CN103025428A - 废气脱硝催化剂及其制造方法 - Google Patents

废气脱硝催化剂及其制造方法 Download PDF

Info

Publication number
CN103025428A
CN103025428A CN2011800361659A CN201180036165A CN103025428A CN 103025428 A CN103025428 A CN 103025428A CN 2011800361659 A CN2011800361659 A CN 2011800361659A CN 201180036165 A CN201180036165 A CN 201180036165A CN 103025428 A CN103025428 A CN 103025428A
Authority
CN
China
Prior art keywords
catalyst
titanium oxide
phosphoric acid
exhaust gas
oxide
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.)
Granted
Application number
CN2011800361659A
Other languages
English (en)
Other versions
CN103025428B (zh
Inventor
加藤泰良
池本清司
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.)
Mitsubishi Power Ltd
Original Assignee
Babcock Hitachi KK
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 Babcock Hitachi KK filed Critical Babcock Hitachi KK
Publication of CN103025428A publication Critical patent/CN103025428A/zh
Application granted granted Critical
Publication of CN103025428B publication Critical patent/CN103025428B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • B01J35/19—
    • B01J35/56—
    • B01J35/613—
    • B01J35/615—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • 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
    • B01D2251/2062—Ammonia
    • 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
    • B01D2255/20707—Titanium
    • 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
    • B01D2255/20723—Vanadium
    • 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
    • B01D2255/20769—Molybdenum
    • 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
    • B01D2255/20776—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B01D2255/504—ZSM 5 zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/70—Non-metallic catalysts, additives or dopants
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst

Abstract

鉴于现有技术的问题，本发明提供在不损害Ti-V-Mo-P系催化剂的优异的耐久性的情况下改善350℃以上的脱硝率，性能·耐久性优异的催化剂。废气脱硝催化剂，是包含钛(Ti)、磷(P)的氧化物，钼(Mo)和/或钨（W）、和钒(V)氧化物，和SiO2/Al2O3比为20以上的高二氧化硅沸石的催化剂组合物，将(1)氧化钛、相对于氧化钛以H3PO4计超过1wt%且15wt%以下的磷酸或磷酸的铵盐，(2)相对于氧化钛分别超过0且8原子%以下的钼(Mo)和/或钨（W）的含氧酸或含氧酸盐以及钒(V)的含氧酸盐或氧钒基盐，(3)相对于氧化钛超过0且20wt%以下的高二氧化硅沸石在水的存在下混炼、干燥、烧成而成。

Description

废气脱硝催化剂及其制造方法
技术领域
本发明涉及废气脱硝催化剂及其制造方法，特别涉及燃烧废气中所含的砷、磷（P）、钾（K）等催化剂毒素导致的劣化小并且使350℃以上的脱硝性能大幅度提高的氨接触还原用废气脱硝催化剂及其制造方法。
背景技术
以氧化钛为主成分的氨接触还原用脱硝催化剂，由于活性高，耐久性优异，因此在国内外锅炉等的排烟处理中广泛地使用，成为了脱硝催化剂的主流（专利文献1等）。
近年来，能量需求激增，已使用硫分高的煤（高S炭）、PRB炭、或生物质等各种燃料，与其相伴，使用时的排烟脱硝催化剂的劣化也变得多样。其代表的劣化可列举高S炭焚烧中产生的砷（As）化合物导致的劣化、PRB炭焚烧废气中容易产生的P化合物导致的劣化、生物质燃烧废气中产生的钾（K）化合物导致的劣化。已知这些都是蓄积性的催化剂毒素导致的劣化，在催化剂中蓄积，短期引起大的脱硝性能的降低。
对此，本申请发明人发明了防止上述毒物吸附、蓄积于氧化钛的Ti-V-Mo-P系的催化剂并已申请（未公知专利文献2）。
现有技术文献
专利文献
专利文献1：特开昭50-128681号公报
专利文献2：特愿2010-026577号
发明内容
发明要解决的课题
上述在先申请涉及的催化剂不仅对于As、P、K化合物具有极高的耐久性，而且具有SO2氧化率低、Hg氧化活性高等各种优点，唯一应改善的方面是反应温度从350℃上升到400℃的情形的脱硝性能的上升度比通常的催化剂小的方面。高S炭焚烧锅炉的排烟脱硝多成为400℃附近的温度，如果能够改善上述的400℃下的脱硝性能，必定成为更优异的催化剂。
本发明申请要解决的课题是在不损害Ti-V-Mo-P系催化剂的优异的耐久性的情况下改善350℃以上的脱硝率，提供性能·耐久性优异的催化剂。
用于解决课题的手段
上述在先申请涉及的未公知的催化剂，是以使作为催化剂毒素的一种的磷酸吸附于氧化钛具有的催化剂毒素的吸附点，要阻止来自废气的催化剂毒素在催化剂的吸附，防止劣化的设想为基础产生的。在该磷酸吸附的点，作为活性成分的V、作为助催化剂成分的Mo或W等的氧化物也吸附，其结果，催化剂上（即氧化钛上）的吸附点被这些成分全部覆盖。其结果，使来自废气的催化剂毒素的吸附大幅度地减轻，但存在NH3的吸附点的减少和吸附力的弱化这样的副作用。其结果，NH3的吸附量在高温下减少，即使温度上升到350℃以上，脱硝性能也难以提高，产生达到顶点的现象。本申请发明人为了改善这点，考虑不吸附As、P等催化剂毒素，添加、补充强烈吸附NH3的成分，使用大量的化学物质进行了研究，但均吸附催化剂成分中的P化合物、或废气中的P、As化合物，使NH3吸附性能丧失，未能使用，然而唯有在高二氧化硅沸石的情况下获得显著的改善效果，完成了本发明。
为了实现上述课题，本申请中要求专利保护的发明如下所述。
（1）废气脱硝催化剂，是包含钛(Ti)、磷(P)的氧化物，钼(Mo)和/或钨（W）、和钒(V)氧化物，SiO2/Al2O3比为20以上的高二氧化硅沸石的催化剂组合物，其是将(1)氧化钛、相对于氧化钛以H3PO4计超过1wt%且15wt%以下的磷酸或磷酸的铵盐，(2)相对于氧化钛分别超过0且8原子%以下的钼(Mo)和/或钨（W）的含氧酸或含氧酸盐以及钒(V)的含氧酸盐或氧钒基盐，和(3)相对于氧化钛超过0且20wt%以下的高二氧化硅沸石，在水的存在下混炼、干燥、烧成而成的。
（2）（1）所述的脱硝催化剂，其特征在于，高二氧化硅沸石为丝光沸石。
（3）废气脱硝催化剂的制造方法，其特征在于，使氧化钛与磷酸或磷酸的铵盐预先在水的存在下接触，使磷酸离子吸附于氧化钛表面后，添加钼(Mo)和/或钨（W）的含氧酸或含氧酸盐、钒(V)的含氧酸盐或氧钒基盐、和高二氧化硅沸石，在水的存在下进行混炼、干燥、烧成。
发明的效果
根据本发明，能够提高耐久性高的催化剂成分的350℃以上的脱硝性能，实现高活性并且高耐久性的脱硝催化剂。其结果，能够使美国等多在400℃附近运转的来自高S炭焚烧锅炉的废气脱硝装置中使用的催化剂使用量减少，使装置小型化。
沸石具有多个
Figure BDA00002767635100031
以下的细孔，在其内部具有能够强地吸附NH3的优异的吸附点。该吸附点被催化剂成分、废气中的毒素成分侵犯而没有发挥添加效果，但幸运地是，在催化剂调制阶段，Mo、V、W、P成分作为其含氧酸盐添加，它们的离子比
Figure BDA00002767635100032
大，因此在催化剂调制阶段，健全地维持沸石上的NH3吸附位点。此外，废气中的As、P的化合物作为对应的氧化物的蒸气飞来，其大小也比大，没有进入到细孔内，使用时也维持NH3的吸附点。
这样，沸石细孔内的NH3吸附点通过催化剂调制阶段和使用阶段得以维持，补充催化剂在使用温度超过350℃下使用的情形下发生的Ti-Mo-V-P成分的NH3的吸附量的减少，高水平地维持脱硝性能。
本发明将如上所述通过调制阶段和使用阶段由P、活性成分的含氧酸盐类保护NH3的吸附点的沸石与耐久性高的催化剂成分的组合的结果，是初次得到的划时代的催化剂。
具体实施方式
如上所述，本发明的催化剂，使用吸附了磷酸离子的TiO2防止催化剂毒素进入催化剂，同时利用沸石成分维持NH3的吸附点，利用这样的二个成分的协同作用，能够初次实现本发明的效果，必须对以下方面进行考虑。
能吸附于氧化钛的PO4离子为TiO2的单位表面积约0.05wt%，对于通常使用的100-300m2/g的TiO2原料，5-15wt%为能吸附的最大量，如果为该量以上，NH3的能够吸附的OH基消失，引起大的活性降低。因此，也因TiO2原料的种类而异，但使H3PO4的添加量为TiO2的15wt%以下、优选10wt%以下，能够兼顾耐久性和脱硝活性，容易产生好的结果。此外，对于添加量少的一方无限制，但为了显示显著的耐毒性，相对于TiO2，在1wt%以上进行选择为宜。
作为与吸附了磷酸离子的TiO2组合的活性成分，能够使用钼(Mo)和/或钨（W）的含氧酸或含氧酸盐以及钒(V)的含氧酸盐或氧钒基盐，对其添加量并无特别限制，相对于TiO2，各自在大于0且8原子%以下进行选择。TiO2原料的比表面积大的情况下，选择高的值，低时选择少的添加量，则能够提高脱硝性能，降低SO2的氧化性能，是有利的。这些活性成分的添加方法可以是任何方法，但在水的存在下进行混炼或加热混炼的方法是经济、优异的方法。
对于与以上的催化剂成分组合的沸石成分，优选SiO2/Al2O3比为20以上的丝光沸石或五硅环型沸石（ZSM-5），SiO2/Al2O3比为20以上、30以下容易产生好结果。如果该比过小，因废气中、催化剂成分中的S分，使结构破坏，如果过高，NH3的活性点变少，难以获得高活性提高率。
活性成分负载后的催化剂成分，除了采用公知的方法成型为蜂窝状使用以外，也能够作为将在加工为网状的金属基板、陶瓷纤维的网状物以将网眼填埋的方式涂布、板状化后以波浪形等成型了间隔部的产物层叠而成的结构体使用。特别地，后者由于包含钾化合物的灰难以在催化剂间堆积，因此容易产生好结果。
再有，能够进行作为用于与本发明无直接关系的成型的粘结剂的硅溶胶等结合剂、以增强为目的的无机纤维的添加，其结果得到的催化剂当然也是本发明的范围。
实施例
以下使用具体例对本发明详细说明。
[实施例1]
将氧化钛（石原产业社制造、比表面积290m2/g）900g、85%磷酸84.5g、硅溶胶（日产化学社制造、商品名OSゾル）219g、水5568g装入捏合机，混炼45分钟，使磷酸吸附于TiO2表面。向其中添加钼酸铵113g、偏钒酸铵105g、H型丝光沸石（东ソー社制造、商品名TSZ-650、SiO2/Al2O3比=23）90g，再混炼1小时，在吸附了磷酸的TiO2表面负载Mo和V的化合物。然后，边慢慢地添加二氧化硅氧化铝系陶瓷纤维（东芝ファインフレックス社制造）151g，边混炼30分钟，得到了均一的糊状物。将得到的糊放置到将厚0.2mm的SUS430制钢板进行了金属板网加工的厚0.7mm的基材上，将其夹持于二张聚乙烯片中，通过一对加压辊，以将金属板网基材的网眼填埋的方式涂布。将其风干后，在500℃下烧成2小时，得到了催化剂。本催化剂的组成为Ti/Mo/V=88/5/7原子比，H3PO4添加量和沸石添加量分别相对于TiO2，为8wt%和10wt%。
[实施例2和3]
实施例1中，将磷酸添加量分别变为10.6g和42.4g以外，与实施例1同样地制备催化剂。
[实施例4]
实施例1中，将磷酸的添加量变为159g，将偏钒酸铵的添加量变为121g，和将H型丝光沸石变为东ソー社制造、商品名TSZ-640(SiO2/Al2O3=22)180g以外，与实施例1同样地制备催化剂。本催化剂的组成为Ti/Mo/V=88/5/8原子比，H3PO4和沸石添加量相对于TiO2，分别为15wt%和20wt%。
[实施例5和6]
将实施例1中使用的氧化钛变为比表面积90m2/g的氧化钛，同时将催化剂的磷酸添加量相对于TiO2变为4wt%，而且将偏钒酸铵和钼酸铵分别变为6.8g和61.8g以及27.7g和62.7g，将H型丝光沸石变为东ソー社制造、商品名TSZ-660（SiO2/Al2O3=31）27g以外，与实施例1同样地制备催化剂。本催化剂的组成为Ti/Mo/V=96.5/3/0.5原子比和95/3/2原子比，H3PO4和沸石添加量相对于TiO2，分别为4wt%和3wt%。
[实施例7]
除了将实施例1的催化剂中使用的钼酸铵113g变为偏钨酸铵162g，将H型丝光沸石的添加量变为9g以外，与实施例1同样地制备催化剂。本催化剂的组成为Ti/W/V=88/5/7原子比，H3PO4和沸石添加量，相对于TiO2，分别为8wt%和1wt%。
[比较例1～7]
实施例1～7中，除了不进行沸石的添加以外，同样地制备催化剂。
[比较例8～11]
实施例1、5～7中，除了不进行磷酸的添加-吸附处理以外，同样地制备催化剂。
[试验例1]
将实施例1～7和比较例1～7的催化剂切出20mm宽×100mm长，在表1的条件下测定各催化剂的脱硝性能。将得到的结果汇总示于表2。
表2中，将本发明的实施例的催化剂的性能与比较例的催化剂的性能比较，可知在350℃下两者的差异小，但在400℃下实施例的催化剂的性能显著地高，是350℃以上的脱硝性能得到了改善的优异的催化剂。
[试验例2和3]
为了明确本发明申请的催化剂的优点，将实施例1、5～7和比较例8～17的催化剂切出20mm宽×100mm长，以相对于催化剂成分，以按K2O计添加0.5wt%的方式含浸碳酸钾的水溶液后，在150℃下干燥，进行了模拟生物质燃烧灰中所含的钾化合物导致的劣化的试验。
另外，使实施例1、5～7和比较例8～17的催化剂含浸亚砷酸的水溶液以相对于催化剂成分使As2O3为2wt%后，在350℃下烧成1小时，实施了模拟高S炭废气中的劣化的试验。
对于上述2种模拟试验后的催化剂与模拟试验前的催化剂，在表3的条件下测定脱硝性能，评价各催化剂的耐毒性。将得到的结果一并示于表4。
表4中，将实施例和比较例的各催化剂的性能进行比较，可知本发明申请的实施例的催化剂的钾和砷化合物导致的劣化极小，耐久性优异。
由本结果和前面所示的试验例的结果可知，本发明的催化剂是不仅350℃以上的高温特性优异，而且具有K、As等催化剂毒素导致的劣化也困难的特征的优异的催化剂。
[表1]
[表2]
催化剂 350℃脱硝率（%） 400℃脱硝率（%）
实施例1 75.5 76.4
实施例2 81.7 85.3
实施例3 79.5 82.1
实施例4 74.2 75.3
实施例5 64.9 69.2
实施例6 70.9 72.2
实施例7 76.1 78.1
比较例1 74.8 73.0
比较例2 81.5 81.5
比较例3 78.9 79.0
比较例4 72.0 71.7
比较例5 62.2 64.0
比较例6 70.6 71.3
比较例7 76.9 74.5
[表3]
Figure BDA00002767635100081
[表4]

Claims (3)

1.废气脱硝催化剂，是包含钛(Ti)、磷(P)的氧化物，钼(Mo)和/或钨（W）、和钒(V)氧化物，SiO2/Al2O3比为20以上的高二氧化硅沸石的催化剂组合物，其是在水的存在下将(1)氧化钛和相对于氧化钛以H3PO4计大于1wt%且15wt%以下的磷酸或磷酸的铵盐、(2)相对于氧化钛分别为大于0且8原子%以下的钼(Mo)和/或钨（W）的含氧酸或含氧酸盐和钒(V)的含氧酸盐或氧钒基盐、和(3)相对于氧化钛大于0且20wt%以下的高二氧化硅沸石混炼、干燥、烧成而成的。
2.权利要求1所述的脱硝催化剂，其特征在于，高二氧化硅沸石为丝光沸石。
3.废气脱硝催化剂的制造方法，其特征在于，使氧化钛、和磷酸或磷酸的铵盐预先在水的存在下接触，使磷酸离子吸附于氧化钛表面后，添加钼(Mo)和/或钨（W）的含氧酸或含氧酸盐、钒(V)的含氧酸盐或氧钒基盐、高二氧化硅沸石，在水的存在下混炼、干燥、烧成。
CN201180036165.9A 2010-09-07 2011-09-05 废气脱硝催化剂及其制造方法 Active CN103025428B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2010199925A JP5604235B2 (ja) 2010-09-07 2010-09-07 排ガス脱硝触媒およびその製造方法
JP2010-199925 2010-09-07
PCT/JP2011/070129 WO2012033039A1 (ja) 2010-09-07 2011-09-05 排ガス脱硝触媒およびその製造方法

Publications (2)

Publication Number Publication Date
CN103025428A true CN103025428A (zh) 2013-04-03
CN103025428B CN103025428B (zh) 2016-08-03

Family

ID=45810640

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180036165.9A Active CN103025428B (zh) 2010-09-07 2011-09-05 废气脱硝催化剂及其制造方法

Country Status (7)

Country Link
US (1) US9550146B2 (zh)
EP (1) EP2614886B1 (zh)
JP (1) JP5604235B2 (zh)
KR (1) KR101787144B1 (zh)
CN (1) CN103025428B (zh)
TW (1) TWI516304B (zh)
WO (1) WO2012033039A1 (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105682798A (zh) * 2013-09-12 2016-06-15 庄信万丰催化剂(德国)有限公司 含钒的催化剂和废气中氮氧化物还原的方法
CN106807393A (zh) * 2017-01-12 2017-06-09 中国科学院兰州化学物理研究所 一种低温低so2氧化率蜂窝式脱硝催化剂及其制备方法
CN106824171A (zh) * 2017-01-12 2017-06-13 中国科学院兰州化学物理研究所 一种宽工作温度抗硫蜂窝式脱硝催化剂及其制备方法
CN110461441A (zh) * 2017-03-31 2019-11-15 庄信万丰股份有限公司 用于处理废气的催化剂、排放系统和方法
CN110461440A (zh) * 2017-03-30 2019-11-15 庄信万丰股份有限公司 用于处理废气的催化剂、排气系统和方法
CN113750981A (zh) * 2021-09-26 2021-12-07 北京市科学技术研究院城市安全与环境科学研究所 一种协同净化多种污染物的催化剂及其制备方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8858907B2 (en) * 2012-08-09 2014-10-14 Exxonmobil Research And Engineering Company Catalytic reduction of NOx with high activity catalysts with NH3 reductant
JP6627225B2 (ja) * 2015-02-19 2020-01-08 いすゞ自動車株式会社 ＮＯｘ選択還元触媒の劣化方法
GB201705279D0 (en) 2017-03-31 2017-05-17 Johnson Matthey Plc Selective catalytic reduction catalyst
GB201705289D0 (en) * 2017-03-31 2017-05-17 Johnson Matthey Catalysts (Germany) Gmbh Selective catalytic reduction catalyst
JP2020182898A (ja) * 2019-05-07 2020-11-12 株式会社キャタラー アンモニア酸化触媒装置
CN112156630B (zh) * 2020-10-10 2022-02-08 清华大学 一种500-900度脱硝增效方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101547740A (zh) * 2007-02-13 2009-09-30 巴布考克日立株式会社 氮氧化物除去用催化剂和氮氧化物除去方法
WO2009119639A1 (ja) * 2008-03-25 2009-10-01 バブコック日立株式会社 鉄化合物の影響を抑制した排ガス浄化触媒

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3279884A (en) * 1963-10-31 1966-10-18 Basf Ag Selective removal of oxides of nitrogen from gas mixtures containing oxygen
JPS56168835A (en) * 1980-05-31 1981-12-25 Mitsubishi Petrochem Co Ltd Denitrating catalyst and denitrating method
JPH07114964B2 (ja) * 1986-07-04 1995-12-13 バブコツク日立株式会社 窒素酸化物還元用触媒およびその製造方法
US4798813A (en) * 1986-07-04 1989-01-17 Babcock-Hitachi Kabushiki Kaisha Catalyst for removing nitrogen oxide and process for producing the catalyst
JPH0817939B2 (ja) * 1986-11-19 1996-02-28 三菱化学株式会社 排煙脱硝触媒
US5024981A (en) * 1989-04-20 1991-06-18 Engelhard Corporation Staged metal-promoted zeolite catalysts and method for catalytic reduction of nitrogen oxides using the same
US5120695A (en) * 1989-07-28 1992-06-09 Degusaa Aktiengesellschaft (Degussa Ag) Catalyst for purifying exhaust gases from internal combustion engines and gas turbines operated at above the stoichiometric ratio
JP3337498B2 (ja) * 1992-08-28 2002-10-21 バブコック日立株式会社 排ガス浄化用触媒の製造方法および排ガス浄化方法
KR100284936B1 (ko) 1998-12-31 2001-04-02 김충섭 촉매 활성 귀금속 담지 제올라이트계 탈질 촉매의 제조 방법
US6914026B2 (en) * 2001-09-07 2005-07-05 Engelhard Corporation Hydrothermally stable metal promoted zeolite beta for NOx reduction
US20080004462A1 (en) 2004-11-22 2008-01-03 Peters Alexander V Catalyst for the Preparation of Fumaronitrile and/or Maleonitrile
US7393511B2 (en) 2005-02-16 2008-07-01 Basf Catalysts Llc Ammonia oxidation catalyst for the coal fired utilities
US7767175B2 (en) * 2007-01-09 2010-08-03 Catalytic Solutions, Inc. Ammonia SCR catalyst and method of using the catalyst
CA2676953A1 (en) * 2007-01-30 2008-08-07 Babcock-Hitachi Kabushiki Kaisha Exhaust gas purification catalyst and method of producing the same
JP2008221203A (ja) 2007-02-13 2008-09-25 Babcock Hitachi Kk 窒素酸化物除去用触媒及び窒素酸化物除去方法
WO2009031234A1 (ja) * 2007-09-07 2009-03-12 Babcock-Hitachi Kabushiki Kaisha 排ガス浄化用触媒
CZ301315B6 (cs) 2008-02-21 2010-01-13 Advanced Materials - Jtj S. R. O. Katalytická struktura TiO2 pro katalytické procesy do 1000 °C a zpusob její výroby
JP5596992B2 (ja) * 2010-02-09 2014-10-01 バブコック日立株式会社 バイオマス燃焼排ガス用脱硝触媒及び脱硝方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101547740A (zh) * 2007-02-13 2009-09-30 巴布考克日立株式会社 氮氧化物除去用催化剂和氮氧化物除去方法
WO2009119639A1 (ja) * 2008-03-25 2009-10-01 バブコック日立株式会社 鉄化合物の影響を抑制した排ガス浄化触媒

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105682798A (zh) * 2013-09-12 2016-06-15 庄信万丰催化剂(德国)有限公司 含钒的催化剂和废气中氮氧化物还原的方法
CN106807393A (zh) * 2017-01-12 2017-06-09 中国科学院兰州化学物理研究所 一种低温低so2氧化率蜂窝式脱硝催化剂及其制备方法
CN106824171A (zh) * 2017-01-12 2017-06-13 中国科学院兰州化学物理研究所 一种宽工作温度抗硫蜂窝式脱硝催化剂及其制备方法
CN110461440A (zh) * 2017-03-30 2019-11-15 庄信万丰股份有限公司 用于处理废气的催化剂、排气系统和方法
CN110461441A (zh) * 2017-03-31 2019-11-15 庄信万丰股份有限公司 用于处理废气的催化剂、排放系统和方法
CN113750981A (zh) * 2021-09-26 2021-12-07 北京市科学技术研究院城市安全与环境科学研究所 一种协同净化多种污染物的催化剂及其制备方法

Also Published As

Publication number Publication date
JP2012055810A (ja) 2012-03-22
US9550146B2 (en) 2017-01-24
US20130190166A1 (en) 2013-07-25
EP2614886B1 (en) 2021-06-16
TW201223624A (en) 2012-06-16
KR101787144B1 (ko) 2017-10-18
EP2614886A4 (en) 2017-09-06
CN103025428B (zh) 2016-08-03
KR20130113347A (ko) 2013-10-15
TWI516304B (zh) 2016-01-11
JP5604235B2 (ja) 2014-10-08
WO2012033039A1 (ja) 2012-03-15
EP2614886A1 (en) 2013-07-17

Similar Documents

Publication Publication Date Title
CN103025428A (zh) 废气脱硝催化剂及其制造方法
DE102014110811B4 (de) Katalysatorgegenstand zur behandlung von abgas
JP5168153B2 (ja) 排ガス浄化用触媒およびその製造方法
KR101139049B1 (ko) 질소 산화물 제거용 촉매 및 질소 산화물 제거 방법
JP5126718B2 (ja) 排ガス浄化用触媒
JP6294126B2 (ja) Ｓｃｒ用触媒及び排ガス浄化触媒システム
CN106582606B (zh) 一种非钒系低温脱硝催化剂及其制备方法
CN103619467B (zh) 具有改善的抗中毒性能的催化剂
KR101717319B1 (ko) 바이오매스 연소 배기 가스용 탈질 촉매 및 탈질 방법
JP6604951B2 (ja) 排ガス中の酸化窒素の還元のためのバナジウム含有触媒及び方法
CN112657541A (zh) 一种分子筛基低温环保型scr脱硝催化剂的制备方法
KR101843214B1 (ko) 배기 가스 정화용 촉매 및 그의 제조 방법, 및 배기 가스 중 질소 산화물의 정화 방법
KR20150023523A (ko) Scr 촉매 및 그것의 제조 방법
JP6294127B2 (ja) Ｓｃｒ用触媒及び排ガス浄化触媒システム
WO2012086413A1 (ja) 脱硝触媒用担体
JP5360834B2 (ja) 鉄化合物の影響を抑制した排ガス浄化触媒
DE102018204797A1 (de) Ein katalysator zur behandlung eines abgases, ein abgassystem und ein verfahren
JP3241115B2 (ja) 脱硝用触媒
CN106268959A (zh) 一种烟气脱硝催化剂及其制备方法
JPS6328452A (ja) 窒素酸化物還元用触媒およびその製造方法
KR20150081903A (ko) 내구성이 향상된 반도체 제조공정의 유해가스 처리용 촉매
JP2011230043A (ja) 窒素酸化物除去触媒及びこれを用いた窒素酸化物除去装置
JP2005081284A (ja) 有害ガス除去用酸化触媒

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
ASS Succession or assignment of patent right

Owner name: MITSUBISHI HITACHI POWER SYSTEM LTD.

Free format text: FORMER OWNER: BABUCOCK-HITACHI KABUSHIKI KAISHA

Effective date: 20150227

C41 Transfer of patent application or patent right or utility model
TA01 Transfer of patent application right

Effective date of registration: 20150227

Address after: Kanagawa, Japan

Applicant after: Mitsubishi Hitachi Power System Ltd.

Address before: Tokyo, Japan

Applicant before: Babucock-Hitachi Kabushiki Kaisha

C14 Grant of patent or utility model
GR01 Patent grant
CP01 Change in the name or title of a patent holder
CP01 Change in the name or title of a patent holder

Address after: Kanagawa, Japan

Patentee after: Mitsubishi Power Co., Ltd

Address before: Kanagawa, Japan

Patentee before: MITSUBISHI HITACHI POWER SYSTEMS, Ltd.