CN110479296A - A kind of catalyst and preparation method thereof reducing denitration the escaping of ammonia - Google Patents
A kind of catalyst and preparation method thereof reducing denitration the escaping of ammonia Download PDFInfo
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- CN110479296A CN110479296A CN201910764917.1A CN201910764917A CN110479296A CN 110479296 A CN110479296 A CN 110479296A CN 201910764917 A CN201910764917 A CN 201910764917A CN 110479296 A CN110479296 A CN 110479296A
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- ammonia
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- denitration
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 7
- 239000011258 core-shell material Substances 0.000 claims abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000003245 coal Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000003546 flue gas Substances 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
A kind of catalyst and preparation method thereof reducing denitration the escaping of ammonia, the catalyst are powdered core-shell structure: " shell " is porous SiO2Layer, with a thickness of 30~50nm, aperture is 3~4nm；" core " is with nano-TiO2For carrier, V2O5、CuSO4And CeO2For the compound particle of active component, compound particle partial size is in 50um or so, wherein V2O5Mass percentage is 1%, CuSO4Mass percentage be 5~7%, CeO2Mass percentage be 9~10%.The catalyst of prepared core-shell structure has the ammonia catalytic efficiency of higher (> 90%) under the conditions of SCR, and its mature preparation process is reliable, can be used for coal fired power plant and carries out the control of denitration escape ammonia.
Description
Technical field
The invention belongs to power environment protection fields, are related to coal fired power plant flue gases purification, and in particular to one kind can reduce de-
The catalyst and preparation method thereof of nitre the escaping of ammonia.
Background technique
Coal fired power plant denitrating flue gas is the emphasis that atmosphere pollution is administered in recent years.SCR method is the mainstream skill of denitrating flue gas
Art has many advantages, such as denitration efficiency height, technical maturity, is widely applied in coal fired power plant, but the method is important there are one
Defect: the escaping of ammonia.Denitration escape ammonia is reacted with the sulfur trioxide in flue gas generates ammonium hydrogen sulfate, can be enriched under SCR reactor
On the low-temperature heat exchange face of trip, and it is bonded flying dust, leads to heat-transfer surface blocking, heat exchange efficiency decline, safe operation and pot to unit
Furnace thermal efficiency generation seriously affects.Therefore, reducing denitration the escaping of ammonia is that the general character urgently to be resolved that coal fired power plant faces is asked
Topic.Common method has the optimization of spray ammonia, control denitration temperature, periodically displacement catalyst etc., and effect is unobvious, develops novel
Escape ammonia control technology is of great significance.
Summary of the invention
It is an object of the invention to overcome the above-mentioned prior art, urging for denitration the escaping of ammonia can be reduced by providing one kind
Agent and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method for the catalyst reducing denitration the escaping of ammonia prepares Ce-V/Ti powder by sol gel process
Then Ce-V/Ti powder is had the Cu-Ce-V/Ti powder of catalysis oxidation ammonia effect by end by equi-volume impregnating preparation,
Cu-Ce-V/Ti powder is passed through againTechnique prepares the catalyst that can reduce denitration the escaping of ammonia.
A further improvement of the present invention lies in that preparing Ce-V/Ti powder by sol gel process, detailed process is as follows:
By butyl titanate, cerous nitrate, ammonium metavanadate, water, dehydrated alcohol and nitric acid, solgel reaction occurs at room temperature to body
It is until viscosity is not further added by, re-dry, calcining obtain Ce-V/Ti powder；Wherein, butyl titanate, cerous nitrate, metavanadic acid
Ammonium, water, dehydrated alcohol and nitric acid molar ratio be 1:0.047~0.052:0.01:6:8:1.
A further improvement of the present invention lies in that dry temperature is 100 DEG C, the time is for 24 hours.
A further improvement of the present invention lies in that the temperature of calcining is 400 DEG C, time 2h.
A further improvement of the present invention lies in that by Ce-V/Ti powder by equi-volume impregnating, preparation has catalysis oxidation
The process of the Cu-Ce-V/Ti powder of ammonia effect is as follows: copper sulphate is configured to aqueous solution, incipient impregnation Ce-V/Ti powder
Afterwards, it in 100 DEG C of dry 2h, then grinds after 400 DEG C of dry 2h, obtains the Cu-Ce-V/Ti powder with catalysis oxidation ammonia effect
End；Wherein, the mass ratio of copper sulphate and Ce-V/Ti powder is (5.26~7.53): 100.
A further improvement of the present invention lies in that Cu-Ce-V/Ti powder is passed throughTechnique preparation can reduce denitration ammonia
The process of the catalyst of escape is as follows: Cu-Ce-V/Ti powder ultrasonic being first dispersed in dehydrated alcohol, deionized water and ammonium hydroxide
In mixture, ethyl orthosilicate is then added dropwise, drop filters after room temperature reaction 5~6 hours after finishing, and it is dry, it obtains to reduce de-
The catalyst Si@Cu-Ce-V/Ti of nitre escape ammonia；Wherein, Cu-Ce-V/Ti powder, dehydrated alcohol, deionized water, ammonium hydroxide with just
The mass ratio of silester is 1:300:400:5:(2.5~5), the mass concentration of ammonium hydroxide is 28%.
A kind of catalyst reducing out of stock the escaping of ammonia, the catalyst are powdered core-shell structure, and core is that have to ammonia
The solid inorganic nano-particle of catalysed oxidn, shell are hydrophobic porous, inorganic shell.
A further improvement of the present invention lies in that the core is with nano-TiO2For carrier, V2O5、CuSO4And CeO2For activity
The compound particle of component, the partial size of compound particle are 40~50un, wherein V2O5Mass percentage is 1%, CuSO4Quality
Percentage composition is 5~7%, CeO2Mass percentage be 9~10%.
A further improvement of the present invention lies in that the shell is porous SiO2Layer, shell thickness are 30~50nm, the aperture of shell
For 3~4nm.
Compared with prior art, the invention has the following beneficial effects:
(1) catalyst disclosed by the invention can by denitration escape ammonia under the conditions of SCR catalysis oxidation be nitrogen and water, thus
Reduce the escaping of ammonia.The catalyst is core-shell structure, and " core " mainly plays catalysed oxidn, and hydrophobic and porous " shell " on the one hand may be used
Influence of the vapor to " core " substance catalytic effect is effectively reduced, on the other hand due to its acidity (SiO2For acidic oxide) it can
To be enriched with more ammonia, it helps improve the whole the catalysis oxidation efficiency of catalyst.Therefore, the catalyst in the present invention is to ammonia
Gas the catalysis oxidation efficiency with higher (> 90%), and (unit load fluctuation) shadow is fluctuated by flue gas condition (smoke temperature, component)
Sound is small.Compared with traditional the escaping of ammonia control method, escape ammonia control is carried out with easy to operate (straight using catalyst of the invention
Connect the end for being arranged in SCR reactor), effect is good, does not influence the advantages that denitration efficiency.
(2) method for preparing catalyst disclosed by the invention include sol gel process (preparation of Ce-V/Ti powder), it is isometric
Impregnation technology (preparation of Cu-Ce-V/Ti powder) andTechnique (porous crust preparation), the above-mentioned equal mature and reliable of technique are fitted
Large-scale production is closed, engineering popularization and application are facilitated.
Detailed description of the invention
Fig. 1 is the catalyst structure schematic diagram that one kind disclosed by the invention can reduce denitration escape ammonia.Wherein, 1 is core, 2
For shell.
Specific embodiment
Present invention will now be described in detail with reference to the accompanying drawings..
A kind of its structure of the catalyst reducing denitration escape ammonia is as shown in Figure 1, be core 1 in shell 2, core 1 is Cu-Ce-V/
Ti powder, shell 2 are porous SiO2Layer.
Its chemical composition is related to preparation process, and the preparation process of catalyst includes the following steps:
(1) preparation of the inorganic nano-particle with the effect of catalysis oxidation ammonia
First with butyl titanate (1mol), cerous nitrate (0.047~0.052mol), ammonium metavanadate (0.01mol) and water
(6mol) is raw material, and dehydrated alcohol is solvent (8mol), and nitric acid (1mol, mass concentration 65-68%) is hydrolysis inhibitor, In
Solgel reaction occurs at room temperature until system viscosity is not further added by.Gained gel is dried for 24 hours at 100 DEG C or so, then
It is calcined 2 hours at 400 DEG C, obtains Ce-V/Ti powder.Then, copper sulphate (5.26~7.53g) is configured to aqueous solution, waits bodies
After product dipping Ce-V/Ti powder (100g), is ground in 100 DEG C or so dry 2h, then after 400 DEG C of dry 2h, finally obtain tool
The inorganic nano-particle Cu-Ce-V/Ti powder for thering is catalysis oxidation ammonia to act on.
In 100 DEG C or so dry 2h in the present invention, then in 400 DEG C of dry 2h, the reason is that: dinectly bruning water loss is too
Fastly, copper sulphate can be brought to catalyst surface, form surface enrichment, i.e., it is so-called " saltouing ".
(2) preparation of porous crust.
It utilizesCu-Ce-V/Ti powder (1 part) ultrasonic disperse is first being had dehydrated alcohol by technique preparation
In the three-necked flask of (300g), deionized water (400g) and concentrated ammonia liquor (mass concentration 28%, 5g), then with vigorous stirring, to
It is added dropwise in three-necked flask after ethyl orthosilicate (2.5~5g) in room temperature reaction 5~6 hours, reaction terminates, and is isolated by filtration
Afterwards, place the product in 50 DEG C, dry 12h is in -0.01MP a baking oven to get to a kind of catalyst that can reduce denitration escape ammonia
Si@Cu-Ce-V/Ti。
Catalyst prepared by the present invention is powdered catalyst with core-casing structure, and core is that have catalysed oxidn to ammonia
Solid inorganic nano-particle, shell are hydrophobic porous, inorganic shell.
The core is with nano-TiO2For carrier, V2O5、CuSO4And CeO2For the compound particle of active component, compound particle
Partial size be 40~50un, wherein V2O5Mass percentage is 1%, CuSO4Mass percentage be 5~7%, CeO2's
Mass percentage is 9~10%.
The shell is porous SiO2Layer, shell thickness are 30~50nm, and the aperture of shell is 3~4nm.
Si@Cu-Ce-V/Ti catalyst obtained is placed in homemade SCR reactor, ammonia catalytic efficiency is carried out
Evaluation.Simulated flue gas condition are as follows: 300~400 DEG C of smoke temperature, NO initial concentration is 50mg/m3, SO2Initial concentration is 2860mg/m3,
NH3Initial concentration is 50mg/m3, 2~8mg/m3, O2Concentration is 6 (v/v) %, H2O concentration is 10 (v/v) %.Pass through test reaction
Device imports and exports the concentration of ammonia in flue gas, calculates ammonia slip, and then characterizes catalyst to the catalysis oxidation efficiency of ammonia.
Embodiment 1
It is with butyl titanate (1mol), cerous nitrate (0.047mol), ammonium metavanadate (0.01mol) and water (6mol) first
Raw material, dehydrated alcohol are solvent (8mol), and nitric acid (1mol) is hydrolysis inhibitor, and solgel reaction occurs at room temperature to body
It is until viscosity is not further added by.Gained gel for 24 hours, then at 400 DEG C is calcined 2 hours in 100 DEG C or so dryings, obtains Ce-V/
Ti powder.
Then, copper sulphate (6.4g) is configured to aqueous solution, after incipient impregnation Ce-V/Ti powder (100g), at 100 DEG C
The dry 2h in left and right, then ground after 400 DEG C of dry 2h, finally obtain the inorganic nano-particle with catalysis oxidation ammonia effect
Cu-Ce-V/Ti powder.
(2) preparation of porous crust.
It utilizesCu-Ce-V/Ti powder (1g) ultrasonic disperse is first being had dehydrated alcohol by technique preparation
In the three-necked flask of (300g), deionized water (400g) and concentrated ammonia liquor (mass concentration 28%, 5g), then with vigorous stirring, to
It is added dropwise in three-necked flask after ethyl orthosilicate (3g) in room temperature reaction 6 hours, reaction terminates, after being isolated by filtration, by product
It is placed in 50 DEG C, dry 12h is in -0.01MP a baking oven to get to the catalyst Si@Cu-Ce-V/Ti that can reduce denitration escape ammonia.
Embodiment 2-7 other conditions are identical as 1 conditional of embodiment, and different see Table 1 for details.
1 embodiment 1-7 result of table
As it can be seen from table 1 the denitration efficiency of catalyst prepared by the present invention is 90% or more, up to 98%.
Catalyst prepared by the present invention is powdered core-shell structure: " shell " is porous SiO2Layer, with a thickness of 30~50nm, hole
Diameter is 3~4nm；" core " is with nano-TiO2For carrier, V2O5、CuSO4And CeO2For the compound particle of active component, compound particle
Partial size be 40~50um, wherein V2O5Mass percentage is 1%, CuSO4Mass percentage be 5~7%, CeO2's
Mass percentage is 9~10%.The preparation process of the catalyst includes: sol-gal process joint equi-volume impregnating preparation
" core " substance andMethod prepares " shell " layer.The catalyst of prepared core-shell structure has higher (> under the conditions of SCR
90%) ammonia catalytic efficiency, and its mature preparation process is reliable, can be used for coal fired power plant and carries out the control of denitration escape ammonia.
Claims (9)
1. the preparation method that one kind can reduce the catalyst of denitration the escaping of ammonia, which is characterized in that prepared by sol gel process
Then Ce-V/Ti powder is had the Cu-Ce- of catalysis oxidation ammonia effect by Ce-V/Ti powder by equi-volume impregnating preparation
V/Ti powder, then Cu-Ce-V/Ti powder is passed throughTechnique prepares the catalyst that can reduce denitration the escaping of ammonia.
2. the preparation method that one kind according to claim 1 can reduce the catalyst of denitration the escaping of ammonia, which is characterized in that logical
Sol gel process is crossed to prepare Ce-V/Ti powder detailed process is as follows: by butyl titanate, cerous nitrate, ammonium metavanadate, water,
Solgel reaction occurs at room temperature for dehydrated alcohol and nitric acid until system viscosity is not further added by, re-dry, calcining,
Obtain Ce-V/Ti powder；Wherein, the molar ratio of butyl titanate, cerous nitrate, ammonium metavanadate, water, dehydrated alcohol and nitric acid is
1:0.047~0.052:0.01:6:8:1.
3. the preparation method that one kind according to claim 2 can reduce the catalyst of denitration the escaping of ammonia, which is characterized in that dry
Dry temperature is 100 DEG C, and the time is for 24 hours.
4. the preparation method that one kind according to claim 2 can reduce the catalyst of denitration the escaping of ammonia, which is characterized in that forge
The temperature of burning is 400 DEG C, time 2h.
5. the preparation method that one kind according to claim 1 can reduce the catalyst of denitration the escaping of ammonia, which is characterized in that will
Ce-V/Ti powder prepares the process of the Cu-Ce-V/Ti powder with the effect of catalysis oxidation ammonia such as by equi-volume impregnating
Under: copper sulphate is configured to aqueous solution, after incipient impregnation Ce-V/Ti powder, in 100 DEG C of dry 2h, then in 400 DEG C of dry 2h
After grind, obtain the Cu-Ce-V/Ti powder with catalysis oxidation ammonia effect；Wherein, the matter of copper sulphate and Ce-V/Ti powder
Amount is than being (5.26~7.53): 100.
6. the preparation method that one kind according to claim 1 can reduce the catalyst of denitration the escaping of ammonia, which is characterized in that will
Cu-Ce-V/Ti powder passes throughThe process for the catalyst that technique preparation can reduce denitration the escaping of ammonia is as follows: first by Cu-Ce-
V/Ti powder ultrasonic is dispersed in the mixture of dehydrated alcohol, deionized water and ammonium hydroxide, ethyl orthosilicate is then added dropwise, after drop finishes
It is filtered after room temperature reaction 5~6 hours, it is dry, obtain the catalyst Si@Cu-Ce-V/Ti that can reduce denitration escape ammonia；Wherein,
Cu-Ce-V/Ti powder, dehydrated alcohol, deionized water, ammonium hydroxide and ethyl orthosilicate mass ratio be 1:300:400:5:(2.5~
5), the mass concentration of ammonium hydroxide is 28%.
7. the catalyst of any one of -6 the methods preparation according to claim 1, which is characterized in that the catalyst is powder
Shape core-shell structure, core are the solid inorganic nano-particles for having catalysed oxidn to ammonia, and shell is hydrophobic porous, inorganic shell.
8. catalyst according to claim 7, which is characterized in that the core is with nano-TiO2For carrier, V2O5、CuSO4
And CeO2For the compound particle of active component, the partial size of compound particle is 40~50un, wherein V2O5Mass percentage is 1%,
CuSO4Mass percentage be 5~7%, CeO2Mass percentage be 9~10%.
9. catalyst according to claim 7, which is characterized in that the shell is porous SiO2Layer, shell thickness be 30~
50nm, the aperture of shell are 3~4nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910764917.1A CN110479296B (en) | 2019-08-19 | 2019-08-19 | Catalyst capable of reducing escape of denitrated ammonia and preparation method thereof |
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| CN111623601A (en) * | 2020-05-29 | 2020-09-04 | 崇阳县青峰科技有限公司 | Ammonium metavanadate dehydration system and ammonium metavanadate ammonia-rich dehydration method |
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| US20090011937A1 (en) * | 2006-02-03 | 2009-01-08 | Vantieghem Herve R | Use of Fungicides for Increasing the Quality and Optionally the Quantity of Oil-Plant Products |
| CN108212146A (en) * | 2018-01-09 | 2018-06-29 | 上海大学 | Nucleocapsid denitrating catalyst of metallic monoliths and preparation method thereof |
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| US20090011937A1 (en) * | 2006-02-03 | 2009-01-08 | Vantieghem Herve R | Use of Fungicides for Increasing the Quality and Optionally the Quantity of Oil-Plant Products |
| CN108212146A (en) * | 2018-01-09 | 2018-06-29 | 上海大学 | Nucleocapsid denitrating catalyst of metallic monoliths and preparation method thereof |
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| CN111623601A (en) * | 2020-05-29 | 2020-09-04 | 崇阳县青峰科技有限公司 | Ammonium metavanadate dehydration system and ammonium metavanadate ammonia-rich dehydration method |
| CN111623601B (en) * | 2020-05-29 | 2021-08-27 | 崇阳县青峰科技有限公司 | Ammonium metavanadate dehydration system and ammonium metavanadate ammonia-rich dehydration method |
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