CN109967069A - A kind of low-temperature SCR catalyst and preparation method thereof for cement kiln flue gas denitration - Google Patents
A kind of low-temperature SCR catalyst and preparation method thereof for cement kiln flue gas denitration Download PDFInfo
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- CN109967069A CN109967069A CN201910367864.XA CN201910367864A CN109967069A CN 109967069 A CN109967069 A CN 109967069A CN 201910367864 A CN201910367864 A CN 201910367864A CN 109967069 A CN109967069 A CN 109967069A
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- flue gas
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- manganese
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000003546 flue gas Substances 0.000 title claims abstract description 28
- 239000004568 cement Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 230000032683 aging Effects 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 29
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 239000011572 manganese Substances 0.000 claims abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 12
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 11
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- 238000001125 extrusion Methods 0.000 claims abstract description 3
- 238000007493 shaping process Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- WBJXZTQXFVDYIZ-UHFFFAOYSA-N [Sb].[N+](=O)(O)[O-] Chemical group [Sb].[N+](=O)(O)[O-] WBJXZTQXFVDYIZ-UHFFFAOYSA-N 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 235000003301 Ceiba pentandra Nutrition 0.000 claims description 4
- 244000146553 Ceiba pentandra Species 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- -1 polyoxy Polymers 0.000 claims 1
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000003837 high-temperature calcination Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 4
- 229910016978 MnOx Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B01J35/56—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
Abstract
The invention discloses a kind of low-temperature SCR catalyst for cement kiln flue gas denitration, the catalyst is using manganese oxide as active component, and cerium oxide and antimony oxide are coagent, and titanium dioxide is carrier；In terms of tenor, manganese in the catalyst, cerium, antimony mass ratio be 15~20:3~5:3~5, the mass ratio of manganese and titanium is 5~10:60~88.Preparation process is after the presoma of the presoma of manganese oxide, the presoma of cerium oxide and antimony oxide is uniformly mixed dissolution, to be added in titanium dioxide, obtained pug is kneaded；It will be kneaded after the pug that finishes successively carries out aging, pre-extruded, extrusion, drying and calcination process, and obtain the low-temperature SCR catalyst.The present invention can reach 85% or more NO removal efficiency at 90~240 DEG C, and to low concentration SO2(100ppm or less), low humid flue gas (flue gas moisture content < 15%) have very strong resistivity.
Description
Technical field
The invention belongs to denitrating catalyst technical fields, more particularly to a kind of low temperature for cement kiln flue gas denitration
SCR catalyst and preparation method thereof.
Background technique
Nitrogen oxide NOx (NO, NO2、N2O etc.) be a kind of important atmosphere pollution, be haze main harmful components it
One, seriously endanger human health.The existing denitration technology of cement kiln is with the development of technology, low by fractional combustion, SNCR technology etc.
Temperature selective catalysis reduction (low-temperature SCR) technology is considered as that cement kiln realizes that the most effective stationary source NOx of ultra-clean discharge disappears
Except technology.
Common catalyst main component is V in industry2O5-WO3/TiO2, with preferable denitration efficiency, oneself is wide
The general nitrogen oxides discharged applied to stationary sources such as coal-burning power plants.This kind of catalyst contains active component vanadic anhydride, should
Substance has toxicity and is readily soluble in water logging, therefore discarded vanadium system denitrating catalyst is danger wastes by national regulation.Water
Stall flue-gas temperature is generally 90~300 DEG C very low, contains the dust of high concentration simultaneously, traditional denitrating catalyst can not be in water
Stall uses.Therefore develop that a kind of light-off temperature is low, the good low-temperature SCR catalyst of denitration effect is extremely urgent.
Summary of the invention
The present invention is to solve the problems, such as that existing vanadium based denitration catalyst is toxic and can not use in cement kiln, proposes one
Kind is used for the low-temperature SCR catalyst and preparation method thereof of cement kiln flue gas denitration.
The present invention is to realize that its purpose adopts the technical scheme that:
A kind of low-temperature SCR catalyst for cement kiln flue gas denitration, the catalyst is using manganese oxide as active component, oxidation
Cerium and antimony oxide are coagent, and titanium dioxide is carrier；
In terms of tenor, manganese in the catalyst, cerium, antimony mass ratio be 15~20:3~5:3~5, the matter of manganese and titanium
Amount is than being 5~10:60~88.
In the above-mentioned technical solutions, it is preferable that in terms of tenor, manganese in the catalyst, cerium, antimony mass ratio be 15~
The mass ratio of 18:3~4:3~4, manganese and titanium is 7~9:65~80.
In the above-mentioned technical solutions, it is preferable that the active component and coagent are respectively corresponding manganese oxide
Presoma, the presoma of cerium oxide and the presoma of the antimony oxide unsetting manganese oxide, the cerium oxide that are formed through calcining and decomposing
And antimony oxide.
In the above-mentioned technical solutions, it is preferable that the presoma of the manganese oxide is manganese acetate, and the presoma of cerium oxide is nitre
Sour cerium, the presoma of antimony oxide are nitric acid antimony.
In the above-mentioned technical solutions, it is preferable that the granularity of the titanium dioxide is 50~200 mesh, and the titanium dioxide is
Anatase titanium dioxide, anatase titanium dioxide specific surface area with higher, stable crystalline structure and surface characteristic,
TiO2Acid site abundant, can preferably adsorb alkaline reducer NH3, improve the rate of SCR reaction；Compared to other carriers,
TiO2The sulfate on surface is more stable, is excellent adsorbent and catalyst carrier.
Catalyst, due to the special valence shell electron configuration (3d54s2) of Mn element, makes using the oxide of manganese as active component
The variation of valence for obtaining Mn element is wider, including+2 ,+3 ,+4 ,+5 equivalent places and some non-integer equivalent places, the Mn of different valence state
Between may be implemented to mutually convert and generate oxidation-reduction quality, the reduction of NO can be promoted, thus promote SCR react progress, and
And there are many active oxygens to be used to complete catalysis reaction by MnOx, leads to the low-temperature catalytic activity of this kind of catalyst largely
On increase.The addition of rare earth metal cerium, antimony can improve MnOx/TiO2The active metal dispersibility and MnOx of catalyst
And TiO2Between form solid solution, improve specific surface area of catalyst catalytic activity and acid-resisting, reduce catalytic reaction temperature window.
In addition, the addition of coagent antimony can increase catalyst to NH3Adsorption capacity, the acidity for increasing acidity of catalyst position is strong
Degree, to improve the low temperature active of catalyst.
The preparation method of the above-mentioned low-temperature SCR catalyst for cement kiln flue gas denitration, comprising the following steps:
1) it after the presoma of the presoma of manganese oxide, the presoma of cerium oxide and antimony oxide being uniformly mixed dissolution, is added
Into titanium dioxide, obtained pug is kneaded；
2) it will be kneaded after the pug that finishes successively carries out aging, pre-extruded, extrusion, drying and calcination process, obtain described
Low-temperature SCR catalyst.
In the above-mentioned technical solutions, it is preferable that add shaping assistant and ammonium hydroxide in the mixing process, adjust pug
Plasticity, moisture content and pH value make the plasticity 6~8 of pug, and moisture content is 20%~35%, and pH value is 6~8.Wherein, it is kneaded
Process needs repeatedly sampling to measure, and the adjustment of shaping assistant and ammonium hydroxide additive amount is carried out according to test result.
The shaping assistant be kaolin, boron nitride, stearic acid, lactic acid, glass fibre, kapok slurry, carboxymethyl cellulose,
Two or more in polyethylene glycol oxide.
The kaolin, boron nitride, stearic acid, lactic acid, glass fibre, kapok slurry, carboxymethyl cellulose, polyethylene glycol oxide
It is 0.01~0.05:0.01~0.05:0.001~0.01:0.01~0.1:0.01~0.1:0.01 with titanium dioxide mass ratio
~0.1:0.001~0.01:0.02~0.05:1.
In the above-mentioned technical solutions, it is preferable that the aging process, 6~24 hours aging time, aging workshop constant temperature
Constant humidity, 25~40 DEG C of temperature, humidity 70~90%.
In the above-mentioned technical solutions, it is preferable that the drying process, drying temperature be 50~80 DEG C, humidity be 30~
50%, drying time is 48~120 hours.
In the above-mentioned technical solutions, it is preferable that the calcination process, 300~650 DEG C of calcination temperature, calcination time 4~
7 hours.
The present invention has the following advantages and beneficial effects:
The catalyst degradation of the invention service temperature of SCR denitration, so that with NH in SCR denitration process3
When for reducing agent, 85% or more NO removal efficiency can be reached at 90~240 DEG C, and to low concentration SO2(100ppm or less), it is low
Humid flue gas (flue gas moisture content < 15%) has very strong resistivity；In addition, the preparation process provided according to the present invention, it can
To reduce the stickiness of catalyst pug green body, briquetting pressure reduces catalyst cracking, finished catalyst rate is improved, with existing skill
Art is compared, and the present invention has some superiority, is suitable for cement kiln low-temperature denitration of flue gas and is used.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than limiting the invention.
Embodiment 1
1) 1.5kg manganese nitrate, 4.18kg cerous nitrate, 3.4kg nitric acid antimony are dissolved in deionized water, are added to 4kg bis-
In titanium oxide, and obtained powder is added in kneading machine, is tentatively kneaded；
2) shaping assistant and ammonium hydroxide is added in preliminary mixing process, adjusts plasticity, moisture content and the pH value of pug, makes pug
Plasticity be 7.5, moisture content 30.1%, pH value 7.2；
3) the aging workshop that the pug that mixing finishes is sent into constant temperature and humidity carries out aging, 24 hours aging time, aging vehicle
Between 30 DEG C of constant temperature of temperature, humidity 70%；
4) the aging pug finished is sent to pre-extruded machine and carries out pre-extruded, and forming shape is cylindrical body strip pug green body；
5) the pug green body of pre-extruded carries out shaping of catalyst by extruder, and forming shape is honeycomb, hole count 20
Hole；
6) catalyst green body after molding is sent into drying room and is dried, and drying temperature is 80 DEG C, and humidity is 30~50%,
Drying time is 120 hours；
7) the catalyst green body after drying had both obtained required catalyst after high-temperature calcination, 550 DEG C of calcination temperature, forged
It burns the time 6 hours.
According to " GB/T31587-2015 honeycomb type flue gas denitration catalyst " the method, it is low that this is tested by denitration performance
The denitration performance of warm SCR catalyst are as follows: 100~200 DEG C, denitration efficiency is 85%~97%.
Embodiment 2
1) 1.79kg manganese nitrate, 3.35kg cerous nitrate, 2.72kg nitric acid antimony are dissolved in deionized water, are added to 4kg
In titanium dioxide, and obtained powder is added in kneading machine, is tentatively kneaded；
2) shaping assistant and ammonium hydroxide is added in preliminary mixing process, adjusts plasticity, moisture content and the pH value of pug, makes pug
Plasticity be 8.0, moisture content 29.5%, pH value 6.5；
3) the aging workshop that the pug that mixing finishes is sent into constant temperature and humidity carries out aging, 24 hours aging time, aging vehicle
Between 30 DEG C of constant temperature of temperature, humidity 70%；
4) the aging pug finished is sent to pre-extruded machine and carries out pre-extruded, and forming shape is cylindrical body strip pug green body；
5) the pug green body of pre-extruded carries out shaping of catalyst by extruder, and forming shape is honeycomb, hole count 20
Hole；
6) catalyst green body after molding is sent into drying room and is dried, and drying temperature is 80 DEG C, and humidity is 30~50%,
Drying time is 120 hours；
7) the catalyst green body after drying had both obtained required catalyst after high-temperature calcination, 450 DEG C of calcination temperature, forged
It burns the time 6 hours.
According to " GB/T31587-2015 honeycomb type flue gas denitration catalyst " the method, by the performance test low temperature
The denitration performance of SCR catalyst are as follows: 90~240 DEG C, denitration efficiency is 85%~95%.
Embodiment 3
1) 1.79kg manganese nitrate, 4.18kg cerous nitrate, 3.4kg nitric acid antimony are dissolved in deionized water, are added to 6kg bis-
In titanium oxide, and obtained powder is added in kneading machine, is tentatively kneaded；
2) shaping assistant and ammonium hydroxide is added in preliminary mixing process, adjusts plasticity, moisture content and the pH value of pug, makes pug
Plasticity be 6.8, moisture content 33.8%, pH value 7.0；
3) the aging workshop that the pug that mixing finishes is sent into constant temperature and humidity carries out aging, 24 hours aging time, aging vehicle
Between 30 DEG C of constant temperature of temperature, humidity 70%；
4) the aging pug finished is sent to pre-extruded machine and carries out pre-extruded, and forming shape is cylindrical body strip pug green body；
5) the pug green body of pre-extruded carries out shaping of catalyst by extruder, and forming shape is honeycomb, hole count 20
Hole；
6) catalyst green body after molding is sent into drying room and is dried, and drying temperature is 80 DEG C, and humidity is 30~50%,
Drying time is 120 hours；
7) the catalyst green body after drying had both obtained required catalyst after high-temperature calcination, 650 DEG C of calcination temperature, forged
It burns the time 6 hours.
According to " GB/T31587-2015 honeycomb type flue gas denitration catalyst " the method, by the performance test low temperature
The denitration performance of SCR catalyst are as follows: 90~220 DEG C, denitration efficiency is 85%~90%.
Embodiment 4
1) 1.79kg manganese nitrate, 2.51kg cerous nitrate, 2.05kg nitric acid antimony are dissolved in deionized water, are added to 6kg
In titanium dioxide, and obtained powder is added in kneading machine, is tentatively kneaded；
2) shaping assistant and ammonium hydroxide is added in preliminary mixing process, adjusts plasticity, moisture content and the pH value of pug, makes pug
Plasticity be 7.6, moisture content 33.8%, pH value 6.2；
3) the aging workshop that the pug that mixing finishes is sent into constant temperature and humidity carries out aging, 24 hours aging time, aging vehicle
Between 30 DEG C of constant temperature of temperature, humidity 70%；
4) the aging pug finished is sent to pre-extruded machine and carries out pre-extruded, and forming shape is cylindrical body strip pug green body；
5) the pug green body of pre-extruded carries out shaping of catalyst by extruder, and forming shape is honeycomb, hole count 20
Hole；
6) catalyst green body after molding is sent into drying room and is dried, and drying temperature is 80 DEG C, and humidity is 30~50%,
Drying time is 120 hours；
7) the catalyst green body after drying had both obtained required catalyst after high-temperature calcination, 500 DEG C of calcination temperature, forged
It burns the time 6 hours.
According to " GB/T31587-2015 honeycomb type flue gas denitration catalyst " the method, by the performance test low temperature
The denitration performance of SCR catalyst are as follows: 90~200 DEG C, denitration efficiency is 85%~93%.
Comparative example
1) by 1.79kg manganese nitrate, the 5.40kg cerous nitrate (ratio and implementation of active component content and manganese in this embodiment
Example 4 is consistent) it is dissolved in deionized water, it is added in 6kg titanium dioxide, and obtained powder is added in kneading machine, into
Row is preliminary to be kneaded；
2) shaping assistant and ammonium hydroxide is added in preliminary mixing process, adjusts plasticity, moisture content and the pH value of pug, makes pug
Plasticity be 7.6, moisture content 32.8%, pH value 6.8；
3) the aging workshop that the pug that mixing finishes is sent into constant temperature and humidity carries out aging, 24 hours aging time, aging vehicle
Between 30 DEG C of constant temperature of temperature, humidity 70%；
4) the aging pug finished is sent to pre-extruded machine and carries out pre-extruded, and forming shape is cylindrical body strip pug green body；
5) the pug green body of pre-extruded carries out shaping of catalyst by extruder, and forming shape is honeycomb, hole count 20
Hole；
6) catalyst green body after molding is sent into drying room and is dried, and drying temperature is 80 DEG C, and humidity is 30~50%,
Drying time is 120 hours；
7) the catalyst green body after drying had both obtained required catalyst after high-temperature calcination, 500 DEG C of calcination temperature, forged
It burns the time 6 hours.
According to " GB/T31587-2015 honeycomb type flue gas denitration catalyst " the method, by the performance test low temperature
The denitration performance of SCR catalyst are as follows: 90~200 DEG C, denitration efficiency is 45%~72%.
Claims (10)
1. a kind of low-temperature SCR catalyst for cement kiln flue gas denitration, which is characterized in that the catalyst is activity with manganese oxide
Component, cerium oxide and antimony oxide are coagent, and titanium dioxide is carrier；
In terms of tenor, manganese in the catalyst, cerium, antimony mass ratio be 15~20:3~5:3~5, the mass ratio of manganese and titanium
For 5~10:60~88.
2. being used for the low-temperature SCR catalyst of cement kiln flue gas denitration as described in claim 1, which is characterized in that contained with metal
Meter, manganese in the catalyst, cerium, antimony mass ratio be 15~18:3~4:3~4, the mass ratio of manganese and titanium be 7~9:65~
80。
3. being used for the low-temperature SCR catalyst of cement kiln flue gas denitration as described in claim 1, which is characterized in that the activity
Component and coagent are respectively the presoma warp of the presoma of corresponding manganese oxide, the presoma of cerium oxide and antimony oxide
Unsetting manganese oxide, cerium oxide and the antimony oxide that calcining and decomposing is formed.
4. being used for the low-temperature SCR catalyst of cement kiln flue gas denitration as claimed in claim 3, which is characterized in that the oxidation
The presoma of manganese is manganese acetate, and the presoma of cerium oxide is cerous nitrate, and the presoma of antimony oxide is nitric acid antimony.
5. being used for the low-temperature SCR catalyst of cement kiln flue gas denitration as described in claim 1, which is characterized in that the dioxy
The granularity for changing titanium is 50~200 mesh, and the titanium dioxide is anatase titanium dioxide.
6. a kind of preparation using the described in any item low-temperature SCR catalysts for cement kiln flue gas denitration of claim 1-5
Method, which comprises the following steps:
1) after the presoma of the presoma of manganese oxide, the presoma of cerium oxide and antimony oxide being uniformly mixed dissolution, two are added to
In titanium oxide, obtained pug is kneaded；
2) it will be kneaded after the pug that finishes successively carries out aging, pre-extruded, extrusion, drying and calcination process, obtain described low
Warm SCR catalyst.
7. the preparation method for the low-temperature SCR catalyst of cement kiln flue gas denitration, feature exist as claimed in claim 6
In addition shaping assistant and ammonium hydroxide, adjust plasticity, moisture content and the pH value of pug, make the modeling of pug in the mixing process
Property be 6~8, moisture content be 20%~35%, pH value be 6~8.
8. the preparation method for the low-temperature SCR catalyst of cement kiln flue gas denitration, feature exist as claimed in claim 7
In the shaping assistant is kaolin, boron nitride, stearic acid, lactic acid, glass fibre, kapok slurry, carboxymethyl cellulose, polyoxy
Change two or more in ethylene.
9. the preparation method for the low-temperature SCR catalyst of cement kiln flue gas denitration, feature exist as claimed in claim 8
In the kaolin, boron nitride, stearic acid, lactic acid, glass fibre, kapok slurry, carboxymethyl cellulose, polyethylene glycol oxide and two
Titanium oxide mass ratio be 0.01~0.05:0.01~0.05:0.001~0.01:0.01~0.1:0.01~0.1:0.01~
0.1:0.001~0.01:0.02~0.05:1.
10. the preparation method for the low-temperature SCR catalyst of cement kiln flue gas denitration, feature exist as claimed in claim 6
In, the aging process, 6~24 hours aging time, aging workshop constant temperature and humidity, 25~40 DEG C of temperature, humidity 70~
90%；
The drying process, drying temperature are 50~80 DEG C, and humidity is 30~50%, and drying time is 48~120 hours；
The calcination process, 300~650 DEG C of calcination temperature, calcination time is 4~7 hours.
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