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WO2010073350A1 - Absorbant de nox, procédé de production de celui-ci, et procédé de suppression de nox - Google Patents

Absorbant de nox, procédé de production de celui-ci, et procédé de suppression de nox Download PDF

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Publication number
WO2010073350A1
WO2010073350A1 PCT/JP2008/073640 JP2008073640W WO2010073350A1 WO 2010073350 A1 WO2010073350 A1 WO 2010073350A1 JP 2008073640 W JP2008073640 W JP 2008073640W WO 2010073350 A1 WO2010073350 A1 WO 2010073350A1
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WO
WIPO (PCT)
Prior art keywords
alkali metal
nox
manganese
compound
permanganate
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/JP2008/073640
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English (en)
Japanese (ja)
Inventor
塩谷　靖
信義 林
八田　正則
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.)
Sued Chemie Catalysts Japan Inc
Original Assignee
Sued Chemie Catalysts Japan Inc
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
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Priority to PCT/JP2008/073640 priority Critical patent/WO2010073350A1/fr
Publication of WO2010073350A1 publication Critical patent/WO2010073350A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B01D53/565—Nitrogen oxides by treating the gases with solids
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0222—Compounds of Mn, Re
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • 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
    • B01J20/3071—Washing or leaching
    • 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
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/306—Surface area, e.g. BET-specific surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/311—Porosity, e.g. pore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/2073—Manganese
    • 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
    • B01D2258/0216—Other waste gases from CVD treatment or semi-conductor manufacturing

Definitions

  • the present invention relates to a catalyst used for adsorbing or catalytically purifying environmental pollutants, a method for producing the same, and use of the catalyst. Specifically, the present invention relates to treatment of NOx-containing exhaust gas discharged from semiconductor factories and various chemical factories.
  • NOx-containing exhaust gas discharged from each factory is considered as a causative substance of acid rain or photochemical smog generation if released as it is, and the influence on the global environment and human body is immeasurable. Therefore, it is obliged to release the air after detoxification treatment.
  • This NOx means compounds such as nitrogen dioxide (NO 2 ) and nitrogen monoxide (NO) among nitrogen oxides present in the atmosphere.
  • NOx there are a catalytic reduction method using a reducing agent such as ammonia, urea and hydrocarbon, and an adsorption removal method using activated carbon or a manganese-based catalyst.
  • NOx is decomposed into harmless nitrogen and water by a catalyst, and a vanadium / titania catalyst (Patent Document 1) and an iron-manganese catalyst (Patent Document 2) are mainly used. There are many.
  • the activated carbon adsorbent generally has a high surface area of about 500 to 1.200 m 2 / g and has high performance as an adsorption capacity.
  • Patent Document 3 describes that the activated carbon obtained by the activation treatment has a high performance in absorption of nitric oxide by having 4 to 10 pores of 0.05 cm 3 or more per 1 g of the adsorbent. ing.
  • manganese oxide surface area 240 m 2 / surface area
  • a potassium permanganate aqueous solution a manganese sulfate aqueous solution containing sulfuric acid and reacting them under strongly acidic conditions. g) is disclosed.
  • Patent Document 5 discloses manganese oxide (surface area 84 to 185 m 2 / g) obtained by thermally decomposing manganese carbonate and then treating with nitric acid, and oxidation by mixing and reacting a potassium permanganate aqueous solution and a manganese nitrate aqueous solution. Manganese (surface area 204 m 2 / g) is described respectively.
  • the reaction in a method using a reducing agent such as ammonia or hydrocarbon, the reaction generally requires a temperature of 200 ° C. or higher, and when heating is not suitable for safety and equipment as in a semiconductor factory. It may be difficult to use. Moreover, since a reducing agent is required in addition to heating, the running cost often increases.
  • a reducing agent such as ammonia or hydrocarbon
  • the technique using an adsorbent has a drawback that its adsorption capacity is limited and the adsorbent needs to be replaced.
  • the adsorbent activated carbon and manganese are generally used, but the activated carbon has a high specific surface area and often exhibits relatively high performance, but once adsorbed and removed by changes in temperature and pressure. NOx desorption becomes a problem. Further, the adsorbed NOx is inflammable and has a risk of ignition and fire, which often causes a problem in terms of safety.
  • NOx and manganese react and are immobilized, so that the desorption of NOx can be suppressed to some extent, but the expected performance is not obtained at present.
  • Patent Document 6 provides a manganese compound having an increased specific surface area by mixing and reacting a divalent manganese salt aqueous solution and an alkali permanganate aqueous solution containing an alkali of stoichiometric or higher.
  • a divalent manganese salt aqueous solution and an alkali permanganate aqueous solution containing an alkali of stoichiometric or higher.
  • the subject of this invention is made
  • the inventors of the present invention have intensively studied a method for preparing a manganese compound having a large surface area, considering that manganese oxide needs to have a high surface area.
  • an alkali metal permanganate aqueous solution containing an alkali metal compound and an alkali metal permanganate in a stoichiometric amount or more with respect to the alkali metal permanganate, and a divalent manganese salt aqueous solution Manganese oxide obtained by mixing and reacting the precipitate produced, then washing with water, filtering and drying was surprisingly measured for the surface area by the BET method, and the surface area was surprisingly 300 m 2 / g or more. It turns out that it has.
  • this material contained a significant amount of alkali metal. Since this substance was obtained by sufficiently washing the reaction product with water, followed by filtration and drying, it was found that the alkali metal was not incorporated as an impurity but was incorporated into the substance structure. Therefore, this substance is considered to be a compound containing a kind of alkali metal, manganese, and oxygen rather than manganese oxide. Further, when an exhaust gas treatment test of a gas containing NOx was performed on this compound at room temperature, it was found that the compound had high NOx removal performance, and the present invention was completed.
  • the NOx removing agent of the present invention comprises an alkali metal in its crystal structure, and further comprises a manganese compound having a pore volume with a diameter of 100 nm or less of 0.4 to 0.8 ml / g. It is characterized by.
  • the manganese compound as the NOx removing agent of the present invention has the above-described physical properties, so that it has a higher specific surface area than conventional manganese oxides and can exhibit extremely excellent NOx removal performance. Moreover, since the NOx removing agent of the present invention shows high performance for removing NOx in a normal temperature range, it is very useful for removing NOx discharged from each factory.
  • the present invention has a BET surface area of 300 m 2 / g or more, a pore volume of 100 nm or less in diameter in the range of 0.4 to 0.8 ml / g,
  • the present invention relates to a NOx removal agent comprising a novel manganese compound in which 10% by weight of an alkali metal compound is incorporated into a material structure, a production method thereof, and a removal method thereof.
  • the manganese compound of the removing agent of the present invention comprises an alkali metal permanganate aqueous solution containing an alkali metal compound and an alkali metal permanganate in a stoichiometric amount or more with respect to the alkali metal permanganate, It is manufactured by washing and drying a precipitate formed by mixing with an aqueous manganese salt solution.
  • nitrates, sulfates, chlorides and the like are used as the divalent manganese salts.
  • alkali metal permanganate sodium salt, potassium salt or the like is used.
  • alkali metal compound that dissolves in the aqueous solution of alkali metal permanganate and makes the alkali metal more than stoichiometric with respect to the alkali metal permanganate include sodium, potassium, lithium, etc.
  • Alkali metal hydroxides or carbonates selected from are used.
  • an aqueous solution of a divalent manganese salt (liquid A) and an aqueous solution of an alkali metal permanganate solution added with an alkali metal hydroxide or an alkali metal carbonate.
  • An alkali metal manganate aqueous solution (Liquid B) is prepared, and liquid B is mixed with liquid A under stirring and reacted to form a precipitate. The precipitate is sufficiently washed and filtered, and then dried within a range of 100 ° C to 300 ° C.
  • the amount of the alkali metal compound dissolved in the aqueous solution of the alkali metal permanganate is expressed as a molar ratio with respect to 1 mole of the alkali metal permanganate and is higher than 1.0 and 4.0 or less. is there. If this ratio is 1.0 or less, the amount of the alkali metal compound dissolved is too small to finally obtain a manganese compound having a high surface area, and if it is higher than 4.0, the compound having a high surface area is too much. Can't get.
  • the alkali metal permanganate may not be an aqueous solution, and a mixed powder of a required amount of the alkali metal permanganate and alkali metal compound may be added to the solution A with stirring.
  • the obtained precipitate is thoroughly washed, filtered, and dried at 100 to 300 ° C. More preferably, it is dried at 100 to 200 ° C.
  • the drying temperature is lower than 100 ° C., it takes a long time for drying, which is not practical.
  • the drying temperature is higher than 300 ° C., the surface area of the manganese compound is decreased, which is not preferable.
  • the content of the alkali metal compound in the manganese compound thus obtained is in the range of 4 to 10% by weight based on the total weight of the manganese compound, and this amount is influenced by the amount of the alkali metal compound used. Preferably it is 6 to 9% of range.
  • the content is less than 4% by weight, the specific surface area of the manganese alkali metal is reduced, and if it exceeds 10% by weight, there is a free alkali metal that is not a manganese compound, which adversely affects the NOx absorption performance. There is a possibility of effect.
  • the BET surface area of the obtained manganese compound was 300 m ⁇ 2 > / g or more.
  • the present invention relates to a method for removing NOx in a gas by circulating and contacting a gas containing NOx with the manganese compound obtained by the above method.
  • the method of absorbing and removing NOx is performed by a flow reactor.
  • the method is a method in which a manganese compound is filled in a reaction tube and installed in an apparatus, and then a gas containing NOx is introduced into the reaction tube and removed by contact.
  • NOx absorption / removal performance is implemented by measuring NOx leakage on the reaction tube outlet side and calculating the amount of NOx absorption from the time until leakage.
  • the manganese compound obtained in the present invention was measured for NOx absorption and removal, and compared with manganese oxide obtained by a known method, it was confirmed that the removal performance was significantly higher than that of known oxides.
  • the present invention has been completed.
  • the manganese compound when the manganese compound is produced in the removing agent of the present invention, if the addition amount of the alkali metal compound before precipitation is changed to change the alkali metal compound content in the material structure, the NOx is proportional to the alkali metal content. Since the amount of absorption changed, it was found that the alkali metal content greatly affects the NOx removal performance. In addition, the alkali metal compound mixed in the manganese compound later by impregnation or kneading shows almost no performance.
  • the highest NOx absorption performance was shown in the range of 0.4 to 0.8 ml / g as the pore volume with a diameter of 100 nm or less. Note that the pore distribution of the obtained manganese compound is measured with a pore distribution measuring device by mercury porosimetry.
  • the pore volume of the manganese compound having a diameter of 100 nm or less is lower than 0.4 ml / g, the amount of pores is small, gas diffusion is lowered, and the contact efficiency between the manganese compound and NOx is lowered. The performance cannot be demonstrated.
  • it is larger than 0.8 ml / g, the performance per volume is lowered due to the lower density of the absorbent itself.
  • industrial catalysts require a certain level of strength for handling. However, if it is greater than 0.8 ml / g, the voids of the absorbent are large and the strength cannot be maintained, which is not preferable.
  • the absorbent according to the present invention can be formed into various shapes such as a honeycomb shape and a spherical shape by a conventionally known forming method.
  • the gas composition containing NOx contains 0 to 10% by volume of nitrogen dioxide (NO 2 ) and nitrogen monoxide (NO) with respect to nitrogen.
  • the target is.
  • the temperature for contacting with the absorbent is preferably 0 to 50 ° C.
  • the treatment pressure is normal pressure.
  • the flow rate of the gas to be treated is not particularly limited, but a space velocity per adsorbent volume of 50 to 100,000 h ⁇ 1 is sufficient.
  • Example 1 shows specific configurations and effects of the present invention, but the present invention is not limited thereto.
  • a manganese compound was obtained in the same manner as in Example 1 except that the amount of caustic potash added in Example 1 was 28 g.
  • the specific surface area at this time was 320 m 2 / g, the K content was 4.1 wt%, and the pore volume with a diameter of 100 nm or less was 0.55 ml / g.
  • a comparative sample was obtained by molding reagent manganese oxide and drying in air at 110 ° C. for 14 hours.
  • the specific surface area at this time was 54 m 2 / g
  • the K content was 0% by weight
  • the pore volume with a diameter of 100 nm or less was 0.08 ml / g.
  • a manganese compound was obtained in the same manner as in Example 1 except that no caustic potash was added in Example 1.
  • the specific surface area at this time was 250 m 2 / g, the K content was 3.0% by weight, and the pore volume with a diameter of 100 nm or less was 0.51 ml / g.
  • a manganese compound was obtained in the same manner as in Example 1 except that a consolidation step was added in Example 1 to reduce the pore volume.
  • the specific surface area at this time was 349 m 2 / g, the K content was 7.7 wt%, and the pore volume with a diameter of 100 nm or less was 0.31 ml / g.
  • the performance evaluation of the manganese compound of the present invention was performed by measuring the NO absorption performance in nitrogen.
  • the catalyst was evaluated by granulating the catalyst obtained in the examples into 1 to 2 mm.
  • the measurement conditions are as follows.
  • the absorption amount is the amount of NO gas absorbed and removed per liter of catalyst.
  • Test condition Gas composition NO 2.0% N 2 balance test temperature 25 ° C SV 300h -1 Table 1 below shows the measurement results of the physical properties and NO removal performance of the absorbents obtained in Examples 1-2 and Comparative Examples 1-3.
  • the BET surface area is 300 m 2 / g or more and the pore volume having a diameter of 100 nm or less belongs to the range of 0.4 to 0.8 ml / g, and 4 to 10 with respect to the total weight of the compound.
  • the manganese compound of the present invention which satisfies all the conditions for incorporating a weight percent alkali metal compound into the material structure, has a higher specific surface area than conventional manganese oxides and exhibits extremely superior NOx removal performance. did.

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

La présente invention concerne un agent de suppression de Nox, comprenant un composé de manganèse contenant un métal alcalin présentant des propriétés physiques spécifiques et présentant une meilleure performance que les agents de suppression traditionnels contenant du manganèse. L'invention concerne particulièrement un composé de manganèse produit en mélangeant et en faisant réagir une solution de permanganate de métal alcalin aqueuse avec une solution de sel de manganèse bivalente aqueuse afin de produire un précipité, et en lavant et en séchant le précipité, la solution de permanganate de métal alcalin aqueuse contenant un composé de métal alcalin et un permanganate de métal alcalin selon une proportion telle que la quantité du composé de métal alcalin soit égale ou supérieure à la quantité stœchiométrique relative à la quantité du permanganate de métal alcalin. Le composé de manganèse contient un composé de métal alcalin dans une quantité de 4 à 10 % en poids, et est par conséquent en grande partie amélioré dans la surface spécifique. Dans le composé de manganèse, le volume de pores présentant chacun un diamètre inférieur ou égal à 100 nm est de 0,4 à 0,8 ml/g. Par conséquent, le composé de manganèse présente une performance de suppression de Nox extrêmement améliorée.
PCT/JP2008/073640 2008-12-25 2008-12-25 Absorbant de nox, procédé de production de celui-ci, et procédé de suppression de nox Ceased WO2010073350A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2008/073640 WO2010073350A1 (fr) 2008-12-25 2008-12-25 Absorbant de nox, procédé de production de celui-ci, et procédé de suppression de nox

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PCT/JP2008/073640 WO2010073350A1 (fr) 2008-12-25 2008-12-25 Absorbant de nox, procédé de production de celui-ci, et procédé de suppression de nox

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111359583A (zh) * 2020-04-09 2020-07-03 中冶华天工程技术有限公司 同步负载锰氧化物/二氧化钛改性活性炭复合材料的制备方法
CN114653195A (zh) * 2021-11-05 2022-06-24 首钢环境产业有限公司 一种用于垃圾焚烧烟气的高效脱硝药剂及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004011376A1 (fr) * 2002-07-26 2004-02-05 Sued-Chemie Catalysts Japan, Inc. Compose de manganese, ainsi que procede de production et procede d'utilisation de ce compose
JP2005518938A (ja) * 2002-03-06 2005-06-30 エンバイロスクラブ テクノロジーズ コーポレイション マンガン酸化物の再生、前処理および沈殿

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005518938A (ja) * 2002-03-06 2005-06-30 エンバイロスクラブ テクノロジーズ コーポレイション マンガン酸化物の再生、前処理および沈殿
WO2004011376A1 (fr) * 2002-07-26 2004-02-05 Sued-Chemie Catalysts Japan, Inc. Compose de manganese, ainsi que procede de production et procede d'utilisation de ce compose

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111359583A (zh) * 2020-04-09 2020-07-03 中冶华天工程技术有限公司 同步负载锰氧化物/二氧化钛改性活性炭复合材料的制备方法
CN114653195A (zh) * 2021-11-05 2022-06-24 首钢环境产业有限公司 一种用于垃圾焚烧烟气的高效脱硝药剂及其制备方法

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