15 山西华青环保股份有限公司 一种活性炭脱硫脱硝实验装置
CN110585854A (zh) * 2019-09-23 2019-12-20 中国科学院过程工程研究所 一种烟气净化吸收装置及活性炭脱硫脱硝***

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JP2003040610A (ja) 2003-02-13
JP4015829B2 (ja) 2007-11-28

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