CN110465283A - A kind of low-temperature denitration catalyst and preparation method thereof - Google Patents
A kind of low-temperature denitration catalyst and preparation method thereof Download PDFInfo
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- CN110465283A CN110465283A CN201910783183.1A CN201910783183A CN110465283A CN 110465283 A CN110465283 A CN 110465283A CN 201910783183 A CN201910783183 A CN 201910783183A CN 110465283 A CN110465283 A CN 110465283A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 41
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 41
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 239000010936 titanium Substances 0.000 claims abstract description 33
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 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 claims abstract description 15
- 238000002485 combustion reaction Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 12
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 3
- 239000012695 Ce precursor Substances 0.000 claims description 12
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 4
- 239000006193 liquid solution Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 21
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000003546 flue gas Substances 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002574 poison Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- USJZIUVMYSUNGB-UHFFFAOYSA-N neodymium;hydrate Chemical compound O.[Nd] USJZIUVMYSUNGB-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- MFWNKCLOYSRHCJ-AGUYFDCRSA-N 1-methyl-N-[(1S,5R)-9-methyl-9-azabicyclo[3.3.1]nonan-3-yl]-3-indazolecarboxamide Chemical compound C1=CC=C2C(C(=O)NC3C[C@H]4CCC[C@@H](C3)N4C)=NN(C)C2=C1 MFWNKCLOYSRHCJ-AGUYFDCRSA-N 0.000 description 1
- 241000883964 Ariocarpus retusus Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000003834 hydroxide co-precipitation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 230000009466 transformation Effects 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- 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 discloses a kind of low-temperature denitration catalysts, and including carrier and the active component being supported on carrier, carrier is titanium dioxide, and active component is cerium and neodymium.In low-temperature denitration catalyst, the molar ratio of Ce elements, neodymium element and titanium elements is (0.1~0.3): (0.2~0.4): 1.Also disclose the preparation method of above-mentioned catalyst: cerous nitrate, neodymium nitrate and the titanium source of formula ratio use deionized water dissolving respectively, are then sufficiently mixed to obtain mixing precursor solution, and the urea that 4~6wt% is added stirs evenly, and obtains catalyst combustion liquid；Catalyst combustion liquid is heated slowly to 250~400 DEG C in air atmosphere, and keeps 0.5~2h of the temperature, obtains head product；Head product calcines 4~6h under the conditions of 400~550 DEG C of temperature to get low-temperature denitration catalyst.Low-temperature denitration catalyst of the invention has denitration activity height, nitrogen selective good, the strong feature of the anti-sulfur dioxide ability of water resistant.Preparation process simplifies, and low energy consumption, and utilization rate is high, environment friendly and pollution-free.
Description
Technical field
The invention belongs to gas denitrifying technology fields, and in particular to a kind of low-temperature denitration catalyst and preparation method thereof.
Background technique
In the prior art, for the NO in stationary source flue gasxThe effective ways of removing be using NH3Selectivity is carried out to urge
Change reduction (SCR), the commercial catalysts of the mainstream used in SCR reaction are V2O5-WO3/TiO2.Although catalyst V2O5-WO3/
TiO2With high activity and high antisulphuric ability, but still there are some problems:
(1), catalyst higher cost causes denitration at high cost.
(2), operation temperature necessarily is greater than 623K (about 350 DEG C).Since temperature reduces flue gas after dedusting and desulfurization, reach
Less than catalyst V2O5-WO3/TiO2Operation temperature, therefore SCR reaction bed must be necessarily arranged at air preheater, deduster and de-
Before sulphur device, and catalyst will necessarily be exposed to SO containing high concentration by this arrangement2Under the flue gas of particle dusty.
High concentration SO2There is very strong poisoning effect to catalyst with particle dusty, seriously affects catalytic efficiency and the use of catalyst
Service life.
(3), water resistant and anti-sulfur dioxide performance are poor.
Therefore, low-temperature SCR catalyst is developed with the denitration process for the flue gas after desulfurization, and cost is relatively low, catalysis effect
Rate is good just necessary.
Summary of the invention
The first aspect of the invention is to provide a kind of low-temperature denitration agent, is existed with solving denitrating catalyst in the prior art
The main problems such as denitration activity is high when low temperature, water resistant and anti-sulfur dioxide performance difference.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of low-temperature denitration catalyst, including carrier, and the active component of load on the carrier, the carrier are two
Titanium oxide, the active component are the oxide of cerium and the oxide of neodymium, in which:
In the low-temperature denitration catalyst, the molar ratio of Ce elements, neodymium element and titanium elements is (0.1~0.3): (0.2~
0.4):1。
It should be understood that in low-temperature denitration catalyst of the invention, if the molar ratio of neodymium element is excessive, active component
Active site on cerium will be suppressed, and activity reduces；If the molar ratio of neodymium element is too small, low-temperature denitration catalyst is in low-temperature zone
The activity of (100~250 DEG C) reaches not good enough.
Under the conditions of above-mentioned element ratio, the low-temperature denitration catalyst of preparation can have good under cryogenic
Activity, perfect combination bimetallic Ce elements and neodymium element produce excellent low-temperature denitration activity.
Preferably, the molar ratio of Ce elements, neodymium element and titanium elements is 0.2:(0.2~0.4): 1.
It is further preferred that the molar ratio of Ce elements, neodymium element and titanium elements is 0.2:0.3:1.
Second object of the present invention is to provide a kind of preparation method of low-temperature denitration catalyst, include the following steps:
(1), the cerous nitrate of formula ratio, neodymium nitrate and titanium source use deionized water dissolving respectively, obtain cerium precursor solution, neodymium
Precursor solution and titanium precursors solution；
(2), the metal front liquid solution in step (1) is sufficiently mixed to obtain mixing precursor solution, and it is added 4~
The urea of 6wt% stirs evenly, and obtains catalyst combustion liquid；
(3), the catalyst combustion liquid of step (2) is heated slowly to 250~350 DEG C in air atmosphere, and keeping should
0.5~2h of temperature, obtains head product；
(4), the head product of step (3) is calcined to 4~6h at 400~550 DEG C to get low-temperature denitration catalyst.
In the step (1), the concentration of the cerous nitrate is 0.04~0.15g/ml；In the neodymium precursor solution, institute
The concentration for stating neodymium nitrate is 0.06~0.15g/ml；In the titanium precursors solution, the concentration of the titanium source is 0.5~2mol/
l。
The molar ratio of the Ce elements, neodymium element and titanium elements is (0.1~0.3): (0.2~0.4): 1.
The titanium source is selected from one or both of butyl titanate, titanium sulfate.
Above-mentioned preparation method, under the conditions of specific recipe ingredient and content, using Self-propagating high-temperature synthesis legal system
Standby low-temperature denitration catalyst, simple process, low energy consumption, and utilization rate is high, be effectively ensured low-temperature denitration catalyst uniformity and
Stability ensures that it is high with denitration activity, nitrogen selective is good, the strong feature of the anti-sulfur dioxide ability of water resistant.Together
When, above-mentioned preparation method is repeatedly washed compared to the preparation method of ammonium hydroxide co-precipitation without deionized water and ethyl alcohol, therefore environmental protection
It is pollution-free, there is stronger industrial application value.
Preferably, in the step (1), the concentration of the cerous nitrate is 0.043~0.130g/ml；The neodymium presoma
In solution, the concentration of the neodymium nitrate is 0.066~0.132g/ml；In the titanium precursors solution, the concentration of the titanium source is
1mol/l。
It is further preferred that in the cerium precursor solution, the concentration of the cerous nitrate is in the step (1)
0.087g/ml；In the neodymium precursor solution, the concentration of the neodymium nitrate is 0.099g/ml.
Preferably, in the step (1), the molar ratio of Ce elements, neodymium element and titanium elements is 0.2:0.3:1；The step
Suddenly in (2), the additional amount of the urea is the 5wt% of the mixing precursor solution.
Preferably, in the step (3), the catalyst combustion liquid is heated slowly to 300 DEG C in air atmosphere, and protects
Temperature 1h is held, head product is obtained.
Preferably, in the step (4), the head product of step (3) is calcined into 5h at 450 DEG C.
Under above-mentioned optimum condition, the better catalyst of low-temperature denitration effect can be prepared, in 100~400 DEG C of models
Enclose it is interior it is equal can have excellent denitration activity, and stability is good, the anti-sulfur dioxide ability of water resistant is strong.
Compared with prior art, the present invention has following advantageous effects:
(1), low-temperature denitration catalyst of the invention using titanium dioxide as carrier, while using cerium, neodymium bimetal element group
Cooperation is active component, under specific conditions of mixture ratios, it can be achieved that the processing of nitrogen oxides of exhaust gas under cryogenic conditions, simultaneously
Good, the strong feature of the anti-sulfur dioxide ability of water resistant with denitration activity height, nitrogen selective.At 100~400 DEG C, especially
At a temperature of being not higher than 300 DEG C, greatly improved in denitration activity, the anti-sulfur dioxide ability of water resistant compared with typical catalyst,
Especially when denitration temperature is 250 DEG C, the conversion ratio of NO still is able to reach 96.8~99%.This is advantageous to make SCR
Denitrification apparatus is arranged in thermal power plant's back-end ductwork, to reduce waste heat loss, improves thermal power plant's performance driving economy.
(2), the preparation method of low-temperature denitration catalyst of the invention, in specific recipe ingredient of the invention and content condition
Under, low-temperature denitration catalyst is prepared using Self-propagating high-temperature synthesis method, simple process, low energy consumption, and utilization rate is high, effectively protects
The uniformity and stability for having demonstrate,proved low-temperature denitration catalyst ensure that it is high with denitration activity, nitrogen selective is good, resist
The strong feature of the anti-sulfur dioxide ability of water.Meanwhile the preparation method of low-temperature denitration catalyst of the invention, it is co-precipitated compared to ammonium hydroxide
Preparation method, repeatedly washed without deionized water and ethyl alcohol, therefore environment friendly and pollution-free, have stronger industrial application value.
(3), further progress theoretical analysis shows that, the addition of neodymium inhibit crystallization particle size growth, enhance cerium member
Element catalyst surface dispersibility so that catalyst surface dispersibility is improved；The addition of neodymium can promote catalyst table
Face Ce3+With the formation of chemically adsorbing oxygen, be conducive to NO2Formation, in addition, the introducing of neodymium can also promote NH3In Ce/TiO2It urges
Absorption in agent, effectively improves catalytic reaction activity.
Detailed description of the invention
Fig. 1 shows the water resistants of different catalysts, anti-SO2Poison the catalytic efficiency of experiment.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.It should be understood that following embodiment is merely to illustrate this
Invention is not for limiting the scope of the invention.
The 4100 type fixed beds of catalytic reactor used purchase from Zhejiang Fan Tai Instrument Ltd. are micro- in following embodiment
Anti- evaluating apparatus, outer diameter 16mm, long 480mm.
Unstripped gas enters catalytic reactor by preheating, and reaction temperature is empty at 100~400 DEG C, flow velocity 1000ml/min
Between speed 108000h-1。
Simulated flue gas composition: NO 600ppm, NH3For 600ppm, O2It is 5%, remaining gas Ar is as Balance Air, gas
Flow is controlled by the CS200 type mass flowmenter purchased from Beijing Co., Ltd, Sevenstar Huachuang Electronic.
NO used in following embodiment, NH3Molar concentration be 1%, surplus Ar, have purchased from the big wound calibrating gas in Shanghai
Limit company, O2, Ar purity be 99.99%, be purchased from Jiangnan mixed gas Co., Ltd；
Drug purity used be 99.9% cerous nitrate, six nitric hydrate neodymiums, butyl titanate, titanium sulfate, be purchased from Ah
Latin.
The preferred technical solution of the present invention is further detailed below by way of specific embodiment.
The preparation of embodiment 1, low-temperature denitration catalyst A
The preparation of the low-temperature denitration catalyst of the present embodiment, the specific steps are as follows:
(1), the six nitric hydrate neodymium of neodymium presoma and 34.03g butyl titanate of the cerium precursor cerous nitrate of 8.68g, 8.77g
100ml deionized water dissolving is used respectively, obtains cerium precursor solution, neodymium precursor solution and titanium precursors solution.
(2), the metallic precursor solution in step (1) is sufficiently mixed to obtain mixing precursor solution, and be added
17.58g urea stirs 1h so as to stir evenly, and obtains catalyst combustion liquid.
(3), the catalyst combustion liquid of step (2) is placed in ceramic crucible, 250 is heated slowly in air atmosphere
DEG C, and temperature 2h is kept, obtain head product；
(4), the head product of step (3) is calcined to 4h at 550 DEG C to get the low-temperature denitration catalyst of the present embodiment, meter
For low-temperature denitration catalyst A.
In the present embodiment, the molar ratio of cerium, neodymium and titanium elements is 0.2:0.2:1, and the urea is mixing precursor solution
The 5wt% of quality.
The preparation of embodiment 2, low-temperature denitration catalyst B
The preparation of the low-temperature denitration catalyst of the present embodiment, specific steps are as follows:
(1), the cerium precursor cerous nitrate of 8.68g, the six nitric hydrate neodymium of neodymium presoma of 13.15g and 34.03g metatitanic acid fourth
Ester uses 100ml deionized water dissolving respectively, obtains cerium precursor solution, neodymium precursor solution and titanium precursors solution.
(2), the metallic precursor solution in step (1) is sufficiently mixed to obtain mixing precursor solution, and is added 18.73
G urea stirs 1h so as to stir evenly, and obtains catalyst combustion liquid.
(3), the catalyst combustion liquid of step (2) is placed in ceramic crucible, 300 is heated slowly in air atmosphere
DEG C, and temperature 1h is kept, obtain head product；
(4), the head product of step (3) is calcined to 5h at 450 DEG C to get the low-temperature denitration catalyst of the present embodiment, meter
For low-temperature denitration catalyst B.
In the present embodiment, the molar ratio of cerium, neodymium and titanium elements is 0.2:0.3:1, and the urea is mixing precursor solution
The 5wt% of quality.
The preparation of embodiment 3, low-temperature denitration catalyst C
The preparation of the low-temperature denitration catalyst of the present embodiment, specific steps are as follows:
(1), the cerium precursor cerous nitrate of 8.68g, the six nitric hydrate neodymium of neodymium presoma of 17.53g and 24g titanium sulfate difference
With 100ml deionized water dissolving, cerium precursor solution, neodymium precursor solution and titanium precursors solution are obtained.
(2), the metallic precursor solution in step (1) is sufficiently mixed to obtain mixing precursor solution, and be added
17.51g urea stirs 1h so as to stir evenly, and obtains catalyst combustion liquid.
(3), the catalyst combustion liquid of step (2) is placed in ceramic crucible, 350 is heated slowly in air atmosphere
DEG C, and temperature 0.5h is kept, obtain head product；
(4), the head product of step (3) is calcined to 6h at 400 DEG C to get the low-temperature denitration catalyst of the present embodiment, meter
For low-temperature denitration catalyst C.
In the present embodiment, the molar ratio of cerium, neodymium and titanium elements is 0.2:0.4:1, and the urea is mixing precursor solution
The 5wt% of quality.
The preparation of embodiment 4, low-temperature denitration catalyst D
Basic step is same as Example 2, and difference is: in step (1), using the cerium precursor cerous nitrate of 13.02g.
In the present embodiment, the molar ratio of cerium, neodymium and titanium elements is 0.3:0.3:1, and the urea is mixing precursor solution quality
4wt%.
The preparation of embodiment 5, low-temperature denitration catalyst E
Basic step is same as Example 2, and difference is: in step (1), using the cerium precursor cerous nitrate of 4.34g.This
In embodiment, the molar ratio of cerium, neodymium and titanium elements is 0.1:0.3:1.The urea is mixing precursor solution quality
6wt%.
Embodiment 6, fixed bed micro anti-evaluation
Low-temperature denitration CeNd/TiO prepared by embodiment 1-52Catalyst A-E and common catalyst V2O5-WO3/
TiO2D (buying from Chengdu east Kytril company) is used as catalyst F, and it is real to carry out denitration reaction at 100~400 DEG C respectively
It tests, loaded catalyst 4ml.
Experiment test is first passed through fixed bed micro anti-evaluation device with the NO in simulated flue gas before starting, and allows low-temperature denitration
CeNd/TiO2Catalyst and V2O5-WO3/TiO2D catalyst adsorbs NO to being saturated respectively, avoids in subsequent reactions because of catalyst pair
The absorption of NO causes the reduction of NO in simulated flue gas.
Simulate gas (flue gas flow rate 1000ml/min, gas concentration: NO 600ppm, NH3For 600ppm, O2It is 5%,
Remaining gas is Ar) mixing after be sent into fixed bed micro anti-evaluation device, under the effect of the catalyst, NH3NO is reduced to N2, instead
Gaseous mixture after answering absorbs unreacted NH through phosphoric acid solution3Be discharged into atmosphere by exhaust pipe, fixed bed micro anti-evaluation device into,
The NO concentration of outlet is detected using the modDl60i flue gas analyzer of U.S.'s thermoelectricity.Activity using NO conversion ratio as catalyst is commented
Valence index, the results are shown in Table 1.
The Activity evaluation of 1 different catalysts of table
As can be seen from Table 1:
In 100~400 DEG C of wide temperature section, low-temperature denitration CeNd/TiO prepared by the present invention2The NO of catalyst A~E turns
Rate is above the NO conversion ratio of typical catalyst F, specifically:
In 100~350 DEG C of low-temperature zone, low-temperature denitration catalyst A~E of the invention is living with good low-temperature denitration
Property.It especially at a temperature of being not higher than 300 DEG C, is greatly improved in denitration activity compared with typical catalyst, especially de-
When nitre temperature is 250 DEG C, the conversion ratio of NO still is able to reach 94.5~99%, and the denitration efficiency than typical catalyst F is higher by
41.0~47.8%.When denitration temperature is set as 100 DEG C, it is catalyzed, still is able to using catalyst A~E of the invention
Effectively NH is converted by NO3, but typical catalyst F can't detect catalytic effect completely.Even at 350~400 DEG C
Higher temperature section, CeNd/TiO prepared by the present invention2The NO conversion ratio of catalyst A-E is still higher than the NO of typical catalyst F
Conversion ratio.
It can be seen that when carrying out denitrating flue gas under the same conditions, CeNd/TiO that embodiment 1-5 is prepared2Catalysis
Agent A~E is higher than common catalyst F denitration efficiency.This is advantageous to that SCR denitration device is made to be arranged in thermal power plant's tail portion cigarette
Thermal power plant's performance driving economy is improved to reduce waste heat loss in road.Illustrate that catalyst operating temperature range of the invention is wide, especially
Suitable for low-temperature denitration.
In conclusion CeNd/TiO prepared by the present invention2Catalyst especially exists at 100~400 DEG C of wide temperature window
250 DEG C or so still have a high denitration efficiency, thus 250~400 DEG C its with wider array of active window, be more conducive to make SCR de-
Nitre device is arranged in thermal power plant's back-end ductwork, to reduce waste heat loss, improves thermal power plant's performance driving economy.Wherein catalyst B exists
Catalytic efficiency when temperature is 150 DEG C still can reach 98.9%, therefore have very excellent low-temperature denitration catalytic performance.
Embodiment 7, water resistant, anti-SO2Poison experiment
By above-mentioned CeNd/TiO2Catalyst A~D and catalyst F are respectively placed in 100ppmSO2And 5%H2It is carried out under the conditions of O
Water resistant, anti-SO2Poison experiment, sets denitration temperature as 250 DEG C, experimental result is as shown in Figure 1.
As seen from Figure 1, the antitoxinization performance of the catalyst A-E of embodiment 1-5 preparation is obviously than typical catalyst F
It is good.Wherein, NO conversion ratio is lower than 50% after NO conversion ratio of the typical catalyst F since experiment is lower than 70%, 10h.
CeNd/TiO of the invention2Catalyst A~E can reach 95% or more NO conversion ratio in 1~5h of test, 5~
In 10h, it can reach 80% or more NO conversion ratio, in 10~20h, CeNd/TiO2Catalyst B still has 75%
Above NO conversion ratio.Catalyst B has optimal water resistant, anti-SO2Poisoning effect.Illustrate low-temperature denitration catalysis of the invention
Agent has excellent water resistant, anti-SO2Poison performance, therefore long service life.
Specific embodiments of the present invention are described in detail above, but it is only used as example, the present invention is not intended to limit
In particular embodiments described above.To those skilled in the art, it any equivalent modifications to the practical progress and replaces
In generation, is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and repair
Change, all should be contained within the scope of the invention.
Claims (9)
1. a kind of low-temperature denitration catalyst, which is characterized in that including carrier, and the active component of load on the carrier, institute
Stating carrier is titanium dioxide, and the active component is cerium and neodymium, in which:
In the low-temperature denitration catalyst, the molar ratio of Ce elements, neodymium element and titanium elements is (0.1~0.3): (0.2~
0.4):1。
2. low-temperature denitration catalyst according to claim 1, which is characterized in that the Ce elements, neodymium element and titanium elements
Molar ratio be 0.2:(0.2~0.4): 1.
3. low-temperature denitration catalyst according to claim 2, which is characterized in that the Ce elements, neodymium element and titanium elements
Molar ratio be 0.2:0.3:1.
4. the preparation method of low-temperature denitration catalyst, which comprises the steps of:
(1), the cerous nitrate of formula ratio, neodymium nitrate and titanium source use deionized water dissolving respectively, obtain cerium precursor solution, neodymium forerunner
Liquid solution and titanium precursors solution；
(2), the metal front liquid solution in step (1) is sufficiently mixed to obtain mixing precursor solution, and 4~6wt% is added
Urea stir evenly, obtain catalyst combustion liquid；
(3), the catalyst combustion liquid of step (2) is heated slowly in air atmosphere 250~350 DEG C, and keeps the temperature
0.5~2h obtains head product；
(4), the head product of step (3) is calcined to 4~6h under the conditions of 400~550 DEG C of temperature to get low-temperature denitration catalyst；
In the step (1), the concentration of the cerous nitrate is 0.04~0.15g/ml；In the neodymium precursor solution, the nitre
The concentration of sour neodymium is 0.06~0.15g/ml；In the titanium precursors solution, the concentration of the titanium source is 0.5~2mol/l；
In the step (1), the molar ratio of Ce elements, neodymium element and titanium elements is (0.1~0.3): (0.2~0.4): 1.
In the step (1), the titanium source is selected from one or both of butyl titanate, titanium sulfate.
5. the preparation method of low-temperature denitration catalyst according to claim 4, which is characterized in that in the step (1), institute
The concentration for stating cerous nitrate is 0.043~0.130g/ml；In the neodymium precursor solution, the concentration of the neodymium nitrate is 0.066~
0.132g/ml, the concentration of the titanium source are 1mol/l.
6. the preparation method of low-temperature denitration catalyst according to claim 5, which is characterized in that in the step (1), institute
It states in cerium precursor solution, the concentration of the cerous nitrate is 0.087g/ml；In the neodymium precursor solution, the neodymium nitrate
Concentration is 0.099g/ml.
7. the preparation method of low-temperature denitration catalyst according to claim 4, which is characterized in that in the step (1), cerium
The molar ratio of element, neodymium element and titanium elements is 0.2:0.3:1；In the step (2), the additional amount of the urea is described mixed
Close the 5wt% of precursor solution.
8. the preparation method of low-temperature denitration catalyst according to claim 4, which is characterized in that in the step (3), institute
It states catalyst combustion liquid and is heated slowly to 300 DEG C in air atmosphere, and keep temperature 1h, obtain head product.
9. the preparation method of low-temperature denitration catalyst according to claim 4, which is characterized in that, will in the step (4)
The head product of step (3) calcines 5h at 450 DEG C.
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