CN110252333A - A kind of preparation method and application of SCR demercuration catalyst - Google Patents
A kind of preparation method and application of SCR demercuration catalyst Download PDFInfo
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- CN110252333A CN110252333A CN201910598250.2A CN201910598250A CN110252333A CN 110252333 A CN110252333 A CN 110252333A CN 201910598250 A CN201910598250 A CN 201910598250A CN 110252333 A CN110252333 A CN 110252333A
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- catalyst
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- flue gas
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- 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
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
Abstract
The invention discloses a kind of preparation method and application of SCR demercuration catalyst, are related to flue gases purification field.Preparation method includes: to prepare carrier with coprecipitation；Carrier includes TiO2、Zr0.5Ti0.5O2And Zr0.45Ti0.45Ce0.10O2；With preparation catalyst composition；Catalyst load combinations object active component is selected from one of Fe, Cu, Mn, V, W, Mo, Cr, Co or several metal salts；By a certain percentage by multiple catalysts load combinations object, it is dissolved in 100mL distilled water, add a certain amount of carrier, magnetic agitation 2h, lh is stood under room temperature, dry 12h, is then placed in Muffle furnace at 200-600 DEG C and roasts 6h at 120 DEG C, grinds and sieves after natural cooling and takes the catalyst granules of 40~80 mesh spare.The present invention is by using TiO2、Zr0.5Ti0.5O2And Zr0.45Ti0.45Ce0.10O2NO in carrier fixed catalyst catalysis oxidation flue gasXAnd mercury, to realize denitrating flue gas demercuration.
Description
Technical field
The invention belongs to flue gases purification field, a kind of preparation method more particularly to SCR demercuration catalyst and answer
With.
Background technique
As the main contributor for causing the atmosphere polluting problems such as acid rain, photochemical fog, haze, nitrogen oxides (NOx)
Prevention and treatment has become urgent problem to be solved.Due to the bio-toxicity, persistence and Accumulative effect of mercury, coal-fired flue-gas mercury is dirty
The control of dye receives the extensive concern of international community in recent years.China is maximum artificial mercury emissions state in the world, great Liang Mei
The direct burning of charcoal is the main source of the artificial mercury emissions in China, and the discharge for controlling Mercury In Coal Combustion Flue Gas is extremely urgent.
Selective catalytic reduction (Selective Catalytic Reduction, SCR) technology is as most mature effective
Denitration technology has been widely used in each coal-burning power plant at present.Mercury in coal-fired flue-gas is mainly with Elemental Mercury (Hg0, particulate form
Mercury (Hgp) and oxidation state mercury (Hg2+) three kinds of forms exist.Hg0Highly volatile and not soluble in water, it is difficult to existing by coal-burning power plant
APCDs removing, therefore control Mercury Emissions from Coal-Fired Boilers key be control Hg0Discharge.Due to Hg2+High water solubility, by coal-fired cigarette
Hg0 in gas is oxidized to Hg2+, then Hg is removed using wet desulfurization system (WFGD)2+It is considered as a kind of combustion of great potential
Coal mercury pollution control technology.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method and application of SCR demercuration catalyst, by with TiO2、
Zr0.5Ti0.5O2And Zr0.45Ti0.45Ce0.10O2NO in carrier fixed catalyst catalysis oxidation flue gasXAnd mercury, to realize that flue gas is de-
Nitre demercuration.
In order to solve the above technical problems, the present invention is achieved by the following technical solutions:
The present invention is a kind of preparation method of SCR demercuration catalyst, comprising:
Carrier is prepared with coprecipitation；
Wherein, the carrier includes TiO2、Zr0.5Ti0.5O2And Zr0.45Ti0.45Ce0.10O2；
With preparation catalyst composition；
Wherein, catalyst load combinations object active component is selected from one of Fe, Cu, Mn, V, W, Mo, Cr, Co or several
Kind metal salt；
By a certain percentage by catalyst load combinations object, it is dissolved in 100mL distilled water, adds a certain amount of carrier, carry
Body is TiO2, Zr0.5Ti0.5O2And Zr0.45Ti0.45Ce0.1O2Carrier, magnetic agitation 2h stand lh under room temperature, dry at 120 DEG C
Then 12h is placed in Muffle kiln roasting 6h at 200-600 DEG C, grinds after natural cooling and sieve the catalyst particles for taking 40~80 mesh
Grain is spare.
Wherein, Fe, Cu element, Mn element, CeO in above-mentioned catalyst load combinations object2、V2O5, W element, Mo element, Cr
Element, Co3O4Carrier gross mass 0-10%, 0-5%, 0-40%, 0-60%, 0-9%, 0-50%, 0-15%, 0- are accounted for respectively
10%, 0-30%.
A kind of application of SCR demercuration catalyst, SCR demercuration catalyst SO in removing flue gas2, NOx, Hg answer
With.
The invention has the following advantages:
1, present invention TiO2、Zr0.5Ti0.5O2And Zr0.45Ti0.45Ce0.10O2Carrier fixed catalyst catalysis oxidation flue gas
Middle NOXAnd mercury, to realize denitrating flue gas demercuration.
2, the present invention can be completed at the same time denitration demercuration, contain a certain amount of sulfur dioxide, H suitable for flue gas composition2O and
The removing of nitrogen oxides and mercury.
Certainly, it implements any of the products of the present invention and does not necessarily require achieving all the advantages described above at the same time.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, will be described below to embodiment required
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for ability
For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached
Figure.
Fig. 1 is that a kind of catalytic association removes SO in flue gas2The experimental provision structural schematic diagram of/NOx/Hg.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts all other
Embodiment shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that, term " aperture ", "upper", "lower", " thickness ", "top", " in ",
Indicating positions or the positional relationship such as " length ", "inner", " surrounding ", are merely for convenience of description of the present invention and simplification of the description, without
It is that the component of indication or suggestion meaning or element must have a particular orientation, is constructed and operated in a specific orientation, therefore not
It can be interpreted as limitation of the present invention.
The present invention is a kind of preparation method of SCR demercuration catalyst, comprising:
Carrier is prepared with coprecipitation；
Wherein, the carrier includes TiO2、Zr0.5Ti0.5O2And Zr0.45Ti0.45Ce0.10O2；
With preparation catalyst composition；
Wherein, catalyst load combinations object active component is selected from one of Fe, Cu, Mn, V, W, Mo, Cr, Co or several
Kind metal salt；
By a certain amount of ferric nitrate Fe (NO)3, copper nitrate Cu (NO3)2-3H2O, manganese acetate Mn (CH3COO)2·4H2O, nitre
Sour cerium Ce (NO3)3·6H2O, ammonium metavanadate NH4VO3, ammonium tungstate, ammonium molybdate H8MoN2O4、Cr(NO3)3·9H2O、Co3O4、
Na2WO4·5H2O (wherein Fe, Cu, Mn, CeO2、V2O5、W、Mo、Cr、Co3O4Account for respectively carrier gross mass 5%, 3%, 20%,
30%, 5%, 0-50%, 8%, 5%, 15%), be once dissolved in 100mL distilled water, add a certain amount of carrier (specific ratio
Example is how many), carrier TiO2, Zr0.5Ti0.5O2And Zr0.45Ti0.45Ce0.1O2Carrier, magnetic agitation 2h stand lh under room temperature,
Then dry 12h at 120 DEG C is adjusted at 200-600 DEG C prior to Muffle kiln roasting 6h, ground after natural cooling and sieve take 40~
The catalyst granules of 80 mesh is spare.
A kind of application of SCR demercuration catalyst, the SCR demercuration catalyst SO2, NOx, Hg in removing flue gas are answered
With.
SO in a kind of catalytic association removing flue gas2The experimental provision of/NOx/Hg；
As shown in Figure 1, including N2Steel cylinder a1, O2Steel cylinder 2, SO2/N2Steel cylinder 3, NO/N2Steel cylinder 4, NH3/N2Steel cylinder 5；It is above-mentioned
Steel cylinder 1-5 have mass flowmenter control gas flow,
Water vapor generation device 6, heating electrothermal furnace 7, transformer 8 are for temperature control, mixed gas cylinder 9, thermometer 10, stainless pipe pipe
Catalytic reactor 11, holding furnace 12, absorbing ammonia bottle 13, flue gas analyzer 14, N2 steel cylinder a15, mercury generating device 16, KCl solution
Bottle 17, SnCl2Solution bottle 18, mercury analyzer 19 and exhaust gas processing device 20.
N2Steel cylinder a1, O2The outlet of steel cylinder 2 is respectively by entering water vapor generation device after coupled mass flowmenter
6；SO2/N2Steel cylinder 3, NO/N2Steel cylinder 4 enters mixed gas cylinder 9 and the N via water vapor generation device 6 after mixing2Steel cylinder a1, O2Steel cylinder
Gas mixing in 2, NH3/N2Steel cylinder 5 is directly entered reactor 11；N2Steel cylinder b15 carries out mercury via mercury generating device 16 and steams
Reactor 11 is entered back into after vapour, all the way the catalytic reactor import on the upper end cover of photo catalysis reactor 11 be connected, all the way with its
Flue gas analyzer 14 is connected；
Catalytic reactor 11, structural schematic diagram is as shown in Figure 1, include photo catalysis reactor entrance, catalytic reactor top
The upper end cover in portion, insulating layer and catalyst carrier titanium wire network, titanium wire network are located at the lower end of catalytic reactor bottom.
Catalyst is placed on the wire mesh in stainless steel tube reactor.
Catalytic reactor material is stainless steel；Insulating layer is wrapped in the outside of catalytic reactor cylinder；
11 upper end of catalytic reactor is equipped with catalytic reactor import, the i.e. import of flue gas, on the lower cover of bottom
It exports equipped with catalytic reactor, i.e. the outlet of flue gas, Fen Sanlu, divides after being passed through liquid phase scrubbing reactor 13 all the way into flue gas
Analyzer 14；KCl solution bottle 17, SnCl are respectively enterd all the way2After carrying out analysis measurement into mercury analyzer 19 after solution bottle 18, by
Computer exports measurement result；Another way is passed through exhaust gas processing device 20.
Reactor 6 is by pressure control heating device 8 come temperature control and control H2O content；
NOx/Hg joint removing in flue gas is carried out using the experimental provision of NOx/Hg in above-mentioned catalyst removal flue gas
Method is as follows:
NO, SO in simulated flue gas2、O2、N2Gas passes through mass flowmenter respectively, and in mercuryvapour generating device 16
NO, SO that the vapor that the Hg steam and water vapor generation device 6 of generation generate generates after the mixing of reactor 112With mixing for Hg
Simulated flue gas is closed, is entered in catalytic reactor 11 by top.
Different mass flowmenters can control the gas flow of different component, the change for vapor and Hg steam component
Change and is adjusted by controlling by the tolerance of water vapor generation device or mercuryvapour generating device 16.
Absorb that treated gas enter flue gas analyzer 14, NO, SO in the gas of measurement reaction front and back by acid solution2With
The variation of Hg concentration, calculates removal efficiency,
This catalyst is to SO in simulated flue gas2/ NOx/Hg removal efficiency is higher,
Removing can be combined with the device of NOx/Hg in a kind of catalyst joint removing flue gas of the invention to show
The method of NOx/Hg is feasible in flue gas.
Catalyst has catalytic action to NOx and Hg, is reduced to N2Be oxidized as bivalent mercury.Bivalent mercury is readily soluble
Yu Shui, can be directly by solution absorbing and removing.To express NO, SO2Reached with Hg by being absorbed after catalysis oxidation by absorbing liquid
Removal effect, set catalytic reactor device entrance NO, SO2It is C1, C2, C3 with Hg concentration, exports NO, SO after liquid phase scrubbing2
Concentration with Hg is C4, C5, C6, then catalysis oxidation combination liquid phase scrubbing removes NO, SO2It is respectively as follows: with the removal efficiency of Hg
In the description of this specification, the description of reference term " one embodiment ", " example ", " specific example " etc. means
Particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained at least one implementation of the invention
In example or example.In the present specification, schematic expression of the above terms may not refer to the same embodiment or example.
Moreover, particular features, structures, materials, or characteristics described can be in any one or more of the embodiments or examples to close
Suitable mode combines.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention
Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (2)
1. a kind of preparation method of SCR demercuration catalyst characterized by comprising
Carrier is prepared with coprecipitation；
Wherein, the carrier includes TiO2、Zr0.5Ti0.5O2And Zr0.45Ti0.45Ce0.10O2；
With preparation catalyst composition；
Wherein, catalyst load combinations object active component is selected from one of Fe, Cu, Mn, V, W, Mo, Cr, Co or several gold
Belong to salt；
Catalyst load combinations object is dissolved in 100mL distilled water, a certain amount of carrier, carrier TiO are added2,
Zr0.5Ti0.5O2And Zr0.45Ti0.45Ce0.1O2Carrier, magnetic agitation 2h stand lh under room temperature, then dry 12h at 120 DEG C exists
It is placed in Muffle furnace at 200-600 DEG C and roasts 6h, ground and sieve after natural cooling and take the catalyst granules of 40~80 mesh spare.
2. a kind of application of SCR demercuration catalyst of preparation method preparation as described in claim 1, which is characterized in that the SCR
Demercuration catalyst SO in removing flue gas2, NOx, Hg application.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721701A (en) * | 2019-10-16 | 2020-01-24 | 山东大学 | Cobalt-chromium modified catalyst and preparation method and application thereof |
| CN113470493A (en) * | 2020-03-31 | 2021-10-01 | 天津大学 | Device and method for simulating photochemical reaction and ozone reaction of active gaseous mercury in laboratory |
| CN113649037A (en) * | 2021-08-31 | 2021-11-16 | 武汉科技大学 | Catalyst suitable for low-temperature catalytic oxidation of mercury in oxygen-rich combustion flue gas and preparation method thereof |
| CN114849772A (en) * | 2022-06-09 | 2022-08-05 | 河北工业大学 | Mercury adsorption-catalyst and preparation method and application thereof |
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Cited By (6)
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| CN113649037A (en) * | 2021-08-31 | 2021-11-16 | 武汉科技大学 | Catalyst suitable for low-temperature catalytic oxidation of mercury in oxygen-rich combustion flue gas and preparation method thereof |
| CN114849772A (en) * | 2022-06-09 | 2022-08-05 | 河北工业大学 | Mercury adsorption-catalyst and preparation method and application thereof |
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Application publication date: 20190920 |