CN109126815A - A kind of low-temperature denitration catalyst and application - Google Patents
A kind of low-temperature denitration catalyst and application Download PDFInfo
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- CN109126815A CN109126815A CN201710497504.2A CN201710497504A CN109126815A CN 109126815 A CN109126815 A CN 109126815A CN 201710497504 A CN201710497504 A CN 201710497504A CN 109126815 A CN109126815 A CN 109126815A
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- catalyst
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- conveyer belt
- flue gas
- ammonia
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- 239000003054 catalyst Substances 0.000 title claims abstract description 128
- 239000003546 flue gas Substances 0.000 claims abstract description 57
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 62
- 239000010410 layer Substances 0.000 claims description 34
- 229910021529 ammonia Inorganic materials 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- 150000003863 ammonium salts Chemical class 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000428 dust Substances 0.000 claims description 13
- 239000008246 gaseous mixture Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 238000006477 desulfuration reaction Methods 0.000 claims description 10
- 230000023556 desulfurization Effects 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 8
- 150000002894 organic compounds Chemical class 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000779 smoke Substances 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 238000002309 gasification Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000002365 multiple layer Substances 0.000 claims description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 6
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000903 blocking effect Effects 0.000 abstract description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 235000019504 cigarettes Nutrition 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 208000020442 loss of weight Diseases 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005200 wet scrubbing Methods 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—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
- B01D53/90—Injecting reactants
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
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- 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
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- 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
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a kind of low-temperature denitration catalyst and applications, on the basis of catalyst weight, comprising: 75% ~ 94% alumina support, 3% ~ 20%Fe2O3With 3% ~ 20%MnO2；Catalyst is microspheroidal, 2 ~ 6mm of diameter, overall porosity 60% ~ 85%, and in all holes, the mesoporous ratio for accounting for overall porosity of 5 ~ 20nm is 15% ~ 55%, and the ratio that the macropore of 100 ~ 1000nm accounts for overall porosity is 40% ~ 75%；Macropore is evenly distributed and three-dimensional perforation；Side pressure breaking strength is 5 ~ 20N/mm.The problem of catalyst of the present invention is applied in low-temperature denitration reaction, can effectively remove the nitrogen oxides and oxysulfide in flue gas, not will cause ammonium hydrogen sulfate blocking bed, extend the cycle of operation of device.
Description
Technical field
The invention belongs to gas denitrifying technology fields, more particularly to a kind of low-temperature denitration catalyst and application.
Background technique
Nitrogen oxides is collectively referred to as NOx, is one of primary pollution source of atmosphere pollution.Endanger it is maximum mainly: NO, NO2。
The main harm of NOx is as follows: (1) to the toxic effect of human body；(2) to the toxic effect of plant；(3) acid rain, acid mist can be formed；
(4) photochemical fog is formed with hydrocarbon；(5) ozone layer is destroyed.
Denitrating flue gas refers to the NOx in removing flue gas, can be divided into wet denitration and Dry denitration by Processing tecchnics.Mainly
It include: sour absorption process, Alkali absorption method, selective catalytic reduction, non-selective catalytic reduction, absorption method, gas ions activation
Method etc..Domestic and international some scientific research personnel also developed with microorganism the method for handling NOx exhaust gas.But there is industrial value,
With being most widely selective catalytic reduction (SCR).
The FCC regenerated flue gas denitration of the flue gas, oil plant of coal-burning power plant at present, which is administered, mainly uses SCR method, and mating wet
Method washing desulphurization dedusting.By taking FCC flue gas as an example, main flow is as follows: 500~600 DEG C of FCC regenerated flue gas first passes through waste heat pot
Furnace carries out recycling heat, and flue-gas temperature is reduced to 320~400 DEG C to enter SCR fixed bed reactors and carries out denitration reaction, removes cigarette
Then NOx in gas returns waste heat boiler and carries out recycling heat, flue-gas temperature is down to 150~200 DEG C, subsequently into desulfurization
SOx in flue gas is washed by dedusting washing tower with dust simultaneously using alkaline absorption solution, and flue-gas temperature is reduced to 55~60 DEG C
Discharge.Desulfurization give up absorbing liquid to be settled, be filtered, be concentrated and etc. progress solid-liquor separation, ask liquid to use after solid-liquor separation
Air aeration oxidation, COD qualified discharge, solid are filled.
Existing SCR denitration process is all made of fixed bed Benitration reactor, and catalyst uses cellular, board-like or ripple
Formula, catalyst are placed in reactor in modular form.Reducing agent NH is initially injected before reaction bed3, allow NH3With cigarette
NOx in gas is sufficiently mixed, and by denitrating catalyst bed, NOx catalysis is reduced to N2。
The prior art has the following problems:
1, due to typically containing SO in flue gas2、SO3, O2With vapor, meeting and SO when (the escaping of ammonia) when reaction zone ammonia surplus3Instead
Ammonium salt, the ammonium salt (NH of generation should be generated4HSO4), it is in a liquid state at 180~240 DEG C of temperature, there is viscosity, it is de- to be liable to stick to SCR
On the heat exchanger tube of the downstream unit economizer of nitre reactor, be bonded flue gas in dust, cause heat exchange tube layer fouling blockage with
Corrosion, influences the device cycle of operation.In order to avoid the escaping of ammonia, SCR fixed bed reactors entrance spray ammonia uniformity is generally required just
Minus deviation is less than 5%.
2, the NOx content in flue gas is related to the process conditions of master device, and variation fluctuation range is larger, and SCR fixed bed
The catalytic amount of reactor be it is fixed, once NOx concentration range exceed design value, then the NOx of purifying smoke cannot row up to standard
It puts.Therefore the operating flexibility of fixed bed is smaller.
3, during operation, the activity of catalyst is gradually reduced fixed bed reactors, when reactor outlet NOx can not be up to standard
When discharge, it is necessary to more catalyst changeout.The cycle of operation of general SCR device at least requires 3-4, otherwise will affect master device
Operating.General SCR device denitrification rate demand is at least 60~90% or more, and when more catalyst changeout, the activity of catalyst is extremely
It is few that there are also 60% or so.It can be seen that too low using utilization rate of the fixed bed SCR reactor to catalyst.
4, after general denitrating flue gas, wet scrubbing dedusting is also used, is carried out together with desulfurization, desulfurization and dedusting process produces
Raw desulfurization waste liquor will also carry out solid-liquor separation, and the numerous length of process is complicated for operation, and investment is high with operating cost.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of low-temperature denitration catalyst and application.Of the invention having is rich
The microspheroidal low-temperature denitration catalyst of rich macropore, can effectively improve the energy in catalyst reaction space and anti-flying dust and salt poisoning
Power.
Low-temperature denitration catalyst of the invention, on the basis of catalyst weight, comprising: 75% ~ 94% alumina support, 3% ~
20%Fe2O3With 3% ~ 20% MnO2；Catalyst is microspheroidal, 2 ~ 6mm of diameter, preferably 3 ~ 5mm, overall porosity 60% ~ 85%, institute
Have in hole, the mesoporous ratio for accounting for overall porosity of 5 ~ 20nm is 15% ~ 55%, and the macropore of 100 ~ 1000nm accounts for the ratio of overall porosity
Example is 40% ~ 75%；Macropore is evenly distributed and three-dimensional perforation；Side pressure breaking strength is 5 ~ 20N/mm, preferably 8 ~ 18N/mm.
The BET specific surface area of denitrating catalyst of the invention is 120 ~ 400m20.45 ~ 1.50cm of/g, Kong Rongwei3/g。
It can also be containing one or more of auxiliary agents such as Zr, Ce or Cu, preferably Zr, with catalysis in catalyst of the present invention
On the basis of agent total weight, auxiliary agent is calculated as 1% ~ 10% with oxide, and the sum of each component content is 100% in catalyst.
The preparation method of low-temperature denitration catalyst of the invention, including following content:
(1) organic compound of silicon source, polyethylene glycol and phosphinylidyne-containing amine group is dissolved in low carbon alcohol solution, be uniformly mixed obtain it is clear
Clear solution；Pyridine is added in step (1) resulting mixture, is uniformly mixed；Wherein the viscosity average molecular weigh of polyethylene glycol is
10000 ~ 3000000, preferably 100000 ~ 2000000；
(2) resulting mixture is added drop-wise in 20 ~ 50 DEG C of oil column and is shaped to microspheroidal, and aging 12 ~ 60 is small at 40 ~ 80 DEG C
When, ageing products are impregnated using low-carbon alcohols or low carbon alcohol solution, then through being separated by solid-liquid separation, solid phase is obtained through dry and roasting
Microspheroidal alumina support；
(3) with the soluble-salt oxide impregnation alumina supporter containing Mn and Fe, then drying and roasting, obtain microspheroidal denitration catalyst
Agent.
On the basis of the weight of step (1) resulting mixture, the additional amount of low carbon alcohol solution is 10% ~ 80%, and silicon source adds
Entering amount is 10% ~ 20%, and the additional amount of polyethylene glycol is 0.1% ~ 3.0%, preferably 0.2% ~ 2.0%；Wherein, in low carbon alcohol solution
Water and the mass ratio of low-carbon alcohols are 1.0 ~ 1.3；The molar ratio of the organic compound of polyethylene glycol and phosphinylidyne-containing amine group be 0.05 ~
1.0, preferably 0.1 ~ 0.8；Pyridine and Al3+Molar ratio be 3.0 ~ 9.0, preferably 3.5 ~ 7.0.
Silicon source described in step (1) is one or more of aluminum nitrate, aluminium chloride and aluminum sulfate.
Low-carbon alcohols described in step (1) and (2) are generally C5Alcohol below, preferably methanol, ethyl alcohol, normal propyl alcohol and isopropyl
One of alcohol is a variety of, preferably ethyl alcohol and/or propyl alcohol.
The organic compound of phosphinylidyne-containing amine group described in step (1) is selected as formamide, one in n,N-Dimethylformamide
Kind is a variety of.
Soaking conditions described in step (2) are as follows: 10 ~ 80 DEG C of soaking temperature, soaking time is 24 ~ 48 hours.
Drying described in step (2), be common constant pressure and dry, drying temperature be not more than 60 DEG C, preferably 20 ~ 40 DEG C,
It is dry to exist to without obvious liquid object.The roasting is to roast at 400 ~ 950 DEG C 1 ~ 24 hour, and preferably 550 ~ 850 DEG C
Roasting 5 ~ 10 hours.
The soluble-salt of step (3) described Mn is manganese nitrate, and the soluble-salt of Fe is ferric nitrate.It is helped when containing in catalyst
When agent, auxiliary agent can introduce during step (3).The soluble salt solutions of Mn and Fe described in step (3) are according to target
Catalyst composition, which calculates, to be prepared.Volume impregnation, incipient impregnation or spray impregnating mode, dip time 1- can be used
5 hours.Drying condition described in step (3): drying temperature is 100-130 DEG C, and drying time is 1-10 hours；The roasting
Condition are as follows: maturing temperature is 450-600 DEG C, and calcining time is 2-6 hours.
In catalyst preparation process of the present invention, the polyethylene glycol of special ratios and the organic compound of phosphinylidyne-containing amine group are introduced
The characteristic of the macropore is formed to meet.The mesoporous of concentration of the invention derives from sol gel network, enriches and perforation is big
Hole derives from solid-liquid two-phase laminated flow caused by polyethylene glycol.Pass through the addition of amide substance, the sol-gel mistake of regulation system
Journey produces sol-gel system more evenly, to obtain more evenly after baking, that is, has mesoporous point more concentrated
Cloth gel rubber material.
On the basis of above-mentioned formation mesoporous gel, polyethylene glycol is also more evenly fine and closely woven in distribution wherein.With pyridine plus
Enter, pH is improved in reaction system, and the organic compound of phosphinylidyne-containing amine group will release a certain amount of ammonia, and make the alkalinity of system liquid phase
Effect is more significant, and under alkaline environment, the polyethylene glycol in liquid phase becomes relative constriction state from opposite extended position, then its
Pore range in space can reduce, generate the relatively small and more macropore in aperture, these increase significantly relative small size it is big
Hole is mutually communicated, and low-carbon alcohols or low carbon alcohol solution is used to impregnate to remove the liquid phases such as polyethylene glycol, such stoste phase after aging
The space occupied becomes the duct that macroporous aluminium oxide is mutually communicated, and former solid fraction constitutes macropore hole wall, improves aluminium oxide
Porosity, while in subsequent drying and roasting process, the pore structure of aluminium oxide can be good at keeping.
Sol-gel process of the present invention due to introducing the adjustable system of phosphinylidyne-containing amine group, generates colloidal sol more evenly
Gel rubber system can make the reduction of Solid-Liquid Separation degree, to accordingly reduce the aperture of macropore.Said effect can be dry in normal pressure
There is uniform stress distribution when dry, roasting, keep the integrality of macropore, avoid the broken of material, be conducive to improve material
Whole mechanical strength.Ageing step of the invention uses higher alcohol-water mixture and higher aging temperature, can make gel particles
Hydration reaction occurs for son, enhances interparticle bond strength, and in constant pressure and dry, roasting, system is substantially shunk, consistency
It is opposite to improve, thus can be further improved mechanical strength.
Low-temperature denitration catalyst of the invention can be applied to denitrating flue gas reaction process.It is preferred that being applied using following
Journey: low-temperature flue gas enters at the top of the Benitration reactor, and the gaseous mixture containing ammonia is filled into flue gas through ammonia-spraying grid, and air-flow is from upper
Across the staggered catalyst bed of multiple-layer horizontal under and, carries out denitration desulphurization reaction and remove NOx and SOx, what desulfurization generated
Ammonium salt (NH4HSO4) be adhered on low-temperature denitration catalyst, the dust in flue gas is filtered by catalyst bed adhere to simultaneously, purification
Flue gas is discharged from reactor bottom；Wherein catalyst bed is by the low-temperature denitration catalyst accumulated on mesh belt and conveyer belt
Composition, the traffic direction of adjacent upper layer and lower layer conveyer belt is on the contrary, upper layer low-temperature denitration catalyst is moved to conveyer belt with conveyer belt
End, the starting point of the traffic direction of lower layer's conveyer belt is dropped down by free gravity, and low-temperature denitration catalyst is passed in the last layer
It send the end of band to fall into catalyst hooper, ammonium salt is stripped off, be recycled.
The flue gas mainly includes coal-fired plant flue gas, FCC regenerated flue gas, refinery processes kiln gas or chemical furnace cigarette
Gas (such as cracking of ethylene kiln gas) etc..Flue gas mainly contains NOx, SOx and impurity, wherein the impurity is generally powder
Dirt, water, CO2And O2Deng wherein the concentration of NOx is generally 700 ~ 4500mg/Nm3, the concentration of SOx is generally 700 ~ 4500mg/
Nm3；Temperature into the low-temperature flue gas of Benitration reactor is 150 ~ 260 DEG C, preferably 180~240 DEG C.
The flue gas flow rate is 2~15m/s, preferably 4 ~ 10m/s；The denitration reaction residence time is 0.5~20s.
In the gaseous mixture containing ammonia of the ammonia-spraying grid filling, the total moles ratio of NOx and SOx in ammonia and flue gas
For 0.9:1 ~ 1.15:1.
The gaseous mixture containing ammonia is the mixture of ammonia and air, and wherein volume of the ammonia in gaseous mixture is dense
Degree is 0.5% ~ 10%.In the method for the present invention, the conveyer belt is using conventional metal net shaped conveyer belt, preferably stainless steel mesh
Conveyer belt, conveyer belt mesh size guarantee less than catalyst particle size, to guarantee that catalyst granules is not fallen from mesh, generally
For 0.1~3mm, preferably 1.5~2.5mm；Conveyer belt uses external motor driven, drives conveyer belt to turn by belt-driven wheel
It is dynamic.
Piling height is 50~500mm, preferably 200~300mm to the low-temperature denitration catalyst on a moving belt.
The conveyer belt transmission speed is 0.1mm/s~10mm/s, preferably 0.5~2mm/s.
The conveyer belt number of plies and width can according to actual needs and reactor size is selected, the conveyer belt number of plies is excellent
Select 3~10 layers, more preferable 3~8 layers, conveyor width is limited with not brushing up against wall of reactor, conveyor width direction with react
Device wall clearances are 2 ~ 50mm, preferably 2 ~ 5mm.
Vertical range between the adjacent two layers conveyer belt is 1200 ~ 2000mm, preferably 1400 ~ 1600mm.
The catalyst in catalyst hooper is fallen into, mortgage originator is filled into first layer conveyer belt and completes catalysis after stripping
The circulation of agent.
The stripping carries out in stripper, stripping process are as follows: low pressure steam is passed through by following, is stained with ammonium salt
Catalyst is taken out of the ammonium salt gasification in catalyst by being passed through above, using low pressure steam, and ammonium salt gasification, which is decomposed, obtains SO2、
NH3、H2O etc., gaseous mixture enter condenser and react to ammonium salt solution.
Compared with prior art, the invention has the following advantages that
(1) in the present invention, for NOx and SOx directly with the mixing solid/liquid/gas reactions containing ammonia, NOx is reduced to N in flue gas2, SOx is direct
Ammonium salt is generated, ammonium salt is to have sticking liquid at this temperature, is adhered on catalyst, the dust in flue gas is with ammonium salt one
It rises and is adhered on catalyst granules, reaction system is left together with catalyst granules, achieve the effect that while dedusting, denitration take off
Sulphur and dedusting can be completed in a reactor, reduce follow-up process, reduce investment and operating cost, while anti-using low temperature
It answers, reduces energy consumption and the requirement to equipment.The present invention has filtering to make in the dust in flue gas using micro-spherical catalyst bed
With due to having better capture effect for the dust less than 1 micron containing dual pore size distribution in its catalyst, it is not easy to
Blocking.
(2) mobile catalyst bed is formed using conveyer belt in the present invention, the ammonium salt of generation is adhered to catalyst granules
On, reaction system is left together with catalyst granules, is avoided the problem of the escaping of ammonia causes ammonium hydrogen sulfate to block bed, is extended
The cycle of operation of device；
(3) present invention can adjust residence time of the catalyst in reactor by adjusting the movement velocity of conveyer belt, pass through
The bed height of catalyst on conveyer belt is adjusted, adjusts reaction time of the flue gas by catalyst bed, therefore can handle not
With the flue gas of NOx and SOx concentration, it is more suitable for the FCC regenerated flue gas of high NOx concentration；
(4) catalyst circulation uses in the present invention, and the return into after ammonium salt is stripped off excessively of the catalyst after reaction is filled into first
The reaction was continued for layer conveyer belt, can substantially reduce the dosage of catalyst, while the ammonium salt that stripping obtains can be used as denitration reaction
Byproduct.
Detailed description of the invention
The schematic diagram of denitrating catalyst application process Fig. 1 of the invention.
1, flue gas, 2, the gaseous mixture containing ammonia, 3, catalyst granules, 4, purified gas, 5, stripping gas, 6, ammonium salt steam,
7, ammonium salt solution, 8, ammonia-spraying grid, 9, catalyst addition pipe, 10, conveyer belt, 11, belt-driven wheel, 12, catalyst discharge
Pipe, 13, catalyst hooper, 14, reactor inner cylinder, 15, shell of reactor, 16, stripper, 17, condenser.
The stereoscan photograph of 1 catalyst of Fig. 2 the embodiment of the present invention.
Specific embodiment
It elaborates, but is not intended to limit the present invention to the method for the present invention below by specific embodiment.The hole
Distribution and porosity with mercury injection method by being characterized, and mechanical strength is characterized with side pressure breaking strength, using Dalian device diagnostic device
II Intelligent testing machine for particle of the ZQJ- measurement of factory's production.
Present invention simultaneously provides a kind of Benitration reactors, including condenser 17, stripper 16, shell of reactor 15, reaction
Pipe 9, conveyer belt 10, belt-driven wheel 11, catalyst exit line 12 and catalysis is added in device inner cylinder 14, ammonia-spraying grid 8, catalyst
Agent hopper 13；It is wherein reactor external seal chamber between shell of reactor 15 and reactor inner cylinder 14, belt-driven wheel 11 exists
Reactor external seal is intracavitary, and conveyer belt 10 is attached on belt-driven wheel 11, crosses reactor inner cylinder 14, and pipe 9 is added in catalyst
In reactor external seal top of chamber, 9 outlet at bottom face conveyer belt one end of pipe is added in catalyst, and catalyst hooper 13 is in reactor
External seal bottom of chamber portion, catalyst exit line 12 connect in 13 bottom of catalyst hooper, 12 outlet at bottom face vapour of catalyst exit line
Device 16 is mentioned, 16 solid outlet of stripper connects catalyst and pipe 9 is added, and the gas vent of stripper connects condenser 17.
The operating process of Benitration reactor of the invention is as follows: microspheroidal denitrating catalyst 3 is added pipe 9 by catalyst and adds
It infuses accumulation on first layer conveyer belt 10 and forms bed, belt-driven wheel 11 drives the bed movement on conveyer belt 10, bed
It is fallen on next conveyer belt under the effect of gravity across reactor inner cylinder 14 into reactor external seal chamber, forms bed,
And moved in the opposite direction under the driving of belt-driven wheel 11, according to the above-mentioned method of operation, formation is continuously run
Conveyer belt bed；Flue gas 1 enters from reactor bottom, and the gaseous mixture 2 containing ammonia is filled into flue gas 1 by ammonia-spraying grid 8,
Air-flow passes through the staggered catalyst bed of multiple-layer horizontal from top to bottom, carries out denitration desulphurization reaction, removes NOx and SOx, together
Shi Fenchen is discharged with the purified gas 4 on catalyst granules, obtained from reactor bottom with ammonium salt adherency, and catalyst is in the last layer
The end of conveyer belt 10 falls into catalyst hooper 13, enters stripper 16 via catalyst exit line 12, the ammonium salt being stripped off steams
Vapour 6 obtains ammonium salt solution 7 by the condensation of condenser 17, and catalyst granules after stripping, which returns to catalyst pipe 9 is added, is filled into the
Circulation is completed on one layer of conveyer belt 10.
Embodiment 1
Water, dehydrated alcohol, aluminium chloride, polyethylene glycol, formamide are uniformly mixed by (20 DEG C) at room temperature, add pyridine, mixing
By weight, content is respectively as follows: water 23%, ethyl alcohol 22%, aluminium chloride 20%, polyethylene glycol (viscosity average molecular weigh 1,000,000) to object each component
0.3%, formamide 1%, pyridine 33.7%.After being uniformly mixed, resulting mixture is added drop-wise in 20 ~ 50 DEG C of oil column and is shaped to
Microspheroidal aging 48 hours at 45 DEG C, then with mixture 48 hours after the mixed liquid dipping aging of ethyl alcohol and water, has been impregnated
After finishing and removing liquid phase, the drying at 40 DEG C is until apparent loss of weight no longer occurs for product.Then it roasts 6 hours, obtains at 600 DEG C
To alumina microsphere carrier；With the maceration extract incipient impregnation alumina support containing ferric nitrate and manganese nitrate, then at 80 DEG C
8 hours dry, 550 DEG C roast 6 hours, are cooled to room temperature, obtain microspheroidal denitrating catalyst A.
MnO2Content is 10wt%, Fe2O3Content is 5wt%, overall porosity 80%, and hole has dual pore size distribution, wherein
Macropore be evenly distributed, macropore average pore size 360nm, macro porosity led accounts for 55%；4 ~ 6nm of mesoporous pore size, mesoporous porosity account for
24%.Side pressure strength 7.1N/mm, BET specific surface area 160m2/ g, Kong Rongwei 0.51cm3/g.Through big known to scanning electron microscopic observation
Hole has three-dimensional connectivity.
Embodiment 2
Water, dehydrated alcohol, aluminium chloride, polyethylene glycol, formamide are uniformly mixed by (20 DEG C) at room temperature, add pyridine, mixing
By weight, content is respectively as follows: water 31%, ethyl alcohol 29%, aluminium chloride 16%, polyethylene glycol (viscosity average molecular weigh 2,000,000) to object each component
0.5%, formamide 3.5%, pyridine 20%.After being uniformly mixed, resulting mixture is added drop-wise in 20 ~ 50 DEG C of oil column and is shaped to
Microspheroidal aging 24 hours at 60 DEG C, is then impregnated mixture 48 hours after aging with ethyl alcohol, immersion finishes and removes liquid phase
Afterwards, it is dried at 50 DEG C until apparent loss of weight no longer occurs for product.Then it is roasted 5 hours at 750 DEG C, obtains microballoon oxidation
Alumina supporter；It is then 5 hours dry at 100 DEG C with the maceration extract incipient impregnation alumina support containing ferric nitrate and manganese nitrate,
550 DEG C roast 5 hours, are cooled to room temperature, obtain microspheroidal denitrating catalyst B.
MnO2Content is 8wt%, Fe2O3Content is 12wt%, overall porosity 73%, and hole has dual pore size distribution, wherein
Macropore be evenly distributed, macropore average pore size 180nm, macro porosity led accounts for 47%；7 ~ 11nm of mesoporous pore size, mesoporous porosity account for
31%.Side pressure strength 8.9N/mm.BET specific surface area is 155 m2/ g, Kong Rongwei 0.61cm3/g.Through big known to scanning electron microscopic observation
Hole has three-dimensional connectivity.
Comparative example 1
This example compares with embodiment 1.The difference is that being added without formamide.Average 4.6 μm of diameter macropores, porosity 45%, macropore
Porosity accounts for 13%.Pore-size distribution: mesoporous 4-20nm, 3.1 ~ 7.9 μm of macropore.Side pressure strength 1.3N/mm.Resulting materials BET compares table
Area is 115 m20.4 cm of/g, Kong Rongwei3/g.It is essentially through macropore known to scanning electron microscopic observation isolated, big pore size distribution is not yet
Too uniformly.
Embodiment 3
FCC regenerated flue gas flow is 150,000 Nm3/ h, temperature are 650 DEG C, pressure 10kPa, NOx concentration 600mg/Nm3, SO2
Concentration is 1000mg/Nm3, SO3Concentration is 20mg/Nm3, dust content 200mg/Nm3.NOx emission standard is 200 mg/Nm3。
Catalyst uses microspheroidal denitrating catalyst A.
FCC regenerated flue gas takes heat by boiler first, and temperature is reduced to 200 DEG C of reaction temperature by 650 DEG C, contains ammonia
Mixed gas flow is 1800Nm3/ h, wherein ammonia volume fraction is 4%, and stripping gas 0.8MPa, 420 DEG C of overheated steam steam
Vapour, flow 15Nm3/h.The present embodiment uses movable reactor, the interior seal chamber size of reactor be long 8m × wide 6m ×
High 8m；Reaction time is 0.5s, and 3 layers of conveyer belt are arranged, and catalyst bed layer height is 300mm on each conveyer belt, transmits mark
Very little is long 9m × wide 5.8m, selects stainless steel mesh conveyer belt, and aperture diameter 3mm drives wheel diameter 300mm, upper layer and lower layer
Outage 1300mm between conveyer belt, there are enough space for maintenances.After reaction, it is ensured that the NOx content of purifying smoke is
100mg/Nm3, SO2Content is 25mg/Nm3, dust content is less than 10mg/ Nm3, meet the environmental requirement of priority control area, cigarette
Gas can pass through smoke stack emission.
Embodiment 4
FCC regenerated flue gas flow, temperature, pressure are the same as embodiment 1, NOx concentration 2000mg/Nm3, SO2Concentration is 2000mg/
Nm3, SO3Concentration is 200mg/Nm3, dust content 400mg/Nm3.NOx emission standard is 100 mg/Nm3。
Catalyst uses microspheroidal denitrating catalyst B.
FCC regenerated flue gas takes heat by boiler first, and temperature is reduced to 200 DEG C of SCR denitration reaction temperature by 650 DEG C；Contain
The mixed gas flow for having ammonia is 1600Nm3/ h, wherein ammonia volume fraction is 3%, stripping gas 0.8MPa, 420 DEG C of overheat
Vapor steam, flow 15Nm3/h；The interior seal chamber size of reactor is long 8m × wide 6m × high 15m；Reaction time is
10 layers of conveyer belt are arranged in 2s, and catalyst bed layer height is 500mm on each conveyer belt, conveyer belt having a size of long 9m × wide 5.8m,
Stainless steel mesh conveyer belt is selected, aperture diameter 3mm drives wheel diameter 300mm, outage between upper layer and lower layer conveyer belt
1500mm, there are enough space for maintenances.After reaction, it is ensured that the NOx content of purifying smoke is 100mg/Nm3, SO2Contain
Amount is 30mg/Nm3, dust content is less than 10mg/ Nm3, meet the environmental requirement of priority control area, flue gas can be arranged by chimney
It puts.
Comparative example 2
With embodiment 1, only reactor replaces with traditional fixed bed reactors, and catalyst uses commercially available vanadium tungsten titanium honeycomb
Catalyst, group are divided into component known in the art, are loaded using modularization, and single catalyst module height is 1m, reactor
Size is 4.4m × 4.6m, and three layers of Catalyst packing, FCC regenerated flue gas first takes heat by boiler, and temperature is reduced to by 650 DEG C
200 DEG C of SCR denitration reaction temperature；The mixed gas flow containing ammonia that raw material drainage area provides is 1600Nm3/ h, wherein ammonia
Concentration is 3v%.Gaseous mixture containing ammonia is added in the upstream flue apart from reactor inlet certain distance, by ammonia-spraying grid
Mixing diffusion after, guarantee reactor inlet flue gas in ammonia concentration deviation less than 5%, enter back into SCR reactor reaction, pass through
After crossing denitration reaction, it is ensured that the NOx content of purifying smoke is 100mg/Nm3, the flue gas after denitration goes successively to downstream unit
It is exchanged heat, desulfurization and dedusting, meets the environmental requirement of priority control area.
Comparative example 3
Still using the reactor in comparative example 1, flue gas composition guarantees that ammonia is escaped since NOx concentration is too big in flue gas with embodiment 2
Escape ﹤ 3mgNm3, NOx concentration is 1000 ~ 1300mg/Nm after denitration3, it is unable to qualified discharge, and dust still needs to enter desulfurization and dedusting
System is handled.
Comparative example 4
With embodiment 2, only reactor replaces with traditional fixed bed reactors, guarantees that the NOx content of purifying smoke is up to standard.
Comparative example 5
With embodiment 4, only reactor replaces with the moving-burden bed reactor in CN102008893A.Select partial size be 2.5 ~
The catalyst of 7.5mm, catalyst shape are graininess, short cylinder or honeycomb etc., and group is divided into component known in the art,
Circulation total amount is 40m3, reactor size is 4.4m × 4.6m, the NH of addition3Molar ratio with NOx in flue gas is 1:1, and mixing is equal
It is even latter and enter Catalytic Layer, it removes the flue gas of NOx and is discharged from top.After denitration reaction, it is ensured that the NOx of purifying smoke
Content is 100mg/Nm3, the flue gas after denitration go successively to downstream unit exchanged heat, desulfurization and dedusting, with meeting priority control
Area's environmental requirement.The cycle of operation of embodiment and comparative example, catalyst amount and clean-up effect are shown in Table 1.
1 embodiment of table and the comparative example cycle of operation, catalyst amount and clean-up effect compare.
Claims (23)
1. a kind of low-temperature denitration catalyst, it is characterised in that: on the basis of catalyst weight, comprising: 75% ~ 94% carrying alumina
Body, 3% ~ 20%Fe2O3With 3% ~ 20% MnO2；Catalyst is microspheroidal, 2 ~ 6mm of diameter, overall porosity 60% ~ 85%, all holes
In, the mesoporous ratio for accounting for overall porosity of 5 ~ 20nm is 15% ~ 55%, and the ratio that the macropore of 100 ~ 1000nm accounts for overall porosity is
40%~75%；Macropore is evenly distributed and three-dimensional perforation.
2. low-temperature denitration catalyst described in accordance with the claim 1, it is characterised in that: side pressure breaking strength is 5 ~ 20N/mm.
3. low-temperature denitration catalyst described in accordance with the claim 1, it is characterised in that: the BET specific surface of low-temperature denitration catalyst
Product is 120 ~ 400m20.45 ~ 1.50cm of/g, Kong Rongwei3/g。
4. low-temperature denitration catalyst described in accordance with the claim 1, it is characterised in that: contain Zr, Ce or Cu auxiliary agent in catalyst
One or more of based on the total catalyst weight, auxiliary agent is calculated as 1% ~ 10% with oxide, each component content in catalyst
The sum of be 100%.
5. a kind of preparation method of low-temperature denitration catalyst, including following content: (1) by silicon source, polyethylene glycol and amide-containing
The organic compound of group is dissolved in low carbon alcohol solution, is uniformly mixed and obtains clear solution；It is resulting that step (1) is added in pyridine
In mixture, it is uniformly mixed；Wherein the viscosity average molecular weigh of polyethylene glycol is 10000 ~ 3000000；(2) resulting mixture is added dropwise
It is shaped to microspheroidal into 20 ~ 50 DEG C of oils column, aging 12 ~ 60 hours at 40 ~ 80 DEG C are water-soluble using low-carbon alcohols or low-carbon alcohols
Liquid impregnates ageing products, and then through being separated by solid-liquid separation, solid phase obtains microspheroidal alumina support through dry and roasting；(3) with containing
The soluble-salt oxide impregnation alumina supporter of Mn and Fe, then dry and roasting, obtains microspheroidal denitrating catalyst.
6. according to the method for claim 5, it is characterised in that: on the basis of the weight of step (1) resulting mixture, low-carbon
The additional amount of alcohol solution is 10% ~ 80%, and silicon source additional amount is 10% ~ 20%, and the additional amount of polyethylene glycol is 0.1% ~ 3.0%；Its
In, water and the mass ratio of low-carbon alcohols are 1.0 ~ 1.3 in low carbon alcohol solution；The organic compound of polyethylene glycol and phosphinylidyne-containing amine group
Molar ratio be 0.05 ~ 1.0；Pyridine and Al3+Molar ratio be 3.0 ~ 9.0.
7. according to the method for claim 5, it is characterised in that: low-carbon alcohols described in step (1) and (2) are that C5 is below
Alcohol.
8. according to the method for claim 5, it is characterised in that: the organic compound of phosphinylidyne-containing amine group described in step (1)
For one of formamide, n,N-Dimethylformamide or a variety of.
9. technique according to claim 5, it is characterised in that: soaking conditions described in step (2) are as follows: soaking temperature 10 ~
80 DEG C, soaking time is 24 ~ 48 hours.
10. a kind of application of the low-temperature denitration catalyst described in claim 1 ~ 4 any claim in denitrating flue gas reaction.
11. applying according to claim 10, it is characterised in that: low-temperature flue gas enters at the top of Benitration reactor, contains ammonia
The gaseous mixture of gas is filled into flue gas through ammonia-spraying grid, and air-flow passes through the staggered catalyst bed of multiple-layer horizontal from top to bottom
Layer carries out denitration desulphurization reaction and removes NOx and SOx, and the ammonium salt that desulfurization generates is adhered on low-temperature denitration catalyst particle, flue gas
In dust simultaneously by catalyst bed filter adherency dedusting, purifying smoke from reactor bottom be discharged；Wherein catalyst bed
It is made of the low-temperature denitration catalyst accumulated on mesh belt and conveyer belt, the traffic direction phase of adjacent upper layer and lower layer conveyer belt
Instead, upper layer low-temperature denitration catalyst is moved to transmission end of tape with conveyer belt, and the fortune of lower layer's conveyer belt is dropped down by free gravity
The starting point of line direction, low-temperature denitration catalyst falls into catalyst hooper in the end of the last layer conveyer belt, through being stripped off
Ammonium salt is recycled.
12. applying according to claim 11, it is characterised in that: the concentration of NOx is 700 ~ 4500mg/ in the flue gas
Nm3, SOx concentration is 700 ~ 4500mg/Nm3。
13. applying according to claim 11, it is characterised in that: the temperature into the low-temperature flue gas of Benitration reactor is
150 ~ 260 DEG C, preferably 180~240 DEG C.
14. applying according to claim 11, it is characterised in that: the flue gas flow rate be 2~15m/s, preferably 4 ~
10m/s；The denitration reaction residence time is 0.5~20s.
15. applying according to claim 11, it is characterised in that: the gaseous mixture containing ammonia of the ammonia-spraying grid filling
In, the total moles ratio of NOx and SOx in ammonia and flue gas are 0.9:1 ~ 1.15:1.
16. applying according to claim 11, it is characterised in that: the gaseous mixture containing ammonia is ammonia and air
Mixture, wherein volumetric concentration of the ammonia in gaseous mixture be 0.5% ~ 10%.
17. applying according to claim 11, it is characterised in that: the conveyer belt uses metal net shaped conveyer belt, passes
Band mesh size is sent to guarantee to be less than catalyst particle size, to guarantee that catalyst granules is not fallen from mesh, conveyer belt is using outer
The motor driven set drives conveyer belt rotation by belt-driven wheel.
18. applying according to claim 11, it is characterised in that: the low-temperature denitration catalyst accumulates height on a moving belt
Degree is 50~500mm.
19. applying according to claim 11, it is characterised in that: the conveyer belt transmission speed is 0.1mm/s~10mm/
s。
20. applying according to claim 11, it is characterised in that: the conveyer belt number of plies is 3~10 layers.
21. applying according to claim 11, it is characterised in that: the vertical range between the adjacent two layers conveyer belt
For 1200 ~ 2000mm.
22. applying according to claim 11, it is characterised in that: the catalyst in catalyst hooper is fallen into, by stripping
Mortgage originator is filled into the circulation that first layer conveyer belt completes catalyst afterwards.
23. applying according to claim 11, it is characterised in that: the stripping carries out in stripper, stripping process
Are as follows: low pressure steam is passed through by following, is stained with the catalyst of ammonium salt by being passed through above, will be in catalyst using low pressure steam
Ammonium salt gasification take out of, ammonium salt gasification decompose obtains SO2、NH3、H2O, gaseous mixture enter condenser and react to ammonium salt solution.
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| CN109126815B (en) | 2020-09-11 |
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