CN109158108A - A kind of catalyst and its preparation method and application for low-temperature denitration of flue gas - Google Patents
A kind of catalyst and its preparation method and application for low-temperature denitration of flue gas Download PDFInfo
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- CN109158108A CN109158108A CN201811057578.5A CN201811057578A CN109158108A CN 109158108 A CN109158108 A CN 109158108A CN 201811057578 A CN201811057578 A CN 201811057578A CN 109158108 A CN109158108 A CN 109158108A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003546 flue gas Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 16
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 9
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 5
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical group O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 7
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical group [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 208000037656 Respiratory Sounds Diseases 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 12
- 229910001868 water Inorganic materials 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 6
- 239000005751 Copper oxide Substances 0.000 abstract description 5
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 10
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000001133 acceleration Effects 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910003087 TiOx Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 241000883964 Ariocarpus retusus Species 0.000 description 1
- -1 Hydroxyl pentavalent antimony Chemical compound 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8435—Antimony
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J35/61—Surface area
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种用于低温烟气脱硝的催化剂及其制备方法和应用，该催化剂以二氧化钛为载体，以氧化铜为活性组分，氧化锑为助剂，其中，锑、铜和钛的摩尔比分别为0.1～0.6：1：10，制备方法包括以下步骤：将铜源和锑源混合溶于溶剂中，并加入钛源溶液，搅拌；搅拌过程中滴加乙醇水溶液，直到混合液形成透明胶状固体为止，然后室温下静置，直到胶状固体出现明显裂纹；当胶状固体干裂后，干燥得到透明晶状前驱体，然后将前驱体高温煅烧，研磨后，即得到产品。与现有技术相比，本发明催化剂在250‑350℃低温段内能达到90％的脱除NOx效率，具有较高的抗硫性能，抗水性能，具备一定抗毒化能力，具有较强的工业应用价值，可广泛应用于烟气中NOx的脱除。
The invention relates to a catalyst for low-temperature flue gas denitration, a preparation method and application thereof. The catalyst uses titanium dioxide as a carrier, copper oxide as an active component, and antimony oxide as an auxiliary agent, wherein the molar ratio of antimony, copper and titanium is The ratios are 0.1-0.6:1:10, respectively. The preparation method includes the following steps: mixing and dissolving the copper source and the antimony source in the solvent, adding the titanium source solution, and stirring; adding the ethanol aqueous solution dropwise during the stirring process until the mixed solution becomes transparent. After the colloidal solid is dry and cracked, the transparent crystalline precursor is obtained by drying, and then the precursor is calcined at high temperature and ground to obtain the product. Compared with the prior art, the catalyst of the invention can achieve 90% removal efficiency of NOx in the low temperature range of 250-350°C, has high sulfur resistance, water resistance, certain anti-poisoning ability, and has strong anti-toxicity. It has industrial application value and can be widely used in the removal of NOx from flue gas.
Description
Technical field
The present invention relates to catalyst technical fields, and in particular to a kind of catalyst and its preparation for low-temperature denitration of flue gas
Methods and applications.
Background technique
NOx is one of the important atmosphere pollution of coal fired thermal power plant discharge, is the important origin cause of formation of acid rain and photochemical fog,
The improvement of NOx becomes the focus that atmosphere pollution is administered.NH3SCR technology (SCR) be with NH3For also
Former agent reacts with NO under the effect of the catalyst and generates N2And H20, the research of catalysts is the key content of SCR research.
The catalyst applied to the mainstream in SCR reaction is V at present2O5-WO3/TiO2Although this catalyst has high activity and height
Sulfur resistance, but still there are some problems: first is that catalyst higher cost, second is that operation temperature necessarily is greater than 623K, it is higher
Catalyst operation temperature must be necessarily arranged at SCR reaction bed before air preheater, deduster and desulfurizer, and this cloth
Catalyst will necessarily be exposed to high concentration SO by the mode of setting2Under the flue gas of particle dusty, there is very strong poison to catalyst
Change effect seriously affects catalyst efficiency and service life, therefore it is necessary to develop cheap effective low-temperature SCR catalyst.
Copper oxide is widely used in low-temperature SCR in past research due to having quite high reproducibility at low temperature
The exploitation of denitrating technique catalyst.It is not high for the copper titanium catalyst activity of low-temperature denitration of flue gas in the prior art, especially
Low-temperature catalyzed efficiency is relatively low, and water resistant, anti-sulfur dioxide ability are poor, and the economy of production run is poor, when practical application, especially
It is in the SCR reaction unit of traditional coal-burning power plant, catalyst life cannot ensure.If it is anti-to develop efficient water resistant
Sulphur SCR low temperature catalyst, then can be very good to solve the above problems.
Summary of the invention
The purpose of the present invention is to solve the above-mentioned problems and provide a kind of catalyst for low-temperature denitration of flue gas and
Preparation method and application.
The purpose of the present invention is achieved through the following technical solutions:
A kind of catalyst for low-temperature denitration of flue gas, the catalyst are activity with copper oxide using titanium dioxide as carrier
Component, antimony oxide are auxiliary agent, wherein the molar ratio of antimony, copper and titanium is respectively 0~0.6:1:10, it is preferable that the antimony, copper and
The molar ratio of titanium is respectively 0.4~0.6:1:10, most preferably 0.4:1:10.
A kind of preparation method of the catalyst for low-temperature denitration of flue gas, comprising the following steps:
(1) copper source and antimony source are mixed and is dissolved in solvent, and titanium source solution is added, stirred；
(2) ethanol water is added dropwise in whipping process, until mixed liquor forms clear gummy solid, then at room temperature
It stands, until obvious crackle occurs in colloidal solid；
(3) after colloidal solid is dry and cracked, it is dried to obtain transparent crystalline presoma, then by presoma high-temperature calcination, grinding
Afterwards to get arrive product.
Preferably, step (1) copper source is nitrate trihydrate copper, and the antimony source is antimony acetate, and the solvent is anhydrous second
The mixed liquor that alcohol and ethylene glycol molar ratio are 10:3.
Preferably, step (1) the titanium source solution is the solution of tetrabutyl titanate for being dissolved in dehydrated alcohol.
Preferably, step (2) ethanol water is the ethanol water of mass fraction 20%.
Preferably, the dry temperature of step (3) is 100 DEG C, and the processing time is 72~96h.
Preferably, the temperature of step (3) high-temperature calcination is 550 DEG C, and calcination time is 4~6h.
The catalyst is used for denitrating flue gas, includes the following steps:
(1) before denitration experiment starts, it is first passed through argon gas 5min, catalyst and gas piping is purged under room temperature, removes residual
Residual air body and impurity；
(2) it is passed through NO, i.e., makes NO gas by catalyst at normal temperature, achievees the purpose that pre- absorption, so that catalyst
To the close saturation of the physical absorption of NO, the subsequent error for calculating denitration efficiency is avoided；
(3) when pre- absorption reaches saturation, opening program is passed through O2And NH3And vapor, fixed bed reactors are sent to,
Controlling reaction temperature is 100 DEG C -350 DEG C, flow velocity 1000ml/min.Air speed is 108000h-1, under the effect of the catalyst, will
NO is reduced to as N2；
(4) flue gas by denitrating catalyst reaction front and back NO concentration by ThermoNicoletiS50 flue gas analyzer Lai
It is recorded, catalyst is calculated to the denitration efficiency of flue gas according to NO amount variation in flue gas.
The simulated flue gas composition: NO 600ppm, NH3For 500ppm, oxygen 4%, H2O content is 5%, residual air
Body is as Balance Air.
For the present invention using titanium dioxide as carrier, in addition copper oxide adds a certain amount of antimony oxide as active component, catalysis
The preparation of agent uses sol-gal process, and titanium dioxide, copper oxide, antimony oxide are flocked together by gel, enables active component
Sufficiently it is supported on above carrier.XRD characterization the result shows that, the doping of antimony element can inhibit the growth of CuO crystallite dimension, enhancing member
Element is conducive to the suction of gas in reaction process to increase the specific surface area of catalyst surface in the dispersibility of catalyst surface
It is attached.XPS characterization result shows that the antimony element in catalyst is mainly embodied with pentavalent, and in active that best catalyst
Hydroxyl pentavalent antimony content is especially more, and hydroxyl quinquevalence antimony is conducive to NH4+- Bronsted acid site is increased, by In-situ Infrared into
Row Analysis on Mechanism, the results showed that optimal catalyst low-temperature zone NH4+- Bronsted acid site increased significantly, the conclusion one with XPS
It causes, in addition, the cupric in optimal catalyst also increases on year-on-year basis, this shows increasing doped with conducive to cupric for antimony element,
It is easily reduced when carrying out SCR reaction.In addition, carrying out the oxidation experiment of NO, optimal catalyst shows best oxidation susceptibility, this
May with antimony element adulterate promote it is cupric increase it is related.Also along with the oxidation of NO in SCR reaction process, and aoxidize
Product NO2More, " Fast-SCR " reacts easier progress, and also the higher present invention compares denitration efficiency with prior art, skill
Art progress is significant.
In addition, In-situ Infrared Characterization the result shows that, the L-H mechanism and E-R mechanism of the catalyst coexist, in the L- of low-temperature zone
In H mechanism, antimony element carries out chemisorption, while the nitrous acid that absorption is easy to react in catalyst surface doped with conducive to ammonia
Class group, gradually stronger Nitrates of thermal stability less.
Catalyst of the present invention can be to the nitrogen oxides of exhaust gas of the discharges such as power generation gas turbine and coal-burning boiler at
Reason can significantly improve low-temperature denitration activity, nitrogen selective and the anti-sulfur dioxide ability of water resistant.
Compared with prior art, the activity of catalyst provided by the invention Reduction of NO with higher in low temperature,
I.e. when denitration temperature is 250 DEG C, the conversion ratio of NO reaches 91% or more.Catalyst preparation process is simple, environment friendly and pollution-free, adopts
Catalyst is overcome because active component is single and easy by vapor and SO with bimetallic oxide component2The problem of influence, tool
There is stronger industrial application value.The catalyst that the present invention is prepared at 150-450 DEG C, especially at 300 DEG C hereinafter, compared with
Baseline catalyst is in activity and the anti-SO of water resistant2It is greatly improved in ability, is more conducive to that SCR denitration device is made to be arranged in thermal power plant's tail
Portion's flue improves thermal power plant's performance driving economy to reduce waste heat loss.
Detailed description of the invention
Fig. 1 is the catalytic efficiency that catalyst of the present invention and typical catalyst carry out denitrating flue gas under the same conditions.
Specific embodiment
The present invention is further described with specific embodiment below, but is not intended to limit the present invention.
Catalytic reactor used in example of the invention use the outer diameter purchased from Zhejiang Fan Tai Instrument Ltd. for
The 4100 type fixed bed micro anti-evaluation devices of 16mm, long 480mm, unstripped gas enter reactor by preheating, and reaction temperature exists
100-350 DEG C, flow velocity 1000ml/min, air speed ratio is 108000h-1。
Simulated flue gas composition: NO 600ppm, NH3For 600ppm and O2It is 5%, remaining gas Ar is as Balance Air, gas
Body flow is controlled by the CS200 type mass flowmenter purchased from Beijing Co., Ltd of Sevenstar Huachuang Electronic.
NO used in the present invention, NH3Molar concentration is 1%, is purchased from Shanghai Wei Chuan calibrating gas Co., Ltd, O2It is 5%,
Remaining gas Ar is purchased from Jiangnan mixed gas Co., Ltd as Balance Air；Drug used is purchased from Aladdin.
Embodiment 1
What is made according to the present invention is used to be catalyzed the catalyst of the NO of reduction, wherein doping component, mole of antimony, copper and titanium
Than for 0:1:10.Specific preparation step is as follows:
By 1.208g nitrate trihydrate copper dissolution in 40 milliliters of dehydrated alcohols, the dissolution of acceleration in 10 minutes is stirred at room temperature, so
It is 17.108g butyl titanate ethanol solution that 30 milliliters of Solute mass, which are followed by added, and stirring makes solution full and uniform mixed for 5 minutes
It closes；Continue to stir, the alcoholic solution of mass fraction 20% is gradually added dropwise in whipping process, is until mixed liquor gradually forms gel
Only.Resulting colloidal solid is stood into 12h at room temperature, colloid cracks, and putting it into drying in baking oven, for 24 hours, removal is urged
Dehydrated alcohol and moisture in agent, obtain crystalline presoma.Then resulting presoma is put into Muffle furnace at 550 DEG C
4h is calcined under environment, can be prepared by a kind of high-efficiency mercury removal catalyst (A).
Embodiment 2
What is made according to the present invention is used to be catalyzed the catalyst of the NO of reduction, wherein doping component, mole of antimony, copper and titanium
Than for 0.1:1:10.Specific preparation step is as follows:
By 1.208g nitrate trihydrate copper dissolution in 40 milliliters of dehydrated alcohols, the dissolution of acceleration in 10 minutes is stirred at room temperature, so
It is 17.108g butyl titanate ethanol solution that 30 milliliters of Solute mass, which are followed by added, and stirring makes solution full and uniform mixed for 5 minutes
It closes；0.149g antimony acetate is dissolved in 20mL ethylene glycol, stirring 30min makes it completely dissolved, and is then added in mixed liquor.
Continue to be stirred liquid, the alcoholic solution of mass fraction 20% be gradually added dropwise in whipping process, until mixed liquor gradually form it is solidifying
Until glue.Resulting colloidal solid is stood into 12h at room temperature, colloid cracks, and puts it into drying in baking oven and for 24 hours, goes
Except the dehydrated alcohol in catalyst, ethylene glycol and moisture obtain crystalline presoma.Resulting presoma is then put into Muffle furnace
In calcine 4h in the environment of 550 DEG C, can be prepared by a kind of efficient cryogenic denitrating catalyst (B).
Embodiment 3
What is made according to the present invention is used to be catalyzed the catalyst of the NO of reduction, wherein doping component, mole of antimony, copper and titanium
Than for 0.2:1:10.Specific preparation step is as follows:
By 1.208g nitrate trihydrate copper dissolution in 40 milliliters of dehydrated alcohols, the dissolution of acceleration in 10 minutes is stirred at room temperature, so
It is 17.108g butyl titanate ethanol solution that 30 milliliters of Solute mass, which are followed by added, and stirring makes solution full and uniform mixed for 5 minutes
It closes；0.2988g antimony acetate is dissolved in 20mL ethylene glycol, stirring 30min makes it completely dissolved, and is then added to mixed liquor
In.Continue to be stirred liquid, the alcoholic solution of mass fraction 20% is gradually added dropwise in whipping process, until mixed liquor gradually forms
Until gel.Resulting colloidal solid is stood into 12h at room temperature, colloid cracks, and it puts it into baking oven and dries for 24 hours,
The dehydrated alcohol in catalyst, ethylene glycol and moisture are removed, crystalline presoma is obtained.Resulting presoma is then put into Muffle
4h is calcined in the environment of 550 DEG C in furnace, can be prepared by a kind of efficient cryogenic denitrating catalyst (C).
Embodiment 4
What is made according to the present invention is used to be catalyzed the catalyst of the NO of reduction, wherein doping component, mole of antimony, copper and titanium
Than for 0.4:1:10.Specific preparation step is as follows:
By 1.208g nitrate trihydrate copper dissolution in 40 milliliters of dehydrated alcohols, the dissolution of acceleration in 10 minutes is stirred at room temperature, so
It is 17.108g butyl titanate ethanol solution that 30 milliliters of Solute mass, which are followed by added, and stirring makes solution full and uniform mixed for 5 minutes
It closes；0.598g antimony acetate is dissolved in 20mL ethylene glycol, stirring 30min makes it completely dissolved, and is then added in mixed liquor.
Continue to be stirred liquid, the alcoholic solution of mass fraction 20% be gradually added dropwise in whipping process, until mixed liquor gradually form it is solidifying
Until glue.Resulting colloidal solid is stood into 12h at room temperature, colloid cracks, and puts it into drying in baking oven and for 24 hours, goes
Except the dehydrated alcohol in catalyst, ethylene glycol and moisture obtain crystalline presoma.Resulting presoma is then put into Muffle furnace
In calcine 4h in the environment of 550 DEG C, can be prepared by a kind of efficient cryogenic denitrating catalyst (D).
Embodiment 5
What is made according to the present invention is used to be catalyzed the catalyst of the NO of reduction, wherein doping component, mole of antimony, copper and titanium
Than for 0.4:1:10.Specific preparation step is as follows:
By 1.208g nitrate trihydrate copper dissolution in 40 milliliters of dehydrated alcohols, the dissolution of acceleration in 10 minutes is stirred at room temperature, so
It is 17.108g butyl titanate ethanol solution that 30 milliliters of Solute mass, which are followed by added, and stirring makes solution full and uniform mixed for 5 minutes
It closes；0.896g antimony acetate is dissolved in 20mL ethylene glycol, stirring 30min makes it completely dissolved, and is then added in mixed liquor.
Continue to be stirred liquid, the alcoholic solution of mass fraction 20% be gradually added dropwise in whipping process, until mixed liquor gradually form it is solidifying
Until glue.Resulting colloidal solid is stood into 12h at room temperature, colloid cracks, and puts it into drying in baking oven and for 24 hours, goes
Except the dehydrated alcohol in catalyst, ethylene glycol and moisture obtain crystalline presoma.Resulting presoma is then put into Muffle furnace
In calcine 4h in the environment of 550 DEG C, can be prepared by a kind of efficient cryogenic denitrating catalyst (E).
Experiment test is first passed through fixed bed micro anti-evaluation device with the gaseous state NO in simulated flue gas before starting, and allows catalyst pair
The absorption of gaseous mercury reaches saturation, avoids the reduction for causing the NO detected when reaction because of suction-operated；Simulate gas (flue gas
Flow velocity 1000ml/min, gas concentration: NO 600ppm, NH3For 600ppm and O2Be 5%, remaining gas Ar) after mixing
It is sent into fixed bed micro anti-evaluation device and NO is reduced to by N by catalyst action at 100 DEG C~350 DEG C2, the NO of inlet and outlet
Concentration is detected using ThermoNicoletiS50 flue gas analyzer, and denitration effect is as shown in table 1.
The Activity evaluation tables of data of 1 different catalysts of table
As can be drawn from Table 1, using the catalyst that is prepared of the present invention and typical catalyst under the same conditions into
350 row denitrating flue gas, it is higher than typical catalyst denitration efficiency, when low-temperature zone denitration temperature is 200-300 DEG C, low-temperature denitration
The denitration efficiency of SbOx-CuOx-TiOx catalyst D is than benchmark CuOx-TiOx catalyst A high 35%~40%.
Catalyst obtained above is respectively placed in 100ppmSO2And 5%H2The anti-SO of water resistant is carried out under O2Poison experiment, it is real
It is as shown in Figure 1 to test result.The result shows that under the same conditions using the catalyst of the invention being prepared and typical catalyst
Carry out anti-H2O, anti-SO2Experiment, the antitoxinization performance of SbOx-CuOx-TiOx catalyst D is than benchmark CuOx-TiOx catalyst A
It is good.
To sum up, the catalyst that the present invention is prepared is anti-with water resistant in activity compared with baseline catalyst at 200~300 DEG C
SO2It is greatly improved in ability, is more conducive to that SCR denitration device is made to be arranged in thermal power plant's back-end ductwork, to reduce waste heat loss, mentions
High thermal power plant's performance driving economy.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (9)
1. a kind of catalyst for low-temperature denitration of flue gas, which is characterized in that the catalyst is using titanium dioxide as carrier, with oxidation
Copper is active component, and antimony oxide is auxiliary agent, wherein the molar ratio of antimony, copper and titanium is respectively 0.1~0.6:1:10.
2. a kind of catalyst for low-temperature denitration of flue gas according to claim 1, which is characterized in that the antimony, copper and
The molar ratio of titanium is respectively 0.4~0.6:1:10.
3. a kind of preparation method of the catalyst for low-temperature denitration of flue gas as described in claim 1, which is characterized in that including
Following steps:
(1) copper source and antimony source are mixed and is dissolved in solvent, and titanium source solution is added, stirred；
(2) ethanol water is added dropwise in whipping process, it is then quiet at room temperature until mixed liquor forms clear gummy solid
It sets, until obvious crackle occurs in colloidal solid；
(3) after colloidal solid is dry and cracked, it is dried to obtain transparent crystalline presoma, then by presoma high-temperature calcination, after grinding, i.e.,
Obtain product.
4. a kind of preparation method of catalyst for low-temperature denitration of flue gas according to claim 3, which is characterized in that step
Suddenly (1) copper source is nitrate trihydrate copper, and the antimony source is antimony acetate, and the solvent is that dehydrated alcohol is with ethylene glycol molar ratio
The mixed liquor of 10:3.
5. a kind of preparation method of catalyst for low-temperature denitration of flue gas according to claim 3, which is characterized in that step
Suddenly (1) described titanium source solution is the solution of tetrabutyl titanate for being dissolved in dehydrated alcohol.
6. a kind of preparation method of catalyst for low-temperature denitration of flue gas according to claim 3, which is characterized in that step
Suddenly (2) described ethanol water is the ethanol water of mass fraction 20%.
7. a kind of preparation method of catalyst for low-temperature denitration of flue gas according to claim 3, which is characterized in that step
Suddenly (3) dry temperature is 100 DEG C, and the processing time is 72~96h.
8. a kind of preparation method of catalyst for low-temperature denitration of flue gas according to claim 3, which is characterized in that step
Suddenly the temperature of (3) high-temperature calcination is 550 DEG C, and calcination time is 4~6h.
9. a kind of application of the catalyst for low-temperature denitration of flue gas as described in claim 1, which is characterized in that the catalyst
For denitrating flue gas.
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