CN109420508A - A kind of denitrating catalyst and preparation method and low-temperature denitration technique - Google Patents
A kind of denitrating catalyst and preparation method and low-temperature denitration technique Download PDFInfo
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- CN109420508A CN109420508A CN201710770915.4A CN201710770915A CN109420508A CN 109420508 A CN109420508 A CN 109420508A CN 201710770915 A CN201710770915 A CN 201710770915A CN 109420508 A CN109420508 A CN 109420508A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 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 54
- 239000003546 flue gas Substances 0.000 claims abstract description 52
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000037396 body weight Effects 0.000 claims abstract description 4
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 69
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 59
- 239000010410 layer Substances 0.000 claims description 31
- 229910021529 ammonia Inorganic materials 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 25
- 150000003863 ammonium salts Chemical class 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000428 dust Substances 0.000 claims description 17
- 238000005470 impregnation Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000008246 gaseous mixture Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000006477 desulfuration reaction Methods 0.000 claims description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 9
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- 239000002243 precursor Substances 0.000 claims description 6
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
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- 239000002365 multiple layer Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 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
- 239000000243 solution Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 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 14
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- 230000000694 effects Effects 0.000 description 8
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
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- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- 238000004064 recycling Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium 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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 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
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000009825 accumulation Methods 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
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
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- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
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- 235000019253 formic acid Nutrition 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 244000005700 microbiome Species 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
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- 125000000185 sucrose group Chemical group 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
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
- B01D53/76—Gas phase processes, e.g. by using aerosols
-
- 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
-
- 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
-
- B01J35/615—
-
- B01J35/635—
-
- 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
-
- 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
Abstract
The invention discloses a kind of denitrating catalyst and preparation methods and low-temperature denitration technique.Denitrating catalyst, on the basis of catalyst weight, comprising: 75% ~ 94% carbon containing alumina support, 3% ~ 20%Fe2O3With 3% ~ 20% MnO2；On the basis of carbon containing carrying alumina body weight, carbon content 5wt%-35wt%, preferably 10wt% ~ 30wt%, specific surface area 250-750m2/ g, crushing strength 100-200N/cm.Denitrating catalyst of the invention has biggish Kong Rong, specific surface and mechanical strength, applied in low-temperature denitration reaction, the problem of nitrogen oxides and oxysulfide in flue gas can effectively be removed, 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 denitrating catalyst and preparation method and denitration work
Skill.
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, when reaction zone ammonia
(the escaping of ammonia) Shi Huiyu SO when superfluous3Reaction generates ammonium salt, the ammonium salt (NH of generation4HSO4), it is in liquid at 180~240 DEG C of temperature
State has viscosity, is liable to stick on the heat exchanger tube of downstream unit economizer of SCR denitration reaction device, the powder being bonded in flue gas
Dirt causes the fouling blockage and corrosion of heat exchange tube layer, influences the device cycle of operation.In order to avoid the escaping of ammonia, SCR fixed bed reaction
Device entrance spray ammonia uniformity generally requires positive and negative deviation less than 5%.2, the process conditions phase of the NOx content in flue gas and master device
It closes, variation fluctuation range is larger, and the catalytic amount of SCR fixed bed reactors is fixed, sets once NOx concentration range exceeds
Evaluation, then the NOx of purifying smoke is unable to qualified discharge.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, general denitrating flue gas
After, wet scrubbing dedusting is also used, is carried out together with desulfurization, the desulfurization waste liquor that desulfurization and dedusting process generates will also carry out liquid
Gu separation, 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 denitrating catalyst and preparation method and low-temperature denitration technique.
Denitrating catalyst of the invention has biggish Kong Rong, specific surface and mechanical strength, is suitable for low-temperature denitration technique.
Denitrating catalyst of the invention, on the basis of catalyst weight, comprising: 75% ~ 94% carbon containing alumina support, 3% ~
20%Fe2O3With 3% ~ 20% MnO2；On the basis of carbon containing carrying alumina body weight, carbon content 5wt%-35wt%, preferably
15wt% ~ 30wt%, specific surface area 250-750m2/ g, preferably 300 ~ 650m2/ g, crushing strength 100-200N/cm, pyridine
It adsorbs in meleic acid, 250 DEG C of weak acid below are distributed as 30%-45%.
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 denitrating catalyst of the invention, including following content:
(1) alumina precursor is uniformly mixed with furfuryl alcohol solution, is then added suitable peptizing agent, and kneading is at plastic, so
After form, dry, roasting obtains carbon containing alumina support；
(2) with the soluble-salt oxide impregnation alumina supporter containing Mn and Fe, then drying and roasting, obtain denitrating catalyst.
In the method for the present invention, alumina precursor described in step (1) is boehmite rubber powder, or through silicon, boron, phosphorus, titanium
Or the boehmite rubber powder that zirconium etc. is element modified, or the aluminum oxide of aluminium oxide can be converted into after being fired, and through silicon,
Boron, phosphorus, titanium or zirconium etc. are element modified and the aluminum oxide of oxide, preferably gamma-alumina can be converted into after roasting
Powder.
In the method for the present invention, the concentration of furfuryl alcohol solution described in step (1) is 1wt%-50wt%, preferably 10wt%-40wt%,
Solvent is C5And the mixture of low-carbon alcohol and water below, wherein low-carbon alcohols/water mass ratio is 0.05-1, preferably 0.1-
0.5.The low-carbon alcohols are preferably ethyl alcohol.The dosage of the furfuryl alcohol solution is determined by the carbon content of product.
In the method for the present invention, furfuryl alcohol solution described in step (1) and alumina precursor volume ratio 1-10:1, further preferably
Dosage is the volume that aluminium oxide furfuryl alcohol solution occurs furfuryl alcohol solution when saturation is adsorbed.Preferably the two to soak in equal volume when mixing
The mode of stain interacts.
In the method for the present invention, peptizing agent described in step (1) is that common are machine acid or inorganic acid or their combination
Object, such as nitric acid, formic acid, acetic acid, citric acid, preferably nitric acid.On the basis of alumina precursor weight, peptizing agent dosage is
0.5wt%-3wt%.Peptizing agent by weight, also containing the sulfuric acid of 0.5wt%-15wt%, preferably 1wt%-10wt% in peptizing agent.
Peptizing agent is preferably formulated as 0.5wt%-10wt% peptizing agent aqueous solution when in use.
In the method for the present invention, molding described in step (1) includes extrusion, tabletting, balling-up, or is shaped to other abnormal shapes, excellent
It is selected as spherical or bar shaped, the granular size of carbon containing alumina support is 2 ~ 6mm, preferably 3 ~ 5mm,
In the method for the present invention, drying process described in step (1) is drying 1-4 hours at 100-120 DEG C, preferred before dry
It dries in the shade at room temperature 10-24 hours.
In the method for the present invention, step (1) roasting process are as follows: first in oxygen-containing atmosphere, 300-400 DEG C roasting 3-6 hours,
Then under an inert atmosphere, roast 3-10 hours at 600-750 DEG C.The oxygen-containing atmosphere can oxygen content be 10% ~ 30%,
Air atmosphere can generally be selected；Or mixtures thereof the inert atmosphere, generally nitrogen, argon gas, helium.
In the method for the present invention, the soluble-salt of step (2) described Mn is manganese nitrate, and the soluble-salt of Fe is ferric nitrate.When
When containing auxiliary agent in catalyst, auxiliary agent can introduce during step (2).The soluble-salt of Mn and Fe described in step (2)
Solution is to form to calculate according to final catalyst to prepare.Volume impregnation, incipient impregnation or spray impregnating side can be used
Formula, dip time are 1-5 hours.Drying condition described in step (2): drying temperature is 100-130 DEG C, drying time 1-10
Hour；The roasting condition are as follows: under inert atmosphere, 450-600 DEG C roasting 2-6 hours.The inert atmosphere, generally nitrogen
Or mixtures thereof gas, argon gas, helium.
Inventor's discovery is carbon source in carbonization process using furfuryl alcohol, can significantly improve the production quantity of carbon, meanwhile, chaff
Alcohol is small molecule organic matter, its solution and alumina powder are impregnated and in kneading, carbonaceous molecule can be made uniformly to penetrate into
Into the hole of alumina powder, so that carbon source is distributed more uniform effect in entire carrier after reaching powder molding；This
The catalyst that the Aci-Jel solvent containing a small amount of sulfuric acid in invention can polymerize as carbon source simultaneously, the carbon source after making low temperature polymerization exist
High temperature cabonization stage polymerization simultaneously generates flourishing pore structure, and the specific surface area of final carrier can be improved.Simultaneously in the carrier
The crushing strength of carrier granular can be improved in the carbide of network polymerization.There is spirit by the denitrating catalyst that the carrier obtains
Controllable carbon content living, uniform carbon distribution, higher specific surface area and Kong Rong, higher crushing strength and more weak acid
The advantageous properties such as distribution.
Present invention simultaneously provides a kind of low-temperature denitration technique, above-mentioned denitrating catalyst is used in the technique.Specific work
Skill process are as follows: low-temperature flue gas enters at the top of Benitration reactor, and the gaseous mixture containing ammonia is filled into flue gas through ammonia-spraying grid, gas
Stream passes through the staggered catalyst bed of multiple-layer horizontal from top to bottom, carries out denitration desulphurization reaction and removes NOx and SOx, desulfurization
Ammonium salt (the NH of generation4HSO4) be adhered on denitrating catalyst, the dust in flue gas is filtered by catalyst bed adhere to simultaneously, only
Change flue gas to be discharged from reactor bottom；Wherein catalyst bed is by the denitrating catalyst group accumulated on mesh belt and conveyer belt
At the traffic direction of, adjacent upper layer and lower layer conveyer belt on the contrary, upper layer denitrating catalyst is moved to transmission end of tape with conveyer belt, according to
The starting point of the traffic direction of lower layer's conveyer belt is dropped down by free gravity, low-temperature denitration catalyst is at the end of the last layer conveyer belt
End falls into catalyst hooper, and ammonium salt is stripped off, and is recycled.
In present invention process, the flue gas mainly includes coal-fired plant flue gas, FCC regenerated flue gas, refinery processes furnace
Flue gas or chemical industry kiln gas (such as cracking of ethylene kiln gas) etc..Flue gas mainly contains NOx, SOx and impurity, wherein described
Impurity is generally dust, 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.
In present invention process, the flue gas flow rate is 2~15m/s, preferably 4 ~ 10m/s；The denitration reaction residence time is
0.5~20s.
In present invention process, in the gaseous mixture containing ammonia of ammonia-spraying grid filling, NOx in ammonia and flue gas and
The total moles ratio of SOx is 0.9:1 ~ 1.15:1.
In present invention process, the gaseous mixture containing ammonia is the mixture of ammonia and air, and wherein ammonia is mixed
Closing the volumetric concentration in gas is 0.5% ~ 10%.In the method for the present invention, the conveyer belt uses conventional metal net shaped conveyer belt,
It is preferred that stainless steel mesh conveyer belt, conveyer belt mesh size guarantees to be less than catalyst particle size, to guarantee catalyst granules not
It is fallen from mesh, generally 0.1~3mm, preferably 1.5~2.5mm；Conveyer belt uses external motor driven, is driven by conveyer belt
Driving wheel drives conveyer belt rotation.
In present invention process, the low-temperature denitration catalyst on a moving belt piling height be 50~500mm, preferably 200
~300mm.
In present invention process, the conveyer belt transmission speed is 0.1mm/s~10mm/s, preferably 0.5~2mm/s.
In present invention process, the conveyer belt number of plies and width can according to actual needs and reactor size is selected
It selects, preferably 3~10 layers of the conveyer belt number of plies, more preferable 3~8 layers, conveyor width is limited with not brushing up against wall of reactor, conveyer belt
Width direction and wall of reactor gap are 2 ~ 50mm, preferably 2 ~ 5mm.
In present invention process, vertical range between the adjacent two layers conveyer belt is 1200 ~ 2000mm, preferably 1400
~1600mm。
In present invention process, the catalyst in catalyst hooper is fallen into, mortgage originator is filled into first layer after stripping
The circulation of conveyer belt completion catalyst.
In present invention process, the stripping carries out in stripper, stripping process are as follows: low pressure steam is by following logical
Enter, is stained with the catalyst of ammonium salt by being passed through above, is taken out of the ammonium salt gasification in catalyst using low pressure steam, ammonium salt gas
Change to decompose and obtains SO2、NH3、H2O etc., gaseous mixture enter condenser and react to ammonium salt solution.
Present invention process have the advantage that in (1) flue gas NOx and SOx directly with the mixing solid/liquid/gas reactions containing ammonia,
NOx is reduced to N2, SOx directly generates ammonium salt, and ammonium salt is to have sticking liquid at this temperature, it is adhered on catalyst,
Dust in flue gas is adhered on catalyst granules with ammonium salt, and reaction system is left together with catalyst granules, reaches same
When dedusting effect, denitration, desulfurization and dedusting can be completed in a reactor, reduce follow-up process, reduce investment and behaviour
Make expense, while using low-temp reaction, reduces energy consumption and the requirement to equipment.The present invention uses micro-spherical catalyst bed pair
Dust in flue gas has filtration, has due to containing dual pore size distribution in its catalyst for the dust less than 1 micron
Better capture effect, it is not easy to block；(2) mobile catalyst bed is formed using conveyer belt, the ammonium salt of generation is adhered to
On catalyst granules, reaction system is left together with catalyst granules, is avoided the escaping of ammonia and is caused ammonium hydrogen sulfate blocking bed
Problem extends the cycle of operation of device；(3) catalyst can be adjusted in reactor by adjusting the movement velocity of conveyer belt
Residence time, by adjust conveyer belt on catalyst bed height, adjust reaction time of the flue gas by catalyst bed,
Therefore the flue gas that can handle different NOx and SOx concentration, is more suitable for the FCC regenerated flue gas of high NOx concentration；(4) catalyst follows
Ring uses, catalyst after reaction into cross ammonium salt is stripped off after return and be filled into first layer conveyer belt the reaction was continued, can be significantly
The dosage of catalyst is reduced, while stripping obtained ammonium salt and can be used as the byproduct of denitration reaction.
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.
Fig. 2 is that the carrying alumina dignity that the carbon containing alumina support carbon of the embodiment of the present invention 1 is evenly distributed sweeps figure.
Fig. 3 is that the carrying alumina dignity that the carbon containing alumina support carbon of comparative example 1 of the present invention is evenly distributed sweeps figure.
Specific embodiment
Specific surface area and Kong Rong measure total acid and acid using infrared method using low temperature liquid nitrogen determination of adsorption method in the present invention
Distribution, carbon content are measured using air calcination method, and crushing strength is according to HG/T 2782-1996 standard, using QCY-602 type
The measurement of catalyst strength analyzer, carbon distribution consistency degree sweep method mapping figure using SEM-EDS energy spectral element face to determine.
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
By 150 grams of furfuryl alcohol solution incipient impregnations into 100 grams of gamma-alumina powders, dries in the shade at room temperature after a certain period of time, make two
Person can stir into inadherent bulk particle.The composition of furfuryl alcohol solution are as follows: furfuryl alcohol 10wt%, ethanol/water 0.1.Then group
Shape particle moves into banded extruder, is slow added into 3.0wt% dust technology 35ml(and contains 0.04g sulfuric acid), abundant kneading is suitable hard
After the plastic of degree, it is extruded into stripe shape.After extrudate is dried overnight at room temperature, dried 4 hours at 110 DEG C.Drying sample is set
In high temperature furnace, 350 DEG C are warming up to, and constant temperature 6 hours at such a temperature, then pass to nitrogen and are continuously heating to 600 DEG C,
This temperature 10 hours, obtains carbon containing alumina support after natural cooling.With the maceration extract etc. containing ferric nitrate and manganese nitrate
Volume impregnation alumina support, then 5 hours dry at 100 DEG C, lower 550 DEG C of nitrogen atmosphere roast 6 hours, are cooled to room temperature,
Obtain denitrating catalyst A.MnO2Content is 10wt%, Fe2O3Content is 5wt%.
Embodiment 2
By 150 grams of furfuryl alcohol solution incipient impregnations into 100 grams of γ phase alumina powders, dries in the shade after a certain period of time, make at room temperature
The two can stir into inadherent bulk particle.The composition of furfuryl alcohol solution are as follows: furfuryl alcohol 20wt%, ethanol/water 0.5.Then it moves
Enter in banded extruder, be slow added into 3.5wt% dust technology 50ml(sulfuric acid containing 0.06g), after abundant kneading is plastic, it is extruded into
Stripe shape.After extrudate is dried overnight at room temperature, dried 4 hours at 110 DEG C.Drying sample is placed in high temperature furnace, is warming up to
300 DEG C, and constant temperature 4 hours at such a temperature, it then passes to nitrogen and is continuously heating to 650 DEG C, at this temperature 6 hours,
Carbon containing alumina support is obtained after natural cooling.With the maceration extract incipient impregnation carrying alumina containing ferric nitrate and manganese nitrate
Body, then 6 hours dry at 110 DEG C, lower 500 DEG C of nitrogen atmosphere roast 7 hours, are cooled to room temperature, obtain denitrating catalyst B.
MnO2Content is 8wt%, Fe2O3Content is 12wt%.
Embodiment 3
By 185 grams of furfuryl alcohol solution incipient impregnations into 100 grams of γ phase alumina powders, dries in the shade after a certain period of time, make at room temperature
The two can stir into inadherent bulk particle.The composition of furfuryl alcohol solution are as follows: furfuryl alcohol 45wt%, ethanol/water 1.It then moves into
In banded extruder, it is slow added into 4.0wt% dust technology 50ml(sulfuric acid containing 0.08g), after abundant kneading is plastic, it is extruded into item
Type.After extrudate is dried overnight at room temperature, dried 4 hours at 110 DEG C.Drying sample is placed in high temperature furnace, is warming up to 400
DEG C, and constant temperature 4 hours at such a temperature, it then passes to nitrogen and is continuously heating to 600 DEG C, it is natural at this temperature 3 hours
Carbon containing alumina support is obtained after cooling.With the maceration extract incipient impregnation alumina support containing ferric nitrate and manganese nitrate, so
5 hours dry at 100 DEG C afterwards, lower 550 DEG C of nitrogen atmosphere roast 6 hours, are cooled to room temperature, obtain denitrating catalyst C.MnO2Contain
Amount is 20wt%, Fe2O3Content is 5wt%.
Embodiment 4
By 185 grams of furfuryl alcohol solution incipient impregnations into 100 grams of gamma-alumina powders, dries in the shade at room temperature after a certain period of time, make two
Person can stir into inadherent bulk particle.The composition of furfuryl alcohol solution are as follows: furfuryl alcohol 40wt%, ethanol/water 1.It then moves into crowded
In machine, it is slow added into 4.0wt% dust technology 50ml(sulfuric acid containing 0.1g), after abundant kneading is plastic, it is extruded into stripe shape.
After extrudate is dried overnight at room temperature, dried 4 hours at 120 DEG C.Drying sample is placed in high temperature furnace, is warming up to 400 DEG C,
And constant temperature 4 hours at such a temperature, it then passes to nitrogen and is continuously heating to 650 DEG C, it is naturally cold at this temperature 4 hours
But carbon containing alumina support is obtained afterwards.With the maceration extract incipient impregnation alumina support containing ferric nitrate and manganese nitrate, then
4 hours dry at 120 DEG C, lower 600 DEG C of nitrogen atmosphere roast 5 hours, are cooled to room temperature, obtain denitrating catalyst D.MnO2Content
For 5wt%, Fe2O3Content is 10wt%.
Comparative example 1
Referring to " Journal of Molecular Catalysis 2010,24(5): the method preparation that 411-416 " is introduced.By 150 grams of sucrose solution incipient impregnations
It into 100 grams of γ phase alumina powders, dries in the shade at room temperature after a certain period of time, makes the two that can stir into inadherent bulk
Grain.The composition of sucrose solution are as follows: sucrose 14.5wt%, water 84.5wt%.Then bulk particle is moved into banded extruder, then slowly added
Enter 3.0wt% dust technology 35ml and is extruded into stripe shape after abundant kneading is the plastic of suitable stiff.Extrudate is dried overnight at room temperature
Afterwards, it is dried 4 hours at 110 DEG C.Drying sample is placed in high temperature furnace, is warming up to 350 DEG C, and constant temperature 6 is small at such a temperature
When, it then passes to nitrogen and is continuously heating to 600 DEG C, at this temperature 10 hours, carbon containing aluminium oxide is obtained after natural cooling
Carrier.It is then 5 hours dry at 100 DEG C with the maceration extract incipient impregnation alumina support containing ferric nitrate and manganese nitrate, nitrogen
Lower 550 DEG C of gas atmosphere roast 6 hours, are cooled to room temperature, obtain denitrating catalyst E.MnO2Content is 10wt%, Fe2O3Content is
5wt%。
Comparative example 2
Reference literature " Journal of Molecular Catalysis 2010,24(5): the method preparation that 411-416 " is introduced.The difference is that by γ phase oxidation aluminium powder
Body is changed to γ phase alumina shaping carrier.It is other identical as comparative example 1.With bodies such as the maceration extracts containing ferric nitrate and manganese nitrate
Product oxide impregnation alumina supporter, then 5 hours dry at 100 DEG C, lower 550 DEG C of nitrogen atmosphere roast 6 hours, are cooled to room temperature, obtain
To denitrating catalyst F.MnO2Content is 10wt%, Fe2O3Content is 5wt%.The object of embodiment and the carbon containing alumina support of comparative example
Change property and is shown in Table 1.
The physico-chemical property of the carbon containing alumina support of table 1.
By embodiment 1-4 and specific surface modified by furfuryl alcohol carbon it can be seen from the comparison of comparative example 1,2, in embodiment
Product, Kong Rong, weak acid content and crushing strength are better than comparative example.
Embodiment 5
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 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 6
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 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 3
With embodiment 5, 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 4
Still using the reactor in comparative example 3, flue gas composition guarantees that ammonia is escaped since NOx concentration is too big in flue gas with embodiment 6
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 5
With embodiment 1, only catalyst uses comparative example 1.
The cycle of operation of embodiment and comparative example, catalyst amount and clean-up effect are shown in Table 2.
2 embodiment of table and the comparative example cycle of operation, catalyst amount and clean-up effect compare.
Claims (21)
1. a kind of denitrating catalyst, it is characterised in that: on the basis of catalyst weight, including 75% ~ 94% carbon containing alumina support,
3%~20%Fe2O3With 3% ~ 20% MnO2；On the basis of carbon containing carrying alumina body weight, carbon content 5wt%-35wt%, specific surface
Product is 250-750m2/ g, crushing strength 100-200N/cm, in pyridine adsorption meleic acid, 250 DEG C of weak acid below are distributed as
30%-45%。
2. denitrating catalyst described in accordance with the claim 1, it is characterised in that: on the basis of carbon containing carrying alumina body weight, carbon
Content is 15wt% ~ 30wt%.
3. denitrating catalyst described in accordance with the claim 1, it is characterised in that: the carbon in carbon containing alumina support is evenly distributed.
4. a kind of preparation method of denitrating catalyst described in claims 1 or 2 or 3, it is characterised in that including following content:
(1) alumina precursor is uniformly mixed with furfuryl alcohol solution, is then added suitable peptizing agent, and kneading is at plastic, then at
Type, dry, roasting, obtains carbon containing alumina support；(2) with the soluble-salt oxide impregnation alumina supporter containing Mn and Fe, then
Dry and roasting, obtains denitrating catalyst.
5. according to the method for claim 4, it is characterised in that: the concentration of furfuryl alcohol solution described in step (1) is 1wt%-
50wt%, solvent C5And the mixture of low-carbon alcohol and water below, wherein the mass ratio of low-carbon alcohols and water is 0.05-1.
6. according to the method for claim 4, it is characterised in that: furfuryl alcohol solution described in step (1) and alumina precursor body
Product compares 1-10:1.
7. according to the method for claim 4, it is characterised in that: contain 0.5wt%- in peptizing agent described in step (1)
The sulfuric acid of 15wt%.
8. according to the method for claim 4, it is characterised in that: the particle of carbon containing alumina support described in step (1) is big
Small is 2 ~ 6mm.
9. according to the method for claim 4, it is characterised in that: step (1) roasting process are as follows: first in oxygen-containing atmosphere,
300-400 DEG C roasting 3-6 hours, then under an inert atmosphere, roasted 3-10 hours at 600-750 DEG C.
10. according to the method for claim 4, it is characterised in that: roasting condition described in step (2) are as follows: under inert atmosphere,
450-600 DEG C roasting 2-6 hours.
11. a kind of low-temperature denitration technique, it is characterised in that using denitration catalyst described in claims 1 or 2 or 3 in the technique
Agent.
12. low-temperature denitration technique according to claim 11, it is characterised in that: low-temperature flue gas at the top of the Benitration reactor into
Enter, the gaseous mixture containing ammonia is filled into flue gas through ammonia-spraying grid, and air-flow passes through that multiple-layer horizontal is staggered to urge from top to bottom
Agent bed carries out denitration desulphurization reaction and removes NOx and SOx, the ammonium salt NH that desulfurization generates4HSO4It is adhered on denitrating catalyst,
Dust in flue gas is filtered by catalyst bed simultaneously to be adhered to, and purifying smoke is discharged from reactor bottom；Wherein catalyst bed
Be made of the denitrating catalyst accumulated on mesh belt and conveyer belt, the traffic direction of adjacent upper layer and lower layer conveyer belt on the contrary,
Upper layer denitrating catalyst is moved to transmission end of tape with conveyer belt, drops down onto the traffic direction of lower layer's conveyer belt by free gravity
Starting point, low-temperature denitration catalyst fall into catalyst hooper in the end of the last layer conveyer belt, and ammonium salt is stripped off, circulation
It uses.
13. low-temperature denitration technique according to claim 11, it is characterised in that: into the low-temperature flue gas of Benitration reactor
Temperature is 150 ~ 260 DEG C.
14. low-temperature denitration technique according to claim 11, it is characterised in that: the flue gas flow rate is 2~15m/s；
The denitration reaction residence time is 0.5~20s.
15. low-temperature denitration technique according to claim 11, it is characterised in that: the ammonia-spraying grid filling contains ammonia
Gaseous mixture in, the total moles ratio of NOx and SOx in ammonia and flue gas are 0.9:1 ~ 1.15:1.
16. low-temperature denitration technique according to claim 11, it is characterised in that: the gaseous mixture containing ammonia is ammonia
The mixture of gas and air, wherein volumetric concentration of the ammonia in gaseous mixture is 0.5% ~ 10%.
17. low-temperature denitration technique according to claim 11, it is characterised in that: the conveyer belt is using conventional metal
Mesh belt, conveyer belt mesh size guarantees to be less than catalyst particle size, to guarantee that catalyst granules is not fallen from mesh.
18. low-temperature denitration technique according to claim 11, it is characterised in that: the low-temperature denitration catalyst is in conveyer belt
Upper piling height is 50~500mm.
19. low-temperature denitration technique according to claim 11, it is characterised in that: the conveyer belt transmission speed is 0.1mm/
S~10mm/s.
20. low-temperature denitration technique according to claim 11, it is characterised in that: the conveyer belt number of plies is 3~10 layers.
21. low-temperature denitration technique according to claim 11, it is characterised in that: between the adjacent two layers conveyer belt
Vertical range is 1200 ~ 2000mm.
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