CN105964284B - Honeycomb low-temperature denitration of flue gas catalyst and preparation method thereof - Google Patents
Honeycomb low-temperature denitration of flue gas catalyst and preparation method thereof Download PDFInfo
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- CN105964284B CN105964284B CN201610284318.6A CN201610284318A CN105964284B CN 105964284 B CN105964284 B CN 105964284B CN 201610284318 A CN201610284318 A CN 201610284318A CN 105964284 B CN105964284 B CN 105964284B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 204
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000003546 flue gas Substances 0.000 title claims abstract description 27
- 238000004898 kneading Methods 0.000 claims abstract description 172
- 238000000034 method Methods 0.000 claims abstract description 32
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005520 cutting process Methods 0.000 claims abstract description 16
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000008367 deionised water Substances 0.000 claims description 47
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- 239000000908 ammonium hydroxide Substances 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
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- 230000032683 aging Effects 0.000 claims description 16
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 14
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
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- 238000001914 filtration Methods 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000006004 Quartz sand Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
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- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
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- 229910052570 clay Inorganic materials 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
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- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
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- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 239000000706 filtrate Substances 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 13
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 39
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
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- 235000018660 ammonium molybdate Nutrition 0.000 description 4
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- 229910003320 CeOx Inorganic materials 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
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- 238000005336 cracking Methods 0.000 description 2
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 2
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
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- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
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- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- B01J35/394—
-
- B01J35/56—
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention relates to honeycomb low-temperature denitration of flue gas catalyst and preparation method, belongs to Air Pollution Control and environmental catalysis material is received, the catalyst is with TiO2, V2O5、MoO3、WO3And rare earth metal (La, Ce, Pr, Nd, Zr, Y) oxide is active component, with P2O5、SO3For modified additive, the catalyst is obtained through powder preparation, mixing and the processes processing such as kneading.The catalyst has excellent removal efficiency to NOx under low-temperature flue gas, and denitration efficiency at 170-180 DEG C is up to 90% or more.Mechanical strength and wear resistance with higher simultaneously, longitudinal compression strength are greater than 2.4MPa, and hardening end ash cutting rate is less than 0.08%/Kg.Reduce flying dust washing away, wear and etching to catalyst, extends the service life of catalyst.The raw materials for production of catalyst of the present invention are simple and easy to get, and preparation process is simple and easy to control, are easy to realize industrial production.
Description
Technical field
The invention belongs to Air Pollution Control and environmental catalysis Material Field, and in particular to a kind of honeycomb low-temperature flue gas is de-
Denox catalyst and preparation method thereof, the catalyst are suitable for non-electricity industry boiler, kiln metallurgy, chemical industry, coking and petrochemical industry etc.
The NOx emission control of the low-temperature flue gas or technology waste gas of industry and the denitrating technique of electric boiler low temperature, low dirt arrangement.
Background technique
Nitrogen oxides (NOx), it has also become after SO2Another global air pollution object later, the NOx in atmosphere is to the whole world
Warm, acid rain, photochemical fog, the raising of surface ozone concentration, many environmental problems such as water pollution have higher contribution margin,
As the primary pollutant in the air of big city.China is NOx emission big country, is derived mainly from station boiler, communications and transportation and each
Kind industrial process, annual emissions are presented increased trend year by year at 20,000,000 tons or more, give public health and ecological environment band
Carry out catastrophic effect, therefore, the emission control of NOx becomes the top priority of air contaminant treatment.In " 13 planning outlines
In (draft) ", clearly proposition China is in 2016 to SO23% is reduced respectively with the discharge amount of NOx, and with requiring control stress point
Area's fine particle (PM2.5) concentration.Therefore, denitration situation in China's is more acute, and the emission control of NOx is administered as current atmospheric
Main task, challenge is proposed to the popularization of denitration technology.
In many NOx emission control technologies, selective catalytic reduction (SCR) is since it is mature, reliable, efficient and obtains
Engineering verification and become denitration industry mainstream technology, can by NOx conversion be harmless N2And H2The core cell of O, SCR technique
For catalyst, the cost and efficiency of denitrating system are directly determined.Currently, the SCR catalyst that station boiler uses is with V2O5-WO3
(MoO3)/TiO2High temperature type based on system, the operating temperature of catalyst are mostly 310-410 DEG C.But many non-electricities
Industrial Boiler, kiln, metallurgy, chemical industry, coking and petrochemical industry of industry etc., due to secondary use waste heat or other mating energy saving skills
Art, exhaust gas or smog discharge temperature are lower (mostly at 200 DEG C or less), it is difficult to be urged using high temperature type (310-410 DEG C) SCR
The emission control of agent progress NOx.
Therefore, develop low temperature high activity SCR catalyst, non-electricity industry low-temperature flue gas use SCR technology, or
Power industry uses the denitrating technique of the low dirt of low temperature, has huge Social benefit and economic benefit.Shan etc. (ShanWB,
LiuFD, etal., Appl.Catal., B, 2012,115-116:100-106) it is living with low temperature using Co deposited synthesis
The CeO of property2-WO3/TiO2Low temperature active, temperature window and N of the ratio of catalyst, Ce and W to catalyst2Selectivity has very
It is big to influence, when the molar ratio of Ce and W is 1:1, the intensity and quantity of catalyst surface acidic site can be significantly improved, is improved
The NH of catalyst3- SCR reactivity.Room etc. (Fang Jingrui, Wu Yanxia wait environmental project journal, 2014,8 (2): 636-640)
With molding TiO2Carrier is prepared for Mn-Ce/TiO by infusion process2Low-temperature SCR catalyst, denitration of the content of Mn to catalyst
Efficiency has a significant impact, the low temperature active highest when Mn/ (Mn+Ce) molar ratio is 0.4 and 0.85.Yan etc. (Yan Dongjie, it is beautiful
Asia, waits chemistry of fuel journal, 2016,44 (2): 232-238) Mn-Ce/TiO is prepared for using sol-gal process2Low-temperature SCR is urged
Agent, SO2There are apparent inhibiting effect, SO to activity2Concentration be 700ppm when, catalyst to the removal efficiency of NOx in 2h from
84% is down to 42%, and activity is irreversible to reduce 50%；The Mn of active specy MnOx crystal transfer generation low activity2O3Object
Kind, it is suppressed that transformation of the gas phase oxygen to Lattice Oxygen reduces the redox performance of CeOx, exists in addition, sulfate is attached to catalyst
Catalyst surface, and an important factor for cause catalyst inactivation.Shen etc. (ShenBX, YaoY, etal.,
Chin.J.Catal, 2011,32 (12): 1803-1811) use ion-exchange to be prepared for titanium-based laminated clay column TiO2-PILC
Carrier loads Mn active component by infusion process and obtains xMn/TiO2- PILC catalyst, CeO2Doping can significantly improve 8%
Mn/TiO2The catalytic activity of-PILC catalyst and anti-SO2Performance, 8%Mn-2%CeO2/TiO2- PILC is at 200 DEG C to NO's
Removal efficiency is up to 95%, CeO2Doping the surface acidity and oxidationreduction ability of catalyst can be improved.Chen etc. (ChenL,
LiJH, etal., J.Phys.Chem.C, 2009,113:21177-21184) utilize CeOx to V2O5-WO3/TiO2Catalyst into
Row doping is modified to improve catalyst performance, the results showed that, Ce doping helps to improve catalyst surfaceIt is acid
The intensity and quantity of position, 0.1%V2O5- 6%WO3- 10%CeO2With preferable low temperature active, anti-H2O and SO2Performance,
200-400 DEG C is maintained at 90% or more to the removal efficiency of NOx.
In patent CN105126922, with diatomite, molecular sieve and nano-TiO2For carrier, rare earth oxide is activity
Center obtains rare-earth base SCR catalyst, has higher removal efficiency, but catalyst raw materials for production type to NOx under cryogenic conditions
It is more, preparation process and the device is complicated.Patent CN102962055 reports V2O5-MoO3/TiO2System low-temperature SCR catalyst powder
The preparation method of body, in model reaction catalyst at 150 DEG C to the removal efficiency of NOx up to 98%.Patent CN103894180
V is adulterated using gel method and infusion process preparation Pr, La with CN1038941812O5-MoO3/TiO2Low-temperature SCR catalyst, it is dilute
Earth elements Pr, La doping enter TiO2Lacking oxygen is formed in lattice, improves the low temperature active of catalyst, but is not directed to catalyst
Molding.Patent CN102266761 reports a kind of preparation method of low-temperature SCR catalyst powder, first with co-precipitation legal system
Standby ZrO2-TiO2Then metal composite oxide carrier passes through infusion process load C eO2、WO3And V2O5Active component, catalyst exist
Good catalytic activity is shown within the scope of 150-450 DEG C, but its preparation process is complicated.Patent CN104841464 discloses one
Kind high efficient cryogenic SCR catalyst, the Br of 0.35-0.5wt%-Adulterate V2O5-WO3/TiO2Catalyst can be improved low in catalyst
Denitration efficiency and resistance to SO_2 when warm further extend the service life of catalyst, but report shaping of catalyst method, industry
Using there is certain limitation.Patent CN105126816 discloses a kind of preparation method of catalyst for denitrating flue gas, relates generally to electricity
It stands the high temperature type SCR catalyst of Denitration in Boiler, with TiO2Compound Al2O3、SiO2Deng for carrier, glass fibre is skeleton, institute
Catalyst mechanical strength with higher and wear-resisting property are obtained, denitration efficiency further improves catalysis up to 92.3% or more
The service life of agent.Therefore, the low-temperature flue gas for industries such as the Industrial Boiler of non-electricity industry, kiln, chemical industry and coking and
Technology waste gas develops low-temperature denitration catalyst and molding technology thereof, the emission control of popularization and NOx to low-temperature denitration technology
It is significant.
Summary of the invention
It is in view of the drawbacks of the prior art and insufficient, the present invention provides a kind of honeycomb low-temperature denitration of flue gas catalyst and its
Preparation method, catalyst are made of carrier, active component and auxiliary agent, have excellent low temperature active and wider temperature window.
The present invention also provides honeycomb low-temperature denitration of flue gas method for preparing catalyst, have many advantages, such as efficient, low cost, Yi Shixian work
Industry continuous production improves the mechanical strength and wear resistance of catalyst, further on the basis of guaranteeing catalytic activity
Extend catalyst life.
The technical scheme to solve the above technical problems is that honeycomb low-temperature denitration of flue gas catalyst, including carry
Body, active component and auxiliary agent, the active component and auxiliary agent are supported on carrier respectively, and the carrier is TiO2Or TiO2Answer
Oxide is closed, the content of the carrier in the catalyst is 70~90wt%；The active component is V2O5And WO3Or MoO3,
Load capacity of the active component on carrier are as follows: V2O5For 0.3~6wt%, WO3For 1.0~15wt% or MoO3For 1.0~
15wt%, the auxiliary agent are P2O5, load capacity of the auxiliary agent on carrier are as follows: P2O5For 0.1-3wt%.
The beneficial effects of the present invention are: honeycomb low-temperature denitration of flue gas catalyst provided by inventing, catalyst have good
Good low temperature active and wider temperature window.Using preparation method of the invention, active component is helped to improve in carrier table
The degree of scatter in face enhances the interaction between active specy and carrier, it is suppressed that is urged due to caused by sintering under high temperature
Agent inactivation.In addition, gained catalyst mechanical strength with higher and abrasion resistant qualities, further improve making for catalyst
Use the service life.
Based on the above technical solution, the present invention can also be improved as follows:
Further, the active component further includes rare earth oxide, and load capacity of the rare earth oxide on carrier is 0
~20wt%, the rare earth oxide are one of oxide of La, Ce, Pr, Nd, Zr, Y or a variety of.
Further, the auxiliary agent further includes SO3, SO3Load capacity on carrier is 0-3wt%.
Further, for the active component by active component precursor preparation, the active component presoma is V2O5、WO3、
MoO3And one of the corresponding oxide of rare earth oxide, inorganic salts or organic salt or a variety of；The auxiliary agent is by auxiliary agent forerunner
Body preparation, the auxiliary agent presoma are P2O5、SO3One of corresponding oxide, inorganic salts or organic salt are a variety of.
The technical solution that the present invention solves another technical problem is as follows: a kind of system of honeycomb low-temperature denitration of flue gas catalyst
Preparation Method includes the following steps:
The preparation of S1 catalyst fines:
Deionized water is added in a kettle and is heated to 40-80 DEG C by S101, and oxalic acid is added or citric acid is stirred to complete
After dissolution, active component presoma and auxiliary agent presoma is added, is sufficiently stirred to obtain activity component impregnation liquid, wherein the V2O5
The molar ratio of presoma and oxalic acid or citric acid is 1:(0.8-4)；
Powdered carrier is added to activity component impregnation liquid obtained in step S101 in S102, is sufficiently stirred to obtain sticky
The sticky shape slurries are handled to obtain catalyst slurry, wherein be added in the carrier and S101 by shape slurries by ultrasonic disperse
Deionized water mass ratio be 1:(0.9-1.4)；
Catalyst slurry obtained in step S102 is dried S103, is roasted after broken, naturally cools to room
Temperature, crushing obtain catalyst fines；
The processing of S2 pug and shaping of catalyst:
The catalyst fines that S201 obtains S103 arrange spare, adjusting strength kneading machine exhaust valve, and are kneaded to strength
The catalyst fines and powdered aggregate of 225-315 parts by weight are added in machine exhaust valve, the powdered aggregate is relative to catalysis
The additional amount of agent powder is 3-20wt%；Then the stearic acid of 2-9 parts by weight, the lactic acid or oleic acid, 1-10 of 2-9 parts by weight is added
The concentration of the glycerol of parts by weight, deionized water and 24-32 parts by weight that 150-210 parts by weight are added is the ammonium hydroxide of 15-25%, is closed
Strength kneading machine exhaust valve is closed, high speed is kneaded 30-80min；
S202 adjusts strength kneading machine exhaust valve, and the catalyst fines of 67-105 parts by weight are added in the operation of kneading machine low speed
With 10-35 weight deionized water, strength kneading machine exhaust valve is closed, high speed is kneaded 10-40min；
S203 adjusts strength kneading machine exhaust valve, and the catalyst fines of 60-130 parts by weight are added in the operation of kneading machine low speed
The ammonium hydroxide that concentration with 3-6 parts by weight is 15-25%, closes strength kneading machine exhaust valve, and high speed is kneaded the mud into kneading machine
Material temperature degree reaches 90-95 DEG C, fully opens the gas generated when exhaust valve discharge is kneaded, continues to be kneaded 30-60min, to pug
Moisture content be 25-29%, end step S203；
S204 be added the glass fibre of 9-27 parts by weight, the wood pulp of 2-7 parts by weight, 2-7 parts by weight RP-CHOP cracking resistance
The deionized water of fiber and 80-128 parts by weight, closes strength kneading machine exhaust valve, and high speed is kneaded 10-40min；
S205 adjusts strength kneading machine exhaust valve, and the organic adhesive of 3-14 parts by weight is added in the operation of kneading machine low-speed reverse
Strength kneading machine exhaust valve is closed in agent, and high-speed reverse is kneaded 10-30min；
S206 adjusts strength kneading machine exhaust valve, and the organic adhesive of 3-14 parts by weight is added in the operation of kneading machine low-speed reverse
The concentration of agent and 2-8 parts by weight is the ammonium hydroxide of 15-25%, closes strength kneading machine exhaust valve, and high-speed reverse is kneaded 15-45min；
S207 open strength kneading machine exhaust valve, with the ammonium hydroxide of deionized water and 15-20% adjust pug plasticity and
Moisture content, when the plasticity of pug is 22-26, and moisture content is 28-31%, mixing terminates；
S208 by be kneaded terminate pug be transferred in kneader, carry out it is wet pinch mixing 1-3h and shaping of catalyst process after
Obtain catalyst；
Wherein, the adjusting strength kneading machine exhaust valve, strength kneading machine exhaust valve opening degree are 10-15%, described mixed
The operation of mill low speed, the revolving speed of mixing machine rotor are 250-450rpm；The kneading machine high-speed cruising, the revolving speed of mixing machine rotor
For 650-850rpm.
Further, the S1 catalyst fines preparation process specifically includes the following steps:
Deionized water is added in a kettle and is heated to 40-80 DEG C by S101, and oxalic acid is added or citric acid is stirred to complete
Dissolution, sequentially adds V2O5、WO3Or MoO3Active component presoma, or add rare earth oxide active component presoma；
P is added2O5Auxiliary agent presoma, or add SO3Auxiliary agent presoma stirs 10-60min at 40-80 DEG C, obtains active component
Maceration extract, wherein the V2O5The molar ratio of presoma and oxalic acid or citric acid is 1:(0.8-4)；
Powdered carrier is added to activity component impregnation liquid obtained in step S101 in S102, stirs at 40-80 DEG C
Sticky shape slurries are obtained after 10-60min, which is obtained into catalyst slurry, wherein
The mass ratio for the deionized water being added in the carrier and S101 is 1:(0.9-1.4)；
S103 to catalyst slurry obtained in step S102 in 200-300 DEG C of dry 2-12h, in 300-600 after being crushed
DEG C roasting 2-8h, naturally cool to room temperature, be crushed to 100-300 mesh and obtain catalyst fines.
Further, in the S208 shaping of catalyst process specifically includes the following steps:
1) filter, is pre- crowded: the filtering is that the pug for obtaining step S208 is placed in twin-screw filter, utilizes mud extraction
The filtering of mouth stainless steel mesh, combing pug, remove impurity in pug；It is described pre- crowded, filtered pug is subjected to pre- extrusion forming,
Obtain rectangular clod；
2) aging: by step 1) it is pre- squeeze after clod under the conditions of 25-40 DEG C and humidity are 45-90% aging 12-
72h；
3) extrusion molding: pug forms to obtain honeycombed catalyst green body through Powerful extruder after will be aging in step 2)；
4) dry: the moisture removal in step 3) in honeycombed catalyst green body is required, the drying with reaching roasting
Including level-one drying and secondary drying, the level-one is dry to be increased to 60-65 DEG C by room temperature, and humidity is reduced to by 90-95%
28-35%；The secondary drying, the dry 24-72h in 45-60 DEG C of hot-air；
5) roast, cut: the roasting is that the catalyst green body in step 4) after secondary drying is placed in mesh-belt kiln,
200-650 DEG C of roasting 20-40h, obtains honeycomb low-temperature SCR catalyst, and the cutting is using double end band saw to catalyst end
Face is cut, and the irregular part in both ends is cut；
6) front end is hardened: cutting rear catalyst end face in step 5) is placed in hardening bath and impregnates 2-10min, impregnating depth
For 20-40mm.
Further, the powdered aggregate includes quartz sand, glass powder with low melting point, Al2O3, silicon powder, white carbon black, gas phase
SiO2, clay, montmorillonite, attapulgite, aluminum phosphate, aluminium dihydrogen phosphate, boehmite, kaolin, sepiolite, in bentonite
It is one or more, the powdered aggregate relative to catalyst fines additional amount be 3-20wt%.
Further, the organic binder includes methylcellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, fibre
Tie up one of plain ammonium, sodium cellulosate, polyacrylamide, polyvinyl alcohol, polyethylene glycol oxide or a variety of, the organic binder phase
Additional amount for catalyst fines is 0.5-10wt%,
Further, the hardening bath is the aqueous solution of hardening medium, and the hardening medium is Al2(SO4)3Or AlPO4Or Al
(H2PO4)3, the mass concentration of the hardening medium is 10-50wt%.
Beneficial effect using above-mentioned further scheme is:
(1) catalyst is in low-temperature range denitration efficiency with higher, be suitable for non-electricity industry boiler, kiln metallurgy,
The industries such as chemical industry, coking and petrochemical industry discharge the NOx emission control of low-temperature flue gas or technology waste gas, and catalyst is at 170-180 DEG C
Denitration efficiency be maintained at 90% or more.
(2) catalyst is able to maintain high removal efficiency in wider temperature range to NOx, can adapt to flue-gas temperature
Wide fluctuations, advantageously reduce the operating cost and energy consumption of denitrating technique.
(3) the resulting catalyst of present invention mechanical strength with higher and wear resistance, catalyst longitudinal direction pressure resistance
Degree is greater than 2.4MPa, and hardening end ash cutting rate is less than 0.08%/Kg.Reduce flying dust washing away, wear and carving to catalyst
Erosion, extends the service life of catalyst.
(4) catalyst of the invention, raw material is simple and easy to get, and preparation process is simple and easy to control, easily realizes that industrialization is continuous raw
It produces.
Specific embodiment
Principles and features of the present invention are described below in conjunction with specific embodiment, example is served only for explaining this hair
It is bright, it is not intended to limit the scope of the present invention.
Honeycomb low-temperature denitration of flue gas catalyst, including carrier, active component and auxiliary agent, the active component and auxiliary agent point
It is not supported on carrier, the carrier is TiO2Or TiO2Composite oxides, the content of the carrier in the catalyst be 70~
90wt%；The active component is V2O5And WO3Or MoO3, load capacity of the active component on carrier are as follows: V2O5For 0.3~
6wt%, WO3For 1.0~15wt% or MoO3For 1.0~15wt%, the auxiliary agent is P2O5, the auxiliary agent bearing on carrier
Carrying capacity are as follows: P2O5For 0.1-3wt%.
The active component further includes rare earth oxide, load capacity of the rare earth oxide on carrier be 0~
20wt%, the rare earth oxide are one of oxide of La, Ce, Pr, Nd, Zr, Y or a variety of.
The auxiliary agent further includes SO3, SO3Load capacity on carrier is 0-3wt%.
For the active component by active component precursor preparation, the active component presoma is V2O5、 WO3、MoO3And
One of the corresponding oxide of rare earth oxide, inorganic salts or organic salt are a variety of；The auxiliary agent by auxiliary agent precursor preparation,
The auxiliary agent presoma is P2O5、SO3One of corresponding oxide, inorganic salts or organic salt are a variety of.
A kind of preparation method of honeycomb low-temperature denitration of flue gas catalyst, includes the following steps:
The preparation of S1 catalyst fines:
Deionized water is added in a kettle and is heated to 40-80 DEG C by S101, and oxalic acid is added or citric acid is stirred to complete
After dissolution, active component presoma and auxiliary agent presoma is added, is sufficiently stirred to obtain activity component impregnation liquid, wherein the V2O5
The molar ratio of presoma and oxalic acid or citric acid is 1:(0.8-4)；Preferably, deionized water is added in a kettle and adds by S101
Heat arrives 40-80 DEG C, and oxalic acid is added or citric acid is stirred to being completely dissolved, sequentially adds V2O5、WO3Or MoO3Active component forerunner
Body, or add rare earth oxide active component presoma；P is added2O5Auxiliary agent presoma, or add SO3Auxiliary agent forerunner
Body stirs 10-60min at 40-80 DEG C, obtains activity component impregnation liquid, wherein the V2O5Presoma and oxalic acid or citric acid
Molar ratio be 1:(0.8-4)；
Powdered carrier is added to activity component impregnation liquid obtained in step S101 in S102, is sufficiently stirred to obtain sticky
The sticky shape slurries are handled to obtain catalyst slurry, wherein be added in the carrier and S101 by shape slurries by ultrasonic disperse
Deionized water mass ratio be 1:(0.9-1.4)；Preferably, S102 is to activity component impregnation liquid obtained in step S101
Powdered carrier is added, obtains sticky shape slurries after stirring 10-60min at 40-80 DEG C, by the sticky shape slurries ultrasound point
It dissipates processing 1-3h and obtains catalyst slurry, wherein the mass ratio for the deionized water being added in the carrier and S101 is 1:
(0.9-1.4)；
Catalyst slurry obtained in step S102 is dried S103, is roasted after broken, naturally cools to room
Temperature, crushing obtain catalyst fines；Preferably, S103 is to catalyst slurry obtained in step S102 in 200-300 DEG C of drying
2-12h naturally cools to room temperature, is crushed to 100-300 mesh and obtains catalyst fines in 300-600 DEG C of roasting 2-8h after being crushed.
The processing of S2 pug and shaping of catalyst:
The catalyst fines that S201 obtains S103 arrange spare, adjusting strength kneading machine exhaust valve, and are kneaded to strength
The catalyst fines and powdered aggregate of 225-315 parts by weight are added in machine exhaust valve, the powdered aggregate is relative to catalysis
The additional amount of agent powder is 3-20wt%；Then the stearic acid of 2-9 parts by weight, the lactic acid or oleic acid, 1-10 of 2-9 parts by weight is added
The concentration of the glycerol of parts by weight, deionized water and 24-32 parts by weight that 150-210 parts by weight are added is the ammonium hydroxide of 15-25%, is closed
Strength kneading machine exhaust valve is closed, high speed is kneaded 30-80min；
S202 adjusts strength kneading machine exhaust valve, and the catalyst fines of 67-105 parts by weight are added in the operation of kneading machine low speed
With 10-35 weight deionized water, strength kneading machine exhaust valve is closed, high speed is kneaded 10-40min；
S203 adjusts strength kneading machine exhaust valve, and the catalyst fines of 60-130 parts by weight are added in the operation of kneading machine low speed
The ammonium hydroxide that concentration with 3-6 parts by weight is 15-25%, closes strength kneading machine exhaust valve, and high speed is kneaded the mud into kneading machine
Material temperature degree reaches 90-95 DEG C, fully opens the gas generated when exhaust valve discharge is kneaded, continues to be kneaded 30-60min, to pug
Moisture content be 25-29%, end step S203；
S204 be added the glass fibre of 9-27 parts by weight, the wood pulp of 2-7 parts by weight, 2-7 parts by weight RP-CHOP cracking resistance
The deionized water of fiber and 80-128 parts by weight, closes strength kneading machine exhaust valve, and high speed is kneaded 10-40min；
S205 adjusts strength kneading machine exhaust valve, and the organic adhesive of 3-14 parts by weight is added in the operation of kneading machine low-speed reverse
Strength kneading machine exhaust valve is closed in agent, and high-speed reverse is kneaded 10-30min；
S206 adjusts strength kneading machine exhaust valve, and the organic adhesive of 3-14 parts by weight is added in the operation of kneading machine low-speed reverse
The concentration of agent and 2-8 parts by weight is the ammonium hydroxide of 15-25%, closes strength kneading machine exhaust valve, and high-speed reverse is kneaded 15-45min；
S207 open strength kneading machine exhaust valve, with the ammonium hydroxide of deionized water and 15-20% adjust pug plasticity and
Moisture content, when the plasticity of pug is 22-26, and moisture content is 28-31%, mixing terminates；
S208 by be kneaded terminate pug be transferred in kneader, carry out it is wet pinch mixing 1-3h and shaping of catalyst process after
Obtain catalyst；
Wherein, the adjusting strength kneading machine exhaust valve, strength kneading machine exhaust valve opening degree are 10-15%, described mixed
The operation of mill low speed, the revolving speed of mixing machine rotor are 250-450rpm；The kneading machine high-speed cruising, the revolving speed of mixing machine rotor
For 650-850rpm.
Preferably, in the S208 shaping of catalyst process specifically includes the following steps: 1) filtering, it is pre- squeeze: the filtering
It is that the pug for obtaining step S208 is placed in twin-screw filter, using the filtering of mud mouth stainless steel mesh, combing pug, goes
Except impurity in pug；It is described pre- crowded, filtered pug is subjected to pre- extrusion forming, obtains rectangular clod；
2) aging: by step 1) it is pre- squeeze after clod under the conditions of 25-40 DEG C and humidity are 45-90% aging 12-
72h；
3) extrusion molding: pug forms to obtain honeycombed catalyst green body through Powerful extruder after will be aging in step 2)；
4) dry: the moisture removal in step 3) in honeycombed catalyst green body is required, the drying with reaching roasting
Including level-one drying and secondary drying, the level-one is dry to be increased to 60-65 DEG C by room temperature, and humidity is reduced to by 90-95%
28-35%；The secondary drying, the dry 24-72h in 45-60 DEG C of hot-air；
5) roast, cut: the roasting is that the catalyst green body in step 4) after secondary drying is placed in mesh-belt kiln,
200-650 DEG C of roasting 20-40h, obtains honeycomb low-temperature SCR catalyst, and the cutting is using double end band saw to catalyst end
Face is cut, and the irregular part in both ends is cut；
6) front end is hardened: cutting rear catalyst end face in step 5) is placed in hardening bath and impregnates 2-10min, impregnating depth
For 20-40mm.
The powdered aggregate includes quartz sand, glass powder with low melting point, Al2O3, silicon powder, white carbon black, gas phase SiO2, it is glutinous
One of soil, montmorillonite, attapulgite, aluminum phosphate, aluminium dihydrogen phosphate, boehmite, kaolin, sepiolite, bentonite
Or it is a variety of, the powdered aggregate is 3-20wt% relative to the additional amount of catalyst fines.
The organic binder include methylcellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, ammonium cellulose,
One of sodium cellulosate, polyacrylamide, polyvinyl alcohol, polyethylene glycol oxide are a variety of, and the organic binder is relative to urging
The additional amount of agent powder is 0.5-10wt%,
The hardening bath is the aqueous solution of hardening medium, and the hardening medium is Al2(SO4)3Or AlPO4Or Al
(H2PO4)3, the mass concentration of the hardening medium is 10-50wt%.
The powdered aggregate, organic bond, hardening bath are what shaping of catalyst process needed.
The present invention is further detailed below by way of specific embodiment:
Embodiment 1
Step in all embodiments is corresponding with step in S1 and S2, and for convenience of describing, step numbers are changed.
1) prepared by catalyst fines
Step 1,750 parts by weight of deionized water are added in a kettle and are heated to 50-55 DEG C, addition 95 parts by weight grass
Acid stirring is slowly added to 23 parts by weight ammonium metavanadates (10-30min is added) to being completely dissolved, and after stirring 20-30min, is added
44.5 parts by weight ammonium molybdates, 8.5 parts by weight of phosphoric acid, three ammonium and 126 parts by weight of cerium nitrate continue stirring 30min at 50 DEG C and obtain
To activity component impregnation solution,
Step 2,600 parts by weight TiO are added2Powder, 45 DEG C of stirring 20min obtain sticky shape slurries, stirring, ultrasonic disperse
1.5h
Step 3, natural in 450 DEG C of roasting 3.5h after being crushed by catalyst slurry in reaction kettle in 250 DEG C of dry 3.0h
200 mesh are crushed to after being cooled to room temperature.
Through catalyst fines prepared by step 1-3, active component and auxiliary agent load capacity are as follows: V2O5For 3wt%, MoO3For
6wt%, CeO2For 8wt%, P2O5For 0.5wt%；
2) pug processing and shaping of catalyst
Step 1, adjust strength kneading machine exhaust valve, by 280 parts by weight 1) in prepare catalyst fines, 6.7 parts by weight
Quartz sand, 4.5 parts by weight glass powder with low melting point are added in kneading machine, and 4.5 parts by weight stearic acid, 4.5 parts by weight oil are added
The ammonium hydroxide of acid, 5.4 parts by weight of glycerin, 188.5 parts by weight of deionized water and 32 parts by weight 15% closes the exhaust of strength kneading machine
Valve, high speed are kneaded 40min；
Step 2, adjust strength kneading machine exhaust valve, kneading machine low speed operation, be added 77 parts by weight 1) in prepare catalysis
The deionized water of agent powder and 16.5 parts by weight, closes exhaust valve, and high speed is kneaded 25min；
Step 3, adjust strength kneading machine exhaust valve, kneading machine low speed operation, be added 93 parts by weight 1) in prepare catalysis
The ammonium hydroxide of agent powder and 6 parts by weight 15%, closes exhaust valve, and high speed is kneaded pug temperature into kneading machine and reaches 95 DEG C, complete
The gas that the generates when discharge of full open exhaust valve is kneaded, continues to be kneaded 35min, pug moisture content 28.0%, end step 3,
Step 4, be added 13.5 parts by weight of glass fiber, 3.6 parts by weight wood pulps, 3.2 parts by weight RP-CHOP fibers and
85.5 parts by weight of deionized water close exhaust valve, and high speed is kneaded 15min,
Step 5, strength kneading machine exhaust valve is adjusted, 3.5 parts by weight hydroxy propyl celluloses are added in the operation of kneading machine low-speed reverse
Element, the pure and mild 1.9 parts by weight polyethylene oxide of 3.5 weight account polyethylenes, close exhaust valve, and high-speed reverse is kneaded 10min；
Step 6, the operation of strength kneading machine exhaust valve kneading machine low-speed reverse is adjusted, 2.3 parts by weight hydroxy propyl celluloses are added
Element, 2.3 weight account polyethylene alcohol, 1.3 polyethylene oxide and 3 parts by weight 15% ammonium hydroxide, close exhaust valve, high-speed reverse be kneaded
25min；
Step 7, strength kneading machine exhaust valve is fully opened, adjusts containing for pug with the ammonium hydroxide of deionized water and 15-20%
Water rate and plasticity, the moisture content of pug are 29.2%, and plasticity 24.7, mixing terminates；
Step 8, the pug terminated will be kneaded to be transferred in kneader, and will carry out wet pinch and mixes 1.5h and shaping of catalyst process
After obtain catalyst；
In step 1- step 7,
Strength kneading machine exhaust valve is adjusted, the exhaust valve opening degree of strength kneading machine is 10-15%,
The operation of kneading machine low speed, the revolving speed of rotor is 300rpm when kneading machine is run,
Kneading machine high-speed cruising, the revolving speed of rotor is 750rpm when kneading machine is run,
3) pre- squeeze is filtered
Pug obtained by kneading process will be kneaded to be placed in twin-screw filter, utilize the filtering of mud mouth stainless steel mesh, comb
Pug is managed, impurity in pug is removed；Pug obtains rectangular clod through pre- extrusion forming after filtering；
4) aging
It is aging 12-72h under the conditions of 45-90% that pre- crowded rear pug, which is placed in 25-40 DEG C and humidity,；
5) extrusion molding
Pug forms to obtain honeycombed catalyst green body, catalyst appearance length and internal holes through Powerful extruder after aging
Road size is determined according to engine request；
6) dry
Catalyst green body is dried in hothouse, removes the moisture in green body, is required with reaching roasting；Drying includes
Level-one is dry and secondary drying, level-one drying are increased to 65 DEG C by room temperature, and humidity is reduced to 35% by 95%；Secondary drying,
Dry 24-72h in 45-60 DEG C of hot-air,
7) roasting cutting
It roasts, the catalyst green body after secondary drying is placed in mesh-belt kiln, in 200-650 DEG C of roasting 20-40h, obtains honeycomb
Shape low-temperature SCR catalyst,
Cutting, cuts catalyst end face using double end band saw, cuts the irregular part in both ends,
8) front end is hardened
Cutting rear catalyst end face is placed in the AlPO of 35wt%45min, impregnating depth 20-40mm are impregnated in solution.
Catalyst prepared by embodiment 1 under the conditions of test case, denitration efficiency at 170 DEG C up to 91.7%, catalyst
Longitudinal compression strength is 2.48MPa, and lateral compression strength is 0.84MPa, and hardening end wear strength is 0.073%/Kg.
Embodiment 2
1) prepared by catalyst fines
Step 1,750 parts by weight of deionized water are added in a kettle and are heated to 50-55 DEG C, addition 95 parts by weight grass
Acid stirring is slowly added to 23 parts by weight ammonium metavanadates (10-30min is added) and stirs 20-30min to being completely dissolved, and is added
32.8 parts by weight ammonium tungstates, 8.5 parts by weight of phosphoric acid, three ammonium, 2.5 parts sulfuric acid ammonium and 126 parts by weight of cerium nitrate, at 50 DEG C after
Continuous stirring 30min obtains activity component impregnation solution；
Step 2,600 parts by weight TiO are added2Powder, 45 DEG C of stirring 20min obtain sticky shape slurries, then stirring, ultrasound
Disperse 1.5h；
Step 3, natural in 450 DEG C of roasting 3.5h after being crushed by catalyst slurry in reaction kettle in 250 DEG C of dry 3.0h
200 mesh are crushed to after being cooled to room temperature.
Through catalyst fines prepared by step 1-3, active component and auxiliary agent load capacity are as follows: V2O5For 3wt%, WO3For
6wt%, CeO2For 8wt%, P2O5For 0.5wt%, SO3For 0.25wt%；
2) it is kneaded and mediates
Step 1, adjust strength kneading machine exhaust valve, be added 300 parts by weight 1) in prepare catalyst fines, 9 parts by weight
Quartz sand be added in kneading machine, be added 3.6 parts by weight stearic acid, 4.5 parts by weight lactic acid, 4.5 parts by weight of glycerin, 174 weights
The ammonium hydroxide of part deionized water and 30 parts by weight 15% is measured, exhaust valve is closed, high speed is kneaded 40min；
Step 2, adjust strength kneading machine exhaust valve, kneading machine low speed operation, be added 75 parts by weight 1) in prepare catalysis
Agent powder and 20 parts by weight of deionized water, close exhaust valve, and high speed is kneaded 25min；
Step 3, adjust strength kneading machine exhaust valve, kneading machine low speed operation, be added 75 parts by weight 1) in prepare catalysis
The ammonium hydroxide of agent powder and 6 parts by weight 15%, closes exhaust valve, and high speed is kneaded pug temperature into kneading machine and reaches 95 DEG C, complete
The gas that the generates when discharge of full open exhaust valve is kneaded, continues to be kneaded 35min, pug moisture content 27.5%, end step 3,
Step 4,13.5 parts by weight of glass fiber, 3.2 parts by weight wood pulps, the 3.6 anti-dimensions of parts by weight RP-CHOP are added
With 96 parts by weight of deionized water, strength kneading machine exhaust valve is closed, high speed is kneaded 15min；
Step 5, strength kneading machine exhaust valve is adjusted, 2.3 parts by weight hydroxy propyl celluloses are added in the operation of kneading machine low-speed reverse
Element, the pure and mild 1.8 parts by weight polyethylene oxide of 2.3 weight account polyethylenes, close strength kneading machine exhaust valve, and high-speed reverse is kneaded
10min；
Step 6, strength kneading machine exhaust valve is adjusted, kneading machine low-speed reverse is run, 2.3 parts by weight hydroxypropyl celluloses,
The ammonium hydroxide of 2.3 weight account polyethylene alcohol, 1.8 parts by weight polyethylene oxide and 4 parts by weight 15% closes the exhaust of strength kneading machine
Valve, high-speed reverse are kneaded 25min,
Step 7, strength kneading machine exhaust valve is fully opened, adjusts containing for pug with the ammonium hydroxide of deionized water and 15-20%
Water rate and plasticity, the moisture content of pug are 28.9%, and plasticity 25.5, mixing terminates；
Step 8, by be kneaded terminate pug be transferred in kneader, carry out it is wet pinch mixing 2h and shaping of catalyst process after
Obtain catalyst；
In step 1- step 7,
Strength kneading machine exhaust valve is adjusted, the exhaust valve opening degree of strength kneading machine is 10-15%,
The operation of kneading machine low speed, the revolving speed of rotor is 300rpm when kneading machine is run,
Kneading machine high-speed cruising, the revolving speed of rotor is 750rpm when kneading machine is run,
The shaping of catalyst of subsequent progress filters pre- crowded, aging, extrusion molding, drying, roasting cutting and front end hardening
Treatment process is the same as embodiment 1.
Catalyst prepared by embodiment 2 under the conditions of test case, denitration efficiency at 170 DEG C up to 90.8%, catalyst
Longitudinal compression strength is 2.52MPa, and lateral compression strength is 0.89MPa, and hardening end wear strength is 0.068%/Kg.
Embodiment 3
1) prepared by catalyst fines
Step 1,750 parts by weight of deionized water are added in a kettle and are heated to 50-55 DEG C, addition 95 parts by weight grass
Acid stirring is slowly added to 23 parts by weight ammonium metavanadates (10-30min is added) to being completely dissolved, and stirs 20-30min, is added 44.5
Three ammonium of parts by weight ammonium molybdate and 8.5 parts by weight of phosphoric acid continues stirring 30min at 50 DEG C and obtains activity component impregnation solution；
Step 2,600 parts by weight TiO are added2Powder, 45 DEG C of stirring 20min obtain sticky shape slurries, stirring, ultrasonic disperse
1.5h；
Step 3, catalyst slurry is naturally cold in 450 DEG C of roasting 3.5h after being crushed in 250 DEG C of dry 3.0h in reaction kettle
But to being crushed to 200 mesh after room temperature；
Through catalyst fines prepared by step 1-3, active component is born and auxiliary agent load capacity are as follows: V2O5For 3wt%, MoO3
For 6wt%, P2O5For 0.5wt%；
2) it is kneaded and mediates
Step 1, adjust strength kneading machine exhaust valve, by 248 parts by weight 1) in prepare catalyst fines and 9 parts by weight gas
Aerosil is added in kneading machine, and 3.6 parts by weight stearic acid, 4.5 parts by weight oleic acid, 5.0 parts by weight of glycerin, 174 are added
The ammonium hydroxide of parts by weight of deionized water and 27.5 parts by weight 15%, closes exhaust valve, and high speed is kneaded 40min；
Step 2, adjust strength kneading machine exhaust valve, kneading machine low speed operation, be added 90 parts by weight 1) in prepare catalysis
The deionized water of agent powder and 17.5 parts by weight, closes strength kneading machine exhaust valve, and high speed is kneaded 25min；
Step 3, adjust strength kneading machine exhaust valve, kneading machine low speed operation, be added 112.5 parts by weight 1) in prepare
The ammonium hydroxide of catalyst fines and 7.5 parts by weight 15%, closes strength kneading machine exhaust valve, and high speed is kneaded the pug into kneading machine
Temperature reaches 95 DEG C, fully opens the gas generated when exhaust valve discharge is kneaded, continues to be kneaded 35min, pug moisture content is26.9%, end step 3；
Step 4,13.5 parts by weight of glass fiber, 3.6 parts by weight wood pulps and 98.5 parts by weight of deionized water are added, close strong
Power kneading machine exhaust valve, high speed are kneaded 15min；
Step 5, strength kneading machine exhaust valve is adjusted, 2.7 parts by weight hydroxy propyl celluloses are added in the operation of kneading machine low-speed reverse
Element, 1.8 weight account polyethylene alcohol, 1.8 parts by weight RP-CHOP fibers and 1.8 parts by weight polyethylene oxide close strength kneading machine
Exhaust valve, high-speed reverse are kneaded 10min；
Step 6, strength kneading machine exhaust valve is adjusted, 2.7 parts by weight hydroxy propyl celluloses are added in the operation of kneading machine low-speed reverse
Element, 1.8 weight account polyethylene alcohol, 1.8 parts by weight RP-CHOP fibers and 1.8 parts by weight polyethylene oxide close strength kneading machine
Exhaust valve, high-speed reverse are kneaded 25min；
Step 7, strength kneading machine exhaust valve is fully opened, adjusts containing for pug with the ammonium hydroxide of deionized water and 15-20%
Water rate and plasticity, the moisture content of pug are 29.4%, and plasticity 24.7, mixing terminates；
Step 8, the pug terminated will be kneaded to be transferred in kneader, and will carry out wet pinch and mixes 1.5h and shaping of catalyst process
After obtain catalyst；
Strength kneading machine exhaust valve is adjusted, the exhaust valve opening degree of strength kneading machine is 10-15%,
The operation of kneading machine low speed, the revolving speed of rotor is 300rpm when kneading machine is run,
Kneading machine high-speed cruising, the revolving speed of rotor is 750rpm when kneading machine is run,
Subsequent carry out shaping of catalyst filters at pre- crowded, aging, extrusion molding, drying, roasting cutting and front end hardening
Reason process is the same as embodiment 1.
Catalyst prepared by embodiment 3 under the conditions of test case, denitration efficiency at 170 DEG C up to 92.5%, catalyst
Longitudinal compression strength is 2.50MPa, and lateral compression strength is 0.85MPa, and hardening end wear strength is 0.065%/Kg.
Embodiment 4
1) prepared by catalyst fines
Step 1,750 parts by weight of deionized water are added in a kettle and are heated to 50-55 DEG C, addition 79 parts by weight grass
Acid stirring is slowly added to 19.2 parts by weight ammonium metavanadates (10-30min is added) to being completely dissolved, and stirs 20-30min, is added
44.5 parts by weight ammonium molybdates, 8.5 parts by weight of phosphoric acid, three ammonium and 126 parts by weight of cerium nitrate, continue to stir under the conditions of 50 DEG C
30min obtains activity component impregnation liquid；
Step 2,600 parts by weight TiO are added2Powder, 45 DEG C of stirring 20min obtain sticky shape slurries, stirring, ultrasonic disperse
1.5h；
Step 3, natural in 450 DEG C of roasting 3.5h after being crushed by catalyst slurry in reaction kettle in 250 DEG C of dry 3.0h
200 mesh are crushed to after being cooled to room temperature；
The catalyst fines prepared through step 1-3, active component is born and auxiliary agent load capacity are as follows: V2O5For 2.5wt%, MoO3
For 6wt%, CeO2For 8wt%, P2O5For 0.5wt%；
2) it is kneaded and mediates
Step 1, adjust strength kneading machine exhaust valve, by 270 parts by weight 1) in prepare catalyst fines, 6.8 parts by weight
Fumed silica, 20 parts by weight of activated aluminium oxide are added in kneading machine, and 4.7 parts by weight stearic acid, 4.7 parts by weight are added
Lactic acid, 5.6 parts by weight of glycerin, 180 parts by weight of deionized water and 28 parts by weight 15% ammonium hydroxide, close strength kneading machine exhaust
Valve, high speed are kneaded 40min；
Step 2, adjust strength kneading machine exhaust valve, kneading machine low speed operation, be added 81 parts by weight 1) in prepare catalysis
Agent powder and 18 parts by weight of deionized water, close strength kneading machine exhaust valve, and high speed is kneaded 25min；
Step 3, adjust strength kneading machine exhaust valve, kneading machine low speed operation, be added 99 parts by weight 1) in prepare catalysis
The ammonium hydroxide of agent powder and 5 parts by weight 15%, closes strength kneading machine exhaust valve, and the pug temperature that high speed is kneaded into kneading machine reaches
To 95 DEG C, the gas generated when exhaust valve discharge is kneaded is fully opened, continues to be kneaded 35min, pug moisture content 26.2%, knot
Beam step 3；
Step 4,14 parts by weight of glass fiber, 3.7 parts by weight wood pulps, 3.7 parts by weight RP-CHOP fibers and 102 weights are added
Part deionized water is measured, strength kneading machine exhaust valve is closed, high speed is kneaded 15min；
Step 5, it adjusts strength mixed connection to run in air valve, 3.1 parts by weight hydroxy propyl celluloses are added in the operation of kneading machine low-speed reverse
Element, the pure and mild 2.0 parts by weight polyethylene oxide of 2.4 weight account polyethylenes, close strength kneading machine exhaust valve, and high-speed reverse is kneaded
10min；
Step 6, it adjusts strength mixed connection to run in air valve, 2.5 parts by weight hydroxy propyl celluloses are added in the operation of kneading machine low-speed reverse
Element, 2.3 weight account polyethylene alcohol, 1.7 polyethylene oxide and 7 parts by weight 15% ammonium hydroxide, close strength kneading machine exhaust valve, it is high
Fast reversed mixing 25min；
Step 7, strength kneading machine exhaust valve is fully opened, adjusts containing for pug with the ammonium hydroxide of deionized water and 15-20%
Water rate and plasticity, the moisture content of pug are 29.2%, and plasticity 23.8, mixing terminates；
Step 8, the pug terminated will be kneaded to be transferred in kneader, step 8, the pug terminated will be kneaded and be transferred to kneading
In machine, carry out it is wet pinch mixing 2.5h and shaping of catalyst process after obtain catalyst；
In step 1- step 7,
Strength kneading machine exhaust valve is adjusted, the exhaust valve opening degree of strength kneading machine is 10-15%,
The operation of kneading machine low speed, the revolving speed of rotor is 300rpm, kneading machine high-speed cruising, kneading machine fortune when kneading machine is run
The revolving speed of rotor is 750rpm when row,
Subsequent carry out shaping of catalyst filters at pre- crowded, aging, extrusion molding, drying, roasting cutting and front end hardening
Reason process is the same as embodiment 1；
Catalyst prepared by embodiment 4 under the conditions of test case, denitration efficiency at 180 DEG C up to 95.7%, catalyst
Longitudinal compression strength is 2.47MPa, and lateral compression strength is 0.85MPa, and hardening end wear strength is 0.073%/Kg.
Embodiment 5
1) prepared by catalyst fines
Step 1,750 parts by weight of deionized water are added in a kettle and are heated to 50-55 DEG C, addition 95 parts by weight grass
Acid stirring is slowly added to 23 parts by weight ammonium metavanadates (10-30min is added) to being completely dissolved, and stirs 20-30min, is added 44.5
Three ammonium of parts by weight ammonium molybdate and 8.5 parts by weight of phosphoric acid continues stirring 30min at 50 DEG C and obtains activity component impregnation liquid；
Step 2,582 parts by weight TiO are added2Powder and 18 parts by weight fumed silicas, 45 DEG C of stirring 20min are sticked
Thick shape slurries, stirring, ultrasonic disperse 1.5h；
Step 3, catalyst slurry is naturally cold in 450 DEG C of roasting 3.5h after being crushed in 250 DEG C of dry 3.0h in reaction kettle
But to being crushed to 200 mesh after room temperature；
Through catalyst fines prepared by step 1-3, active component is born and auxiliary agent load capacity are as follows: V2O5For 3wt%, MoO3
For 6wt%, P2O5For 0.5wt%；SiO2For 3wt%；
2) it is kneaded and mediates
Step 1, adjust strength kneading machine exhaust valve, by 261 parts by weight 1) in prepare catalyst fines be added to mixing
In machine, 4.5 parts by weight stearic acid, 4.5 parts by weight oleic acid, 5.4 parts by weight of glycerin, 180 parts by weight of deionized water and 28 weights are added
The ammonium hydroxide of part 15% is measured, exhaust valve is closed, high speed is kneaded 40min；
Step 2, adjust strength kneading machine exhaust valve, kneading machine low speed operation, be added 81 parts by weight 1) in prepare catalysis
The deionized water of agent powder and 20 parts by weight, closes strength kneading machine exhaust valve, and high speed is kneaded 25min；
Step 3, adjust strength kneading machine exhaust valve, kneading machine low speed operation, be added 108 parts by weight 1) in prepare urge
The ammonium hydroxide of agent powder and 6.2 parts by weight 15%, closes strength kneading machine exhaust valve, and high speed is kneaded the pug temperature into kneading machine
Degree reaches 95 DEG C, fully opens the gas generated when exhaust valve discharge is kneaded, continues to be kneaded 35min, pug moisture content is
27.8%, end step 3；
Step 4,15.8 parts by weight of glass fiber, 3.6 parts by weight wood pulps, 3.2 parts by weight RP-CHOP fibers and 90 are added
Parts by weight of deionized water, closes strength kneading machine exhaust valve, and high speed is kneaded 15min；
Step 5, strength kneading machine exhaust valve is adjusted, 2.7 parts by weight hydroxy propyl celluloses are added in the operation of kneading machine low-speed reverse
Element, the pure and mild 1.6 parts by weight polyethylene oxide of 2.3 weight account polyethylenes, close strength kneading machine exhaust valve, and high-speed reverse is kneaded
10min；
Step 6, strength kneading machine exhaust valve is adjusted, 2.7 parts by weight hydroxy propyl celluloses are added in the operation of kneading machine low-speed reverse
Element, the pure and mild 1.6 parts by weight polyethylene oxide of 2.3 weight account polyethylenes, close strength kneading machine exhaust valve, and high-speed reverse is kneaded
25min；
Step 7, strength kneading machine exhaust valve is fully opened, adjusts containing for pug with the ammonium hydroxide of deionized water and 15-20%
Water rate and plasticity, the moisture content of pug are 28.9%, and plasticity 24.9, mixing terminates；
Step 8, the pug terminated will be kneaded to be transferred in kneader, and will carry out wet pinch and mixes 1.5h and shaping of catalyst process
After obtain catalyst；
In step 1- step 7,
Strength kneading machine exhaust valve is adjusted, the exhaust valve opening degree of strength kneading machine is 10-15%,
The operation of kneading machine low speed, the revolving speed of rotor is 300rpm when kneading machine is run,
Kneading machine high-speed cruising, the revolving speed of rotor is 750rpm when kneading machine is run,
Subsequent carry out shaping of catalyst filters at pre- crowded, aging, extrusion molding, drying, roasting cutting and front end hardening
Reason process is the same as embodiment 1；
Catalyst prepared by embodiment 5 under the conditions of test case, denitration efficiency at 180 DEG C up to 92.7%, catalyst
Longitudinal compression strength is 2.55MPa, and lateral compression strength is 0.91MPa, and hardening end wear strength is 0.062%/Kg.
Test case
The catalytic activity of catalyst, reaction gas are evaluated using simulated flue gas as reaction gas in fixed bed SCR reactor
Composition NOx is 1000mg/m3, SO2For 200mg/m3, O2It is 1.0, N for 6.0% (v/v), ammonia nitrogen molar ratio MR2As Balance Air,
Reaction velocity SV=4000h-1。
Embodiment of the present invention be only embodiment and preparation method are described in detail and are illustrated, but the present invention
Protection scope be not limited to operating process described in embodiment and step, cited raw material, raw material bound section take
The values such as value and technological parameter can realize the present invention, that is, do not mean that the present invention be necessarily dependent upon above-mentioned preparation process and
Step could be implemented.The technical staff in the field it will be clearly understood that any improvement in the present invention, to raw material selected by the present invention,
Material, the addition of size equivalence replacement and auxiliary element or change, the selection of specific embodiment etc., all fall within guarantor of the invention
It protects within range and the open scope.
Claims (7)
1. a kind of preparation method of honeycomb low-temperature denitration of flue gas catalyst, the catalyst include carrier, active component and help
Agent, the active component and auxiliary agent are supported on carrier respectively, and the carrier is TiO2Or TiO2Composite oxides, the load
The content of body in the catalyst is 70 ~ 90wt%；The active component is V2O5And WO3Or MoO3, the active component is in carrier
On load capacity are as follows: V2O5For 0.3 ~ 6wt%, WO3For 1.0 ~ 15wt% or MoO3For 1.0 ~ 15wt%, the auxiliary agent is P2O5With
SO3, wherein the SO3Load capacity on carrier is 0-3wt%, load capacity of the auxiliary agent on carrier are as follows: P2O5For 0.1-
3wt%；For the active component by active component precursor preparation, the active component presoma is V2O5And WO3Or MoO3Institute is right
One of oxide, inorganic salts or organic salt for answering are a variety of；The auxiliary agent is by auxiliary agent precursor preparation, the auxiliary agent forerunner
Body is P2O5、SO3One of corresponding oxide, inorganic salts or organic salt are a variety of；The preparation method packet of the catalyst
Include following steps:
The preparation of S1 catalyst fines:
Deionized water is added in a kettle and is heated to 40-80 DEG C by S101, is added oxalic acid or citric acid is stirred to being completely dissolved,
Sequentially add V2O5、WO3Or MoO3Active component presoma；P is added2O5Auxiliary agent presoma, or add SO3Auxiliary agent forerunner
Body stirs 10-60min at 40-80 DEG C, obtains activity component impregnation liquid, wherein the V2O5Presoma and oxalic acid or citric acid
Molar ratio be 1:(0.8-4)；
Powdered carrier is added to activity component impregnation liquid obtained in step S101 in S102, stirs 10- at 40-80 DEG C
Sticky shape slurries are obtained after 60min, which are obtained into catalyst slurry, wherein described
The mass ratio for the deionized water being added in carrier and S101 is 1:(0.9-1.4)；
S103 in 200-300 DEG C of dry 2-12h, roasts catalyst slurry obtained in step S102 at 300-600 DEG C after being crushed
2-8h is burnt, room temperature is naturally cooled to, is crushed to 100-300 mesh and obtains catalyst fines；
The processing of S2 pug and shaping of catalyst:
The catalyst fines that S201 obtains S103 arrange spare, adjusting strength kneading machine exhaust valve, and arrange to strength kneading machine
The catalyst fines and powdered aggregate of 225-315 parts by weight are added in air valve, the powdered aggregate is relative to catalyst powder
The additional amount at end is 3-20wt%；Then the stearic acid of 2-9 parts by weight, the lactic acid or oleic acid, 1-10 weight of 2-9 parts by weight is added
The concentration of the glycerol of part, deionized water and 24-32 parts by weight that 150-210 parts by weight are added is the ammonium hydroxide of 15-25%, is closed strong
Power kneading machine exhaust valve, high speed are kneaded 30-80min；
S202 adjusts strength kneading machine exhaust valve, and the catalyst fines and 10- of 67-105 parts by weight are added in the operation of kneading machine low speed
The deionized water of 35 parts by weight, closes strength kneading machine exhaust valve, and high speed is kneaded 10-40min；
S203 adjusts strength kneading machine exhaust valve, and the catalyst fines and 3-6 of 60-130 parts by weight are added in the operation of kneading machine low speed
The concentration of parts by weight is the ammonium hydroxide of 15-25%, closes strength kneading machine exhaust valve, and high speed is kneaded the pug temperature into kneading machine
Reach 90-95 DEG C, fully opens the gas generated when exhaust valve discharge is kneaded, continue to be kneaded 30-60min, to the aqueous of pug
Rate is 25-29%, end step S203；
S204 be added the glass fibre of 9-27 parts by weight, the wood pulp of 2-7 parts by weight, 2-7 parts by weight RP-CHOP anti-crack fiber and
The deionized water of 80-128 parts by weight, closes strength kneading machine exhaust valve, and high speed is kneaded 10-40min；
S205 adjusts strength kneading machine exhaust valve, the operation of kneading machine low-speed reverse, and the organic binder that 3-14 parts by weight are added closes
Strength kneading machine exhaust valve is closed, high-speed reverse is kneaded 10-30min；
S206 adjust strength kneading machine exhaust valve, kneading machine low-speed reverse operation, be added 3-14 parts by weight organic binder and
The concentration of 2-8 parts by weight is the ammonium hydroxide of 15-25%, closes strength kneading machine exhaust valve, and high-speed reverse is kneaded 15-45min；
S207 opens strength kneading machine exhaust valve, adjusts the plasticity of pug and aqueous with the ammonium hydroxide of deionized water and 15-20%
Rate, when the plasticity of pug is 22-26, and moisture content is 28-31%, mixing terminates；
S208 by be kneaded terminate pug be transferred in kneader, carry out it is wet pinch mixing 1-3h and shaping of catalyst process after obtain
Catalyst；
Wherein, the adjusting strength kneading machine exhaust valve, strength kneading machine exhaust valve opening degree are 10-15%, and the kneading machine is low
Speed operation, the revolving speed of mixing machine rotor are 250-450rpm；The kneading machine high-speed cruising, the revolving speed of mixing machine rotor are 650-
850rpm；
Shaping of catalyst process in the S208 specifically includes the following steps:
1) filter, is pre- crowded: the filtering is that the pug for obtaining step S208 is placed in twin-screw filter, not using mud mouth
Rust steel the screen to filtrate, combing pug, remove impurity in pug；It is described pre- crowded, filtered pug is subjected to pre- extrusion forming, is obtained
Rectangular clod；
2) aging: by step 1) it is pre- squeeze after clod under the conditions of 25-40 DEG C and humidity are 45-90% aging 12-72h；
3) extrusion molding: pug forms to obtain honeycombed catalyst green body through Powerful extruder after will be aging in step 2；
4) dry: the moisture removal in step 3) in honeycombed catalyst green body is required, the drying includes with reaching roasting
Level-one is dry and secondary drying, the level-one drying are increased to 60-65 DEG C by room temperature, and humidity is reduced to 28-35% by 90-95%；
The secondary drying, the dry 24-72h in 45-60 DEG C of hot-air；
5) roast, cut: the roasting is that the catalyst green body in step 4) after secondary drying is placed in mesh-belt kiln, in 200-
650 DEG C of roasting 20-40h, obtain honeycomb low-temperature SCR catalyst, the cutting be using double end band saw to catalyst end face into
Row cutting, cuts the irregular part in both ends；
6) front end is hardened: impregnating 2-10min for cutting rear catalyst end face in step 5) and being placed in hardening bath, impregnating depth is
20-40mm。
2. the preparation method of honeycomb low-temperature denitration of flue gas catalyst according to claim 1, which is characterized in that the activity
Component further includes rare earth oxide, and load capacity of the rare earth oxide on carrier is 0 ~ 20wt%, and the rare earth oxide is
One of oxide of La, Ce, Pr, Nd, Y is a variety of.
3. the preparation method of honeycomb low-temperature denitration of flue gas catalyst according to claim 1 or claim 2, which is characterized in that described
Powdered aggregate includes quartz sand, glass powder with low melting point, Al2O3, silicon powder, white carbon black, gas phase SiO2, clay, aluminum phosphate, phosphorus
One of acid dihydride aluminium and boehmite are a variety of, and the powdered aggregate is 3- relative to the additional amount of catalyst fines
20wt%。
4. the preparation method of honeycomb low-temperature denitration of flue gas catalyst according to claim 3, which is characterized in that the clay
Including one or more of montmorillonite, attapulgite, kaolin, sepiolite and bentonit.
5. the preparation method of honeycomb low-temperature denitration of flue gas catalyst according to claim 1 or claim 2, which is characterized in that described
Organic binder includes methylcellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, ammonium cellulose, sodium cellulosate, poly- third
One of acrylamide, polyvinyl alcohol, polyethylene glycol oxide are a variety of, addition of the organic binder relative to catalyst fines
Amount is 0.5-10wt%.
6. the preparation method of honeycomb low-temperature denitration of flue gas catalyst according to claim 1, which is characterized in that the hardening
Liquid is the aqueous solution of hardening medium, and the hardening medium is Al2(SO4)3Or AlPO4Or Al (H2PO4)3, the hardening medium
Mass concentration is 10-50wt%.
7. a kind of preparation method preparation by any one of claim 1 to the 6 honeycomb low-temperature denitration of flue gas catalyst
Honeycomb low-temperature denitration of flue gas catalyst.
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| CN106563439A (en) * | 2016-11-03 | 2017-04-19 | 新沂市中诺新材料科技有限公司 | La-modified La-V2O5/TiO2 desulfurization catalyst |
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| CN109603917B (en) * | 2018-11-29 | 2021-08-24 | 江苏龙源催化剂有限公司 | Preparation method of denitration catalyst mud material |
| CN109759051B (en) * | 2019-01-15 | 2021-10-22 | 昆明理工大学 | Preparation method of catalyst for modifying white carbon black by using Zr-Nd-O |
| CN110433837B (en) * | 2019-06-06 | 2022-04-12 | 大唐南京环保科技有限责任公司 | Denitration and demercuration catalyst for flue gas and preparation method thereof |
| CN110773211B (en) * | 2019-09-18 | 2022-09-13 | 上海瀚昱环保材料有限公司 | High-low temperature denitration catalyst and preparation method thereof |
| CN110743581B (en) * | 2019-11-04 | 2020-12-01 | 国家能源投资集团有限责任公司 | Hydrogenated TiO2Denitration catalyst and preparation method and application thereof |
| CN111672504B (en) * | 2020-06-03 | 2024-03-19 | 北京海顺德钛催化剂有限公司 | Catalyst for moving bed and/or fluidized bed denitration device and preparation method and application thereof |
| CN111686713A (en) * | 2020-06-22 | 2020-09-22 | 安徽省博广运环保科技有限公司 | Binder for improving mechanical strength of denitration catalyst and denitration catalyst |
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