CN106732546B - A kind of spherical shape SCR denitration and preparation method thereof - Google Patents
A kind of spherical shape SCR denitration and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 58
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 21
- 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 19
- 239000011812 mixed powder Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000007654 immersion Methods 0.000 claims description 10
- GEZAXHSNIQTPMM-UHFFFAOYSA-N dysprosium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Dy+3].[Dy+3] GEZAXHSNIQTPMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000001473 noxious effect Effects 0.000 abstract description 3
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 7
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- -1 easy blocking Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 231100000567 intoxicating Toxicity 0.000 description 1
- 230000002673 intoxicating effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to industrial catalyst technical field, it is related to a kind of spherical SCR denitration and preparation method thereof.Specifically, 1) preparation method of the invention is the following steps are included: prepare kernel using gama-alumina, nitric acid and binder；2) outer membrane is prepared using the mixed powder of metal oxide, nitric acid and binder；3) it dries and roasts for the first time；4) it impregnates vanadium oxalate aqueous solution and second dries and roast.The spherical shape SCR denitration as made from this method can not only overcome the blockage problem of honeycombed catalyst, extend the service life of catalyst, and catalysis reaction can be carried out with fluidized state, the noxious material for being covered in spherome surface active sites is fallen by the mutual collision between sphere, avoids catalyst poisoning phenomenon.In addition, can be applied again when the active coating (outer membrane) that the spherical shape SCR denitration is located at outer surface falls excessive, it is set to restore catalytic activity with minimum cost.
Description
Technical field
The invention belongs to industrial catalyst technical field, it is related to a kind of spherical SCR denitration and preparation method thereof.
Background technique
Currently, industrial general denitrating catalyst is mainly cordierite-base honeycombed catalyst, preparation process is powder
Body mixing one-pass molding.Since the technique is reshaping after being thoroughly mixed active component and powder, active component is equal
It is even to be distributed in channel surfaces and carrier inside, so that can not really play catalytic action in internal a large amount of active components, make
The function waste of Viability component, so that the whole denitration efficiency of catalyst declines.In addition, since the surface of catalyst is honeycomb
Shape, the dust contained in industrial waste gas can block duct after a period of time, cause the resistance of entire catalysis system to increase, is de-
Nitre efficiency declines so that scrapping, and the sulfur dioxide in flue gas can cover the active site of inner surfaces of pores, cause in sulphur
Poison makes catalyst deactivation.
Summary of the invention
For above situation, the present invention is intended to provide a kind of novel spherical SCR denitration and preparation method thereof, with
The problems such as overcoming low activity existing for existing Faveolate denitration catalyst, easy blocking, sulfur poisoning.
Specifically, the present invention adopts the following technical scheme:
On the one hand, the present invention provides a kind of preparation methods of spherical SCR denitration comprising following steps:
1) kernel is prepared:
Edge knurling machine is opened, sequentially adds gama-alumina (γ-Al thereto2O3), nitric acid (HNO3) and binder, make object
Material rolls in edge knurling machine, until forming the kernel that diameter is 10~20mm；Wherein:
Weight ratio between gama-alumina, nitric acid and binder is 1:0.05~0.15:0.1~0.3；
2) outer membrane is prepared:
In interior karyomorphism at later, being sequentially added into edge knurling machine comprising gama-alumina, titanium dioxide (TiO2), three oxidation
Tungsten (WO3) and Dysprosium trioxide (Dy2O3) mixed powder, nitric acid and binder, so that material is rolled and is wrapped up in edge knurling machine
Kernel obtained in step 1) closes edge knurling machine, is taken out globular material until forming the outer membrane with a thickness of 1~10mm；Its
In:
Weight ratio between mixed powder, nitric acid and binder is 1:0.05~0.15:0.1~0.3；
Weight ratio in mixed powder between gama-alumina, titanium dioxide, tungstic acid and Dysprosium trioxide be 10:5~
8:0.5~1.5:1~3；
3) it dries and roasts for the first time:
First globular material obtained in step 2) is placed in baking oven, is dried 6~10 hours in 80~150 DEG C, then by the
Globular material after first drying is placed in roaster, and is roasted according to following procedure: initial temperature is 100~120 DEG C,
Heating rate is 1~5 DEG C/min, and midway keeps the temperature 0.5 hour at 200 DEG C and 300 DEG C respectively, and target temperature is 450~500 DEG C,
5 hours are kept the temperature after reaching target temperature；After roasting, roaster and cooled to room temperature are closed, is taken out for the first time
Globular material after roasting；
4) it impregnates and second dries and roast:
Globular material after roasting for the first time obtained in step 3) is added to vanadium oxalate (V2(C2O4)5) in aqueous solution,
It impregnates 0.5~1 hour；After immersion, the globular material after immersion is pulled out, drains and is placed in baking oven, in 80~150 DEG C
Drying 6~10 hours, then the globular material after second of drying is placed in roaster, and is roasted according to following procedure:
Initial temperature is 100~120 DEG C, and heating rate is 1~5 DEG C/min, and target temperature is 450~500 DEG C, after reaching target temperature
Heat preservation 2 hours；After roasting, roaster and cooled to room temperature, the round after being taken out second of roasting are closed
Material, as spherical SCR denitration；Wherein:
The weight ratio between globular material and vanadium oxalate aqueous solution after roasting for the first time is 1:0.05~0.2；
The weight percent of vanadium oxalate aqueous solution mesoxalic acid vanadium is 15%~25%.
In the above preparation method, the binder is sodium carboxymethylcellulose (CMC-Na) or sodium metasilicate (Na2SiO3)。
Weight ratio in a preferred technical solution, between gama-alumina described in step 1), nitric acid and binder
For 1:0.1:0.2.
Weight ratio in a preferred technical solution, between mixed powder described in step 2), nitric acid and binder
Weight ratio for 1:0.1:0.2, in the mixed powder between gama-alumina, titanium dioxide, tungstic acid and Dysprosium trioxide
For 10:7:1:2.
In a preferred technical solution, mixed powder described in step 2) also includes the oxygen of at least one microelement
Compound, the microelement includes vanadium, dysprosium, molybdenum, manganese, lanthanum, yttrium, cerium and zirconium, and the sum of the weight of the microelement accounts for institute
State the 10%~15% of mixed powder total weight.
In a preferred technical solution, the temperature of drying described in step 3) is 120 DEG C, and the time is 8 hours.
In a preferred technical solution, roasting described in step 3) is carried out according to following procedure: initial temperature 100
DEG C, heating rate is 1 DEG C/min, and midway keeps the temperature 0.5 hour at 200 DEG C and 300 DEG C respectively, and target temperature is 450 DEG C, reaches mesh
5 hours are kept the temperature after mark temperature.
In a preferred technical solution, the globular material and vanadium oxalate after roasting for the first time described in step 4) are water-soluble
Weight ratio between liquid is 1:0.1, and the weight percent of the vanadium oxalate aqueous solution mesoxalic acid vanadium is 20%.
In a preferred technical solution, the time of immersion described in step 4) is 0.5 hour.
In a preferred technical solution, the temperature of drying described in step 4) is 120 DEG C, and the time is 8 hours.
In a preferred technical solution, roasting described in step 4) is carried out according to following procedure: initial temperature 100
DEG C, heating rate is 1 DEG C/min, and target temperature is 450 DEG C, keeps the temperature 2 hours after reaching target temperature.
On the other hand, it the present invention provides a kind of spherical SCR denitration, is made by above-mentioned preparation method.
Compared with prior art, the present invention by adopting the above technical scheme has the advantage that
(1) anti-clogging-spherical SCR denitration of the invention can overcome the blockage problem of honeycombed catalyst, prolong
The service life of long catalyst.
(2) anti-poisoning-of the invention spherical SCR denitration can be carried out in Benitration reactor with fluidized state
Catalysis reaction；Due to mutually colliding between sphere, the noxious material for being covered in spherome surface active sites can be made to fall, so again this
Exposure active sites, avoid catalyst poisoning phenomenon；
(3) Yi Xiufu-is fallen when the active coating (outer membrane) that spherical SCR denitration of the invention is located at outer surface
It when excessive, can be applied again, so that it is restored catalytic activity with minimum cost.
Detailed description of the invention
Fig. 1 is the denitrating flue gas effect picture of spherical SCR denitration in embodiment 1.
Fig. 2 is the denitrating flue gas effect picture of spherical SCR denitration in embodiment 2.
Fig. 3 is the denitrating flue gas effect picture of spherical SCR denitration in embodiment 3.
Specific embodiment
Further description will be made to the technical solution in the present invention by the drawings and specific embodiments below.This field
Technical staff is it will be appreciated that the following example is only used for the technical solution in the explanation and illustration present invention, and is understood not to limit
Protection scope of the present invention is made.Unless defined otherwise, material, reagent used in the following example, instrument etc.
It is obtained by routine business means.
Embodiment 1: the preparation of spherical SCR denitration.
Edge knurling machine is opened, sequentially adds gama-alumina (66g), nitric acid (6.6g) and sodium carboxymethylcellulose thereto
(13.2g) makes above-mentioned material fast scroll in edge knurling machine, gradually forms the kernel (82.5g) that diameter is 16mm.
Interior karyomorphism at later, sequentially added into edge knurling machine comprising gama-alumina (34g), titanium dioxide (23.8g),
The mixed powder of tungstic acid (3.4g) and Dysprosium trioxide (6.8g), nitric acid (6.8g) and sodium carboxymethylcellulose (13.6g),
So that above-mentioned material fast scroll and is wrapped up kernel in edge knurling machine, gradually form the outer membrane with a thickness of 2mm, closes edge knurling machine, from
Middle taking-up globular material (162.7g, diameter 20mm).
First globular material is placed in baking oven, is placed in roaster in 120 DEG C of drying 8h, then by the globular material after drying
In, and roasted according to following procedure: initial temperature is 100 DEG C, and heating rate is 1 DEG C/min, midway respectively at 200 DEG C and
300 DEG C of heat preservation 30min, target temperature are 450 DEG C, keep the temperature 5h after reaching target temperature.After roasting, roaster, furnace are closed
Interior temperature is cooled to room temperature naturally, the globular material (158.9g) after taking out roasting.
Globular material after roasting is added in the vanadium oxalate aqueous solution (15.9g) of 20wt%, 30min is impregnated.It impregnates
After, the globular material after immersion is pulled out with sieve, surface liquid is drained, is placed in baking oven, in 120 DEG C of drying 8h,
The globular material after drying is placed in roaster again, and is roasted according to following procedure: initial temperature is 100 DEG C, heating
Speed is 1 DEG C/min, and target temperature is 450 DEG C, keeps the temperature 2h after reaching target temperature.After roasting, roaster is closed, in furnace
Temperature is cooled to room temperature naturally, the globular material after taking out roasting, as spherical SCR denitration.
The radius of the spherical shape SCR denitration is 10mm, wherein outer membrane with a thickness of 2mm, the radius of kernel is 6mm；
Surface is in yellow green, and intensity is greater than 300N.
It is 300ppm, SO in NO concentration2Concentration is 500ppm, H2O content is 10%, O2Content is 4%, ammonia nitrogen molar ratio
1:1, air speed 6000h-1, reactor size is 45mm × 45mm × 220mm, and filling height carries out flue gas under conditions of being 20mm
Denitration, initiation temperature be 260 DEG C (as shown in Figure 1), show in the present embodiment it is obtained spherical shape SCR denitration have well
Catalytic activity.
Embodiment 2: the preparation of spherical SCR denitration.
Edge knurling machine is opened, gama-alumina (60g), nitric acid (6g) and sodium metasilicate (12g) is sequentially added thereto, makes above-mentioned
Material fast scroll in edge knurling machine gradually forms the kernel that diameter is 14mm.
In interior karyomorphism at later, being sequentially added into edge knurling machine comprising gama-alumina (40g), titanium dioxide (28g), three
The mixed powder of tungsten oxide (4g) and Dysprosium trioxide (8g) (wherein also includes a small amount of vanadic anhydride, molybdenum trioxide and two
Manganese oxide, and the weight percentage of vanadium, molybdenum, manganese is respectively 1%, 5%, 8%), nitric acid (8g) and sodium metasilicate (16g), make
Above-mentioned material fast scroll and wraps up kernel in edge knurling machine, gradually forms the outer membrane with a thickness of 3mm, closes edge knurling machine, therefrom
It takes out globular material (diameter 20mm).
First globular material is placed in baking oven, is placed in roaster in 100 DEG C of drying 10h, then by the globular material after drying
In, and roasted according to following procedure: initial temperature is 110 DEG C, and heating rate is 5 DEG C/min, midway respectively at 200 DEG C and
300 DEG C of heat preservation 30min, target temperature are 470 DEG C, keep the temperature 5h after reaching target temperature.After roasting, roaster, furnace are closed
Interior temperature is cooled to room temperature naturally, the globular material after taking out roasting.
Globular material after roasting is added in the vanadium oxalate aqueous solution (10g) of 15wt%, 1h is impregnated.Immersion terminates
Afterwards, the globular material after immersion is pulled out with sieve, drains surface liquid, is placed in baking oven, in 100 DEG C of drying 10h, then will
Globular material after drying is placed in roaster, and is roasted according to following procedure: initial temperature is 110 DEG C, heating rate
For 5 DEG C/min, target temperature is 470 DEG C, keeps the temperature 2h after reaching target temperature.After roasting, roaster, in-furnace temperature are closed
Naturally it is cooled to room temperature, the globular material after taking out roasting, as spherical SCR denitration.
The radius of the spherical shape SCR denitration is 10mm, wherein outer membrane with a thickness of 3mm, the radius of kernel is 7mm；
Surface is in yellow green, and intensity is greater than 300N.
It is 300ppm, SO in NO concentration2Concentration is 500ppm, H2O content is 10%, O2Content is 4%, ammonia nitrogen molar ratio
1:1, air speed 6000h-1, reactor size is 45mm × 45mm × 220mm, and filling height carries out flue gas under conditions of being 20mm
Denitration, initiation temperature be 220 DEG C (as shown in Figure 2), show in the present embodiment it is obtained spherical shape SCR denitration have well
Catalytic activity.
Embodiment 3: the preparation of spherical SCR denitration.
Edge knurling machine is opened, sequentially adds gama-alumina (66g), nitric acid (6.6g) and sodium carboxymethylcellulose thereto
(13.2g) makes above-mentioned material fast scroll in edge knurling machine, gradually forms the kernel that diameter is 16mm.
In interior karyomorphism at later, it is added into edge knurling machine comprising gama-alumina (34g), titanium dioxide (23.8g), three oxygen
Change tungsten (3.4g) and Dysprosium trioxide (6.8g) mixed powder (wherein also include a small amount of vanadic anhydride, molybdenum trioxide and
Manganese dioxide, and the weight percentage of vanadium, molybdenum, manganese is respectively 1%, 5%, 8%), nitric acid (6.8g) and sodium metasilicate
(13.6g) makes above-mentioned material fast scroll and wrap up kernel in edge knurling machine, gradually forms the outer membrane with a thickness of 2mm, closes rolling
Side machine is taken out globular material (diameter 20mm).
First globular material is placed in baking oven, is placed in roaster in 90 DEG C of drying 10h, then by the globular material after drying
In, and roasted according to following procedure: initial temperature is 100 DEG C, and heating rate is 3 DEG C/min, midway respectively at 200 DEG C and
300 DEG C of heat preservation 30min, target temperature are 450 DEG C, keep the temperature 5h after reaching target temperature.After roasting, roaster, furnace are closed
Interior temperature is cooled to room temperature naturally, the globular material after taking out roasting.
Globular material after roasting is added in the vanadium oxalate aqueous solution (10g) of 25wt%, 30min is impregnated.Impregnate knot
Globular material after immersion is pulled out with sieve, drains surface liquid, be placed in baking oven by Shu Hou, in 90 DEG C of drying 10h, then
Globular material after drying is placed in roaster, and is roasted according to following procedure: initial temperature is 100 DEG C, heating speed
Degree is 3 DEG C/min, and target temperature is 450 DEG C, keeps the temperature 2h after reaching target temperature.After roasting, roaster, temperature in furnace are closed
Degree nature is cooled to room temperature, the globular material after taking out roasting, as spherical SCR denitration.
The radius of the spherical shape SCR denitration is 10mm, wherein outer membrane with a thickness of 2mm, the radius of kernel is 8mm；
Surface is in yellow green, and intensity is greater than 300N.
It is 300ppm, SO in NO concentration2Concentration is 500ppm, H2O content is 10%, O2Content is 4%, ammonia nitrogen molar ratio
1:1, air speed 6000h-1, reactor size is 45mm × 45mm × 220mm, and filling height carries out flue gas under conditions of being 20mm
Denitration, initiation temperature be 185 DEG C (as shown in Figure 3), show in the present embodiment it is obtained spherical shape SCR denitration have well
Catalytic activity.
In addition, spherical shape SCR denitration obtained, can be de- due to spherical shapes in above-described embodiment 1-3
Catalysis reaction is carried out with fluidized state in nitre reactor, can occur frequently to collide between sphere, so that being covered in spherome surface
The noxious material of active sites is fallen, and then this exposure active sites again, avoids catalyst that intoxicating phenomenon occurs.
Above-described embodiment is only used for explanation and illustration specific embodiments of the present invention, and is not intended to limit of the invention
Protection scope.It should be understood that anyone skilled in the art presently disclosed technical scope it
The modifications or substitutions inside made should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of spherical shape SCR denitration comprising following steps:
1) kernel is prepared:
Edge knurling machine is opened, gama-alumina, nitric acid and binder is sequentially added thereto, rolls material in edge knurling machine, directly
To the kernel that formation diameter is 10~20mm；Wherein:
Weight ratio between gama-alumina, nitric acid and binder is 1:0.05~0.15:0.1~0.3；
2) outer membrane is prepared:
Interior karyomorphism at later, sequentially added into edge knurling machine comprising gama-alumina, titanium dioxide, tungstic acid and three oxidation
Mixed powder, nitric acid and the binder of two dysprosiums roll material in edge knurling machine and wrap up kernel obtained in step 1), directly
To the outer membrane formed with a thickness of 1~10mm, edge knurling machine is closed, globular material is taken out；Wherein:
Weight ratio between mixed powder, nitric acid and binder is 1:0.05~0.15:0.1~0.3；
Weight ratio in mixed powder between gama-alumina, titanium dioxide, tungstic acid and Dysprosium trioxide is 10:5~8:
0.5~1.5:1~3；
3) it dries and roasts for the first time:
First globular material obtained in step 2) is placed in baking oven, is dried 6~10 hours in 80~150 DEG C, then will for the first time
Globular material after drying is placed in roaster, and is roasted according to following procedure: initial temperature is 100~120 DEG C, heating
Speed is 1~5 DEG C/min, and midway keeps the temperature 0.5 hour at 200 DEG C and 300 DEG C respectively, and target temperature is 450~500 DEG C, is reached
5 hours are kept the temperature after target temperature；After roasting, roaster and cooled to room temperature are closed, is taken out and roasts for the first time
Globular material afterwards；
4) it impregnates and second dries and roast:
Globular material after roasting for the first time obtained in step 3) is added in vanadium oxalate aqueous solution, it is small to impregnate 0.5~1
When；After immersion, the globular material after immersion is pulled out, drains and is placed in baking oven, it is small in 80~150 DEG C of drying 6~10
When, then the globular material after second of drying is placed in roaster, and is roasted according to following procedure: initial temperature is
100~120 DEG C, heating rate is 1~5 DEG C/min, and target temperature is 450~500 DEG C, keeps the temperature 2 hours after reaching target temperature；
After roasting, roaster and cooled to room temperature are closed, the globular material after being taken out second of roasting is as spherical
SCR denitration；Wherein:
The weight ratio between globular material and vanadium oxalate aqueous solution after roasting for the first time is 1:0.05~0.2；
The weight percent of vanadium oxalate aqueous solution mesoxalic acid vanadium is 15%~25%.
2. preparation method according to claim 1, it is characterised in that:
The binder is sodium carboxymethylcellulose or sodium metasilicate.
3. preparation method according to claim 1, it is characterised in that:
Weight ratio between gama-alumina described in step 1), nitric acid and binder is 1:0.1:0.2.
4. preparation method according to claim 1, it is characterised in that:
Weight ratio between mixed powder described in step 2), nitric acid and binder is 1:0.1:0.2, in the mixed powder
Weight ratio between gama-alumina, titanium dioxide, tungstic acid and Dysprosium trioxide is 10:7:1:2.
5. preparation method according to claim 1, it is characterised in that:
Mixed powder described in step 2) also includes the oxide of at least one microelement, the microelement include vanadium, molybdenum,
Manganese, lanthanum, yttrium, cerium and zirconium, and the sum of the weight of the microelement accounts for the 10%~15% of the mixed powder total weight.
6. preparation method according to claim 1, it is characterised in that:
The temperature of drying described in step 3) is 120 DEG C, and the time is 8 hours；
Roasting described in step 3) is carried out according to following procedure: initial temperature is 100 DEG C, and heating rate is 1 DEG C/min, midway point
0.5 hour is not kept the temperature at 200 DEG C and 300 DEG C, target temperature is 450 DEG C, keeps the temperature 5 hours after reaching target temperature.
7. preparation method according to claim 1, it is characterised in that:
The weight ratio between globular material and vanadium oxalate aqueous solution after roasting for the first time described in step 4) is 1:0.1, described
The weight percent of vanadium oxalate aqueous solution mesoxalic acid vanadium is 20%.
8. preparation method according to claim 1, it is characterised in that:
The time of immersion described in step 4) is 0.5 hour；
The temperature of drying described in step 4) is 120 DEG C, and the time is 8 hours；
Roasting described in step 4) is carried out according to following procedure: initial temperature is 100 DEG C, and heating rate is 1 DEG C/min, target temperature
Degree is 450 DEG C, keeps the temperature 2 hours after reaching target temperature.
9. a kind of spherical shape SCR denitration, is made by preparation method according to any one of claim 1 to 8.
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