CN107413327A - A kind of catalyst of low temperature removing nitrogen oxides in effluent and its preparation method and application - Google Patents
A kind of catalyst of low temperature removing nitrogen oxides in effluent and its preparation method and application Download PDFInfo
- Publication number
- CN107413327A CN107413327A CN201710395734.8A CN201710395734A CN107413327A CN 107413327 A CN107413327 A CN 107413327A CN 201710395734 A CN201710395734 A CN 201710395734A CN 107413327 A CN107413327 A CN 107413327A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- tio
- ceo
- certain amount
- support type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 238000001802 infusion Methods 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- 239000003546 flue gas Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- ODPUKHWKHYKMRK-UHFFFAOYSA-N cerium;nitric acid Chemical compound [Ce].O[N+]([O-])=O ODPUKHWKHYKMRK-UHFFFAOYSA-N 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 230000009466 transformation Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 5
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001243 acetic acids Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005367 electrostatic precipitation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 metavanadic acid Ammonium salt Chemical class 0.000 description 1
- ORQBXQOJMQIAOY-UHFFFAOYSA-N nobelium Chemical compound [No] ORQBXQOJMQIAOY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- 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
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
A kind of catalyst for being used to remove nitrogen oxides in effluent, it is a kind of support type V2O5‑CeO2/TiO2Catalyst, described catalyst be the anatase titania using 001 crystal face of preferential exposure as carrier, using infusion process successively load C e and V, CeO in catalyst2Weight/mass percentage composition be 1%~10%, V2O5Weight/mass percentage composition be 1%~10%.The catalyst possesses good denitration activity in middle low-temperature zone (200~300 DEG C), and NO Transformation efficiency is up to 90 %, conversion ratio is almost 100%, and has good water resistant sulfur resistance.The invention discloses its preparation method.
Description
Technical field：
The present invention relates to a kind of support type V2O5-CeO2/TiO2Catalyst and its answering in nitrogen oxides in effluent is removed
With.
Background technology：
Nitrogen oxides (including NO2And NO) it is one of main atmosphere pollution, they can cause serious environmental problem,
Including acid rain, photochemical fog, ozone depletion and greenhouse effects, the growth to the health and plant of the mankind causes serious danger
Evil.Nitrogen oxides is mainly derived from the burning of stationary source fossil fuel, such as Industrial Boiler, power station, waste incinerator, vaporization
Stove, engine, gas fired-boiler.
In the Flue Gas Denitration Technology of Coal-buming Power Plant applied at present, selective catalytic reduction (Selective Catalytic
Reduction, SCR) it is that most widely used, efficiency highest, service condition are gentle at present, and denitration master advanced in the world at present
Flow Technique, worldwide it is used widely.Active temperature windows, denitration efficiency, the N of catalyst2Selectivity, sulfur resistive,
Water resistant and alkali resistant metal poisoning ability determine practicality of the catalyst in SCR denitration system.In whole SCR denitration system
In, the cost of catalyst whole denitrating system investment accounting more than 40%.Therefore, the selection of catalyst is particularly critical, this
Us are required constantly to research and develop with high activity, high stability and the SCR denitration of high life.At present, industrial SCR
Denitrating system predominantly V used2O5-WO3/TiO2And V2O5-MoO3/TiO2Catalyst, their active temperature sections be 300 DEG C~
400 DEG C, be to belong to High-temperature scr catalyst.This kind of catalyst has preferable denitration ability and resistance to SO_2, still, applied to
Many problems are remained during flue gas denitrification system：V2O5-WO3/TiO2And V2O5-MoO3/TiO2The active temperature area of catalyst
Between be 300 DEG C~400 DEG C, so, because the limitation of operating temperature, flue gas denitrification system needs to be arranged on boiler and air preheat
Between device, but reaction gas now does not pass through electrostatic precipitation and desulfurization process, in flue gas containing substantial amounts of dust, alkali metal,
SO2Deng easily making catalyst be lost activity because duct is all filled in and is poisoned.On the other hand, flue-gas temperature is too high also easily makes NH3Oxidation
Generate NOx, influence the activity of catalyst.Therefore, the SCR catalyst of research and development high activity and high stability has critically important
Realistic meaning.
Catalyst using manganese as active component has preferable low-temperature SCR activity.Chinese patent CN201210014144.3
A kind of flue gas SCR denitration catalyst prepared using sol-gal process combination microwave technology is disclosed, traditional vanadium titanium is improved and urges
The SCR denitration efficiency of agent, 31.7 percentage points are improved in 250 DEG C of denitration effects than conventional commercial catalyst, is reached
83.6%.Chinese patent CN201110453171.6 discloses one kind using alundum (Al2O3) as carrier, and manganese oxide etc. is activearm
The middle low temperature SCR denitration catalyst divided, at 200 DEG C, NO conversion ratios reach 85%, and have preferable water resistant sulfur resistance..
Chinese patent CN201110407300.8 discloses one kind using attapulgite as carrier, in the catalysis of the oxide of Supported Manganese thereon
Agent composition, in addition plus catalysis of the oxide as auxiliary agent of two or more variable valency metal iron, copper, vanadium, cerium, nobelium
Agent.Reach 90% or so in 200 DEG C of nitrogen oxides in effluent removal efficiencies.But the sulfur resistance of manganese series catalyzer is poor, therefore one
Directly fail to realize industrial application.
The content of the invention：
It is an object of the invention to provide a kind of support type V2O5-CeO2/TiO2The preparation of catalyst and the nitrogen in flue gas is removed
Application in oxide.
Technical scheme is as follows：
A kind of catalyst for being used to remove nitrogen oxides in effluent, it is characterized in that：It is a kind of support type V2O5-CeO2/
TiO2Catalyst, described catalyst be using it is preferential exposure 001 crystal face anatase titania as carrier, using infusion process according to
Secondary load C e and V, CeO in catalyst2Weight/mass percentage composition be 1%~10%, V2O5Weight/mass percentage composition for 1%~
10%.
A kind of above-mentioned support type V2O5-CeO2/TiO2The preparation method of catalyst, it comprises the following steps：
Step 1, weigh a certain amount of cerous nitrate Ce (NO3)2·6H2O is dissolved in deionized water, is configured to 0.1mol/L's
Cerous nitrate solution, weigh a certain amount of anatase TiO2{ 001 } in small beaker, according to required load capacity, measured amounts
Cerous nitrate solution in beaker, ultrasonic agitation uniformly after be put into baking oven be evaporated to dipping night do not had TiO just2Powder surface,
After standing at room temperature, it is air-dried, CeO is made through air roasting again afterwards2/TiO2；
Step 2, the oxalic acid C for weighing 2.1g2H2O4·2H2O and a certain amount of ammonium metavanadate NH4VO3It is dissolved in deionized water,
It is configured to 0.1mol/L ammonium metavanadate solution；Weigh a certain amount of CeO2/TiO2Sample is in small beaker, according to required load
Amount, the ammonium metavanadate solution of measured amounts in beaker, be put into after ultrasonic 10s in 80 DEG C of baking ovens be evaporated to dipping night do not have just
Cross CeO2/TiO2Powder surface, after standing 24h at room temperature, 110 DEG C are air-dried 12h, afterwards 450 DEG C of air roasting 4h again, system
The support type V for removing nitrogen oxides in effluent must be used for2O5-CeO2/TiO2Catalyst.
The support type V of the present invention2O5-CeO2/TiO2Catalyst, nitrogen oxidation is removed available for low-temperature selective catalytic reduction
Thing reacts.
The support type V of the present invention2O5-CeO2/TiO2The application process of catalyst reduction removing nitrogen oxides is as follows：
Catalyst fines is ground, tabletting, after broken, sieving, takes 20~40 mesh catalyst 0.2g in U-shaped crystal reaction tube
In.Room temperature is passed through reactor feed gas, unstripped gas composition：NH31100ppm, NO 1000ppm, O24.%vol, remaining is Ar.Reaction
Condition：Reaction pressure is 0.1MPa, overall flow rate 210mL.min-1, reaction temperature is 100~400 DEG C.
Test result indicates that the anatase titania with specific preferential exposure (001) is carrier, soaked by substep
Stain method prepares support type V2O5-CeO2/TiO2Catalyst has good denitration activity for (200~300 DEG C) in middle low-temperature zone,
NO Transformation efficiency is up to 90 %, selectivity is almost 100%, and has good water resistant sulfur resistance.
The characteristics of catalyst of the present invention, is to contrast conventional commercial catalyst, the anatase two of preferential exposure (001)
Titanium oxide is carrier, the support type V prepared by step impregnation method2O5-CeO2/TiO2The SCR activity temperature window of catalyst is toward low temperature
Place widens, and the selectivity of catalyst is up to 100%.
Brief description of the drawings
Fig. 1 is that reference examples and embodiment catalyst carry out the catalytic-reduction denitrified reactivity worth result of nitrous oxides selectivity
Data.
Embodiment
Reference examples 1
(101) the Detitanium-ore-type TiO that face preferentially exposes2Carrier is prepared using traditional sol-gal process.In clean beaker
Middle addition 126mL n-butanols n-C4H10O, 14mL glacial acetic acids CH3COOH and 12mL deionized waters, are slowly added under agitation
48mL butyl titanate Ti (OC4H9)4, it is stirred vigorously to form gel at room temperature.The gel aged at room temperature 24h that will be formed, then
4h is calcined in 110 DEG C of dry removal organic solution, then 450 DEG C of air atmospheres.
Weigh a certain amount of cerous nitrate Ce (NO3)2·6H2O is dissolved in deionized water, is configured to 0.1mol/L cerous nitrate
Solution.Weigh a certain amount of TiO2In small beaker beaker, according to required load capacity, the cerous nitrate solution of measured amounts is in burning
Cup in, be put into after ultrasonic 10s in 80 DEG C of baking ovens be evaporated to dipping night do not had TiO just2Powder surface, after standing 24h at room temperature,
110 DEG C are air-dried 12h, afterwards 450 DEG C of air roasting 4h again, and CeO is made2/TiO2Sample.
Weigh a certain amount of oxalic acid C2H2O4·2H2O and a certain amount of ammonium metavanadate NH4VO3It is dissolved in deionized water, prepares
Into 0.1mol/L ammonium metavanadate solution.Weigh a certain amount of CeO2/TiO2Sample is in small beaker beaker, according to required load
Amount, the ammonium metavanadate solution of measured amounts in beaker, be put into after ultrasonic 10s in 80 DEG C of baking ovens be evaporated to dipping night do not have just
Cross TiO2Powder surface, after standing 24h at room temperature, 110 DEG C are air-dried 12h, afterwards 450 DEG C of air roasting 4h again.
Embodiment 1
(001) the Detitanium-ore-type TiO that face preferentially exposes2Carrier is prepared using HF- hydro-thermal methods.20mL is added in water heating kettle
Butyl titanate Ti (OC4H9)4, 3.2mL 40wt.%HF are slowly added dropwise under the conditions of being stirred at room temperature.Then 200 DEG C of hydro-thermal process
24h, white TiO is collected after cooling2Precipitation, sediment is by deionized water and ethanol washing and filtering, then repeatedly dry at 110 DEG C
It is dry.
Weigh a certain amount of cerous nitrate Ce (NO3)2·6H2O (Chemical Reagent Co., Ltd., Sinopharm Group A.R.) be dissolved in from
In sub- water, 0.1moVL cerous nitrate solution is configured to.Weigh a certain amount of above-mentioned TiO2In small beaker beaker, according to institute
Load capacity is needed, for the cerous nitrate solution of measured amounts in beaker, ultrasound is put into 80 DEG C of baking ovens after 10 seconds is evaporated to dipping night
Do not had TiO just2Powder surface, after standing 24h at room temperature, 110 DEG C are air-dried 12h, afterwards 450 DEG C of air roasting 4h again,
CeO is made2/TiO2Sample.
Weigh 2.1g oxalic acid C2H2O4·2H2O (Chemical Reagent Co., Ltd., Sinopharm Group A.R.) and a certain amount of inclined vanadium
Sour ammonium NH4VO3(Chemical Reagent Co., Ltd., Sinopharm Group A.R.) is dissolved in deionized water, is configured to 0.1mol/L metavanadic acid
Ammonium salt solution.Weigh a certain amount of CeO2/TiO2Sample is in small beaker beaker, load capacity needed for control, the inclined vanadium of measured amounts
Acid ammonium solution is in beaker, ultrasound 10sAfter be put into 80 DEG C of baking ovens be evaporated to dipping night do not had TiO just2Powder surface, room temperature
After lower standing 24h, 110 DEG C are air-dried 12h, afterwards 450 DEG C of air roasting 4h again, are made for removing nitrogen oxides in effluent
Support type V2O5-CeO2/TiO2Catalyst..
Application method
Low-temperature SCR performance is carried out on one group of miniature catalyst reaction device voluntarily assembled.Catalyst fines is through grinding
After mill, tabletting, broken, sieving, 20~40 mesh catalyst sample 0.2g are taken in U-shaped crystal reaction tube.It is former that room temperature is passed through reaction
Expect gas.Unstripped gas forms：NH31100ppm, NO 1000ppm, O24.%vol, remaining is Ar.Reaction condition：Reaction pressure is
0.1MPa, overall flow rate 210mL.min-1.Before mass spectrograph (Dycor Dymaxion DM300M, AMETEK) detection reaction
N afterwards2、NO、NO2And N2O concentration.Reference examples and embodiment catalyst performance result are as shown in Figure 1.Test result indicates that tool
The anatase titania for having specific preferential exposure (001) is carrier, and support type V is prepared by step impregnation method2O5-
CeO2/TiO2Catalyst possesses good denitration activity, NO Transformation efficiency is up to 90 %, conversion in middle low-temperature zone (200~300 DEG C)
Rate is almost 100%.
Claims (3)
1. a kind of catalyst for being used to remove nitrogen oxides in effluent, it is characterized in that：It is a kind of support type V2O5-CeO2/TiO2
Catalyst, described catalyst are using the preferential anatase titania for exposing 001 crystal face as carrier, are born successively using infusion process
Ce and V is carried, CeO in catalyst2Weight/mass percentage composition be 1%~10%, V2O5Weight/mass percentage composition be 1%~10%.
A kind of 2. support type V described in claim 12O5-CeO2/TiO2The preparation method of catalyst, it is characterized in that it is included such as
Lower step：
Step 1, weigh a certain amount of cerous nitrate Ce (NO3)2·6H2O is dissolved in deionized water, is configured to 0.1mol/L nitric acid
Cerium solution, weigh a certain amount of anatase TiO2{ 001 } carrier is in small beaker, according to required load capacity, measured amounts
Cerous nitrate solution in beaker, ultrasonic agitation uniformly after be put into baking oven be evaporated to dipping night do not had TiO just2Powder surface,
After standing a period of time at room temperature, it is air-dried completely, CeO is made through air roasting again afterwards2/TiO2；
Step 2, the oxalic acid C for weighing 2.1g2H2O4·2H2O and a certain amount of ammonium metavanadate NH4VO3It is dissolved in deionized water, prepares
Into 0.1mol/L ammonium metavanadate solution；Weigh a certain amount of CeO2/TiO2Sample is in small beaker, according to required load capacity, amount
A certain amount of ammonium metavanadate solution is taken in beaker, ultrasound 10 seconds after be put into 80 DEG C of baking ovens be evaporated to dipping night do not had just
CeO2/TiO2Powder surface, after standing 24h at room temperature, 110 DEG C are air-dried 12h, afterwards 450 DEG C of air roasting 4h again, are made
For removing the support type V of nitrogen oxides in effluent2O5-CeO2/TiO2Catalyst.
3. the support type V described in claim 12O5-CeO2/TiO2Catalyst, nitrogen is removed in flue gas low-temperature SCR
Application in oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710395734.8A CN107413327A (en) | 2017-05-27 | 2017-05-27 | A kind of catalyst of low temperature removing nitrogen oxides in effluent and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710395734.8A CN107413327A (en) | 2017-05-27 | 2017-05-27 | A kind of catalyst of low temperature removing nitrogen oxides in effluent and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107413327A true CN107413327A (en) | 2017-12-01 |
Family
ID=60429265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710395734.8A Pending CN107413327A (en) | 2017-05-27 | 2017-05-27 | A kind of catalyst of low temperature removing nitrogen oxides in effluent and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107413327A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108355648A (en) * | 2018-03-05 | 2018-08-03 | 河北工业大学 | A kind of preparation method and applications of titanium-based nano piece composite catalyst |
| CN109225200A (en) * | 2018-10-26 | 2019-01-18 | 安徽工业大学 | A kind of combined denitration takes off the V-Ce-Ti catalyst of dioxin |
| CN109569093A (en) * | 2018-12-12 | 2019-04-05 | 徐金宝 | A kind of air purifier ceramic element and its production method |
| CN110280315A (en) * | 2019-07-16 | 2019-09-27 | 中国科学院兰州化学物理研究所 | The method of low-temperature SCR catalyst anti-ABS and water resistant anti-dust performance in a kind of raising |
| CN112023907A (en) * | 2020-08-04 | 2020-12-04 | 华北电力大学 | Nitrogen oxide removal catalyst and preparation method thereof |
| CN112495446A (en) * | 2020-12-17 | 2021-03-16 | 南京永能新材料有限公司 | Cement denitration catalyst and preparation method and application thereof |
| CN113522299A (en) * | 2021-05-25 | 2021-10-22 | 宁夏亘峰嘉能能源科技股份有限公司 | Desulfurization, denitrification and mercury removal catalyst and preparation method thereof |
| CN116099529A (en) * | 2023-01-28 | 2023-05-12 | 中国科学院城市环境研究所 | Transition metal modified vanadium-based catalyst and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106423143A (en) * | 2016-05-30 | 2017-02-22 | 南京大学扬州化学化工研究院 | Catalyst for removing nitric oxide in exhaust gas at low temperature and preparation method and application of catalyst |
-
2017
- 2017-05-27 CN CN201710395734.8A patent/CN107413327A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106423143A (en) * | 2016-05-30 | 2017-02-22 | 南京大学扬州化学化工研究院 | Catalyst for removing nitric oxide in exhaust gas at low temperature and preparation method and application of catalyst |
Non-Patent Citations (2)
| Title |
|---|
| XUNAN ZHANG ET AL.: "Simultaneous removal of elemental mercury and NO from flue gas by V2O5-CeO2/TiO2 catalysts", 《APPLIED SURFACE SCIENCE》 * |
| 孟婷婷等: "载体优先暴露(001)面的负载型V2O5/TiO2催化剂SCR 性能", 《第九届全国环境催化与环境材料学术会议—助力两型社会快速发展的环境催化与环境材料会议论文集》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108355648A (en) * | 2018-03-05 | 2018-08-03 | 河北工业大学 | A kind of preparation method and applications of titanium-based nano piece composite catalyst |
| CN109225200A (en) * | 2018-10-26 | 2019-01-18 | 安徽工业大学 | A kind of combined denitration takes off the V-Ce-Ti catalyst of dioxin |
| CN109569093A (en) * | 2018-12-12 | 2019-04-05 | 徐金宝 | A kind of air purifier ceramic element and its production method |
| CN110280315A (en) * | 2019-07-16 | 2019-09-27 | 中国科学院兰州化学物理研究所 | The method of low-temperature SCR catalyst anti-ABS and water resistant anti-dust performance in a kind of raising |
| CN112023907A (en) * | 2020-08-04 | 2020-12-04 | 华北电力大学 | Nitrogen oxide removal catalyst and preparation method thereof |
| CN112023907B (en) * | 2020-08-04 | 2023-04-25 | 华北电力大学 | Nitrogen oxide removal catalyst and preparation method thereof |
| CN112495446A (en) * | 2020-12-17 | 2021-03-16 | 南京永能新材料有限公司 | Cement denitration catalyst and preparation method and application thereof |
| CN113522299A (en) * | 2021-05-25 | 2021-10-22 | 宁夏亘峰嘉能能源科技股份有限公司 | Desulfurization, denitrification and mercury removal catalyst and preparation method thereof |
| CN116099529A (en) * | 2023-01-28 | 2023-05-12 | 中国科学院城市环境研究所 | Transition metal modified vanadium-based catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107413327A (en) | A kind of catalyst of low temperature removing nitrogen oxides in effluent and its preparation method and application | |
| CN102350340B (en) | Composite smoke denitration catalyst capable of oxidizing zero-valence mercury | |
| CN105032395B (en) | Zirconium doping cerium vanadate denitrating catalyst, preparation method and application | |
| CN105833894B (en) | Have both the denitrating catalyst and its preparation method and application of alkali resistant (soil) metal and sulfur resistive water resistant function | |
| CN101773824B (en) | Catalyst for removing NOx in incineration gas and preparation method thereof | |
| CN107899568A (en) | A kind of preparation method for loading O composite metallic oxide catalyst and its application in exhaust-gas treatment field | |
| CN102335604B (en) | SCR (selective catalyctic reduction) low-temperature denitrification catalyst with nano core-shell structure and preparation method thereof | |
| CN104941630B (en) | Low-temperature high-activity flue gas denitration catalyst and preparation thereof | |
| JP5748895B1 (en) | Exhaust gas treatment system and treatment method | |
| CA2599114A1 (en) | Ammonia oxidation catalyst for the coal fired utilities | |
| CN108295840A (en) | Manganese-based catalyst and its preparation and application of a kind of efficient synergistic purification nitrogen oxides He bioxin | |
| CN104888795A (en) | Titanium oxide loaded vanadate denitration catalyst as well as preparation method and application thereof | |
| CN106423143A (en) | Catalyst for removing nitric oxide in exhaust gas at low temperature and preparation method and application of catalyst | |
| CN108212146A (en) | Nucleocapsid denitrating catalyst of metallic monoliths and preparation method thereof | |
| CN103962126B (en) | Catalyst for selectively catalyzing and reducing nitrogen oxides and preparation method thereof | |
| CN102553572A (en) | Selective catalytic reduction (SCR) catalyst of wide active temperature window and preparation method thereof | |
| CN106731226B (en) | The method that one step in-situ synthesis prepares binary denitration sulfur resistant catalyst load filtrate | |
| CN101773780A (en) | Method for depriving nitric oxide by plasma cooperating with low-temperature catalytic oxidation NO | |
| CN204865783U (en) | Low temperature flue gas denitration catalytic reaction device | |
| CN105148927B (en) | A kind of water resistant sulfur resistive type denitrating flue gas powder catalyst, preparation method and its usage | |
| CN114160123A (en) | Manganese-based metal oxide monomer catalyst, supported catalyst, preparation method and application method thereof | |
| CN113786828A (en) | Catalyst for synergistic removal of NOx and CVOCs and preparation method and application thereof | |
| CN105903477A (en) | Low temperature wide-active temperature window SCR denitration catalyst and preparation method thereof | |
| CN104437512A (en) | Transition-metal-modified Cu/CeO2 ordered mesopore material for NOx purification of stationary source | |
| CN108671931A (en) | A kind of method of modifying of the denitrating catalyst with anti-toxicity energy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171201 |
|
| WD01 | Invention patent application deemed withdrawn after publication |