CN109999828A - A kind of preparation of pillared manganese base montmorillonite (Ni/Mn-MMT) low-temperature denitration catalyst of Ni - Google Patents
A kind of preparation of pillared manganese base montmorillonite (Ni/Mn-MMT) low-temperature denitration catalyst of Ni Download PDFInfo
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- CN109999828A CN109999828A CN201910343132.7A CN201910343132A CN109999828A CN 109999828 A CN109999828 A CN 109999828A CN 201910343132 A CN201910343132 A CN 201910343132A CN 109999828 A CN109999828 A CN 109999828A
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- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 50
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 239000011572 manganese Substances 0.000 title claims abstract description 20
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003643 water by type Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 206010013786 Dry skin Diseases 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000003546 flue gas Substances 0.000 abstract description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000002474 experimental method Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000001802 infusion Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000004927 clay Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000005516 engineering process Methods 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
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001767 cationic compounds Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910001411 inorganic cation Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/60—
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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 fields, especially a kind of pillared manganese base montmorillonite (Ni/Mn-MMT) low-temperature denitration catalyst of Ni prepares and application, the method of the present invention for raw material, is prepared Ni/Mn-MMT low-temperature denitration catalyst by infusion process and its denitration performance at low temperature is studied and evaluated with montmorillonite (MMT).This experiment utilizes the characteristic of montmorillonite, and uses Ni and Mn pillared montmorillonite, and the big interlamellar spacing of montmorillonite of support makes it have better carrier effect, while the composite catalyst has good performance for denitration, there is good denitration reduction at a lower temperature.Preparation process of the invention is simple, it is economical and practical and be not necessarily to any template, increase effectively the specific surface area of catalyst, improve denitration activity and have preferable stability.
Description
Technical field
The invention belongs to denitrating flue gas field, especially a kind of pillared manganese base montmorillonite (Ni/Mn-MMT) low-temperature denitration of Ni
Catalyst.
Background technique
The environmental problem in China is inversely proportional with economic fast development now, the burning of mass energy in industrial production,
Cause the nitrous oxides concentration in atmospheric environment to severely exceed, thus form acid rain and photochemical pollution, it is strong to influence human body
Health, welding.It if things go on like this will seriously restrict China's sustainable development of socio-economy.In China, according to incompletely statistics, NOx
Discharge amount have reached the 67% of harmful gas total emission volumn.Ammine selectivity catalytic reduction (SCR) technology is a kind of current ratio
Relatively effectively administer the method for nitrogen oxide pollutant.The core of this technology is the application of catalyst, the weight studied at present
The novel catalytic process characterized by low cost and low temperature of point mainly catalysis denitrating flue gas process development.It should be noted that
It is, due to SO intrinsic in flue gas2It is higher with dust concentration, lead to catalyst poisoning, shortens its service life.Therefore, it to weigh
Depending on technique desulfurization technology as exploitation SCR.Traditional commercial catalysts V2O5-WO3/TiO2(anatase) system only exists
300-400oThere is preferable activity in C temperature range, after dedusting and sulfur removal technology, the temperature of whole system can be down to
300oC is hereinafter, be unfavorable for V2O5-WO3/TiO2(anatase) system plays a role, therefore the SCR catalyst gesture researched and developed under low temperature exists
It must go.Column clay is a kind of catalysis material of novel molecular sieve analog structure.Usually using inorganic cation (Al, Zr, Ti, Fe
With Cr etc.) this substance is carried out as crosslinking agent pillared, lamellar clay interlayer is supported, so that interlamellar spacing broadens, most end form
At the porous network structure of two-dimensional channel.The molecular sieve analog structure that clay after pillared has has biggish surface acidity, ratio
Surface area and aperture.Catalyst can be individually made, can also be used as carrier.In terms of practical application, column clay is being urged
Change field and adsorbing domain are used widely, such as VOCs and H2The catalytic elimination of S.In recent years, Many researchers are answered
NO is removed for SCRxDirection.
Summary of the invention
The shortcomings such as the present invention is directed to existing denitration catalyst carrier interlamellar spacing, specific surface area is small, stability is poor, use
Inorganic cation Ni, Mn are pillared to the progress of this substance as crosslinking agent, support lamellar clay interlayer, so that interlamellar spacing becomes
Width ultimately forms the porous network structure of two-dimensional channel.Pillared montmorillonite and molecular sieve seemingly, have more stable than montmorillonite
Pore structure and bigger specific surface area.Pillared montmorillonite is to pass through cationic exchanged form by pillaring agent or directly into people Meng Tuo
Between soil layer, montmorillonite interlamination region environment is made to change.Crosslinking agent enters interlayer and supports in " column " shape, forms a kind of new layer
Shape alumina silicate mineral.Crosslinking agent mostly uses greatly the macrocation of organic or inorganic, has synthesized various pillared montmorillonites.
The technical scheme adopted by the invention is as follows: with montmorillonite (MMT) for raw material, Ni/Mn-MMT is prepared by infusion process
Low-temperature denitration catalyst is simultaneously studied and is evaluated to its denitration performance at low temperature.This experiment utilizes the characteristic of montmorillonite,
And with Ni and Mn pillared montmorillonite, supportted the interlamellar spacing of montmorillonite big, it made to have a better carrier effect, at the same the element for
Denitration has good performance, there is good denitration reduction at a lower temperature.
Optionally, the pillared amount of Ni is 5 ~ 15 %(mass fractions), the load capacity of Mn is corresponding 5 ~ 15 %(mass fraction),
Remaining is montmorillonite.
Above-mentioned Ni/Mn-MMT low-temperature denitration of flue gas catalyst, specific preparation process are as follows:
Montmorillonite must first carry out purification process in catalyst prepared by step (1), be placed in 1 L beaker and be added 800 mL's
Deionized water adds calgon, with phosphorus acid for adjusting pH to 3.4 or so.1 h is vigorously stirred in 60 DEG C of waters bath with thermostatic control
(4500 r/min), which stands one hour, separates its slurries, filters, discards lower layer's impurity, take upper layer slurries, then in 80 DEG C of items
Sample is dried under part.
Step (2) takes montmorillonite prepared in appropriate step 1, and is swollen 6 h with 1000 mL deionized waters, then distinguish
Take mass fraction be 5 %, 10 %, 15% pillared amount Ni (CH3COO)2·4H2O solid is dissolved with appropriate distilled water.
Ni (the CH that step (3) takes step (2) to prepare3COO)2·4H2O is molten with montmorillonite mixed liquor, under the conditions of 180 DEG C
After the completion of stirring, suspension is moved into autoclave by 6 h of heating stirring, reacted under the conditions of 180 DEG C take out after 5 h from
The heart washs 3-4 times.It is placed in baking oven after 100 DEG C of dryings again, in 500 DEG C of Muffle kiln roastings 4 hours to get arriving Ni-based column
Montmorillonite (Ni-MMT).
Step (4) prepares Ni/Mn-MMT catalyst by equi-volume impregnating.15 g montmorillonite carriers are weighed, manganese is born
15 %(mass fraction of carrying capacity), the MnSO of required quality4· H2(the NH of O and identical mole of proportion4)2S2O8It is dissolved in appropriate steaming
Distilled water.
Step (5) is added to solution prepared in step (3) in Ni-based pillared montmorillonite, in 180 DEG C of condition
After the completion of stirring, suspension is moved into autoclave, 24 hours is stood, is then placed in baking again for lower heating stirring 6 hours
In case after 120 DEG C of dryings.Solid sample obtained is pulverized, is placed in 400 DEG C of Muffle kiln roastings 4 hours to get arriving
Mn/Ni-MMT catalyst.
Wherein low-temperature denitration catalyst prepared by step (3) must first heating stirring 6 be small under conditions of 180 DEG C
When.
In step (4), (5), maturing temperature is 400 DEG C and roasts 4 hours.
The invention has the benefit that
1, use cheap and large specific surface area clay class montmorillonite as carrier, this layer chain structure has good
Mechanical and thermal stability keeps the catalyst of preparation easy to form and stable structure；There is porosity, strong adsorptivity simultaneously, can locate
It manages improved bigger serface and surface itself and has faintly acid, be a kind of good catalyst carrier.
2, a series of Ni/Mn-MMT that this experiment is prepared, compared to Ni, Mn of individual element, low-temperature denitration rate is obtained
To being obviously improved.Wherein 10%Ni/Mn-MMT denitration activity reaches 95% conversion rate of NOx at 260 DEG C or so, it was demonstrated that preparation is urged
Agent has preferable low temperature active.
Detailed description of the invention
Fig. 1 is the XRD diagram that mass fraction is 5%, 10%, 15% Ni/Mn-MMT.
Specific embodiment
Below with reference to embodiment and comparative example, a kind of preparation of Ni/Mn-MMT low-temperature denitration catalyst is illustrated.
Embodiment 1:
(1) montmorillonite of 20 g after purification is taken, and is swollen 6 h with 1000 mL deionized waters, then taking mass fraction is 5% pillared
Ni (the CH of amount3COO)2·4H2O solid, with being added in the sufficient montmorillonite of swelling after the dissolution of appropriate distilled water, at 180 DEG C
Under conditions of 6 h of heating stirring, after the completion of stirring, by suspension move into autoclave in, react 5 under conditions of 180 DEG C
It is taken out centrifuge washing 3-4 times after h.Be placed in baking oven after 100 DEG C of dryings again, in 500 DEG C of Muffle kiln roastings 4 hours to get
To Ni-based pillared montmorillonite (5%Ni-MMT).Ni/Mn-MMT catalyst is prepared by equi-volume impregnating.Weigh 15 g montmorillonites
Carrier, the 15 %(mass fraction of load capacity of manganese), the MnSO of required quality4· H2(the NH of O and identical mole of proportion4)2S2O8It is molten
Solution is in appropriate distilled water.Prepared solution is added in Ni-based pillared montmorillonite, the heating stirring 6 under conditions of 180 DEG C
Hour, after the completion of stirring, suspension is moved into autoclave, stands 24 hours, is then placed in baking oven and does again for 120 DEG C
After dry.Solid sample obtained is pulverized, is placed in 400 DEG C of Muffle kiln roastings 4 hours to get to 5% Ni/Mn-MMT
Catalyst.
Embodiment 2:
Taking mass fraction is the Ni (CH of 10% pillared amount3COO)2·4H2O solid, remaining step is with embodiment 1 to get to 10%
Ni/Mn-MMT catalyst.
Embodiment 3:
Taking mass fraction is the Ni (CH of 15% pillared amount3COO)2·4H2O solid, remaining step is with embodiment 1 to get to 15%
Ni/Mn-MMT catalyst.
Fig. 1 is the XRD diagram of the Ni/Mn-MMT catalyst prepared in embodiment 1.It can be seen from the figure that 2θIt is 19.9
The peak of o is to belong to (100) crystal face, belongs to the characteristic peak of montmorillonite.After dipping solution dipping, which does not change, table
The active constituent of bright load does not influence the structure of carrier.2θ=37.2 °, 43.2 °, 62.8 ° detect NiO diffraction maximum, right
(111), (200), (220) crystal face of NiO are answered, while 2θ=19.86°、22.82°、35.04°、42.42°、5.84°、
62.36 ° observing MnO2Peak, correspond to (100), (110), (040), (140), (240), (151) crystal face, illustrate Ni, Mn
It is pillared between montmorillonite well.
Comparative example 1:
Mn element is not added in catalyst in example 1, specific steps are as follows:
Appropriate montmorillonite after purification is taken, and is swollen 6 h with 1000 mL deionized waters, then taking mass fraction is 5% pillared amount
Ni(CH3COO)2·4H2O solid, with being added in the sufficient montmorillonite of swelling after the dissolution of appropriate distilled water, in 180 DEG C of item
6 h of heating stirring under part after the completion of stirring, suspension is moved into autoclave, after reacting 5 h under conditions of 180 DEG C
It takes out centrifuge washing 3-4 times.It is placed in baking oven after 100 DEG C of dryings again, in 500 DEG C of Muffle kiln roastings 4 hours to get arriving
Ni-based pillared montmorillonite (5%Ni-MMT).
Comparative example 2:
It is prepared by the purifying of montmorillonite, specific steps are as follows:
Montmorillonite must first carry out purification process in prepared catalyst, be placed in 1 L beaker and be added the deionization of 800 mL
Water adds calgon, with phosphorus acid for adjusting pH to 3.4 or so.1 h(4500 is vigorously stirred in 60 DEG C of waters bath with thermostatic control
R/min) standing one hour separates its slurries, filters, discards lower layer's impurity, take upper layer slurries, then under the conditions of 80 DEG C
Dry sample.
The active testing of low-temperature denitration of flue gas catalyst
The present invention is catalyzed in dual-purpose fixed bed in SCR and carries out active testing, and it is anti-that measurement about 3mL catalyst is placed in fixed bed quartz ampoule
It answers in device, 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]=1000 ppm, [NH3]=1000 ppm, O2=5 vol.%, reaction velocity are=45000 h-1。
Carry out anti-SO2Property test when, equally with N2As carrier gas, gas composition is [NO]=1000 ppm, [NH3]=1000 ppm、
[SO2The ppm of]=200, other operations are constant；
First Continuous aeration 30min before test, so that Catalyst Adsorption is saturated, to exclude NOxIt is adsorbed and under bring concentration
Drop.Inlet concentration is detected using the KM9106 flue gas analyzer of German Kain Co., Ltd.'s production simultaneously, obtains accurate import NOxIt is dense
Degree, is denoted as [NOx]in.Then gradually heat up while detecting the NO of outletxConcentration is denoted as [NOx]out.It is required according to reaction temperature,
It is stepped up reaction temperature, reads the NO exported at this temperature after stablizing every 20 DEG CxConcentration calculates denitration efficiency
Seen from table 1, the 10Ni/Mn-MMT low-temperature denitration of flue gas catalyst prepared by the present invention has lower active temperature,
Wider active temperature section.10Ni/Mn-MMT denitration activity is best, and 95% conversion rate of NOx is reached at 260 DEG C or so, it was demonstrated that
The catalyst of preparation has preferable low temperature active.
Table 1: denitration performance evaluation test data
Claims (6)
1. a kind of pillared manganese base montmorillonite (Ni/Mn-MMT) low-temperature denitration catalyst preparation of Ni, it is characterised in that: the catalyst
Using montmorillonite as carrier, with the pillared manganese base montmorillonite of Ni.
2. according to claim 1, the pillared manganese base montmorillonite low-temperature denitration catalyst of the Ni, it is characterised in that: prepared
Montmorillonite must first carry out purification process in catalyst, be placed in 1 L beaker and be added 800 mL deionized waters, add six inclined phosphorus
Sour sodium, with phosphorus acid for adjusting pH=3.4 or so；(4500 r/min) stands one after being vigorously stirred in 60 DEG C of waters bath with thermostatic control 1 hour
Hour makes the separation of its slurries, filters, and discards lower layer's impurity, takes upper layer slurries, then dries sample under the conditions of 80 DEG C.
3. according to claim 1 or 2, the pillared manganese base montmorillonite low-temperature denitration catalyst of the Ni, it is characterised in that prepared
In catalyst, the pillared amount of Ni is that mass fraction is the % of 5 % ~ 15.
4. the pillared manganese base montmorillonite low-temperature denitration catalyst of Ni described according to claim 1 ~ any one of 3 and preparation method,
It is characterized by: step (1): taking 20 g montmorillonites and be swollen 6 h with 1000 mL deionized waters, then taking mass fraction respectively is 5
%, 10 %, 15% pillared amount Ni (CH3COO)2·4H2O solid is dissolved with appropriate distilled water respectively；Step (2): step (1) is taken
Ni (the CH of preparation3COO)2·4H2O and montmorillonite mixed liquor, the heating stirring 6 hours under the conditions of 180 DEG C, after the completion of stirring,
Suspension is moved into autoclave, is taken out centrifuge washing 3-4 times after being reacted 5 hours under the conditions of 180 DEG C；It is placed in baking again
In case after 100 DEG C of dryings, in 500 DEG C of Muffle kiln roastings 4 hours to get arriving Ni-based pillared montmorillonite (Ni-MMT)；Step
(3): Ni/Mn-MMT catalyst is prepared by equi-volume impregnating；Weigh 15 g montmorillonite carriers, the 15 % (matter of load capacity of manganese
Measure score), the MnSO of required quality4· H2(the NH of O and identical mole of proportion4)2S2O8It is dissolved in appropriate distilled water；Step
(4): solution prepared in step (2) being added in Ni-MMT, the heating stirring 6 hours under conditions of 180 DEG C, stirring
After the completion, suspension is moved into autoclave, stands 24 hours, is then placed in again in baking oven after 120 DEG C of dryings；It will system
The solid sample obtained is pulverized, and is placed in 500 DEG C of Muffle kiln roastings 4 hours to get Ni/Mn-MMT catalyst is arrived.
5. the preparation method of low-temperature denitration catalyst as claimed in claim 4, it is characterised in that: first under conditions of 180 DEG C
Heating stirring 6 hours.
6. the preparation method of low-temperature denitration catalyst as claimed in claim 4, it is characterised in that: in step (2), (3), roasting
Temperature is 500 DEG C and roasts 4 hours.
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