CN108465470B - A kind of γ-Fe2O3Nano-particle modified nf-MnO2/ ATP low-temperature denitration catalyst - Google Patents
A kind of γ-Fe2O3Nano-particle modified nf-MnO2/ ATP low-temperature denitration catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000002245 particle Substances 0.000 title description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 35
- 229960000892 attapulgite Drugs 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- 239000004927 clay Substances 0.000 claims abstract description 17
- 229910001566 austenite Inorganic materials 0.000 claims abstract description 10
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 10
- 238000010521 absorption reaction Methods 0.000 claims abstract 2
- 239000003638 chemical reducing agent Substances 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000002689 soil Substances 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 239000012456 homogeneous solution Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 2
- 229960000583 acetic acid Drugs 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000003426 co-catalyst Substances 0.000 claims 1
- 239000012362 glacial acetic acid 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
- 239000007800 oxidant agent Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003546 flue gas Substances 0.000 abstract description 7
- 238000005253 cladding Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- 235000021419 vinegar Nutrition 0.000 description 4
- 239000000052 vinegar Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052603 melanterite Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 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 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 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 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- 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
Abstract
The invention belongs to denitrating flue gas field, especially a kind of γ-Fe2O3Nano-particle modified nf-MnO2/ ATP low-temperature denitration catalyst.The present invention low, anti-SO for existing catalyst for denitrating flue gas support strength2The disadvantage that performance is poor and preparation method is complicated, provides a kind of γ-Fe2O3Nano-particle modified nf-MnO2/ ATP low-temperature denitration catalyst and preparation method thereof, the present invention using bigger serface, high absorption property attapulgite clay as carrier and reducing agent, by with KMnO4Nano flower-like MnO is prepared in reaction under hydrothermal conditions2Attapulgite clay (the nf-MnO of cladding2- ATP) catalyst, while high-performance γ-Fe is prepared under the conditions of low-temperature hydrothermal2O3Nano particle is to nf-MnO2/ ATP is surface modified, and prepares γ-Fe2O3/nf‑MnO2- ATP denitrating catalyst.Improve nf-MnO2The N of-ATP2Selective and anti-SO2Performance.The preparation condition that the present invention uses simultaneously is mild, and preparation method is simple, is a kind of safe and efficient low-temperature denitration catalyst preparation method.
Description
Technical field
The invention belongs to denitrating flue gas field, especially a kind of γ-Fe2O3Nano-particle modified nf-MnO2/ ATP low temperature is de-
Denox catalyst.
Background technique
NO in atmospherexIt is one of the main reason for leading to the serious environmental problems such as acid rain, photochemical fog.From 1973
Selective catalytic oxidation restores NOxTechnology NH3- SCR (Selective Ctalalytic Reduction, NH3- SCR) technology goes out
Since existing, the technology is due to that can be reduced to N for the nitrogen oxides in exhaust gas with high selectivity under excess oxygen2And it is answered extensively
With.Common commercial NH3SCR catalyst is V-W-TiO2, the running temperature that such catalyst needs is higher (310~430 DEG C),
Therefore SCR reactor is typically mounted between boiler economizer and air preheater, but such arrangement is easy to cause catalyst
Blocking and poisoning and deactivation, reduce the service life of catalyst.If, can after SCR reactor is arranged in dedusting, desulphurization system
Effectively avoid dust and SO2Influence, and convenient for and existing boiler system matching, save improvement cost.But the difficult point of the technology
It is flue gas after dedusting and desulfurization, smoke temperature is down to 150 DEG C or so, if selecting current commercial catalyst still to remove cigarette
NO in gasx, then need to reheat to improve flue-gas temperature, energy consumption is very big.Therefore, low temperature, efficient, performance are developed
Stable NH3SCR catalyst has become the key of the technology Successful utilization.Chinese patent CN107175103A discloses one kind
With TiO2、SiO2, tungsten titanium valve or Al2O3As carrier, with manganese salt (manganese oxalate, manganese acetate, at least one of high violent sour calcium and nitre
At least one of sour manganese, manganese sulfate and manganese chloride composition salt-mixture) and cerium salt (cerous nitrate or cerous acetate) be presoma, pass through
Carrier is added after heating is blended in the two, crushes using vacuum drying and obtains denitrating catalyst powder, finally mediated by powder,
It squeezes out, is dry, roasting obtains denitrating catalyst.The preparation method is disadvantageous in that: 1. complex manufacturing technology, is added by being blended
The mixed powder that thermal method obtains needs that product could be obtained by sequence of operations, and method is complicated.2. with rodlike TiO2、SiO2、
Tungsten titanium valve or Al2O3Carrier adulterates Mn, Ce, increases the cost of catalyst.3. with catalyst powder through excessively high in the preparation process
Temperature calcining can make MnO2Crystal form changes, and cannot form the highest γ-MnO of activity2。
Summary of the invention
The present invention is for the narrow, active temperature of the invention for reactivity section existing for existing catalyst for denitrating flue gas
High, anti-SO2The problems such as performance is insufficient, catalyst carrier is expensive, preparation method is complicated, provide a kind of γ-Fe2O3It receives
Rice grain modifies nf-MnO2/ ATP low-temperature denitration catalyst and preparation method thereof.Method for preparing catalyst letter prepared by the present invention
It is single, attract to form special composite construction by intermolecular magnetic force, active temperature range is wide and anti-SO2It has excellent performance.Furthermore
The carrier that the present invention uses is nonmetallic clay pit, in China's rich reserves, while the active metal loaded be non-toxic inexpensive and
γ-Fe with high activity2O3And MnO2, the active section of catalyst is greatly improved, the production cost of catalyst is reduced,
Formation denitration performance is high, temperature range is wide, anti-SO2The denitrating catalyst haveing excellent performance.
The technical scheme adopted by the invention is as follows: a kind of γ-Fe2O3Nano-particle modified nf-MnO2/ ATP low-temperature denitration is urged
Agent.Using attapulgite clay as carrier, the active component of load is γ-Fe2O3And MnO2Denitrating catalyst.
Above-mentioned γ-Fe2O3Nano-particle modified nf-MnO2/ ATP low-temperature denitration catalyst preparation method is as follows:
(1) attapulgite original soil uses the HNO of 3mol/mL first3Reflux pretreatment 3h is carried out under 80 DEG C of water bath conditions, is gone
Except the impurity on attapulgite original soil surface, attapulgite original soil is purified.It filters, is washed with deionized after the water bath is over
To neutrality, then it is dried for standby for 80 DEG C, attapulgite clay after purification is abbreviated as (ATP).
(2) ATP by above-mentioned drying is ground up, sieved, and is then weighed 1g ATP and is dissolved in 400mL deionized water, ultrasonic treatment
30min dissociates ATP crystalline substance beam, obtains finely dispersed ATP suspension.Weigh 2gKMnO4It is dissolved in ATP suspension, continues to surpass
Sound 20min, makes ATP and KMnO4It is uniformly mixed.Then above-mentioned solution is moved into 500mL three-necked flask, 40mL ice vinegar is added
Acid adjusts PH~3, heats up 78 DEG C, reacts 4h, filters after reaction, washing to neutrality.Then by 80 DEG C of filter cake drying to get
nf-MnO2-ATP。
(3) 0.15g FeSO is weighed4·7H2O and 0.29gFeCl3·6H2O is dissolved in 50mL deionized water, then moves into three
Mouth flask, heat up 90 DEG C of water-bath back flow reactions, is bubbled during reaction with air pump injection air, forms homogeneous solution, instead
It is cooled to room temperature after answering 2h, is added dropwise with ammonium hydroxide and adjusts PH=10, then proceeded to the back flow reaction 5h under water bath condition, make to sink
Long-pending crystal grain is gradually grown up.Solution PH=7 are measured after reaction, then by nf-MnO2- ATP suspension is slowly added to, at room temperature
Continue to stir 1h, γ-Fe2O3Nano particle is gradually adsorbed onto nf-MnO by charge effect2γ-Fe is made in the surface-ATP2O3/
nf-MnO2- ATP monolithic catalyst.
The invention has the benefit that
It 1, the use of cheap and bigger serface fibrous attapulgite clay is carrier, loading has preferable high temperature active
γ-Fe2O3Active component.On the one hand, attapulgite clay used in the present invention itself contains a certain amount of Mg, Al, Fe ingredient,
With certain denitration ability.On the other hand, the fibrous structure of attapulgite clay ontology is conducive to active component in reaction gas
Body comes into full contact with, while loading the γ-Fe most outstanding of denitration ability in Fe series catalysts2O3Active component.So that catalyst has
There is denitration ability strong, cheap, easy to form advantage.
2, with single γ-Fe2O3It is compared as active component, MnO is added2Component can significantly improve the low of catalyst
Warm denitration ability, with γ-Fe2O3Component realizes the effect having complementary advantages, and widens the active temperature section of catalyst further.
3, to pass through roasting process when compared to the preparation of more general denitrating catalyst, pass through in the preparation method of this catalyst anti-
The sucking action between component is answered, denitrating catalyst finished product is made in one step under conditions of mild heat, no longer carries out roasting behaviour
Make, avoids under catalyst high temperature appearance structure and destroy and the case where waste of energy.
Detailed description of the invention
Fig. 1 is the nf-MnO of preparation2- ATP and γ-Fe2O3Nano-particle modified nf-MnO2The TEM of/ATP schemes.
Fig. 2 is concave-convex stone stick clay (ATP), nf-MnO2- ATP and γ-Fe2O3Nano-particle modified nf-MnO2/ATP
XRD diagram.
Specific embodiment
Below with reference to embodiment and comparative example, to illustrate a kind of γ-Fe2O3Nano-particle modified nf-MnO2/ ATP is de-
Denox catalyst and preparation method thereof, but unlimited the scope of the present invention.
Embodiment 1
(1) attapulgite original soil uses the HNO of 3mol/mL first3Reflux pretreatment 3h is carried out under 80 DEG C of water bath conditions, is gone
Except the impurity on attapulgite original soil surface, attapulgite original soil is purified.It filters, is washed with deionized after the water bath is over
To neutrality, then it is dried for standby for 80 DEG C, attapulgite clay after purification is abbreviated as (ATP).
(2) ATP by above-mentioned drying is ground up, sieved, and is then weighed 1g ATP and is dissolved in 400mL deionized water, ultrasonic treatment
30min dissociates ATP crystalline substance beam, obtains finely dispersed ATP suspension.Weigh 2gKMnO4It is dissolved in ATP suspension, continues to surpass
Sound 20min, makes ATP and KMnO4It is uniformly mixed.Then above-mentioned solution is moved into 500mL three-necked flask, 40mL ice vinegar is added
Acid adjusts PH~3, heats up 78 DEG C, reacts 4h, filters after reaction, washing to neutrality.Then by 80 DEG C of filter cake drying to get
nf-MnO2-ATP。
(3) 0.15g FeSO is weighed4·7H2O and 0.29gFeCl3·6H2O is dissolved in 50mL deionized water, then moves into three
Mouth flask, heat up 90 DEG C of water-bath back flow reactions, is bubbled during reaction with air pump injection air, forms homogeneous solution, instead
It is cooled to room temperature after answering 2h, is added dropwise with ammonium hydroxide and adjusts PH=10, then proceeded to the back flow reaction 5h under water bath condition, make to sink
Long-pending crystal grain is gradually grown up.Solution PH=7 are measured after reaction, then by nf-MnO2- ATP suspension is slowly added to, at room temperature
Continue to stir 1h, γ-Fe2O3Nano particle is gradually adsorbed onto nf-MnO by charge effect2γ-Fe is made in the surface-ATP2O3/
nf-MnO2- ATP monolithic catalyst.
Fig. 1 a is nf-MnO2The TEM spectrogram of-ATP, Cong Tuzhong can be clearly seen that in nano flower-like MnO2On the surface ATP
It coats more uniform and more close in conjunction with ATP., by MnO2Nano flower cladding after ATP diameter 150~250nm it
Between, it coats with a thickness of 30~60 nm.Fig. 1 b is γ-Fe2O3/nf-MnO2The TEM of-ATP schemes, as can be seen from the figure Mn element
It is coated on the outer surface ATP in nano flower-like, Fe element is with granular adsorption in nf-MnO2The surface-ATP.
Fig. 2 is ATP, γ-Fe of preparation2O3、nf-MnO2- ATP and γ-Fe2O3/nf-MnO2The XRD spectra of-ATP.From
As can be seen that γ-the Fe of hydrothermal reaction at low temperature preparation in figure2O3Respectively in 2 θ=30.2 °, 35.6 °, 43.2 °, 53.7 °, 57.2 °,
62.9 ° there is apparent diffraction maximum, consistent with JCPDS standard card NO.29-1346, are respectively belonging to γ-Fe2O3(220),
(311), (400), (422), (511) and (440) crystal face, it was demonstrated that the Fe of hydrothermal reaction at low temperature preparation2O3Mainly with γ-Fe2O3It is brilliant
Type exists.From nf-MnO2The XRD spectrum of-ATP can be seen that ATP in process and KMnO4After hydro-thermal reaction, not only in 2 θ=8 °
Left and right remains (001) crystallographic plane diffraction peak of attapulgite clay, while going out at 2 θ=12.5 °, 25.2 °, 37.3 °, 65.4 °
New diffraction maximum is showed, peak position and peak intensity phase with JPCDS NO.80-1098 standard card is found by careful comparative analysis
Unanimously, mainly with birnessite type MnO2(δ-MnO2) form exist.Meanwhile the XRD diagram of ATP is carefully compared it can be found that In
By with KMnO4After reaction, nf-MnO2There is apparent reduction in ATP (001) the crystallographic plane diffraction peak intensity of-ATP at 2 θ=8 °,
It is primarily due to KMnO4It is reacted in acid condition with ATP and decomposes slabbing MnO2, then adsorbed by ATP and be coated on table
The decline of ATP diffraction peak intensity is caused in face.From γ-Fe2O3/nf-MnO2As can be seen that passing through γ-Fe in the XRD diagram of-ATP2O3
Surface modification, nf-MnO2- ATP is in 2 θ=30.2 °, and 35.6 °, 43.2 °, 57.2 °, 62.9 ° occur belonging to γ-Fe2O3
New diffraction maximum, while ATP and δ-MnO is belonged at 2 θ=8 °, 12.5 °2Diffraction peak intensity also there is certain drop
It is low, it was demonstrated that γ-Fe2O3Nano particle is successfully supported on nf-MnO2The surface-ATP.
Embodiment 2
(1) attapulgite original soil uses the HNO of 3mol/mL first3Reflux pretreatment 3h is carried out under 80 DEG C of water bath conditions, is gone
Except the impurity on attapulgite original soil surface, attapulgite original soil is purified.It filters, is washed with deionized after the water bath is over
To neutrality, then it is dried for standby for 80 DEG C, attapulgite clay after purification is abbreviated as (ATP).
(2) ATP by above-mentioned drying is ground up, sieved, and is then weighed 1g ATP and is dissolved in 400mL deionized water, ultrasonic treatment
30min dissociates ATP crystalline substance beam, obtains finely dispersed ATP suspension.Weigh 2gKMnO4It is dissolved in ATP suspension, continues to surpass
Sound 20min, makes ATP and KMnO4It is uniformly mixed.Then above-mentioned solution is moved into 500mL three-necked flask, 40mL ice vinegar is added
Acid adjusts PH~3, heats up 78 DEG C, reacts 4h, filters after reaction, washing to neutrality.Then by 80 DEG C of filter cake drying to get
nf-MnO2-ATP。
Embodiment 3
(1) attapulgite original soil uses the HNO of 3mol/mL first3Reflux pretreatment 3h is carried out under 80 DEG C of water bath conditions, is gone
Except the impurity on attapulgite original soil surface, attapulgite original soil is purified.It filters, is washed with deionized after the water bath is over
To neutrality, then it is dried for standby for 80 DEG C, attapulgite clay after purification is abbreviated as (ATP).
(2) ATP by above-mentioned drying is ground up, sieved, and is then weighed 1g ATP and is dissolved in 400mL deionized water, ultrasonic treatment
30min dissociates ATP crystalline substance beam, obtains finely dispersed ATP suspension.Weigh 0.15g FeSO4·7H2O and
0.29gFeCl3·6H2O is dissolved in ATP suspension, continues ultrasound 20min, is uniformly mixed ATP with solution.Then by above-mentioned solution
It moves into 500mL three-necked flask, heat up 90 DEG C of water-bath back flow reactions, is bubbled during reaction with air pump injection air, shape
At homogeneous solution, be cooled to room temperature after reacting 2h, be added dropwise with ammonium hydroxide and adjust PH=10, then proceed to water bath condition next time
Stream reaction 5h, makes the crystal grain of deposition gradually grow up.Measure solution PH=7 after reaction to get γ-Fe2O3-ATP。
Comparative example 1
The preparation method in 2 catalyst of embodiment is changed to roasting method in comparative example 1, specific steps are as follows:
(1) attapulgite original soil uses the HNO of 3mol/mL first3Reflux pretreatment 3h is carried out under 80 DEG C of water bath conditions, is gone
Except the impurity on attapulgite original soil surface, attapulgite original soil is purified.It filters, is washed with deionized after the water bath is over
To neutrality, then it is dried for standby for 80 DEG C, attapulgite clay after purification is abbreviated as (ATP).
(2) ATP by above-mentioned drying is ground up, sieved, and is then weighed 1g ATP and is dissolved in 400mL deionized water, ultrasonic treatment
30min dissociates ATP crystalline substance beam, obtains finely dispersed ATP suspension.Weigh 2gKMnO4It is dissolved in ATP suspension, continues to surpass
Sound 20min, makes ATP and KMnO4It is uniformly mixed.Then above-mentioned solution is moved into 500mL three-necked flask, 40mL ice vinegar is added
Acid adjusts PH~3, heats up 78 DEG C, reacts 4h, filters after reaction, washing to neutrality.Then 80 DEG C of filter cake are dried, Muffle
300 DEG C of roasting 2h of furnace are to get nf-MnO2-ATP。
Comparative example 2
The preparation method in 3 catalyst of embodiment is changed to roasting method in comparative example 2, specific steps are as follows:
(1) attapulgite original soil uses the HNO of 3mol/mL first3Reflux pretreatment 3h is carried out under 80 DEG C of water bath conditions, is gone
Except the impurity on attapulgite original soil surface, attapulgite original soil is purified.It filters, is washed with deionized after the water bath is over
To neutrality, then it is dried for standby for 80 DEG C, attapulgite clay after purification is abbreviated as (ATP).
(2) ATP by above-mentioned drying is ground up, sieved, and is then weighed 1g ATP and is dissolved in 400mL deionized water, ultrasonic treatment
30min dissociates ATP crystalline substance beam, obtains finely dispersed ATP suspension.Weigh 0.15g FeSO4·7H2O and
0.29gFeCl3·6H2O is dissolved in ATP suspension, continues ultrasound 20min, is uniformly mixed ATP with solution.Then by above-mentioned solution
It moves into 500mL three-necked flask, heat up 90 DEG C of water-bath back flow reactions, is bubbled during reaction with air pump injection air, shape
At homogeneous solution, be cooled to room temperature after reacting 2h, be added dropwise with ammonium hydroxide and adjust PH=10, then proceed to water bath condition next time
Stream reaction 5h, makes the crystal grain of deposition gradually grow up.Solution PH=7 are measured after reaction, are then dried 80 DEG C of filter cake, Muffle
300 DEG C of roasting 2h of furnace are to get γ-Fe2O3-ATP。
Comparative example 3
The carrier ATP in 2 catalyst of comparative example is removed in comparative example 3, specific steps are as follows:
Weigh 0.15g FeSO4·7H2O and 0.29gFeCl3·6H2O is dissolved in ATP suspension, continues ultrasound 20min, makes
ATP is uniformly mixed with solution.Then above-mentioned solution is moved into 500mL three-necked flask, heat up 90 DEG C of water-bath back flow reactions, reaction
Period injects air with air pump and is bubbled, and forms homogeneous solution, is cooled to room temperature after reacting 2h, tune is added dropwise with ammonium hydroxide
PH=10 is saved, the back flow reaction 5h under water bath condition is then proceeded to, the crystal grain of deposition is made gradually to grow up.It measures after reaction molten
Then liquid PH=7 dries 80 DEG C of filter cake, 300 DEG C of roasting 2h of Muffle furnace are to get γ-Fe2O3。
γ-Fe2O3Nano-particle modified nf-MnO2/ ATP low-temperature denitration catalyst performance test
The present invention carries out active testing in the dual-purpose fixed bed of SCR photocatalysis, measures about 3mL catalyst and is placed in fixed bed stone
In English pipe reactor, inlet gas flow is accurately controlled using high-precision mass flowmenter (Sevenstar-HC, D07-19B type), with
N2As carrier gas, gas composition are as follows: [NO]=1000ppm, [NH3]=1000ppm, SO2=300ppm, O2=3vol%, instead
Answering air speed is=45000h-1, in order to test anti-S, it is passed through 300ppm SO during the reaction in test2.First continue before test
Ventilate 30min, so that Catalyst Adsorption is saturated, to exclude NOxIt is adsorbed and the decline of bring concentration.Use the triumphant benefactor of Germany
The KM9106 flue gas analyzer of department's production detects inlet concentration, obtains accurate import NOxConcentration is denoted as [NOx]in.Heating 50
DEG C, after temperature is constant, detection outlet NOxConcentration is denoted as [NOx]out.It is required according to reaction temperature, is stepped up reaction temperature,
The NO exported at this temperature is read after stabilizationxConcentration, measurement data are as shown in table 1.
The calculation formula of denitration efficiency is as follows:
Seen from table 1, the γ-Fe prepared by the present invention2O3Nano-particle modified nf-MnO2/ ATP denitrating catalyst has
Lower active temperature, wider active temperature section and excellent anti-SO2Performance.γ-Fe in the case of comparison roasting2O3/
ATP and nf-MnO2- ATP, hydro-thermal method prepare γ-Fe2O3Nano-particle modified nf-MnO2The technique of/ATP low-temperature denitration catalyst
Method is simple, short preparation period, it was demonstrated that denitrating catalyst prepared by the present invention is a kind of potential excellent substitute, can be extensive
Applied to practical denitration field.1 denitration performance evaluation test data of table
Claims (1)
1. a kind of γ-Fe2O3Nano-particle modified nf-MnO2/ ATP low-temperature denitration catalyst, it is characterised in that: with Large ratio surface
Long-pending, high absorption property attapulgite clay is carrier and reducing agent, with KMnO4For oxidant, prepared using one step hydro thermal method
With γ-Fe2O3High denitration performance, high N for co-catalyst2Selectivity and highly resistance SO2Denitrating catalyst；The catalyst
Middle γ-Fe2O3Content be 5wt% ~ 11wt%；γ-the Fe2O3Nano-particle modified nf-MnO2The catalysis of/ATP low-temperature denitration
The preparation step of agent is as follows:
(1) attapulgite original soil uses the HNO of 3mol/mL first3Reflux pretreatment 3h is carried out under 80 DEG C of water bath conditions, is removed recessed
The impurity on convex stick stone original soil surface, purifies attapulgite original soil, filters after the water bath is over, be washed with deionized into
Property, it is then dried for standby for 80 DEG C, attapulgite clay after purification is abbreviated as ATP；
(2) ATP by above-mentioned drying is ground up, sieved, and is then weighed 1g ATP and is dissolved in 400mL deionized water, is ultrasonically treated 30min,
ATP crystalline substance beam is dissociated, finely dispersed ATP suspension is obtained, weighs 2gKMnO4It is dissolved in ATP suspension, continues ultrasound 20min,
Make ATP and KMnO4It is uniformly mixed, then moves into above-mentioned solution in 500mL three-necked flask, addition 40mL glacial acetic acid adjusting pH ~
3, it heats up 78 DEG C, reacts 4h, filter after reaction, washing to neutrality, then by 80 DEG C of filter cake drying to get nf-MnO2-
ATP；
(3) 0.15g FeSO is weighed4·7H2O and 0.29gFeCl3·6H2O is dissolved in 50mL deionized water, then moves into three mouthfuls of burnings
Bottle, heat up 90 DEG C of water-bath back flow reactions, is bubbled during reaction with air pump injection air, forms homogeneous solution, react 2h
After be cooled to room temperature, with ammonium hydroxide be added dropwise adjust pH=10, then proceed to the back flow reaction 5h under water bath condition, make deposition
Crystal grain is gradually grown up, and measures pH value of solution=7 after reaction, then by nf-MnO2- ATP suspension is slowly added to, and is continued at room temperature
Stir 1h, γ-Fe2O3Nano particle is gradually adsorbed onto nf-MnO by charge effect2γ-Fe is made in the surface-ATP2O3/ nf-
MnO2- ATP monolithic catalyst.
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